J. Semicond. > 2022, Volume 43 > Issue 3 > 032701
|

ARTICLES

Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

Zhe Yin1, Min Hu1, Jun Liu2, 3, Hao Fu1, Zhijie Wang2, 3, 4, and Aiwei Tang1,

+ Author Affiliations

 Corresponding author: Zhijie Wang, wangzj@semi.ac.cn; Aiwei Tang, awtang@bjtu.edu.cn

DOI: 10.1088/1674-4926/43/3/032701

PDF

Turn off MathJax

Abstract: Hydrogen energy is a powerful and efficient energy resource, which can be produced by photocatalytic water splitting. Among the photocatalysis, multinary copper-based chalcogenide semiconductor nanocrystals exhibit great potential due to their tunable crystal structures, adjustable optical band gap, eco-friendly, and abundant resources. In this paper, Cu–Zn–Sn–S (CZTS) nanocrystals with different Cu content have been synthesized by using the one-pot method. By regulating the surface ligands, the reaction temperature, and the Cu content, kesterite and hexagonal wurtzite CZTS nanocrystals were obtained. The critical factors for the controllable transition between two phases were discussed. Subsequently, a series of quaternary CZTS nanocrystals with different Cu content were used for photocatalytic hydrogen evolution. And their band gap, energy level structure, and charge transfer ability were compared comprehensively. As a result, the pure hexagonal wurtzite CZTS nanocrystals have exhibited an improved photocatalytic hydrogen evolution activity.

Key words: photocatalytic hydrogen evolution, wurtzite, Cu–Zn–Sn–S nanocrystals

Hydrogen energy is a sustainable and clean energy source because it only produces water with no harmful emission for applications[1-3]. With the energy shortage and global warming problems, hydrogen energy has overwhelming economic competitiveness and environmental benefits, especially as fuel cells for cars, rockets, and spaceships. In 1972, Fujishima et al. reported that TiO2 semiconductor material could be used for the electrochemical photolysis of water[4]. This discovery guided the way for scholars to explore hydrogen energy[5-7]. The photocatalytic decomposition efficiency is closely related to the photoelectric properties of semiconductor materials[8]. In recent years, semiconductor nanomaterials have developed rapidly[9-11]. However, most of the research topics are mainly focused on Cd- or Pb-based semiconductor nanocrystals, which have high toxicity and environmental pollution[12]. Thus it is of great interest to search for environmental-benign alternatives to replace Cd/Pb-based nanocrystals[13]. Among the alternatives, multinary copper-based chalcogenide semiconductor nanocrystals have attracted widespread attention due to their adjustable band gap and less-toxic advantages[14-16]. In recent years, great progress has been made in the synthesis, photoelectric conversion, and photocatalysis applications of multinary copper-based chalcogenide semiconductor nanocrystals. But there is still a big gap between the practical efficiency and theoretical conversion efficiency[17]. Pioneers have found that the band gap, defect concentration and electronic conductivity of the synthesized multinary copper-based chalcogenide semiconductor nanocrystals could affect their photocatalytic performance[18, 19]. Therefore, it is necessary to improve photocatalytic performances of multinary copper-based chalcogenide semiconductor nanocrystals through controlling the crystal structure, absorption band gap and catalytic active sites[19-21]. The quaternary Cu–Zn–Sn–S (CZTS) nanocrystals have aroused the interest due to the following advantages: firstly, they have abundant storage of elements with low prices and environmentally friendly benefits; secondly, they have a suitable absorption band gap and carrier mobility; thirdly, the nanocrystal composition and internal structure can be precisely controlled through changing the reaction parameters[22].

In this paper, we presented the controllable synthesis of quaternary CZTS semiconductor nanocrystals and demonstrated its applications in the photocatalytic evolution, with emphasis on the regulation of Cu content for improving photocatalytic performance. Pure hexagonal wurtzite CZTS nanocrystals were successfully synthesized through regulating the Cu content, the surface ligand, and reaction temperature. The photoelectrical and photocatalytic properties of the CZTS nanocrystals with different crystal phases for hydrogen production were compared and studied in depth. Specifically, the effects of Cu content on the band gap of CZTS nanocrystals and the photocatalytic hydrogen evolution performance were concluded.

2.1 Synthesis

A series of quaternary CZTS nanocrystals were synthesized by a one-pot method as shown in Fig. 1(a). Firstly, the precursors (Cu(acac)2 and Zn(acac)2) were dispersed in the oleylamine (OM), and then the reaction mixture was purged with nitrogen under magnetic stirring. Afterward, the reaction mixture was heated to 130 °C slowly and then kept at this temperature for 30 min till the precursor was fully dissolved. Then, a mixed solvent containing anhydrous SnCl4 and dodecanethiol (DDT) was injected into the system, and the reaction system was continuously stirred for 30 min to realize the full dissolving of precursors. Subsequently, the system started to heat up with the reaction temperature of 240 °C. After reaching the target reaction temperature, the system was kept for 120 min. Finally, after the reaction was over, the system was naturally cooled to room temperature under the protection of nitrogen after the removal of the heating source. Post-treatment of the reaction product was as follows: the as-obtained CIZS NCs were precipitated through the addition of dichloromethane and ethanol by a centrifuge. The above procedure was repeated four times for purification and then the precipitate was collected. At last, the sample was dissolved in dichloromethane to obtain a liquid sample, and then it was treated with a freeze dryer for 24 h to obtain a solid powder.

Figure  1.  (Color online) (a) Schematic illustration of one-pot synthesis of CZTS nanocrystals. XRD patterns of CZTS nanocrystals obtained at (b) low Cu content, (c) high Cu content. (d) TEM images of hexagonal wurtzite CZTS. The inset is an enlarged view. (e) SAED pattern of hexagonal wurtzite CZTS. (f) HRTEM images of hexagonal wurtzite CZTS nanocrystals in (002) crystal plane and (g) in (101) crystal plane.
DownLoad: Full-Size Img PowerPoint

2.2 Photocatalytic hydrogen reaction

2.2.1   Pretreatment of CZTS nanocrystals

The nanocrystal solution was dropped to the 3-mercaptopropionic acid solution (3%), and then it was kept stirring for 10 h in dark for transferring the samples from the oil phase to the aqueous phase. The mixture was centrifuged at high speed, and then the as-obtained samples were dissolved in ethanol. After that, methanol was added to precipitate the samples and the solution was centrifuged again. The above process was repeated 5 times. Then the precipitation was dissolved in water and centrifuged, which was repeated 3 times. Finally, the precipitation was dissolved in deionized water and lyophilized for 24 h to obtain the powder.

