CIS thin film solar cells with evaporated InSe buffer layers

This paper describes the investigations of CIS-based solar cells with a new In_xSe_y (IS) buffer layer. Studies were concentrated on determining the deposition conditions to get In_xSe_y thin films with adequate properties to be used in substitution of the CdS buffer layer, usually employed in the fabrication of this type of devices. Before the solar cell fabrication, the buffer layers grown by evaporation of the In₂Se₃ compound were characterized through transmittance and X-ray diffraction measurements. It was found that good results can be obtained using indium selenide film as the buffer layer, grown in the In₂Se₃ phase.Solar cells with structure Mo/CIS/In₂Se₃/ZnO were fabricated. The ZnO layer was deposited by reactive evaporation and the absorber CIS layer was grown on Mo by a two-stage process. The preliminary results obtained with this type of solar cells are J_sc=30.8 mA/cm², V_oc=0.445 V, FF≈0.6 and η=8.3% with an irradiance of 100 mW/cm². Solar cells fabricated using a CdS buffer layer deposited by CBD on CIS substrate, prepared under the same conditions used in the fabrication of Mo/CIS/In₂Se₃/ZnO cells, gave the following results: V_oc=0.43 V, J_sc=34 mA/cm², FF≈0.63 and η=9.2%.     

Improved Jsc in CIGS thin film solar cells using a transparent conducting ZnO:B window layer

A comparative study of the cell performance of CIGS thin-film solar cells fabricated using ZnO:Al and ZnO:B window layers has been carried out. ZnO:B films were deposited by RF magnetron sputtering using an undoped ZnO target in a B₂H₆–Ar gas mixture. The short-circuit current (J_sc) was found to improve upon the replacement of the ZnO:Al layer with ZnO:B layers. This improvement in J_sc is attributed to an increase in quantum efficiency due to the higher optical transmission of the ZnO:B layer in the near-infrared region. The best cell fabricated with a MgF₂/ZnO:B/i-ZnO/CdS/CIGS/Mo structure yielded an active area efficiency of 18.0% with V_oc=0.645 V, J_sc=36.8 mA/cm², FF=0.76, and an active area of 0.2 cm² under AM 1.5 illumination.     

CIS/CdS/ZnO/ZnO:Al modified photocathode for enhanced photoelectrochemical behavior under visible irradiation: Effects of pH and concentration of electrolyte solution

In this paper, the CuInS₂ films were firstly modified with CdS and CdS/ZnO/ZnO:Al/Au layers in order to improve the photoelectrochemical (PEC) water splitting efficiency. The CuInS₂ photoelectrode was synthesized by electrodeposition method as a facial and green method, on the FTO substrate. The effects of pH and concentration of Na₂S electrolyte solution on the photocurrent density of photoelectrode samples were studied. As a p-n junction photocathode, the CIS/CdS/ZnO/ZnO:Al/Au photoelectrode indicates the enhanced PEC activity. The photocurrent density of CIS/CdS/ZnO/ZnO:Al/Au photoelectrode reaches to 1.91 mA/cm², while is about 2.5 times higher than that for CuInS₂ film at pH = 8 (−0.6 V vs Ag/AgCl). The formation of a p-n junction at the CuInS₂ photoelectrode surface not only reduces the recombination of electron-hole pairs but also increases the PEC response and water splitting performance of the as-prepared CIS/CdS/ZnO/ZnO:Al/Au photoelectrode.     

Chemical studies of solar cell structures based on electrodeposited CuInSe2

ZnO/CdS/CIS solar cell structures have been made by using different deposition techniques for each layer: standard rf-magnetron sputtering and chemical bath deposition for ZnO and CdS, respectively, and direct electrodeposition for CIS as a low-cost alternative to the co-evaporated absorber. Chemical studies of ZnO, CdS and CIS films, ZnO–CdS and CdS–CIS bilayers, and ZnO–CdS–CIS cells have been performed by utilising XPS. No chemical reactions were detected in the interfaces. Photovoltaic quality was evaluated from the spectral response data.     

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%.     

