Thin films of copper indium gallium selenide Cu（In,Ga）Se2 （CIGS） were prepared by sequential elemental layer deposition in vacuum at room temperature. The as-deposited films were heated in vacuum for compound form...Thin films of copper indium gallium selenide Cu（In,Ga）Se2 （CIGS） were prepared by sequential elemental layer deposition in vacuum at room temperature. The as-deposited films were heated in vacuum for compound formation, and were studied at temperature as high as 1250℃ for the first time. These films were concurrently studied for their structural properties by X-ray diffraction （XRD） technique. The XRD analyses include phase transition studies, grain size variation and microstrain measurements with the reaction temperature and time.It has been observed that there are three distinct regions of variation in all these parameters. These regions belong to three temperature regimes： 〈450℃, 450-950℃, and 〉950℃. It is also seen that the compound formation starts at 250℃, with ternary phases appearing at 350℃ or above. Whereas, there is another phase shift at 950℃ without any preference to the quaternary compound.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
High Ga content Cu(In,Ga)Se2 thin films incorporated sulfur were prepared by sequential evaporation from CuGaSe2 and CuInSe2 ternary compounds and subsequently Ga2Se3, In2Se3 and In2S3 binary compounds. The In2S3/(Ga2...High Ga content Cu(In,Ga)Se2 thin films incorporated sulfur were prepared by sequential evaporation from CuGaSe2 and CuInSe2 ternary compounds and subsequently Ga2Se3, In2Se3 and In2S3 binary compounds. The In2S3/(Ga2Se3+ In2Se3) ratio was varied from 0 to 0.13, and the properties of the thin films were investigated. XRD studies demonstrated that the prepared thin films had a chalcopyrite Cu(In,Ga)Se2 structure. The S/(Se+S) mole ratio in the thin films was within the range from 0 to 0.04. The band gaps of Cu(In,Ga)Se2 thin films increased from 1.30 eV to 1.59 eV with increasing the ?In2S3 /(Ga2Se3+ In2Se3) ratio.展开更多
Polycrystalline CuGaSe2 thin films on Mo-coated soda-lime glass substrates have been synthesized by coevaporation process from Cu, Ga and Se sources. Structural and electrical properties of the as-grown CuGaSe2 films ...Polycrystalline CuGaSe2 thin films on Mo-coated soda-lime glass substrates have been synthesized by coevaporation process from Cu, Ga and Se sources. Structural and electrical properties of the as-grown CuGaSe2 films strongly depend on the film composition. Stoichiometric CuGaSe2 is fabricated, as indicated by x-ray diffraction spectroscope （XRD） and x-ray fluorescence （XRF）. A two-phase region is composed of CuGaSe2 and Cu2-xSe phases for Cu-rich films, and CuGaSe2 and CuGa3Se5 phases for Ga-rich films, respectively. Morphological properties are detected by scanning electron microscope （SEM） for various compositional films, the grain sizes of the CuGaSe2films decrease with the extent of deviation from stoichiometric composition. Raman spectroscopy of Cu-rich samples shows that there exist large Cu-Se particles on the film surface. The results from Hall effect measurements for typical samples indicate that CuGaSe2 films are always of p-type semiconductor from Cu-rich to Ga-rich. Stoichiometric CuGaSe2 films exhibit relatively large mobility than any other compositional films. Finally, polycrystalline CuGaSe2 thin film solar cell with a best conversion efficiency of 6.02% has been achieved under the standard air mass （AM）1.5 spectrum for 100mW/cm^2 at room temperature （aperture area, 0.24cm^2）. The open circuit voltage of the CuGaSe2 solar cells is close to770 mV.展开更多
Cu(In, Al)Se2 thin films were prepared by electrodeposition from the aqueous solution consisting of CuCl2, InCl3, AlCl3 and SeO2 onto ITO coated glass substrates. The as-deposited films were annealed under vacuum for ...Cu(In, Al)Se2 thin films were prepared by electrodeposition from the aqueous solution consisting of CuCl2, InCl3, AlCl3 and SeO2 onto ITO coated glass substrates. The as-deposited films were annealed under vacuum for 30 min at temperature ranging between 200°C and 400°C. The structural, composition, morphology, optical band gap and electrical resistivity of elaborated thin films were studied, respectively using x-ray diffraction, energy dispersive analysis of x-ray, scanning electron microscopy, UV spectrophotometer and four-point probe method. The lattice constant and structural parameters viz. crystallite size, dislocation density and strain of the films were also calculated. After vacuum annealing, x-ray diffraction results revealed that all films were polycrystalline in nature and exhibit chalcopyrite structure with (112) as preferred orientation. The film annealed at 350°C showed the coexistence of CIASe and InSe phases. The average crystallite size increases linearly with annealing temperature, reaching a maximum value for 350°C. The films show a direct allowed band gap which increases from 1.59 to 1.78 eV with annealing temperature. We have also found that the electrical resistivity of films is controlled by the carrier concentration rather than by their mobility.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