2.2.2   Photocatalytic test

A photocatalytic hydrogen reaction was conducted in glassware from Perfectlight Inc and the hydrogen measurements were carried out on a Shimadzu GC2014 under PM 100D xenon lamp of 500 W. The cavitation sacrificial agent (0.3 M Na2S∙9H2O and 0.3 M Na2SO3) was added to 100 mL deionized water and it was stirred for 20 min. Next, 20 mg of the powder was ultrasonically dissolved in this solution. All air was exhausted to ensure that the entire photocatalytic system was in vacuum. The temperature of the system was kept at 5 ± 0.1 °C by circulating cooling water. A 500 W xenon lamp (PM 100D) was used to simulate the sunlight. When the xenon lamp was turned on to illuminate the system, the timing was started. The photocatalytic hydrogen evolution continued for 4 h. The hydrogen production was collected every 0.5 h automatically, and it was measured by gas chromatography (Shimadzu GC2014).

2.3 Characterization

X-ray diffraction (XRD) patterns were recorded on a Bruker D8X diffractometer using a Cu Kα radiation source (λ = 1.54056 Å). Transmission electron microscopy (TEM) images were obtained from a JEM-1400 transmission electron microscope with a voltage of 80 kV. High-resolution TEM (HRTEM) images and selected area electron diffraction (SAED) were recorded on a JEM-2010. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) was recorded on a Hitachi S4800 with a voltage of 15 kV. X-ray photoelectron spectroscopy (XPS) was recorded on a Thermo ESCALAB 250Xi spectrometer with a 300 W Al Kα radiation source. All binding energies for different elements were calibrated to the C 1s line at 284.8 eV. The XPS results were analyzed by XPSPEAK41 software. UV–Vis diffuse reflectance spectroscopy was recorded on a Varian 5000 spectrophotometer with BaSO4 as a reference. Ultraviolet photoemission spectroscopy (UPS) was recorded on an Axis Ultra DLD spectrometer. Photocurrent and electrochemical impedance spectroscopy (EIS) was recorded on a CHI 660D electrochemical workstation.

3.1 Crystal structure with regulated Cu content

The Cu content in the synthesis process is important for controlling its crystal phase, thus improving its photoelectric performance. Kesterite and hexagonal wurtzite phases are the most common phases of CZTS nanocrystals. The stability of the phase is closely related to its component content, especially Cu content. Researchers usually adjusted the composition of nanocrystals by changing the type or concentration of precursors, which would influence their crystal structure and morphology as well[15]. To find the appropriate Cu content for the synthesis of CZTS nanocrystals, the dosage of Zn(acac)2 (0.5 mmol), anhydrous SnCl4 (0.5 mmol), DDT (3 mL), and OM (10 mL) was kept unchanged, while the dosage of Cu(acac)2 was changed from 0.1 to 1.5 mmol. For the convenience of description, the CZTS nanocrystal with a Cu(acac)2 precursor of 0.1 mmol is named Cu0.1, and so forth. Figs. 1(b) and 1(c) shows the XRD patterns of the samples with different Cu content, which can be used for studying the effects of Cu content changes on the crystal structure. As shown in Fig. 1(b), when the precursor of Cu content is low, the Cu0.1 and Cu0.2 samples are SnS phases. But when the Cu content is increased to 0.3 mmol, the phase transformed into a mixed phase of kesterite and hexagonal wurtzite. It can be deduced that when the Cu precursor dosage is 0.3 mmol, it reaches the minimum concentration threshold for the formation of hexagonal wurtzite phase CZTS nanocrystals. In this process, Cu ions enter the inside of the nanocrystals, fully combined with S ions to form copper-based chalcogenide nanocrystals, and then Sn ions enter to assist the incorporation of Zn ions, finally generating quaternary CZTS nanocrystals.

Fig. 1(c) shows the XRD pattern of the samples with high Cu content, with Cu0.5, Cu1.0, Cu1.2, and Cu1.5 samples. Comparing with the standard powder diffraction file, it is found that the Cu0.5 and Cu1.0 samples are hexagonal wurtzite CZTS nanocrystals without other impurity phases. As the Cu content continues to increase, the diffraction peaks of the kesterite gradually increase. When the Cu content reaches 1.5 mmol, the crystal phase changes from the main phase of hexagonal wurtzite to the main kesterite phase. The Cu1.5 sample has mixed phases of kesterite and wurtzite, in which the kesterite phase is the main phase. At the same time, its XRD diffraction peaks are regular and flat, which is caused by the gradual increase in the size of the crystal grains and the gradual completeness of the kesterite phase as the Cu content increases.

The TEM image of the hexagonal wurtzite CZTS nanocrystals is shown in Fig. 1(d). The hexagonal wurtzite CZTS nanocrystals were synthesized in an OM ligand solvent with good monodispersity and uniform size. From the enlarged view of TEM, it can be seen that most of the particles are hat-shaped. The average length of the hat-shaped nanocrystals is 10.9 ± 1.6 nm and the average width is 8.2 ± 1.2 nm. The SAED pattern in Fig. 1(e) shows that the characteristic diffraction rings corresponding to the (002) and (110) are brighter, indicating that these two crystal planes are the dominant growth crystal planes for nanocrystals. The HRTEM image in Fig. 1(f) shows the lattice stripes of hexagonal wurtzite phase nanocrystals with a lattice space of 3.13 Å, which corresponds to the (002) crystal plane of the hexagonal wurtzite phase CZTS nanocrystal. Fig. 1(g) shows the HRTEM images of the lower bottom surfaces of the hexagonal wurtzite phase CZTS nanocrystals with a lattice space of 2.93 Å, corresponding to the (101) crystal plane. It is found that the upper and lower surfaces of the synthesized hexagonal wurtzite CZTS nanocrystals are mainly exposed (101) crystal planes. It can be concluded that the (101) crystal plane is the most exposed on the horizontal plane, while the (002) crystal plane is the most exposed on the vertical plane, which are the dominant growth direction of the synthesized hexagonal wurtzite phase CZTS nanocrystals. It can be speculated that the OM effectively regulates the morphology of the nanocrystals and inhibits the growth in other directions. With partial growth, a hat shape was finally formed.

