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.     

Fabrication and characterisation of Cu(In,Ga)Se2 solar cells on polyimide

Solar cells with the structure ZnO:Al/i-ZnO/CdS/Cu(In,Ga)Se₂/Mo/polyimide were examined using a range of techniques. The elemental composition of the Cu(InGa)Se₂ (CIGS) layers, their crystalline structure and optical properties were studied. Photoluminescence (PL) spectra of the CIGS absorber layers were studied as functions of temperature (4.2-240 K) and excitation power density. The band gap energy E_g of the CIGS layers was determined by employing photoluminescence excitation (PLE) spectroscopy. The influence of sodium incorporation on the PL properties of CIGS was analysed. Correlations of the optical properties of the CIGS absorber layers and the photovoltaic parameters of the solar cells were revealed.     

Alternative sodium sources for Cu(In,Ga)Se2 thin-film solar cells on flexible substrates

Sodium (Na) is an important doping element for Cu(In,Ga)Se₂ (CIGS) solar cells. However, when using Na-free flexible substrates like steel foil or polyimide film, it is necessary to ensure an efficient supply of sodium to achieve high cell efficiencies. The common incorporation methods for Na on these Na-free substrates are either to deposit a Na-containing precursor layer (e.g. NaF) onto the molybdenum (Mo) back contact prior to CIGS growth or to coevaporate a Na compound during CIGS growth. Another way is to incorporate sodium after CIGS growth by a post-deposition treatment with NaF. In this work, we tested two alternative Na doping methods which are well suited for a production line due to their easy controllability. One approach is to dope the molybdenum target with Na. With Na-doped Mo layers (Mo:Na) as the back contact, we could achieve efficiencies of 13.1% both on titanium (Ti) and stainless Cr steel foil using a single-stage inline CIGS process. With a low-temperature single-stage CIGS process on polyimide (PI) we reached an efficiency of 11.2% using a Mo:Na back contact. Another doping method involves sol-gel-deposited silicon oxide layers which contain Na (SiO_x:Na). We have successfully deposited these sol-gel layers onto stainless steel foil by a roll-to-roll (R2R) method with short annealing times as needed in production. With these SiO_x:Na layers we could achieve efficiencies of 13.7% on stainless steel foil and 11.5% on mild steel sheet using a single-stage inline CIGS process.     

Optical properties of Cu(In,Ga)Se2 and Cu2ZnSn(S,Se)4

The optical properties of CuInSe₂, CuGaSe₂, Cu₂ZnSnS₄, and Cu₂ZnSnSe₄ are investigated using three different first-principles methods, namely the generalized gradient approximation by Perdew, Burke, and Ernzerhof (PBE), the hybrid Hartree-Fock-like functional by Heyd, Scuseria, and Ernzerhof (HSE), and a Green's function approach (GW). The density-of-states, the complex dielectric function ε(ω) = ε₁(ω) + iε₂(ω), and the optical absorption coefficient α(ω) are determined, providing fundamental understanding of these materials. We find that even though the PBE method generates fairly accurate effective crystal potentials, the HSE and GW methods improve considerably the band-gap energies E_g and also the localization of the semicore states, thereby describing the optical properties much better. Furthermore, we also present optimized convergence parameters for the self-consistent HSE calculation in order to reduce the computational time of this orbital-dependent method.     

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.     

Structural properties of Cu(In,Ga)Se2 thin films prepared from chemically processed precursor layers

We have developed a chemical process for incorporating copper into indium gallium selenide layers with the goal of creating a precursor structure for the formation of copper indium gallium diselenide (CIGS) photovoltaic absorbers. Stylus profilometry, EDX, Raman spectroscopy, XRD and SIMS measurements show that when indium gallium selenide layers are immersed in a hot copper chloride solution, copper is incorporated as copper selenide with no increase in the thickness of the layers. Further measurements show that annealing this precursor structure in the presence of selenium results in the formation of CIGS and that the supply of selenium during the annealing process has a strong effect on the morphology and preferred orientation of these layers. When the supply of Se during annealing begins only once the substrate temperature reaches ≈ 400 °C, the resulting CIGS layers are smoother and have more pronounced preferred orientation than when Se is supplied throughout the entire annealing process.     

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.     

