The low temperature phase transformation in the Cu_2ZnSnS_4(CZTS) films was investigated by laser annealing and low temperature thermal annealing.The Raman measurements show that a-high-power laser annealing could c...The low temperature phase transformation in the Cu_2ZnSnS_4(CZTS) films was investigated by laser annealing and low temperature thermal annealing.The Raman measurements show that a-high-power laser annealing could cause a red shift of the Raman scattering peaks of the kesterite(KS) structure and promotes the formation of the partially disordered kesterite(PD-KS) structure in the CZTS films,and the low-temperature thermal annealing only shifts the Raman scattering peak of KS phase by several wavenumber to low frequency and the broads Raman peaks in the low frequency region.Moreover,the above two processes were reversible.The Raman analyses of the CZTS samples prepared under different process show that the PD-KS structure tends to be found at low temperatures and low sulfur vapor pressures.Our results reveal that the control of the phase structure in CZTS films is feasible by adjusting the preparation process of the films.展开更多
Cu2ZnSnS4 (CZTS) thin films were successfully prepared by sulfurization of ion bean sputtered precursors on soda-lime glass substrate. The single phase of stannite-type structure CZTS films were obtained as revealed i...Cu2ZnSnS4 (CZTS) thin films were successfully prepared by sulfurization of ion bean sputtered precursors on soda-lime glass substrate. The single phase of stannite-type structure CZTS films were obtained as revealed in EDS and XRD analysis when the ratios of the constituents of CZTS thin films are close to stoichiometric by optimizing the conditions of precursor preparation and sulfurization. A low sheet resistivity as about 0.156 Ω·cm and a high absorption coefficient as 1×104 cm-1 were achieved in this method by Hall effect measurements and UV-VIS spectrophotometer. The optical band-gap energy of the CZTS sample is about 1.51 eV, which is very close to the optimum value for a solar-cell absorber.展开更多
Ni0.4Cu0.2Zn0.4Fe2O4 thin films were fabricated on Si substrates by using the sol-gel method and rapid thermal annealing (RTA), and their magnetic properties and crystalline structures were investigated. The samples...Ni0.4Cu0.2Zn0.4Fe2O4 thin films were fabricated on Si substrates by using the sol-gel method and rapid thermal annealing (RTA), and their magnetic properties and crystalline structures were investigated. The samples calcined at and above 600 ℃ have a single-phase spinel structure and the average grain size of the sample calcined at 600 ℃ is about 20 nm. The initial permeability μi, saturation magnetization M and coercivity H of the samples increase with the increasing calcination temperature. The sample calcined at 600 ℃ exhibits an excellent soft magnetic performance, which has μi=33.97 (10 MHz), Hc=15.62 Oe and Ms=228.877 emu/cm^3. Low-temperature annealing can enhance the magnetic properties of the samples. The work shows that using the sol-gel method in conjunction with RTA is a promising way to fabricate integrated thin-film devices.展开更多
为研究PVP含量对CZTS颗粒形貌以及分散性的影响,本文采用溶剂热法,以CuCl2·2H2O、Zn(Ac)2·2H2O、SnCl4·5H2O作金属源,硫脲作硫源,乙二醇为溶剂,在体系中加入不同含量的PVP,成功制备了CZTS微球。通过XRD、Raman、SEM、TEM...为研究PVP含量对CZTS颗粒形貌以及分散性的影响,本文采用溶剂热法,以CuCl2·2H2O、Zn(Ac)2·2H2O、SnCl4·5H2O作金属源,硫脲作硫源,乙二醇为溶剂,在体系中加入不同含量的PVP,成功制备了CZTS微球。通过XRD、Raman、SEM、TEM、UVVis等方法检测分析CZTS纳米微球的物相、结构、形貌以及光学性能。结果表明:所得CZTS纳米颗粒具有锌黄锡矿结构;当体系中PVP含量为0.2 g时,颗粒分散性较好,制备的颗粒形貌为表面嵌有纳米薄片的微球,纳米片较在体系中加入0.1 g PVP更致密;光学带隙约为1.47 eV,与太阳能电池所需的最佳带隙接近。最后,对表面嵌有纳米薄片的CZTS微球可能的形成机理进行了推测。展开更多
Cu2ZnSnS(e)4 (CZTS(e)) solar cells have attracted much attention due to the elemental abundance and the non- toxicity. However, the record efficiency of 12.6% for CuzZnSn(S,Se)4 (CZTSSe) solar cells is much ...Cu2ZnSnS(e)4 (CZTS(e)) solar cells have attracted much attention due to the elemental abundance and the non- toxicity. However, the record efficiency of 12.6% for CuzZnSn(S,Se)4 (CZTSSe) solar cells is much lower than that of Cu(In,Ga)See (CIGS) solar cells. One crucial reason is the recombination at interfaces. In recent years, large amount inves- tigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods. This paper gives a review of progresses on interfaces of CZTS(e) solar cells, including: (i) the band alignment optimization at buffer/CZTS(e) interface, (ii) tailoring the thickness of MoS(e)2 interfacial layers between CZTS(e) absorber and Mo back contact, (iii) the passivation of rear interface, (iv) the passivation of front interface, and (v) the etching of secondary phases.展开更多
