• Advanced Photonics
  • Vol. 7, Issue 3, 034004 (2025)
Huaping Jia1, Fengjia Xie1, Elyes Nefzaoui2, Tarik Bourouina2,3..., Heng Jiang1,* and Xuming Zhang1,4,*|Show fewer author(s)
Author Affiliations
  • 1The Hong Kong Polytechnic University, Photonics Research Institute, Department of Applied Physics, Hong Kong, China
  • 2Université Gustave Eiffel, ESYCOM Lab, UMR 9007 CNRS, Marne-la-Vallée, France
  • 3Nanyang Technological University, CINTRA, IRL 3288 CNRS-NTU-THALES, Singapore
  • 4The Hong Kong Polytechnic University, Research Institute for Advanced Manufacturing (RIAM), Hong Kong, China
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    DOI: 10.1117/1.AP.7.3.034004 Cite this Article Set citation alerts
    Huaping Jia, Fengjia Xie, Elyes Nefzaoui, Tarik Bourouina, Heng Jiang, Xuming Zhang, "Black silicon nanostructures for solar energy conversion and photonic applications: a review," Adv. Photon. 7, 034004 (2025) Copy Citation Text show less

    Abstract

    The rapid advancement of renewable energy technologies is essential for combating global climate change and achieving energy sustainability. Among the various renewable sources, solar energy stands out, with silicon playing a pivotal role in solar energy conversion. However, traditional silicon-based devices often face challenges due to high surface reflectance, which limits their efficiency. The emergence of black silicon (b-Si) offers a transformative solution, thanks to its micro- and nanoscale structures that provide ultra-low reflectivity and enhanced light absorption. This makes b-Si an ideal candidate for improving solar energy devices. Beyond solar energy applications, b-Si has drawn notable interest in photonics, including applications in photodetectors, surface-enhanced Raman scattering, and imaging. This review explores b-Si comprehensively, discussing its fabrication processes, distinctive properties, and contributions to both solar energy conversion and photonic technologies. Key topics include its roles in solar cells, photoelectrochemical systems, solar thermal energy conversion, and advanced photonic devices. Furthermore, the review addresses the challenges and future directions for optimizing b-Si to facilitate its practical deployment across a range of energy and photonic applications.

    1 Introduction

    Advancing renewable energy technologies is essential for addressing the dual challenges of climate change and energy sustainability.13 Among the wide range of renewable energy sources, solar energy, as the most abundant resource on earth, offers tremendous potential for scalable solutions and global deployment, making it a cornerstone of future energy strategies.48 Silicon plays a vital role in solar energy applications,912 where its semiconductor properties enable efficient light absorption and conversion capacity. However, its indirect bandgap nature and high reflectance usually around 40% from visible light to mid-infrared wavelength, greatly restrict its applicability in photon-sensitive devices.1316 Addressing these challenges to improve the efficiency and cost-effectiveness of silicon-based solar technologies remains a critical area of research and development.17

    Black silicon (b-Si) is a unique silicon material characterized by its micro- and nanoscale structures, which have developed rapidly in recent years.1823 This material is notable for its ultra-low reflectivity, absorbing nearly all visible light and appearing pitch black to the naked eye, hence the designation “black silicon.”24 In contrast to conventional silicon which reflects light and appears gray, b-Si can absorb up to 99% in a broad wavelength range between 350 nm and 2250 nm, reflecting only about 1%.25,26 It is usually produced through various fabrication techniques, such as electrochemical etching, stain etching, metal-assisted chemical etching (MACE), reactive ion etching (RIE), and laser treatment, which create a textured surface with high aspect ratios.22,23,27 This unique structure not only improves optical absorption over a wide range of wavelengths but also enhances charge carrier dynamics, making it a promising candidate for solar energy conversion.28 In addition, when doped with specific impurities, such as sulfur, b-Si can extend its absorption capabilities into the near-mid infrared (NIR-MIR) range. These remarkable properties have spurred extensive research into various solar energy conversion applications in recent years.2934 Beyond energy conversion, b-Si nanostructures have emerged as versatile materials for photonic applications, in which the tunable optical properties enable advancements in photodetectors,35,36 surface-enhanced Raman scattering (SERS),3740 and imaging optoelectronic devices.4144 The incorporation of b-Si into these areas is paving the way for innovative technologies that can operate effectively across various wavelengths.

    Although several prior review articles have examined individual nanostructures of b-Si,45,46 and specific applications such as solar cells,19,30 or photodetectors,22 they often overlook the diverse nanostructures of b-Si, including holes, pyramids, and pillars, as well as comprehensive applications in solar energy conversion (such as, solar to electricity, chemical and thermal energy) and photonics devices (such as photodetector, SERS, imaging). This review aims to offer a comprehensive and up-to-date exploration of nanostructured b-Si and its applications in solar conversion and photonic applications (Fig. 1). First, it will discuss the various fabrication techniques and unique properties of b-Si, which helps to understand the underlying mechanisms responsible for its optical characteristics. Next, the recent advancements in integrating b-Si into solar energy conversion and high-performance photonics devices will be elaborated across four key areas: (i) solar cells, (ii) photoelectrochemical solar energy conversion, (iii) solar thermal energy conversion, and (iv) photonics-related applications, including photodetectors, SERS, and imaging applications. Finally, the challenges and future perspectives in the continued development and optimization of b-Si for practical applications will be explored.

    Illustrative overview of the topics covered in this review on black silicon (b-Si) nanostructures for solar energy conversion and photonic applications.

    Figure 1.Illustrative overview of the topics covered in this review on black silicon (b-Si) nanostructures for solar energy conversion and photonic applications.

    2 Nanostructured Black Silicon (b-Si) Properties and Fabrication Techniques

    2.1 Unique Properties of b-Si

    B-Si exhibits unique properties that make it highly suitable for solar energy conversion and photonic applications, distinguishing it from bulk silicon. In solar cells with thick wafers, optical management focuses on minimizing front-surface reflection by applying anti-reflection (AR) coatings and creating textured surfaces. The textured surface not only reduces reflection but also acts to trap photons, enhancing light capture and absorption, particularly at longer wavelengths.20

    As is shown in Fig. 2(a), b-Si significantly reduces reflectance through various mechanisms, which are influenced by the dimensions and geometry of its nanoscale surface features. First, multiple light interactions with the textured surface decrease reflection. Second, when the features are considerably larger compared with the wavelength of sunlight, surface scattering extends the light path, increasing absorption. Third, extremely small texture features create a gradual refractive index transition between air and silicon, facilitated by the nanostructured surfaces, as illustrated in Fig. 2(b).48 In this graded-index AR effect, the porous layer of b-Si acts as a medium with a reduced refractive index. With uniform porosity, the b-Si layer presents a refractive index that is intermediate between that of air and bulk silicon, leading to a step change at the interfaces as illustrated in Fig. 2(b-ii). A porosity gradient in Fig. 2(b-iii) further smoothens the refractive index transition, reducing reflectance even more effectively. The greatest reduction occurs when the b-Si layer thickness increases and the nanostructure size decreases [Fig. 2(b-iv)]. As illustrated in Figs. 2(c) and 2(d), the nano-textured surface comprises sub-wavelength structures with two rough interfaces: one at the transition between air and the nanostructured (nT) layer (top), and the other between the nT and bulk silicon (bottom). These subwavelength structures, combined with boundary roughness, enable the nT layer to act as a transitional medium where the refractive index smoothly changes between air and silicon. As incident light is reflected at various depths within the nT layer, destructive interference reduces reflection losses across a broad wavelength range.50 Moreover, the bandgap of b-Si can be modified through doping with specific impurities, which may make it optically ideal for advanced photonic devices. Figure 2(e) illustrates the development of enhanced b-Si absorption across broad spectral ranges (from visible-NIR26,52,53 to MIR regions51,54,55) through optimizing the etching and doping parameters. Remarkably, by combining heavy phosphorus doping with a high-aspect-ratio nanostructure, b-Si can function as a broadband perfect absorber with exceptional spectral coverage extending to 25  μm.

    (a) Light interaction mechanisms within nanostructured surfaces. (b) Four basic spatial refractive index profiles of thickness d: (i) refractive index profiles between air and a silicon substrate without any ARC; (ii) silicon wafer featuring a uniformly porous layer; (iii), (iv) silicon wafers with graded porosity profiles. Reproduced with permission,48 © 2002 AIP Publishing. (c) Schematic of a graded density or refractive index behavior in a silicon nanostructure (Si NS) array layer. Symbols: nair, nSi, and neff represent the refractive indices of air, silicon, and the Si NS layer, respectively. Reproduced with permission,49 © 2020 Springer Nature. (d) Illustration of the air-to-mc-Si boundary: left schematic presentation showing a sharp refractive index (n) shift at the boundary in region 1; right schematic presentation illustrating the gradual refractive index transition that enhances light trapping and absorption by introducing the nT-mc-Si layer in region 2. Reproduced with permission,50 © 2015 Elsevier. (e) The development of enhanced b-Si absorption across the visible-NIR region to the MIR region. Reproduced with permission,51 © 2022 John Wiley and Sons.

    Figure 2.(a) Light interaction mechanisms within nanostructured surfaces. (b) Four basic spatial refractive index profiles of thickness d: (i) refractive index profiles between air and a silicon substrate without any ARC; (ii) silicon wafer featuring a uniformly porous layer; (iii), (iv) silicon wafers with graded porosity profiles. Reproduced with permission,48 © 2002 AIP Publishing. (c) Schematic of a graded density or refractive index behavior in a silicon nanostructure (Si NS) array layer. Symbols: nair, nSi, and neff represent the refractive indices of air, silicon, and the Si NS layer, respectively. Reproduced with permission,49 © 2020 Springer Nature. (d) Illustration of the air-to-mc-Si boundary: left schematic presentation showing a sharp refractive index (n) shift at the boundary in region 1; right schematic presentation illustrating the gradual refractive index transition that enhances light trapping and absorption by introducing the nT-mc-Si layer in region 2. Reproduced with permission,50 © 2015 Elsevier. (e) The development of enhanced b-Si absorption across the visible-NIR region to the MIR region. Reproduced with permission,51 © 2022 John Wiley and Sons.

    In addition, numerical modeling has emerged as a critical tool for both understanding the fundamental properties of b-Si and optimizing its nanostructures for photonic applications.30,5658 State-of-the-art computational approaches, including finite-difference time-domain (FDTD) methods and rigorous coupled-wave analysis (RCWA), have quantitatively demonstrated that the unique nanostructured surface of b-Si can attribute to exceptional broadband antireflection capabilities. Zhu et al. systematically investigated the impact of variations in height (h) and bottom radius (r) on the absorptance of b-Si microstructures, demonstrating that h is directly proportional to absorptance, whereas r shows an inverse relationship.59 By simulating periodic pyramidal-like structures, Sai et al. further demonstrated that a sub-microstructured surface with a period exceeding 500  nm can simultaneously achieve minimal reflection and efficient light trapping.60 These modeling studies have proven instrumental in unraveling the intricate structure-property relationships between various nanostructure morphologies (e.g., nanowires, nanocones, and random textures) and optical performance, thereby facilitating the rational design of optimized light-trapping architectures. Most significantly, advanced multiphysics simulations integrating optical and electrical phenomena have elucidated crucial trade-offs between light absorption enhancement and surface recombination losses, providing critical guidance for developing optimized passivation strategies.

    Furthermore, due to its relatively low mechanical strength, b-Si facilitates the separation of ultra-thin wafers from silicon ingots. The large surface area and high activity of b-Si enhance its ability to act as a getter, effectively reducing impurities within the wafer.20

    2.2 Fabrication Methods of b-Si

    Over the past several decades, a variety of manufacturing techniques for b-Si have been developed and tested, including electrochemical etching, stain etching, MACE, RIE, and laser processing (Fig. 3). Each of these etching methods produces unique micro- and nanostructures, resulting in distinct optical and electrical properties.

    Schematic of b-Si fabrication methods: (a) electrochemical etching for macroporous silicon production, (b) stain etching process, (c) metal-assisted chemical etching (MACE) process, (d) reactive ion etching (RIE) process, (e) laser treatment process. Panels (a), (c), (d), and (e) are reproduced with permission,19 © 2014 John Wiley and Sons. The definitions of abbreviated characters (e.g., J, Nd, t, T, p, P, Φ) are provided in Table 1.

    Figure 3.Schematic of b-Si fabrication methods: (a) electrochemical etching for macroporous silicon production, (b) stain etching process, (c) metal-assisted chemical etching (MACE) process, (d) reactive ion etching (RIE) process, (e) laser treatment process. Panels (a), (c), (d), and (e) are reproduced with permission,19 © 2014 John Wiley and Sons. The definitions of abbreviated characters (e.g., J, Nd, t, T, p, P, Φ) are provided in Table 1.

    2.2.1 Electrochemical etching

    The electrochemical etching process utilizes silicon as the anode in a solution mainly containing hydrofluoric acid (HF). By fine-tuning parameters such as current density, HF concentration, etching duration, and illumination, this method enables precise control over the morphology of b-Si. Originally introduced by Memming and Schwandt,61 this technique gained prominence following the discovery of the luminescence phenomenon in porous silicon, signifying the advent of a novel silicon-based nanomaterial. As illustrated in Fig. 4(a), a silicon wafer (either n-type or p-type) is attached to the anode of an electrochemical cell and immersed in a mixture of HF, water, and ethanol.20 HF is essential for dissolving the silicon oxides produced during the etching, forming complexes that are soluble in water. Meanwhile, water participates in the oxidation reactions and helps regulate HF concentration to control reaction rates. Ethanol reduces silicon’s surface tension, improving wettability, facilitating the release of hydrogen (H2) gas, and enhancing HF penetration into silicon pores.

    (a) Typical experimental configurations for electrochemical HF etching of p-Si (left) and n-Si (right). Reproduced with permission,20 © 2014 Royal Society of Chemistry. (b) Energy band diagrams of n-Si/HF and p-Si/HF junctions at the equilibrium. (c) Typical J–V curves for Si/HF junctions: p-Si/HF (red line) and n-Si/HF in the dark (blue line) and under illumination (blue dashed line). (d) Simulated etching kinetics and corresponding etched morphologies. The blue line and color map represent JPS and Ctip variations due to HF molecule diffusion within the pore. Etched profiles and current densities are shown for cases where the hole supply exceeds (yellow line), falls short of (green line), or perfectly matches (red line) HF diffusion. (b)–(d) Reproduced with permission,62 © 2024 John Wiley and Sons. (e) SEM picture of porous silicon fabricated by electrochemical etching. Reproduced with permission,63 © 2007 IOP Publishing.

    Figure 4.(a) Typical experimental configurations for electrochemical HF etching of p-Si (left) and n-Si (right). Reproduced with permission,20 © 2014 Royal Society of Chemistry. (b) Energy band diagrams of n-Si/HF and p-Si/HF junctions at the equilibrium. (c) Typical JV curves for Si/HF junctions: p-Si/HF (red line) and n-Si/HF in the dark (blue line) and under illumination (blue dashed line). (d) Simulated etching kinetics and corresponding etched morphologies. The blue line and color map represent JPS and Ctip variations due to HF molecule diffusion within the pore. Etched profiles and current densities are shown for cases where the hole supply exceeds (yellow line), falls short of (green line), or perfectly matches (red line) HF diffusion. (b)–(d) Reproduced with permission,62 © 2024 John Wiley and Sons. (e) SEM picture of porous silicon fabricated by electrochemical etching. Reproduced with permission,63 © 2007 IOP Publishing.

    During the process, charge transfer occurs between the silicon and the electrolyte until equilibrium is reached, aligning the silicon’s Fermi level (EF) with the electrolyte’s electrochemical potential (ER). For n-type silicon (n-Si), where EF>ER, electrons transfer from the silicon to the electrolyte, which creates a space-charge region (SCR) beneath the surface and induces an upward bending of the silicon energy bands. Conversely, in p-type silicon (p-Si), where EF<ER, electrons flow from the electrolyte to the silicon, resulting in the energy bands to bend downward [Fig. 4(b)]. The distinct behaviors of n- and p-Si are evident in their current density–voltage (JV) characteristics. As illustrated in Fig. 4(c), the p-Si/HF junction is forward-biased for V>0, whereas the n-Si/HF junction is reverse-biased. Notably, the JV curves of n-Si/HF resemble those of p-Si when exposed to light, indicating that silicon’s electronic properties minimally impact its electrochemical behavior. Both p-type and n-type silicon share similar dissolution mechanisms and chemistry during etching, and the peak current density (JPS) signifies the transition between the two states.62,64 Experimental studies reveal that JPS follows an Arrhenius relationship with temperature and depends exponentially on the HF concentration. This behavior is captured by the semi-empirical equation: JPS=CPS·CHFξ·exp(EaKT),where CPS (Am2) is an empirical constant, CHF (%) is the volumetric HF fraction, ξ is an empirical exponent, Ea is the activation energy, K=1.38×1023  JK1 is the Boltzmann constant, and T is the thermodynamic temperature. This equation is critical for controlling electrochemical etching to form well-ordered silicon micro- and nanostructures. Simulated etching kinetics, corresponding morphologies, and SEM images of porous silicon are shown in Figs. 4(d) and 4(e).62,63

    Using photolithographically defined masks, selective polishing of regions can be achieved through electrochemical etching, enabling the fabrication of three-dimensional micro- and nanostructures.6567 At lower current levels, factors such as current strength, HF concentration, etching time, and illumination influence the etching process. Increasing the current or reducing the HF concentration leads to larger pore diameters, while extended etching times result in deeper pores. The type and concentration of doping in the silicon wafer also impact its morphology: in p-type silicon, higher doping levels lead to an increase in pore diameter, with values spanning from 1 to 100 nm; conversely, in n-type silicon, higher doping concentrations result in a reduction of pore diameter, ranging from 10  μm to 10 nm.20,68 These dependencies provide precise control for the fabrication of silicon nanostructures to meet various application needs. This method is unsuitable for large-scale production and causes fluoride wastewater in the process.

    2.2.2 Stain etching

    Stain etching usually utilizes a mixture of HF and HNO3 to chemically etch silicon, creating porous silicon structures [Fig. 5(a)]. This method is typically considered a localized electrochemical etching process, similar to electrochemical HF etching.20 To control the etching process, H2O or acetic acid is commonly used to reduce the concentrations of HF and HNO3, with acetic acid additionally acting as a wetting agent. The etching process follows a stepwise oxidation-dissolution mechanism: HNO3 enters the pores to oxidize the silicon, while HF eliminates the resulting silicon oxide. The porous layer becomes thicker as the etching duration increases, with Fig. 5(b) illustrating the reflectance spectra of porous silicon etched on a multicrystalline silicon (mc-Si) wafer for varying durations.70

    (a) Stain etching process. Reproduced with permission,69 © 2023 Ishik University. (b) Reflectance spectra of stain-etched porous silicon on an mc-Si wafer. Reproduced with permission,70 © 2017 IOP Publishing; reproduced with permission,20 © 2014 Royal Society of Chemistry. (c)–(e) SEM images of Si micropillars obtained by the stain etching under different conditions, showing various shapes: (c) Si tubes incorporating a homogeneous porous silicon layer etched from the BHNO solution; (d) Si tubes covered with porous silicon after etching in an HVO solution; and (e) Si micro-cones covered with porous silicon. Scale bar: 2 μm. (c)–(e) Reproduced with permission,71 © 2017 IOP Publishing.

