CuGaSe2 Thin Film Research Articles

Homogeneous CuGaSe2 growth by the CuPRO process with In-Situ AgBr treatment

Homogeneous CuGaSe2 thin film growth is limited by slow kinetics of formation. A modified growth process was previously developed to address this issue but requires two separate long, high temperature anneals. Here, we demonstrate that a short AgBr treatment can replace this modified growth process. The AgBr works as a transport agent to catalyze CuGaSe2 formation and atomic mobility. This treatment results in large grains with homogeneous composition through the bulk. Solar cells made with this material show better performance.

Polycrystalline CuGaSe2 thin film growth and photovoltaic devices fabricated on alkali-free and alkali-containing substrates

Abstract Polycrystalline thin films of ternary CuGaSe2 (CGS), which are one of the potential materials for wide-gap top cells in tandem structure photovoltaic devices, are grown on alkali-free and alkali-containing substrates. The effects of alkali-metals on CGS film morphology, grain size, and photovoltaic device properties are studied. High temperature (>600 °C) growth of CGS films is also investigated with a focus upon variations in alkali-metal distribution profiles in CGS films and the formation of a surface Cu-deficient layer (CDL), which plays an important role in p-n junction formation. The use of a high growth temperature is effective in realizing large grain sizes due to enhanced elemental migration during growth, whereas the formation of a surface CDL is diminished and the alkali-distribution profiles in CGS films are modified resulting in a decrease in carrier density. It is suggested that large CGS grain sizes contribute to obtaining high photocurrent values, but coping with modifications in surface/interface and carrier density with alkali-metals is important to enhance overall photovoltaic performance.

Fabrication of wide band-gap CuGaSe2 solar cells for tandem device applications by sputtering from a ternary target and post selenization treatment

Fabrication of wide band-gap (Eg) CuGaSe2 (CGSe) thin film solar cells with large area uniformity and good reproducibility is difficult, which is crucial for tandem cells. In this work, a method was proposed and investigated to overcome this problem. CGSe solar cells were fabricated by sputtering from a ternary CGSe target and post selenization treatment at different temperatures. After selenization, the CGSe grains grow up gradually, and the copper-poor and selenium-rich CGSe absorbers are obtained successfully. The X-ray diffraction peaks are all corresponded to CGSe phase. As the temperature increases from 530 to 570 °C, the average efficiency increases from 1.57% to 3.11%. When the temperature reaches 590 °C, the efficiency drops to 2.38%. The champion device obtained at 570 °C shows an Eg of 1.66 eV and an efficiency of 3.21%, which indicates the potential for the top cell in tandem solar cells.

Characterization of Defect Properties in Wide-Gap CuGaSe2 Thin-Film Solar-Cells

Characterization of Defect Properties in Wide-Gap CuGaSe₂ Thin-Film Solar-Cells

Electrodeposition of CuGaSe2 and CuGaS2 thin films for photovoltaic applications

CuGaSe2 and CuGaS2 polycrystalline thin film absorbers were prepared by one-step electrodeposition from an aqueous electrolyte containing CuCl2, GaCl3 and H2SeO3. The pH of the solution was adjusted to 2.3 by adding HCl and KOH. Annealing improved crystallinity of CuGaSe2 and further annealing in sulphur atmosphere was required to obtain CuGaS2 layers. The morphology, topography, chemical composition and crystal structure of the deposited thin films were analysed by scanning electron microscopy, atomic force microscopy, energy dispersive spectroscopy and X-ray diffraction, respectively. X-Ray diffraction showed that the as-deposited CuGaSe2 film exhibited poor crystallinity, but which improved dramatically when the layers were annealed in forming gas atmosphere for 40 min. Subsequent sulphurization of CuGaSe2 films was performed at 400 °C for 10 min in presence of molecular sulphur and under forming gas atmosphere. The effect of sulphurization was the conversion of CuGaSe2 into CuGaS2. The formation of CuGaS2 thin films was evidenced by the shift observed in the X-ray diffraction pattern and by the blue shift of the optical bandgap. The bandgap of CuGaSe2 was found to be 1.66 eV, while for CuGaS2 it raised up to 2.2 eV. A broad intermediate absorption band associated to Cr and centred at 1.63 eV was observed in Cr-doped CuGaS2 films.