Through the analysis of the XRD and TEM results, it can be found that pure hexagonal wurtzite CZTS nanocrystals only exist within appropriate Cu content. When the Cu content is low, it is hard to synthesize CZTS nanocrystals, and the as-obtained samples coexist with irregular morphology and larger size. When the Cu component is too high, multiple phases coexist in the nanocrystals, and the particles are also easier to agglomerate. Therefore, when the Cu content is appropriate, that is, when the dosage of Cu is 1.0 mmol in our experiment, the nanocrystals are pure hexagonal wurtzite phase CZTS nanocrystals with good dispersity. And the morphology is regular hat-shaped.

3.2 Composition of hexagonal wurtzite CZTS nanocrystals

In order to further confirm the element composition ratio and valence state of hexagonal wurtzite phase CZTS nanocrystals, XPS, and SEM-EDS techniques were used for analysis. The SEM-EDS element distribution of the hexagonal wurtzite phase CZTS nanocrystals is shown in Fig. 2(a), where the elements of Cu, Zn, and Sn are evenly distributed on the surface of the nanocrystals. The Cu, Zn, Sn, and S atomic percentages of the CZTS nanocrystals with different Cu content are shown in Fig. 2(b). For the Cu1.0 sample, the Cu, Zn, Sn, and S atomic percentages are 26.90%, 10.20%, 15.08%, and 47.04%, respectively. Figs. 2(c)–2(f) show the XPS spectra results of the hexagonal wurtzite structure CZTS. Fig. 2(c) shows the 2p peak of Cu, which correlated to Cu(I). Fig. 2(d) shows the 2p peak of the Zn element, which correlated to Zn2+. Fig. 2(e) shows the 3d peak of the Sn element, which correlated to Sn4+. Fig. 2(f) shows 2p characteristic peaks of S. After peak fitting, it is found that S in CZTS nanocrystals has two states, corresponding to the sulfur in the lattice of the nanocrystals and the ligand thiol on the surface[23, 24].

Figure  2.  (Color online) (a) SEM-EDS element distribution diagram of hexagonal wurtzite CZTS nanocrystals. (b) The cation percentages of CTZS nanocrystals obtained from EDS results. XPS signals of (c) Cu, (d) Sn, (e) Zn, and (f) S elements in hexagonal wurtzite CZTS nanocrystals.
DownLoad: Full-Size Img PowerPoint

3.3 Optical properties and energy level structure

The optical properties and energy level structure of CZTS nanocrystals prepared with different Cu dosages were explored. Typically, samples Cu0.2, Cu1.0, and Cu1.5 were selected as the research objects. The absorption spectra of CZTS nanocrystals were obtained by converting solid diffuse reflectance spectra, which were shown in Fig. 3(a). The CZTS nanocrystals with three different Cu content have a similar absorption range with different intensity. When the Cu dosage is low (Cu0.2), the light absorption intensity is the weakest in the wavelength range of 350–750 nm; when the Cu dosage is increased, the light absorption intensity increases. Compared to Cu1.5, the light absorption intensity of Cu1.0 is higher. When the dosage of Cu reaches 1.0 mmol, the light absorption intensity of nanocrystals is the highest. Therefore, the appropriate Cu dosage has a key effect on the absorption intensity of the nanocrystal in the wavelength range of 350–750 nm. The Tauc formula was used to convert the absorption spectrum data into a Tauc plot curve, and the optical band gaps of CZTS nanocrystals prepared with different Cu dosages were calculated. As shown in Fig. 3(b), the optical band gap of Cu0.2, Cu1.0, and Cu1.5 is 2.04, 1.74, and 1.91 eV, respectively. The results show that the band gap of CZTS nanocrystals firstly becomes smaller, and then becomes larger with the gradual increase of Cu content. Nanocrystals with a smaller band gap have a higher utilization rate of visible light.

Figure  3.  (Color online) (a) Diffuse reflectance spectra and (b) the plots of (αhv)2 versus the photon energy of CZTS nanocrystals with different Cu content. UPS spectra of (c) high-binding energy secondary-electron cutoff and (d) valence-band edge regions of hexagonal wurtzite CZTS nanocrystals. (e) Energy level structure diagram of hexagonal wurtzite CZTS nanocrystals.
DownLoad: Full-Size Img PowerPoint

Furthermore, the UPS energy spectrum test was performed on the Cu1.0 sample to determine the energy level structure of the hexagonal wurtzite CZTS nanocrystals (Figs. 3(c) and 3(d)). The incident photon energy is 21.22 eV, the secondary electron cut-off (Ecut-off) is 17.68 eV (shown in Fig. 3(c)), and the onset energy (Eonset) is 1.28 eV versus the vacuum level (shown in Fig. 3(d)). Based on the equation of valence band maximum (VBM) = 21.22 − (Ecut-off − Eonset), the VBM position of CZTS is calculated to be 4.82 eV below the vacuum level. The conduction band minimum (CBM) level can be determined by the optical band gaps and the VBM level. The optical band gap of Cu1.0 is 1.74 eV, which is calculated from the absorption results. Therefore, the CBM is 3.08 eV below the vacuum level. The potentials for the reduction and oxidation reactions of water are –4.44 and –5.67 eV versus the vacuum level (or −0.41 V and 0.82 V vs. NHE at pH 7 in aqueous solution), respectively[25-27]. The energy level information of hexagonal wurtzite CZTS nanocrystals (Cu1.0) is summarized in Table 1. The CBM of the hexagonal wurtzite CZTS nanocrystals is higher than the reduction potential of water, so the hexagonal wurtzite phase CZTS nanocrystals can be used for the photocatalytic decomposition of water to produce hydrogen (Fig. 3(e)).

