Abstract
1. Introduction
Colloidal quantum dots (QDs) refer to the uniform small semiconductor particles, in which the charge carrier transportation is confined by three dimensions[
I–III–VI chalcogenides and their solid solutions have the advantages of low toxicity and continuously adjustable band gap covering the UV–vis to near infrared region which has attracted huge amount of attention as promising alternatives to the traditional cadmium- or lead-containing QDs[
QDs have played a key role in many fields such as biology, devices and catalysis. Among these application, photocatalysis, as potentially the key solution to both environmental and energy problems, has been the most prominent and widely studied field not only for traditional QDs, but also for I–III–VI QDs and carbon dots[
Figure 1.(Color online) Schematic illustration for the bridging role of I–III–VI QDs between traditional II–VI QDs and emerging new carbon dots.
2. Structure
I–III–VI chalcogenides constitute a large class of semiconductor materials, whose band gap can be tuned not only by size and shape, but also by continuous composition manipulation[
The energy band structure of the multinary I−III−VI chalcogenide compounds can be adjusted by the alloy composition, thereby affecting the light absorption and reducing capability[
3. Synthesis
The preparation method and growth mechanism of ternary and multinary I–III–VI QDs are similar to traditional binary II–VI QDs, since the basic synthetic principles are similar. Currently, the hot injection method is still the main synthesis strategy of the complex I–III–VI QDs containing three or more elements. The metal precursors and chalcogen precursors can be formed in the same way capped with corresponding ligands. The main synthesis challenge of I–III–VI QDs is the reactivity balancing of multiple metal cations with strong capping ligands, which is a prerequisite for the formation of particles with uniform composition, phase and controllable structure (Fig. 2)[
Figure 2.(Color online) Schematic synthetic processes of I–III–VI QDs. Reprinted from Ref. [
Aqueous synthesis methods are receiving more and more attention because of the promising biological and catalytic applications of I–III–VI QDs. With mercaptoacetic acid, mercaptopropionic acid and other thiol-containing amines/alcohols as ligands, different types of I–III–VI QDs can be synthesized[
Semiconductor heterojunctions are critical in the bandgap engineering and wave function engineering of QDs. In the binary II–VI QD system, surface passivation by growing a larger band gap semiconductor shell, are used to decrease surface defects and improve PL quantum yield (QY)[
Figure 3.(Color online) Schematic alloying and selective cation exchange process of quaternary AgInS2–ZnS QDs. Reprinted from Ref. [
The declaration of particle growth mechanism played a crucial on the delicate control of QDs as well as the development of nanoscience and nanotechnology. In general, the related work of I–III–VI QDs preparation still cannot summarize out a clear nucleation and growth mechanism, especially the different aspects from that of II–VI QDs. It should be noted that although there have been a lot of reports on related research, the adjustment of the size distribution, surface structure and optical properties of I–III–VI QDs are still not comparable to that of II–VI QDs, and in-depth mechanism research is still lacking. This has brought a lot of challenges for the regulation of optoelectronic properties. Without compromising quality, mass production of ternary QDs remains a challenge, so optimized reactions that exceed laboratory scale is an urgent requirement. In order to achieve this goal, an in-depth understanding of chemical synthesis mechanism is necessary. From a basic scientific point of view, the precise structure and composition control is still challenging, which subsequently limits the manipulation and understanding of its optical properties. Comprehensive single-dot characterizations and spectroscopic measurements might be the key to clarify the correlation of optical performance and other physical parameters with structure. In addition, the synthesis and growth control research is carried out focusing on the ground state QDs, while the excited state mechanisms of these I–III–VI QDs are of great significance, especially their size, composition and surface/interface effects that are more critical in the design and preparation of photoelectric materials and clean energy applications (such as photovoltaics and photocatalysis).
4. Optical properties
4.1. Basic optical properties
There is no doubt that the I–III–VI QDs show the widest tunable optical properties due to changes in both size and composition. These materials also show special features, including longer excited state lifetimes, wider full width at half maximum (fwhm), larger Stokes shift, high quantum efficiency, along with simple and economical synthesis[
Figure 4.(Color online) (a) Theoretical calculated[
4.2. Mechanisms and defect states
The I–III–VI materials have photoelectric properties that are significantly different from traditional II–VI QDs, where the clarification of the excited state photophysical properties is crucial. The most important feature of I–III–VI QDs is their deep donor–acceptor pairs (DAPs, Fig. 5), which results in wide PL peaks and relatively large Stokes shifts. DAPs consist of different types of defects such as vacancies (VCu and VS), interstitial atoms (Cui) and substituting (CuIn), which are abundant in these ternary semiconductors due to the coexistence of multiple cations in the crystal lattice[
Figure 5.(Color online) Schematic defect states[
For chalcopyrite CuInS2 QDs, the main contributions of optical transitions are assigned to the electrons at VS and InCu, and holes at VCu[
5. Photocatalytic applications
5.1. General considerations
Band gap of I–III–VI QDs can be adjusted within a very wide range due to their composition manipulation capability, which represent the most promising visible-light-active photocatalysts for hydrogen production due to their excellent optoelectrical properties. Bulk I–III–VI sulfides were actually the first reported visible light photocatalysts with adjustable band gap used for photocatalytic water splitting[
5.2. Size and shape control