    Figure 5.(a) Stain etching process. Reproduced with permission,69 © 2023 Ishik University. (b) Reflectance spectra of stain-etched porous silicon on an mc-Si wafer. Reproduced with permission,70 © 2017 IOP Publishing; reproduced with permission,20 © 2014 Royal Society of Chemistry. (c)–(e) SEM images of Si micropillars obtained by the stain etching under different conditions, showing various shapes: (c) Si tubes incorporating a homogeneous porous silicon layer etched from the BHNO solution; (d) Si tubes covered with porous silicon after etching in an HVO solution; and (e) Si micro-cones covered with porous silicon. Scale bar: 2  μm. (c)–(e) Reproduced with permission,71 © 2017 IOP Publishing.

    In addition, the silicon surface morphology can be tailored by adjusting the HF-to-HNO3 concentration ratio (C=[HF]/[HNO3]). When [HF] exceeds [HNO3], the etching rate is governed by the oxidation rate, resulting in porous silicon. Conversely, when [HNO3] is much higher than [HF], the reaction is constrained by HF’s ability to remove silicon oxide. In this high-[HNO3] regime, the etching process is typically employed for surface cleaning, damage removal, or polishing. By fine-tuning C, stain etching can texturize mc-Si, which is challenging for conventional alkaline etching due to the material’s diverse crystal orientations. Figures 5(c)5(e) demonstrate how different etching parameters—such as silicon doping, solution pH, and etching time—yield varied nanostructures starting from the same geometry of pillars.71

    It is worth noting that stain etching rapidly removes the silicon surface, creating a gradual transition from solid silicon to full porosity.72 However, this method has a limit on the maximum thickness of the porous layer20 and may also lead to fluoride wastewater and NOx emissions. As the layer thickens, pore growth slows because the diffusion of reactants and products decreases in the deeper pores. The maximum thickness is reached when the pore growth rate matches the etching rate at the surface.

    2.2.3 Metal-assisted chemical etching

    MACE is a widely employed technique for fabricating b-Si with high aspect ratios and tunable dimensions and morphologies.62,73 In this approach, a metal catalyst layer is applied to a silicon substrate, guiding the etching process when exposed to HF and an oxidizing agent. The metal catalyst, commonly gold (Au),7477 silver (Ag),78,79 copper (Cu),8082 or Ni,83,84 facilitates the formation of micro- and nano-structured surfaces. Metals can be deposited using vacuum-based techniques, such as thermal evaporation, sputtering, or electron beam evaporation, or through solution-based methods such as electroless or electrodeposition. Vacuum deposition provides precise control over the morphology of the metal film, whereas electroless deposition provides a simpler approach, better suited for applications with less demanding surface requirements. Acting as an etching mask, the metal layer selectively protects parts of the silicon surface, allowing etching in exposed regions and controlling the direction and depth of the etching. Figure 6(a) illustrates the MACE process: (1) reduction of the oxidizer (e.g., H2O2) under the catalysis of noble metal particles; (2) hole injection into the silicon substrate, with the highest concentration beneath the metal particle; (3) hole migration to silicon sidewalls and surfaces; and (4) HF removes the silicon oxide. Equations (2) and (3) describe the chemical reactions involved, using gold nanoparticles as an example. H2O2+2H+Au2H2O+2h+,Si+4HF2+2h+SiF62+2HF+H2(gas).

    (a) Schematic of the metal-assisted chemical etching (MACE) process. (b) Energy band diagrams (top) of the Au/Si interface and the corresponding MACE morphology schematic (bottom) for n- and p-type silicon. (c) SEM images of the experimental MACE morphologies for various n- and p-Si electrodes. (a)–(c) Reproduced with permission,85 © 2016 American Chemical Society. (d) Top-view SEM image of commercially boron-doped (1 to 3 Ω cm), (100) oriented c-Si wafers etched for 15 min at 50°C in a 5 mmol/L Cu(NO3)2, 4.6 mol/L HF, and 0.55 mol/L H2O2 mixed solution. The inset shows the cross-sectional SEM image. Reproduced with permission,86 © 2017 Royal Society of Chemistry. (e) FDTD simulation results illustrating the electric field intensity profiles for silicon with inverted pyramid structures (left) and upright pyramid structures (right). Reproduced with permission,80 © 2017 Elsevier.

    Figure 6.(a) Schematic of the metal-assisted chemical etching (MACE) process. (b) Energy band diagrams (top) of the Au/Si interface and the corresponding MACE morphology schematic (bottom) for n- and p-type silicon. (c) SEM images of the experimental MACE morphologies for various n- and p-Si electrodes. (a)–(c) Reproduced with permission,85 © 2016 American Chemical Society. (d) Top-view SEM image of commercially boron-doped (1 to 3 Ω cm), (100) oriented c-Si wafers etched for 15 min at 50°C in a 5 mmol/L Cu(NO3)2, 4.6 mol/L HF, and 0.55 mol/L H2O2 mixed solution. The inset shows the cross-sectional SEM image. Reproduced with permission,86 © 2017 Royal Society of Chemistry. (e) FDTD simulation results illustrating the electric field intensity profiles for silicon with inverted pyramid structures (left) and upright pyramid structures (right). Reproduced with permission,80 © 2017 Elsevier.

    In the MACE process, silicon oxide forms beneath metal particles and is etched away by HF, allowing the metal to penetrate into the silicon and develop a porous structure, in which the pore depth is controlled by the etching duration. After achieving the desired structure, the metal nanoparticles are dissolved with an etchant such as HNO3, followed by a cleaning procedure. Figure 6(b) illustrates the energy band diagrams of the Au/Si interface and the morphologies of n-type and p-type silicon after MACE. SEM images of the etched morphologies for various n- and p-Si electrodes are shown in Fig. 6(c).85 Toor et al. demonstrated nanoporous b-Si fabricated via cost-effective copper-assisted etching, achieving an average solar spectrum reflection as low as 3.1%.60 As shown in Fig. 6(d), Wang et al. demonstrated the formation of inverted pyramid structures on the silicon surface through a similar MACE process using Cu nanoparticles. Figure 6(e) illustrates the FDTD simulation results, showing the electric field intensity distribution in both inverted pyramid and upright pyramid structures.80 These findings highlight the potential of Cu nanoparticle-assisted etching for fabricating structures with distinct optical and electronic properties. In addition, by adopting masking materials, such as polystyrene (PS) spheres, anodic aluminum oxide (AAO) templates, and photoresists, this method can ensure consistent and uniform nanostructures on b-Si surfaces.23 Huang et al. fabricated b-Si nanowire arrays using PS sphere masks, achieving precise control over nanowire diameter, height, and spacing.87 They also employed AAO templates fixed on silicon via spin-coated polystyrene, producing silicon nanowires (SiNWs) with diameters below 10 nm.74

    To conclude, MACE is a simple, fast, cost-effective, and adaptable technique for producing various nanostructures, requiring only basic equipment. Wet etching methods using Ag and Cu catalysts are especially promising for the affordable and large-scale production of b-Si in commercial silicon photovoltaic (PV) applications.88 The resulting surface morphology of b-Si depends on factors such as the type, size, shape, and coverage of metal nanoparticles, as well as the etching time, etchant composition, and temperature.8890 Over the past few decades, MACE has garnered widespread attention in research and remains a leading method for etching. However, metal contamination presents a major challenge for solar cell applications; thus, it is crucial to employ effective metal removal and cleaning procedures to guarantee optimal performance and reliability. In addition, the resulting Ag/heavy metal-contaminated fluoride wastewater may pose toxicity risks; therefore, further recovery of nanoparticles or the use of Fe/Cu catalysts could help mitigate heavy metal pollution.

    2.2.4 Reactive ion etching

    RIE is a dry etching technique characterized by its high anisotropy and excellent selectivity, achieved through ion-induced chemical reactions [Fig. 7(a)].91 First introduced by Gittleman et al. at RCA Laboratories in 1979, RIE was used to create non-reflective b-Si surfaces for applications such as solar thermal energy conversion.94 In 1995, Jansen et al. demonstrated the application of RIE to produce grass-like b-Si surfaces.95 As illustrated in Fig. 7(b), this approach uses SF6 and O2 gases to produce F* and O* radicals. F* etches silicon, forming volatile products such as SiFx, whereas SiF4 reacts with O* to create a passivation layer of SiOxFy on the silicon surface.91 Ion bombardment selectively removes this passivation layer on exposed areas, allowing further etching by F*. On the sidewalls of silicon columns, where ion bombardment is minimal, the passivation layer remains intact, shielding these areas from additional etching. This interplay between etching and passivation results in the self-masked formation of random, high-aspect-ratio silicon microstructures. Huang et al. reported a simple approach for creating aperiodic silicon nanotip (SiNT) arrays on 6-in. wafers with sub-wavelength structures. These structures significantly reduce light reflection across a wide spectral range, spanning from ultraviolet to terahertz. Figures 7(d)7(f) display SEM images of the SiNTs and their corresponding absorption spectra.93

    (a) Schematic illustrating the fabrication of b-Si via plasma-assisted reactive ion etching (RIE) with inductively coupled plasma (ICP). (b) Process diagram showing alternating etching and deposition steps to create high-aspect-ratio features on Si wafers. (a) and (b) Reproduced with permission,91 © 2017 Royal Society of Chemistry. (c) Schematic representation of RIE-induced damage on a silicon substrate. Reproduced with permission,92 © 1999 American Vacuum Society; reproduced with permission,20 © 2014 Royal Society of Chemistry. (d) Tilted top-view and (e) cross-sectional SEM images of SiNTs with a length of 1600 nm. (f) Absorption spectra comparison of SiNTs (filled squares) and crystalline silicon (solid line) across the UV-vis-NIR range. (d)–(f) Reproduced with permission,93 © 2007 Springer Nature.

    Figure 7.(a) Schematic illustrating the fabrication of b-Si via plasma-assisted reactive ion etching (RIE) with inductively coupled plasma (ICP). (b) Process diagram showing alternating etching and deposition steps to create high-aspect-ratio features on Si wafers. (a) and (b) Reproduced with permission,91 © 2017 Royal Society of Chemistry. (c) Schematic representation of RIE-induced damage on a silicon substrate. Reproduced with permission,92 © 1999 American Vacuum Society; reproduced with permission,20 © 2014 Royal Society of Chemistry. (d) Tilted top-view and (e) cross-sectional SEM images of SiNTs with a length of 1600 nm. (f) Absorption spectra comparison of SiNTs (filled squares) and crystalline silicon (solid line) across the UV-vis-NIR range. (d)–(f) Reproduced with permission,93 © 2007 Springer Nature.

    The morphology of b-Si fabricated through RIE can be controlled by adjusting factors such as gas composition, flow rate, system temperature, substrate bias, and RF power. A higher O2 flow rate promotes the formation of the passivation layer, whereas elevated temperatures accelerate its removal. By tuning the passivation layer coverage, the nanostructure density can be precisely controlled. In addition, increasing the substrate bias modifies ion energy, affecting ion bombardment and controlling the etching rate. However, RIE can impact the silicon surface, leading to damage that shortens the minority carrier lifetime near the surface [Fig. 7(c)].92 To address this, a post-etching step is commonly used to eliminate the uppermost 20 to 50 nm of the silicon layer. Alternative approaches include reducing RF power and substrate bias, minimizing O2 usage, shortening the etching time, or annealing the wafer at elevated temperatures (e.g., 400°C) to restore minority carrier lifetime. However, these measures may reduce etching efficiency, throughput, and increase operational costs.92 In addition, the process may produce greenhouse gases and toxic plasma byproducts, highlighting the critical need for future research into alternative gases.

    2.2.5 Laser treatment

    Femtosecond laser processing offers a flexible method for texturing the surface of silicon substrates.9698 The setup for b-Si preparation using femtosecond laser pulses is shown in Fig. 8(a).99 Various settings can be adjusted to enhance the properties and structure of b-Si, including laser polarization, spot size, intensity, pulse number, scanning parameters, and environmental conditions. The laser intensity controls the material removal rate and silicon evaporation, whereas the number of pulses determines the interaction time, with longer exposure allowing deeper energy penetration into the silicon wafer. By optimizing these parameters, very high spikes can be produced. Huang’s studies highlight the importance of laser fluence in shaping surface morphology. As fluence increases, the size of micro- and nanostructures on the surface expands, leading to increased surface roughness. The frequency of these features follows a distinct sequence (e.g., 2f, f, f/2, f/4, and f/8), with higher-order grating couplings producing finer features.102 Sharp conical spikes created in SF6 at 500 Torr are shown in Fig. 8(b), viewed both at a 45-deg angle and parallel to the cleaved surface.100 Vorobyev et al. demonstrated the production of equally spaced parallel microgrooves with nanostructured textures on silicon using direct femtosecond laser treatment.101 The SEM image in Fig. 8(c) shows the treated surface, and the 3D optical image in Fig. 8(d) illustrates microgrooves with an average depth of 55  μm. The optical spectrum [Fig. 8(e)] reveals significantly reduced reflectance for the b-Si sample compared with polished silicon over wavelengths spanning 0.25 to 16  μm.

    (a) Illustration of the setup for producing b-Si with femtosecond laser pulses. The inset on the left depicts the vacuum chamber designed for placing the silicon samples. Reproduced with permission,99 © 2016 IEEE. (b) SEM images of sharp conical spikes generated on Si (100) by 500 fs laser pulses (100 fs duration), viewed at 45 deg to the surface normal (top) and parallel to the surface (bottom). Reproduced with permission,100 © 1998 AIP Publishing. (c) SEM image of the microgroove structures; inset is a photograph of the b-Si sample. (d) 3D optical image of microgroove structure with nano-textured patterns. (e) The reflectance spectrum of the b-Si fabricated through femtosecond laser ablation in an air environment. (c)–(e) Reproduced with permission,101 © 2011 Elsevier.

    Figure 8.(a) Illustration of the setup for producing b-Si with femtosecond laser pulses. The inset on the left depicts the vacuum chamber designed for placing the silicon samples. Reproduced with permission,99 © 2016 IEEE. (b) SEM images of sharp conical spikes generated on Si (100) by 500 fs laser pulses (100 fs duration), viewed at 45 deg to the surface normal (top) and parallel to the surface (bottom). Reproduced with permission,100 © 1998 AIP Publishing. (c) SEM image of the microgroove structures; inset is a photograph of the b-Si sample. (d) 3D optical image of microgroove structure with nano-textured patterns. (e) The reflectance spectrum of the b-Si fabricated through femtosecond laser ablation in an air environment. (c)–(e) Reproduced with permission,101 © 2011 Elsevier.

    In addition, prior studies demonstrate that laser treatment in water or oil can generate much finer structures, reaching sub-100 nm—up to 100 times smaller compared with those formed in gas environments or vacuum conditions.103,104 In addition, combining laser irradiation with a periodic mask allows for the formation of well-defined, regularly spaced structures on silicon wafers. Unlike many techniques, laser processing is not limited by grain orientation, making it suitable for both crystalline silicon (c-Si) and mc-Si.20 B-Si produced through laser treatment, especially with sulfur doping, has demonstrated versatility across a wide range of applications.

    Although higher laser repetition rates, power levels, or larger spot sizes can improve the processing rate, laser manufacturing remains relatively slow compared with alternative etching methods, particularly for industrial applications. Furthermore, the material damage caused by lasers may be substantial, requiring thorough defect-removal etching to achieve high material quality, which is essential for PV applications. In addition, silicon dust or nanoparticles are generated during the fabrication process, necessitating the implementation of a further filtration system.

    Various techniques have been developed to create b-Si surfaces with micro- and nanostructures, enabling highly controlled surface morphologies.20 A summary and comparison of different b-Si fabrication methods are presented in Table 1. For instance, porosity and thickness can be tailored during electrochemical etching in HF by adjusting the current density and etching time. Wet etching methods, such as MACE, are particularly promising for large-scale industrial applications due to their simplicity and high etching speed. The RIE process can produce silicon nanoneedles, enabling smooth refractive index transitions and achieving reflectance below 1% across a broad wavelength range and different polarizations. Thanks to the isotropic characteristics of fluorine etching and the physical removal of the passivation layer, this method is compatible with mc-Si, microcrystalline silicon (μc-Si), and amorphous silicon (a-Si).19

    Fabrication methodsAdvantagesChallengesTypes of SiaControlled parametersbEnvironmental impactsMorphologies
    Electrochemical etchingLow cost, easy to implement, capable of fabricating 3D micro/nanostructuresUnsuitable for large-scale productionc-Si,105 mc-Si72Current density (J), wafer doping (Nd), C, t, TFluoride wastewaterPorous silicon
    Stain etchingFast, cost-effective, and scalableLimited control, unsuitable for thick layersmc-Si70,106Solution pH, C, tFluoride wastewater, NOx emissionsPorous silicon
    Metal-assisted chemical etchingSimple, fast, cost-effective, scalable production, versatile, capable of producing ordered structures87Metal contaminationc-Si,107109 mc-Si78,79Metal nanostructure, C, t, TAg/heavy metal contaminated fluoride wastewaterPorous structure81
    Nanostructures: nanowire,78,109,110 nanohole,111,112 inverted pyramid,86 bowl-like,113 zone plate77
    Arrays: nanowire7476,87
    Reactive ion etchingCommercially available, large-scale fabricationComplicated, high cost, surface damagec-Si,23 mc-Si,19 pc-Si,23μc-Si,19 a-Si19Gas composition and flow rate, substrate bias (p), RF power (P), TGreenhouse gases, toxic plasma byproductsNeedle-like,114,115 round-top (RT) cone,114 aperiodic nanotips array,93 inverted pyramid114
    Laser treatmentGrain orientation-independent, sub-100 nm (in water or oil), capable of producing ordered structuresSlow, material damagec-Si,116,117 mc-Si60,116,117Laser pulses (polarization, spot size, intensity, pulse number, scanning parameters), laser fluence (Φ), ambient conditionsSilicon dust/ nanoparticlesNanostructures: conical cones,100 microgroove structures101
    Arrays: ordered micro-spikes

    Table 1. Overview and comparison of various b-Si fabrication methods.

    3 Applications

    Due to its micro- and nanoscale surface structures that promote broad-spectrum light absorption, b-Si devices are anticipated to deliver improved solar energy conversion efficiency and perform exceptionally well in a range of photonic applications. Researchers and engineers worldwide continue to advance b-Si technologies, aiming to enhance its performance and economic viability.