We present a self-assembly method to prepare array nano-wires of colloidal CdSe quantum dots on a substrate of porous Al2 O3 film modified by gold nanoparticles. The photoluminescence(PL) spectra of nanowires are in s...We present a self-assembly method to prepare array nano-wires of colloidal CdSe quantum dots on a substrate of porous Al2 O3 film modified by gold nanoparticles. The photoluminescence(PL) spectra of nanowires are in situ measured by using a scanning near-field optical microscopy(SNOM) probe tip with 100-nm aperture on the scanning near-field optical microscope. The results show that the binding sites from the edge of porous Al2 O3 nanopores are combined with the carboxyl of CdSe quantum dots’ surface to form an array of CdSe nanowires in the process of losing background solvent because of the gold nanoparticles filling the nano-holes of porous Al2 O3 film. Compared with the area of nonself-assembled nano-wire, the fluorescence on the Al2 O3/Au/CdSe interface is significantly enhanced in the self-assembly nano-wire regions due to the electron transfer conductor effect of the gold nanoparticles’ surface. In addition, its full width at half maximum(FWHM) is also obviously widened. The method of enhancing fluorescence and energy transfer can widely be applied to photodetector, photocatalysis, optical display, optical sensing, and biomedical imaging, and so on.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
Reducing the manufacturing cost of solar cells is necessary to their industrial production. Electrodepositing is an effective, non-vacuum method which is very suitable for cutting the manufacturing cost of thin films ...Reducing the manufacturing cost of solar cells is necessary to their industrial production. Electrodepositing is an effective, non-vacuum method which is very suitable for cutting the manufacturing cost of thin films as well as developing its large-scale industrial production. In this study, about 1-μm-thick Cu（In,Ga）Se2（CIGS） precursors were electrodeposited on Mo/glass substrates in aqueous solution utilizing a three-electrode potentiostatic system.Triethanolamine was used as complexing agent, and all parameters of electrodeposition were precisely controlled.After that, the electrodeposited precursors were selenized in a Se atmosphere with different heating ramp rates（60 and 600℃·min^（-1））. High-quality CIGS films were obtained, and their characteristics were investigated by X-ray fluorescence, scanning electron microscopy, energydispersive spectroscopy, X-ray diffraction, Raman spectra and near-infrared-visible（NIR-Vis） spectra. The results reveal that there are many differences between the properties of the films under different heating rates. Finally,CIGS solar cells were fabricated using a fast and a slow heating rate. The maximum efficiencies achieved for the films selenized at 60 and 600℃-min^（-1） are 3.15% and 0.71%, respectively.展开更多
In this paper, several structures for multilayer Cu(In1-xGax) Se2 (CIGS) thin film solar cells are proposed to achieve high conversion efficiency. All of the modeling and simulations were based on the actual data of e...In this paper, several structures for multilayer Cu(In1-xGax) Se2 (CIGS) thin film solar cells are proposed to achieve high conversion efficiency. All of the modeling and simulations were based on the actual data of experimentally produced CIGS cells reported in the literature. In standard CIGS cells with a single absorber layer, the effects of acceptor density and Ga content on device performance were studied, and then optimized for maximum conversion efficiency. The same procedure was performed for cells with two and three sectioned CIGS absorber layers in which Cu and/or Ga contents were varied within each consecutive section. This produces an internal additional electric field within the absorber layer, which resulted in an increase in carrier collection for longer wavelength photons, and hence, improvement in the conversion efficiency of the cell. An increase of approximately 3% in efficiency is predicted for cells with two layer absorbers. For multilayer cells in which Cu and Ga distribution were stepped simultaneously, the improvement could be approximately 3.5%. This improvement is due to; enhanced carrier collection for longer-wavelength photons, and reduced recombination at the heterojunction and back regions of the cell. These results are confirmed by the physics of the cells.展开更多
文摘Thin films of copper indium gallium selenide Cu（In,Ga）Se2 （CIGS） were prepared by sequential elemental layer deposition in vacuum at room temperature. The as-deposited films were heated in vacuum for compound formation, and were studied at temperature as high as 1250℃ for the first time. These films were concurrently studied for their structural properties by X-ray diffraction （XRD） technique. The XRD analyses include phase transition studies, grain size variation and microstrain measurements with the reaction temperature and time.It has been observed that there are three distinct regions of variation in all these parameters. These regions belong to three temperature regimes： 〈450℃, 450-950℃, and 〉950℃. It is also seen that the compound formation starts at 250℃, with ternary phases appearing at 350℃ or above. Whereas, there is another phase shift at 950℃ without any preference to the quaternary compound.
