Effect of selenization pressure on CuInSe2 thin films selenized using co-sputtered Cu-In precursors

CuInSe₂ thin films were formed from the selenization of co-sputtered Cu–In alloy layers. These layers consisted of only two phases, CuIn₂ and Cu₁₁In₉, over broad Cu–In composition ratio. The concentration of Cu₁₁In₉ phase increased by varying the composition from In-rich to Cu-rich. The composition of co-sputtered Cu–In alloy layers was linearly dependent on the sputtering power of Cu and In targets. The metallic layers were selenized either at a low pressure of 10 mTorr or at 1 atm Ar. A small number of Cu–Se and In–Se compounds were observed during the early stage of selenization and single-phase CuInSe₂ was more easily formed in vacuum than at 1 atm Ar. Therefore, CuInSe₂ films selenized in vacuum showed smoother surface and denser microstructure than those selenized at 1 atm. The results showed that CuInSe₂ films selenized in vacuum had good properties suitable for a solar cell.     

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%).     

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.     

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.     

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 of Culn(SxSe1−x)2 thin films by sulfurization and selenization

A CuIn(S_xSe_1−x)₂ alloy thin-film was prepared by selenization of CuInS₂: its composition ratio x can be controlled by the number of selenization cycles implemented. Crystallinity of the films was improved by annealing in vacuum. The resistivity of the film was about 1 Ω cm and increased by one to two orders of magnitude after KCN treatment. An 8.1 % efficiency solar cell was obtained by using this annealed alloy thin-film.     

Depth profile analysis of CuInSe2 (CIS) thin films grown by the electrodeposition technique

In this study, we report the results obtained from the auger electron spectroscopy (AES) depth profiling of CIS thin films grown by the electrodeposition technique. This result enables one to do a comparison between the bulk and superficial elemental compositions. The AES result is also compared with that obtained by the inductively coupled plasma (ICP) spectroscopy. These results support our proposition that the electrodeposited CIS film has a Cu-rich bulk region and an In rich surface, which leads to the formation of an n-layer (CuIn₂Se_3.5) on the top of the p-type CIS (CuInSe₂) phase     

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.     

Compound polycrystalline solar cells:: Recent progress and Y2 K perspective

A historical perspective on the development of polycrystalline thin-film solar cells based on CdTe and CuInSe₂ is presented, and recent progress of these thin-film technologies is discussed. Impressive improvements in the efficiency of laboratory scale devices has not been easy to translate to the manufacturing environment, principally due to our lack of understanding of the basic science and engineering of these materials and devices. “Next-generation” high-performance thin-film solar cells utilizing multijunction device configurations should achieve efficiencies of more than 25% within ten years. However, our cost-effective manufacturing of these more complex devices will be problematic unless the science and engineering issues associated with processing of thin-film PV devices are addressed.     

Complexing agent effect on the stoichiometric ratio of the electrochemically prepared CuInSe2 thin films

The electrodeposition of CuInSe₂ is investigated to improve the stoichiometric properties of CuInSe₂ layers on indium tin oxide (ITO)-coated glass substrates and to develop one-step electrodeposition method for solar cell applications. XPS was utilized for the characterization of the surface properties of CuInSe₂ layers. The influence of the complexing agent, e.g. benzotriazole, bulk concentration of Cu and Se and deposition potentials on the stoichiometric properties, are discussed.     

An investigation into effect of cationic precursor solutions on formation of CuInSe2 thin films by SILAR method

SILAR deposition of CuInSe₂ films was performed by using Cu²⁺–TEAH₃ (cupric chloride and triethanolamine) and In³⁺–CitNa (indium chloride and sodium citrate) chelating solutions with weak basic pH as well as Na₂SeSO₃ solution at 70 °C. A separate mode and a mixed one of cationic precursor solutions were adopted to investigate effects of the immersion programs on crystallization, composition and morphology of the deposited CuInSe₂ films. Chelating chemistry in two solution modes was deducted based on IR measurement. The XRD, XPS and SEM results showed that well-crystallized, smoothly and distinctly particular CuInSe₂ films could be obtained after annealing in Ar at 400 °C for 1 h by using the mixed cationic solution mode.     