    3.1 Solar Cells

    Becquerel’s observation of the PV effect in 1839 inspired the development of solar cells capable of converting sunlight into electrical energy. 118 Nowadays, silicon wafer-based solar cells lead the PV market, accounting for 95% of global production and serving as a cornerstone of renewable energy technologies. Over the past four decades, the costs of solar PV systems have significantly decreased due to lower manufacturing expenses and enhanced efficiencies. As silicon wafers account for a substantial portion of production expenses, the quality of the material plays a key role in determining device performance.119 At present, silicon solar cells are divided into three primary types according to their underlying device technology: (i) homojunction solar cells,120 (ii) passivating contacts, and (iii) silicon-based tandem cells [Fig. 9(a)].121

    (a) Potential technological advancements in silicon PVs based on historical efficiency improvements and ongoing research, including Al-BSF cells and PERCs. Homojunction c-Si solar cells here include Al-BSF and PERCs. Passivated contacts consist mainly of tunnel oxide-passivated contacts and silicon heterojunction-based c-Si PV modules. Reproduced with permission,121 © 2020 AIP Publishing. (b) Schematic diagram of an Al-BSF cell. (c) Schematic diagram of a PERC. (b) and (c) Reproduced with permission,122 © 2017 Elsevier. (d) Structure and carrier transport mechanisms of passivated contact solar cells. Reproduced with permission,123 © 2022 Elsevier. (e) Spectral response of tandem-configured perovskite top cells and silicon bottom cells (left). Schematic of the device structures of 2T and 4T perovskite/silicon tandem solar cells (right). Reproduced with permission,124 © 2021 John Wiley and Sons.

    Figure 9.(a) Potential technological advancements in silicon PVs based on historical efficiency improvements and ongoing research, including Al-BSF cells and PERCs. Homojunction c-Si solar cells here include Al-BSF and PERCs. Passivated contacts consist mainly of tunnel oxide-passivated contacts and silicon heterojunction-based c-Si PV modules. Reproduced with permission,121 © 2020 AIP Publishing. (b) Schematic diagram of an Al-BSF cell. (c) Schematic diagram of a PERC. (b) and (c) Reproduced with permission,122 © 2017 Elsevier. (d) Structure and carrier transport mechanisms of passivated contact solar cells. Reproduced with permission,123 © 2022 Elsevier. (e) Spectral response of tandem-configured perovskite top cells and silicon bottom cells (left). Schematic of the device structures of 2T and 4T perovskite/silicon tandem solar cells (right). Reproduced with permission,124 © 2021 John Wiley and Sons.

    Among these, homojunction c-Si solar cells are the most prevalent. Compared with aluminum back surface field (Al-BSF) cells shown in Fig. 9(b), passivated emitter and rear cell (PERC) technology incorporates a layer of dielectric material to isolate the silicon backside from the aluminum contacts [Fig. 9(c)], thus minimizing rear surface recombination.122 Further advancements in silicon solar cells leveraging advanced passivating contact technology,32,125 such as metal–insulator–semiconductor (MIS) contacts, tunnel oxide passivated contact (TOPCon), dopant free asymmetric heterocontact (DASH), and silicon heterojunctions (SHJs), are expected to push efficiencies to 25% or higher. The carrier transport process in solar cells with passivating contacts is illustrated in Fig. 9(d).123 In contrast to single-junction solar cells, which are constrained by their optical bandgap, tandem solar cells [Fig. 9(e)] utilize materials with varying bandgaps to harness a broader range of sunlight. The upper cell, characterized by a large bandgap, targets high-energy photons, whereas the lower cell, featuring a smaller bandgap, effectively collects lower-energy photons, including those in the NIR range.124 The applications of b-Si in solar cells will be discussed in relation to these three categories.

    3.1.1 Homojunction b-Si solar cells

    To enhance efficiency and reduce costs, b-Si eliminates the need for AR coatings while achieving comparable light-trapping, making it a cost-effective option to achieve 20% cost reduction.126 Even though the nanostructures on the silicon surface significantly reduce reflectivity and improve light absorption, challenges arise from increased photo-carrier recombination. Oh and colleagues revealed that the high surface area often assumed to cause surface recombination is not the primary limiting factor as previously assumed.127 Instead, the primary limitation arises from excessive doping-induced Auger recombination linked to the diffusion of the pn junction into the nanostructures, which hinders carrier collection and efficiency in the majority of nanostructured silicon solar cells [Fig. 10(a)]. The effective carrier lifetime (teff) of nanostructured silicon featuring passivated n+p junctions with four different surface areas is shown in Fig. 10(b). By mitigating the recombination through light and shallow doping, combined with minimizing surface area via tetramethylammonium hydroxide (TMAH) etching, b-Si solar cells achieved a validated efficiency of 18.2% under standard AM 1.5G simulated sunlight conditions [Fig. 10(c)]. For large-area b-Si cells, the structure resembles traditional solar cell designs but integrates a b-Si layer on the topmost surface.30 These cells generally consist of a base made from p- or n-type silicon, with heavily doped regions at the front and back, and are equipped with metal contacts on both sides. As shown in Fig. 10(d), Davidsen et al. developed a p-type solar cell featuring a laser-patterned selective emitter design, using copper and nickel for the front contacts and aluminum for the rear contacts.128 The emitter layer of b-Si was strongly doped with phosphorus and coated with a SiNx passivation layer, achieving a conversion efficiency of 18.1%. By combining MACE with a post-etching process, inverted pyramidal nanostructure-based mc-Si solar cells were fabricated. Shen et al. and Su et al. reported this approach in their research.133135 By proposing nanostructure rebuilding (NSR) solution treatment, the obtained solar cell based on an inverted pyramid structure showed a high conversion efficiency of 18.62% in large size (156  mm×156  mm), which was 0.45% higher than the traditional acid textured devices.133

    (a) Diagram illustrating the mechanisms of excess carrier recombination in silicon nanostructures, in which photogenerated carriers (blue dots) are lost via Auger and surface recombination channels. (b) Carrier lifetime (τeff) of both polished and nanostructured silicon, with symbols in different colors indicating various surface area enhancement ratios. Zones I–III correspond to lifetime ranges influenced by sheet resistance. (c) J–V characteristics of nanostructured b-Si, polished silicon, and pyramid-textured silicon coated with a SiNx AR layer, measured under AM 1.5G solar simulation. (a)–(c) Reproduced with permission,127 © 2012 Springer Nature. (d) Illustration of a laser-doped selective emitter solar cell based on b-Si. Reproduced with permission,128 © 2016 Elsevier. (e) Diagram of a nanotextured b-Si solar cell featuring an n+-emitter/p-base configuration (left) and a high-resolution TEM image showing a SiNW coated with an Al2O3 layer (right). Reproduced with permission,129 © 2013 American Chemical Society. (f) Illustration of an NBSi solar cell with an n+-emitter/p-base configuration (left). High-resolution TEM images reveal silicon nanowires surrounded by an Al2O3/TiO2 bilayer passivation structure (right). Reproduced with permission,130 © 2015 American Chemical Society. (g) Structure of the IBC cell, where a thin Al2O3 layer is deposited on the nanostructured front surface. (h) Normalized photocurrent versus incidence angle of b-Si (circles) and reference (squares) solar cells. The inset defines the light incidence angle θ. (g) and (h) Reproduced with permission,131 © 2015 Springer Nature. (i) Cross-sectional schematic of NPP TOPCon solar cells. (j) Normalized short-circuit current density [Jsc(θ)/Jsc(0 deg)] for NPP and conventional reference cells across incidence angles of 0 deg to 70 deg. (i) and (j) are reproduced with permission,132 © 2022 Elsevier. (k) Schematic of monolithic perovskite/black-silicon tandems based on tunnel oxide passivated contacts. Inset: photographs of c-Si with the planar surface (left), reconstructed b-Si (middle), and pyramidal texture (right). (l) Device architecture of the nanotextured perovskite/silicon tandem solar cell architecture. (m) EQE and total absorbance (1–R, gray shading) spectra for planar and nanotextured perovskite/silicon tandem solar cells, where R represents reflectance. (n), (o) Crystallization mechanisms for (n) randomly oriented perovskite on planar surfaces and (o) vertically aligned perovskite on nanotextured surfaces. (k)–(o) Reproduced with permission,33 © 2022 Elsevier.

    Figure 10.(a) Diagram illustrating the mechanisms of excess carrier recombination in silicon nanostructures, in which photogenerated carriers (blue dots) are lost via Auger and surface recombination channels. (b) Carrier lifetime (τeff) of both polished and nanostructured silicon, with symbols in different colors indicating various surface area enhancement ratios. Zones I–III correspond to lifetime ranges influenced by sheet resistance. (c) JV characteristics of nanostructured b-Si, polished silicon, and pyramid-textured silicon coated with a SiNx AR layer, measured under AM 1.5G solar simulation. (a)–(c) Reproduced with permission,127 © 2012 Springer Nature. (d) Illustration of a laser-doped selective emitter solar cell based on b-Si. Reproduced with permission,128 © 2016 Elsevier. (e) Diagram of a nanotextured b-Si solar cell featuring an n+-emitter/p-base configuration (left) and a high-resolution TEM image showing a SiNW coated with an Al2O3 layer (right). Reproduced with permission,129 © 2013 American Chemical Society. (f) Illustration of an NBSi solar cell with an n+-emitter/p-base configuration (left). High-resolution TEM images reveal silicon nanowires surrounded by an Al2O3/TiO2 bilayer passivation structure (right). Reproduced with permission,130 © 2015 American Chemical Society. (g) Structure of the IBC cell, where a thin Al2O3 layer is deposited on the nanostructured front surface. (h) Normalized photocurrent versus incidence angle of b-Si (circles) and reference (squares) solar cells. The inset defines the light incidence angle msub. (g) and (h) Reproduced with permission,131 © 2015 Springer Nature. (i) Cross-sectional schematic of NPP TOPCon solar cells. (j) Normalized short-circuit current density [Jsc(msub)/Jsc(0 deg)] for NPP and conventional reference cells across incidence angles of 0 deg to 70 deg. (i) and (j) are reproduced with permission,132 © 2022 Elsevier. (k) Schematic of monolithic perovskite/black-silicon tandems based on tunnel oxide passivated contacts. Inset: photographs of c-Si with the planar surface (left), reconstructed b-Si (middle), and pyramidal texture (right). (l) Device architecture of the nanotextured perovskite/silicon tandem solar cell architecture. (m) EQE and total absorbance (1–R, gray shading) spectra for planar and nanotextured perovskite/silicon tandem solar cells, where R represents reflectance. (n), (o) Crystallization mechanisms for (n) randomly oriented perovskite on planar surfaces and (o) vertically aligned perovskite on nanotextured surfaces. (k)–(o) Reproduced with permission,33 © 2022 Elsevier.

    With the advantages of reduced rear surface recombination and enhanced rear surface reflectivity, PERC solar cells based on b-Si have been further explored in some works.136139 Huang et al. conducted a simulation-based analysis of PERC silicon solar cells with nano-inverted-pyramid (NIP) textures at both the cell and module levels.140 Their findings revealed that NIP-PERC solar cells could achieve an efficiency of 22.1%, representing a 1.4% relative gain over conventional micro-pyramid PERCs. Simulation results further indicated that 60-cell modules incorporating NIP-PERC technology could deliver a peak power output of 310 W—an 8 W increase compared with modules using standard textured PERCs. This improvement is attributed to better reflectivity performance across both short and long wavelength ranges.

    3.1.2 Passivating contacts in b-Si

    Using a dielectric passivation layer is a widely recognized approach to minimize surface recombination rates in solar cells. This reduction occurs via two primary mechanisms: chemical passivation, which decreases the density of interfacial states, and field-effect passivation, where an internal electric field suppresses minority-carrier density near the interface. For b-Si solar cells, the main obstacle lies in reducing recombination losses resulting from the larger surface area and its associated defects. To address these issues, Wang et al. employed thermal atomic layer deposition (ALD) to fabricate passivation layers, such as conformal Al2O3 or Al2O3/TiO2 dual-layer stacks, effectively reducing surface recombination and total reflectance [Figs. 10(e) and 10(f)].129,130 By employing these passivation strategies in an n+-emitter/p-base configuration, nanotextured black silicon (NBSi) solar cells reached a maximum efficiency of 18.5%. Savin et al., in 2015, proposed an interdigitated back contact (IBC) architecture to fully passivate the front surface, reducing front surface recombination rates.131 Their approach demonstrated that a conformal Al2O3 film (20 nm) provided excellent chemical and electrical passivation [Fig. 10(g)], achieving a record efficiency of 22.1% in b-Si solar cells. The b-Si-based device demonstrates significantly reduced reflectance across both short (300 to 500 nm) and long (>700  nm) wavelength ranges compared with reference cells featuring conventional random micron pyramids with a thicker Al2O3 AR coating (90 nm). Due to the improved angular acceptance of b-Si shown in Fig. 10(h), the device based on b-Si can enhance daily energy production by 3%.

    Currently, conventional micron-pyramid textures are approaching their performance limits in minimizing optical reflection losses and boosting power conversion efficiency (PCE) for TOPCon solar cells. Addressing this challenge, Li et al. developed an innovative micron-pyramid/nanopore pyramid (NPP) silicon architecture, achieving remarkable average efficiencies exceeding 23%.132,141,142Figure 10(i) shows the cross-sectional device architecture of TOPCon solar cells based on NPP structure. Compared with conventional micron-pyramid textures, the TOPCon solar cell based on NPP structure exhibited higher average PCE and exceptional wide-angle absorption capability [from 0 deg to 70 deg, Fig. 10(j)]—critical advantages for real-world outdoor photovoltaic applications.

    3.1.3 B-Si–based tandem system

    Recently, tandem solar cells combining perovskite and silicon have emerged as a promising innovation, offering the potential to exceed the efficiency limits of traditional silicon-based solar cells. This advancement is achieved through the strategic combination of perovskite top cells, which efficiently capture high-energy photons, and crystalline silicon bottom cells, which effectively harvest lower-energy photons. This tandem configuration enables a broader spectral response and significantly enhances overall energy conversion efficiency. In 2022, Ying et al. reported the first monolithic perovskite/silicon tandem solar cell that incorporates industrially applicable front-side nanostructured b-Si integrated with TOPCon technology [Fig. 10(k)].33 The device architecture of the nanotextured perovskite/silicon tandem solar cell is shown in Fig. 10(l). As the external quantum efficiency (EQE) and spectral response analysis shown in Fig. 10(m), the nanotexture significantly suppresses the reflectance and the nanotextured tandem achieves near-constant low reflectance due to the gradient of refractive index effect, resulting in the enhanced EQE responses for both perovskite and silicon. This design achieves effective surface passivation without compromising broadband light trapping. In addition, the reconstructed nanotexture significantly enhances perovskite wetting. As shown in Figs. 10(n) and 10(o), the reconstructed nanotexture acts as a nanoconfining scaffold, guiding vertical perovskite growth, whereas planar surfaces result in randomly oriented structures. These advances lead to a notable increase in both the current density and fill factor (FF) of tandems, ultimately achieving a certified PCE of 28.2%.

    Furthermore, they conducted in-depth studies on perovskite/TOPCon tandem solar cells based on b-Si. By integrating a poly-Si(p+)/poly-Si(n+) tunneling recombination layer (poly-Si TRL), the device achieved a remarkable efficiency of 29.2%, significantly surpassing conventional indium zinc oxide (IZO)-based tandem solar cells (28%).143 By employing a facile surface reconstruction strategy to mitigate residual strain in perovskite films—post-treatment with an isopropanol solution containing N,N-dimethylformamide (DMF) and n-butylammonium iodide (BAI), an efficient and stable perovskite/b-Si tandem solar cell with a certified stabilized PCE of 29.0% was achieved.144 In addition, they developed an oblique angle evaporation method to deposit a conformal, ultra-thin SiOx passivation layer, which can alleviate the recombination losses at the defective perovskite/C60 interface without damaging the underlying perovskite.145 When applied to 4-T and 2-T perovskite/b-Si tandem solar cells, this strategy achieved stable PCEs of 29.2% and 30.2%, respectively—far exceeding those of perovskite/TOPCon silicon tandem based on conventional textured silicon (e.g., 25.1%,146 25.84%147).

    It is worth mentioning that the b-Si exhibits no crystallinity-related limitations during the fabrication,148 making it suitable for mc-Si with anisotropic texturing that is ineffective in alkaline solutions, as well as for diamond-wire cut mc-Si that is challenging to texture with conventional acidic solutions.149,150 Moreover, b-Si demonstrates superior metal impurity-gettering efficiency compared with planar surfaces in PV applications.151 These advantages further enhance its potential for high-performance solar cells.

    3.2 Photoelectrochemical (PEC) Solar Energy Conversion

    In PEC solar energy conversion, enhancing multiple properties through surface and interface engineering approaches is essential, as depicted schematically in Fig. 11. By implementing appropriate interface enhancements, such as optimized junction designs and protective/passivation coatings, it can attain strong mechanical durability and efficient charge transport. In addition, cocatalysts applied to the surface can significantly improve the reaction kinetics at the interface.10

    Diagram depicting key surface and interface engineering approaches for b-Si photoelectrodes and their mechanisms for enhancing PEC performance.

    Figure 11.Diagram depicting key surface and interface engineering approaches for b-Si photoelectrodes and their mechanisms for enhancing PEC performance.

    3.2.1 H2 generation

    Junction designs for efficient interface charge transfer

    A key factor limiting the performance of planar and b-Si photocathodes is the limited Voc of the p-Si/H2O interface, which constrains energy conversion efficiency. To overcome this limitation, the n+/p junction at the surface of b-Si, acting as a typical buried structure, is frequently employed to generate an internal electric field that facilitates the outward movement of photogenerated carriers. In addition, a buried metallurgical n+/p junction has also been integrated into Si wires [Fig. 12(b)].153 The buried junction separates the band bending and photovoltage properties of the electrode from the energy dynamics at the semiconductor/liquid interface. This design achieves higher Voc values as a result of the enhanced band bending at the n+/p interface compared with that at the p-Si/solution interface. These findings align with previous studies on p-Si/H2O systems, which demonstrate that the valence-band edge of Si is insufficiently positive relative to E(H+/H2) to achieve a high photovoltage.153

    (a) Microwire array featuring tandem junctions with an embedded homojunction (n-p+-Si) covered by layers of ITO and n-WO3. Reproduced with permission,152 © 2014 Royal Society of Chemistry. (b) Energy band diagrams for p-Si (left) and n+p-Si (right) photocathodes interfacing with the H+/H2 redox pair in solution in the dark (top) and under illumination (bottom). Ecb: conduction band edge, Evb: valence band edge, EF: Fermi level. EFp and EFn: quasi-Fermi levels for the holes and electrons under illumination. Reproduced with permission,153 © 2011 American Chemical Society. (c) Diagram depicting the charge generation and oxygen evolution in the b-Si/TiO2/Co(OH)2 system. (d) Spectra showing light reflection and scattering for planar Si, b-Si, and b-Si/TiO2 samples. Inset: images of the wafers (size ∼2 cm×2 cm). (e) Jph–t plots for b-Si/Co(OH)2 and b-Si/TiO2/Co(OH)2 under a fixed bias of 0.6 V versus SCE. (c)–(e) Reproduced with permission,154 © 2017 Springer Nature. (f) Cross-sectional SEM image showing the AgNPs/PEDOT/SiNW arrays. (g) TEM image of a SiNW coated with PEDOT and AgNPs. (h) HRTEM of the AgNPs/PEDOT/SiNW arrangement. (i) IPCE of various photoanodes measured at 0 V versus SCE. (f)–(i) Reproduced with permission,155 © 2014 American Chemical Society. (j) J–V curves comparing SiNWs, SiNWs/Ni-B (1 s), SiNWs/Co-B (10 s), and SiNWs/Pt (12 min) photocathodes under AM 1.5G illumination. Reproduced with permission,156 © 2016 American Chemical Society. (k) Illustration of b-Si integrated with a-MoSx for PEC hydrogen generation. (l) LSV curves for planar and b-Si photocathodes with a-MoSx layers, showing significant reduction in overpotential for b-Si with a-MoSx. (k) and (l) Reproduced with permission,157 © 2022 American Chemical Society.