Table  1.  Summary of the energy level information of wurtzite CZTS nanocrystals.
SampleEcut-off
(eV)		Eonset
(eV)		VBM
(eV)		Band gap
(eV)		CBM
(eV)
Wurtzite CZTS17.681.284.821.743.08
DownLoad: CSV  | Show Table

3.4 Photocatalytic hydrogen evolution performance

Fig. 4 shows the photocatalytic performance of CZTS nanocrystals with different Cu content. Fig. 4(a) shows the photoelectric response test results with a constant voltage of −0.6 V under a xenon light source with a power of 100 mW/cm2. Fig. 4(a) depicts the photoelectric response intensity of nanocrystals with different Cu contents under four cycles with the light on/off. We found that the Cu0.2 sample had the weakest photocurrent, followed by the Cu1.5 sample, and the Cu 1.0 sample performs best. The highest current density of Cu1.0 is about 0.5 μA/cm2. After stabilization, the photocurrent of Cu1.0 is about twice the value of Cu1.5. This result proves that hexagonal wurtzite CZTS nanocrystals with appropriate Cu content can promote the separation of photo-generated electron–hole pairs, and thus shows higher photoelectric responsivity. To further investigate the carrier mobility of CZTS with different Cu content, electrochemical impedance spectroscopy (EIS) tests were performed (Fig. 4(b)). Comparing the impedance maps of the three CZTS nanocrystals, it can be found that the semicircular ring diameter of impedance in Cu0.2 and Cu1.5 nanocrystals is larger, while that of Cu1.0 nanocrystals is smaller. This result shows that the CZTS nanocrystals with appropriate Cu content have lower electrical resistance, which is beneficial for the effective transfer of carriers. Therefore, Cu1.0 has better photoelectric responsivity.

Figure  4.  (Color online) (a) Photocurrent of CZTS nanocrystals with different Cu content. (b) Impedance spectra of CZTS nanocrystals with different Cu content. (c) Photocatalytic hydrogen evolution for hydrogen amount variation with time. (d) Photocatalytic hydrogen production rates.
DownLoad: Full-Size Img PowerPoint

The results for photocatalytic hydrogen evolution are shown in Figs. 4(c) and 4(d). Fig. 4(c) shows the results of the hydrogen production of CZTS nanocrystals prepared with different Cu content over time. The amount of hydrogen produced by Cu1.0 is the highest in our experiment. Fig. 4(d) depicts the corresponding hydrogen production rate. The hydrogen production rate of Cu1.0 sample is the highest, compared with Cu0.2 and Cu1.5. But there is little difference between the other two values. The calculated results show that the Cu1.0 has the highest hydrogen production rate, which is 825.6 µmol/(g·h). This rate is 2.6 times that of Cu0.2 and 1.5 times that of Cu1.5. The hydrogen production rate of CZTS nanocrystals with a Cu dosage of 0.2 mmol is the lowest. The test result further confirms that too much or too little Cu element content of the nanocrystals will weaken the light absorption capacity of the CZTS nanocrystals, which leads to lower photocatalytic hydrogen amount. In this research, the light absorption capacity of Cu1.0 is the strongest, which corresponds to the best photocatalytic performances.

In conclusion, hexagonal wurtzite CZTS nanocrystals have been developed by regulating the Cu content via a one-pot synthesis, which show great potential in photocatalytic hydrogen evolution. In our experimental system, the optimal Cu dosage is 1.0 mmol and it helps to form a pure hexagonal wurtzite structure with the best photocatalytic performance. When the Cu content is too low, the nanocrystals are mainly SnS, which has poor photocatalytic hydrogen evolution performance. When the Cu content is too high, the nanocrystals are the mixed phase of kesterite and hexagonal wurtzite, or kesterite with poor photocatalytic performance. Hexagonal wurtzite CZTS nanocrystals show higher photoelectric response and lower electrochemical impedance than other samples, exhibiting the best hydrogen production rate of 825.6 µmol/(g·h). This work may provide a great foundation for further optimization of cadmium-free multinary copper-based chalcogenide photocatalysis.

This work was supported by the National Natural Science Foundation of China (Nos. 61974009, 62075005, and 62105019).



