Cux（Cu2O）1-x（0.09 x 1.00） granular films with thickness about 280 nm have been fabricated by direct current reactive magnetron sputtering. The atomic ratio x can be controlled by the oxygen flow rate during Cux（C...Cux（Cu2O）1-x（0.09 x 1.00） granular films with thickness about 280 nm have been fabricated by direct current reactive magnetron sputtering. The atomic ratio x can be controlled by the oxygen flow rate during Cux（Cu2O）1-x deposition. Room-temperature ferromagnetism（FM） is found in all of the samples. The saturated magnetization increases at first and then decreases with the decrease of x. The photoluminescence spectra show that the magnetization is closely correlated with the Cu vacancies in the Cux（Cu2O）1-x granular films. Fundamentally, the FM could be understood by the Stoner model based on the charge transfer mechanism. These results may provide solid evidence and physical insights on the origin of FM in the Cu2O-based oxides diluted magnetic semiconductors, especially for systems without intentional magnetic atom doping.展开更多
Copper sulfide thin films are deposited onto different substrates at room temperature using the thermal evaporation technique. X-ray diffraction spectra show that the film has an orthorhombicchalcocite （7-Cu2S） phas...Copper sulfide thin films are deposited onto different substrates at room temperature using the thermal evaporation technique. X-ray diffraction spectra show that the film has an orthorhombicchalcocite （7-Cu2S） phase. The atomic force microscopy images indicate that the film exhibits nanoparticles with an average size of nearly 44 nm. Specrtophotometric measurements for the transmittance and reflectance are carried out at normal incidence in a spectral wavelength range of 450 nm-2500 nm. The refractive index, n, as well as the absorption index, k is calculated. Some dispersion parameters are determined. The analyses of el and e2 reveal several absorption peaks. The analysis of the spectral behavior of the absorption coefficient, c~, in the absorption region reveals direct and indirect allowed transitions. The dark electrical resistivity is studied as a function of film thickness and temperature. Tellier＇s model is adopted for determining the mean free path and bulk resistance.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
Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still h...Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.展开更多
Cu2ZnSn（S,Se）4（CZTSSe） thin film was prepared using a simple two-step approach based on the single-source evaporation and synchronous sulfo-selenization.Composition,microstructure,morphology,and properties of the ...Cu2ZnSn（S,Se）4（CZTSSe） thin film was prepared using a simple two-step approach based on the single-source evaporation and synchronous sulfo-selenization.Composition,microstructure,morphology,and properties of the asprepared CZTSSe thin films were investigated.XRD and Raman patterns confirmed the formation of single-phase CZTSSe solid solutions.SEM results showed that the CZTSSe thin film had a uniform morphology and large grains.EDS results revealed the composition of CZTSSe film was Cu：Zn：Sn：S：Se = 23.7：12.6：12.2：37.7：13.8（in at%）,which was in accordance with the stoichiometric Cu2ZnSn（S,Se）4.The optical band gap of CZTSSe thin film evaluated from its UV–Vis spectrum was 1.33 eV.The resistivity,carrier concentration,and mobility were 0.53 X cm,7.9 9 1018cm3,and 7.5 cm2/（Vs）,respectively.展开更多
One of the most promising near-term applications of high T_c superconductingfilms is in the area of passive microwave devices. The most remarkable feature ofthese microwave devices is that the high-frequency surface r...One of the most promising near-term applications of high T_c superconductingfilms is in the area of passive microwave devices. The most remarkable feature ofthese microwave devices is that the high-frequency surface resistance ofsuperconducting films is smaller than that of metal thin films. The size of themicrowave devices is dictated by wavelength and the thin films are generally requiredto be not smaller than a few square centimeters. Though pulsed laser deposition展开更多
Cu_2ZnSn(S, Se)_4(CZTSSe) thin films were deposited on flexible substrates by three evaporation processes at high temperature. The chemical compositions, microstructures and crystal phases of the CZTSSe thin films wer...Cu_2ZnSn(S, Se)_4(CZTSSe) thin films were deposited on flexible substrates by three evaporation processes at high temperature. The chemical compositions, microstructures and crystal phases of the CZTSSe thin films were respectively characterized by inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscopy(SEM), X-ray diffraction(XRD) and Raman scattering spectrum. The results show that the single-step evaporation method at high temperature yields CZTSSe thin films with nearly pure phase and high Sn-related phases. The elemental ratios of Cu/(Zn+Sn)=1.00 and Zn/Sn=1.03 are close to the characteristics of stoichiometric CZTSSe. There is the smooth and uniform crystalline at the surface and large grain size at the cross section for the films, and no other phases exist in the film by XRD and Raman shift measurement. The films are no more with the Sn-related phase deficiency.展开更多
