Growth, structural and optical properties of copper indium diselenide thin films deposited by thermal evaporation method

Copper indium diselenide (CuInSe₂) compound was synthesized by reacting its constituent’s elements copper, indium and selenium in near stoichiometric proportions (i.e. 1:1:2 with 5% excess selenium) in an evacuated quartz ampoule. Synthesized pulverized compound material was used as an evaporant material to deposit thin films of CuInSe₂ onto organically cleaned sodalime glass substrates, held at different temperatures (300-573 K), by means of single source thermal evaporation method. The phase structure and the composition of chemical constituents present in the synthesized compound and thin films have been investigated using X-ray diffraction and energy dispersive X-ray analysis, respectively. The investigations show that CuInSe₂ thin films grown above 423 K are single phase, having preferred orientation of grains along the (112) direction, and having near stoichiometric composition of elements. The surface morphology of CuInSe₂ films, deposited at different substrate temperatures, has been studied using the atomic force microscopy to estimate its surface roughness. An analysis of the transmission spectra of CuInSe₂ films, recorded in the wavelength range of 500-1500 nm, revealed that the optical absorption coefficient and the energy band gap for CuInSe₂ films, deposited at different substrate temperatures, are ∼10⁴ cm⁻¹ and 1.01-1.06 eV, respectively. The transmission spectrum was analyzed using iterative method to calculate the refractive index and the extinction coefficient of CuInSe₂ thin film deposited at 523 K. The Hall effect measurements and the temperature dependence of the electrical conductivity of CuInSe₂ thin films, deposited at different substrate temperatures, revealed that the films had electrical resistivity in the range of 0.15-20 ohm cm, and the activation energy 82-42 meV, both being influenced by the substrate temperature.     

The influence of the vacuum annealing process on electrodeposited CuInSe2 films

CuInSe₂ films were electrodeposited on mechanical polished Mo substrates. The applied potential was adjusted to get a stoichiometric composition. The as-deposited films were annealed in a high vacuum system for a short time. The films have been characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, Auger electron spectroscopy. The results indicate that the crystallization of the films was greatly improved by the short time vacuum annealing process without significant change in composition. The capacitance–voltage measurement shows characteristic p-type behaviors. This annealing process after electrodeposition was proved to be a useful method to prepare the polycrystalline CuInSe₂ films for solar cell application.     

Preparation and study of structural and optical properties of CSVT deposited CuInSe2 thin films

A simple close-spaced vapour transport (CSVT) system has been designed and fabricated. Copper indium diselenide (CuInSe₂) thin films of wide range of thickness (4000–60000 Å) have been prepared using the fabricated CSVT system at source temperatures 713, 758 and 843 K. A detailed study on the deposition temperature has been made and the temperature profile along with the reaction kinetics is reported. The composition of the chemical constituents of the films has been determined by energy dispersive X-ray analysis. The structural characterization of the as-deposited CuInSe₂ films of various thicknesses has been carried out by X-ray diffraction method. The diffractogram revealed that the CuInSe₂ films are polycrystalline in nature with chalcopyrite structure. The structural parameters such as lattice constants, axial ratio, tetragonal distortion, crystallite size, dislocation density and strain have been evaluated and the results are discussed. The surface morphology of the as-deposited CuInSe₂ thin films has been studied using scanning electron microscope. The transmittance characteristics of the CuInSe₂ films have been studied using double beam spectrophotometer in the wavelength range 4000–15000 Å and the optical constants n and k are evaluated. The absorption coefficient has been found to be very high and is of the order of 10⁵–10⁶ m⁻¹. CuInSe₂ films are found to have a direct allowed transition and the optical band gap is found to be in the range 0.85–1.05 eV.     

Thin films of CuInSe2 prepared by RF sputtering from various compositional powder targets

CuInSe₂ thin films were prepared in the temperature range of 300–500°C by RF sputtering from powder targets, which were previously synthesized by reacting Cu, In, and Se in various ratios. The peaks from X-ray diffraction analyses were assigned to the planes of the CuInSe₂ chalcopyrite structure. The full width at half maximum of the (112) diffraction peak decreased with an increase in Cu/In ratio in the thin films. The photoelectron energies of the prepared thin films agreed with those reported for single crystalline CuInSe₂ from X-ray photoelectron spectroscopy measurements. The electronic conduction type and optical properties were found to change according to the Cu/In ratio in the thin films.     

