Cu2ZnSn(S,Se)4(CZTSSe)solar cells have resource distribution and economic advantages.The main cause of their low efficiency is carrier loss resulting from recombination of photo-generated electron and hole.To overcome...Cu2ZnSn(S,Se)4(CZTSSe)solar cells have resource distribution and economic advantages.The main cause of their low efficiency is carrier loss resulting from recombination of photo-generated electron and hole.To overcome this,it is important to understand their electron-hole behavior characteristics.To determine the carrier separation characteristics,we measured the surface potential and the local current in terms of the absorber depth.The elemental variation in the intragrains(IGs)and at the grain boundaries(GBs)caused a band edge shift and bandgap(Eg)change.At the absorber surface and subsurface,an upward Ec and Ev band bending structure was observed at the GBs,and the carrier separation was improved.At the absorber center,both upward Ec and Ev and downward Ec-upward Ev band bending structures were observed at the GBs,and the carrier separation was degraded.To improve the carrier separation and suppress carrier recombination,an upward Ec and Ev band bending structure at the GBs is desirable.展开更多
In spite of the high potential economic feasibility of the tandem solar cells consisting of the halide perovskite and the kesterite Cu2ZnSn(S,Se)4(CZTSSe),they have rarely been demonstrated due to the difficulty in im...In spite of the high potential economic feasibility of the tandem solar cells consisting of the halide perovskite and the kesterite Cu2ZnSn(S,Se)4(CZTSSe),they have rarely been demonstrated due to the difficulty in implementing solution-processed perovskite top cell on the rough surface of the bottom cells.Here,we firstly demonstrate an efficient monolithic two-terminal perovskite/CZTSSe tandem solar cell by significantly reducing the surface roughness of the electrochemically deposited CZTSSe bottom cell.The surface roughness(R_(rms))of the CZTSSe thin film could be reduced from 424 to 86 nm by using the potentiostatic mode rather than using the conventional galvanostatic mode,which can be further reduced to 22 nm after the subsequent ion-milling process.The perovskite top cell with a bandgap of 1.65 eV could be prepared using a solution process on the flattened CZTSSe bottom cell,resulting in the efficient perovskite/CZTSSe tandem solar cells.After the current matching between two subcells involving the thickness control of the perovskite layer,the best performing tandem device exhibited a high conversion efficiency of 17.5%without the hysteresis effect.展开更多
Ag substitution in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is a promising way to mitigate Cu/Zn related defects,electrostatic fluctuations and Shockley-Read-Hall(SRH)recombination centers.However,high performance ACZTSSe solar ce...Ag substitution in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is a promising way to mitigate Cu/Zn related defects,electrostatic fluctuations and Shockley-Read-Hall(SRH)recombination centers.However,high performance ACZTSSe solar cells are generally demonstrated with more Ag amounts and strenuous fabrication processes,which are not ideal when using cheap constituent materials CZTSSe.To reduce the Ag amount(2%-3%),local Ag substitutions into CZTSSe at front(F),back(B)and dual front/back(FB)were proposed.Experimental results revealed that F-passivation effectively reduced the Cu/Zn related defects and further limits the interface/bulk recombination whereas B-passivation improved the grain growth at the back interface and further allows enhanced transport of charge carriers.By employing the dual Agpassivation approach,the final ACZTSSe device parameters were significantly improved and remarkable power conversion efficiency(PCE)of 12.43%was achieved with eco-friendly aqueous solution process.展开更多
