Influence of absorber copper concentration on the Cu(In,Ga)Se2/(PVD)In2S3 and Cu(In,Ga)Se2/(CBD)CdS based solar cells performance

The present contribution deals with the influence of the copper concentration in Cu(In,Ga)Se₂ (CIGSe) on the solar cells based on CIGSe/(PVD)In₂S₃ and CIGSe/(CBD)CdS. We find that, depending on the buffer layer, the optimum open circuit voltage (Voc) is not reached for the same copper concentration. The values of Voc for the CIGSe/(CBD)CdS solar cells are higher when the copper content is very close to stoichiometry (25%), whereas, the Voc values for CIGSe/(PVD)In₂S₃ solar cells attain their maximum for lower copper contents. On the other hand, contrary to the case of the (CBD)CdS buffer, the Jsc is strongly hindered for the (PVD)In₂S₃ buffered cells when the copper content is lowered. The study has been made for different absorber gallium contents and the evolution is coherent with the presence of a cliff at the CIGSe/(PVD)In₂S₃ interface.     

Investigation of Cu(In,Ga)Se2/In2S3 diffuse interface by Raman scattering

The CIGSe/In₂S₃ interface is known to be highly diffuse because of the migration of Cu from the CIGSe into the In₂S₃. Most of the analytical techniques allowing the determination of composition profiles throughout this interface involve ion etching either during the samples preparation or during data acquisitions. In the present work, we have explored the potential of the Raman scattering for the characterization of such interfaces. This technique is non destructive and provides information on both the composition and the structure of the materials that are probed. Three CIGSe/In₂S₃ structures have been investigated; the parameter varying being the substrate temperature during the In₂S₃ deposition. For the first time we could demonstrate that at high temperature, the CuInS₂ Cu-Au phase is formed at the CIGSe/In₂S₃ interface. Furthermore, the thickness of the ordered defect compound at the CIGSe surface increases with the deposition temperature. All of the new knowledge collected during this work shows the relevance of using the Raman scattering technique for the characterization of the CIGSe/In₂S₃ interface.     

Characterisation of ultrasonically sprayed InxSy buffer layers for Cu(In,Ga)Se2 solar cells

In order to replace chemical bath deposited (CBD) CdS buffer layers in Cu(In,Ga)Se₂ (CIGS) solar cells by an alternative material, In_xS_y thin-film buffer layers were prepared by ultrasonic spray pyrolysis at various substrate temperatures. X-ray Diffraction measurements confirmed that the films contained primarily the tetragonal In₂S₃ phase. X-ray Photoelectron Spectroscopy measurements revealed a small concentration of chlorine impurity throughout the In_xS_y layer. By depositing the indium sulphide layer as buffer layer in the CIGS solar cell configuration, a maximum solar cell efficiency of 8.9% was achieved, whilst the reference cell with CdS/CIGS on a similar absorber exhibited 12.7% efficiency. Additionally, light soaking enhanced the efficiency of In_xS_y/CIGS cells primarily by improvements in fill factor and open circuit voltage.     

Ultrasonically sprayed indium sulfide buffer layers for Cu(In,Ga)(S,Se)2 thin-film solar cells

Indium sulfide layers were grown by an ultrasonic spray pyrolysis method for application in Cu(In,Ga)(S,Se)₂ solar cells. X-ray diffraction measurements of layers on soda lime glass showed polycrystalline In₂S₃ with preferential orientation along the [103] direction and X-ray photoelectron spectroscopy revealed presence or absence of oxygen and chlorine impurities depending on the composition of the spray solution. For more quantitative chemical composition measurements In₂S₃ layers were sprayed on silicon substrates and analyzed with Rutherford backscattering spectrometry. The structural and chemical information on the In₂S₃ layer sprayed with different sulfur concentrations in the chemical precursor solution are correlated to the photovoltaic performance of solar cells. Best cell efficiency of 12.4% was achieved with an ultrasonically sprayed In₂S₃ buffer layer on a Cu(In,Ga)(S,Se)₂ absorber.     

Fast Cu(In,Ga)Se2 precursor growth: Impact on solar cell

In order to reduce the co-evaporation time of Cu(In,Ga)Se₂ (CIGSe) thin film absorber, a sequential approach has been investigated. CIGSe layers have been grown using the three-step based CUPRO (Cu-Poor/Rich/Off) process at substrate temperature of 600 and 500 °C. The first step consists in the growth of Cu-poor ([Cu]/[In + Ga] = 0.9) precursor layers. This paper aims at investigating the impact of this layer deposition duration on the CIGSe and respective solar cell properties. It is observed that for the two substrate temperatures investigated, the morphological and structural properties of the CIGSe layers do not change with increasing precursor deposition speed, even when it is increased by ten. Furthermore, the respective device performance also appears not affected by this reduction of the precursor growth time; all cells demonstrate 15% efficiency. From this work, the duration of our standard deposition process could be decreased from 23 to 14 min without performance loss independently of the substrate temperature.     

