Electroconversion of CdS to CuxS for thin film solar cells

Electroconversion of vacuum-evaporated CdS films to cuprous sulphide (Cu_xS) for the fabrication of thin film CdS/Cu_xS solar cells was investigated. The Cu_xS films so formed were characterized by electrochemical and electron diffraction methods. The dependence of the stoichiometry x of the Cu_xS on conversion parameters such as the concentration, pH and temperature of the electrolyte (CuSO₄) and the cathode (CdS) current density was established. A 0.4 M concentration bath with the pH value maintained at 2.5 was found to be most suitable. For this bath, optimum combinations of the bath temperature and cathode current density yielding the most stoichiometric Cu_xS (x?1.99) were found to be in the ranges 55–65°C and 2.5-5.0 mA cm^-2 respectively. The films converted under the optimum conditions exhibit predominantly a chalcocite structure. The observed kinetics of the conversion process was understood in terms of a proposed two-step reaction at the cathode, involving a chemical ion exchange and an electrochemical reduction reaction.     

Cu2ZnSnS4 solar cells prepared with sulphurized dc-sputtered stacked metallic precursors

In the present work we report the details of the preparation and characterization results of Cu₂ZnSnS₄ (CZTS) based solar cells. The CZTS absorber was obtained by sulphurization of dc magnetron sputtered Zn/Sn/Cu precursor layers. The morphology, composition and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering. The majority carrier type was identified via a hot point probe analysis. The hole density, space charge region width and band gap energy were estimated from the external quantum efficiency measurements. A MoS₂ layer that formed during the sulphurization process was also identified and analyzed in this work. The solar cells had the following structure: soda lime glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid. The best solar cell showed an open-circuit voltage of 345 mV, a short-circuit current density of 4.42 mA/cm², a fill factor of 44.29% and an efficiency of 0.68% under illumination in simulated standard test conditions: AM 1.5 and 100 mW/cm².     

International conference on thin and thick film technology,Augsburg, F.R.G., 28–30 September, 1977

Cu₂S thin films of well-controlled thickness and stoichiometry were prepared by a solid state reaction between CdS and CuCl films in the temperature range 200–250°C. The Cu₂S films exist in the orthorhombic chalcocite phase. The growth of Cu₂S on CdS is topotactial, and the chalcocite phase is obtained on reaction with both wurtzite and sphalerite structures of CdS. The electrical and optical properties of the Cu₂S films are consistent with the Cu₂S composition. These films were utilized to fabricate Cu₂S/CdS solar cells.     

Evaporation of CuCl and CuCl2 for the fabrication of Cu2S/CdS thin film solar cells

The so-called dry method for the fabrication of Cu₂S/CdS thin film solar cells uses a thin CuCl film,in order to convert the surface layer of the CdS film into Cu₂S. Usually, the CuCl film is deposited by evaporation of freshly prepared CuCl powder. In the present paper we investigate the influence of contamination of this evaporation material by CuCl₂ and by CuCl₂·2H₂O. The experiments show that about 99% of these contaminants decompose into CuCl during the evaporation process.     

The design and fabrication of high efficiency thin film CdS/Cu2S solar cells

Thin film photovoltaic cells of CdS/Cu₂S which exhibit conversion efficiencies in excess of 9% have been designed and fabricated. Specific cell designs are prepared from an analysis of optical and electronic loss mechanisms operative in the cell. Material and engineering modifications to the fabrication process are then made to minimize specific energy conversion losses. The present cell design consists of five thin film layers which are sequentially prepared on a copper substrate 35 μm thick. In addition to the material control required for each component layer, the electrical, chemical, mechanical and topological compatibilities at the interfaces between each adjoining layer must be assured to achieve the desired cell performance. Our present analysis shows that a fully optimized solar cell based on a CdS/Cu₂S junction will have a practical conversion efficiency limit of about 11%. It is anticipated that practical conversion efficiencies of 14–15% can be achieved utilizing a (CdZn)S/Cu₂S junction designed to produce the maximum open-circuit voltage possible using Cu₂S as the absorbing layer. Present cell results which incorporate this design are presented.     

