Fabrication of CuInSe2 films and solar cells by the sequential evaporation of In2Se3 and Cu2Se binary compounds

Cu₂Se/In_xSe(x≈1) double layers were prepared by sequentially evaporating In₂Se₃ and Cu₂Se binary compounds at room temperature on glass or Mo-coated glass substrates and CuInSe₂ films were formed by annealing them in a Se atmosphere at 550°C in the same vacuum chamber. The In_xSe thickness was fixed at 1 μm and the Cu₂Se thickness was varied from 0.2 to 0.5 μm. The CuInSe₂ films were single phase and the compositions were Cu-rich when the Cu₂Se thickness was above 0.35 μm. And then, a thin CuIn₃Se₅ layer was formed on the top of the CuInSe₂ film by co-evaporating In₂Se₃ and Se at 550°C. When the thickness of CuIn₃Se₅ layer was about 150 nm, the CuInSe₂ cell showed the active area efficiency of 5.4% with V_oc=286 mV, J_sc=36 mA/cm² and FF=0.52. As the CuIn₃Se₅ thickness increased further, the efficiency decreased.     

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 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.     

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.     

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.     

Synthesis and transport properties of prospective photovoltaic systems related to CuInSe2 and CuGaSe2

Solid solutions in CuGaSe₂–ZnSe and CuInSe₂–ZnSe systems have been obtained by radio frequency heating. In order to prepare n-type phases based on CuGaSe₂, p-type (CuGa)_1−xZn_2xSe₄ and (CuIn)_1−xZn_2xSe₄ (0.05x0.1) single crystals were doped by Ag, Hg, Cd, Zn implantation. The crystal structure of the solid solutions was studied by X-ray diffraction; the substitutors as well as the implantant valence states were analyzed using X-ray photoelectron spectroscopy. Hall effect, electrical conductivity, and the charge carrier mobility of an n-type zinc-implantated solid solution (CuGa)_1−xZn_2xSe₄ and (CuIn)_1−xZn_2xSe₄ (0.05x0.1) were studied.     

Selenization of Cu and In thin films for the preparation of selenide photo-absorber layers in solar cells using Se vapour source

Gas phase selenization of vacuum deposited Cu and In thin films employing an elemental Se vapour source is demonstrated as an essential first step in the search for optimized process parameters for the formation of single phase CuInSe₂ materials suitable for solar cell applications. The selenization was accomplished in Se vapour, derived from an elemental Se source, held at 240–260°C. This source was placed in a flow of nitrogen gas at 500 Torr to transport the Se vapour to the metal films. The selenization reaction readily occurs at Cu and In films kept at 340–400°C. Lower selenization temperatures invariably lead to the formation of Cu and In selenides with well defined crystalline microstructures. Hexagonal CuSe with an excess of Se in the matrix is the equilibrium growth phase, while the cubic Cu_2−xSe phase evolves under conditions of excess Se flux. Selenization of the In films consistently led to the formation of the β-form of hexagonal In₂Se₃. At high selenization temperatures (400°C), while the β-form still emerges as the major component, traces of the α-form of In₂Se₃ are also detected. Detailed X-ray diffraction, electron probe analysis and microstructure data are presented.     

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.     

Microstructure evolution of CuInSe2 thin films prepared by single-bath electrodeposition

The composition and the microstructure evolutions of CuInSe₂ thin films under single-bath electrodeposition processes were investigated. It was found that the film composition was mainly determined by the [Se⁴⁺]/[Cu²⁺] ratios in solution, but the film microstructure is strongly dependent on the initial concentrations of Se⁴⁺, Cu²⁺, and In³⁺ precursors. Higher initial concentrations of Cu²⁺ and In³⁺ in solution are beneficial for the fabrication of compact CuInSe₂ thin films with highly crystallized and large grain sized chalcopyrite phase. The microstructure evolution suggests that prior adsorption and reduction of Cu²⁺ ions and the formation of Cu₂Se compound on the substrate can promote the nucleation, growth, and coarsening of CuInSe₂ crystal to form a high quality thin film during the electrodeposition processes.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

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.     

Growth and properties of single-phase γ-In2Se3 thin films on (1 1 1) Si substrate by AP-MOCVD using H2Se precursor

A set of In₂Se₃ films was grown on (1 1 1) Si substrate with AlN buffer by metalorganic chemical vapor deposition (MOCVD) using H₂Se as the metalogramic precursors for Se. The In₂Se₃ films on (1 1 1) Si substrate were pinhole-free with homogeneous and lamellar structures. It was found that by properly controlling the substrate temperatures, single-phase γ-In₂Se₃ films with fairly good optical properties can be well fabricated. Photoluminescence spectra of single-phase γ-In₂Se₃ show exciton emissions at 2.140 eV at 10 K. The band gap of single-phase γ-In₂Se₃ at room temperature is estimated at 1.943 eV.     