[1]
Huang Y B, Liu J, Deng Y C, et al. The application of perovskite materials in solar water splitting. J Semicond, 2020, 41(1), 011701 doi: 10.1088/1674-4926/41/1/011701
[2]
Hoffmann M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis. Chem Rev, 1995, 95(1), 69 doi: 10.1021/cr00033a004
[3]
Wei W Q, Ouyang S X, Zhang T R. Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications. J Semicond, 2020, 41(9), 091708 doi: 10.1088/1674-4926/41/9/091708
[4]
Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358), 37 doi: 10.1038/238037a0
[5]
Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43(22), 7520 doi: 10.1039/C3CS60378D
[6]
Fujishima A, Zhang X, Tryk D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup. Int J Hydrogen Energ, 2007, 32(14), 2664 doi: 10.1016/j.ijhydene.2006.09.009
[7]
Chen S, Takata T, Domen K. Particulate photocatalysts for overall water splitting. Nat Rev Mater, 2017, 2(10), 17050 doi: 10.1038/natrevmats.2017.50
[8]
Low J, Yu J, Jaroniec M, et al. Heterojunction photocatalysts. Adv Mater, 2017, 29(20), 1601694 doi: 10.1002/adma.201601694
[9]
Huang Y, Liu J, Cao D, et al. Separation of hot electrons and holes in Au/LaFeO3 to boost the photocatalytic activities both for water reduction and oxidation. Int J Hydrogen Energ, 2019, 44(26), 13242 doi: 10.1016/j.ijhydene.2019.03.182
[10]
Wang H, Wu Z, Liu Y, et al. The characterization of ZnO-anatase-rutile three-component semiconductor and enhanced photocatalytic activity of nitrogen oxides. J Mater Chem C, 2008, 287(1/2), 176 doi: 10.1016/j.molcata.2008.03.010
[11]
Logvinovich D, Bocher L, Sheptyakov D, et al. Microstructure, surface composition and chemical stability of partly ordered LaTiO2N. Solid State Sci, 2009, 11(8), 1513 doi: 10.1016/j.solidstatesciences.2009.05.024
[12]
Bao N, Shen L, Takata T, et al. Self-templated synthesis of nanoporous CdS nanostructures for highly efficient photocatalytic hydrogen production under visible light. Chem Mater, 2008, 20(1), 110 doi: 10.1021/cm7029344
[13]
Liu Z, Zhao K, Tang A, et al. Solution-processed high-efficiency cadmium-free Cu-Zn-In-S-based quantum-dot light-emitting diodes with low turn-on voltage. Org Electron, 2016, 36, 97 doi: 10.1016/j.orgel.2016.05.040
[14]
Coughlan C, Ibanez M, Dobrozhan O, et al. Compound copper chalcogenide nanocrystals. Chem Rev, 2017, 117(9), 5865 doi: 10.1021/acs.chemrev.6b00376
[15]
Chang J, Waclawik E R. Colloidal semiconductor nanocrystals: controlled synthesis and surface chemistry in organic media. RSC Adv, 2014, 4(45), 23505 doi: 10.1039/C4RA02684E
[16]
Aldakov D, Lefrançois A, Reiss P. Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C, 2013, 1(24), 3756 doi: 10.1039/c3tc30273c
[17]
Liu Z, Tang A, Wang M, et al. Heating-up synthesis of cadimum-free and color-tunable quaternary and five-component Cu-In-Zn-S-based semiconductor nanocrystals. J Mater Chem C, 2015, 3(39), 10114 doi: 10.1039/C5TC02469B
[18]
Fu H, Tang A. Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution. J Semicond, 2020, 41(9), 91706 doi: 10.1088/1674-4926/41/9/091706
[19]
Fan X B, Yu S, Zhan F, et al. Nonstoichiometric Cu xInyS quantum dots for efficient photocatalytic hydrogen evolution. Chemsuschem, 2017, 10(24), 4833 doi: 10.1002/cssc.201701950
[20]
Schmidt S S, Abou-Ras D, Unold T, et al. Effect of Zn incorporation into CuInS2 solar cell absorbers on microstructural and electrical properties. J Appl Phys, 2011, 110(6), 64515 doi: 10.1063/1.3639284
[21]
Li Y, Chen G, Wang Q, et al. Hierarchical ZnS-In2S3-CuS nanospheres with nanoporous structure: Facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater, 2010, 20(19), 3390 doi: 10.1002/adfm.201000604
[22]
Zhu D, Ye H, Liu Z, et al. Seed-mediated growth of heterostructured Cu1.94S–MS (M = Zn, Cd, Mn) and alloyed CuNS2 (N = In, Ga) nanocrystals for use in structure-and composition-dependent photocatalytic hydrogen evolution. Nanoscale, 2020, 12(10), 6111 doi: 10.1039/C9NR10004K
[23]
Saldanha P L, Brescia R, Prato M, et al. Generalized one-pot synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater, 2014, 26(3), 1442 doi: 10.1021/cm4035598
[24]
Zhu D, Tang A, Kong Q, et al. Roles of sulfur sources in the formation of alloyed Cu2– xS ySe1– y nanocrystals: Controllable synthesis and tuning of plasmonic resonance absorption. J Phys Chem C, 2017, 121(29), 15922 doi: 10.1021/acs.jpcc.7b03826
[25]
Kuzuya T, Hamanaka Y, Itoh K, et al. Phase control and its mechanism of CuInS2 nanoparticles. J Colloid Interf Sci, 2012, 388(1), 137 doi: 10.1016/j.jcis.2012.08.013
[26]
Liu Z, Liu J, Huang Y, et al. From one-dimensional to two-dimensional wurtzite CuGaS2 nanocrystals: non-injection synthesis and photocatalytic evolution. Nanoscale, 2019, 11(1), 158 doi: 10.1039/C8NR07353H
[27]
Liu Z, Tang A, Liu J, et al. Non-injection synthesis of L-shaped wurtzite Cu–Ga–Zn–S alloyed nanorods and their advantageous application in photocatalytic hydrogen evolution. J Mater Chem A, 2018, 6(38), 18649 doi: 10.1039/C8TA05395B
Fig. 1.  (Color online) (a) Schematic illustration of one-pot synthesis of CZTS nanocrystals. XRD patterns of CZTS nanocrystals obtained at (b) low Cu content, (c) high Cu content. (d) TEM images of hexagonal wurtzite CZTS. The inset is an enlarged view. (e) SAED pattern of hexagonal wurtzite CZTS. (f) HRTEM images of hexagonal wurtzite CZTS nanocrystals in (002) crystal plane and (g) in (101) crystal plane.

DownLoad: Full-Size Img PowerPoint
Fig. 2.  (Color online) (a) SEM-EDS element distribution diagram of hexagonal wurtzite CZTS nanocrystals. (b) The cation percentages of CTZS nanocrystals obtained from EDS results. XPS signals of (c) Cu, (d) Sn, (e) Zn, and (f) S elements in hexagonal wurtzite CZTS nanocrystals.

DownLoad: Full-Size Img PowerPoint
Fig. 3.  (Color online) (a) Diffuse reflectance spectra and (b) the plots of (αhv)2 versus the photon energy of CZTS nanocrystals with different Cu content. UPS spectra of (c) high-binding energy secondary-electron cutoff and (d) valence-band edge regions of hexagonal wurtzite CZTS nanocrystals. (e) Energy level structure diagram of hexagonal wurtzite CZTS nanocrystals.

DownLoad: Full-Size Img PowerPoint
Fig. 4.  (Color online) (a) Photocurrent of CZTS nanocrystals with different Cu content. (b) Impedance spectra of CZTS nanocrystals with different Cu content. (c) Photocatalytic hydrogen evolution for hydrogen amount variation with time. (d) Photocatalytic hydrogen production rates.

DownLoad: Full-Size Img PowerPoint

Table 1.   Summary of the energy level information of wurtzite CZTS nanocrystals.