    Figure 12.(a) Microwire array featuring tandem junctions with an embedded homojunction (n-p+-Si) covered by layers of ITO and n-WO3. Reproduced with permission,152 © 2014 Royal Society of Chemistry. (b) Energy band diagrams for p-Si (left) and n+p-Si (right) photocathodes interfacing with the H+/H2 redox pair in solution in the dark (top) and under illumination (bottom). Ecb: conduction band edge, Evb: valence band edge, EF: Fermi level. EFp and EFn: quasi-Fermi levels for the holes and electrons under illumination. Reproduced with permission,153 © 2011 American Chemical Society. (c) Diagram depicting the charge generation and oxygen evolution in the b-Si/TiO2/Co(OH)2 system. (d) Spectra showing light reflection and scattering for planar Si, b-Si, and b-Si/TiO2 samples. Inset: images of the wafers (size 2  cm×2  cm). (e) Jpht plots for b-Si/Co(OH)2 and b-Si/TiO2/Co(OH)2 under a fixed bias of 0.6 V versus SCE. (c)–(e) Reproduced with permission,154 © 2017 Springer Nature. (f) Cross-sectional SEM image showing the AgNPs/PEDOT/SiNW arrays. (g) TEM image of a SiNW coated with PEDOT and AgNPs. (h) HRTEM of the AgNPs/PEDOT/SiNW arrangement. (i) IPCE of various photoanodes measured at 0 V versus SCE. (f)–(i) Reproduced with permission,155 © 2014 American Chemical Society. (j) JV curves comparing SiNWs, SiNWs/Ni-B (1 s), SiNWs/Co-B (10 s), and SiNWs/Pt (12 min) photocathodes under AM 1.5G illumination. Reproduced with permission,156 © 2016 American Chemical Society. (k) Illustration of b-Si integrated with a-MoSx for PEC hydrogen generation. (l) LSV curves for planar and b-Si photocathodes with a-MoSx layers, showing significant reduction in overpotential for b-Si with a-MoSx. (k) and (l) Reproduced with permission,157 © 2022 American Chemical Society.

    Besides buried pn junctions, metal interfacial layers, including Ag 158 and Pt159 on the surface of b-Si, are effective in enhancing the separation and movement of photoexcited electrons. Furthermore, Lewis et al. developed an np+-Si microwire array featuring a coating of indium tin oxide (ITO) and n-WO3 [Fig. 12(a)].152 The ITO layer provides an ohmic contact between the Si microwire PV unit and the WO3 layer, enabling the demonstration of a self-sustained, integrated solar-powered water-splitting system. This innovative design leverages the unique properties of the microwire array structure to achieve efficient solar water splitting.

    Protection/passivation layers for enhanced stability

    Many metal oxides are known for their optical transparency and chemical stability, making them effective for protecting Si-based photocathodes. Among these, TiO2 is particularly notable for its durability in a wide range of pH environments (acidic to alkaline) and its high transmittance in the visible spectrum, owing to its wide bandgap. In 2017, Yu et al. demonstrated the deposition of a conformal, ultrathin amorphous TiO2 film (8 nm) on b-Si using low-temperature ALD.154 This coating extended the functional lifespan of b-Si photocathodes from under 30 min to 4 h. Figure 12(c) illustrates the structural layout of the electrode along with the oxygen evolution mechanism. As illustrated in Fig. 12(d), b-Si demonstrated much lower reflectance (10%) than planar Si (over 30%) across the UV-vis-NIR spectra. The combined reflectance and scattering data for b-Si and b-Si/TiO2 revealed minimal variation, confirming that the TiO2 layer did not adversely affect light absorption. By comparison, as depicted in Fig. 12(e), b-Si/Co(OH)2 lacking a TiO2 layer showed a rapid decline in photocurrent density (Jph) within 30 min, with deterioration becoming more pronounced after 2.5 h, resulting in a 77.3% loss of Jph after 3 h, likely due to structural damage. Beyond TiO2, other materials such as Cu2O,160,161Fe2O3,162165SnO2,163NiRuOx,166MoS2, C3N4,167 carbon,168 and PEDOT155 have also been explored as protection layers. Figures 12(f)12(h) show SEM and TEM images of a typical SiNW modified with PEDOT and Ag nanoparticles (AgNPs). The incident photon-to-current efficiency (IPCE) spectra in Fig. 12(i) demonstrate that modified SiNW arrays exhibit significantly enhanced IPCE compared to H-SiNW arrays, with the AgNPs/PEDOT/SiNW arrays reaching a peak efficiency of 42% at 510 nm.

    Cocatalysts for improved HER/OER kinetics

    Some previous studies have shown that decorating Si photocathodes with Pt can enhance their photoelectrochemical (PEC) properties.112,169 However, the scarcity and high cost of Pt pose challenges for its use in widespread applications. As an alternative, earth-abundant transition metals (e.g., Mo, Co, and Ni) and their compounds (e.g., sulfides, phosphides, selenides) have been extensively explored due to their comparable catalytic activity.10 For example, the PEC performance of n+p b-Si photocathodes can be significantly improved with the addition of a cobalt (Co) layer, leading to a 560-mV positive shift in onset potential to 0.33 V (versus RHE) and an increase in the saturation photocurrent density from 22.7 to 32.6  mA/cm2.170 Similarly, M-B (M=Ni, Co) compounds loaded onto SiNW arrays via electroless plating show enhanced PEC performance with a positively shifted onset potential [Fig. 12(j)].156 The optimized configurations of SiNWs/Co-B and SiNWs/Ni-B exhibit half-cell photo power conversion efficiencies of 2.53% and 2.45%, respectively, comparable to the 2.46% efficiency of SiNWs/Pt.

    Among transition metal compounds, Mo-based sulfides are particularly effective cocatalysts for hydrogen generation on black Si, such as MoSx quantum dot,171[Mo3S13]-2(MS) clusters,172MoS3,173,174 and cubane-like clusters (Mo3S4).175 In 2022, Kim et al. fabricated a uniform amorphous MoSx (a-MoSx) coating on nanostructured b-Si using ALD [Fig. 12(k)].157 The a-MoSx layer, characterized by a reduced work function of 4.0 eV compared with the 4.5 eV of crystalline 2H-MoS2, improves the electronic alignment at the p-Si interface, promoting efficient charge transfer. It achieves an impressive overpotential of 0.2  V at 10  mA/cm2 [Fig. 12(l)] and provides robust protection against corrosion, enabling PEC operation for over 50 h while retaining 87% or more of its performance. In addition, transition metal bimetallic compounds have also been explored as cocatalysts on b-Si. For instance, heterometal-doped amorphous MMoSx (M=Fe, Co, Ni) materials improve water photoelectrolysis by exposing more S-terminated edges.176 Similarly, amorphous NiCoSex has emerged as a competitive HER electrocatalyst due to its high activity and optical transparency. The p-Si/NiCoSex photocathode exhibits improved PEC activity, achieving a photocurrent density of 37.5  mA/cm2 at 0 V (versus RHE) under simulated AM 1.5G illumination, attributed to the combined effect of the transparent properties of NiCoSex and the superior optical absorption capability of the Si nanopillar array.

    3.2.2 N2/CO2 reduction

    B-Si based photoelectrodes have also been explored for nitrogen reduction applications. Ammonia (NH3), a chemical produced on a massive scale worldwide, is essential for manufacturing fertilizers and shows promise as an eco-friendly energy carrier and energy storage intermediate. Ali et al. developed a solar-driven, plasmon-enhanced PEC cell using nanostructured b-Si to convert atmospheric N2 into ammonia, achieving a production rate of 13.3  mgm2h1 under two suns illumination.177 As shown in Fig. 13(a), the nitrogen photo-reduction cell utilizes nitrogen gas bubbled over the electrode surface, illuminated with artificial solar light. The 24-h yield data [Fig. 13(b)] reveal that bare b-Si produces a low amount of ammonia, which increases nearly four-fold after coating with gold nanoparticles (AuNPs). Adding a chromium (Cr) layer as a hole sink and an anode further prevents silicon oxidation and enhances charge separation. This configuration, the AuNP/b-Si/Cr cell, achieved an impressive yield of 320  mgm2 over 24 h. Quantum yield analysis [Fig. 13(c)] confirmed nitrogen reduction across the visible spectrum, with efficiency dropping near silicon’s bandgap. A quantum efficiency peak around 500 nm was attributed to surface plasmon excitation in the AuNPs, providing an additional photo-excitation mechanism. In addition, Qingji Xie’s group reported a Ni-doped MoS2/Si nanowire (Ni-MoS2/SiNW) photocathode exhibiting excellent efficiency and specificity in nitrogen reduction reactions (NRR).179 In a 0.1 mol/L Na2SO4 solution saturated with N2 and containing PCP, this photocathode achieved an NH3 yield of 12.0  mmolh1m2 at a low bias of 0.25 V versus RHE, along with an apparent Faradaic efficiency (AFE) exceeding 100%. This high efficiency was attributed to photocurrent-independent photocatalysis during the PEC process. The study introduced a novel classification of PEC electrons: (i) dark-current electrons, (ii) photocurrent electrons, and (iii) photocurrent-free photocatalysis electrons. This study presents an affordable and efficient strategy for developing NRR nanocatalysts and emphasizes the advantage of using solutions with enhanced N2 solubility to enable effective PEC-driven ammonia production, with potential applications in other gas-phase renewable energy conversions.

    (a) Illustration of the setup for PEC N2 reduction using AuNPs/b-Si/Cr. (b) Ammonia production over 24 h on various substrates: (i) p-type silicon, (ii) b-Si, (iii) AuNPs/b-Si, (iv) AuNPs/b-Si/Cr, (v) Au/Si/Cr under illumination with two suns, and (vi) AuNPs/b-Si/Cr in the dark. (c) Quantum efficiency of ammonia generation by the AuNPs/b-Si/Cr PEC system across different wavelengths. (a)–(c) Reproduced with permission,177 © 2016 Springer Nature. (d) Diagram of a bias-free photochemical diode device comprising a p-type SiNW biophotocathode (blue) and an n-type SiNW photoanode (green) separated by a bipolar membrane under red light. (e) Energy diagram of the photochemical diode under red light irradiation. Photovoltages of 0.4 V (photocathode) and 0.45 V (photoanode) couple the CO2 RR and GOR without external bias. Acetyl-CoA: acetyl coenzyme A; Mox: oxidized mediators; Mred: reduced mediators. (f) Faradaic efficiencies of the cathodic product (blue), total anodic products (pink), and individual anodic products during bias-free operation of the photochemical diode under red light (740 nm, 20 mW/cm2). (d)–(f) Reproduced with permission,178 © 2024 Springer Nature.

    Figure 13.(a) Illustration of the setup for PEC N2 reduction using AuNPs/b-Si/Cr. (b) Ammonia production over 24 h on various substrates: (i) p-type silicon, (ii) b-Si, (iii) AuNPs/b-Si, (iv) AuNPs/b-Si/Cr, (v) Au/Si/Cr under illumination with two suns, and (vi) AuNPs/b-Si/Cr in the dark. (c) Quantum efficiency of ammonia generation by the AuNPs/b-Si/Cr PEC system across different wavelengths. (a)–(c) Reproduced with permission,177 © 2016 Springer Nature. (d) Diagram of a bias-free photochemical diode device comprising a p-type SiNW biophotocathode (blue) and an n-type SiNW photoanode (green) separated by a bipolar membrane under red light. (e) Energy diagram of the photochemical diode under red light irradiation. Photovoltages of 0.4 V (photocathode) and 0.45 V (photoanode) couple the CO2 RR and GOR without external bias. Acetyl-CoA: acetyl coenzyme A; Mox: oxidized mediators; Mred: reduced mediators. (f) Faradaic efficiencies of the cathodic product (blue), total anodic products (pink), and individual anodic products during bias-free operation of the photochemical diode under red light (740 nm, 20  mW/cm2). (d)–(f) Reproduced with permission,178 © 2024 Springer Nature.

    In 2024, Peidong Yang’s group presented a silicon nanowire-based device for red light applications, enabling facilitating CO2 conversion to multicarbon compounds at the biophotocathode and glycerol oxidation at the photoanode.178 As depicted in Fig. 13(d), the system combines a CO2-utilizing microorganism, Sporomusa ovata (S. ovata), with a SiNW cathode and a SiNW anode loaded with Pt–Au. Here, S. ovata functions as the biological catalyst for CO2 reduction, whereas the co-deposited Pt–Au layer serves as the catalyst for the oxidation of glycerol. The energy diagram [Fig. 13(e)] illustrates a photoactive diode operating under illumination with red light, producing a voltage of 0.4 V at the cathode and 0.45 V at the anode. This configuration integrates the reduction of CO2 (CO2RR) with glycerol oxidation (GOR) without requiring an external bias. Achieving a Faradaic efficiency of 80% for both the reduction and oxidation products under dim red light, this self-sustaining photochemical device [Fig. 13(f)] offers a novel photosynthetic pathway to reduce CO2 emissions while producing valuable chemicals efficiently.

    3.3 Solar Thermal Energy Conversion

    In recent years, considerable attention has been given to optimizing solar thermal energy applications through b-Si. Due to its semiconductor properties, silicon is restricted to absorbing solar wavelengths below 1110 nm (corresponding to a bandgap Eg=1.12  eV) for applications in PV or PEC. To overcome this limitation, researchers have been exploring innovative strategies such as surface plasmonic effect (SPR) of metal nanoparticles, doping/defect engineering, and advanced surface texturing, to enhance the NIR light absorption and photothermal energy capabilities of b-Si. The applications of solar photothermal energy based on b-Si are illustrated in Fig. 14 and will be discussed in detail below.

    Applications of solar photothermal energy based on b-Si.

    Figure 14.Applications of solar photothermal energy based on b-Si.

    3.3.1 Photothermal catalysis

    Photothermal catalysis involves the activation or enhancement of catalytic reactions through photothermal effects. In some cases, catalysts also serve as photothermal agents, converting sunlight into heat to raise the reaction temperature. This increase in temperature can activate the reaction or enhance reaction kinetics, similar to the mechanisms observed in thermocatalysis.180182 In 2016, Ozin’s group introduced a combined photothermal and photochemical strategy for producing solar fuels.183Figure 15(a) illustrates the light absorption of nanocrystalline In2O3x(OH)y (blue line) alongside the utilization of photons by the In2O3x(OH)y@SiNW hybrid structures. The yellow and red areas illustrate two separate light-harvesting mechanisms: photons with energies exceeding the bandgap of In2O3x(OH)y (yellow) create electron-hole pairs in the nanocrystals, driving the solar-powered reverse water-gas shift process; by contrast, photons below the bandgap (red) are taken up by the SiNW support and transformed into heat through photothermal effects. The hybrid material exhibited improved utilization of sunlight compared to In2O3x(OH)y on its own, benefiting from heat generated by the SiNWs to drive the reaction. Photons with energies above the bandgap of In2O3x(OH)y contribute to the CO2 reduction process through photocatalysis, while sub-bandgap photons captured by the SiNWs supply thermal energy to enhance the reaction efficiency. Uniformly coating In2O3x(OH)y onto SiNW arrays reduced reflective losses, improved light harvesting, and facilitated heat transfer, collectively boosting the CO2 photocatalytic reduction rate compared to non-uniform coatings or unsupported In2O3x(OH)y. Applying a uniform layer of In2O3x(OH)y to SiNW arrays minimized light reflection, enhanced absorption, and improved thermal transfer, resulting in a higher CO2 reduction efficiency compared with uneven coatings or standalone In2O3x(OH)y.

    (a) Optical absorption of In2O3−x(OH)y nanoparticles compared with the efficiency of photon capture in In2O3−x(OH)y/SiNW composite materials under solar light. Inset: diagram showing the process of CO2 conversion to CO under simulated sunlight. Reproduced with permission,183 © 2016 American Chemical Society. (b) Reaction rates for methane synthesis using Ru-based catalysts on SiNW, glass, and polished Si substrates at 150°C and 45 psi. (c) Variation of methane production rates with temperature under conditions of no light (black) and simulated solar illumination (yellow). Dashed lines indicate exponential trends for batch reactions. Inset: Arrhenius plot (ln(k) versus 1000/T) employed to determine the activation energy for Ru/SiNW catalysts under light and dark. (a)–(c) are reproduced with permission,184 © 2014 John Wiley and Sons. (d) Assembly of b-Si, generator, and cooling fin with thermally conductive silicone, with aluminum fins submerged in a mixture of ice and water. (e) Schematic showing the AR principle of optical wave propagation through surfaces with micropores (top) and micro-nanopores (bottom). (f) Variation in the voltage output of the thermoelectric generator over time. (d)–(f) are reproduced with permission,25 © 2019 Elsevier. (g) Diagram of the photothermal experimental setup. (h) Real-time temperature of the surfaces of pristine silicon and b-Si samples. (g) and (h) Reproduced with permission,185 © 2021 American Chemical Society. (i)–(k) Diagram illustrating the structural design of hydrovoltaic generator (HG) and solar steam generation (SSG). (i) Overview of the SiNWs-based HG/SSG device, which integrates electricity generation and freshwater production via a hydrophobic condensation layer during evaporation. (j) Detailed layout of the functional components in the SiNWs-based HG and SSG system. Carbon nanofiber (CNF) was created by selectively depositing CNTs onto nonwoven fabric, providing water transport and electrical conductivity for the HG. (k) Cross-sectional SEM image of SiNWs, with the inset displaying a photograph of a 6-in. SiNW sample prepared at wafer scale. (i)–(k) Reproduced with permission,186 © 2022 John Wiley and Sons.

    Figure 15.(a) Optical absorption of In2O3x(OH)y nanoparticles compared with the efficiency of photon capture in In2O3x(OH)y/SiNW composite materials under solar light. Inset: diagram showing the process of CO2 conversion to CO under simulated sunlight. Reproduced with permission,183 © 2016 American Chemical Society. (b) Reaction rates for methane synthesis using Ru-based catalysts on SiNW, glass, and polished Si substrates at 150°C and 45 psi. (c) Variation of methane production rates with temperature under conditions of no light (black) and simulated solar illumination (yellow). Dashed lines indicate exponential trends for batch reactions. Inset: Arrhenius plot (ln(k) versus 1000/T) employed to determine the activation energy for Ru/SiNW catalysts under light and dark. (a)–(c) are reproduced with permission,184 © 2014 John Wiley and Sons. (d) Assembly of b-Si, generator, and cooling fin with thermally conductive silicone, with aluminum fins submerged in a mixture of ice and water. (e) Schematic showing the AR principle of optical wave propagation through surfaces with micropores (top) and micro-nanopores (bottom). (f) Variation in the voltage output of the thermoelectric generator over time. (d)–(f) are reproduced with permission,25 © 2019 Elsevier. (g) Diagram of the photothermal experimental setup. (h) Real-time temperature of the surfaces of pristine silicon and b-Si samples. (g) and (h) Reproduced with permission,185 © 2021 American Chemical Society. (i)–(k) Diagram illustrating the structural design of hydrovoltaic generator (HG) and solar steam generation (SSG). (i) Overview of the SiNWs-based HG/SSG device, which integrates electricity generation and freshwater production via a hydrophobic condensation layer during evaporation. (j) Detailed layout of the functional components in the SiNWs-based HG and SSG system. Carbon nanofiber (CNF) was created by selectively depositing CNTs onto nonwoven fabric, providing water transport and electrical conductivity for the HG. (k) Cross-sectional SEM image of SiNWs, with the inset displaying a photograph of a 6-in. SiNW sample prepared at wafer scale. (i)–(k) Reproduced with permission,186 © 2022 John Wiley and Sons.

