Flexible and light weight copper indium diselenide solar cells on polyimide substrates

Thin film flexible CuInSe₂ (CIS) solar cells have been fabricated for the first time on light-weight polymeric substrates. Evaporated Cu---In alloy precursors were selenized in H₂Se atmosphere at around 400°C to grow the CIS absorber layers. Low temperature techniques which are compatible with the polymeric substrates were used to deposit the window layers of CdS and ZnO. The demonstrated active area conversion efficiency of 9.3% makes this light-weight device very attractive for many terrestrial and space power generation applications where high specific power and mechanical flexibility are needed.     

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.     

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.     

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.     

Compositional and optoelectronic properties of CIS and CIGS thin films formed by electrodeposition

CuInSe₂ (CIS) and Cu(In,Ga)Se₂ (CIGS) thin films were prepared by electrodeposition and processing. The influence of film deposition parameters such as bath composition, pH, deposition potential and material purity on film properties was studied. The structural, morphological, compositional and opto-electronic properties of electrodeposited and selenized CIS and CIGS thin films were characterized using various techniques. As-deposited as well as selenized films exhibited a compact or a granular morphology depending on the composition. The film stoichiometry was improved after selenization at 550°C in a tubular furnace. The films are formed with a mixed phase composition of CuInSe₂ and CuIn₂Se_3.5 ternary phases.     

Different phases of indium selenide prepared by annealing In/Se bilayer at various temperatures: Characterization studies

Thin films of indium selenide were prepared by annealing Indium/Selenium stack layers at different temperatures ranging from 100 to 400 °C. Structural and optical characterizations were done using X-ray diffraction and optical absorption studies, respectively. Compositional analysis was done by employing Rutherford backscattering spectroscopy and X-ray photoelectron spectroscopy confirmed the compound formation. Photosensitivity and sheet resistance of these samples were also determined at room temperature. It was found that multi-phased films were formed at lower annealing temperatures and single phase films at higher annealing temperatures. A structural re-orientation as well as a phase transformation from β-In₂Se₃ to γ-In₂Se₃ was observed on annealing at 400 °C.     

Sub-micrometer thick CuInSe2 films for solar cells using sequential elemental evaporation

CuInSe₂ thin films were prepared using sequential vacuum evaporation of In, Se and Cu at moderately low substrate temperatures, avoiding any treatment using toxic H₂Se gas. The samples were annealed at 400 °C at a pressure of 10⁻⁵ mbar to form CuInSe₂. Structural, optical, electrical, compositional and morphological characterizations were carried out on these films. We could obtain highly stoichiometric film, using this simple method, without opting for co-evaporation or high substrate temperature for deposition.     

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.     

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.     

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.     

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.     

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.     

Back contact formation using Cu2Te as a Cu-doping source and as an electrode in CdTe solar cells

Cu₂Te was utilized as a Cu source for p⁺ doping in CdTe and as a primary back contact material in CdTe solar cells. A 60 nm-thick Cu₂Te layer was deposited on CdTe film by evaporating Cu₂Te and the samples were annealed at various temperatures. An amorphous layer was found at the Cu₂Te/CdTe interface, while the Cu₂Te has both orthorhombic and hexagonal phases. Annealing at 200°C completely crystallized the amorphous interlayer and enhanced the transformation of orthorhombic phase into hexagonal phase that has a coherent interface with CdTe. A good p⁺ contact was formed at 180°C annealing, where the series resistance of CdTe cells was a minimum of 0.5 Ω·cm² and the fill factor and open-circuit voltage were significantly improved. With the good p⁺ contact, it is possible to determine the exact dopant profile at the CdS/CdTe junction.     

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%).     

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 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.     

Deposition of transparent and conductive Al-doped ZnO thin films for photovoltaic solar cells

The effect of the substrate temperature on the optoelectronic properties of ZnO-based thin films prepared by rf magnetron sputtering has been studied. Three different targets (Zn/Al 98/2 at%, ZnO:Al 98/2 at% and ZnO:Al₂O₃ 98/2 wt%) have been investigated in order to compare resulting samples and try to reduce the substrate temperature down to room temperature. From the ZnO:Al₂O₃ target, transparent conductive zinc oxide has been obtained at 25°C with the average optical transmission in the 400–800 nm wavelength range, T = 80–90% and resistivity, = 3−5 × 10⁻³ Ωcm. In Al:Zn0 layers, the spatial distribution of the electrical properties across the substrate placed parallel to the target has been improved by depositing at high substrate temperatures, above 200°C. Besides, owing to diffusion processes of CuInSe₂ and CdS take place at 200°C, an AI:ZnO/CdS/CuInSe₂ polycrystalline solar cell made with the Al:ZnO deposited at 25°C as the transparent conductive oxide, has shown a more efficient photovoltaic response, η = 6.8%, than the one measured when the aluminium-doped zinc oxide has been prepared at 200°C, η = 1.8%.     

Three-stage growth of Cu–In–Se polycrystalline thin films by chemical spray pyrolysis

Structural, optical and electrical properties of polycrystalline Cu–In–Se films, such as CuInSe₂ and ordered vacancy compounds (OVC), prepared by three-stage process of sequential chemical spray pyrolysis (CSP) of In–Se (first stage), Cu–Se (second stage) and In–Se (third stage) solutions have been studied in terms of substrate temperature at the second stage (T_S2). The films grown at T_S2420 °C exhibited larger grains in comparison with the Cu–In–Se films grown by the usual CSP method. Optical gap energy was approximately 1.06 eV for 360 °CT_S2420 °C, but increased dramatically from 1.06 to 1.35 eV when the T_S2 rose from 420 to 500 °C. Conductivity type was p-type for T_S2<420 °C, but n-type for T_S2>420 °C.     

Cu–Ga–Se thin films prepared by a combination of electrodeposition and evaporation techniques

Cu–Ga–Se thin films were prepared using a combination of electrodeposition and evaporation techniques. A Cu–Se/Mo/glass precursor thin film was first prepared by galvanostatic electrodeposition. On top of this film three different thicknesses of Ga were deposited by evaporation. The Cu–Ga–Se thin films were formed by annealing the Ga/Cu–Se/Mo/glass thin film configuration in a tubular chamber with Se powder, at different temperatures. Thin films were characterized by X-ray diffraction (XRD), photocurrent spectroscopy (PS), inductively coupled plasma (ICP) analysis, and scanning electron microscopy (SEM). The detailed analysis from X-ray reveals that after annealing at 550 °C the CuGaSe₂ phase is formed when the thickness of Ga is 0.25 μm, however at 0.5 μm and 1.0 μm Ga the formation of CuGa₃Se₅ and CuGa₅Se₈ phases is observed respectively. Band gap values were obtained using photocurrent spectroscopy.     

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).