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.     

Thin films of Cu(In,Ga)Se2 and ordered vacancy compound prepared by thermal crystallization and their photovoltaic applications

Thin films of Cu–In–Ga–Se alloy system with various composition were prepared by thermal crystallization from In/CuInGaSe/In precursor. Electron probe microanalysis and X-ray diffraction study revealed that these samples were assigned to chalcopyrite Cu(In,Ga)Se₂ or ordered vacancy compound Cu(In,Ga)₂Se_3.5. Solar cell with ZnO:Al/i–ZnO/CdS/Cu(In,Ga)Se₂/Mo/soda-lime glass substrate structure was fabricated by using thermal crystallization technique, and demonstrated a 9.58% efficiency without AR-coating.     

Precursor modification for preparation of CIS films by selenization technique

CuInSe₂ films have been prepared using the selenization technique. Preparation of the precursor as well as selenization were carried out by the vacuum evaporation technique. The sequence of copper and Indium layer deposition during precursor preparation affects the morphological and structural properties of precursor which directly have effects on the properties of selenized CIS films. A thin layer of amorphous selenium at the substrate/film interface has been used to improve the adherence of the film. The effect of the Se under-layer has been studied on the layers of copper, indium, CuIn precursors and CIS films, using structural, morphological and optical properties. The surface morphology of a single layer of copper and indium, with and without the Selenium under-layer, are quite different and drastically affect the properties of the precursor and selenized films. The Se under-layer does not take part in the chemical reaction of CIS formation during the selenization process. The modified CIS films are uniform, single phase, polycrystalline, chalcopyrite with (1 1 2) preferred orientation showing an energy band gap of 0.99 eV and an absorption coefficient of 10⁵ cm⁻¹, and have good adherence to the substrate for the scotch tape test.     

Preparation of CuIn1−xGaxSe2 thin films by sputtering and selenization process

CuIn_1−xGa_xSe₂ polycrystalline thin films were prepared by a two-step method. The metal precursors were deposited either sequentially or simultaneously using Cu–Ga (23 at%) alloy and In targets by DC magnetron sputtering. The Cu–In–Ga alloy precursor was deposited on glass or on Mo/glass substrates at either room temperature or 150°C. These metallic precursors were then selenized with Se pellets in a vacuum furnace. The CuIn_1−xGa_xSe₂ films had a smooth surface morphology and a single chalcopyrite phase.     

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.     

Preparation of Cu(In,Ga)Se2 thin films from Cu–Se/In–Ga–Se precursors for high-efficiency solar cells

Improved preparation process of a device quality Cu(In,Ga)Se₂ (CIGS) thin film was proposed for production of CIGS solar cells. In–Ga–Se layer were deposited on Mo-coated soda-lime glass, and then the layer was exposed to Cu and Se fluxes to form Cu–Se/In–Ga–Se precursor film at substrate temperature of over 200°C. The precursor film was annealed in Se flux at substrate temperature of over 500°C to obtain high-quality CIGS film. The solar cell with a MgF₂/ITO/ZnO/CdS/CIGS/Mo/glass structure showed an efficiency of 17.5% (V_oc=0.634 V, J_sc=36.4 mA/cm², FF=0.756).     

CuIn(Ga)Se2-based devices via a novel absorber formation process

A novel pathway for the formation of copper–indium (gallium) diselenide has been developed. This two-stage process consists of (a) the formation of Cu–In–(Ga)–Se precursors, and (b) subsequent thermal treatment to form CuIn(Ga)Se₂. The morphology, structure and growth mechanism for several different precursor structures prepared under various conditions were studied and correlated to the deposition parameters as well as the structure and morphology of the annealed films. Photovoltaic devices prepared from CuInSe₂ and CuIn_0.75Ga_0.25Se₂ resulted in efficiencies of 10% and 13%, respectively.     

Electrodeposited CuInS2-based thin-film solar cells

CuInS₂ thin films were prepared by sulfurization of electrodeposited Cu–In precursors. Morphological improvement enabled us to fabricate the solar cells using electrodeposited Cu–In precursors. The photovoltaic property of a conversion efficiency of 1.3% was obtained.     

Cu(In,Ga)Se2 based photovoltaic structure by electrodeposition and processing

CuIn_1−xGa_xSe₂ (CIGS) thin films were formed from an electrodeposited CuInSe₂ (CIS) precursor by thermal processing in vacuum in which the film stoichiometry was adjusted by adding In, Ga and Se. The structure, composition, morphology and opto-electronic properties of the as-deposited and selenized CIS precursors were characterized by various techniques. A 9.8% CIGS based thin film solar cell was developed using the electrodeposited and processed film. The cell structure consisted of Mo/CIGS/CdS/ZnO/MgF₂. The cell parameters such as J_sc, V_oc, FF and η were determined from I–V characterization of the cell.     