A highly efficient and stable CdTe/CdS thin film solar cell

In this paper we describe the fabrication and characteristics of highly efficient and stable CdTe/CdS thin film solar cells. Our cells are prepared in three subsequent phases. Firstly, we deposit via sputtering, without solution of continuity a layer of CdS on top of the front contact made up of a double layer of ITO/SnO₂ deposited on a soda lime glass substrate. The second phase consists in the treatment of the CdS layer, which is the key factor for the fabrication of a good heterojunction, with CdCl₂ and in the subsequent deposition of the CdTe layer via close space sublimation technique. Finally, the back contact is fabricated via sputtering making use of the Sb₂Te₃ compound which guarantees the cell stability. Under global AM1.5 conditions the open-circuit voltage, short-circuit current and fill factor of our best cell, fabricated without antireflecting coating and normalized to the area of 1 cm², were V_oc=858 mV, J_sc=23 mA/cm² and ff=74%, respectively, corresponding to a total area conversion efficiency of η=14.6%.     

Properties of RF sputtered zinc oxide based thin films made from different targets

The effect of deposition parameters on optoelectronic and properties of ZnO based thin films prepared by RF magnetron sputtering have been studied. Different targets (pure Zn, ZnO, Zn---Al (98/2 at 2%), ZnO---Al (98/2 at%), and ZnO---Al₂O₃ (98/2 wt%)) have been investigated to compare resulting samples and establish the best target composition. From reactive sputtering, using a Zn---Al target, transparent conductive zinc oxide has been obtained at 380°C with E_g = 3.25–3.35 eV and = 4.8 × 10⁻⁴ ω cm. Reduction of substrate temperature at 200°C has been possible by nonreactive sputtering from ZnO---Al and ZnO---Al₂O₃ targets. The values of the energy gap and resistivity under these conditions are 3.30–3.35 eV and 1 × 10⁻³ ω can respectively.     

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.     

Procedure to obtain higher than 14% efficient thin film CdS/CdTe solar cells activated with HCF2Cl gas

This work reports a process used to obtain CdS/CdTe thin film solar cells with high efficiencies between 14% and 14.6%. The procedure consists of sequentially depositing by RF sputtering and close space sublimation (CSS) of several layers onto a glass substrate, configured as glass/ITO/ZnO/CdS/CdTe/Cu/Mo. The CdTe layer was deposited by CSS at low substrate temperature (500 °C) under Ar–O₂ atmosphere and the activation process is performed with a mixture of Freon gas (HCF₂Cl) and other gases.     

Chemically and electrochemically deposited thin films for solar energy materials

Direct energy gap materials, e.g. CdTe, CuInSe₂, CuInGaSe₂, CdSe, ZnP₂ and Zn₃P₂, are the most interesting for thin-film solar cell applications. Among the various methods of preparation of these films, chemical bath deposition and electrodeposition deserve special attention because they have been shown to be inexpensive, low-temperature and non-polluting methods. Based on Pourbaix diagrams of CdS, CdTe, CuInSe₂, CdSe, etc., drawn from basic considerations, the best parameters for their electrodeposition are deduced. Theoretical considerations on the chemical-bath deposition of CdS, CdSe and Sb₂S₃ are also indicated. In particular, the role of the complexing agent and of the ligands in chemical bath deposition quality is discussed, as are the uniformity and stability of the films. The photoelectrochemical, Schottky barrier and heterojunction solar cell properties based on chemically and electrochemically deposited thin films with heteropolyacids are shown. Future trends for chemically and electrochemically deposited polycrystalline thin films are addressed. Results from very recent work done in the improvement of chemically and electrochemically deposited thin films are presented. Significant results obtained on advanced CdS/CdTe, CdS/CIS and CdS/CIGS solar cells developed by industry and by laboratory groups worldwide are indicated. Emerging low cost materials or/and less environmental hazards materials which may introduce solar cells into worldwide market are considered in the conclusion.     