In CZTSSe solar cells,a simple sodium-incorporation post-treatment method toward solution-processed Cu2Zn Sn S4precursor films is presented in this work.An ultrathin NaCl film is deposited on Cu2Zn Sn S4precursor film...In CZTSSe solar cells,a simple sodium-incorporation post-treatment method toward solution-processed Cu2Zn Sn S4precursor films is presented in this work.An ultrathin NaCl film is deposited on Cu2Zn Sn S4precursor films by spin-coating NaCl solution.In subsequent selenization process,the introduction of Na Cl is found to be benefacial for the formation of Cu2-xSe,which can further facilitate the element transportation,leading to dense and smooth CZTSSe films with large grains and less impurity Cu2Sn(S,Se)3phase.SIMS depth profiles confirm the gradient distribution of the sodium element in Na-doped absorbers.Photoluminescence spectra show that the introduction of appropriate sodium into the absorber can inhibit the band tail states.As high as 11.18% of power conversion efficiency(PCE)is achieved for the device treated with 5 mg mL^-1 NaCl solution,and an average efficiency of Na-doped devices is 10.71%,13%higher than that of the control groups(9.45%).Besides,the depletion width and the charge recombination lifetime can also have regular variation with sodium treatment.This work offers an easy modification method for high-quality Na-doped CZTSSe films and high-performance devices,in the meantime,it can also help to further understand the effects of sodium in CZTSSe solar cells.展开更多
The passivation of non-radiative states and inhibition of band tailings are desirable for improving the open-circuit voltage(V_(oc))of CZTSSe thin-film solar cells.Recently,alkali metal doping has been investigated to...The passivation of non-radiative states and inhibition of band tailings are desirable for improving the open-circuit voltage(V_(oc))of CZTSSe thin-film solar cells.Recently,alkali metal doping has been investigated to passivate defects in CZTSSe films.Herein,we investigate Li doping effects by applying Li OH into CZTSSe precursor solutions,and verify that carrier transport is enhanced in the CZTSSe solar cells.Systematic characterizations demonstrate that Li doping can effectively passivate non-radiative recombination centers and reduce band tailings of the CZTSSe films,leading to the decrease in total defect density and the increase in separation distance between donor and acceptor.Fewer free carriers are trapped in the band tail states,which speeds up carrier transport and reduces the probability of deep-level defects capturing carriers.The charge recombination lifetime is about twice as long as that of the undoped CZTSSe device,implying the heterojunction interface recombination is also inhibited.Besides,Li doping can increase carrier concentration and enhance build-in voltage,leading to a better carrier collection.By adjusting the Li/(Li+Cu)ratio to 18%,the solar cell efficiency is increased significantly to 9.68%with the fill factor(FF)of 65.94%,which is the highest FF reported so far for the flexible CZTSSe solar cells.The increased efficiency is mainly attributed to the reduction of V_(oc)deficit and the improved CZTSSe/Cd S junction quality.These results open up a simple route to passivate non-radiative states and reduce the band tailings of the CZTSSe films and improve the efficiency of the flexible CZTSSe solar cells.展开更多
为分析CZTSSe薄膜太阳能电池的背电极接触特性,采用AFORS-HET(Automat for Simulation of HETerostructures)v2.5软件对CZTSSe/Mo(S,Se)2/Mo结构进行数值分析,研究CZTSSe的带隙和电子亲和能、Mo(S,Se)2界面层的厚度以及带隙对CZTSSe与M...为分析CZTSSe薄膜太阳能电池的背电极接触特性,采用AFORS-HET(Automat for Simulation of HETerostructures)v2.5软件对CZTSSe/Mo(S,Se)2/Mo结构进行数值分析,研究CZTSSe的带隙和电子亲和能、Mo(S,Se)2界面层的厚度以及带隙对CZTSSe与Mo电极的电学接触特性的影响。结果表明CZTSSe的带隙和电子亲和能的增大,使得CZTSSe/Mo(S,Se)2/Mo的欧姆接触减弱并向整流接触转变;对于带隙较窄的CZTSSe,加入界面层使CZTSSe/Mo(S,Se)2/Mo形成的欧姆接触转变为整流接触,随着界面层厚度的增大,整流接触逐渐减弱;对于带隙较宽的CZTSSe,加入2 nm的界面层使得CZTSSe/Mo(S,Se)2/Mo形成的整流接触增强,但随着界面层厚度的继续增大,整流接触减弱。当CZTSSe的带隙和电子亲和能较小时,CZTSSe/Mo(S,Se)2/Mo形成欧姆接触,控制界面层厚度为100 nm左右可以得到最优的电学接触特性。展开更多
采用共溅射法结合后硒化成功制备出CZTSSe薄膜,主要研究了不同的硒化温度对CZTSSe薄膜与电池性能的影响。分别采用X射线衍射仪、拉曼光谱仪、扫描电子显微镜、紫外-可见-近红外分光光度计、霍尔效应测量仪及数字电源表对不同硒化温度下...采用共溅射法结合后硒化成功制备出CZTSSe薄膜,主要研究了不同的硒化温度对CZTSSe薄膜与电池性能的影响。分别采用X射线衍射仪、拉曼光谱仪、扫描电子显微镜、紫外-可见-近红外分光光度计、霍尔效应测量仪及数字电源表对不同硒化温度下制备的CZTSSe薄膜的结构、形貌、光电与太阳电池性能进行了表征与分析。结果表明,当硒化温度为580℃时,CZTSSe薄膜的结晶性最好,薄膜表面均匀致密且其电阻率和载流子浓度达到最小值和最大值,分别为1.57Ω·cm和8.2×10^(17)cm^(-3),该硒化温度下制备得到的CZTSSe太阳电池的短路电流和转换效率最高达到30.68 m A/cm^2和5.17%。相对于550℃和600℃硒化温度下的CZTSSe太阳电池,其光电转换效率分别提高了36%和6%。另外,随着硒化温度的升高,CZTSSe薄膜在XRD中的(112)峰位和Raman中的A1模式振动峰位都向小衍射角和短波数方向移动,薄膜的禁带宽度也从1.26 e V减小至1.21 e V。展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Ministry of Science and ICT(No.2022M3J1A1085371)by the DGIST R&D programs of the Ministry of Science and ICT(23-ET-08 and 23-CoE-ET-01)supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2018R1A6A1A03025340).