Electrochemical preparation and structural characterization of CuGaSe2 thin films

CuGaSe2 thin films have been synthesized by one-step electrodeposition on titanium and SnO2/glass substrates from aqueous solutions that contain thiocyanate ion as a complexing agent. According to composition, and morphology analysis at deposition potential of -0.55V vs SCE (Standard Calomel Electrode) for 20 minutes from aqueous solutions of 4.6mM CuCl, 25.0mM GaCl3 y 9.2mM SeO2 in 2.0M de KSCN at pH 2.5 was found the optimum condition for obtain the CuGaSe2 thin films with good morphology and good stoichiometric. The samples were annealed at temperature of 520°C in inert atmosphere for 30 minutes to improve their crystallinity. The obtained CuGaSe2 thin film has a direct band gap (Eg) of 1.65eV. In addition, the cyclic voltammetry (CV) studies were performed in order to elucidate the electrodic processes that occur for the formation of semiconductor CuGaSe2. Therefore, the electrochemical behaviour for each ion (Cu+, Ga3+ and Se4+), for binary (Cu-Se, Ga-Se, and Cu- Ga) and for ternary (Cu-Ga-Se) systems are described. This material has potential application in solar cells.

Wide-bandgap CuGaSe2 thin film solar cell fabrication using ITO back contacts

In the tandem Cu(In1−xGax)Se2 (CIGS) thin film solar cell fabrication, Indium tin oxide thin film (ITO) is a promising material as back contacts of the top cell. ITO thin films were deposited by radio frequency (rf) magnetron sputtering in pure argon atmosphere at a working pressure of 9 × 10−4 Torr with substrate temperature (Tsub) of 300 °C. The sheet resistance of as-deposited 200 nm-thick ITO thin films was about 1.3 × 10−4 Ω cm. The ITO thin films were subsequently annealed by rapid thermal annealing (RTA) at a temperature range between 400 and 550 °C for application of the high-temperature CuGaSe2 (CGS) deposition process. After the annealing processes of ITO thin films, we have examined the optical and electrical properties as transparent conducting oxide (TCO) back contacts. CGS thin films were prepared for the top cell in a tandem solar cell structure with wide bandgap of above 1.6 eV as high open circuit voltage photovoltaic devices. The optical and electrical properties of CGS thin film solar cells with ITO back contacts were investigated as compared with that of metallic Mo back contacts. Also, the CGS thin film solar cells were fabricated using ITO and MO back contacts with a conversion efficiency of 5 and 8.2%, respectively.

Structural tuning of wide-gap chalcopyrite CuGaSe2 thin films and highly efficient solar cells: differences from narrow-gap Cu(In,Ga)Se2

Simultaneous realization of high values of open circuit voltage (Voc), fill factor (FF), and energy conversion efficiency (η) in wide-gap CuGaSe2 (CGS) solar cells has long been one of the most challenging issues in the realm of chalcopyrite photovoltaics. In this communication, structural tuning of CGS thin films by means of controlling the amount of Se flux used during CGS film growth and improvements in solar cell performance (Voc > 0.9 V, FF > 0.7, and η > 10%) are demonstrated. Systematic variations in CGS film properties with the Se flux and correlation with device properties are shown. The unique CGS thin-film growth kinetics, which are different from narrow-gap Cu(In,Ga)Se2, are also presented and discussed. This development of double digit efficiency for CGS solar cells opens a new frontier for the broad application of a new class of chalcopyrite-based devices. Copyright © 2014 John Wiley & Sons, Ltd.