SampleEcut-off
(eV)		Eonset
(eV)		VBM
(eV)		Band gap
(eV)		CBM
(eV)
Wurtzite CZTS17.681.284.821.743.08
DownLoad: CSV
[1]
Huang Y B, Liu J, Deng Y C, et al. The application of perovskite materials in solar water splitting. J Semicond, 2020, 41(1), 011701 doi: 10.1088/1674-4926/41/1/011701
[2]
Hoffmann M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis. Chem Rev, 1995, 95(1), 69 doi: 10.1021/cr00033a004
[3]
Wei W Q, Ouyang S X, Zhang T R. Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications. J Semicond, 2020, 41(9), 091708 doi: 10.1088/1674-4926/41/9/091708
[4]
Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358), 37 doi: 10.1038/238037a0
[5]
Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43(22), 7520 doi: 10.1039/C3CS60378D
[6]
Fujishima A, Zhang X, Tryk D A. Heterogeneous photocatalysis: from water photolysis to applications in environmental cleanup. Int J Hydrogen Energ, 2007, 32(14), 2664 doi: 10.1016/j.ijhydene.2006.09.009
[7]
Chen S, Takata T, Domen K. Particulate photocatalysts for overall water splitting. Nat Rev Mater, 2017, 2(10), 17050 doi: 10.1038/natrevmats.2017.50
[8]
Low J, Yu J, Jaroniec M, et al. Heterojunction photocatalysts. Adv Mater, 2017, 29(20), 1601694 doi: 10.1002/adma.201601694
[9]
Huang Y, Liu J, Cao D, et al. Separation of hot electrons and holes in Au/LaFeO3 to boost the photocatalytic activities both for water reduction and oxidation. Int J Hydrogen Energ, 2019, 44(26), 13242 doi: 10.1016/j.ijhydene.2019.03.182
[10]
Wang H, Wu Z, Liu Y, et al. The characterization of ZnO-anatase-rutile three-component semiconductor and enhanced photocatalytic activity of nitrogen oxides. J Mater Chem C, 2008, 287(1/2), 176 doi: 10.1016/j.molcata.2008.03.010
[11]
Logvinovich D, Bocher L, Sheptyakov D, et al. Microstructure, surface composition and chemical stability of partly ordered LaTiO2N. Solid State Sci, 2009, 11(8), 1513 doi: 10.1016/j.solidstatesciences.2009.05.024
[12]
Bao N, Shen L, Takata T, et al. Self-templated synthesis of nanoporous CdS nanostructures for highly efficient photocatalytic hydrogen production under visible light. Chem Mater, 2008, 20(1), 110 doi: 10.1021/cm7029344
[13]
Liu Z, Zhao K, Tang A, et al. Solution-processed high-efficiency cadmium-free Cu-Zn-In-S-based quantum-dot light-emitting diodes with low turn-on voltage. Org Electron, 2016, 36, 97 doi: 10.1016/j.orgel.2016.05.040
[14]
Coughlan C, Ibanez M, Dobrozhan O, et al. Compound copper chalcogenide nanocrystals. Chem Rev, 2017, 117(9), 5865 doi: 10.1021/acs.chemrev.6b00376
[15]
Chang J, Waclawik E R. Colloidal semiconductor nanocrystals: controlled synthesis and surface chemistry in organic media. RSC Adv, 2014, 4(45), 23505 doi: 10.1039/C4RA02684E
[16]
Aldakov D, Lefrançois A, Reiss P. Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C, 2013, 1(24), 3756 doi: 10.1039/c3tc30273c
[17]
Liu Z, Tang A, Wang M, et al. Heating-up synthesis of cadimum-free and color-tunable quaternary and five-component Cu-In-Zn-S-based semiconductor nanocrystals. J Mater Chem C, 2015, 3(39), 10114 doi: 10.1039/C5TC02469B
[18]
Fu H, Tang A. Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution. J Semicond, 2020, 41(9), 91706 doi: 10.1088/1674-4926/41/9/091706
[19]
Fan X B, Yu S, Zhan F, et al. Nonstoichiometric Cu xInyS quantum dots for efficient photocatalytic hydrogen evolution. Chemsuschem, 2017, 10(24), 4833 doi: 10.1002/cssc.201701950
[20]
Schmidt S S, Abou-Ras D, Unold T, et al. Effect of Zn incorporation into CuInS2 solar cell absorbers on microstructural and electrical properties. J Appl Phys, 2011, 110(6), 64515 doi: 10.1063/1.3639284
[21]
Li Y, Chen G, Wang Q, et al. Hierarchical ZnS-In2S3-CuS nanospheres with nanoporous structure: Facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater, 2010, 20(19), 3390 doi: 10.1002/adfm.201000604
[22]
Zhu D, Ye H, Liu Z, et al. Seed-mediated growth of heterostructured Cu1.94S–MS (M = Zn, Cd, Mn) and alloyed CuNS2 (N = In, Ga) nanocrystals for use in structure-and composition-dependent photocatalytic hydrogen evolution. Nanoscale, 2020, 12(10), 6111 doi: 10.1039/C9NR10004K
[23]
Saldanha P L, Brescia R, Prato M, et al. Generalized one-pot synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater, 2014, 26(3), 1442 doi: 10.1021/cm4035598
[24]
Zhu D, Tang A, Kong Q, et al. Roles of sulfur sources in the formation of alloyed Cu2– xS ySe1– y nanocrystals: Controllable synthesis and tuning of plasmonic resonance absorption. J Phys Chem C, 2017, 121(29), 15922 doi: 10.1021/acs.jpcc.7b03826
[25]
Kuzuya T, Hamanaka Y, Itoh K, et al. Phase control and its mechanism of CuInS2 nanoparticles. J Colloid Interf Sci, 2012, 388(1), 137 doi: 10.1016/j.jcis.2012.08.013
[26]
Liu Z, Liu J, Huang Y, et al. From one-dimensional to two-dimensional wurtzite CuGaS2 nanocrystals: non-injection synthesis and photocatalytic evolution. Nanoscale, 2019, 11(1), 158 doi: 10.1039/C8NR07353H
[27]
Liu Z, Tang A, Liu J, et al. Non-injection synthesis of L-shaped wurtzite Cu–Ga–Zn–S alloyed nanorods and their advantageous application in photocatalytic hydrogen evolution. J Mater Chem A, 2018, 6(38), 18649 doi: 10.1039/C8TA05395B
1

From kesterite 2D nanosheets to wurtzite 1D nanorods: controllable synthesis of Cu−Zn−Sn−S and their application in electrocatalytic hydrogen evolution

Yu Li, Shuaibing Wang, Jie Chen, Ouyang Lin, Zhe Yin, et al.

Journal of Semiconductors, 2023, 44(12): 122701. doi: 10.1088/1674-4926/44/12/122701
2

Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution

Hao Fu, Aiwei Tang

Journal of Semiconductors, 2020, 41(9): 091706. doi: 10.1088/1674-4926/41/9/091706
3

Precision photonic integration for future large-scale photonic integrated circuits

Xiangfei Chen

Journal of Semiconductors, 2019, 40(5): 050301. doi: 10.1088/1674-4926/40/5/050301
4

Improving the photocatalytic performance of TiO2 via hybridizing with graphene

K S Divya, Athulya K Madhu, T U Umadevi, T Suprabha, P. Radhakrishnan Nair, et al.

Journal of Semiconductors, 2017, 38(6): 063002. doi: 10.1088/1674-4926/38/6/063002
5

The electronic and magnetic properties of wurtzite Mn:CdS, Cr:CdS and Mn:Cr:CdS: first principles calculations

Azeem Nabi, Zarmeena Akhtar, Tahir Iqbal, Atif Ali, Arshad Javid, et al.