文摘Cu2ZnSn(S,Se)4(CZTSSe)solar cells have resource distribution and economic advantages.The main cause of their low efficiency is carrier loss resulting from recombination of photo-generated electron and hole.To overcome this,it is important to understand their electron-hole behavior characteristics.To determine the carrier separation characteristics,we measured the surface potential and the local current in terms of the absorber depth.The elemental variation in the intragrains(IGs)and at the grain boundaries(GBs)caused a band edge shift and bandgap(Eg)change.At the absorber surface and subsurface,an upward Ec and Ev band bending structure was observed at the GBs,and the carrier separation was improved.At the absorber center,both upward Ec and Ev and downward Ec-upward Ev band bending structures were observed at the GBs,and the carrier separation was degraded.To improve the carrier separation and suppress carrier recombination,an upward Ec and Ev band bending structure at the GBs is desirable.
基金supported by the National Research Foundation of Korea(NRF)funded by the Korean government's Ministry of Science and ICT(NRF-2022M3J1A1063226,2021M3H4A1A 03057403,2017M3D1A1039377,and NRF-2021R1C1C1011882)supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.20203040010320)
文摘In spite of the high potential economic feasibility of the tandem solar cells consisting of the halide perovskite and the kesterite Cu2ZnSn(S,Se)4(CZTSSe),they have rarely been demonstrated due to the difficulty in implementing solution-processed perovskite top cell on the rough surface of the bottom cells.Here,we firstly demonstrate an efficient monolithic two-terminal perovskite/CZTSSe tandem solar cell by significantly reducing the surface roughness of the electrochemically deposited CZTSSe bottom cell.The surface roughness(R_(rms))of the CZTSSe thin film could be reduced from 424 to 86 nm by using the potentiostatic mode rather than using the conventional galvanostatic mode,which can be further reduced to 22 nm after the subsequent ion-milling process.The perovskite top cell with a bandgap of 1.65 eV could be prepared using a solution process on the flattened CZTSSe bottom cell,resulting in the efficient perovskite/CZTSSe tandem solar cells.After the current matching between two subcells involving the thickness control of the perovskite layer,the best performing tandem device exhibited a high conversion efficiency of 17.5%without the hysteresis effect.
基金supported by the National Research Foundation of Korea(NRF)funded by the Korean Government(NRF2021R1A2C1008598)the program of Phased Development of Carbon Neutral Technologies through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT(NRF-2022M3J1A1064220)。
文摘Ag substitution in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is a promising way to mitigate Cu/Zn related defects,electrostatic fluctuations and Shockley-Read-Hall(SRH)recombination centers.However,high performance ACZTSSe solar cells are generally demonstrated with more Ag amounts and strenuous fabrication processes,which are not ideal when using cheap constituent materials CZTSSe.To reduce the Ag amount(2%-3%),local Ag substitutions into CZTSSe at front(F),back(B)and dual front/back(FB)were proposed.Experimental results revealed that F-passivation effectively reduced the Cu/Zn related defects and further limits the interface/bulk recombination whereas B-passivation improved the grain growth at the back interface and further allows enhanced transport of charge carriers.By employing the dual Agpassivation approach,the final ACZTSSe device parameters were significantly improved and remarkable power conversion efficiency(PCE)of 12.43%was achieved with eco-friendly aqueous solution process.
基金financially supported by the National Natural Science Foundation of China (Nos. 51421002, 51627803, 91733301, 51761145042, 21501183, 51402348, 53872321, and 11874402)the Knowledge Innovation Program and the Strategic Priority Research Program (Grant XDB 12010400) of the Chinese Academy of Sciences
文摘In CZTSSe solar cells,a simple sodium-incorporation post-treatment method toward solution-processed Cu2Zn Sn S4precursor films is presented in this work.An ultrathin NaCl film is deposited on Cu2Zn Sn S4precursor films by spin-coating NaCl solution.In subsequent selenization process,the introduction of Na Cl is found to be benefacial for the formation of Cu2-xSe,which can further facilitate the element transportation,leading to dense and smooth CZTSSe films with large grains and less impurity Cu2Sn(S,Se)3phase.SIMS depth profiles confirm the gradient distribution of the sodium element in Na-doped absorbers.Photoluminescence spectra show that the introduction of appropriate sodium into the absorber can inhibit the band tail states.As high as 11.18% of power conversion efficiency(PCE)is achieved for the device treated with 5 mg mL^-1 NaCl solution,and an average efficiency of Na-doped devices is 10.71%,13%higher than that of the control groups(9.45%).Besides,the depletion width and the charge recombination lifetime can also have regular variation with sodium treatment.This work offers an easy modification method for high-quality Na-doped CZTSSe films and high-performance devices,in the meantime,it can also help to further understand the effects of sodium in CZTSSe solar cells.
