Abstract
1. Introduction
It is well known that the industry based on silicon faces many challenges due to the continuous scaling down the feature size[
Since graphene discovery, many kinds of 2D materials have been discovered and developed, such as hexagonal boron nitride (hBN)[
Black phosphorus (BP) has a puckered structure that is one of the few-layered crystals and demonstrates strong in-plane anisotropy. The phosphorus was first recorded in “The Book of Odes and Hymns” (
In this review, as shown in Fig. 1, we will introduce the BP sandwich structure with hBN, BP homojunction devices, BP heterojunction devices with other 2D and 3D bulk materials, and BP doped by As with tunable bandgap. There are three important issues (interface contact, interfacial modification and carrier separation) related to the BP electrical and optoelectronic devices. (1) For BP interface contact, different work-function metals can enable different transport behaviors. If Au or Ni is used, since the work function of Au is close to the middle of the bandgap of BP, so BP FET shows bipolar transport[
Figure 1.(Color online) Overview of BP crystal structure and BP devices.
2. Black phosphorus sandwich structure with hBN
Hexagonal boron nitride is a large-bandgap and chemically stable two-dimensional dielectric material, usually forming a sandwich structure with black phosphorus (Fig. 2(a)). As shown in Fig. 2(b), density functional theory calculation shows that characters such as direct bandgap and linear dichroism are preserved when capping an hBN layer on to protect BP[
Figure 2.(Color online) Black phosphorus sandwich structure integration with hBN and its band structure. (a) A 3D schematic of hBN/BP/hBN heterostructure. (b) The HSE06 calculation results of the band structure and the local density of states (LDOS) for the hBN/BP heterostructure. Modified with permission from Ref. [
Combining the advantages of hBN, researchers have realized the hBN/BP/hBN structure to improve the transport properties and stability of BP (Fig. 3(a)). Tao et al. calculated the physical properties of hBN/BP/hBN heterostructures with different hBN thicknesses[
Figure 3.(Color online) Fabrication process and mobility of hBN/BP/hBN heterostructure devices. (a) A 3D schematic of hBN/BP/hBN heterostructure device fabrication process. (b) Mobility results of the different structures including BP/SiO2 (red), BP/hBN (green), and hBN/BP/hBN (blue). (c) Mobility results of the trilayer and 20-layer were measured at liquid helium temperatures. (d) Mobility as a function of temperature for different carrier densities were measured. (e) Quantum Hall states with filling factors from 2 to 12 are observed. (f) FET and Hall mobilities at different temperature. Modified with permission from (a) Ref. [
Quantum Hall (QH) effect was observed in hBN/BP/hBN two-dimensional electron systems (2DES). Likai et al. improved mobility of the system by placing the hBN-encapsulated BP on a graphite back gate. The graphite gate results in a high carrier Hall mobility up to 6000 cm2/(V·s) at temperatures T < 30 K. The high mobility enabled them to observe the integer QH effect in BP. QH plateaus were observed at integer filling factors ν from 1 to 7[
3. Black phosphorus homojunction by dual-gate structure
The p–n junction is a fundamental building block for the realization of incumbent electronic and optoelectronic devices. In conventional semiconductors, substitutional doping is commonly used to gain n- or p-type characteristics. BP, an ambipolar 2D material, can form n–n, n–p, p–n, and p–p junctions by doping or combining with other 2D materials such as hBN or graphene, respectively. Buscema et al. fabricated p–n junctions based on 2D materials, namely, hBN and BP, which are gate dielectric and channel material, respectively. They observed photovoltaic properties and the detection wavelength up to the near-infrared. Meanwhile, the transfer curves can be turned into four operational quadrants by different gate voltages (Fig. 4)[
Figure 4.(Color online) Drain current mapping and band diagrams of the few-layer black phosphorus PN junction. Drain current mapping at (a) + 100 mV and (b) –100 mV as a function of