For multinary I–III–VI QDs, the small size of QDs and the narrow band gap of sulfides have important effects on the photocatalytic water splitting technology. As the size decreases, the band structure of QDs changes from continuous to discrete along with upshift of VB, resulting in the enhanced photoreduction capability, so reducing the size will usually facilitate photocatalytic H2 production. The reduction in particle size results in larger surface area and more active sites on the surface[
Figure 6.(Color online) Size- and composition-dependent photocatalytic properties of ZAIS QDs. Reprinted from Ref. [
5.3. Composition manipulation
Composition manipulation plays a critical role in I–III–VI QDs photocatalysts, not only for bang gap engineering, but also for catalytic activity. The band structure of the multinary compounds can be adjusted by composition, thereby affecting the light absorption ability and reduction ability to improve the photocatalytic performance (Fig. 6). Through theoretical calculation and analysis of energy band structure, it was found that Cu 3d or Ag 4d orbits play a critical role in the VB, while In 5s5p orbital constructs the CB of I–III–VI QDs[
5.4. Surface manipulation
The surface ligands not only determine the aqueous/organic dispersibility of the QDs, but may also serve as the surface catalytic center[
5.5. Heterojunctions
In heterojunctions formed by combining semiconductor materials with different band gaps and energy levels, especially type-II heterojunctions, photogenerated electrons can transfer from high CB materials to relatively low CB materials, while photogenerated holes can migrate reversibly. This band arrangement thereby achieves efficient separation of electrons and holes. CuIn5S8/Ag2S, CuInSe2/TiO2[
5.6. Cocatalysts
Various cocatalysts, especially noble metals, are widely used as high-efficiency promoters in water splitting systems to enhance charge separation and catalytic activity. The Fermi level of the noble metals are often lower than that of the semiconductors and the electrons generated by the semiconductor can smoothly migrate to the active site of the precious metal to reduce the surface adsorbed H+ to H2[
5.7. Stability and hole scarification
Photocorrosion caused by the oxidative holes is a problem faced by most narrow-band-gap sulfide photocatalysts[
6. Bridging between QDs and emerging carbon dots
As mentioned above, the QDs family has shown amazing developing vitality, and the connotation is also constantly expanding, bringing a series of new phenomena, new principles and new challenges to the QDs field. Now, as it expands from traditional II–VI semiconductors to carbon and other emerging materials, there is a huge gap in the composition and structure, leading to completely different synthetic chemistry, PL mechanisms and applications[
7. Conclusions
In summary, I–III–VI QDs own lots of unique structural and optical properties and play a key role in photoelectric fields, including photocatalysis. It has similar advantages and characteristics of traditional QDs, such as the size-dependent quantum confinement effect and high specific surface area. On one hand, traditional QDs have developed lots of useful strategies to improve light harvesting and charge separation, such as the delicate control over size, shape, surface exposure and heterostructures. On the other hand, these ternary or multinary I–III–VI QDs provide several characteristic advantages that traditional binary QDs do not have, especially the wide range regulation of composition and band gap, as well as the rich long-lived trap states, which greatly expands the design of solid solution QDs and composite photocatalysts with complex compositions and structures. However, the complicated composition also brought a series of challenges on the structure and synthesis of these QDs, such as the precise control of the composition, the balancing of cation reactivity, the unwanted cation exchange and diffusion for heterojunction construction. This may rely on the in-situ monitoring of the growing process and the deep understanding of the synthetic chemistry. Subsequently, more efforts are needed on the clarification of size- vs. composition-dependent band gap, the PL origin from the abundant trap states, the engineering and utilization of the long-lived charge carriers, which requires investigation and manipulation of the excited states by ultrafast spectroscopy. As mentioned above, all structure controled methods of traditional QDs photocatalysts have been applied to the I–III–VI QDs system, including particle size, composition, surface ligands, cocatalysts, hole sacrificial agents, etc., which provide systematic research on related strategies as very good model system. In addition, the performance shortcomings of the traditional chalcogenide photocatalysts usually can also be found in the I–III–VI QDs system, such as poor stability, slow hole extraction, low charge carrier utilization efficiency, etc. These problems rely on ultrafast spectroscopic research, which also provides a good inspiration for other photocatalytic systems. In principle, photocatalysis is a special form of electrocatalysis, where the electrons and holes are provided by light irradiation. The advantages of I–III–VI QDs in mechanism research can also be extended to the entire photo/electrocatalysis fields Furthermore, as a natural multi-composition and multi-interface catalyst, I–III–VI QDs can be useful in the distribution process of active species, the adsorption of active species, and electron transfer in other catalytic systems in a much broader way. The identification and change of the active sites and other issues may provide useful help as a suitable model system for understanding the catalyst from the perspective of physical and chemical interface engineering, for which more profound ultrafast and in situ spectroscopy studies are the key. In terms of the overall significance of photocatalysis and other catalytic studies, I–III–VI QDs are a class of materials that far surpasses traditional binary QDs. With the joint efforts of researchers in related fields, we hope that they will play an increasingly important role in catalysis research.
Acknowledgements
This work is supported by the National Natural Science Foundation of China (21908081, 21501072, 51972216, 51725204, 21771132 and 52041202), the National MCF Energy R&D Program (2018YFE0306105), Innovative Research Group Project of the National Natural Science Foundation of China (51821002), the Jiangsu Specially-Appointed Professors Program, and the Natural Science Foundation of Jiangsu Province (BK20190041, BK20190828 and BK20150489).
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