Journal of Semiconductors, 2017, 38(7): 073001. doi: 10.1088/1674-4926/38/7/073001
6

Steady-state solution growth of microcrystalline silicon on nanocrystalline seed layers on glass

R. Bansen, C. Ehlers, Th. Teubner, T. Boeck

Journal of Semiconductors, 2016, 37(9): 093001. doi: 10.1088/1674-4926/37/9/093001
7

Crystallization kinetics of Sn40Se60 thin films for phase change memory applications

Joshua M. Kundu, Patrick M. Karimi, Walter K. Njoroge

Journal of Semiconductors, 2015, 36(6): 063002. doi: 10.1088/1674-4926/36/6/063002
8

Large-signal characterizations of DDR IMPATT devices based on group Ⅲ-Ⅴ semiconductors at millimeter-wave and terahertz frequencies

Aritra Acharyya, Aliva Mallik, Debopriya Banerjee, Suman Ganguli, Arindam Das, et al.

Journal of Semiconductors, 2014, 35(8): 084003. doi: 10.1088/1674-4926/35/8/084003
9

Photoconductivity and surface chemical analysis of ZnO thin films deposited by solution-processing techniques for nano and microstructure fabrication

V.K. Dwivedi, P. Srivastava, G. Vijaya Prakash

Journal of Semiconductors, 2013, 34(3): 033001. doi: 10.1088/1674-4926/34/3/033001
10

First-principles study of the electronic structures and optical properties of C–F–Be doped wurtzite ZnO

Zuo Chunying, Wen Jing, Zhong Cheng

Journal of Semiconductors, 2012, 33(7): 072001. doi: 10.1088/1674-4926/33/7/072001
11

Binding energies of shallow impurities in asymmetric strained wurtzite AlxGa1-xN/GaN/AlyGa1-yN quantum wells

Ha Sihua, Ban Shiliang, Zhu Jun

Journal of Semiconductors, 2011, 32(4): 042001. doi: 10.1088/1674-4926/32/4/042001
12

Property comparison of polarons in zinc-blende and wurtzite GaN/AlN quantum wells

Zhu Jun, Ban Shiliang, Ha Sihua

Journal of Semiconductors, 2011, 32(11): 112002. doi: 10.1088/1674-4926/32/11/112002
13

Wafer level hermetic packaging based on Cu–Sn isothermal solidification technology

Cao Yuhan, Luo Le

Journal of Semiconductors, 2009, 30(8): 086001. doi: 10.1088/1674-4926/30/8/086001
14

Influence of zinc phthalocyanines on photoelectrical properties of hydrogenated amorphous silicon

Zhang Changsha, Zeng Xiangbo, Peng Wenbo, Shi Mingji, Liu Shiyong, et al.

Journal of Semiconductors, 2009, 30(8): 083004. doi: 10.1088/1674-4926/30/8/083004
15

Influence of optical phonons on the electronic mobility in a strained wurtzite AlN/GaN heterojunction under hydrostatic pressure

Zhou Xiaojuan, Ban Shiliang

Journal of Semiconductors, 2009, 30(8): 082001. doi: 10.1088/1674-4926/30/8/082001
16

Formation of stacked ruthenium nanocrystals embedded in SiO2 for nonvolatile memory applications

Mao Ping, Zhang Zhigang, Pan Liyang, Xu Jun, Chen Peiyi, et al.

Journal of Semiconductors, 2009, 30(9): 093003. doi: 10.1088/1674-4926/30/9/093003
17

Growth of Free-Standing AlN Nanocrystals on Nanorod ZnO Template

Hu Weiguo, Wei Hongyuan, Jiao Chunmei, Kang Tingting, Zhang Riqing, et al.

Chinese Journal of Semiconductors , 2007, 28(10): 1508-1512.

18

Resonant Raman Scattering and Photoluminescence Emissions from Above Bandgap Levels in Dilute GaAsN Alloys

Tan P H, Luo X D, Ge W K, Xu Z Y, Zhang Y, et al.

Chinese Journal of Semiconductors , 2006, 27(3): 397-402.

19

Polar Quasi-Confined Optical Phonon Modes in Wurtzite Quasi-One-Dimensional GaN/AlxGa1-xN Quantum Well Wires

Zhang Li

Chinese Journal of Semiconductors , 2006, 27(10): 1717-1724.

20

Electronic Structure of Semiconductor Nanocrystals

Li Jingbo, Wang Linwang, Wei Suhuai

Chinese Journal of Semiconductors , 2006, 27(2): 191-196.