Characterisation of Cu(In,Ga)Se2-based thin film solar cells on polyimide

Thin films of Cu(In,Ga)Se₂ (CIGS) were deposited at temperatures below 450 °C on polyimide (PI) substrates coated with Mo in a roll-to-roll set up by a combination of co-evaporation and ion-beam techniques. Flexible solar cells ITO/i-ZnO/CdS/CIGS/Mo/PI with and without Na incorporation were then fabricated. The films and solar cells were examined by: X-ray fluorescence spectroscopy (XRF) and Auger electron spectroscopy (AES), to determine the elemental composition, as well as by X-ray diffraction for structure- and scanning electron microscopy (SEM) for morphology-analysis. Photoluminescence (PL) and PL-excitation (PLE) at temperatures from 4.2 to 78 K were also used to estimate the band-gap energy of CIGS, examine the electronic properties and defect nature. The aim of this study was to correlate the incorporation of Na with optical and structural parameters of the CIGS layers as well as with the solar cell performance.     

Instantaneous preparation of CuInSe2 films from elemental In, Cu, Se particles precursor films in a non-vacuum process

CuInSe₂ (CIS) films are successfully prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se particles precursor films without prior synthesis of CIS nanoparticle precursors and without selenization with H₂Se or Se vapor. Our precursor films were prepared on metal substrates by spraying the solvent with added elemental In, Cu, and Se particles. Precursor films were instantaneously sintered using a spot welding machine. When the electric power was fixed to 0.6 kVA, elemental In, Cu, or Se peaks were not observed and only peaks of CIS are observed by X-ray diffraction (XRD) on the film sintered for 7/8 s. We can observe XRD peaks indicative of the chalcopyrite-type structure, such as (101), (103) and (211) diffraction peaks. We conclude that the synthesized CIS crystals have chalcopyrite-type structure with high crystallinity.     

Chemical properties of the Cu(In,Ga)Se2/Mo/glass interfaces in thin film solar cells

The Cu(In,Ga)Se₂/Mo and the Mo/glass interfaces in high efficiency thin film solar cells have been investigated by surface-sensitive photoelectron spectroscopy and bulk-sensitive X-ray emission spectroscopy. The interfaces were accessed by a suitable lift-off technique. Our experiments show a strong Se diffusion from the absorber into the Mo film, suggesting the formation of a MoSe₂ layer in the surface-near region of the back contact. In addition, we find a Ga diffusion into the Mo back contact, while no diffusion of In and Cu occurs. Furthermore, we derive a detailed picture of the Na distribution near the back and front side of the Cu(In,Ga)Se₂ absorber.     

Properties of Cu(In,Ga)(S,Se)2 thin films prepared by selenization/sulfurization of metallic alloys

Single-phase Cu(In,Ga)(S,Se)₂ (CIGSS) thin films have been prepared using a two-step process consisting of annealing of Cu-In-Ga precursors in S/Se ambient. Full characterizations have been carried out using XRD, SEM, EDS, Raman spectroscopy and optical absorption measurements. The depth profiles of constituent elements Cu, In, Ga, S and Se were almost constant throughout the film. Depending on overall Ga content and recrystallization temperature CIGSS thin films exhibited a shift in band gap from 1.04 to 1.19 eV.     

Optimization of Ti/TiN/Mo back contact properties for Cu(In,Ga)Se2 solar cells on polyimide foils

Molybdenum is conventionally used as electrical back contact for Cu(In,Ga)Se₂ (CIGS) solar cells. In this work, a multifunctional stack of Ti/TiN/Mo is introduced as back contact for flexible CIGS solar cells. The multilayer back contact was deposited on 25 μm thick polyimide foil by means of DC reactive sputtering.To optimize electrical conductivity and film stress of the alternative back contact sputter parameters such as total gas pressure, sputtering power, substrate temperature and RF substrate bias have been varied. XRD measurements and quantitative analysis of foil curvature revealed that the film stress is significantly influenced by the argon gas pressure and sputtering power. The electrical conductivity was improved by applying higher sputtering power or RF substrate bias. Analysis of the film microstructure with SEM shows that applied substrate bias influences the density of the sputtered film. The solar cells processed on Ti/TiN/Mo as well as on a conventional Mo bilayer back contact have been compared using standard current density to voltage (J-V) measurements and external quantum efficiency measurements. Conversion efficiencies of 13.4% for the alternative and 14.9% for the conventional design have been obtained.     