Cu(In,Ga)Se2 solar cells with double layered buffers grown by chemical bath deposition

In based mixture In_x(OH,S)_y buffer layers deposited by chemical bath deposition technique are a viable alternative to the traditional cadmium sulfide buffer layer in thin film solar cells. We report on the results of manipulating the absorber/buffer interface between the chalcopyrite Cu(In,Ga)Se₂ (CIGS) absorber and CdS or ZnS buffer by addition of a thin In based mixture layer. It is shown that the presence of thin In_x(OH,S)_y at the CIGS absorber/CdS or ZnS buffer interfaces greatly improve the solar cell performances. The performances of CIGS cells using dual buffer layers composed of In_x(OH,S)_y/CdS or In_x(OH,S)_y/ZnS increased by 22.4% and 51.6%, as compared to the single and standard CdS or ZnS buffered cells, respectively.     

Influence of sodium compounds at the Cu(In,Ga)Se2/(PVD)In2S3 interface on solar cell properties

The present contribution deals with indium sulfide buffer layers grown by thermal co-evaporation of elemental indium and sulfur. It has been found necessary to deposit these buffer layers at low substrate temperatures in order to reach V_oc values similar to those with (CBD)CdS. However, such deposition conditions lead to the formation of a highly recombinative Cu(In,Ga)Se₂/indium sulfide interface. This behaviour may be associated to the presence of sodium carbonates/oxides at the interface even though the Cu(In,Ga)Se₂ surface was cleaned in NH₃ (1 M, room temperature) prior to the indium sulfide deposition. An explanation is that, despite the chemical etch, sodium carbonates/oxides remain in the air exposed Cu(In,Ga)Se₂ grain boundaries and can migrate towards the surface when the Cu(In,Ga)Se₂ is heated under vacuum. These polluted interface areas act as recombination zones and thus inferior devices. A possibility to improve the device performance (i.e. improve the interface quality) is to sulfurize the remaining sodium carbonates/oxides. The resulting Na₂S can then leave the interface by formation of a solid solution with the indium sulfide. By adapting the buffer layer deposition process, 13.3% efficiency devices with co-evaporated indium sulfide are realized, performance which is close to that reached with (CBD)CdS.     

Performance of CuIn1 − xGaxSe2/(PVD)In2S3 solar cells versus gallium content

The present work studies the influence of the Ga content (x = Ga / (Ga + In)) in the absorber on the solar cell performance for devices using (PVD)In₂S₃-based buffers. Input to the hypothesis of the relative conduction band positions can be found in the evolution of the device parameters with x. For experiments with x between 0 and 0.5 devices using (PVD)In₂S₃-based buffers are compared to reference devices using (CBD)CdS. Both buffers give similar cell characteristics for narrow band gap absorbers, typically E_gCIGSe < 1.1 eV. However, the parameters of the cells buffered with (PVD)In₂S₃ are degraded when the absorber gap is widened whereas (CBD)CdS reference devices are only slightly affected. Consequently, the solar cell efficiency is similar for both buffer layers at the lower x values and increases with x only in the case of (CBD)CdS. These evolutions are coherent with the existence of a conduction band cliff at the CIGSe/(PVD)In₂S₃ interface.     

Structural and chemical analyses of sputtered InxSy buffer layers in Cu(In,Ga)Se2 thin-film solar cells

Sputtered In_xS_y layers deposited on borosilicate glass and Si at substrate temperatures ranging from about 60 °C to 340 °C were analyzed by means of X-ray diffraction, energy-dispersive X-ray spectrometry, and optical transmission and reflection measurements. With increasing substrate temperature, the In_xS_y layers exhibit increasing sulfur concentration and also increasing absorption-edge energies. In_xS_y layers on Cu(In,Ga)Se₂(CIGS)/Mo/glass stacks were additionally studied by scanning and transmission electron microscopy. With increasing substrate temperature, Cu, Ga, and In interdiffusion between CIGS and In_xS_y becomes more enhanced. At 340 °C, CuIn₅S₈ forms instead of In_xS_y. The CuIn₅S₈ formation at elevated temperatures may be the reason for the very low efficiency of solar cells with indium sulfide buffers deposited at temperatures above about 250 °C by various techniques.     

Effect of precursor structure on Cu(InGa)Se2 formation by reactive annealing

Precursor structures of Mo/CuGa/In, Mo/In/CuGa, Mo/In/CuGa/In and Mo/CuGaIn were prepared on thin sodium-free glass by the sputtering of CuGa and In targets. In-situ phase evolution of precursors with temperature was investigated by a high-temperature X-ray diffraction system, which verified the existence and transformation of several intermetallics: Cu₂In, Cu₁₁In₉, Cu₃Ga, Cu₇In₃, Cu₉Ga₄ and Cu₁₆In₉ as well as elemental In. MoSe₂ layers produced during selenization were detected by scanning electron microscope and X-ray diffraction, with their thicknesses varying by precursor structure. Adhesion strength of Cu(InGa)Se₂ to each Mo layer was assessed by applying CdS chemical bath deposition process to each sample.     