Investigations on the parameters limiting the performance of CdS/SnS solar cell

Debutant analysis of the parameters impeding the efficiency of the CdS/SnS‐based photovoltaic device is the chief novelty of the present report. We have developed thin‐film heterojunction solar cells with the stacking sequence: glass/Al‐doped ZnO/CdS/SnS/In. The two crucial issues, band offsets and cell studies, are discussed in detail. The band offsets at the CdS/SnS interface have been systematically evaluated by semidirect X‐ray photoelectron spectroscopy. The calculated valance band offset (ΔE_v) and conduction band offsets (ΔE_c) are found to be 1.46 and ?0.36 eV, respectively. The negative value of conduction band offset indicates that the junction formed is of type‐II (staggered‐type heterojunction). Electrical studies revealed power conversion efficiency of 0.32% with V_OC, J_SC, and fill factor as 170.61 mV, 7.26 mA/cm², and 0.26, respectively. The impact of the offset values on the cell studies is clearly elucidated. The reasons for the low efficiency are spotlighted. Collectively, this article gives the overview of the systematic approach undertaken to get obvious picture about the barriers that limit the conversion efficiency of the CdS/SnS‐based solar cell and the measurements required for enhancing the efficiency of the SnS‐based solar device.     

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.     

Present status and future prospects of CIGSS thin film solar cells

Efficiencies of CuIn_1−xGa_xSe_2−yS_y (CIGSS) modules are comparable to those of lower end crystalline-Si modules. CIGSS layers are prepared by reactive co-evaporation, selenization/sulfurization of metallic or compound precursors, reactive co-sputtering and non-vacuum techniques. CuIn_1−xGa_xS₂ (CIGS2) layers are prepared by sulfurization of Cu-rich metallic precursors and etching of excess Cu_2−xS. Usually heterojunction partner CdS and transparent-conducting bilayer ZnO/ZnO:Al layers are deposited by chemical bath deposition (CBD) or RF magnetron sputtering. CIGSS solar cell efficiencies have been improved by optimizing Cu, Ga and S proportions and providing a minute amount of Na. This paper reviews preparation and efficiency improvement techniques for CIGSS solar cells.     

RF sputter deposition of the high-quality intrinsic and n-type ZnO window layers for Cu(In,Ga)Se2-based solar cell applications

Transparent ZnO films were prepared by rf magnetron sputtering, and their electrical, optical, and structural properties were investigated under various sputtering conditions. Aluminum-doped n-type(n-ZnO) and undoped intrinsic-ZnO (i-ZnO) layers were deposited on a glass substrate by incorporating different targets in the same reaction chamber. The n-ZnO films were strongly affected by argon ambient pressure and substrate temperature, and films deposited at 2 mTorr and 100°C showed superior properties in resistivity, transmission, and figure of merit (FOM). The sheet resistance of ZnO film was less dependent on film thickness when the substrate was heated during deposition. These positive effects of elevated substrate temperature are presumably attributed to the rearrangement of the sputtered atoms by the heat energy. Also, the films are electrically uniform through the 5 cm×5 cm substrate. The maximum deviation in sheet resistance is less than 10%. All of the films showed strong (0 0 2) diffraction peak near 2θ =34°. The undoped i-ZnO films deposited in the mixture of argon and oxygen gases showed high transmission properties in the visible range, independent of the Ar/O₂ ratio, while resistivity rose with increased oxygen partial pressure. The Cu(In,Ga)Se₂ solar cells, incorporating bi-layer ZnO films (n-ZnO/i-ZnO) as window layer, were finally fabricated. The fabricated solar cells showed 14.48% solar efficiency under AM 1.5 conditions (100 mW/cm²).     

Nanostructured solar cell based on spray pyrolysis deposited ZnO nanorod array

In this paper we present a realization of an extremely thin absorber (ETA) layer solar cell by the chemical spray pyrolysis method. CuInS₂ absorber was deposited onto a blocking layer coated ZnO nanorods grown on a transparent conductive oxide. Layers and cells were characterized by optical and Raman spectroscopy, and scanning electron microscopy. Current–voltage, spectral response and electron beam induced current measurements were applied to solar cells. ZnO nanorod cell showed twice higher short circuit current density than the flat reference. ETA cells with efficiency of 2.2% (j=12 mA/cm², V_oc=425 mV, FF=43%) and of 2.5% were prepared using TiO₂-anatase and an indium sulfide blocking layer, respectively.     

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.     