4. Black phosphorus heterojunction with other 2D materials (graphene, MoS2, etc.)
In the conventional p–n homojunction, the p- and n-type regions are formed by chemically doping a bulk semiconductor depleted of free charge carriers, creating built-in potentials. However, 2D semiconductors like BP, graphene, and transition metal dichalcogenides (TMDCs) can stack, forming their unique van der Waals (vdW) structures, which are predicted to exhibit utterly different charge transport characteristics than bulk heterojunctions. The novel bulk crystals are composed of individual layers, in which the van der Waals forces vertically stack each layer instead of covalent bonds. Because of their particular structures, they have great potential for the next-generation electronic and optoelectronic applications[
4.1. Graphene and black phosphorus
Two-dimensional materials such as graphene have exhibited excellent optical characteristics and offer an attractive prospect for next-generation optoelectronics applications. Graphene has been used for the wideband photodetection from ultraviolet to terahertz[
Figure 5.(Color online) Bandgap and structure of graphene/BP heterojunction. (a) The top and side views of schematics of BP (violet)/graphene (gray) heterojunction. (b) The HSE06 calculation results of the band structure are graphene, phosphorene and graphene/BP heterojunction, respectively. (c) Transfer characteristic curves for an encapsulated device by measuring under both vacuum and ambient conditions. The inset shows a nonencapsulated device test. (d) Transfer characteristic curves at ranging various temperatures from 300 to 30 K in 30 K steps. Modified with permission from (a) and (b) Ref. [
4.2. TMDCs and black phosphorus
TMDCs are atomically thin two-dimensional semiconductors of the type MX2. M is a transition metal atom (Mo, Re, etc.) and X is a chalcogen atom (S, Se, etc.). Molybdenum disulfide (MoS2) is the most exciting material in the TMDCs owing to its robustness[
Figure 6.(Color online) The photodetectors based on TMDCs/BP heterojunctions. (a) A 3D schematic of the BP/MoS2 heterojunction device. (b) On/off switching characteristics of the BP/MoS2 junction device under illumination of 1.55
Depending on the carrier transport path, the FET structure based on vdW heterostructures is mainly divided into two categories: lateral heterojunction structure and vertical heterojunction structure. In a lateral heterojunction, the "edge-to-edge" structure allows carriers to conduct primaries in the material plane. However, the "up–down" structure allows carriers to conduct primarily between layers of material for a vertical heterojunction. Xu et al. fabricated a tunneling field-effect transistor based on a BP/MoS2 junction. The device's subthreshold swing (SS) values were ~65 and 51 mV/dec at room temperature and 160 K, respectively[
Figure 7.(Color online) Structure and performance of the lateral and vertical BP/MoS2 heterostructures. (a) A 3D schematic of the BP/MoS2 heterojunction device. (b) The diode current (
5. Black phosphorus heterojunction with 3D bulk material
The 2D material can be combined with 3D bulk material to form a new heterojunction due to their atomic thin body thickness and the lack of dangling bonds on the surfaces. The integration of 2D material with bulk material can also promote industry applications. The mixed-dimensional 2D/3D vdW heterostructures can improve optical absorption cross-sections than all-2D vdW heterostructures[
Figure 8.(Color online) Performance of BP/ 3D bulk material heterojunction device. (a) EQE as a function of laser power for different laser light wavelengths at zero source–drain bias based on BP/GaAs heterojunction. (b) Semi-log plot of the transfer characteristics of the JFET based on BP/
6. BP doped by As with tunable bandgap
Black phosphorus doped by arsenic or black arsenic–phosphorus (b-AsP), a family of layered semiconductors, has attracted extensive attention due to the excellent tunability of bandgaps. Liu et al. demonstrated the bandgap could be tuned to 0.15 eV smaller than BP (0.3 eV). It means that the detection range of the photodetectors based on b-AsP can reach the long-wavelength infrared (LWIR) (Figs. 9(a) and 9(b))[
Figure 9.(Color online) Performance of the related b-AsP photodetectors. (a) Infrared absorption as a function of wavenumber for different samples including b-P, b-As0.25P0.75, b-As0.4P0.6 and b-As0.83P0.17, respectively. (b) Bandgap and wavelength as a function of different composition-tunable b-AsxP1−x or different polarization angle of the same composition, respectively. (c) Response curve as a function of time under illumination of 4.034
7. Summary and perspectives
In this review, heterostructures based on BP and their electrical and optical applications were discussed in detail. With the tremendous development of applications based on BP owing to its superior characteristics, an increasing number of novel devices based on BP broadly potential from laboratory research to practical use. To achieve this goal, researchers have to suffer from several challenging problems in further research and some possible solutions for dealing with the challenges as follows. (1) Synthesize high-quality wafer-scale crystalline and controllable thicknesses of BP. Fabrication of controllable thicknesses of BP with high quality is essential to design the BP-based devices and applications due to the thickness-dependent intrinsic direct bandgap. Most recently, Xu et al. show the large-area of BP grown on insulating silicon substrates by a gas-phase growth method[
Acknowledgements
This work was supported in part by Fundamental Research Project of National Institute of Metrology China under Grant AKYZZ2116, in part by National Natural Science Foundation of China under Grant 62022047, Grant 61874065 and Grant 51861145202, in part by the National Key R&D Program under Grant 2016YFA0200400, in part by the Research Fund from Beijing Innovation Center for Future Chip and the Independent Research Program of Tsinghua University under Grant 20193080047, in part by Young Elite Scientists Sponsorship Program by CAST under Grant 2018QNRC001, and in part by Fok Ying-Tong Education Foundation under Grant 171051.
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