Effect of copper-deficiency on multi-stage co-evaporated Cu(In,Ga)S2 absorber layers and solar cells

Solar cell absorber films of Cu(In,Ga)S₂ have been fabricated by multi-stage co-evaporation resulting in compositional ratios [Cu]/([In] + [Ga]) = 0.93-0.99 and [Ga]/([In] + [Ga]) = 0.15. Intentional doping is provided by sodium supplied from NaF precursor layers of different thicknesses. Phases, structure and morphology of the resulting films are investigated by X-ray diffraction (XRD) and scanning electron microscopy. The XRD patterns show CuIn₅S₈ thiospinel formation predominantly at the surface in order to accommodate decreasing Cu content. Correlated with the CuIn₅S₈ formation, a Ga-enrichment of the chalcopyrite phase is seen at the surface. Since no CuS layer is present on the as-deposited films, functioning solar cells with CdS buffer and ZnO window layers were fabricated without KCN etch. The open-circuit voltage of solar cells correlates with the copper content and with the amount of sodium supplied. The highest efficiency cell (open-circuit voltage 738 mV, short-circuit current 19.3 mA/cm², fill factor 65%, efficiency 9.3%) is based on the absorber with the least Cu deficiency, [Cu]/([In] + [Ga]) = 0.99. The activation energy of the diode saturation current density of such a cell is extracted from temperature- and illumination-dependent current-voltage measurements. A value of 1.04 eV, less than the band gap, suggests the heterojunction interface as the dominant recombination zone, just as in cells based on Cu-rich grown Cu(In,Ga)S₂.     

Near-interface doping by ion implantation in Cu(In,Ga)Se2 solar cells

Cu(In,Ga)Se₂ absorber layers were implanted with 20 keV Cd ions in order to investigate the influence of changes in the near-interface doping profile. Modifications in this region are shown by AMPS-1D simulations to have substantial impact on solar cell properties. Ion implantation and subsequent thermal annealing steps were monitored by SIMS measurements to control the thermal diffusion of the dopant. Solar cells both with and without CdS buffer layer were made from the implanted absorbers and characterized by j-V and EQE measurements. These experimental results in conjunction with simulations of the quantum efficiency show that a well-defined type-inversion of the implanted layer can be achieved by low-energy ion implantation.     

Microstructural characterization of Cu-poor Cu (In, Ga)Se2 surface layer

Grazing incidence X-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX) are combined to investigate the microstructure and chemical composition of the surface layer in Cu(In, Ga)Se₂ (CIGS) thin films deposited using a three-stage co-evaporation process. According to the GIXRD and micro-region electron diffraction analyses, ordered defect chalcopyrite (ODC) structure does not exist in the surface layer and the surface and the bulk region of the CIGS film have the similar crystal structure. However, the results from the EDX data show that the compositional ratios of the Cu/(In + Ga) (Cu/III) have a gradient distribution across the whole surface layer. The surface layer shows a Cu-poor compositional characteristics and the Cu content increases gradually from the surface to the bulk of the material. The compositional depth profiles determined by XPS agree very well with the results of the EDX measurements. The thickness of the surface layer has been determined to be about 50-100 nm in consistence with that estimated from the compositional ratio of Cu/III. High density dislocations have been observed in the surface region of these samples by high resolution TEM analyses. Our results suggest that different compositions would induce different point defects in the surface layer.     

Preparation and visible-light photocatalytic activity of In2S3/TiO2 composite

A novel In₂S₃/TiO₂ composite with visible-light photocatalytic activity was prepared by a chemical precipitation method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope and UV–vis diffuse reflectance spectroscopy. Under both UV- and visible-light irradiation, the In₂S₃/TiO₂ composite shows good photocatalytic activity to degrade methyl orange, ascribed to the absorption of visible light by In₂S₃ sensitizer and enhanced separation of photoinduced electron–hole pairs in the composite semiconductors.     

Evaluation of electron beam induced current profiles of Cu(In,Ga)Se2 solar cells with different Ga-contents

The measurement of electron beam induced current profiles in junction configuration (JEBIC) is a settled method for several semiconductor devices. We discuss the JEBIC method in the light of the special conditions present in the case of thin film Cu(In,Ga)Se₂ solar cells.Our previously published results indicate that the charge state of defects close to or at the Cu(In,Ga)Se₂/CdS interface depends on the minority carrier distribution, which changes strongly during a scan of the cross section with an electron beam. The charge distribution influences the electrostatic potential and therewith the collection of minority carriers.Here, we present an evaluation method of JEBIC profiles that accounts for this effect. Monte Carlo simulations of the carrier generation help us to consider in detail the influence of surface recombination. We determine the diffusion length, space charge width, surface- and back contact recombination velocity of Cu(In_(1-r),Ga_r)Se₂ devices with different Ga-contents r from JEBIC line scans.     