Hydrogen evolution from water using AgxCu1−xGaSe2 photocathodes under visible light

Photoelectrochemical (PEC) water splitting using CuGaSe2 (CGSe) thin film photocathodes modified by partial substitution of Cu with Ag was investigated. The AgxCu1-xGaSe2 (ACGSe) thin films were deposited onto Mo-coated soda-lime glass substrates by means of co-evaporation using a molecular beam epitaxy (MBE) system. The valence band maximum (VBM) potential of ACGSe is deeper than that of CGSe, and its grain size is greatly increased compared to that of CGSe. A Pt and CdS modified ACGSe electrode (Pt/CdS/ACGSe) with a Ag/(Cu + Ag) ratio of about 5% showed a cathodic photocurrent of 8.1 mA cm(-2) at 0 VRHE and an onset potential of 0.70 VRHE (defined as a cathodic photocurrent of 0.05 mA cm(-2)) under simulated sunlight in a 0.1 M Na2SO4 solution (pH 9.5). Moreover, Pt/CdS/ACGSe exhibited a stable cathodic photocurrent for over 55 h, with no clear decrease.

One-step electrodeposition of CuGaSe2 thin films

CuGaSe2 thin films have been prepared by one-step electrodeposition and rapid thermal annealing process. According to composition and morphology analysis, deposition potential of −0.6V vs. SCE is considered to be optimum for electrodeposition. From the X-ray diffraction and Raman studies, the as-deposited film exhibits poor crystallinity without the evidence of CuGaSe2 or other Ga-containing phases, while the rapid thermal annealing-treated film shows chalcopyrite structure CuGaSe2 phase containing MoSe2 phase between the Mo substrate and the absorber and minor second phase Cu2−xSe. The obtained CuGaSe2 thin film has a band gap of about 1.68eV and p-type conductivity.

Controlled electrodeposition of Cu–Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.

The chemical and electronic surface and interface structure of CuGaSe2 thin-film solar cell absorbers

The chemical and electronic surface and interface structure of CuGaSe2 thin films was investigated by photoelectron spectroscopy. With bulk [Ga]/[Cu] ratios increasing from 0.94 to 1.39 a transition of the Cu:Ga:Se surface composition from 1:1:2 to 1:3:5 and a downward shift of the valence band maximum with respect to the Fermi energy were observed. The comparison with the conduction band minimum (CBM) of CdS reveals that at the CdS/CuGaSe2 interface the recombination barrier height simultaneously increases and a “clifflike” offset is formed to the CBM of CuGaSe2.

The effect of composition on structural and electronic properties in polycrystalline CuGaSe2 thin film

Polycrystalline CuGaSe2 thin films on Mo-coated soda-lime glass substrates have been synthesized by co evaporation 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 dirraction 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 CuGaSe2 films 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 effciency of 6.02% has been achieved under the standard air mass (AM)1.5 spectrum for 100 mW/cm2 at room temperature (aperture area, 0.24 cm2). The open circuit voltage of the CuGaSe2 solar cells is close to 770 mV.

On the capability of revealing the pseudosymmetry of the chalcopyrite‐type crystal structure

AbstractThe tetragonal crystal‐structure type of chalcopyrites (chemical formula AIBIIICVI2) is a superstructure of sphalerite type. The c /a ratio differs generally from the ideal value 2, i.e., the crystal structure is pseudocubically distorted. For CuInSe2 and CuGaSe2 thin films, simulations demonstrate that it is theoretically possible to reveal the tetragonality in electron backscatter‐diffraction (EBSD) patterns for CuGaSe2, whereas it may not be possible for CuInSe2. EBSD experiments on CuGaSe2 thin films using the ”Advanced Fit” band‐detection method show that it is possible to extract accurate misorientation‐angle distributions from the CuGaSe2 thin film. Pole figures revealing the texture of the CuGaSe2 thin film are shown, which agree well with X‐ray texture measurements from the same layer. (© 2008 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Electrical properties of CuGaSe2 single crystals and polycrystalline coevaporated thin films

Abstract CuGaSe2 single crystals were grown by iodine vapour transport method, whereas polycrystalline thin films were obtained by coevaporation technique from three sources. The variation of the hole concentration with temperature of CuGaSe2 single crystal in the high temperature region is interpreted assuming thermal activation in the valence band. The density of states effective mass of the holes is deduced. Acceptor and donor concentrations as well as their compensation ratio are reported. The temperature dependence of the hole mobility in valence band is analysed by taking into account several scattering mechanisms of the charge carriers. To account for the temperature dependant conductivity of polycrystalline CuGaSe2 thin film, grain boundary conduction process was suggested. Quantitative values of the mean potential barrier height at grain boundaries and the standard deviation are reported. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Preferred Orientation, Grain Sizes and Grain Boundaries of Chalcopyrite-Type Thin Films