Study of phases formed during production of copper indium diselenide by reacting copper, indium and selenium layers

CuInSe₂ films were grown by reacting stacked layers of Cu, In and Se in an atmosphere of Se vapor. Incremental growth of the various phases was followed at different temperatures until a single phase CuInSe₂ film was formed. Conventional X-ray diffraction was used in identifying the different phases formed. Along with the knowledge of different phases formed at increasing reaction temperatures, it was concluded that CuInSe₂ is formed at temperatures as low as 235°C, although a single phase film is obtained only at higher temperatures (≈350°C).     

The formation of CuInSe2 thin films by rapid thermal processing

Formation of polycrystalline thin film CuInSe₂ was achieved by the rapid thermal processing of vacuum-deposited copper, indium, and selenium. Films were fabricated and characterized in three composition regions: copper-poor (approximately 20 at.% Cu). stoichiometric (25 at.% Cu) and copper-rich (approximately 28 at.% Cu). Characterization results including X-ray diffraction analysis, electron probe for microanalysis, scanning electron microscopy, and optical reflection and transmission measurements are presented. The results show that nearly single-phase material has been formed from co-deposited precursors with a post-deposition annealing time of less than 2 min. The films have smooth morphologies amenable for photovoltaic device fabrication, optical absorption coefficients in the high 10⁴ cm⁻¹ range, and an optical band gap of 1.0 eV.     

Investigation of the chalcogen interdiffusion in CuIn(TeSe)2 thin films

Graded thin films of CuInSe₂ on CuInTe₂ have been obtained by annealing of precursor structures containing Se and Te separated in depth. The depth profile of the phases in the film was investigated using X-ray diffraction with grazing incidence of the primary beam. Quasi-epitaxial growth of CuInSe₂ on a CuInTe₂ film next to the Mo back-electrode was observed after annealing at 450°C in vacuum. Annealing at higher temperature lead to chalcogen interdiffusion resulting in quaternary films. However, heat treatments of already reacted films did not result in any detectable interdiffusion. From these results the mechanisms governing the growth of films from precursors containing the chalcogens Se and Te separated in depth are discussed with respect to their application for thin film solar cells.     

Preparation and properties of a Cu---In alloy precursor for CuInSe2 films

We describe a new nonaqueous method to electrodeposit Cu---In alloy precursor for n-CuInSe₂ films. The structural and compositional analysis of the Cu---In alloy carried out by X-ray diffraction and X-ray photoelectron spectroscopy have also been discussed. The stoichiometry of the films has been found to be influenced by the deposition potential. It is shown that a Cu---In alloy precursor with bulk Cu/In ratio of 1.00 can be electrodeposited at a potential of −1.05 V (versus Pt). Flash annealing of the stacked Cu---In alloy/Se layers has been used to prepare CuInSe₂ films. It is shown that the flashed n-CuInSe₂ films have a chalcopyrite structure with strongly oriented (112) U planes.     

Electrodeposition of CuInSe2 from ethylene glycol at 150 °C

Polycrystalline chalcopyrite thin films were potentiostatically electrodeposited from ethylene glycol solution onto SnO₂-coated glass substrates at 150 °C. The thickness of the layers was estimated using talysurf at 1.0 μm after deposition for 60 min. X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analyses were used to identify and characterise compounds formed at different potentials. It was found that Cu_1.75Se formation was dominant at −0.80 V vs Se and indium assimilation increased at more negative voltages forming a mixture of compounds including numerous Cu-Se binary phases and copper indium diselenide (CuInSe₂) at the cathode. As-deposited materials showed poor crystallinity and therefore films were annealed in Ar/5%H₂ in the presence of Se to improve the material quality for all investigations. Although the films were deposited at 150 °C, no noticeable improvement of the CuInSe₂ was observed, suggesting growth from aqueous media at room temperature to be preferable.     

The growth by the hybrid sputtering and evaporation method and microstructural studies of CuInSe2 films

Polycrystalline CuInSe₂ was deposited by a hybrid sputtering and evaporation process at various temperatures and compositions. The resulting material was characterized by electron microscopy, X-ray diffraction and other techniques. It was shown that the point defect density in CuInSe₂ thin films can be decreased and the compositional uniformity of the film increased by raising the growth temperature of the second stage of the bilayer deposition process used. Increasing the temperature results in more pronounced segregation of second phases to the surface. An explanation for the behaviour of Cu₂Se surface segregation and precipitate formation is proposed based on residual lattice misfit between the Cu₂Se and the CuInSe₂ grains.     