Optical and electrical studies on molybdenum sulphoselenide [Mo(S1−xSex)2] thin films prepared by arrested precipitation technique (APT)

Nanocrystalline stoichiometric [Mo(S_1−xSe_x)₂] thin films were deposited by using arrested precipitation technique (APT) developed in our laboratory. The precursors used for this are namely, molybdenum triethanolamine complex, thioacetamide and sodium selenosulphite; and various preparative conditions are finalised at the initial stages of deposition. Formation of [Mo(S_1−xSe_x)₂] semiconducting thin films are confirmed by studying growth mechanism, optical and electrical properties. X-ray diffraction analysis showed that the composites are nanocrystalline being mixed ternary chalcogenides of the general formula [Mo(S_1−xSe_x)₂]. The optical studies revealed that the films are highly absorptive (α×10⁴ cm⁻¹) with a band-to-band direct type of transitions and the energy gap decreased typically from 1.86 eV for pure MoS₂ down to 1.42 eV for MoSe₂. The thermoelectrical power measurement shows negative polarity for the generated voltage across the two ends of semiconductor thin films. This indicate that the [Mo(S_1−xSe_x)₂] thin film samples show n-type conduction.     

Quantification of losses in thin-film polycrystalline solar cells

Comparison of measured solar-cell parameters with calculations for ideal cells is a powerful tool to assist fundamental understanding and to focus on the most effective fabrication procedures. The emphasis here will be on quantitative separation of individual loss mechanisms in polycrystalline thin-film cells based on CdTe, CuInSe₂ (CIS), and related alloys such as CuIn_1−xGa_xSe₂ (CIGS). Several techniques to facilitate separation of losses are described.     

Comparison of point defects in CuInSe2 and CuGaSe2 single crystals

Hall-effect and photoluminescence measurements have been carried out on as-grown and In/Ga-annealed CuInSe₂ and CuGaSe₂ single crystals grown by chemical vapor transport. Various defect levels in these related compounds have been identified and compared. V_Cu and V_Se show similar properties and activation energies in both materials. A tremendous difference is observed in the behavior of III_Cu antisite defects. Ga_Cu levels in CuGaSe₂ are much deeper than In_Cu in CuInSe₂, and furthermore, the formation of In_Cu is much easier compared to Ga_Cu. This is related to the higher formation energy of Ga_Cu in CuGaSe₂. Due to this difference in the defect chemistry of both compounds, it has not been possible until now, to prepare n-type CuGaSe₂ crystals, whereas CuInSe₂ is easily transformed from p- to n-type by annealing in vacuum or In-atmosphere.     

Characterization and electrochromic properties of CuxNi1−xO films prepared by sol–gel dip-coating

Cu_xNi_1−xO electrochromic thin films were prepared by sol–gel dip coating and characterized by XRD, UV–vis absorption and electrochromic test. XRD results show that the structure of the Cu_x Ni_1−xO thin films is still in cubic NiO structure. UV–vis absorption spectra show that the absorption edges of the Cu_xNi_1−xO films can be tuned from 335 nm (x = 0) to 550 nm (x = 0.3), and the transmittance of the colored films decrease as the content of Cu increases. Cu_xNi_1−xO films show good electrochromic behavior, both the coloring and bleaching time for a Cu_0.2Ni_0.8O film were less than 1 s, with a variation of transmittance up to 75% at the wavelength of 632.8 nm.     

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.     

Properties of CuIn1−xGaxSe2

Polycrystalline bulk samples of CuIn_1−xGa_xSe₂ weregrown with nominal x = 0.15, 0.25 and 0.5. Mobility, conductivity and band gap were measured at room and low temperatures. Mobilities for x = 0.21 were several hundred cm² V⁻¹s⁻¹ at room temperature and for x = 0.15 were 10³ cm² V⁻¹ s⁻¹, all n type. The band gaps were estimated from the spectra of photoelectrochemical cells at room temperature (with 8.5 K photoluminescence estimates shown in brackets), as 1.10 eV (1.14) for x = 0.21, and 1.07 eV (1.093) for x = 0.15. Crystal mechanical properties as regards cracks were not as good as for CuInSe₂, using similar growth techniques.     

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%).     

A structural study of RF-sputtered …Cu/Te… multi-layers

Cu/Te multi-layers with a composition of 50 at% of Te were deposited onto glass substrates by radio frequency (RF) sputtering. Their structure was investigated by the grazing-incidence X-ray diffraction technique (GIXD). The spectra of the as-deposited sample show the formation of hexagonal Cu_2−xTe and the presence of free Te. The heat treatments at 450 K during 30 min, 1 h and 2 h show the progressive disappearance of the Cu_2−xTe phase and the appearance of a new compound—the orthorhombic rickardite Cu₇Te₅, suggesting that a Cu_2−xTe→Cu₇Te₅ transformation took place.The samples annealed for a period of 3 h at 450 K show that Cu₇Te₅ completely disappeared in favour of Cu_2−xTe and, more precisely, the Cu_0.647Te_0.353 phase dominates the spectra, suggesting that a Cu₇Te₅→Cu_2−xTe inverse phase transformation took place.The results are discussed in light of the strong inter-diffusion that occurred between the Cu and Te layers during the deposition at ambient temperature and to elemental diffusion during annealing. The phase transformations are attributed to a diffusion-induced homogenization of the sample and a loss of Te by sublimation during annealing for an extended time.