A comparative study of CuInSe2 and CuIn3Se5 films using transmission electron microscopy, optical absorption and Rutherford backscattering spectrometry

CuInSe₂ and CuIn₃Se₅ films were grown by stepwise flash evaporation onto glass and Si substrates held at different temperatures. Transmission electron microscopy (TEM) studies revealed that the films grown above 370 K were polycrystalline, with CuInSe₂ films exhibiting larger average grain size than CuIn₃Se₅. Optical absorption studies yielded band gaps of 0.97±0.02 and 1.26±0.02 eV for CuInSe₂ and CuIn₃Se₅, respectively. Rutherford backscattering spectrometry (RBS) study of the films on Si showed that CuInSe₂/Si structures included an inhomogeneous interface region consisting of Cu and Si, whereas CuIn₃Se₅/Si structures presented sharp interface.     

The formation of CuInSe2 thin-film solar cell absorbers by laser annealing of electrodeposited precursors

The formation of the compound semiconductor CuInSe₂ by laser annealing of electroplated precursor films in inert gas atmosphere represents an entire non-vacuum production process of thin-film solar cell absorbers. Besides this technological aspect, the impact of extreme annealing rates on structural properties of the resulting semiconductor is interesting from a fundamental research point of view. For this reason, we compared absorbers processed by laser annealing with absorbers annealed with moderate heating rates in the range of 1 K/s by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX). All absorbers processed with laser or furnace annealing consist of crystalline CuInSe₂ in the chalcopyrite crystal structure with a high degree of cation disorder. We show that laser annealing does not lead to unintentional selenium loss during the semiconductor formation process.     

Effects of annealing on CuInSe2 films grown by molecular beam epitaxy

CuInSe₂ (CIS) thin films with a range of Cu/In ratios were grown by molecular beam epitaxy on GaAs (0 0 1) at substrate temperatures of T_s = 450–500°C and the effects of annealing under various atmospheres have been investigated. Photoluminescence spectra obtained from an ex-situ vacuum annealed CIS film at a temperature of T_A = 350°C showed a red-shift and a broadening of an emission peak (peak c) which originally appeared at 0.970 eV before annealing and the red-shifted peak c was found to consist of two overlapping peaks. The excitation power dependence of these overlapping peaks indicated the radiative recombination processes associated with the emissions to be a conduction band to acceptor transition (peak at 0.970 eV) and a transition due to donor-acceptor pairs (peak at 0.959 eV), indicating the formation of a shallow donor-type defect during the vacuum annealing process. The origin of this defect has tentatively been attributed to Se vacancies. On the other hand, the molar fraction of oxygen increased with increasing annealing temperature in dry-air. An epitaxially grown In₂O₃ phase was found both in Cu-rich and In-rich films annealed at T_A 350°C, which was not observed in the films annealed in Ar atmosphere. Thermodynamic calculations based on the Cu---In---Se---O---N system showed In₂O₃ to be the most stable phase in good agreement with the experimental results.     

The influence of sodium on the properties of CuInS2 thin films and solar cells

The controlled incorporation of sodium into the absorber layer of CuInS₂ solar cells improved cell performance remarkably. Without toxic KCN treatment, conversion efficiencies of over 6% were achieved by sulfurization of sodium-containing precursors. We also investigated the characteristics of the sodium-incorporated CuInS₂ films by intentional addition and diffusion from a soda-lime glass. The ternary compound semiconductor of NaInS₂ was found to form mainly on the surface of each of the CuInS₂ films.     

Electrical and luminescent properties of CuGaSe2 crystals and thin films

CuGaSe₂ thin films with thicknesses of about 2 μm were prepared by flash and single source evaporation onto mica and (1 1 0)-oriented ZnSe substrates in the substrate temperature range 150–450°C. The obtained polycrystalline CuGaSe₂ films had the chalcopyrite structure with the predominant growth direction 2 2 1. Hall effect, conductivity and luminescence measurements have been carried out on CuGaSe₂ thin films and source materials: CuGaSe₂ single crystals grown by Bridgman technique and by chemical vapour transport using I₂ as transport agent. All films and crystals are p-type. Two acceptor levels with ionization energies E_A150–56 meV and E_A2130–150 meV have been identified as due to Ga vacancy and presence of Se atoms on interstitial sites respectively.     