The beneficial effect of the alkali metals such as Na and K on the Cu(In.Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe) solar cells has been extensively investigated in the past two decades, however, in most of the...The beneficial effect of the alkali metals such as Na and K on the Cu(In.Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe) solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum (VBM) level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.展开更多
Zn/Sn/Cu (CZT) stacks were prepared by RF magnetron sputtering. The stacks were pretreated at different tem- peratures (200℃, 300 ℃, 350 ℃, and 400 ℃) for 0.5 h and then followed by sulfurization at 500℃ for ...Zn/Sn/Cu (CZT) stacks were prepared by RF magnetron sputtering. The stacks were pretreated at different tem- peratures (200℃, 300 ℃, 350 ℃, and 400 ℃) for 0.5 h and then followed by sulfurization at 500℃ for 2 h. Then, the structures, morphologies, and optical properties of the as-obtained Cu2ZnSnS4 (CZTS) films were studied by x-ray diffraction (XRD), Raman spectroscopy, UV-Vis-NIR, scanning electron microscope (SEM), and energy-dispersive x-ray spectroscopy (EDX). The XRD and Raman spectroscopy results indicated that the sample pretreated at 350℃ had no secondary phase and good crystallization. At the same time, SEM confirmed that it had large and dense grains. According to the UV-Vis-NIR spectrum, the sample had an absorption coefficient larger than 10^4 cm-1 in the visible light range and a band gap close to 1.5 eV.展开更多
基金Project supported by the Natural Science Foundation for Youth Fund of Hebei Province,China(Grant No.A2016201087)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.20131301120003)the National Natural Science Foundation of China(Grant Nos.11504078and 61504054)
文摘The low temperature phase transformation in the Cu_2ZnSnS_4(CZTS) films was investigated by laser annealing and low temperature thermal annealing.The Raman measurements show that a-high-power laser annealing could cause a red shift of the Raman scattering peaks of the kesterite(KS) structure and promotes the formation of the partially disordered kesterite(PD-KS) structure in the CZTS films,and the low-temperature thermal annealing only shifts the Raman scattering peak of KS phase by several wavenumber to low frequency and the broads Raman peaks in the low frequency region.Moreover,the above two processes were reversible.The Raman analyses of the CZTS samples prepared under different process show that the PD-KS structure tends to be found at low temperatures and low sulfur vapor pressures.Our results reveal that the control of the phase structure in CZTS films is feasible by adjusting the preparation process of the films.
基金This work was financially supported by the National Natural Science Foundation (No.10574106), the Science & Technology Plan of Guangdong Province (No.2003C105005) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars of Chinese State Education Ministry (No.(2004)176).
文摘Cu2ZnSnS4 (CZTS) thin films were successfully prepared by sulfurization of ion bean sputtered precursors on soda-lime glass substrate. The single phase of stannite-type structure CZTS films were obtained as revealed in EDS and XRD analysis when the ratios of the constituents of CZTS thin films are close to stoichiometric by optimizing the conditions of precursor preparation and sulfurization. A low sheet resistivity as about 0.156 Ω·cm and a high absorption coefficient as 1×104 cm-1 were achieved in this method by Hall effect measurements and UV-VIS spectrophotometer. The optical band-gap energy of the CZTS sample is about 1.51 eV, which is very close to the optimum value for a solar-cell absorber.
基金the National Natural Science Foundation of China (No. 90607021).
文摘Ni0.4Cu0.2Zn0.4Fe2O4 thin films were fabricated on Si substrates by using the sol-gel method and rapid thermal annealing (RTA), and their magnetic properties and crystalline structures were investigated. The samples calcined at and above 600 ℃ have a single-phase spinel structure and the average grain size of the sample calcined at 600 ℃ is about 20 nm. The initial permeability μi, saturation magnetization M and coercivity H of the samples increase with the increasing calcination temperature. The sample calcined at 600 ℃ exhibits an excellent soft magnetic performance, which has μi=33.97 (10 MHz), Hc=15.62 Oe and Ms=228.877 emu/cm^3. Low-temperature annealing can enhance the magnetic properties of the samples. The work shows that using the sol-gel method in conjunction with RTA is a promising way to fabricate integrated thin-film devices.