In or Ga gradients in the Cu(In1-xGax)Se2(CIGS)absorbing layer lead to change the lattice parameters of the absorbing layer,giving rise to the bandgap grading in the absorbing layer which is directly associated with t...In or Ga gradients in the Cu(In1-xGax)Se2(CIGS)absorbing layer lead to change the lattice parameters of the absorbing layer,giving rise to the bandgap grading in the absorbing layer which is directly associated with the degree of absorbing ability of the CIGS solar cell.We tried to characterize the depth profile of the lattice parameters of the CIGS absorbing layer using a glancing incidence X-ray diffraction(GIXRD)technique,and then investigate the bandgap grading of the CIGS absorbing layer.When the glancing incident angle increased from 0.50 to 5.00°,the a and c lattice parameters of the CIGS absorbing layer gradually decreased from 5.7776(3)to 5.6905(2)?,and 11.3917(3)to 11.2114(2)?,respectively.The depth profile of the lattice parameters as a function of the incident angle was consistent with vertical variation in the compositionof In or Ga with depth in the absorbing layer.The variation of the lattice parameters was due to the difference between the ionic radius of In and Ga co-occupying at the same crystallographic site.According to the results of the depth profile of the refined parameters using GIXRD data,the bandgap of the CIGS absorber layer was graded over a range of 1.222-1.532 eV.This approach allows to determine the In or Ga gradients in the CIGS absorbing layer,and to nondestructively guess the bandgap depth profile through the refinement of the lattice parameters using GIXRD data on the assumption that the changes of the lattice parameters or unit-cell volume follow a good approximation to Vegard’s law.展开更多
Cu2ZnSnS4 thin films were prepared by cosputtering with Cu(or Cu2S),ZnS and SnS2 targets in this study.S amount in the precursor of Cu2ZnSnS4 thin film was verified by using Cu or Cu2S target.The effect of S amount in...Cu2ZnSnS4 thin films were prepared by cosputtering with Cu(or Cu2S),ZnS and SnS2 targets in this study.S amount in the precursor of Cu2ZnSnS4 thin film was verified by using Cu or Cu2S target.The effect of S amount in the precursor on the microstructure and element distribution of Cu2ZnSnS4 thin film was discussed.It was found that S content is sufficient in the precursor thin film using Cu2 S instead of Cu target.The microstructure,composition homogeneity,and secondary phase formation of the Cu2ZnSnS4 thin film are seriously affected by S amount in the precursor thin film.Namely,sufficient S can improve the crystallization and orientation of the precursor thin film and enhance the compactness as well as composition homogeneity of the Cu2ZnSnS4 thin film after sulfurization.Moreover,the secondary phase formation in Cu2ZnSnS4 thin film can be greatly inhibited by increasing S content in the precursor thin film.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11104148,51101088,and 51171082)the Tianjin Natural Science Foundation,China(Grant Nos.14JCZDJC37700 and 13JCQNJC02800)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education,China(Grant No.20110031110034)the Fundamental Research Funds for the Central Universities,China
文摘Cux（Cu2O）1-x（0.09 x 1.00） granular films with thickness about 280 nm have been fabricated by direct current reactive magnetron sputtering. The atomic ratio x can be controlled by the oxygen flow rate during Cux（Cu2O）1-x deposition. Room-temperature ferromagnetism（FM） is found in all of the samples. The saturated magnetization increases at first and then decreases with the decrease of x. The photoluminescence spectra show that the magnetization is closely correlated with the Cu vacancies in the Cux（Cu2O）1-x granular films. Fundamentally, the FM could be understood by the Stoner model based on the charge transfer mechanism. These results may provide solid evidence and physical insights on the origin of FM in the Cu2O-based oxides diluted magnetic semiconductors, especially for systems without intentional magnetic atom doping.
文摘Copper sulfide thin films are deposited onto different substrates at room temperature using the thermal evaporation technique. X-ray diffraction spectra show that the film has an orthorhombicchalcocite （7-Cu2S） phase. The atomic force microscopy images indicate that the film exhibits nanoparticles with an average size of nearly 44 nm. Specrtophotometric measurements for the transmittance and reflectance are carried out at normal incidence in a spectral wavelength range of 450 nm-2500 nm. The refractive index, n, as well as the absorption index, k is calculated. Some dispersion parameters are determined. The analyses of el and e2 reveal several absorption peaks. The analysis of the spectral behavior of the absorption coefficient, c~, in the absorption region reveals direct and indirect allowed transitions. The dark electrical resistivity is studied as a function of film thickness and temperature. Tellier＇s model is adopted for determining the mean free path and bulk resistance.
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the National Natural Science Foundation of China(61874159,61974173,51702085,51802081 and 21603058)the Joint Talent Cultivation Funds of NSFC-HN(U1704151)the Science and Technology Innovation Talents in Universities of Henan Province(18HASTIT016)。
文摘Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.