Effects of CdCl2 treatment and annealing on CdS/SnO2/glass heterostructures for solar cells

Effects of CdCl₂ post-growth treatments and annealing under different conditions on the surface and interface properties of CdS/SnO₂/glass heterostructure were studied. CdS thin films were grown on SnO₂-coated glass substrates for CdS/CdTe heterojunction solar cells by the solution growth technique. It was found that CdCl₂ post-growth treatments and annealing enhanced the CdS-related XRD peaks, narrowed the CdS characteristic Raman bands, removed or depressed the disorder related Raman features, and improved the CdS film crystalline quality significantly, which are advantageous to the application in solar cells as a window layer material.     

Cu2ZnSnS4 solar cell prepared entirely by non-vacuum processes

Cu₂ZnSnS₄ (CZTS) solar cell with superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/CZTS/Carbon was prepared entirely by non-vacuum processes. The compact TiO₂ window and In₂S₃ buffer layers, CZTS absorber layer and Carbon electrode layer were prepared by spray pyrolysis method, ball milling and screen printing combination processes and screen printing process, respectively. The short-circuit current density, open-circuit voltage, fill factor and conversion efficiency of the best fabricated solar cell are 8.76 mA/cm², 250 mV, 0.27 and 0.6%, respectively. The fabrication process for the CZTS solar cell did not employ any vacuum conditions or high-toxic materials (such as CdS, H₂Se, H₂S or Se).     

Kinetics of the dry formation of Cu2S in Cu2S/CdS solar cells

Atomic absorption spectroscopy and electron spectroscopy for chemical analysis were used to study the growth of Cu₂S by the dry barrier process in Cu₂S/CdS solar cells at various reaction temperatures and for various thicknesses of the evaporated CuCl layer. Coulometric titration was used to measure the stoichiometry of the Cu₂S. It was shown that for reaction temperatures lower than 140°C the diffusion of cadmium in Cu₂S limits the Cu₂S growth, whereas at higher temperatures the cadmium-copper exchange reaction rate is the limiting factor.     

Cu content dependence of Cu<Subscript>2</Subscript>Zn(SnGe)Se<Subscript>4</Subscript> solar cells prepared by using sequential thermal evaporation technique of Cu/Sn/Cu/Zn/Ge stacked layers

The doping of Cu₂ZnSnSe₄ semiconductor with Ge element has demonstrated improvements to kesterite solar cell efficiency. However, the impact of different Cu concentrations on Cu₂ZnSnGeSe₄/CdS solar cell performance has been poorly studied. In this work, Cu₂ZnSnGeSe₄ thin films with different Cu contents were synthesized by selenization of sequential thermal evaporation precursors. Solar cells based on kesterite-type Cu₂ZnSnGeSe₄ (CZTGSe) were fabricated and the influence of the Cu thickness on the chemical composition and morphology of the layers and electro-optical properties of solar cells was studied. The stacking process was performed at room substrate temperature. Efficiency values in the range of 2.0–6.8% are reported as a function of Cu concentration. The highest efficiency of 6.8%, was achieved for solar cell with glass/Mo/CZTGSe/CdS/i-ZnO/ITO structure using the stacking of Cu (3 nm)/Sn (248 nm)/Cu (112 nm)/Zn (174 nm)/Ge (20 nm).     