Cu2ZnSnS4 solar cell prepared entirely by non-vacuum processes

Cu₂ZnSnS₄ (CZTS) solar cell with superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/CZTS/Carbon was prepared entirely by non-vacuum processes. The compact TiO₂ window and In₂S₃ buffer layers, CZTS absorber layer and Carbon electrode layer were prepared by spray pyrolysis method, ball milling and screen printing combination processes and screen printing process, respectively. The short-circuit current density, open-circuit voltage, fill factor and conversion efficiency of the best fabricated solar cell are 8.76 mA/cm², 250 mV, 0.27 and 0.6%, respectively. The fabrication process for the CZTS solar cell did not employ any vacuum conditions or high-toxic materials (such as CdS, H₂Se, H₂S or Se).     

Interpretation of quasi-Fermi level splitting in Cu(Ga,In)Se2-absorbers by confocally recorded spectral luminescence and numerical modeling

Spectral room temperature photoluminescence (pl) of polycrystalline Cu(In,Ga)Se₂ films (CIGSe) is evaluated with respect to optoelectronic properties and in particular for the determination of the splitting of quasi-Fermi levels (E_Fn − E_Fp). For lateral resolution of ≤ 1 µm a confocal pl-setup is used. The depth profile of the excess carrier densities determining the rates of radiative transitions strongly govern the spectral pl-shape which has been numerically modeled with a matrix transfer formalism. In this optical approach we discriminate for wave propagation and attenuation in a multilayer system between a plane-wave ansatz and a 3D-spherical formalism, depending on excitation area large or small/similar compared to the thickness of the absorber. In both cases re-absorption of photons in energetic regimes with absorption approaches unity, from which the splitting of the quasi-Fermi levels is preferentially deduced, substantially influence the spectral luminescence signal. For heterojunctions usually located at the light entrance side of the device our evaluation with good agreement reflects (E_Fn − E_Fp) in the vicinity of the barrier and thus indicates the maximum achievable open circuit voltage of the finally processed diode. Departures of the spectral pl from the idealized Bose-term signalize unfavorable carrier profiles and a depth dependence of optoelectronic absorber properties.     

Time-resolved photoluminescence in Cu(In,Ga)Se2 thin films and solar cells

Room temperature time-resolved photoluminescence (TR-PL) measurements have been performed on Cu(In,Ga)Se₂ (CIGS) thin films and solar cells to clarify the recombination process of the photo-generated minority carrier. Both films and solar cells exhibited PL decay curves composed of the dominant fast (0.7-2 ns) and weak slow (3-10 ns) exponential decay curves. PL lifetime of the cell is longer than that of the thin films, indicating the longer minority carrier lifetime for the hetero-structures than in thin films. The increase of PL lifetime is consistent with the enhancement of the PL intensity and the elimination of defect-related PL as a result of the solar cell formation. These results are discussed in terms of the recombination process of carriers in films and hetero-structures. The relationship between the PL lifetime of the CIGS solar cells and the cell conversion efficiency is described.     

The reaction mechanism of the spray Ion Layer Gas Reaction process to deposit In2S3 thin films

The spray Ion Layer Gas Reaction (ILGAR) is a well-established, patented and commercial process used primarily to deposit In₂S₃ as buffer layers in thin film solar cells. In this paper we investigate the growth mechanism of the spray In₂S₃ ILGAR process by characterising the intermediate growth stages of films, following the growth mechanism with a quartz crystal microbalance and tracking the gaseous side-and-intermediate products during film growth, using a mass spectrometer. A basic growth mechanism model is then proposed based on an aerosol assisted chemical vapour deposition of an In(O_x,Cl_y,(OH)_z) film, as the first stage process, followed by the conversion of the intermediate film using H₂S gas to In₂S₃.     

Solvothermal synthesis of In(OH)3 nanorods and their conversion to In2O3

In this work, we demonstrate that monodisperse indium hydroxide (In(OH)₃) nanorods constructed with parallel wire-like subunits have been fabricated via a acrylamide-assisted synthesis route without any template. NH₃ from the hydrolysis of acrylamide acts as the OH⁻ provider. The structure and morphology of as-prepared products have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis (TG). A detailed mechanism has been proposed on the basis of time-dependent experimental results. Furthermore, by annealing In(OH)₃ precursors at 500 °C for 3 h in air, In₂O₃ samples were obtained with the designed morphology.