    Researchers also have explored photothermal catalysis utilizing innovative metal particles on b-Si. O’Brien et al. have investigated silicon nanowires supported with Ru nanoparticles (Ru@SiNW) for the Sabatier methanation process, CO2+4H2CH4+2H2O.184 This study revealed that Ru nanoparticles combined with SiNWs could absorb as much as 85% of solar irradiance over a wide wavelength range. The high efficiency stems from the low reflectivity of the vertically arranged nanowires and the broad absorption properties of the Ru nanoparticles, driven by electronic transitions across the visble-NIR spectrum. Figure 15(b) highlights the catalytic activity of Ru/SiNW, Ru/glass, and Ru/Si catalysts under solar-simulated illumination at 150°C over 6 h. Among these, the Ru/SiNW catalyst showed superior performance, achieving a CO2 methanation rate of 0.51  mmolg1h1 without light, which increased by 94% to 0.99  mmolg1h1 with illumination, significantly outperforming both Ru/glass and Ru/Si catalysts. Figure 15(c) displays the temperature-dependent CO2 methanation rates for Ru/SiNW in the dark, with an inset activation energy of 54.5  kJmol1. Batch reactions conducted under different light intensities without external heating indicated a Sabatier reaction rate [yellow line, Fig. 15(c)] with a calculated activation energy of 53.1  kJmol1. Although reaction rates improved under simulated solar illumination, the activation energy remained consistent regardless of whether heating was provided by light or a resistive element. These results demonstrate the efficiency and versatility of Ru/SiNW catalysts for photothermal CO2 methanation.

    3.3.2 Photo-thermoelectric conversion

    PV cells produce electricity by capturing high-energy photons. In thermophotovoltaic (TPV) systems, this principle is employed using thermal emitters that absorb heat and reach temperatures high enough to emit energetic photons. These photons are subsequently harvested by PV cells, effectively converting thermal radiation into electrical energy. In recent years, photo-thermoelectric conversion applications based on b-Si have attracted considerable interest for their promising potential in energy conversion technologies.187191 Novel b-Si combining ordered micropores and disordered nanopores was reported by Kaiying Wang’s group in 2019.25 The device, composed of b-Si, a generator, and a cooling fin, is shown in Fig. 15(d). The multiscale pores play distinct roles: larger pores extend the light path and offer space for incorporating functional materials, whereas smaller pores improve the interaction between incoming solar radiation and the substrate. The schematic in Fig. 15(e) illustrates the AR mechanism, where light waves travel across surfaces with diverse structural characteristics. This etching technique enhances the light-harvesting efficiency of traditional nanostructured b-Si, resulting in improved absorption over a wide wavelength range. Furthermore, introducing Au nanoparticles enhances light absorption in the NIR region (1100 to 1700 nm). As demonstrated in Fig. 15(f), the order-disordered silicon structure with Au nanoparticles produces the highest output voltage of 140 mV, confirming the effectiveness of multiscale-pore structures for photothermal conversion. This study uncovers a strong connection between the three-dimensional configuration and the photon-trapping characteristics of b-Si, providing valuable guidance for substrate designs that optimize light-to-energy conversion.

    In addition, it is worth mentioning that highly conductive b-Si, fabricated using an RIE technique, is capable of absorbing light across a broad wavelength range, extending well into the NIR region (2500  nm).185 The improved b-Si featuring surface texturing exhibits a specular reflection reflectance below 0.1%, with a total average reflectance (combining specular and diffuse components) of 1.1%. Moreover, the reflective properties and underlying mechanisms of surface-textured b-Si have been further explored. Utilizing b-Si materials significantly enhances the efficiency of converting solar energy into electricity, effectively capturing wavelengths beyond 1110 nm. Pengfei Cheng et al. have conducted photothermal and photo-thermoelectric experiments to demonstrate the superior light absorption capabilities of b-Si, attributed to its rich surface micro- and nanostructures.185 A diagram of the photothermal experiment setup is presented in Fig. 15(g). In this configuration, the sample is exposed to solar light from above, whereas an IR camera positioned diagonally monitors surface temperature changes in real time. The data reveal that b-Si heats up more quickly during the initial 5 min and achieves a maximum surface temperature of 53.8°C, surpassing that of bare silicon [Fig. 15(h)]. This superior light-trapping ability highlights the potential of b-Si for various photothermal applications, including imaging, seawater desalination, and other advanced technologies.

    3.3.3 Solar vapour generation

    Water evaporation, a natural process occurring everywhere from oceans to the human skin, carries significant energy. For example, sunlight-driven evaporation on the ocean’s surface absorbs vast amounts of energy globally. Recently, innovative technologies such as triboelectric nanogenerators192,193 and hydrovoltaic generators (HGs)194197 have been developed to generate electricity from water or ambient moisture. Notably, HGs driven by evaporation have attracted interest due to their capacity to leverage the natural evaporation process, making them ideal for off-grid power generation. Thus, integrating HGs with solar steam generation (SSG) systems presents an exciting opportunity, which enables simultaneous electricity generation and the production of clean water by capturing water molecules from evaporation, offering a sustainable solution to water and energy challenges. Baoquan Sun’s group designed a self-floating thermal insulating layer based on b-Si to be incorporated into the interfacial SSG to enhance the conversion efficiency from solar energy to vapor and reduce thermal energy dissipation, as shown in Figs. 15(i)15(k).186 Under standard AM 1.5G irradiation, the SiNW-enabled HG/SSG system achieves a Von of 0.81 V, a short-circuit current of 108.0  μAcm2, and a water evaporation rate of 1.31  kgm2h1. Even with external resistances applied, the device sustains optimized power output above 80.0  μWcm2, establishing a new benchmark for continuous output in HGs. Furthermore, a cutting-edge 6-in. wafer-scale SiNWs device achieved a water evaporation rate of 1.06  kgm2h1, a current of 8.65 mA, and a power output of 6 mW during outdoor simulation experiments conducted over an 8-h period. This achievement represents the highest sustained electrical output ever documented for an individual HG system, paving the way for potential large-scale applications. This design approach opens new possibilities for water-activated device applications and positions itself as a promising solution for future energy systems in off-grid buildings, capable of generating both electricity and freshwater solely from sunlight and seawater.

    3.4 Photonic-Related Applications

    3.4.1 Photodetector

    An ideal photodetector is designed to efficiently capture and detect photons across a broad range of wavelengths, angles, and light intensities, ensuring consistent performance under diverse optical conditions. Currently, the most advanced photodetectors are typically fabricated by integrating silicon pixel arrays (flip-chip) with “bandgap-friendly” materials such as indium arsenide (InAs) and indium antimonide (InSb). However, this process is expensive compared with using silicon alone, and other traditional photodiodes often face optical losses, with charge carriers frequently lost to recombination. As discussed above, traditional silicon does not absorb infrared (IR) energies above 1110 nm, restricting its functionality primarily to the visible region, particularly in photodetection applications. Progress in silicon-based IR photodetectors is vital for enhancing silicon-integrated optoelectronics and communication systems.36 A promising strategy to achieve this involves using b-Si, which extends the absorption edge of silicon into IR wavelengths below its bandgap.198 This method facilitates the development of IR detectors seamlessly incorporated into silicon wafers for use in optical communication and sensing applications. Compared with III–V semiconductors, b-Si offers three significant advantages: (i) silicon is significantly more cost-effective and has been extensively studied, ensuring its suitability for large-scale manufacturing; (ii) as a sensing material, b-Si aligns well with existing integrated circuit (IC) fabrication methods, facilitating its straightforward integration into upcoming fully silicon-based optoelectronic devices; and (iii) in contrast to epitaxial growth, ultrafast laser doping allows selective area processing without requiring masking. The “cold” nature of ultrashort laser pulses preserves the original physical and chemical characteristics of untreated areas, ensuring that unaffected regions in integrated systems remain intact. Given these advantages, b-Si materials created via ultrafast laser doping represent a promising pathway for addressing the challenges of developing efficient and cost-effective IR photodetectors, paving the way for enhanced Si-based optoelectronic integration.199

    The use of ion implantation for doping in b-Si presents a versatile approach for developing IR photodetectors with tunable concentration profiles. In 2022, Tarik Bourouina’s group demonstrated that surface-doped b-Si, using phosphorus as the dopant, achieved a remarkable 98% absorptivity in the 1 to 5  μm range.200 They further produced a broadband absorber (spanning over 20  μm) by creating highly doped b-Si bulk via cryogenic plasma processing. This material exhibited 99.5% absorbance up to 8  μm and maintained over 90% absorbance at 20  μm [as detailed in Fig. 2(e)].51 Their findings, supported by numerical simulations, revealed that higher doping levels effectively enhanced absorption intensity, whereas moderate doping provided improved performance across a broader wavelength range. Thus, optimizing doping levels is essential to balance performance for specific applications. The duration of the etching process, which defines the conical structure depth, was found to be a key parameter affecting absorption efficiency. In addition, Song et al. employed the SPR effects of gold nanoparticles to design an absorber that operates across the 350 to 2500 nm spectrum without relying on lithographic methods.201 By combining RIE with Au nanoparticle deposition, they achieved a high-absorption b-Si surface (96.5%). This versatile absorber offers potential in photodetectors and solar energy collection.

    In 2016, Hele Savin’s group introduced an innovative photodiode design [Fig. 16(a)].202 It incorporates silicon nanostructures for enhanced light absorption, uniform ALD alumina coatings to suppress surface recombination, and an induced junction to address recombination caused by dopants and irregular junction formations. This device achieves an EQE exceeding 96% across 250 to 950 nm wavelengths and maintains performance at incident angles up to 70 deg. Building on these advancements, Zhang et al. designed a self-powered Schottky photodiode based on nanocrystal indium tin oxide and b-Si (nc-ITO/b-Si).203 As illustrated in Fig. 16(b), the device incorporates nanostalagmite structures created on high-resistivity n-Si, with ITO nanocrystals serving as the rectifying layer and aluminum functioning as the rear ohmic contact. The images in Figs. 16(c) and 16(d) reveal the nc-ITO-coated nanostalagmites and b-Si photodiodes with varying ITO contact thicknesses compared with untreated planar Si. As depicted in Fig. 16(e), the built-in electric field from the nc-ITO contact, forms a “strong-field depletion region” near the surface and a “weak-field region” extending 100  μm into the silicon absorber. This single-contact b-Si photodiode achieves exceptional performance, with an average broadband EQE exceeding 98% from 570 to 925 nm and over 95% from 500 to 960 nm. It operates effectively across visible and NIR wavelengths (470 to 1050 nm) and can detect nanowatt-level illumination, demonstrating its capability as a highly sensitive heart rate sensor. With near-unity EQE, a self-powered configuration and a straightforward fabrication process make this photodiode an excellent candidate for compact, lightweight optical and electronic devices. In addition, its effectiveness in monitoring heart rates under low-light conditions highlights its potential for advanced, energy-efficient applications. These advances underscore the promise of cost-effective b-Si–based optoelectronic devices for diverse and enhanced functionalities.

    (a) Diagram showing the vertical layout of a photodiode structure utilizing b-Si. Inset: SEM image of the b-Si active region coated with Al2O3. Reproduced with permission,202 © 2016 Springer Nature. (b) 3D device structure of a Schottky heterojunction photodiode featuring b-Si and nanocrystal indium tin oxide (nc-ITO). (c) High-resolution SEM image showing a cross-section of nc-ITO/Si nanostalagmites. (d) Photographs comparing b-Si devices covered with different thicknesses of ITO films to a planar silicon surface without treatment. (e) 2D diagram illustrating the device layout. (b)–(e) Reproduced with permission,203 © 2022 John Wiley and Sons. (f) Mechanism of electrochemically enhanced SERS detection, highlighting changes in surface charge on Au-coated nanopillar SERS substrates and their engagement with melamine molecules. (g) Depiction of the customized electrochemical-SERS platform and its integrated interface. (h) Image of the assembled detection chamber paired with an SEM view of Au-capped nanopillar structures designed for SERS detection. (f)–(h) Reproduced with permission,204 © 2020 American Chemical Society. (i) Cross-sectional SEM images of b-Si (left) and AuBSi (right). (j) Schematic of fingerprint metabolite detection using functionalized AuBSi substrates. (i) and (j) Reproduced with permission,43 © 2020 American Chemical Society. (k) Schematic illustration of the laser desorption and ionization process for NGQD@MoS2/SiNWs. Reproduced with permission,205 © 2022 American Chemical Society.

    Figure 16.(a) Diagram showing the vertical layout of a photodiode structure utilizing b-Si. Inset: SEM image of the b-Si active region coated with Al2O3. Reproduced with permission,202 © 2016 Springer Nature. (b) 3D device structure of a Schottky heterojunction photodiode featuring b-Si and nanocrystal indium tin oxide (nc-ITO). (c) High-resolution SEM image showing a cross-section of nc-ITO/Si nanostalagmites. (d) Photographs comparing b-Si devices covered with different thicknesses of ITO films to a planar silicon surface without treatment. (e) 2D diagram illustrating the device layout. (b)–(e) Reproduced with permission,203 © 2022 John Wiley and Sons. (f) Mechanism of electrochemically enhanced SERS detection, highlighting changes in surface charge on Au-coated nanopillar SERS substrates and their engagement with melamine molecules. (g) Depiction of the customized electrochemical-SERS platform and its integrated interface. (h) Image of the assembled detection chamber paired with an SEM view of Au-capped nanopillar structures designed for SERS detection. (f)–(h) Reproduced with permission,204 © 2020 American Chemical Society. (i) Cross-sectional SEM images of b-Si (left) and AuBSi (right). (j) Schematic of fingerprint metabolite detection using functionalized AuBSi substrates. (i) and (j) Reproduced with permission,43 © 2020 American Chemical Society. (k) Schematic illustration of the laser desorption and ionization process for NGQD@MoS2/SiNWs. Reproduced with permission,205 © 2022 American Chemical Society.

    Beyond visible-NIR applications, b-Si has also emerged as a promising solution for UV photodetection, where conventional technologies face two critical limitations: (i) high reflectance losses and (ii) low quantum efficiency and poor UV detection sensitivity due to surface recombination. Recent innovations have addressed these challenges by employing lightly doped b-Si to suppress dark current and enhance sensitivity, coupled with conformal Al2O3 passivation layers to minimize recombination losses through induced junction formation. In 2020, Garin et al. developed a b-Si photodiode featuring a self-induced junction from Al2O3, which surpassed the theoretical one-photon–one-electron barrier to achieve a certified EQE exceeding 130% in the UV spectrum without external amplification.206 Numerical simulations attributed this exceptional performance to impact ionization-driven multiple carrier generation within the nanostructures. Furthermore, Tsang et al. extended the investigations into vacuum ultraviolet (VUV) detection using b-Si photodiodes.207 Combining conformal alumina with an induced junction, the device shows a responsivity of 0.2  A/W at 175 nm under room temperature in vacuum. Notably, the findings revealed that the quantum efficiency exceeded unity and scaled linearly with photon energy above 4  eV, opening new opportunities for high-efficiency UV/VUV detection. These advancements drive innovation in UV detection and pave the way for developing high quantum-efficiency b-Si photomultipliers (b-SiPMs)—critical for direct VUV photon detection in noble gas and liquid scintillation systems.

    3.4.2 Surface-enhanced Raman scattering (SERS)

    SERS is an advanced approach for the detection and analysis of materials, offering exceptional sensitivity, robustness against photobleaching, narrow spectral bandwidth, and the ability to detect molecular features.21 These advantages make SERS widely applicable in fields such as food safety, biomedical research, environmental monitoring, and beyond. Traditionally, SERS substrates are constructed from rough surfaces incorporating noble metals. In recent years, b-Si has attracted notable interest as a potential SERS substrate, thanks to its extensive surface area and aspect ratio, providing an excellent platform for enhanced Raman scattering.208 Viehrig et al. introduced a b-Si–based electrochemical SERS platform that adjusts the analyte–surface interaction while maintaining the integrity of the SERS substrate, allowing the sensor to be reused effectively.204 The system incorporates uniformly Au-capped Si nanopillars with electrochemical techniques to facilitate efficient real-time reuse of the SERS substrate during assays. The mechanism of this electrochemical SERS detection system, shown in Fig. 16(f), highlights the variation in surface charges on the Au-capped nanopillars and their engagement with melamine. Figure 16(g) presents an image of the fully assembled detection chamber along with an SEM image of the Au-capped nanopillar structures utilized for SERS detection. In addition, Fig. 16(h) illustrates the tailored electrochemical-SERS system and its interface arrangement. This study demonstrates an integrated electrochemical-SERS platform with enhanced detection performance, enabling real-time calibration, sensing, and substrate reusability.

    Moreover, some researchers demonstrated a realistic 3D modeling methodology to simulate b-Si–based multi-stacked nanostructures with randomly distributed gold nanoparticles on the highly roughened nonflat surface.40 This method effectively links theoretical analyses to experimental optical responses, with far-field calculations accurately reproducing reflectance spectra to reveal the dependence of light trapping on the thickness of the conformal reflector and nanoparticle size, whereas near-field analysis identifies three stochastic “hotspots.” Both factors contribute significantly to overall field enhancement, which is highly sensitive to nanoscale surface morphology. This framework enables efficient control of stack configurations, amplifying localized fields in nanoparticle gaps and nanocavities, thereby maximizing electromagnetic field enhancement and the analytical enhancement factor (AEF) for SERS detection.

    In brief, SERS devices based on b-Si overcome the sensitivity limitations of conventional Raman spectroscopy, offering a powerful tool for obtaining detailed structural and interface information. It is extensively applied in surface science, adsorption studies, and the analysis of molecular orientation, conformation, and structural properties. The integration of b-Si as a substrate has further elevated SERS capabilities, significantly enhancing signal strength and detection sensitivity, and paving the way for broader and more advanced applications in various fields.

    3.4.3 Imaging applications

    Mass spectrometry imaging (MSI) is gaining prominence in the field of omics, particularly in proteomics and metabolomics. Stefania et al. explored the fabrication and application of b-Si and gold-coated black silicon (AuBSi) substrates in surface-assisted laser desorption/ionization mass spectrometry imaging (SALDI-MSI) for analyzing animal tissues and human fingerprints.43 Cross-sectional SEM images of b-Si and AuBSi are displayed in Fig. 16(i). During the experiment, the SALDI-MS performance was improved by coating b-Si surfaces with gold nanoparticles through sputtering. As demonstrated in Fig. 16(j), the sample based on AuBSi substrates effectively detected fingerprint metabolites and analytes originating from animal tissues under both positive and negative ionization conditions, enabling high-quality imaging of mouse brain and liver tissues. Utilizing biocompatible materials such as silicon and gold allows for matrix-independent analysis of metabolites directly on biological samples, paving the way for safer and more versatile imaging techniques.