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.
文摘High Ga content Cu(In,Ga)Se2 thin films incorporated sulfur were prepared by sequential evaporation from CuGaSe2 and CuInSe2 ternary compounds and subsequently Ga2Se3, In2Se3 and In2S3 binary compounds. The In2S3/(Ga2Se3+ In2Se3) ratio was varied from 0 to 0.13, and the properties of the thin films were investigated. XRD studies demonstrated that the prepared thin films had a chalcopyrite Cu(In,Ga)Se2 structure. The S/(Se+S) mole ratio in the thin films was within the range from 0 to 0.04. The band gaps of Cu(In,Ga)Se2 thin films increased from 1.30 eV to 1.59 eV with increasing the ?In2S3 /(Ga2Se3+ In2Se3) ratio.
基金Project supported by the National High Technology Joint Research Program of China (Grant No 2004AA513020)
文摘Polycrystalline CuGaSe2 thin films on Mo-coated soda-lime glass substrates have been synthesized by coevaporation process from Cu, Ga and Se sources. Structural and electrical properties of the as-grown CuGaSe2 films strongly depend on the film composition. Stoichiometric CuGaSe2 is fabricated, as indicated by x-ray diffraction spectroscope （XRD） and x-ray fluorescence （XRF）. A two-phase region is composed of CuGaSe2 and Cu2-xSe phases for Cu-rich films, and CuGaSe2 and CuGa3Se5 phases for Ga-rich films, respectively. Morphological properties are detected by scanning electron microscope （SEM） for various compositional films, the grain sizes of the CuGaSe2films decrease with the extent of deviation from stoichiometric composition. Raman spectroscopy of Cu-rich samples shows that there exist large Cu-Se particles on the film surface. The results from Hall effect measurements for typical samples indicate that CuGaSe2 films are always of p-type semiconductor from Cu-rich to Ga-rich. Stoichiometric CuGaSe2 films exhibit relatively large mobility than any other compositional films. Finally, polycrystalline CuGaSe2 thin film solar cell with a best conversion efficiency of 6.02% has been achieved under the standard air mass （AM）1.5 spectrum for 100mW/cm^2 at room temperature （aperture area, 0.24cm^2）. The open circuit voltage of the CuGaSe2 solar cells is close to770 mV.
文摘Cu(In, Al)Se2 thin films were prepared by electrodeposition from the aqueous solution consisting of CuCl2, InCl3, AlCl3 and SeO2 onto ITO coated glass substrates. The as-deposited films were annealed under vacuum for 30 min at temperature ranging between 200°C and 400°C. The structural, composition, morphology, optical band gap and electrical resistivity of elaborated thin films were studied, respectively using x-ray diffraction, energy dispersive analysis of x-ray, scanning electron microscopy, UV spectrophotometer and four-point probe method. The lattice constant and structural parameters viz. crystallite size, dislocation density and strain of the films were also calculated. After vacuum annealing, x-ray diffraction results revealed that all films were polycrystalline in nature and exhibit chalcopyrite structure with (112) as preferred orientation. The film annealed at 350°C showed the coexistence of CIASe and InSe phases. The average crystallite size increases linearly with annealing temperature, reaching a maximum value for 350°C. The films show a direct allowed band gap which increases from 1.59 to 1.78 eV with annealing temperature. We have also found that the electrical resistivity of films is controlled by the carrier concentration rather than by their mobility.
