Reaction between Cu_2S and Cu_2O was investigated at 1150 to 1250℃.The reaction rate in- creases with the increase of surface area of Cu_2O grains and depends unobviously on temper- ature.At the suggestion of control...Reaction between Cu_2S and Cu_2O was investigated at 1150 to 1250℃.The reaction rate in- creases with the increase of surface area of Cu_2O grains and depends unobviously on temper- ature.At the suggestion of controlling step of reaction rate being oxygen diffusion through the liquid layer along reaction boundaries,two final kinetical equations would be made as follows: x=6.69×10^(-2)At for 0<α<0.74 and ln(l-α)=-A(9.83×10^(-2)t+1.76)for 0.74<α<1,where α is SO_2 evolved in time t and A is surface area of Cu_2O particles.展开更多
The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Re...The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Regulating the adsorption of furfural(FF)and OH^(-)species holds paramount importance in enhancing the overall performance.Herein,we have developed a unique CuO catalyst enriched with oxygen vacancies(O_(v)-CuO)resulting from the electrochemical reconstruction ofα-Cu_(2)S,which demonstrates exceptional FFOR performance,with a conversion of 95.3%,near-perfect selectivity and Faraday efficiency(FE)for furoic acid(FA)at 1.475 V vs.RHE.The study provides detailed comparison of the structural evolution of different sulfide precatalysts and their impact on FFOR.Furthermore,it delves into the structure-activity relationship through a combination of characterization and theoretical calculations.The O_(v)-CuO not only enhances OH^(-)adsorption,changes the rate-determining step,but also reduces the reaction energy barrier toward FFOR.Additionally,a much lower cell voltage is required to coproduce FA and hydrogen in the two-electrode co-electrolysis system.This work would provide valuable insights into the reaction mechanism of FFOR on Cu based catalysts and establish guidelines for designing defective electrocatalysts for biomass conversion.展开更多
The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large ...The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.展开更多
It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple soluti...It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple solution method,and then the effects on the surface properties of the absorber layer,the buffer layer growth,and the modifications of the solar cell performance induced by the Na doping are studied.The surface of the absorber layer is more Cu-depletion and less roughness due to the Na doping.In addition,the contact angle of the surface increases because of Na doping.As a consequence,the thickness of the CdS buffer layer is significantly reduced and the optical losses in the CdS buffer layer are decreased.The difference of quasi-Fermi levels(EFn-EFp) increases with a small amount of Na doping in the CZTSSe solar cell,so that open circuit voltage(VOC) increased significantly.This work offers new insights into the effects of Na doping on CZTSSe via a solution-based approach and provides a deeper understanding of the origin of the efficiency improvement of Na-doped CZTSSe thin film solar cells.展开更多
Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)has attracted considerable attention as a non-toxic and earthabundant solar cell material.During selenization of CZTSSe film at high temperature,the reaction between CZTSSe and Mo...Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)has attracted considerable attention as a non-toxic and earthabundant solar cell material.During selenization of CZTSSe film at high temperature,the reaction between CZTSSe and Mo is one of the main reasons that result in unfavorable absorber and interface quality,which leads to large open circuit voltage deficit(VOC-def)and low fill factor(FF).Herein,a WO_(3)intermediate layer introduced at the back interface can effectually inhibit the unfavorable interface reaction between absorber and back electrode in the preliminary selenization progress;thus high-quality crystals are obtained.Through this back interface engineering,the traditional problems of phase segregation,voids in the absorber and over thick Mo(S,Se)_(2)at the back interface can be well solved,which greatly lessens the recombination in the bulk and at the interface.The increased minority carrier diffusion length,decreased barrier height at back interface contact and reduced deep acceptor defects give rise to systematic improvement in VOCand FF,finally a 12.66%conversion efficiency for CZTSSe solar cell has been achieved.This work provides a simple way to fabricate highly efficient solar cells and promotes a deeper understanding of the function of intermediate layer at back interface in kesterite-based solar cells.展开更多
Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface...Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface and passivate deep level defects in CZTSSe bulk concurrently for improving the performance of flexible device.The results show that In doping effectively inhibits the formation of secondary phase(Cu(S,Se)_(2))and VSndefects.Further studies demonstrate that the barrier height at the back interface is decreased and the deep level defects(Cu_(Sn)defects)in CZTSSe bulk are passivated.Moreover,the carrier concentration is increased and the V_(OC) deficit(V_(OC,def))is decreased significantly due to In doping.Finally,the flexible CZTSSe solar cell with 10.01%power conversion efficiency(PCE)has been obtained.The synergistic strategy of interface modification and bulk defects passivation through In incorporation provides a new thought for the fabrication of efficient flexible kesterite-based solar cells.展开更多
Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handl...Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handling spin-coating method, a thin PCBM([6,6]-phenyl-C61-butyric acid methyl ester) layer as an electron extraction layer has been introduced on the top of CdS buffer layer to modify CZTSSe/CdS/ZnO-ITO(In_(2)O_(3):Sn) interfacial properties. Based on Sn^(4+)/DMSO(dimethyl sulfoxide) solution system, a totalarea efficiency of 12.87% with a VOC of 529 m V has been achieved. A comprehensive investigation on the influence of PCBM layer on carrier extraction, transportation and recombination processes has been carried out. It is found that the PCBM layer can smooth over the Cd S film roughness, thus beneficial for a dense and flat window layer. Furthermore, this CZTSSe/Cd S/PCBM heterostructure can accelerate carrier separation and extraction and block holes from the front interface as well, which is mainly ascribed to the downward band bending of the absorber and a widened space charge region. Our work provides a feasible way to improve the front interfacial property and the cell performance of CZTSSe solar cells by the aid of organic interfacial materials.展开更多
文摘Reaction between Cu_2S and Cu_2O was investigated at 1150 to 1250℃.The reaction rate in- creases with the increase of surface area of Cu_2O grains and depends unobviously on temper- ature.At the suggestion of controlling step of reaction rate being oxygen diffusion through the liquid layer along reaction boundaries,two final kinetical equations would be made as follows: x=6.69×10^(-2)At for 0<α<0.74 and ln(l-α)=-A(9.83×10^(-2)t+1.76)for 0.74<α<1,where α is SO_2 evolved in time t and A is surface area of Cu_2O particles.
基金supported by the Natural Science Foundation of Zhejiang Province(ZCLZ24B0301)the Lhasa Central Government Guiding Local Science and Technology Development Funds(No.LSKJ202458)the National Natural Science Foundation of China(No.22472150)。
文摘The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Regulating the adsorption of furfural(FF)and OH^(-)species holds paramount importance in enhancing the overall performance.Herein,we have developed a unique CuO catalyst enriched with oxygen vacancies(O_(v)-CuO)resulting from the electrochemical reconstruction ofα-Cu_(2)S,which demonstrates exceptional FFOR performance,with a conversion of 95.3%,near-perfect selectivity and Faraday efficiency(FE)for furoic acid(FA)at 1.475 V vs.RHE.The study provides detailed comparison of the structural evolution of different sulfide precatalysts and their impact on FFOR.Furthermore,it delves into the structure-activity relationship through a combination of characterization and theoretical calculations.The O_(v)-CuO not only enhances OH^(-)adsorption,changes the rate-determining step,but also reduces the reaction energy barrier toward FFOR.Additionally,a much lower cell voltage is required to coproduce FA and hydrogen in the two-electrode co-electrolysis system.This work would provide valuable insights into the reaction mechanism of FFOR on Cu based catalysts and establish guidelines for designing defective electrocatalysts for biomass conversion.
基金supported by the National Natural Science Foundation of China(61874159,62074052,61974173,52072327,51702085 and 51802081)the Joint Talent Cultivation Funds of NSFC-HN(U1704151 and U1904192)+1 种基金the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(202101510004)the Science and Technology Innovation Talents in Universities of Henan Province(21HASTIT023)。
文摘The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.