Performance evaluation of a novel visible-driven CNT/TiO2/WO3/CdS heterojunction in photocatalytic fuel cell: Photodegradation of Reactive Blue 19 and electricity production

A photoelectrochemical degradation of reactive blue 19 (RB19) and electricity generation was modeled and optimized in a photocatalytic fuel cell with CNT/TiO₂/WO₃/CdS/FTO photoanode and Cu₂S/FTO photocathode using response surface methodology-central composite design. The coated photocatalyst on fluorine-doped tin oxide (FTO) was characterized by surface and cross-section FESEM, EDX spectrum, EDS mapping, XRD, and DRS analysis. The CNT/TiO₂/WO₃/CdS and Cu₂S were coated on FTO glass by applying the dip coating and combined dip coating-SILAR method, respectively. The efficiency of RB19 and Chemical oxygen demand removal under the optimum circumstances of 15 mg/L dye concentration, pH = 4, and the light intensity of 890 lm were obtained at 99.9 % and 70 % after 4.5 h, respectively. Moreover, the generated current density during the photocatalytic process was calculated at about 41.3 µA/cm² after 90 min. The effect of air injection, open and closed electrical circuits, light radiation, and adsorption rate of photocatalysts on RB19 removal was examined. The five times reusability confirmed the good stability and photoactivity of coated catalyst on the FTO electrodes at the optimum conditions. The result indicated that the photocatalytic fuel cell is an excellent technology not only for wastewater treatment but also for energy production.     

Metal chalcogenide-oxide composite coatings prepared by spray pyrolysis

The spray pyrolysis technique has been employed to deposit composite coatings of chalcogenides of cadmium, zinc, lead and cobalt with oxides of aluminium, tin, lead, zinc and cobalt. Widely varying microstructural, electronic, optical and chemical properties have been obtained for such layers by monitoring the oxide composition, its spatial distribution and profile along the thickness. The large area chalcogenide-oxide composite films prepared by this technique are eminently suited for photovoltaic energy conversion, photothermal energy conversion and voltage-dependent resistor (Varistor) applications.In this paper we report our studies on co-pyrolytically deposited CdS:Al₂O₃ and CdS:SnO₂ layers and their application to improved thin film solar cells. Each of the oxides is insoluble in CdS and is segregated at the grain boundaries in the deposited films. Small amounts (less than 10%) of oxide in CdS are found to reduce its grain size negligibly and to make the film more compact, hard, adherent and less susceptible to chemical attack. The altered microstructure modifies the surface topography of the CdS film from a pebble-like roughness to an improved void-free serpentine texture. Segregated oxide in CdS does not affect the optical band gap of the films, although the composites exhibit enhanced diffuse optical scattering.Large area CdS films with a gradient profile of oxide have been utilized to fabricate thin film CdS/Cu₂S solar cells. The growth (length and distribution) of Cu₂S fingers and/or curtains deep into the top CdS layers during the topotaxial conversion reaction of chemiplating is controlled by the presence of oxide along the grain boundaries. This has not only resulted in improved interface topography for better carrier collection and reduced shunt losses but has also enabled us to decrease drastically the CdS film thickness necessary for the solar cells. Furthermore, the subsequent degradation of the junction via the well-known mechanism of the loss of copper from the Cu₂S layer by diffusion into CdS is expected to be considerably reduced by the presence of the oxide gradient in the CdS layer.     

Cu2ZnSnS4 thin film solar cells from electroplated precursors: Novel low-cost perspective

Thin-film solar cells based on Cu₂ZnSnS₄ (CZTS) absorbers were fabricated successfully by solid-state reaction in H₂S atmosphere of electrodeposited Cu-Zn-Sn precursors. These ternary alloys were deposited in one step from a cyanide-free alkaline electrolyte containing Cu(II), Zn(II) and Sn(IV) metal salts on Mo-coated glass substrates. The solar cell was completed by a chemical bath-deposited CdS buffer layer and a sputtered i-ZnO/ZnO:Al bilayer. The best solar cell performance was obtained with Cu-poor samples. A total area (0.5 cm²) efficiency of 3.4% is achieved (V_oc = 563 mV, j_sc = 14.8 mA/cm², FF = 41%) with a maximum external quantum efficiency (EQE) of 80%. The estimated band-gap energy from the external quantum efficiency (EQE) measurements is about 1.54 eV. Electron backscatter-diffraction maps of cross-section samples revealed CZTS grain sizes of up to 10 µm. Elemental distribution maps of the CZTS absorber show Zn-rich precipitates, probably ZnS, and a Zn-poor region, presumably Cu₂SnS₃, close to the interface Mo/CZTS.     