    In addition, Jianmin Wu’s group introduced a method for tissue imprinting based on SiNWs capped with 2D nanoflakes (NGQD@MoS2/SiNWs) for MSI and cancer diagnosis [Fig. 16(k)].205 This innovative approach demonstrated superior lipid extraction, enhanced laser desorption/ionization (LDI) efficiency, and improved molecular imaging capabilities. Compared with conventional SiNW substrates, NGQD@MoS2/SiNWs achieved a four- to five-fold enhancement in the detection of lipid signals and total ion intensity from animal lung tissues, underscoring its potential in advanced MSI applications and medical diagnostics.

    Notably, extensive studies have explored the potential applications of b-Si in sensing209211 and antibacterial materials212215 in recent years. However, as these topics fall outside the scope of photonics, they are not discussed in this article.

    3.5 Challenges of b-Si in Solar and Photonic Applications

    Based on the discussion above, b-Si exhibits significant potential for solar energy conversion and photonics applications; however, its implementation encounters several challenges. Although its nanostructured surface significantly reduces reflectance and enhances light absorption—particularly in the ultraviolet and infrared ranges—the inherent surface roughness and associated defects can increase carrier recombination, shortening the lifetime of non-equilibrium charge carriers. In addition, the rough surface morphology may introduce high and sometimes non-uniform doping concentrations, posing significant challenges for forming a reliable silicon/metal contact.20 These factors collectively diminish solar energy conversion efficiency, reduce the signal-to-noise ratio in photodetectors, introduce unwanted background noise in SERS, and degrade image resolution in optical sensing applications. For SERS application, further functionalization with plasmonic nanoparticles (e.g., Au or Ag) is necessary to achieve high enhancement factors, but this introduces fabrication complexity and may compromise stability under laser irradiation. Thus, optimizing the trade-off between optical absorption and surface recombination remains critical for photonic devices based on b-Si.

    Second, b-Si structures suffer from the bottleneck of hasty surface photo-oxidation, photo-corrosion, and indigent acid stability, where the high surface area accelerates surface corrosion in the PEC system. This instability limits quantum efficiency and long-term performance.29,216 Passivation techniques, such as protective coatings, chemical treatments, or catalyst integration, are often needed to mitigate these issues and improve surface charge transfer but also increase manufacturing complexity and cost.

    Third, the irregular morphology of b-Si can enhance plasmonic effects, but achieving uniform and reproducible signal amplification remains difficult due to inconsistent nanostructuring for SERS application. Across these applications, precise control over nanostructure geometry and seamless integration with existing optoelectronic systems complicate fabrication and scalability. Balancing optical performance with device reliability and manufacturability is an ongoing challenge in advancing b-Si–based technologies.

    Finally, although some aforementioned fundamental limitations related to b-Si applications have been addressed in laboratory settings, industrial viability in scalable fabrication presents additional challenges. More comprehensive cost and lifecycle analysis would be required for b-Si to transition into the mainstream technology for solar energy conversion. Techniques such as MACE and RIE have obtained high expectations in industrial production. MACE, in particular, is favored for commercial solar cells due to its compatibility with the existing manufacturing lines based on wet chemical etching, and there are pioneers in the field already mass-producing b-Si solar cells.217,218 However, challenges such as metal contamination and waste etching solution treatment remain critical concerns, thus reducing the metal consumption during silicon surface texturing should be recommended as a reliable route. RIE, on the other hand, offers advantages for industrial applications, including large-scale preparation, rapid processing, and the absence of noble metal contamination.132 However, RIE faces its own challenges, such as high equipment costs, the need for precise plasma control to avoid excessive ion-induced surface damage, and potential limitations in achieving ultra-deep nanostructures with uniform aspect ratios.

    4 Conclusions and Perspectives

    B-Si nanostructures have demonstrated immense potential for a variety of solar energy conversion and photonic applications. Various techniques are available for creating b-Si with diverse structures, including nanoscale spikes, cones, vertical cylinders, and porous silicon. These methods are typically more cost-effective than many advanced fabrication approaches, making b-Si a promising candidate for commercialization in various applications. The remarkable unique optical and electronic properties imparted by the high-aspect-ratio nanostructures, including broadband light absorption, enhanced carrier collection, and tailorable optical responses, position b-Si as a highly appealing material for pushing the boundaries of solar energy conversion and various photonic devices.

    In the realm of solar energy conversion to electrical, chemical, and thermal energy, b-Si has demonstrated superior capabilities in improving light absorption and carrier collection compared to planar silicon, leading to record-breaking solar cell efficiencies. Further optimizations in nanostructure design, passivation schemes, and device architectures hold promise for continued advancements in b-Si solar cell performance. Integrating b-Si into tandem and multi-junction solar cell configurations could also unlock new pathways for boosting overall conversion efficiencies. In PEC systems and thermal energy conversion, the development of hybrid systems that combine the strengths of b-Si with other nanostructured materials may pave the way for innovative solutions in renewable energy technologies.

    For photonic applications, the broadband and tunable optical absorption of b-Si enables high-sensitivity, spectrally versatile devices. Recent developments in b-Si photodetector have demonstrated impressive responsivities and bandwidths, opening new opportunities for their adoption in diverse sensing and imaging technologies. Exploring novel device structures and incorporating them with complementary metal-oxide-semiconductor (CMOS) electronics could further enhance the functionality and practicality of b-Si photodetectors. Moreover, the distinctive optical characteristics of b-Si nanostructures show great promise in AR coatings, optical filters, metamaterials, and so on. Harnessing the ability to precisely control the optical responses of b-Si through nanostructure engineering could lead to the development of innovative photonic technologies and components.

    As the research on b-Si nanostructures continues to evolve, several key areas of investigation warrant further exploration. These include developing scalable and cost-effective fabrication techniques, optimizing nanostructure morphologies for specific applications, enhancing the thermal and mechanical stability of b-Si, and seamlessly integrating it with existing semiconductor technologies. Of these, control over the uniformity and reproducibility of nanostructures is critical for scaling up production and ensuring consistent performance in commercial applications. Furthermore, although b-Si demonstrates excellent absorption in the visible spectrum, enhancing its performance in the NIR region remains an area for further research. Addressing these challenges will be crucial for translating the promising laboratory-scale demonstrations of b-Si into practical, large-scale, and commercially viable products. Notably, recent advancements in artificial intelligence (AI) present exciting opportunities for accelerating progress, and AI-assisted approaches on b-Si have the potential to accelerate advancements by optimizing fabrication processes, predicting material properties, and identifying novel applications across energy and photonic technologies.149 This integration of AI into b-Si research holds significant promise for driving innovation in efficient and scalable solutions in the future.

    Overall, the remarkable optical and electronic features of b-Si nanostructures, coupled with the ongoing refinement of fabrication processes, highlight its potential to drive innovation in solar energy conversion and a wide range of photonic devices.

    Huaping Jia is currently a postdoctoral fellow in the Department of Applied Physics at the Hong Kong Polytechnic University. She received her BEng degree in communication engineering in 2013 and her PhD in electronics science and technology in 2022, both from Taiyuan University of Technology. Her current research interests cover mainly surface plasmonic effects in solar energy conversion and photonics.

    Fengjia Xie obtained her PhD from the Department of Applied Physics at the Hong Kong Polytechnic University in 2024. She is currently a postdoctoral fellow focusing on photocatalysis and microfluidics.

    Elyes Nefzaoui earned his PhD from the University of Poitiers, France, in 2013. Following a postdoctoral appointment at the CNRS Centre for Energy and Thermal Sciences of Lyon (CETHIL), he joined the University Gustave Eiffel where he managed the Energy Graduate Program at the ESIEE Paris School of Engineering. Currently, he is an associate professor at the University of Gustave Eiffel, CNRS, ESYCOM Laboratory, leading the energy harvesting group. His research focuses on infrared meta-materials for energy applications, heat transfer in electronic devices, thermal energy harvesting, and the development of sensors, sensor networks, and data analytics for environmental and energy monitoring.

    Tarik Bourouina received his PhD in 1991 and his habilitation (HDR) in 2000 from Université Paris-Saclay. He has been a professor in physics at ESIEE Paris, Université Gustave Eiffel since 2002. He is also affiliated with the French National Center for Scientific Research (CNRS), within the CINTRA laboratory IRL 3288 in Singapore jointly with Nanyang Technological University (NTU) and THALES, and within the ESYCOM laboratory UMR9007 in France. His interests include micro-scale physics and silicon-based metasurfaces.

    Heng Jiang obtained his BE and ME degrees from the School of Power and Energy, Northwestern Polytechnical University, China, in 2018 and 2021, respectively. He earned his PhD from the Department of Applied Physics at the Hong Kong Polytechnic University in 2025, where he is currently a postdoctoral fellow. His research interests include artificial compound eyes and microfluidics.

    Xuming Zhang is currently a full professor at the Photonics Research Institute and Department of Applied Physics, The Hong Kong Polytechnic University. He received his BEng degree from the University of Science & Technology of China (USTC) in 1994 and his PhD from Nanyang Technological University (NTU) in 2006. His research has produced more than 160 journal papers. Recently, he set up two start-up companies. His current research interests cover mainly nanophotonics, plasmonics, microfluidics, artificial photosynthesis, biomimetics, and green energy.

    References

    [1] H. Nishiyama et al. Photocatalytic solar hydrogen production from water on a 100-m2 scale. Nature, 598, 304-307(2021). https://doi.org/10.1038/s41586-021-03907-3

    [2] J. L. Young et al. Direct solar-to-hydrogen conversion via inverted metamorphic multi-junction semiconductor architectures. Nat. Energy, 2, 17028(2017). https://doi.org/10.1038/nenergy.2017.28

    [3] J. Liu et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science, 347, 970-974(2015).

    [4] D. Gunawan et al. Materials advances in photocatalytic solar hydrogen production: integrating systems and economics for a sustainable future. Adv. Mater., 36, 2404618(2024). https://doi.org/10.1002/adma.202404618

    [5] L. Zhang, Y. Wang. Decoupled artificial photosynthesis. Angew. Chem. Int. Ed., 62, e202219076(2023).

    [6] X. Li et al. Water splitting: from electrode to green energy system. Nano-Micro Lett., 12, 131(2020).

    [7] P. Tao et al. Solar-driven interfacial evaporation. Nat. Energy, 3, 1031-1041(2018). https://doi.org/10.1038/s41560-018-0260-7

    [8] S. Tembhurne, F. Nandjou, S. Haussener. A thermally synergistic photo-electrochemical hydrogen generator operating under concentrated solar irradiation. Nat. Energy, 4, 399-407(2019). https://doi.org/10.1038/s41560-019-0373-7

    [9] T. S. Teitsworth et al. Water splitting with silicon p–i–n superlattices suspended in solution. Nature, 614, 270-274(2023). https://doi.org/10.1038/s41586-022-05549-5

    [10] S. Li et al. Surface/interface engineering of Si-based photocathodes for efficient hydrogen evolution. ACS Photonics, 9, 3786-3806(2022). https://doi.org/10.1021/acsphotonics.2c00708

    [11] S. Y. Reece et al. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science, 334, 645-648(2011).

    [12] M. J. Kenney et al. High-performance silicon photoanodes. Science, 342, 836-840(2013).

    [13] J. Lv et al. Review application of nanostructured black silicon. Nanoscale Res. Lett., 13, 110(2018). https://doi.org/10.1186/s11671-018-2523-4

    [14] E. S. Kolesar, V. M. Bright, D. M. Sowders. Optical reflectance reduction of textured silicon surfaces coated with an antireflective thin film. Thin Solid Films, 290–291, 23-29(1996). https://doi.org/10.1016/S0040-6090(96)09064-5

    [15] Y. Liu et al. Nanostructure formation and passivation of large-area black silicon for solar cell applications. Small, 8, 1392-1397(2012). https://doi.org/10.1002/smll.201101792

    [16] C.-S. Yang et al. THz conductivities of indium-tin-oxide nanowhiskers as a graded-refractive-index structure. Opt. Express, 20, A441-A451(2012). https://doi.org/10.1364/OE.20.00A441

    [17] M. C. Beard, R. J. Ellingson. Multiple exciton generation in semiconductor nanocrystals: toward efficient solar energy conversion. Laser Photonics Rev., 2, 377-399(2008). https://doi.org/10.1002/lpor.200810013

    [18] J. Yang et al. Design and fabrication of broadband ultralow reflectivity black Si surfaces by laser micro/nanoprocessing. Light Sci. Appl., 3, e185(2014). https://doi.org/10.1038/lsa.2014.66

    [19] M. Otto et al. Black silicon photovoltaics. Adv. Opt. Mater., 3, 147-164(2015). https://doi.org/10.1002/adom.201400395

    [20] X. Liu et al. Black silicon: fabrication methods, properties and solar energy applications. Energy Environ. Sci., 7, 3223-3263(2014). https://doi.org/10.1039/C4EE01152J

    [21] Z. Fan et al. Recent progress of black silicon: from fabrications to applications. Nanomaterials, 11, 41(2021).

    [22] J. Soueiti et al. A review of cost-effective black silicon fabrication techniques and applications. Nanoscale, 15, 4738-4761(2023). https://doi.org/10.1039/D2NR06087F

    [23] Q. Tan et al. Nano-fabrication methods and novel applications of black silicon. Sens. Actuators A Phys., 295, 560-573(2019). https://doi.org/10.1016/j.sna.2019.04.044

    [24] B. Fazio et al. Strongly enhanced light trapping in a two-dimensional silicon nanowire random fractal array. Light Sci. Appl., 5, e16062(2016). https://doi.org/10.1038/lsa.2016.62

    [25] Z. Zhang et al. Black silicon with order-disordered structures for enhanced light trapping and photothermic conversion. Nano Energy, 65, 103992(2019). https://doi.org/10.1016/j.nanoen.2019.103992

    [26] M. Steglich et al. An ultra-black silicon absorber. Laser Photonics Rev., 8, 13-17(2014). https://doi.org/10.1002/lpor.201300142

    [27] M. Joshi, R. Verma. Black silicon photovoltaics: fabrication methods and properties. Int. J. Res. Eng. Sci., 5, 62-72(2017).

    [28] F. Priolo et al. Silicon nanostructures for photonics and photovoltaics. Nat. Nanotechnol., 9, 19-32(2014). https://doi.org/10.1038/nnano.2013.271

    [29] Y. Wang et al. Silicon nanowires for biosensing, energy storage, and conversion. Adv. Mater., 25, 5177-5195(2013). https://doi.org/10.1002/adma.201301943

    [30] J. Y. H. Chai, B. T. Wong, S. Juodkazis. Black-silicon-assisted photovoltaic cells for better conversion efficiencies: a review on recent research and development efforts. Mater. Today Energy, 18, 100539(2020). https://doi.org/10.1016/j.mtener.2020.100539

    [31] M. D. Kelzenberg et al. Enhanced absorption and carrier collection in Si wire arrays for photovoltaic applications. Nat. Mater., 9, 239-244(2010). https://doi.org/10.1038/nmat2635

    [32] T. G. Allen et al. Passivating contacts for crystalline silicon solar cells. Nat. Energy, 4, 914-928(2019). https://doi.org/10.1038/s41560-019-0463-6

    [33] Z. Ying et al. Monolithic perovskite/black-silicon tandems based on tunnel oxide passivated contacts. Joule, 6, 2644-2661(2022). https://doi.org/10.1016/j.joule.2022.09.006

    [34] C. Xie et al. High-efficiency, air stable graphene/Si micro-hole array Schottky junction solar cells. J. Mater. Chem A Mater., 1, 15348-15354(2013). https://doi.org/10.1039/c3ta13750c

    [35] A. Alsolami et al. Recent advances in black silicon surface modification for enhanced light trapping in photodetectors. Appl. Sci., 14, 9841(2024). https://doi.org/10.3390/app14219841

    [36] Z. Zhao et al. Black silicon for near-infrared and ultraviolet photodetection: a review. APL Mater., 11, 021107(2023).

    [37] Y. Gwon, J. H. Kim, S. W. Lee. Quantification of plasma dopamine in depressed patients using silver-enriched silicon nanowires as SERS-active substrates. ACS Sens., 9, 870-882(2024). https://doi.org/10.1021/acssensors.3c02202

    [38] F. Rauh et al. Nanostructured black silicon as a stable and surface-sensitive platform for time-resolved in situ electrochemical infrared absorption spectroscopy. ACS Appl. Mater. Interfaces, 16, 6653-6664(2024). https://doi.org/10.1021/acsami.3c17294

    [39] L. Golubewa et al. Surface-enhanced raman spectroscopy of organic molecules and living cells with gold-plated black silicon. ACS Appl. Mater. Interfaces, 12, 50971-50984(2020). https://doi.org/10.1021/acsami.0c13570

    [40] Y. Li et al. Evaluating the optical response of heavily decorated black silicon based on a realistic 3D modeling methodology. ACS Appl. Mater. Interfaces, 14, 36189-36199(2022). https://doi.org/10.1021/acsami.2c05652

    [41] L. Z. Samarah et al. Mass spectrometry imaging of bio-oligomer polydispersity in plant tissues by laser desorption ionization from silicon nanopost arrays. Angew. Chem. Int. Ed., 60, 9071-9077(2021). https://doi.org/10.1002/anie.202015251

    [42] J. Qian et al. Recent developments in porous silicon nanovectors with various imaging modalities in the framework of theranostics. ChemMedChem, 17, e202200004(2022). https://doi.org/10.1002/cmdc.202200004

    [43] S. A. Iakab et al. Gold nanoparticle-assisted black silicon substrates for mass spectrometry imaging applications. ACS Nano, 14, 6785-6794(2020). https://doi.org/10.1021/acsnano.0c00201

    [44] Y. Zhang et al. Scanning electron microscopy dopant contrast imaging of phosphorus-diffused silicon. Adv. Mater. Technol., 8, 2200737(2023). https://doi.org/10.1002/admt.202200737

    [45] S. Raman, A. Ravi Sankar, M. Sindhuja. Advances in silicon nanowire applications in energy generation, storage, sensing, and electronics: a review. Nanotechnology, 34, 182001(2023). https://doi.org/10.1088/1361-6528/acb320

    [46] K. Q. Peng, S. T. Lee. Silicon nanowires for photovoltaic solar energy conversion. Adv. Mater., 23, 198-215(2011). https://doi.org/10.1002/adma.201002410

    [47] G. Ayvazyan. Black Silicon: Formation, Properties, and Application(2024).

    [48] C. C. Striemer, P. M. Fauchet. Dynamic etching of silicon for broadband antireflection applications. Appl. Phys. Lett., 81, 2980-2982(2002). https://doi.org/10.1063/1.1514832

    [49] S. K. Srivastava et al. Nanostructured black silicon for efficient thin silicon solar cells: potential and challenges. Recent Advances in Thin Films, 549-623(2020).