Growth of large-grain CuInSe2 thin films by flash-evaporation and sputtering

Thin films of (112) oriented CuInSe₂, with an average grain size larger than 50 μm, have been grown by flash-evaporation and sputtering. Platelets of Corning glass 7059, 1 in² in size, covered by a layer of lead 2 μm thick, have been used as substrates. The lead layer is prepared by a new method which allows one to obtain (111) oriented films with a grain size ranging between 30 and 500 μm. This method is now being patented. Solar cells sing CuInSe₂/CdS thin films, prepared by flash-evaporating low resistivity CdS thin films on top of CuInSe₂, have so far exhibited high photocurrents close to 40 mA cm⁻² at 100 mW cm⁻² solar illumination, and a maximum efficiency of about 4%.     

Chemical-bath ZnO buffer layer for CuInS2 thin-film solar cells

ZnO buffer layers were grown by a chemical-bath deposition (CBD) in order to improve the interface quality in p-CuInS₂ based solar cells, to improve the light transmission in the blue wavelength region, but also as an alternative to eliminate the toxic cadmium. The process consists of immersion of different substrates (glass, CIS) in a dilute solution of tetraamminezinc II, [Zn(NH₂)₄]²⁺, complex at 60–95°C. During the growth process, a homogeneous growth mechanism which proceeds by the sedimentation of a mixture of ZnO and Zn(OH)₂ clusters formed in solution, competes with the heterogeneous growth mechanism. The mechanism consists of specific adsorption of a complex Zn(II) followed by a chemical reaction. The last process of growth results in thin, hard, adherent and specularly reflecting films. The characterization of the deposited CBD-ZnO layers was performed by X-ray diffraction (XRD), optical transmittance, scanning electron microscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-deposited films on glass show hexagonal zincite structure with two preferred orientations (1 0 0) and (1 0 1). High optical transmittance up to 80% in the near-infrared and part of the visible region was observed. The low growth rate of the films on CIS suggests an atomic layer-by-layer growth process.The device parameters and performance are compared to heterojunction with a standard CdS buffer layer.     

Thin film deposition of Cu2O and application for solar cells

Deposition conditions of cuprous oxide (Cu₂O) thin films on glass substrates and nitrogen doping into Cu₂O were studied by using reactive radio-frequency magnetron sputtering method. The effects of defect passivation by crown-ether cyanide treatment, which simply involves immersion in KCN solutions containing 18-crown-6 followed by rinse, were also studied. By the crown-ether cyanide treatment, the luminescence intensity due to the near-band-edge emission of Cu₂O at around 680 nm was enhanced, and the hole density was increased from 10¹⁶ to 10¹⁷ cm⁻³. Finally, polycrystalline p-Cu₂O/n-ZnO heterojunctions were grown for use in solar cells. Two deposition sequences were studied, ZnO deposited on Cu₂O and Cu₂O deposited on ZnO. It was found that the crystallographic orientation and current–voltage characteristics of the heterojunction were significantly influenced by the deposition sequence, both being far superior for the heterojunction with structure Cu₂O on ZnO than for the inverse structure. We successfully obtained a photoresponse for the first time in the deposited thin film of Cu₂O/ZnO.     

Facile fabrication and optimization of bowl-like ZnO/CdS nano-composite thin films with hierarchical nanopores and nano-cracks for high-performance photoelectrochemistry

A special nano-structured composite ZnO/CdS thin film with hierarchical nanopores and nano-cracks has been synthesized by a facile two-step method for the first time, in which both loadings of ZnO and CdS are optimized. We first fabricated the hierarchical nanoporous ZnO thin film through rapid gas/liquid interface assembly and layer-by-layer transfers of bowl-like ZnO nanoparticles for thirteen times. The ZnO nanobowls are prepared by a simple solution chemical reaction without using any templates. After annealing, the assembled ZnO film is sensitized with CdS nanoparticles by successive ionic layer adsorption and reactions for six cycles. Nano-cracks form for the ZnO/CdS nano-composite film by calcination, which is due to the different thermal expansion behavior between the ZnO film and the CdS layer. The facilely optimized ZnO/CdS films can serve as a promising photoanode in a photoelectrochemical cell, and it can generate a saturated photocurrent density as high as 7.8 mA cm^?2 at ?0.9 V (vs. Hg|Hg₂SO₄|saturated K₂SO₄) under visible light illumination of 100 mW cm^?2 in an aqueous solution of 0.5 M Na₂S, corresponding to a solar-to-electricity conversion efficiency of 6.6%.