Preparation and characterization of CdS–Bi2S3 nanocomposite thin film by successive ionic layer adsorption and reaction (SILAR) method

CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. These films were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurement systems. A comparative study was made between CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films. The XRD patterns reveal that CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film have hexagonal, orthorhombic and mixed phase of hexagonal CdS and orthorhombic Bi₂S₃ crystal structure, respectively. SEM images showed uniform deposition of the material over the entire glass substrate. The energy band gap for CdS, Bi₂S₃ and CdS–Bi₂S₃ thin films were revealed from the optical studies and were found to be 2.4, 1.6 and 1.69 eV, respectively. The thermoemf measurements of CdS–Bi₂S₃ nanocomposite thin film revealed n-type electrical conductivity, while the I–V measurement of CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film under dark and illumination condition (100 mW/cm²) exhibited photoconductivity phenomena suggesting its applicability in photosensors devices.     

CdS annealing treatments in various atmospheres and effects on performances of CdTe/CdS solar cells

In this work, a systematic research on CdS annealing treatments under various atmospheres had been done to understand their effects on CdS/CdTe solar cells. CdS films were prepared by a standard CBD method and annealed under various atmospheres, including Ar, Ar+H₂, O₂, Ar+S and Ar+CdCl₂. Morphological, structural, optical and chemical properties were investigated using Atom force microscope (AFM), X-ray diffraction (XRD), UV–VIS spectroscopy and X-ray photoelectron spectroscopy (XPS). Annealing treatments enhanced modifications of morphology, structure and electrical properties of CdS films. AFM showed different surface morphologies and roughnesses of CdS films annealed under various atmospheres. XRD indicated the transition of CdS films from metastable cubic structure to stable hexagonal structure after annealing treatment, especially annealed in Ar+CdCl₂. From XPS analysis, Fermi levels of CdS films shifted closer to conduction band after annealing under O₂ and Ar+CdCl₂, while the levels shifted away from conduction band under Ar+H₂ and Ar+S. The relationships between those modifications by annealing treatments and effects on the performance of solar cells were discussed. Solar cell based on CdS annealed with Ar+CdCl₂ had the best performance due to the high n-doping of CdS layer introduced by annealing process.     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core–shell CdSe/CdS quantum dots (QDs) in aqueous solution. CdSe QDs are prepared by introducing H₂Se gas into the aqueous medium containing Cd²⁺ ions. The synthesized CdSe QDs are further capped with CdS to form core–shell CdSe/CdS QDs by reacting with H₂S gas. The gaseous precursors, H₂Se and H₂S, are generated on-line by reducing SeO₃ ^2? with NaBH₄ and the reaction between Na₂S and H₂SO₄, and introduced sequentially into the solution to form CdSe and CdSe/CdS QDs, respectively. The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield (3 and 20 %) and narrow full-width-at-half-maximum (43 and 38 nm). The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals. The relatively standard deviation of maxima fluorescence intensity is only 2.1 % (n = 7) for CdSe and 3.6 % (n = 7) for CdSe/CdS QDs. This developed route is simple, environmentally friendly and can be readily extended to the large-scale aqueous synthesis of QDs.     

Cu(In,Ga)Se2 solar cells with double layered buffers grown by chemical bath deposition

In based mixture In_x(OH,S)_y buffer layers deposited by chemical bath deposition technique are a viable alternative to the traditional cadmium sulfide buffer layer in thin film solar cells. We report on the results of manipulating the absorber/buffer interface between the chalcopyrite Cu(In,Ga)Se₂ (CIGS) absorber and CdS or ZnS buffer by addition of a thin In based mixture layer. It is shown that the presence of thin In_x(OH,S)_y at the CIGS absorber/CdS or ZnS buffer interfaces greatly improve the solar cell performances. The performances of CIGS cells using dual buffer layers composed of In_x(OH,S)_y/CdS or In_x(OH,S)_y/ZnS increased by 22.4% and 51.6%, as compared to the single and standard CdS or ZnS buffered cells, respectively.     