1. Ma, H., Zhu, Q., Zou, L. et al. Bulk Carrier Recombination Mechanisms and Photovoltage Deficit in Kesterite Solar Cells. Advanced Energy Materials, 2025. doi:10.1002/aenm.202405033
2. Zhou, Y., Mao, Y., Ye, C. et al. Ru Single Atoms Anchored on Co3O4 Nanorods for Efficient Overall Water Splitting under pH-Universal Conditions. Advanced Energy Materials, 2025. doi:10.1002/aenm.202500700
3. Li, Y., Ma, M., Yi, D. et al. Ultrathin 2D Alloyed Cu−Ga−Zn−S Curved Nanobelts for Boosting Visible-Light Photocatalytic Hydrogen Evolution. Advanced Functional Materials, 2024, 34(45): 2407271. doi:10.1002/adfm.202407271
4. El-Sayyad, G.S., Elfadil, D., Mosleh, M.A. et al. Eco-friendly Strategies for Biological Synthesis of Green Nanoparticles with Promising Applications. BioNanoScience, 2024, 14(3): 3617-3659. doi:10.1007/s12668-024-01494-x
5. Tanaya Das, H., Dutta, S., Gaurav, K. et al. CZTS (Cu2ZnSnS4)-based Nanomaterials in Photocatalytic and Hydrogen Production Applications: A Recent Progress towards Sustainable Environment. Chemistry - An Asian Journal, 2024, 19(16): e202300813. doi:10.1002/asia.202300813
6. Li, Y., Liu, Z., Chen, J. et al. Recent advances in quaternary copper-based sulfides and their derivatives for solar hydrogen evolution. Journal of Materials Chemistry A, 2024, 12(39): 26390-26420. doi:10.1039/d4ta03912b
7. Tian, W., Xie, X., Zhang, X. et al. Synergistic Interfacial Effect of Ru/Co3O4 Heterojunctions for Boosting Overall Water Splitting. Small, 2024, 20(27): 2309633. doi:10.1002/smll.202309633
8. Kumari, A., Vaidya, S. Influence of Structural Parameters of a Catalyst on Its Photocatalytic Activity. ACS Symposium Series, 2024. doi:10.1021/bk-2024-1467.ch002
9. Li, J., Wang, L., Yuan, Z. et al. d-electron regulation of Ru clusters via conductive V4C3Tx MXene and cation vacancy to boost efficient oxygen evolution. Applied Catalysis B: Environmental, 2024. doi:10.1016/j.apcatb.2023.123558
10. Qiu, W., Wang, Z., He, S. et al. Recent progress and future prospects of high-entropy materials for battery applications. Journal of Semiconductors, 2024, 45(3): 030202. doi:10.1088/1674-4926/45/3/030202
11. Ma, M., Li, J., Zhu, X. et al. Enhancing multifunctional photocatalysis with acetate-assisted cesium doping and unlocking the potential of Z-scheme solar water splitting. Carbon Energy, 2024, 6(3): e447. doi:10.1002/cey2.447
12. He, S., Wang, Z., Qiu, W. et al. Effect of Partial Cation Replacement on Anode Performance of Sodium-Ion Batteries. Batteries, 2024, 10(2): 44. doi:10.3390/batteries10020044
13. Wu, Z., Sha, M., Ji, D. et al. Ordered Anodic Aluminum Oxide-Based Nanostructures for Surface-Enhanced Raman Scattering: A Review. ACS Applied Nano Materials, 2024, 7(1): 11-31. doi:10.1021/acsanm.3c04652
14. Ran, Y., Xu, C., Ji, D. et al. Research progress of transition metal compounds as bifunctional catalysts for zinc-air batteries. Nano Research Energy, 2024, 3(1): e9120092. doi:10.26599/NRE.2023.9120092
15. Li, Y., Wang, S., Chen, J. et al. From kesterite 2D nanosheets to wurtzite 1D nanorods: controllable synthesis of Cu−Zn−Sn−S and their application in electrocatalytic hydrogen evolution. Journal of Semiconductors, 2023, 44(12): 122701. doi:10.1088/1674-4926/44/12/122701
16. Ma, M., Liu, J., Zhao, H. et al. Broadened photocatalytic capability to near-infrared for CdS hybrids and positioning hydrogen evolution sites. Applied Catalysis B: Environmental, 2023. doi:10.1016/j.apcatb.2022.122327
17. Chao, X., Yan, C., Zhao, H. et al. Micro-nano structural electrode architecture for high power energy storage. Journal of Semiconductors, 2023, 44(5): 050201. doi:10.1088/1674-4926/44/5/050201
18. Ma, M., Zhao, H., Wang, Z. et al. Designing Atomic Interfaces in Chalcogenides for Boosting Photocatalysis. Solar RRL, 2023, 7(9): 2300025. doi:10.1002/solr.202300025
19. Zhong, L., Li, X., Wang, W. et al. Electromechanical and photoelectric properties of a novel semiconducting Janus InGaSSe monolayer. Journal of Semiconductors, 2023, 44(1): 012701. doi:10.1088/1674-4926/44/1/012701

    • Search

    Advanced Search >>

    GET CITATION

    Zhe Yin, Min Hu, Jun Liu, Hao Fu, Zhijie Wang, Aiwei Tang. Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. Journal of Semiconductors, 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701
    Z Yin, M Hu, J Liu, H Fu, Z J Wang, A W Tang, Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. J. Semicond., 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701.
    shu

    Export: BibTex EndNote

    Article Metrics

    Article has an altmetric score of 1
    Article has an altmetric score of 1

    Article views: 2296 Times PDF downloads: 139 Times Cited by: 19 Times

    History

    Received: 08 September 2021 Revised: 06 October 2021 Online: Uncorrected proof: 16 November 2021Accepted Manuscript: 16 November 2021Published: 10 March 2022

    Catalog

      Email This Article

      User name:
      Email:*请输入正确邮箱
      Code:*验证码错误
      Send
      Article Navigation >  Journal of Semiconductors  > 2022  >  43(3): 032701
      Zhe Yin, Min Hu, Jun Liu, Hao Fu, Zhijie Wang, Aiwei Tang. Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. Journal of Semiconductors, 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701 ****Z Yin, M Hu, J Liu, H Fu, Z J Wang, A W Tang, Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. J. Semicond., 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701.
      Citation:
      Zhe Yin, Min Hu, Jun Liu, Hao Fu, Zhijie Wang, Aiwei Tang. Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. Journal of Semiconductors, 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701 ****
      Z Yin, M Hu, J Liu, H Fu, Z J Wang, A W Tang, Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation[J]. J. Semicond., 2022, 43(3): 032701. doi: 10.1088/1674-4926/43/3/032701.
      shu

      Tunable crystal structure of Cu–Zn–Sn–S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation

      DOI: 10.1088/1674-4926/43/3/032701
      • 1.

        Key Laboratory of Luminescence and Optical Information, Ministry of Education, School of Science, Beijing Jiaotong University, Beijing 100044, China

      • 2.

        Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China

      • 3.

        Beijing Key Laboratory of Low Dimensional Semiconductor Materials and Devices, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China

      • 4.

        College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

      More Information
      • Zhe Yin：received her PhD degree from Tsinghua University in 2020. Then she joined Beijing Jiaotong University as a lecturer. Her research includes synthesizing of copper-based chalcogenide nanocrystals, lead-free perovskites, and exploring their application in flexible optoelectronics
      • Aiwei Tang：is a full professor at the School of Science in Beijing Jiaotong University. He received his PhD degree from Beijing Jiaotong University in 2009. He then spent two years at the Institute of Semiconductors at the Chinese Academy of Sciences as a postdoctoral researcher. He joined Beijing Jiaotong University in 2011. His recent research interests are mainly focused on design of low-dimensional semiconductor nanomaterials and their optoelectronic applications
      • Corresponding author: wangzj@semi.ac.cn; awtang@bjtu.edu.cn
      • Received Date: 2021-09-08
      • Revised Date: 2021-10-06
      • Published Date: 2022-03-10

      Catalog

        Journal of Semiconductors © 2017 All Rights Reserved   京ICP备05085259号-2

        /

        DownLoad:  Full-Size Img  PowerPoint
        Return
        Return