AbstractChalcopyrite-type thin films - CuInS2, CuInSe2, CuGaSe2, and Cu(In,Ga)Se2 - in various completed solar cells were studied in cross-section by means of electron-backscatter diffraction (EBSD). Valuable information on grain sizes, local grain orientations, film textures, and grain boundaries were extracted from the EBSD linescans and maps. The grain-size distributions from the chalcopyrite-type thin films can be represented well by lognormal distribution functions. The EBSD measurements on CuGaSe2 thin film reveal a <110> fiber texture, in good agreement with x-ray diffraction texture analysis performed on the same sample. The EBSD maps from all samples studied exhibit considerable twinning in the chalcopyrite-type thin films. Indeed, the most frequent types of grain boundaries in these thin films are (near) Σ3 60°-<221> and 71°-<110> twins. It is shown that rotational 180°-<221> twins (which are symmetrically equivalent to 71°-<110>) are more frequently found than anion- or cation-terminated 60°-<221> twin boundaries.

Control of secondary phase segregations during CuGaSe2 thin-film growth

The influence of the Se evaporation rate during deposition of CuGaSe2 thin films by coevaporation of the elements on Na-containing glass substrates is investigated. A high Se rate is found to avoid the segregation of a Na-containing secondary phase which, in the case of too low Se rates, is deleterious for the performance of the CuGaSe2 films. In addition, the article proposes a model for the phase segregation under low-Se conditions invoking sodium monoselenide as a precursor for the secondary phase. The segregation of the Na-containing compound in CuGaSe2 is further assisted by Ga diffusion from the CuGaSe2 film into the glass substrate. The present results also show that ionic exchange between Na from the glass and Ga from the absorber is active during the growth of Cu(In,Ga)Se2 alloys on Na-containing glass.

Diffusion Behavior and Microstructural Properties of the CBD-ZnS/CIGS Interface Boundary

ABSTRACTThe diffusion behavior and microstructural properties of the CBD-ZnS/Cu(In,Ga)Se2 (CIGS) interface of high-efficiency Cd-free CIGS thin film solar cells with efficiencies exceeding 17 % have been investigated using energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). CBD-ZnS thin layers are found to grow with small polycrystalline grains that consist of sphalerite and wurtzite phases. This is in sharp contrast to CBD-CdS layers which grow epitaxially on CIGS grains. Micro-EDX analysis revealed Zn indiffusion into the CIGS thin layer a distance of approximately 40 nm from the CBD-ZnS/CIGS interface boundary after air-annealing at 200°C, whereas no diffusion of Zn was observed before annealing. These results suggest that the main role of the air-annealing process is not substitution of Se vacancies by oxygen atoms but the diffusion of Zn into CIGS which may result in the formation of a pn homojunction. On the other hand, negligible Zn-diffusion into a CuGaSe2 thin film was found at the CBD-ZnS/CuGaSe2 interface boundary even after air-annealing. The cell performance of CBD-ZnS/CIGS thin film solar cells is discussed in connection with the Ga/(In+Ga) atomic ratio, conduction band-offset and Zn-diffusion.

In-Situ Surface Composition Measurements of CuGaSe2 Thin Films

AbstractTwo CuGaSe2 films were grown by molecular beam epitaxy onto GaAs (001) substrates with varying Cu/Ga flux ratios under Se overpressure conditions. Growth was interrupted at predetermined times and the surface composition was measured using Auger electron spectroscopy after which growth was continued. After growth, the film composition was analyzed using voltage dependent electron microprobe spectroscopy. Film structure and morphology were also analyzed using x-ray diffraction and atomic force microscopy. The film with a Cu/Ga ratio larger than unity showed evidence of surface segregation of a second Cu-rich phase with a Cu/Se composition ratio slightly greater than unity. A second CuGaSe2 film with a Cu/Ga ratio of less than unity showed no change in surface composition with time and was also consistent with bulk composition measurements. Diffraction measurements indicated a high concentration of twins as well as the presence of domains with mixed c and a axes in the Ga-rich film. The Cu-rich films by contrast were single domain and had a narrower mosaics. High sensitivity scans along the [001] reciprocal axis did not exhibit any new peaks not attributable to either the substrate or the CuGaSe2 thin film.