Photoreduction of CO2 to fuels under sunlight using optical-fiber reactor

An optical-fiber reactor is employed to photocatalytically reduce CO₂ with H₂O to fuels under UVA artificial light and concentrated natural sunlight. The optical fiber is coated with gel-derived TiO₂–SiO₂ mixed oxide-based photocatalysts. Fe atom is found to insert into the TiO₂–SiO₂ lattice during sol–gel process, resulting in the full visible light absorption as well as the effect on product selectivity of the derived catalyst. Under UVA, ethylene is mainly produced on Cu–Fe/TiO₂ catalyst with the quantum yield of 0.0235%, whereas Cu–Fe/TiO₂–SiO₂ catalyst is observed to favor methane production with the quantum yield of 0.05%. Meanwhile, the overall energy efficiency is found to be much higher on Cu–Fe/TiO₂–SiO₂ (0.0182%) than on its Cu–Fe/TiO₂ counterpart (0.0159%). There is only methane evolved over both bare TiO₂–SiO₂ and Cu–Fe/TiO₂–SiO₂ catalysts under natural sunlight with the production rates of 0.177 and 0.279 μmol/g-cat h, respectively. For the former catalyst, the increase in light intensity is not found to compensate the inherent electron–hole recombination in the TiO₂–SiO₂–acac catalyst, whereas the superior photoactivity of Cu–Fe/TiO₂–SiO₂ catalyst under natural sunlight could be ascribed to its full absorption of visible light.     

Deposition and characterization of CuInSe2

Polycrystalline CuInSe₂ thin film solar cells were prepared by two methods: three-source evaporation and co-electrodeposition from a single bath. Structural and compositional characterization was carried out by X-ray diffraction, energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The evaporation technique produced chalcopyrite CIS for stoichmetric and In-rich films while the Cu-rich films exhibited only the sphalerite phase. SEM analysis shows grain sizes of 0.5–0.7 μum for stoichmetric CIS. Electron diffraction also revealed the presence of CIS. It was found that sufficient Cu, In and Se could be co-electrodeposited from a single bath. EDS analysis showed that annealing resulted in the loss of Se. The adhesion of the film to the substrate depends critically on the current density and time of deposition.     

Preparation and photocharacterization of Cu–Sb–Se films by electrodeposition technique

Ternary semiconductor Cu–Sb–Se films were grown on 304 stainless-steel/Cr and ITO-glass using a combination of electrodeposition and chemical bath techniques. The samples were annealed in a N₂ atmosphere at various temperatures and characterized by X-ray, electron probe microanalysis, current–voltage, capacitance–voltage and photocurrent spectroscopy. Photoelectrochemical studies were used to determinate the flat-band potential and the doping density of the material. These data lead to energetic considerations on the applicability of the Cu–Sb–Se electrode in the photoelectrochemical decomposition of water.     

Preparation and thermochromic property of tungsten-doped vanadium dioxide particles

Tungsten (W)-doped vanadium dioxide (VO₂) particles were successfully synthesized by hydrolysis of vanadyl sulfate mingled with a small amount of sodium tungstate dihydrate and subsequent calcination. XPS analyses demonstrated that the vanadium oxide was composed of stoichiometric VO₂, and the doped W content in VO₂ particles could be easily controlled by the concentration of W precursor. XRD patterns indicated that all the W-doped VO₂ particles were monoclinic crystals, and the W dopant almost had no influence on the crystal structure of VO₂ particles. DSC analyses displayed that the critical phase transition temperature of VO₂ particles could be reduced to room temperature or even lower by increasing the doped W fraction. UV–vis–NIR spectra showed that the W-doped VO₂ particles embedded acrylic coating had very good thermochromic performance.     