Electrodeposition based synthesis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Raman scattering analysis of electrodeposited CuInSe2 precursors

Single step electrodeposition (ED) of Se-rich CuInSe₂ precursors, followed by RTP annealing under sulphurising conditions leading to S-rich CuIn(S,Se)₂ films, constitutes a promising technology for low cost high efficiency solar cells. In this work, a Raman scattering (RS) analysis of Se rich precursors grown under ED conditions leading to different chemical compositions is reported. RS has allowed identification of the main secondary phases in these layers with elemental Se, Cu-Se binary and ordered vacancy compound (OVC) phases. The experimental data show a strong dependence of the spectral contributions related to Se and Cu-Se with the layer molecularity, and the formation of these phases is mainly determined by the content of excess Se in the layers. The correlation of these data with the characteristics of the solar cells fabricated with these precursors, shows the strong impact of the presence of the Cu-Se phase on the performance of the final devices. These results point out the key role played by this binary phase on the formation of secondary phases after the sulphurising step.     

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.     

Interfacial chemistry control in thin film solar cells based on electrodeposited CuIn(S,Se)2

In this work, we present a study on CuIn(S,Se)₂ absorbers prepared by electrodeposition followed by rapid thermal annealing promising to lower manufacturing cost. However the annealed material contains copper sulpho-selenide of Cu(S_y,Se_1 − y) type which is harmful for the electrical properties of photovoltaic devices. These phases are removed by a cyanide etching. Because of an intrinsic variability of absorber fabrication process, the presented survey is based on statistic approach. We highlighted the influence of a cyanide treatment on surface and bulk compositions. The surface composition follows a distribution according to a Cu(S,Se)-CuIn(S,Se)₂ system and the bulk composition agrees with Cu(S,Se)₂-CuIn₃(S,Se)₅ system. Moreover, surface composition can be modified by adjusting the cyanide concentrations of etching solution without any changes in the bulk one. It ensues that Cu(S,Se) is not only present on the surface but also in the bulk of samples.     

A study of textured non-stoichiometric MoTe2 thin films used as substrates for textured stoichiometric MoS2 thin films

Textured MoTe₂ films have been prepared by sequential evaporation of the constituents followed by annealing under a tellurium pressure. The films are systematically textured with the c-axis of the crystallites perpendicular to the plane of substrate, however, the film composition is difficult to control and even after process optimization the films are tellurium deficient. This is thought to be caused by the electro negativity difference of the constituents.The textured MoTe₂ films have been used as substrates on which to grow MoS₂ films by annealing under a pressure of sulfur that allows textured MoS₂ films to be grown with good crystalline properties. The presence of sulfur at the surface and annealing under dynamic vacuum is important for this process and moreover, suppresses the superficial oxidation of the Mo and Te constituents.     

Relaxation of light induced metastabilities in Cu(In,Ga)Se2 with different Ga content

Relaxation of the persistent photoconductivity (PPC) in Cu(In,Ga)Se₂ has been investigated. Conductance transients have been measured for thin layers in order to analyze carrier trapping and emission processes and compared with capacitance kinetics obtained for a complete solar cell. Relaxation time constants have been recorded as a function of temperature to calculate activation energies of observed processes. Dependence of the relaxation time constant on the light pulse width is also presented both for the layers and a complete solar cell. The origin of the metastability is discussed in terms of a DX-type defect conversion model involving a strong lattice relaxation.     

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.     

Hydrothermal synthesis and characterization of MoS2 nanorods

MoS₂ nanorods were successfully synthesized via hydrothermal method by adding sillicontungstic acid as an additive. The products were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectrum (XPS) and field-emission scanning electron microscopy (FESEM). XRD pattern result indicated that the as-prepared sample can be indexed to a mixture of hexagonal and rhombohedral phase MoS₂. XPS showed that the nanorods were only composed of Mo and S with atomic ratio of 1:2. FESEM images revealed that the MoS₂ rods had uniform sizes with mean diameters of about 20-50 nm and lengths of 400-500 nm. It was found that the addition of sillicontungstic acid played a crucial role in the formation of the rod-like MoS₂ in our experiment. The possible formation mechanism of MoS₂ nanorods is also discussed.     

Generation of electrical defects in ion beam assisted deposition of Cu(In,Ga)Se2 thin film solar cells

Thin films of Cu(In,Ga)Se₂ (CIGS) absorber layers for thin film solar cells have been manufactured on polyimide foil in a low temperature, ion beam assisted co-evaporation process.In the present work a set of CIGS thin films was produced with varying selenium ion energy. Solar cell devices have been manufactured from the films and characterized via admittance spectroscopy and capacitance-voltage profiling to determine the influence of the selenium ion energy on the electric parameters of the solar cells. It is shown that the impact of energetic selenium ions in the CIGS deposition process leads to a change in the activation energy and defect density and also in the spatial distribution of electrically active defects.For the interpretation of the results two defect models are taken into account.