Blue-photon modification of nonstandard diode barrier in CuInSe2 solar cells

The current–voltage curves of many ZnO/CdS/CuInSe₂ solar cells display significant distortion when only red light illumination is employed. This distortion generally disappears or partially disappears for a period of time following illumination with blue light. Similarly, the dark diode curve shortly after illumination containing blue light is shifted significantly from the equilibrium dark curve. This effect is more common than generally realized and indicates a mechanism that is potentially detrimental to photovoltaic efficiency. A model is presented that is based on a low free-electron concentration and a high concentration of deep levels in the CdS window layer. This model is consistent with observed variations in current–voltage, capacitance, and laser scan data with illumination wavelength and history.     

Synthesis of LiCoO2 thin films by sol/gel process

LiCoO₂ thin films were synthesized by sol/gel process using acrylic acid (AA) as chelating agent. The gel formulation was optimized by varying solvent (ethylene glycol or water) and precursors molar ratios (Li, Co, AA) in order to obtain a dense film for positive electrode of lithium batteries. The gel was deposited by spin-coating technique on an Au/TiO₂/SiN/SiO₂/Si substrate. Thin films were deposited by either single or multistep process to enhance the density of the thin film and then calcined during 5 h at 800 °C to obtain the R-3m phase (HT-LiCoO₂).A chemical characterization of the solution was realized by Fourier Transform Infrared (FTIR) spectroscopy. Thermal decomposition of precursors and gel was studied by Thermo Gravimetric Analyses (TGA). Further investigations were done to characterize rheologic behaviour of the gel and solvents affinity with the substrate. Crystallinity and morphology were analyzed respectively by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM).The formation of R-3m phase was confirmed by the electrochemical behaviour of the gel derived LiCoO₂. Cyclic voltammograms and galvanostatic cycling show typical curve shape of the HT-LiCoO₂.     

The formation of CuInSe2 thin film solar cell absorbers from electroplated precursors with varying selenium content

We present results from real-time X-ray diffraction experiments on the formation of CuInSe₂ solar cell absorbers by annealing precursors, produced by simultaneous electrodeposition of copper, indium and selenium. The investigations reveal, that a reduced amount of electrochemically deposited selenium is the decisive parameter in order to realise a chalcopyrite formation behaviour as observed for sputtered stacked elemental layer (SEL) precursors. A simultaneous electrodeposition of the elements copper, indium and selenium in the molar ratio 1:1:2 of the chalcopyrite CuInSe₂ leads to the formation of binary copper and indium selenides during the electrodeposition process. The existence of binary selenides besides the intermetallic phase Cu₁₁In₉ as initial phases leads to an unfavourable absorber morphology. This can be explained by the observed semiconductor formation mechanism. A reduction of the deposited amount of selenium favours the formation of the intermetallic compound Cu₁₁In₉ and reduces the amount of binary selenides. These precursors show a formation behaviour and resulting absorber morphology as known for sputtered SEL precursors.     

Ex-situ and in-situ analyses on reaction mechanism of CuInSe2 (CIS) formed by selenization of sputter deposited CuIn precursor with Se vapor

Formation mechanism of CIS thin films by selenization of sputter deposited CuIn precursor with Se vapor was investigated by ex-situ and in-situ phase analysis tools. Precursor films were composed of In, CuIn and Cu₂In compounds, and their relative fractions were systematically changed with Cu/In ratios. Those films were found to have a double layered structure with nearly pure In particles (top layer) placed on the flat Cu-rich bottom layer, and the morphologies were also significantly affected by Cu/In ratio. At the initial stage of selenization, the outer In-rich layer reacted with Se vapor to form In-Se binary, which is the first selenide phase appeared, and inner Cu-rich phases acted as a Cu source to supply Cu to outer In-Se phase to form ordered vacancy compounds (OVC). As these reactions continues, in conjunction with Se incorporation into inner Cu-rich region, the films gradually changes from OVC to α-CIS, reflecting that the formation route of CIS is closely related to the elemental and phase distribution in precursor films. Selenized CIS films were further processed to fabricate CIS thin film solar cells, resulting in the best cell efficiency of 10.44%.