CuInS2/SiNWs/Si composite material for application as potential photoelectrode for photoelectrochemical hydrogen generation

This work aims at developing a new composite material based on nanosized semiconducting CuInS₂ (CIS) particles combined with silicon nanowires grown on a silicon substrate (SiNWs/Si) for photoelectrochemical (PEC)-splitting of water. The CIS particles were prepared via a colloidal method using N-methylimidazole (NMI) as the solvent and an annealing treatment. The SiNWs were obtained by chemical etching of silicon (100) substrates assisted by a metal. The CIS/SiNWs/Si composite material was obtained by deposition of an aliquot of a suspension of CIS particles onto the SiNWs/Si substrate, using spin coating followed by a drying step. The XRD pattern demonstrated that CuInS₂ grows in the tetragonal/chalcopyrite phase, while SiNWs/Si presents a cubic structure. The SEM images show semi-spherical particles (～10 nm) distributed on the surface of silicon nanowires (～10 μm). The EIS measurements reveal n-type conductivity for CIS, SiNWs/Si and CIS/SiNWs/Si materials, which could favour the oxidation reaction of water molecules.     

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%.     

Pentanary chalcopyrite compounds without tetragonal deformation in the heptanary system Cu(Al,Ga,In)(S,Se,Te)2

The c/a ratios of the nine ternary Cu–III–VI₂ compounds in the system Cu(Al,Ga,In)(S,Se,Te)₂ range from 1.939 for CuAlSe₂ to 2.014 (CuInS₂) at room temperature. The validity of Vegard's law was presumed to determine the tetragonal deformation 1–c/(2a) for all pentanary mixed crystal compounds Cu–(III,III)–(VI–VI)₂. For six of these nine compounds it is possible to achieve zero tetragonal deformation by adjusting the correct cation and anion substitution. The calculations are performed for room temperature as well as for 500 °C, which is a typical temperature for the synthesis of thin films of these semiconductor compounds.     

Antireflecting–passivating dielectric films on crystalline silicon solar cells for space applications

Antireflecting–passivating TiO₂–SiO₂ double layers on crystalline silicon (Si) were optimized and characterized for space solar cells applications. In the numeric optimization, the MgF₂–glass–adhesive–TiO₂–SiO₂–Si structure was considered. In order to fabricate the TiO₂–SiO₂ double layer, titanium films were deposited on Si wafers in a vacuum chamber, and then, the sample was annealed in oxygen at high temperatures. Glasses with evaporated MgF₂ thin films were bonded to the TiO₂–SiO₂–Si samples so as to obtain the complete structure. A gain of up to 23.5% in the maximum power is demonstrated for simulated c-Si solar cells using the optimized structure. Characterization of the TiO₂–SiO₂–Si structure using transmission electron microscopy (TEM) and X-ray reflectivity (XRR) as well as optical characterization are presented.     

Electrochromic characterization of Co(OH)2 thin film prepared by sol–gel process

Electrochemical, spectroscopic and structural measurements were used to characterize the electrochromic behavior and stability of sol–gel deposited Co(OH)₂ thin films. These films were prepared from polymeric solutions containing cobalt methoxyethoxide precursor by spin coating technique. The as-deposited films are amorphous and show crystalline structure after heat treatment at 450°C. Sol–gel-deposited cobalt hydroxide films show reversible electrochromic response in 1 M LiClO₄/ propylene carbonate solution beyond 500 cycles. The structural and chemical properties of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Spectral transmittance change was T_p=29.9–60.2% for cobalt hydroxide films. It is argued that reversible lithium insertion capacity, good cyclic reversibility of Co(OH)₂ films make them suitable as counterelectrode layers in the electrochromic devices.     

Structure, morphology and photoelectrochemical activity of CuInSe2 thin films as determined by the characteristics of evaporated metallic precursors

CuInSe₂ thin films have been obtained by the sequential evaporation of Cu and In layers, and subsequent reaction at 400°C with elemental selenium vapor. The individual metallic film thickness and the substrate temperature during evaporation have been varied in order to promote intermixing and alloy formation before the selenization. The structure, morphology and photoelectrochemical activity of the CuInSe₂ films have been determined by the characteristics of the evaporated metallic precursors. An improvement in the CuInSe₂ quantum efficiency, related mainly to the increased homogeneity and smoothing of the sample surface, can be gained by using as precursors multiple stacked Cu–In bilayers evaporated onto unheated substrates.     

CIS and CIGS based photovoltaic structures developed from electrodeposited precursors

In the present study we report the electrodeposition and characterization of CIS and CIGS thin films and a post-deposition thermal processing in vacuum to improve the film stoichiometry by incorporating additional In, Ga and Se. Different kinds of analyses showed that CIS as well as CIGS possess a very thin In-rich surface n-layer. The formation and characterization of solar cell structures from the electrodeposited precursor with the configuration glass/Cr/Mo/CIS(CIGS)/CdS/ZnO/MgF₂ is also reported. The optoelectronic properties such as Voc, Isc, FF, η etc. of the cells are presented.