Effect of heat treatment on electrodeposited CuInSe2 films

Thin films of CuInSe₂ prepared by an electrodeposition method have been heat treated at temperatures up to about 450°C. The heat treatments were done in an evacuated environment. After the heat treatment, the samples were examined by electron probe microanalysis for composition and by X-ray diffraction for determination of crystalline quality. The results obtained showed that the quality of the films was improved by the heat treatment. From the compositional results, it was found that there was a loss of selenium during the heat treatment.     

Scanning tunneling microscopy of electrodeposited CuInSe2 nanoscale multilayers

We have investigated the electrochemical deposition of modulated thin films based on the Cu_xIn_2−xSe₂ system. CuInSe₂ is a leading alternative to silicon for use in thin film photovoltaic solar cells due to its optical absorption and electrical characteristics. Alternating layers of two different compositions based on the Cu_xIn_2−xSe₂ system were potentiostatically deposited. These nanometer-scale layers are used to form reduced-dimensionality structures such as superlattices that can be used in concentrator solar cells. We have used X-ray diffraction, energy-dispersive spectroscopy, and scanning tunneling microscopy to characterize our asdeposited thin films. The ability of the scanning tunneling microscope to resolve the individual nanoscale layers of our multilayered thin films is shown and is used to determine modulation wavelengths.     

Thermal diffusion of Cu into In2Se3: A better approach to SEL technique in the deposition of CuInSe2 thin films

This paper reports the modifications made in the preparation techniques of getting CuInSe₂ thin films starting with chemical bath deposited (CBD) selenium films. In the present study, CBD Se film was converted into CuInSe₂ by stacked elemental layer (SEL) technique and also by thermal diffusion of Cu into In₂Se₃. In both the cases CBD Se films were used to avoid toxic Se vapor and H₂Se gas. Improvements were made in these techniques through a detailed study, varying the composition of the films over a wide range by changing the Cu/In ratio. Structural, optical and electrical characterizations were performed. On comparing the material properties of CuInSe₂ deposited by these two techniques, it was found that photosensitivity was better for samples prepared by thermal diffusion of Cu into In₂Se₃. So the technique of thermal diffusion of Cu into In₂Se₃ was found to be better than SEL technique in the preparation of CuInSe₂ using CBD Se. Cu-rich, In-rich and nearly stoichiometric samples could be prepared by thermal diffusion of Cu into In₂Se₃. These samples were analyzed using energy dispersive spectroscopy, Raman spectroscopy and atomic force microscopy also.     

Characterization of co-sputtered Cu-In alloy precursors for CuInSe2 thin films fabrication by close-spaced selenization

Sputtering technique for Cu–In precursor films fabrication using different Cu and In layer sequences have been widely investigated for CuInSe₂ production. But the CuInSe₂ films fabricated from these precursors using H₂Se or Se vapour selenization mostly exhibited poor microstructural properties. The co-sputtering technique for producing Cu–In alloy films and selenization within a close-spaced graphite box resulting in quality CuInSe₂ films was developed. All films were analysed using SEM, EDX, XRD and four-point probe measurements. Alloy films with a broad range of compositions were fabricated and XRD showed mainly In, CuIn₂ and Cu₁₁In₉ phases which were found to vary in intensities as the composition changes. Different morphological properties were displayed as the alloy composition changes. The selenized CuInSe₂ films exhibited different microstructural properties. Very In-rich films yielded the ODC compound with small crystal sizes whilst slightly In-rich or Cu-rich alloys yielded single phase CuInSe₂ films with dense crystals and sizes of about 5 μm. Film resistivities varied from 10⁻²–10⁸ Ω cm. The films had compositions with Cu/In of 0.40–2.3 and Se/(Cu+In) of 0.74–1.35. All CuInSe₂ films with the exception of very Cu-rich ones contained high amount of Se (>50%).     