Substitution of the CdS buffer layer in CIGS thin‐film solar cells

This contribution provides an overview of current activities in the area of alternative buffer layers for Cu(In,Ga)(S,Se)₂ (CIGS) thin‐film solar cells. Good cell and module results were achieved by replacing the standard Cds buffer with Zn(O,S), In₂S₃, (Zn,Sn)O_y or (Zn,Mg)O grown by various methods like chemical bath deposition (CBD), thermal evaporation, sputtering, atomic layer deposition, and spray ion layer gas reaction. The “dry” deposition methods like sputtering and thermal evaporation could be favorable in an industrial environment on glass substrates or application in a roll‐to‐roll coater. Significant progress was made within the last two years for various Cd‐free CIGS devices. We list current records for cells with alternative buffers, e. g. Zn(O,S)‐buffered champion cells with efficiencies between 18—20 % and In₂S₃‐buffered cells with 16—17 %. Both materials have the potential to substitute CdS with efficiencies approaching the 20 % mark already surpassed by CIGS cells with CBD CdS buffers.     

Formation of CuxS thin films through a chemical bath deposition process

A method for the preparation of Cu_xS thin films through chemical bath deposition is described. The films have been formed on a glass substrate from a bath containing a triethanolamine complex of copper ions, ammonia and thiourea. The stoichiometry and optical characteristics of the films have been determined. This method has been used to form a solar cell through deposition of Cu_x S on a CdS substrate. The I–V characteristics of the cell are reported.     

Fabrication of Cu<Subscript>2</Subscript>SnS<Subscript>3</Subscript> thin-film solar cells with oxide precursor by pulsed laser deposition

In this paper, Cu₂SnS₃ (CTS) thin film is fabricated through sulfurization of oxide precursor which is deposited by pulsed laser deposition with a mixed CuO/SnO₂ target. XRD and Raman analyses indicate a pure monoclinic Cu₂SnS₃ phase has been obtained by sulfurization at temperature from 500 to 600 °C. A compact and smooth film with polycrystalline structure is observed through SEM result. In addition, the CTS films show excellent absorbance with the band gap around 0.91 eV estimated by UV–Vis, which is suitable for the absorption layer of solar cells. Final devices were fabricated with a SLG/Mo/CTS/CdS/i-ZnO/AZO/Al structure. Device performance is improved with the temperature increasing. The best efficiency of CTS-based solar cells is 0.69% with an open-circuit voltage of 144 mV and a short-circuit current density of 18.30 mA/cm^?2.     

Conductive polymer PEDOT:PSS back contact for CdTe solar cell

Two types of superstrate glass/ITO/CdS/CdTe PV structures were prepared by high vacuum evaporation technique with (i) activation of CdS layer and CdS/CdTe bi-layer structure step-by-step and (ii) activation of CdS/CdTe bi-layer structure. The activation was performed by annealing the structures with CdCl₂ in air at 400 °C for 15 min. Main conditions for CdS and CdTe thin films deposition and following treatment were selected from the literature data with the purpose to prepare and compare complete CdTe solar cells with standard p + Cu_xTe back contact and conductive polymer poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (PEDOT:PSS) back contact. Obtained layers and structures were characterized using the XRD, SEM and I-V methods. Both the methods of activation treatment give comparable results from the point of view PV properties of complete solar cells. It was found that highly conductive PEDOT:PSS intermediate layer can significantly improve the back contact characteristics of CdTe. However these hybrid structures need to be further optimized to compete successfully with conventional inorganic back contacts in complete CdTe solar cells.