基金supported by the National Natural Science Foundation of China(62074037,52002073)the Science and Technology Department of Fujian Province(2020I0006)+3 种基金the Natural Science Foundation of Fujian Province(2019J01218)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ124)the Education and Scientific Research Project of Fujian Province(JAT200372)the Scientific Research Project of Fujian Jiangxia University(JXZ2019006)。
文摘The passivation of non-radiative states and inhibition of band tailings are desirable for improving the open-circuit voltage(V_(oc))of CZTSSe thin-film solar cells.Recently,alkali metal doping has been investigated to passivate defects in CZTSSe films.Herein,we investigate Li doping effects by applying Li OH into CZTSSe precursor solutions,and verify that carrier transport is enhanced in the CZTSSe solar cells.Systematic characterizations demonstrate that Li doping can effectively passivate non-radiative recombination centers and reduce band tailings of the CZTSSe films,leading to the decrease in total defect density and the increase in separation distance between donor and acceptor.Fewer free carriers are trapped in the band tail states,which speeds up carrier transport and reduces the probability of deep-level defects capturing carriers.The charge recombination lifetime is about twice as long as that of the undoped CZTSSe device,implying the heterojunction interface recombination is also inhibited.Besides,Li doping can increase carrier concentration and enhance build-in voltage,leading to a better carrier collection.By adjusting the Li/(Li+Cu)ratio to 18%,the solar cell efficiency is increased significantly to 9.68%with the fill factor(FF)of 65.94%,which is the highest FF reported so far for the flexible CZTSSe solar cells.The increased efficiency is mainly attributed to the reduction of V_(oc)deficit and the improved CZTSSe/Cd S junction quality.These results open up a simple route to passivate non-radiative states and reduce the band tailings of the CZTSSe films and improve the efficiency of the flexible CZTSSe solar cells.
文摘为分析CZTSSe薄膜太阳能电池的背电极接触特性,采用AFORS-HET(Automat for Simulation of HETerostructures)v2.5软件对CZTSSe/Mo(S,Se)2/Mo结构进行数值分析,研究CZTSSe的带隙和电子亲和能、Mo(S,Se)2界面层的厚度以及带隙对CZTSSe与Mo电极的电学接触特性的影响。结果表明CZTSSe的带隙和电子亲和能的增大,使得CZTSSe/Mo(S,Se)2/Mo的欧姆接触减弱并向整流接触转变;对于带隙较窄的CZTSSe,加入界面层使CZTSSe/Mo(S,Se)2/Mo形成的欧姆接触转变为整流接触,随着界面层厚度的增大,整流接触逐渐减弱;对于带隙较宽的CZTSSe,加入2 nm的界面层使得CZTSSe/Mo(S,Se)2/Mo形成的整流接触增强,但随着界面层厚度的继续增大,整流接触减弱。当CZTSSe的带隙和电子亲和能较小时,CZTSSe/Mo(S,Se)2/Mo形成欧姆接触,控制界面层厚度为100 nm左右可以得到最优的电学接触特性。
文摘采用共溅射法结合后硒化成功制备出CZTSSe薄膜,主要研究了不同的硒化温度对CZTSSe薄膜与电池性能的影响。分别采用X射线衍射仪、拉曼光谱仪、扫描电子显微镜、紫外-可见-近红外分光光度计、霍尔效应测量仪及数字电源表对不同硒化温度下制备的CZTSSe薄膜的结构、形貌、光电与太阳电池性能进行了表征与分析。结果表明,当硒化温度为580℃时,CZTSSe薄膜的结晶性最好,薄膜表面均匀致密且其电阻率和载流子浓度达到最小值和最大值,分别为1.57Ω·cm和8.2×10^(17)cm^(-3),该硒化温度下制备得到的CZTSSe太阳电池的短路电流和转换效率最高达到30.68 m A/cm^2和5.17%。相对于550℃和600℃硒化温度下的CZTSSe太阳电池,其光电转换效率分别提高了36%和6%。另外,随着硒化温度的升高,CZTSSe薄膜在XRD中的(112)峰位和Raman中的A1模式振动峰位都向小衍射角和短波数方向移动,薄膜的禁带宽度也从1.26 e V减小至1.21 e V。