Study of CuInSe2 thin films prepared by electrodeposition

Thin films of p-type CuInSe₂ prepared by a one-step electrodeposition method have been studied by constructing CdS/CuInSe2 junctions. After the electrodeposition, the CuInSe₂ films were treated either in vacuum or in Ar. Cells of the form CdS (high σ)/CdS (low σ)/CuInSe₂ were then fabricated for studying the electrodeposited films. Measurements were specifically carried out to determine the diffusion length of minority carriers in the p-type CuInSe₂. It was found that the minority carrier diffusion length in CuInSe₂ films treated in Ar was generally greater than that for films treated in vacuum under similar conditions. A small area cell (active area 0.11 cm²) with a conversion efficiency of about 7% (under 125 mW/cm² illumination) has been fabricated.     

Effect of Cl ion implantation on electrical properties of CuInSe2 thin films

The effects of Cl ion implantation on the properties of CuInSe₂ epitaxial thin films have been investigated. Using five kinds of accelerating energies, the doped layer with a constant profile of Cl concentration along the depth direction was fabricated. From the results of reflection of high-energy electron diffraction, the damages due to implantation were removed by annealing at 400°C in N₂. The conductivity type in all implanted films was n-type, and the carrier concentration was increased with increasing Cl concentration in the thin films. Consequently, it is considered that Cl acts as a donor in CuInSe₂.     

Electrodeposition of CuInxGa1−xSe2 thin films

CuIn_xGa_1−xSe₂ (CIGS) polycrystalline thin films with various Ga to In ratios were grown using a new two-step electrodeposition process. This process involves the electrodeposition of a Cu–Ga precursor film onto a molybdenum substrate, followed by the electrodeposition of a Cu–In–Se thin film. The resulting CuGa/CuInSe bilayer is then annealed at 600°C for 60 min in flowing Argon to form a CIGS thin film. The individual precursor films and subsequent CIGS films were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and Auger electron spectroscopy. The as-deposited precursor films were found to be crystalline with a crystal structure matching that of CuGa₂. The annealed bi-layers were found to have the same basic chalcopyrite structure of CuInSe₂, but with peak shifts due to the Ga incorporation. Energy dispersive spectroscopy results show that the observed shifts correlate to the composition of the films.     

The structural and material properties of CuInSe2 and Cu(In,Ga)Se2 prepared by selenization of stacks of metal and compound precursors by Se vapor for solar cell applications

CuInSe₂ films and related alloys were prepared by thermal evaporation of Cu, InSe and GaSe compounds instead of elemental sources. Band-gap tailoring in Cu(In,Ga)Se₂-based solar cells is an interesting path to improve their performance. In order to get comparable results, solar cells with Ga/(In+Ga) ratios x=0 and 0.3 were prepared, all with a simple two-step sequential evaporation process. The morphology of the resulting films grown at 550 °C was characterized by the presence of large facetted chalcopyrite grains, which are typical for device quality material. It is important to note that absorber films with elemental gallium resulted in a significant decrease in the average grain size of the film. The X-ray diffraction (XRD) diffraction pattern of single-phase Cu(In,Ga)Se₂ films depicts diffraction peaks shifting to higher 2θ values compared to that of pure CuInSe₂. The photoluminiscence (PL) spectrum of Cu(In,Ga)Se₂ thin films also depicts the presence of the peak at higher energy that is attributed to the incorporation of gallium into the chalcopyrite lattice. As the band gap of CIGS increases with gallium content, desirable effects of producing higher open-circuit voltage and low current density devices were achieved. A corresponding increase in device efficiency with gallium content caused by a higher fill factor was observed. The best results show passive area efficiencies of up to 10.2% and open-circuit voltage (V_oc) up to 519 mV at a minimum band gap of 1.18 eV.     

Electrodeposited and selenized (CuInSe2) (CIS) thin films for photovoltaic applications

In the present communication, the authors report results on the characterization of electrodeposited and selenized (CuInSe₂) (CIS) thin films. The selenization process was carried out using a technique called chemical vapor transport by gas (CVTG). The precursors as well as selenized films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron microprobe analysis (EPMA). The film stoichiometry improved after selenization at 550°C. The films were formed with a mixed composition of the binary as well as the ternary phases.     

Study of the sub-bandgap absorption and the optical transitions in CuInSe2 polycrystalline thin films

Optical transitions near the fundamental band edge are studied for CuInSe₂ films having various Cu/In ratios by analysing the variations of the absorption coefficient with incident photon energy. The results indicate different transitions depending upon the Cu/In ratio. There are sub-bandgap absorption for near stoichiometric and Cu-rich films. The results are compared to some literature data.