The presence of SnZn-related defects in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)absorber results in large irreversible energy loss and extra irreversible electron-hole non-radiative recombination,thus hindering the efficiency enh...The presence of SnZn-related defects in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)absorber results in large irreversible energy loss and extra irreversible electron-hole non-radiative recombination,thus hindering the efficiency enhancement of CZTSSe devices.Although the incorporation of Ag in CZTSSe can effectively suppress the SnZn-related defects and significantly improve the resulting cell performance,an excellent efficiency has not been achieved to date primarily owing to the poor electrical-conductivity and the low carrier density of the CZTSSe film induced by Ag substitution.Herein,this study exquisitely devises an Ag/H co-doping strategy in CZTSSe absorber via Ag substitution programs followed by hydrogen-plasma treatment procedure to suppress SnZn defects for achieving efficient CZTSSe devices.In-depth investigation results demonstrate that the incorporation of H in Ag-based CZTSSe absorber is expected to improve the poor electrical-conductivity and the low carrier density caused by Ag substitution.Importantly,the C=O and O-H functional groups induced by hydrogen incorporation,serving as an electron donor,can interact with under-coordinated cations in CZTSSe material,effectively passivating the SnZn-related defects.Consequently,the incorporation of an appropriate amount of Ag/H in CZTSSe mitigates carrier non-radiative recombination,prolongs minority carrier lifetime,and thus yields a champion efficiency of 14.74%,showing its promising application in kesterite-based CZTSSe devices.展开更多
Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is considered to be the most potential light-absorbing material to replace CuInGaSe_(2)(CIGS),but the actual photoelectric conversion efficiency of such cells is much lower than that of CIG...Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is considered to be the most potential light-absorbing material to replace CuInGaSe_(2)(CIGS),but the actual photoelectric conversion efficiency of such cells is much lower than that of CIGS.One of the reasons is the high recombination rate of carriers at the interface.In this paper,in order to reduce the carrier recombination,a new solar cell structure with double absorber layers of Al-doped ZnO(AZO)/intrinsic(i)-ZnO/CdS/CZTS_(x1)Se_(1−x1)(CZTSSe_(1))/CZTS_(x2)Se_(1−x2)(CZTSSe_(2))/Mo was proposed,and the optimal conduction band offsets(CBOs)of CdS/CZTSSe_(1) interface and CZTSSe_(1)/CZTSSe_(2) interface were determined by changing the S ratio in CZTSSe_(1) and CZTSSe_(2),and the effect of thickness of CZTSSe_(1) on the performance of the cell was studied.The efficiencies of the optimized single and double absorber layers reached 17.97%and 23.4%,respectively.Compared with the single absorber layer structure,the proposed structure with double absorber layers has better cell performance.展开更多
High performances of Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells are heavily influenced by the quality of heterojunctions.Herein,an oxygen(O)doping of CZTSSe/CdS heterojunction is performed to suppress the formation of th...High performances of Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells are heavily influenced by the quality of heterojunctions.Herein,an oxygen(O)doping of CZTSSe/CdS heterojunction is performed to suppress the formation of the defects by an ultraviolet ozone(UV-O_(3))treatment for the efficient flexible CZTSSe solar cells.The introduction of O reduces the non-radiative recombination and increases the carrier concentration of the CdS films.Furthermore,the defect density of the CdS film has been reduced from 8.24×10^(16)to2.91×10^(16)cm^(-3)by the O-doping.The results indicate that the electron transport is effectively promoted due to the decreased conduction band offset(CBO)at the heterojunction interface.As a result,the champion flexible CZTSSe solar cell achieves a power conversion efficiency(PCE)of 11.21%,with a significantly improved short circuit current density.The study for improving the CZTSSe/CdS heterojunction through O-doping treatment provides a new insight for enhancing the PCE of the flexible CZTSSe solar cells.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
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
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
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
基金supported by the National Natural Science Foundation of China(51802081,62074052,and 62104061)the Natural Science Foundation of Henan Province(232300420145).
文摘The presence of SnZn-related defects in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)absorber results in large irreversible energy loss and extra irreversible electron-hole non-radiative recombination,thus hindering the efficiency enhancement of CZTSSe devices.Although the incorporation of Ag in CZTSSe can effectively suppress the SnZn-related defects and significantly improve the resulting cell performance,an excellent efficiency has not been achieved to date primarily owing to the poor electrical-conductivity and the low carrier density of the CZTSSe film induced by Ag substitution.Herein,this study exquisitely devises an Ag/H co-doping strategy in CZTSSe absorber via Ag substitution programs followed by hydrogen-plasma treatment procedure to suppress SnZn defects for achieving efficient CZTSSe devices.In-depth investigation results demonstrate that the incorporation of H in Ag-based CZTSSe absorber is expected to improve the poor electrical-conductivity and the low carrier density caused by Ag substitution.Importantly,the C=O and O-H functional groups induced by hydrogen incorporation,serving as an electron donor,can interact with under-coordinated cations in CZTSSe material,effectively passivating the SnZn-related defects.Consequently,the incorporation of an appropriate amount of Ag/H in CZTSSe mitigates carrier non-radiative recombination,prolongs minority carrier lifetime,and thus yields a champion efficiency of 14.74%,showing its promising application in kesterite-based CZTSSe devices.
基金supported by the Science and Technology Innovation Development Program(No.70304901).
文摘Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is considered to be the most potential light-absorbing material to replace CuInGaSe_(2)(CIGS),but the actual photoelectric conversion efficiency of such cells is much lower than that of CIGS.One of the reasons is the high recombination rate of carriers at the interface.In this paper,in order to reduce the carrier recombination,a new solar cell structure with double absorber layers of Al-doped ZnO(AZO)/intrinsic(i)-ZnO/CdS/CZTS_(x1)Se_(1−x1)(CZTSSe_(1))/CZTS_(x2)Se_(1−x2)(CZTSSe_(2))/Mo was proposed,and the optimal conduction band offsets(CBOs)of CdS/CZTSSe_(1) interface and CZTSSe_(1)/CZTSSe_(2) interface were determined by changing the S ratio in CZTSSe_(1) and CZTSSe_(2),and the effect of thickness of CZTSSe_(1) on the performance of the cell was studied.The efficiencies of the optimized single and double absorber layers reached 17.97%and 23.4%,respectively.Compared with the single absorber layer structure,the proposed structure with double absorber layers has better cell performance.
基金supported by the National Natural Science Foundation of China(62474043,62074037,52372183)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ124)+1 种基金Fujian Provincial Natural Science Foundation of China(2024J09015)the Foundation of Fujian Provincial Department of Industry and Information Technology of China(82318075)。
文摘High performances of Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells are heavily influenced by the quality of heterojunctions.Herein,an oxygen(O)doping of CZTSSe/CdS heterojunction is performed to suppress the formation of the defects by an ultraviolet ozone(UV-O_(3))treatment for the efficient flexible CZTSSe solar cells.The introduction of O reduces the non-radiative recombination and increases the carrier concentration of the CdS films.Furthermore,the defect density of the CdS film has been reduced from 8.24×10^(16)to2.91×10^(16)cm^(-3)by the O-doping.The results indicate that the electron transport is effectively promoted due to the decreased conduction band offset(CBO)at the heterojunction interface.As a result,the champion flexible CZTSSe solar cell achieves a power conversion efficiency(PCE)of 11.21%,with a significantly improved short circuit current density.The study for improving the CZTSSe/CdS heterojunction through O-doping treatment provides a new insight for enhancing the PCE of the flexible CZTSSe solar cells.
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.
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.
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。