    [50] S. K. Srivastava et al. Antireflective ultra-fast nanoscale texturing for efficient multi-crystalline silicon solar cells. Solar Energy, 115, 656-666(2015). https://doi.org/10.1016/j.solener.2015.03.010

    [51] S. Sarkar et al. Black silicon revisited as an ultrabroadband perfect infrared absorber over 20  μm wavelength range. Adv. Photonics Res., 4, 2200223(2023). https://doi.org/10.1002/adpr.202200223

    [52] C. H. Crouch et al. Infrared absorption by sulfur-doped silicon formed by femtosecond laser irradiation. Appl. Phys. A Mater. Sci. Process., 79, 1635-1641(2004). https://doi.org/10.1007/s00339-004-2676-0

    [53] C. Wu et al. Near-unity below-band-gap absorption by microstructured silicon. Appl. Phys. Lett., 78, 1850-1852(2001). https://doi.org/10.1063/1.1358846

    [54] Y. Liu et al. Broad band enhanced infrared light absorption of a femtosecond laser microstructured silicon. Laser Phys., 18, 1148-1152(2008). https://doi.org/10.1134/S1054660X08100071

    [55] P. G. Maloney et al. Emissivity of microstructured silicon. Appl. Opt., 49, 1065-1068(2010). https://doi.org/10.1364/AO.49.001065

    [56] S. Ma et al. A theoretical study on the optical properties of black silicon. AIP Adv., 8, 035010(2018).

    [57] G. Sanchez-Plaza, A. Urquia. Process and optical modeling of black silicon. Opt. Express, 32, 17704-17718(2024). https://doi.org/10.1364/OE.516245

    [58] Y. Zhang et al. Plasma focused ion beam tomography for accurate characterization of black silicon validated by full wave optical simulation. Adv. Mater. Technol., 7, 2200068(2022).

    [59] X. Zhang et al. Effects of black silicon surface morphology induced by a femtosecond laser on absorptance and photoelectric response efficiency. Photonics, 11, 947(2024).

    [60] D. A. R. Barkhouse et al. Yield predictions for photovoltaic power plants: empirical validation, recent advances and remaining uncertainties. Prog. Photovolt. Res. Appl., 20, 6-11(2015). https://doi.org/10.1002/pip.1160

    [61] R. Memming, G. Schwandt. Anodic dissolution of silicon in hydrofluoric acid solutions. Surf. Sci., 4, 109-124(1966). https://doi.org/10.1016/0039-6028(66)90071-9

    [62] S. Surdo, G. Barillaro. Voltage- and metal-assisted chemical etching of micro and nano structures in silicon: a comprehensive review. Small, 20, 2400499(2024).

    [63] L. Sainiemi et al. Rapid fabrication of high aspect ratio silicon nanopillars for chemical analysis. Nanotechnology, 18, 505303(2007). https://doi.org/10.1088/0957-4484/18/50/505303

    [64] X. G. Zhang, S. D. Collins, R. L. Smith. Porous silicon formation and electropolishing of silicon by anodic polarization in HF solution. J. Electrochem. Soc., 136, 1561(1989). https://doi.org/10.1149/1.2096961

    [65] P. Kleimann, J. Linnros, R. Juhasz. Formation of three-dimensional microstructures by electrochemical etching of silicon. Appl. Phys. Lett., 79, 1727-1729(2001). https://doi.org/10.1063/1.1401792

    [66] S. Matthias et al. Large-area three-dimensional structuring by electrochemical etching and lithography. Adv. Mater., 16, 2166-2170(2004). https://doi.org/10.1002/adma.200400436

    [67] P. Kleimann, X. Badel, J. Linnros. Toward the formation of three-dimensional nanostructures by electrochemical etching of silicon. Appl. Phys. Lett., 86, 183108(2005). https://doi.org/10.1063/1.1924883

    [68] X. G. Zhang. Morphology and formation mechanisms of porous silicon. J. Electrochem. Soc., 151, C69(2004). https://doi.org/10.1149/1.1632477

    [69] H. A. D. Ali, Y. M. Hassan. Metal assisted stain etched porous silicon for detecting Klebsiella bacteria. Eur. J. Sci. Eng., 9, 353-362(2023).

    [70] R. Bilyalov, L. Stalmans, J. Poortmans. Comparative analysis of chemically and electrochemically formed porous Si antireflection coating for solar cells. J. Electrochem. Soc., 150, G216(2003). https://doi.org/10.1149/1.1545468

    [71] J. V. Pleština et al. Nanoporous silicon tubes: the role of geometry in nanostructure formation and application to light emitting diodes. J. Phys. D Appl. Phys., 50, 265101(2017).

    [72] R. R. Bilyalov et al. Multicrystalline silicon solar cells with porous silicon emitter. Solar Energy Mater. Solar Cells, 60, 391-420(2000). https://doi.org/10.1016/S0927-0248(99)00102-6

    [73] M. Y. Arafat et al. Fabrication of black silicon via metal-assisted chemical etching—a review. Sustainability, 13, 10766(2021). https://doi.org/10.3390/su131910766

    [74] Z. Huang et al. Extended arrays of vertically aligned sub-10 nm diameter [100] Si nanowires by metal-assisted chemical etching. Nano Lett., 8, 3046-3051(2008). https://doi.org/10.1021/nl802324y

    [75] Z. Zuo et al. Gold-thickness-dependent Schottky barrier height for charge transfer in metal-assisted chemical etching of silicon. Nanoscale Res. Lett., 8, 193(2013). https://doi.org/10.1186/1556-276X-8-193

    [76] J. Kim et al. Curved silicon nanowires with ribbon-like cross sections by metal-assisted chemical etching. ACS Nano, 5, 5242-5248(2011). https://doi.org/10.1021/nn2014358

    [77] R. Akan et al. Reaction control of metal-assisted chemical etching for silicon-based zone plate nanostructures. RSC Adv., 8, 12628-12634(2018). https://doi.org/10.1039/C8RA01627E

    [78] S. Li et al. Structure and antireflection properties of SiNWs arrays form mc-Si wafer through Ag-catalyzed chemical etching. Appl. Surf. Sci., 369, 232-240(2016). https://doi.org/10.1016/j.apsusc.2016.02.028

    [79] X. Li et al. High-efficiency multi-crystalline black silicon solar cells achieved by additive assisted Ag-MACE. Solar Energy, 195, 176-184(2020). https://doi.org/10.1016/j.solener.2019.11.045

    [80] L. Yang et al. 18.87%-efficient inverted pyramid structured silicon solar cell by one-step Cu-assisted texturization technique. Solar Energy Mater. Solar Cells, 166, 121-126(2017). https://doi.org/10.1016/j.solmat.2017.03.017

    [81] Y. Cao et al. Progress and mechanism of cu assisted chemical etching of silicon in a low Cu2+ concentration region. ECS J. Solid State Sci. Technol., 4, P331-P336(2015). https://doi.org/10.1149/2.0191508jss

    [82] J. P. Lee, S. Choi, S. Park. Extremely superhydrophobic surfaces with micro- and nanostructures fabricated by copper catalytic etching. Langmuir, 27, 809-814(2011). https://doi.org/10.1021/la1045354

    [83] L. Kong, S. Y. Chiam, W. K. Chim. Metal-assisted silicon chemical etching using self-assembled sacrificial nickel nanoparticles template for antireflection layers in photovoltaic and light-trapping devices. ACS Appl. Nano Mater., 2, 7025-7031(2019). https://doi.org/10.1021/acsanm.9b01528

    [84] K. Gao et al. Fabrication of black silicon by Ni assisted chemical etching. Mater. Res. Express, 5, 015020(2018).

    [85] R. A. Lai et al. Schottky barrier catalysis mechanism in metal-assisted chemical etching of silicon. ACS Appl. Mater. Interfaces, 8, 8875-8879(2016). https://doi.org/10.1021/acsami.6b01020

    [86] Y. Wang et al. Micro-structured inverted pyramid texturization of Si inspired by self-assembled Cu nanoparticles. Nanoscale, 9, 907-914(2017). https://doi.org/10.1039/C6NR08126F

    [87] Z. Huang, H. Fang, J. Zhu. Fabrication of silicon nanowire arrays with controlled diameter, length, and density. Adv. Mater., 19, 744-748(2007). https://doi.org/10.1002/adma.200600892

    [88] C. Huo et al. Metal-assisted chemical etching of silicon in oxidizing HF solutions: origin, mechanism, development, and black silicon solar cell application. Adv. Funct. Mater., 30, 2005744(2020).

    [89] Y. Matsui, S. Adachi. Optical properties of black silicon formed by catalytic etching of Au/Si(100) wafers. J. Appl. Phys., 113, 173502(2013).

    [90] A. Mateen et al. Silicon nanowires via metal-assisted chemical etching for energy storage applications. ChemSusChem, 18, 202400777(2024). https://doi.org/10.1002/cssc.202400777

    [91] D. P. Linklater, S. Juodkazis, E. P. Ivanova. Nanofabrication of mechano-bactericidal surfaces. Nanoscale, 9, 16564-16585(2017). https://doi.org/10.1039/C7NR05881K

    [92] S. Schaefer, R. Lüdemann. Low damage reactive ion etching for photovoltaic applications. J. Vac. Sci. Technol. A Vac. Surf. Films, 17, 749-754(1999). https://doi.org/10.1116/1.581644

    [93] Y. F. Huang et al. Improved broadband and quasi-omnidirectional anti-reflection properties with biomimetic silicon nanostructures. Nat. Nanotechnol., 2, 770-774(2007). https://doi.org/10.1038/nnano.2007.389

    [94] J. I. Gittleman et al. Textured silicon: a selective absorber for solar thermal conversion. Appl. Phys. Lett., 35, 742-744(1979). https://doi.org/10.1063/1.90953

    [95] H. Jansen et al. The black silicon method: a universal method for determining the parameter setting of a fluorine-based reactive ion etcher in deep silicon trench etching with profile control. J. Micromech. Microeng., 5, 115-120(1995). https://doi.org/10.1088/0960-1317/5/2/015

    [96] J. Yin, M. Hong. Seed-guided high-repetition-rate femtosecond laser oxidation for functional three-dimensional silicon structure fabrication. Opt. Laser Technol., 179, 111348(2024). https://doi.org/10.1016/j.optlastec.2024.111348

    [97] Y. Li, M. Hong. Parallel laser micro/nano-processing for functional device fabrication. Laser Photonics Rev., 14, 1900062(2020).

    [98] A. Y. Vorobyev, C. Guo. Direct femtosecond laser surface nano/microstructuring and its applications. Laser Photonics Rev., 7, 385-407(2013). https://doi.org/10.1002/lpor.201200017

    [99] X. Y. Yu et al. The optical and electrical properties of co-doped black silicon textured by a femtosecond laser and its application to infrared light sensing. IEEE Sens. J., 16, 5227-5231(2016). https://doi.org/10.1109/JSEN.2016.2564500

    [100] T. H. Her et al. Microstructuring of silicon with femtosecond laser pulses. Appl. Phys. Lett., 73, 1673-1675(1998). https://doi.org/10.1063/1.122241

    [101] A. Y. Vorobyev, C. Guo. Direct creation of black silicon using femtosecond laser pulses. Appl. Surf. Sci., 257, 7291-7294(2011). https://doi.org/10.1016/j.apsusc.2011.03.106

    [102] M. Huang et al. The morphological and optical characteristics of femtosecond laser-induced large-area micro/nanostructures on GaAs, Si, and brass. Opt. Express, 18, A600-A619(2010). https://doi.org/10.1364/OE.18.00A600

    [103] M. Y. Shen et al. Femtosecond laser-induced formation of submicrometer spikes on silicon in water. Appl. Phys. Lett., 85, 5694-5696(2004). https://doi.org/10.1063/1.1828575

    [104] R. Le Harzic et al. Sub-100 nm nanostructuring of silicon by ultrashort laser pulses. Opt. Express, 13, 6651-6656(2005). https://doi.org/10.1364/OPEX.13.006651

    [105] L. Stalmans et al. Porous silicon in crystalline silicon solar cells: a review and the effect on the internal quantum efficiency. Prog. Photovolt. Res. Appl., 6, 233-246(1998). https://doi.org/10.1002/(SICI)1099-159X(199807/08)6:4<233::AID-PIP207>3.0.CO;2-D

    [106] H. Zhang et al. A continuous, single-face wet texturing process for industrial multicrystalline silicon solar cells using a surfactant treated photoresist mask. Solar Energy Mater. Solar Cells, 180, 173-183(2018). https://doi.org/10.1016/j.solmat.2018.03.003

    [107] K. Peng et al. Fabrication of single-crystalline silicon nanowires by scratching a silicon surface with catalytic metal particles. Adv. Funct. Mater., 16, 387-394(2006). https://doi.org/10.1002/adfm.200500392

    [108] C. Zhang et al. Fabrication of 20.19% efficient single-crystalline silicon solar cell with inverted pyramid microstructure. Nanoscale Res. Lett., 13, 4-11(2018). https://doi.org/10.1186/s11671-017-2414-0

    [109] A. Abdulkadir, A. bin Abdul Aziz, M. Z. Pakhuruddin. Optimization of etching time for broadband absorption enhancement in black silicon fabricated by one-step electroless silver-assisted wet chemical etching. Optik, 187, 74-80(2019). https://doi.org/10.1016/j.ijleo.2019.05.019

    [110] K. Peng et al. Aligned single-crystalline Si nanowire arrays for photovoltaic applications. Small, 1, 1062-1067(2005). https://doi.org/10.1002/smll.200500137

    [111] K. Q. Peng et al. High-performance silicon nanohole solar cells. J. Am. Chem. Soc., 132, 6872-6873(2010). https://doi.org/10.1021/ja910082y

    [112] J. Ji et al. Fabrication and photoelectrochemical properties of ordered Si nanohole arrays. Appl. Surf. Sci., 292, 86-92(2014). https://doi.org/10.1016/j.apsusc.2013.11.080

    [113] X. Yang et al. Influence of bowl-like nanostructures on the efficiency and module power of black silicon solar cells. Solar Energy, 189, 67-73(2019). https://doi.org/10.1016/j.solener.2019.07.044

    [114] K. M. Park, M. B. Lee, S. Y. Choi. Investigation of surface features for 17.2% efficiency multi-crystalline silicon solar cells. Solar Energy Mater. Solar Cells, 132, 356-362(2015). https://doi.org/10.1016/j.solmat.2014.07.023

    [115] Y. Xia et al. X-ray photoelectron spectroscopic studies of black silicon for solar cell. J. Electron. Spectrosc. Relat. Phenom., 184, 589-592(2012). https://doi.org/10.1016/j.elspec.2011.10.004

    [116] V. V. Iyengar, B. K. Nayak, M. C. Gupta. Optical properties of silicon light trapping structures for photovoltaics. Solar Energy Mater. Solar Cells, 94, 2251-2257(2010). https://doi.org/10.1016/j.solmat.2010.07.020

    [117] B. K. Nayak, V. V. Iyengar, M. C. Gupta. Efficient light trapping in silicon solar cells by ultrafast-laser-induced self-assembled micro/nano structures. Prog. Photovolt.: Res. Appl., 19, 631-639(2011). https://doi.org/10.1002/pip.1067

    [118] M. E. Becquerel. Mémoire sur les effets électriques produits sous l’influence des rayons solaires. C. R. Hebd. Seances Acad. Sci., 9, 561-567(1839).

    [119] A. Y. Liu, S. P. Phang, D. Macdonald. Gettering in silicon photovoltaics: a review. Solar Energy Mater. Solar Cells, 234, 111447(2022). https://doi.org/10.1016/j.solmat.2021.111447

    [120] W. Cui et al. Status and perspectives of transparent conductive oxide films for silicon heterojunction solar cells. Mater. Today Nano, 22, 100329(2023). https://doi.org/10.1016/j.mtnano.2023.100329

    [121] M. Hermle et al. Passivating contacts and tandem concepts: approaches for the highest silicon-based solar cell efficiencies. Appl. Phys. Rev., 7, 021305(2020). https://doi.org/10.1063/1.5139202

    [122] F. Fertig et al. Mass production of p-type Cz silicon solar cells approaching average stable conversion efficiencies of 22%. Energy Procedia, 124, 338-345(2017). https://doi.org/10.1016/j.egypro.2017.09.308

    [123] J. Zhou et al. Passivating contacts for high-efficiency silicon-based solar cells: from single-junction to tandem architecture. Nano Energy, 92, 106712(2022). https://doi.org/10.1016/j.nanoen.2021.106712

    [124] Y. Cheng, L. Ding. Perovskite/Si tandem solar cells: fundamentals, advances, challenges, and novel applications. SusMat, 1, 324-344(2021). https://doi.org/10.1002/sus2.25

    [125] Y. Zhang et al. Progress in passivating selective contacts for heterojunction silicon solar cells. Nano Energy, 131, 110282(2024). https://doi.org/10.1016/j.nanoen.2024.110282

    [126] A. R. Barron. Cost reduction in the solar industry. Mater. Today, 18, 2-3(2015). https://doi.org/10.1016/j.mattod.2014.10.022

    [127] J. Oh, H. C. Yuan, H. M. Branz. An 18.2%-efficient black-silicon solar cell achieved through control of carrier recombination in nanostructures. Nat. Nanotechnol., 7, 743-748(2012). https://doi.org/10.1038/nnano.2012.166

    [128] R. S. Davidsen et al. Black silicon laser-doped selective emitter solar cell with 18.1% efficiency. Solar Energy Mater. Solar Cells, 144, 740-747(2016). https://doi.org/10.1016/j.solmat.2015.10.018

    [129] W. C. Wang et al. Surface passivation of efficient nanotextured black silicon solar cells using thermal atomic layer deposition. ACS Appl. Mater. Interfaces, 5, 9752-9759(2013). https://doi.org/10.1021/am402889k

    [130] W. C. Wang et al. Efficiency enhancement of nanotextured black silicon solar cells using Al2O3/TiO2 dual-layer passivation stack prepared by atomic layer deposition. ACS Appl. Mater. Interfaces, 7, 10228-10237(2015). https://doi.org/10.1021/acsami.5b00677

    [131] H. Savin et al. Black silicon solar cells with interdigitated back-contacts achieve 22.1% efficiency. Nat. Nanotechnol., 10, 624-628(2015). https://doi.org/10.1038/nnano.2015.89

    [132] J. Xu et al. High efficiency TOPCon solar cells with micron/nano-structured emitter for a balance of light-trapping and surface passivation. Solar Energy Mater. Solar Cells, 238, 111606(2022). https://doi.org/10.1016/j.solmat.2022.111606

    [133] Y. Jiang et al. High efficiency multi-crystalline silicon solar cell with inverted pyramid nanostructure. Solar Energy, 142, 91-96(2017). https://doi.org/10.1016/j.solener.2016.12.007

    [134] X. Ye et al. 18.45%-efficient multi-crystalline silicon solar cells with novel nanoscale pseudo-pyramid texture. Adv. Funct. Mater., 24, 6708-6716(2014). https://doi.org/10.1002/adfm.201401589

    [135] Z. Yue et al. Large-scale black multi-crystalline silicon solar cell with conversion efficiency over 18%. Appl. Phys. A Mater. Sci. Process., 116, 683-688(2014). https://doi.org/10.1007/s00339-014-8414-3

    [136] J. S. Chiu et al. The role of laser ablated backside contact pattern in efficiency improvement of mono crystalline silicon PERC solar cells. Solar Energy, 196, 462-467(2020). https://doi.org/10.1016/j.solener.2019.12.044

    [137] K. Gao et al. High-efficiency silicon inverted pyramid-based passivated emitter and rear cells. Nanoscale Res. Lett., 15, 174(2020).