基金supported by the National Key R&D Program of China(2019YFB1503500,2018YFB1500200,2018YEE0203400)the Natural Science Foundation of China(U1902218,11774187)the 111 project(B16027)。
文摘It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple solution method,and then the effects on the surface properties of the absorber layer,the buffer layer growth,and the modifications of the solar cell performance induced by the Na doping are studied.The surface of the absorber layer is more Cu-depletion and less roughness due to the Na doping.In addition,the contact angle of the surface increases because of Na doping.As a consequence,the thickness of the CdS buffer layer is significantly reduced and the optical losses in the CdS buffer layer are decreased.The difference of quasi-Fermi levels(EFn-EFp) increases with a small amount of Na doping in the CZTSSe solar cell,so that open circuit voltage(VOC) increased significantly.This work offers new insights into the effects of Na doping on CZTSSe via a solution-based approach and provides a deeper understanding of the origin of the efficiency improvement of Na-doped CZTSSe thin film solar cells.
基金supported by the National Key R&D Program of China(no.2018YFE0203400)the National Natural Science Foundation of China(no.62074102)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(no.2022A1515010979)the Science and Technology plan project of Shenzhen(nos.JCYJ20190808120001755 and 20220808165025003)。
文摘Kesterite Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)has attracted considerable attention as a non-toxic and earthabundant solar cell material.During selenization of CZTSSe film at high temperature,the reaction between CZTSSe and Mo is one of the main reasons that result in unfavorable absorber and interface quality,which leads to large open circuit voltage deficit(VOC-def)and low fill factor(FF).Herein,a WO_(3)intermediate layer introduced at the back interface can effectually inhibit the unfavorable interface reaction between absorber and back electrode in the preliminary selenization progress;thus high-quality crystals are obtained.Through this back interface engineering,the traditional problems of phase segregation,voids in the absorber and over thick Mo(S,Se)_(2)at the back interface can be well solved,which greatly lessens the recombination in the bulk and at the interface.The increased minority carrier diffusion length,decreased barrier height at back interface contact and reduced deep acceptor defects give rise to systematic improvement in VOCand FF,finally a 12.66%conversion efficiency for CZTSSe solar cell has been achieved.This work provides a simple way to fabricate highly efficient solar cells and promotes a deeper understanding of the function of intermediate layer at back interface in kesterite-based solar cells.
基金supported by the National Natural Science Foundation of China(62074037)the Science and Technology Department of Fujian Province(2020I0006)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ124)。
文摘Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface and passivate deep level defects in CZTSSe bulk concurrently for improving the performance of flexible device.The results show that In doping effectively inhibits the formation of secondary phase(Cu(S,Se)_(2))and VSndefects.Further studies demonstrate that the barrier height at the back interface is decreased and the deep level defects(Cu_(Sn)defects)in CZTSSe bulk are passivated.Moreover,the carrier concentration is increased and the V_(OC) deficit(V_(OC,def))is decreased significantly due to In doping.Finally,the flexible CZTSSe solar cell with 10.01%power conversion efficiency(PCE)has been obtained.The synergistic strategy of interface modification and bulk defects passivation through In incorporation provides a new thought for the fabrication of efficient flexible kesterite-based solar cells.
基金supported by the National Natural Science Foundation of China(U2002216,52172261,51627803,51972332,22075150,and U1902218)the National Key Research and Development Program of China(2019YFE0118100)。
文摘Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handling spin-coating method, a thin PCBM([6,6]-phenyl-C61-butyric acid methyl ester) layer as an electron extraction layer has been introduced on the top of CdS buffer layer to modify CZTSSe/CdS/ZnO-ITO(In_(2)O_(3):Sn) interfacial properties. Based on Sn^(4+)/DMSO(dimethyl sulfoxide) solution system, a totalarea efficiency of 12.87% with a VOC of 529 m V has been achieved. A comprehensive investigation on the influence of PCBM layer on carrier extraction, transportation and recombination processes has been carried out. It is found that the PCBM layer can smooth over the Cd S film roughness, thus beneficial for a dense and flat window layer. Furthermore, this CZTSSe/Cd S/PCBM heterostructure can accelerate carrier separation and extraction and block holes from the front interface as well, which is mainly ascribed to the downward band bending of the absorber and a widened space charge region. Our work provides a feasible way to improve the front interfacial property and the cell performance of CZTSSe solar cells by the aid of organic interfacial materials.