基金financially supported by the National Natural Science Foundation of China (Nos.51275509 and 51175491)
文摘Cu2ZnSn（S,Se）4（CZTSSe） thin film was prepared using a simple two-step approach based on the single-source evaporation and synchronous sulfo-selenization.Composition,microstructure,morphology,and properties of the asprepared CZTSSe thin films were investigated.XRD and Raman patterns confirmed the formation of single-phase CZTSSe solid solutions.SEM results showed that the CZTSSe thin film had a uniform morphology and large grains.EDS results revealed the composition of CZTSSe film was Cu：Zn：Sn：S：Se = 23.7：12.6：12.2：37.7：13.8（in at%）,which was in accordance with the stoichiometric Cu2ZnSn（S,Se）4.The optical band gap of CZTSSe thin film evaluated from its UV–Vis spectrum was 1.33 eV.The resistivity,carrier concentration,and mobility were 0.53 X cm,7.9 9 1018cm3,and 7.5 cm2/（Vs）,respectively.
文摘One of the most promising near-term applications of high T_c superconductingfilms is in the area of passive microwave devices. The most remarkable feature ofthese microwave devices is that the high-frequency surface resistance ofsuperconducting films is smaller than that of metal thin films. The size of themicrowave devices is dictated by wavelength and the thin films are generally requiredto be not smaller than a few square centimeters. Though pulsed laser deposition
基金supported by the National High Technology Research and Development Program of China(No.2012AA050701)the Innovation and Entrepreneurship Training Program for College Students in Tianjin(No.201410060036)
文摘Cu_2ZnSn(S, Se)_4(CZTSSe) thin films were deposited on flexible substrates by three evaporation processes at high temperature. The chemical compositions, microstructures and crystal phases of the CZTSSe thin films were respectively characterized by inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscopy(SEM), X-ray diffraction(XRD) and Raman scattering spectrum. The results show that the single-step evaporation method at high temperature yields CZTSSe thin films with nearly pure phase and high Sn-related phases. The elemental ratios of Cu/(Zn+Sn)=1.00 and Zn/Sn=1.03 are close to the characteristics of stoichiometric CZTSSe. There is the smooth and uniform crystalline at the surface and large grain size at the cross section for the films, and no other phases exist in the film by XRD and Raman shift measurement. The films are no more with the Sn-related phase deficiency.
基金supported by Korea Research Institute of Standards and Science(KRISS–2019–GP2019-0014)。
文摘In or Ga gradients in the Cu(In1-xGax)Se2(CIGS)absorbing layer lead to change the lattice parameters of the absorbing layer,giving rise to the bandgap grading in the absorbing layer which is directly associated with the degree of absorbing ability of the CIGS solar cell.We tried to characterize the depth profile of the lattice parameters of the CIGS absorbing layer using a glancing incidence X-ray diffraction(GIXRD)technique,and then investigate the bandgap grading of the CIGS absorbing layer.When the glancing incident angle increased from 0.50 to 5.00°,the a and c lattice parameters of the CIGS absorbing layer gradually decreased from 5.7776(3)to 5.6905(2)?,and 11.3917(3)to 11.2114(2)?,respectively.The depth profile of the lattice parameters as a function of the incident angle was consistent with vertical variation in the compositionof In or Ga with depth in the absorbing layer.The variation of the lattice parameters was due to the difference between the ionic radius of In and Ga co-occupying at the same crystallographic site.According to the results of the depth profile of the refined parameters using GIXRD data,the bandgap of the CIGS absorber layer was graded over a range of 1.222-1.532 eV.This approach allows to determine the In or Ga gradients in the CIGS absorbing layer,and to nondestructively guess the bandgap depth profile through the refinement of the lattice parameters using GIXRD data on the assumption that the changes of the lattice parameters or unit-cell volume follow a good approximation to Vegard’s law.
基金financially supported by the Foundation of Special Scientific Research Institutes(No.2013EG115002)the Innovation Foundation of General Research Institute for Nonferrous Metals(No.52215).
文摘Cu2ZnSnS4 thin films were prepared by cosputtering with Cu(or Cu2S),ZnS and SnS2 targets in this study.S amount in the precursor of Cu2ZnSnS4 thin film was verified by using Cu or Cu2S target.The effect of S amount in the precursor on the microstructure and element distribution of Cu2ZnSnS4 thin film was discussed.It was found that S content is sufficient in the precursor thin film using Cu2 S instead of Cu target.The microstructure,composition homogeneity,and secondary phase formation of the Cu2ZnSnS4 thin film are seriously affected by S amount in the precursor thin film.Namely,sufficient S can improve the crystallization and orientation of the precursor thin film and enhance the compactness as well as composition homogeneity of the Cu2ZnSnS4 thin film after sulfurization.Moreover,the secondary phase formation in Cu2ZnSnS4 thin film can be greatly inhibited by increasing S content in the precursor thin film.