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Project supported by the National Natural Science Foundation of China(Grant Nos.61741505 and 61865002)the Guizhou Provincial Science and Technology Support Plan,China(Grant No QKHZ [2017]2887)+3 种基金the Guiding Local Science and Technology Development Plan of the Central Government of China(Grant No.QKZYD [2017]4004)the Guizhou Province Education and Teaching Reform for Graduate Student(Grant No.QJYH-JG [2016]15)the Guizhou University Introduces Talent Projects,China(Grant No.2016002)the Talents of Guizhou Municipal Science and Technology Cooperation Platform,China(Grant No.[2018]5781)
文摘We present a self-assembly method to prepare array nano-wires of colloidal CdSe quantum dots on a substrate of porous Al2 O3 film modified by gold nanoparticles. The photoluminescence(PL) spectra of nanowires are in situ measured by using a scanning near-field optical microscopy(SNOM) probe tip with 100-nm aperture on the scanning near-field optical microscope. The results show that the binding sites from the edge of porous Al2 O3 nanopores are combined with the carboxyl of CdSe quantum dots’ surface to form an array of CdSe nanowires in the process of losing background solvent because of the gold nanoparticles filling the nano-holes of porous Al2 O3 film. Compared with the area of nonself-assembled nano-wire, the fluorescence on the Al2 O3/Au/CdSe interface is significantly enhanced in the self-assembly nano-wire regions due to the electron transfer conductor effect of the gold nanoparticles’ surface. In addition, its full width at half maximum(FWHM) is also obviously widened. The method of enhancing fluorescence and energy transfer can widely be applied to photodetector, photocatalysis, optical display, optical sensing, and biomedical imaging, and so on.
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.
基金financially supported by the National High Technology Research and Development Program of China(No.2015AA034201)the National Natural Science Foundation of China(No.11474355)the Chinese Universities Scientific Fund(No.2017LX002)
文摘Reducing the manufacturing cost of solar cells is necessary to their industrial production. Electrodepositing is an effective, non-vacuum method which is very suitable for cutting the manufacturing cost of thin films as well as developing its large-scale industrial production. In this study, about 1-μm-thick Cu（In,Ga）Se2（CIGS） precursors were electrodeposited on Mo/glass substrates in aqueous solution utilizing a three-electrode potentiostatic system.Triethanolamine was used as complexing agent, and all parameters of electrodeposition were precisely controlled.After that, the electrodeposited precursors were selenized in a Se atmosphere with different heating ramp rates（60 and 600℃·min^（-1））. High-quality CIGS films were obtained, and their characteristics were investigated by X-ray fluorescence, scanning electron microscopy, energydispersive spectroscopy, X-ray diffraction, Raman spectra and near-infrared-visible（NIR-Vis） spectra. The results reveal that there are many differences between the properties of the films under different heating rates. Finally,CIGS solar cells were fabricated using a fast and a slow heating rate. The maximum efficiencies achieved for the films selenized at 60 and 600℃-min^（-1） are 3.15% and 0.71%, respectively.
文摘In this paper, several structures for multilayer Cu(In1-xGax) Se2 (CIGS) thin film solar cells are proposed to achieve high conversion efficiency. All of the modeling and simulations were based on the actual data of experimentally produced CIGS cells reported in the literature. In standard CIGS cells with a single absorber layer, the effects of acceptor density and Ga content on device performance were studied, and then optimized for maximum conversion efficiency. The same procedure was performed for cells with two and three sectioned CIGS absorber layers in which Cu and/or Ga contents were varied within each consecutive section. This produces an internal additional electric field within the absorber layer, which resulted in an increase in carrier collection for longer wavelength photons, and hence, improvement in the conversion efficiency of the cell. An increase of approximately 3% in efficiency is predicted for cells with two layer absorbers. For multilayer cells in which Cu and Ga distribution were stepped simultaneously, the improvement could be approximately 3.5%. This improvement is due to; enhanced carrier collection for longer-wavelength photons, and reduced recombination at the heterojunction and back regions of the cell. These results are confirmed by the physics of the cells.