Calculation of distribution Equilibrium of amphoteric silicon in gallium arsenide: Iwao Teramoto, Research Laboratory, Matsushita Electronics Corporation, Takatsuki, Osaka, Japan

Device-grade ternary Cu–Ga–Se chalcopyrite thin films used for photovoltaic energy conversion have been prepared by a novel chemical close-spaced vapor transport (CCSVT) technique developed for a deposition on areas of up to 10×10 cm2. A two-step process has been developed which allows the fine tuning of the film composition and the electronic properties. The extension of deposition times in the two-step process led to final film compositions with [Ga]/[Cu] ratios ranging from 0.9 to 5.7, allowing the study of the structural phase transitions. In this paper the main focus of interest is related to the material properties of the device-grade thin films prepared by CCSVT technique. We present our recent studies on (i) the growth, compositional, structural and electronic structural properties, (ii) the degradation under ambient conditions and (iii) the feasibility of n-type doping this p-type semiconducting material by germanium. Thin films were grown with chalcopyrite (1:1:2) and CuGaSe2-related defect compound structures (DC) with stoichiometries of CuGa3Se5 and CuGa5Se8. In order to derive the DC structure, X-ray and neutron powder diffraction investigations have been carried out on powders of these CuGaSe2-related compounds grown by elemental synthesis (powder) and CCSVT (thin films), respectively. We found no hints for an ordering of defects, as proposed in the past and giving name to the so-called Ordered Defect Compounds (ODC) in this and related structures. From our results a growth model is presented for CuGa3Se5 formation in gallium-rich CCSVT-grown CuGaxSey films. The chemical and electronic surface and interface structure of CuGaSe2 thin films with bulk [Ga]/[Cu] ratios between 0.94 and 1.39 is investigated by X-ray and UV-excited photoelectron spectroscopy (XPS and UPS, respectively). A transition of the Cu:Ga:Se surface composition from 1:1:2 for the Cu-rich bulk sample to 1:3:5 for the sample with the highest bulk [Ga]/[Cu] ratio is observed. Simultaneously, a downward shift of the valence band maximum position with respect to the Fermi energy is found. The comparison of the estimated conduction band minimum with that of CdS reveals the formation of a pronounced “cliff-like” conduction band offset at the respective interface.Furthermore, the CuGaSe2 thin film degradation under ambient as well as under thermal conditions of CuGaSe2 thin films has been studied by XPS. During thermal oxidation, the formation of predominantly Ga2O3 and some amount of SeO2 were observed, but no copper oxides could be detected in the near-surface region of the thin films. The same oxides are found after native oxidation in air under ambient conditions. An additional sodium oxide compound formed at the thin film surface, NaxO and Na2CO3 after thermal and native oxidation, respectively.Germanium ion implantation technique of the near-surface region of CuGaSe2 thin films has been used in order to prove the feasibility of n-type doping. In photoluminescence (PL) studies, the occurrence of a new emission line is identified as Ge related and explained as a donor–acceptor-pair (DAP) recombination. The precise role the Ge is playing in this doping of CuGaSe2 is revealed by X-ray absorption spectroscopy (XANES and EXAFS) and ab initio calculations based on the density functional theory. The studies indicate that the incorporated Ge atoms preferentially occupy Ga sites when relaxation around the dopant is taken into account. Additionally, our corresponding theoretical band structure model predicts the existence of additional localized electronic acceptor and donor defect bands within the band gap of CuGaSe2 originating from a strong covalent interaction between Ge 4s and Se 4p states for Ge atoms tetrahedrally surrounded by the Se nearest-neighbor atoms. A theoretically predicted anti-bonding Ge–Se4sp3 defect band appearing well above the Fermi level for the Ge1+Ga point defect system can be directly linked to a Ge-dopant-related donor–acceptor-pair transition as observed in our photoluminescence spectra.