    [138] S. Maus et al. SMART cast-monocrystalline p-type silicon passivated emitter and rear cells: efficiency benchmark and bulk lifetime analysis. Solar RRL, 5, 2000752(2021). https://doi.org/10.1002/solr.202000752

    [139] C. Modanese et al. Economic advantages of dry-etched black silicon in passivated emitter rear cell (PERC) photovoltaic manufacturing. Energies, 11, 2337(2018). https://doi.org/10.3390/en11092337

    [140] Z. G. Huang et al. Large-area MACE Si nano-inverted-pyramids for PERC solar cell application. Solar Energy, 188, 300-304(2019). https://doi.org/10.1016/j.solener.2019.06.015

    [141] J. Xu et al. High-efficiency black silicon tunnel oxide passivating contact solar cells through modifying the nano-texture on micron-pyramid surface. Solar Energy Mater. Solar Cells, 233, 111409(2021). https://doi.org/10.1016/j.solmat.2021.111409

    [142] C. Liu et al. High-efficiency black silicon tunnel oxide passivated contact solar cells achieved by adjusting the boron diffusion process. J. Mater. Sci. Mater. Electron., 32, 23465-23471(2021).

    [143] J. Zheng et al. Polycrystalline silicon tunnelling recombination layers for high-efficiency perovskite/tunnel oxide passivating contact tandem solar cells. Nat. Energy, 8, 1250-1261(2023). https://doi.org/10.1038/s41560-023-01382-w

    [144] X. Li et al. Surface reconstruction for efficient and stable monolithic perovskite/silicon tandem solar cells with greatly suppressed residual strain. Adv. Mater., 35, 2211962(2023).

    [145] X. Guo et al. Oblique-angle damage-free evaporation of silicon oxide electron-selective passivation contacts for efficient and stable perovskite and perovskite/TOPCon tandem solar cells. Adv. Energy Mater., 15, 2403021(2024). https://doi.org/10.1002/aenm.202403021

    [146] G. Nogay et al. 25.1%-efficient monolithic perovskite/silicon tandem solar cell based on a p-type monocrystalline textured silicon wafer and high-temperature passivating contacts. ACS Energy Lett., 4, 844-845(2019). https://doi.org/10.1021/acsenergylett.9b00377

    [147] Z. Ying et al. Bathocuproine: Ag complex functionalized tunneling junction for efficient monolithic perovskite/TOPCon silicon tandem solar cell. Solar RRL, 6, 2200793(2022). https://doi.org/10.1002/solr.202200793

    [148] P. Repo et al. Effective passivation of black silicon surfaces by atomic layer deposition. IEEE J. Photovolt., 3, 90-94(2012). https://doi.org/10.1109/JPHOTOV.2012.2210031

    [149] S. Wang et al. An artificial-intelligence-assisted investigation on the potential of black silicon nanotextures for silicon solar cells. ACS Appl. Nano Mater., 5, 11636-11647(2022). https://doi.org/10.1021/acsanm.2c02619

    [150] B. Meinel et al. Comparison of diamond wire cut and silicon carbide slurry processed silicon wafer surfaces after acidic texturisation. Mater. Sci. Semicond. Process., 26, 93-100(2014). https://doi.org/10.1016/j.mssp.2014.03.046

    [151] T. P. Pasanen et al. Impact of black silicon on light- and elevated temperature-induced degradation in industrial passivated emitter and rear cells. Prog. Photovolt. Res. Appl., 27, 918-925(2019). https://doi.org/10.1002/pip.3088

    [152] M. R. Shaner et al. Photoelectrochemistry of core–shell tandem junction n-p+-Si/n-WO3 microwire array photoelectrodes. Energy Environ. Sci., 7, 779-790(2014). https://doi.org/10.1039/C3EE43048K

    [153] S. W. Boettcher et al. Photoelectrochemical hydrogen evolution using Si microwire arrays. J. Am. Chem. Soc., 133, 1216-1219(2011). https://doi.org/10.1021/ja108801m

    [154] Y. Yu et al. Enhanced photoelectrochemical efficiency and stability using a conformal TiO2 film on a black silicon photoanode. Nat. Energy, 2, 17045(2017). https://doi.org/10.1038/nenergy.2017.45

    [155] C. Duan et al. Efficient visible light photocatalyst fabricated by depositing plasmonic Ag nanoparticles on conductive polymer-protected Si nanowire arrays for photoelectrochemical hydrogen generation. ACS Appl. Mater. Interfaces, 6, 9742-9750(2014). https://doi.org/10.1021/am5021414

    [156] Y. Yang et al. Evident enhancement of photoelectrochemical hydrogen production by electroless deposition of M-B (M = Ni, Co) catalysts on silicon nanowire arrays. ACS Appl. Mater. Interfaces, 8, 30143-30151(2016). https://doi.org/10.1021/acsami.6b09600

    [157] D. W. Kim et al. Black Si photocathode with a conformal and amorphous MoSx catalytic layer grown using atomic layer deposition for photoelectrochemical hydrogen evolution. ACS Appl. Mater. Interfaces, 14, 14137-14145(2022). https://doi.org/10.1021/acsami.1c22273

    [158] L. Qiao et al. Molybdenum disulfide/silver/p-silicon nanowire heterostructure with enhanced photoelectrocatalytic activity for hydrogen evolution. Int. J. Hydrogen Energy, 43, 22235-22242(2018). https://doi.org/10.1016/j.ijhydene.2018.10.090

    [159] S. Li et al. Photoelectrochemical hydrogen production of TiO2 passivated Pt/Si-nanowire composite photocathode. ACS Appl. Mater. Interfaces, 7, 18560-18565(2015). https://doi.org/10.1021/acsami.5b04936

    [160] S. Zhang et al. Si-H induced synthesis of Si/Cu2O nanowire arrays for photoelectrochemical water splitting. Nanotechnology, 29, 035601(2018).

    [161] Z. Xiong et al. Silicon nanowire array/Cu2O crystalline core-shell nanosystem for solar-driven photocatalytic water splitting. Nanotechnology, 24, 265402(2013). https://doi.org/10.1088/0957-4484/24/26/265402

    [162] A. Kargar et al. Nanowire/nanotube array tandem cells for overall solar neutral water splitting. Nano Energy, 19, 289-296(2016). https://doi.org/10.1016/j.nanoen.2015.11.019

    [163] A. Kargar et al. P-Si/SnO2/Fe2O3 core/shell/shell nanowire photocathodes for neutral ph water splitting. Adv. Funct. Mater., 25, 2609-2615(2015). https://doi.org/10.1002/adfm.201404571

    [164] X. Wang et al. Silicon/hematite core/shell nanowire array decorated with gold nanoparticles for unbiased solar water oxidation. Nano Lett., 14, 18-23(2014). https://doi.org/10.1021/nl402205f

    [165] M. T. Mayer, C. Du, D. Wang. Hematite/Si nanowire dual-absorber system for photoelectrochemical water splitting at low applied potentials. J. Am. Chem. Soc., 134, 12406-12409(2012). https://doi.org/10.1021/ja3051734

    [166] K. Sun et al. Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation. Nano Lett., 13, 2064-2072(2013). https://doi.org/10.1021/nl400343a

    [167] Y. Zhang et al. Fabrication and photoelectrochemical properties of silicon nanowires/g-C3N4 core/shell arrays. Appl. Surf. Sci., 396, 609-615(2017).

    [168] X. Wang et al. High-performance silicon nanowire array photoelectrochemical solar cells through surface passivation and modification. Angew. Chem., 123, 10035-10039(2011). https://doi.org/10.1002/ange.201104102

    [169] X. Wang et al. Single crystalline ordered silicon wire/Pt nanoparticle hybrids for solar energy harvesting. Electrochem. Commun., 12, 509-512(2010). https://doi.org/10.1016/j.elecom.2010.01.027

    [170] W. Cai et al. Enhanced photoelectrochemical properties of copper-assisted catalyzed etching black silicon by electrodepositing cobalt. Appl. Phys. Lett., 111, 203902(2017).

    [171] B. Wang et al. MoSx quantum dot-modified black silicon for highly efficient photoelectrochemical hydrogen evolution. ACS Sustain. Chem. Eng., 7, 17598-17605(2019). https://doi.org/10.1021/acssuschemeng.9b03248

    [172] Y. Hou et al. Efficient photoelectrochemical hydrogen production over p-Si nanowire arrays coupled with molybdenum–sulfur clusters. Int. J. Hydrogen Energy, 42, 2832-2838(2017). https://doi.org/10.1016/j.ijhydene.2016.09.106

    [173] G. L. Zang et al. A bio-photoelectrochemical cell with a MoS3-modified silicon nanowire photocathode for hydrogen and electricity production. Energy Environ. Sci., 7, 3033-3039(2014). https://doi.org/10.1039/C4EE00654B

    [174] Z. Huang et al. Enhanced photoelectrochemical hydrogen production using silicon nanowires@MoS3. Nano Energy, 2, 1337-1346(2013). https://doi.org/10.1016/j.nanoen.2013.06.016

    [175] Y. Hou et al. Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution. Nat. Mater., 10, 434-438(2011). https://doi.org/10.1038/nmat3008

    [176] C. J. Chen et al. Silicon microwire arrays decorated with amorphous heterometal-doped molybdenum sulfide for water photoelectrolysis. Nano Energy, 32, 422-432(2017). https://doi.org/10.1016/j.nanoen.2016.12.045

    [177] M. Ali et al. Nanostructured photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced black silicon. Nat. Commun., 7, 11335(2016). https://doi.org/10.1038/ncomms11335

    [178] J. Kim et al. A red-light-powered silicon nanowire biophotochemical diode for simultaneous CO2 reduction and glycerol valorization. Nat. Catal., 7, 977-986(2024). https://doi.org/10.1038/s41929-024-01198-1

    [179] C. Sun et al. Photoelectrocatalysis synthesis of ammonia based on a Ni-doped MoS2/Si nanowires photocathode and porous water with high N2 solubility. ACS Appl. Mater Interfaces, 15, 23085-23092(2023). https://doi.org/10.1021/acsami.3c01304

    [180] P. Cheng, D. Wang, P. Schaaf. A review on photothermal conversion of solar energy with nanomaterials and nanostructures: from fundamentals to applications. Adv. Sustain. Syst., 6, 2200115(2022). https://doi.org/10.1002/adsu.202200115

    [181] Z. Wang et al. Coupling of solar energy and thermal energy for carbon dioxide reduction: status and prospects. Angew. Chem. Int. Ed., 59, 8016-8035(2020). https://doi.org/10.1002/anie.201907443

    [182] F. Yu et al. Enhanced solar photothermal catalysis over solution plasma activated TiO2. Adv. Sci., 7, 2000204(2020). https://doi.org/10.1002/advs.202000204

    [183] L. B. Hoch et al. Nanostructured indium oxide coated silicon nanowire arrays: a hybrid photothermal/photochemical approach to solar fuels. ACS Nano, 10, 9017-9025(2016). https://doi.org/10.1021/acsnano.6b05416

    [184] P. G. O’Brien et al. Photomethanation of gaseous CO2 over Ru/silicon nanowire catalysts with visible and near-infrared photons. Adv. Sci., 1, 1400001(2014). https://doi.org/10.1002/advs.201400001

    [185] P. Cheng et al. Photo-thermoelectric conversion using black silicon with enhanced light trapping performance far beyond the band edge absorption. ACS Appl. Mater. Interfaces, 13, 1818-1826(2021). https://doi.org/10.1021/acsami.0c17279

    [186] Z. Song et al. Synergistic solar-driven freshwater generation and electricity output empowered by wafer-scale nanostructured silicon. Small, 19, 2205265(2023). https://doi.org/10.1002/smll.202205265

    [187] J. Y. H. Chai, B. T. Wong, S. Juodkazis. A theoretical study on the efficiencies of black silicon photovoltaic cells in thermophotovoltaic applications, 23-33(2022).

    [188] J. Y. H. Chai, B. T. Wong, J. Sunarso. An opto-electro-thermal model for black-silicon assisted photovoltaic cells in thermophotovoltaic applications. Photonics, 10, 565(2023). https://doi.org/10.3390/photonics10050565

    [189] J. Y. H. Chai. Study of black-silicon thermophotovoltaics for waste-heat-to-electricity harnessing via novel fundamental modeling(2023).

    [190] A. A. Khairul Azri et al. Development of surface-texturized black silicon through metal-assisted chemical etching and its application in the thermophotovoltaic field: a review and recommendation. Semicond. Sci. Technol., 013001, 013001(2024). https://doi.org/10.1088/1361-6641/ad9175

    [191] A. I. Hochbaum et al. Enhanced thermoelectric performance of rough silicon nanowires. Nature, 451, 163-167(2008). https://doi.org/10.1038/nature06381

    [192] J. Chi et al. Harvesting water-evaporation-induced electricity based on liquid–solid triboelectric nanogenerator. Adv. Sci., 9, 2201586(2022).

    [193] W. Xu et al. A droplet-based electricity generator with high instantaneous power density. Nature, 578, 392-396(2020). https://doi.org/10.1038/s41586-020-1985-6

    [194] G. Xue et al. Water-evaporation-induced electricity with nanostructured carbon materials. Nat. Nanotechnol., 12, 317-321(2017). https://doi.org/10.1038/nnano.2016.300

    [195] Z. Zhang et al. Emerging hydrovoltaic technology. Nat. Nanotechnol., 13, 1109-1119(2018). https://doi.org/10.1038/s41565-018-0228-6

    [196] Y. Qin et al. Constant electricity generation in nanostructured silicon by evaporation-driven water flow. Angew. Chem., 132, 10706-10712(2020). https://doi.org/10.1002/ange.202002762

    [197] H. Wang et al. Bilayer of polyelectrolyte films for spontaneous power generation in air up to an integrated 1000 V output. Nat. Nanotechnol., 16, 811-819(2021). https://doi.org/10.1038/s41565-021-00903-6

    [198] X. Nan et al. In situ photoelectric biosensing based on ultranarrowband near-infrared plasmonic hot electron photodetection. Adv. Photonics, 6, 026007(2024). https://doi.org/10.1117/1.AP.6.2.026007

    [199] J. H. Zhao et al. Ultrafast laser-induced black silicon, from micro-nanostructuring, infrared absorption mechanism, to high performance detecting devices. Mater. Today Nano, 11, 100078(2020). https://doi.org/10.1016/j.mtnano.2020.100078

    [200] S. Sarkar et al. Wideband mid infrared absorber using surface doped black silicon. Appl. Phys. Lett., 121, 231703(2022). https://doi.org/10.1063/5.0117289

    [201] Y. Song et al. A plasmon-enhanced broadband absorber fabricated by black silicon with self-assembled gold nanoparticles. J. Mater. Sci. Mater. Electron., 31, 4696-4701(2020).

    [202] M. A. Juntunen et al. Near-unity quantum efficiency of broadband black silicon photodiodes with an induced junction. Nat. Photonics, 10, 777-781(2016). https://doi.org/10.1038/nphoton.2016.226

    [203] Y. Zhang, J. Y. Y. Loh, N. P. Kherani. Facilely achieved self-biased black silicon heterojunction photodiode with broadband quantum efficiency approaching 100%. Adv. Sci., 9, 2203234(2022). https://doi.org/10.1002/advs.202203234

    [204] M. Viehrig et al. Quantitative SERS assay on a single chip enabled by electrochemically assisted regeneration: a method for detection of melamine in milk. Anal. Chem., 92, 4317-4325(2020). https://doi.org/10.1021/acs.analchem.9b05060

    [205] X. Liu et al. Tissue imprinting on 2D nanoflakes-capped silicon nanowires for lipidomic mass spectrometry imaging and cancer diagnosis. ACS Nano, 16, 6916-6928(2022). https://doi.org/10.1021/acsnano.2c02616

    [206] M. Garin et al. Black-silicon ultraviolet photodiodes achieve external quantum efficiency above 130%. Phys. Rev. Lett., 125, 117702(2020). https://doi.org/10.1103/PhysRevLett.125.117702

    [207] T. Tsang et al. Quantum efficiency of black silicon photodiodes at VUV wavelengths. Opt. Express, 28, 13299-13309(2020). https://doi.org/10.1364/OE.385448

    [208] J. Yin et al. Formation of armored silicon nanowires array via high-repetition-rate femtosecond laser oxidation for robust surface-enhanced Raman scattering detection. ACS Appl. Mater. Interfaces, 16, 48667-48675(2024). https://doi.org/10.1021/acsami.4c11308

    [209] J. Yang et al. In-tube micro-pyramidal silicon nanopore for inertial-kinetic sensing of single molecules. Nat. Commun., 15, 5132(2024). https://doi.org/10.1038/s41467-024-48630-5

    [210] X. L. Liu et al. ‘Infinite sensitivity’ of black silicon ammonia sensor achieved by optical and electric dual drives. ACS Appl. Mater. Interfaces, 10, 5061-5071(2018). https://doi.org/10.1021/acsami.7b16542

    [211] A. Y. Mironenko et al. Ultratrace nitroaromatic vapor detection via surface-enhanced fluorescence on carbazole-terminated black silicon. ACS Sens., 4, 2879-2884(2019). https://doi.org/10.1021/acssensors.9b01063

    [212] S. Zhao et al. Programmed death of injured Pseudomonas Aeruginosa on mechano-bactericidal surfaces. Nano Lett., 22, 1129-1137(2022). https://doi.org/10.1021/acs.nanolett.1c04243

    [213] J. Singh et al. Designing photocatalytic nanostructured antibacterial surfaces: why is black silica better than black silicon?. ACS Appl. Mater. Interfaces, 12, 20202-20213(2020). https://doi.org/10.1021/acsami.0c02854

    [214] D. P. Linklater et al. Mechano-bactericidal actions of nanostructured surfaces. Nat. Rev. Microbiol., 19, 8-22(2021). https://doi.org/10.1038/s41579-020-0414-z

    [215] E. P. Ivanova et al. Bactericidal activity of black silicon. Nat. Commun., 4, 2838(2013). https://doi.org/10.1038/ncomms3838

    [216] P. Gnanasekar et al. Highly efficient and stable photoelectrochemical hydrogen evolution with 2D-NbS2/Si nanowire heterojunction. ACS Appl. Mater. Interfaces, 11, 44179-44185(2019). https://doi.org/10.1021/acsami.9b14713

    [217] A. Anctil et al. Status report on emerging photovoltaics. J. Photonics Energy, 13, 042301(2023). https://doi.org/10.1117/1.JPE.13.042301

    [218] T. Pasanen et al. Industrial applicability of antireflection-coating-free black silicon on PERC solar cells and modules, 552-556(2018).

    Huaping Jia, Fengjia Xie, Elyes Nefzaoui, Tarik Bourouina, Heng Jiang, Xuming Zhang, "Black silicon nanostructures for solar energy conversion and photonic applications: a review," Adv. Photon. 7, 034004 (2025)
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