基金supported by the National Natural Science Foundation of China(21663030,21666039)the Open Project of State Key Laboratory of Organic-Inorganic Composites Beijing Key Laboratory,Beijing University of Chemical Technology(oic-201901009)+2 种基金the Project of Science&Technology Office of Shannxi Province(2018TSCXL-NY-02-01,2013K11-08,2013SZS20-P01)Industrial Key Project of Yan’an Science and Technology Bureau(2018KG-04)the Project of Yan’an Science Graduate Innovation Project of Yan’an University(YCX201988)~~
文摘为研究PVP含量对CZTS颗粒形貌以及分散性的影响,本文采用溶剂热法,以CuCl2·2H2O、Zn(Ac)2·2H2O、SnCl4·5H2O作金属源,硫脲作硫源,乙二醇为溶剂,在体系中加入不同含量的PVP,成功制备了CZTS微球。通过XRD、Raman、SEM、TEM、UVVis等方法检测分析CZTS纳米微球的物相、结构、形貌以及光学性能。结果表明:所得CZTS纳米颗粒具有锌黄锡矿结构;当体系中PVP含量为0.2 g时,颗粒分散性较好,制备的颗粒形貌为表面嵌有纳米薄片的微球,纳米片较在体系中加入0.1 g PVP更致密;光学带隙约为1.47 eV,与太阳能电池所需的最佳带隙接近。最后,对表面嵌有纳米薄片的CZTS微球可能的形成机理进行了推测。
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51572132,51372121,and 61674082)the Natural Science Foundation of Key Project of Tianjin City,China(Grant No.16JCZDJC30700)+1 种基金the Yang Fan Innovative and Entrepreneurial Research Team Project of China(Grant No.2014YT02N037)111 Project,China(Grant No.B16027)
文摘Cu2ZnSnS(e)4 (CZTS(e)) solar cells have attracted much attention due to the elemental abundance and the non- toxicity. However, the record efficiency of 12.6% for CuzZnSn(S,Se)4 (CZTSSe) solar cells is much lower than that of Cu(In,Ga)See (CIGS) solar cells. One crucial reason is the recombination at interfaces. In recent years, large amount inves- tigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods. This paper gives a review of progresses on interfaces of CZTS(e) solar cells, including: (i) the band alignment optimization at buffer/CZTS(e) interface, (ii) tailoring the thickness of MoS(e)2 interfacial layers between CZTS(e) absorber and Mo back contact, (iii) the passivation of rear interface, (iv) the passivation of front interface, and (v) the etching of secondary phases.
基金supported by the National Natural Science Foundation of China(NSFC)under grant nos.61574059 and 61722402the National Key Research and Development Program of China(2016YFB0700700)+1 种基金Shu-Guang program(15SG20)CC of ECNU
文摘The beneficial effect of the alkali metals such as Na and K on the Cu(In.Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe) solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum (VBM) level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.
基金supported by Funding for Outstanding Doctoral Dissertation in NUAA,China(Grant No.BCXJ13-12)the Jiangsu Innovation Program for Graduate Education,China(Grant No.CXLX13 150)+2 种基金the Fundamental Research Funds for the Central Universities,China(Grant No.61176062)the Science and Technology Supporting Project of Jiangsu Province,China(Grant No.BE2012103)the Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘Zn/Sn/Cu (CZT) stacks were prepared by RF magnetron sputtering. The stacks were pretreated at different tem- peratures (200℃, 300 ℃, 350 ℃, and 400 ℃) for 0.5 h and then followed by sulfurization at 500℃ for 2 h. Then, the structures, morphologies, and optical properties of the as-obtained Cu2ZnSnS4 (CZTS) films were studied by x-ray diffraction (XRD), Raman spectroscopy, UV-Vis-NIR, scanning electron microscope (SEM), and energy-dispersive x-ray spectroscopy (EDX). The XRD and Raman spectroscopy results indicated that the sample pretreated at 350℃ had no secondary phase and good crystallization. At the same time, SEM confirmed that it had large and dense grains. According to the UV-Vis-NIR spectrum, the sample had an absorption coefficient larger than 10^4 cm-1 in the visible light range and a band gap close to 1.5 eV.