Galvanic deposition of cadmium sulfide thin films

A technique is presented for the deposition of high quality cadmium sulfide (CdS) thin films onto SnO₂ substrates by a galvanic method. Single phase films were deposited in a bath of cadmium chloride and sodium thiosulfate at pH = 4 and TEMPERATURE = 85°C at a growth rate of 1 nm/min. In the pH range of 3 to 4, the deposition rate is sensitive to cadmium chloride concentration. At higher pH the deposition rate is very low while at lower pH mixed phase films were obtained and homogeneous US formation occurred in the bath. The structural and optical properties of the US films are also presented and are comparable to films deposited by other methods. CdS/CdTe solar cells with efficiencies over 8% were fabricated using evaporated CdTe to demonstrate the utility of US films deposited by this simple technique. The galvanic deposition technique is useful in laboratory settings with limited deposition hardware and limited chemical waste disposal facilities.     

The effect of heteropolyacids and isopolyacids on the properties of chemically bath deposited CdS thin films

The deposition of CdS films on ITO/glass substrates from a chemical bath containing cadmium acetate, ammonia, ammonium acetate and thiourea has been carried out with and without small amounts of heteropolyacids (HPA) (phosphotungstic acid (PTA): H₃[PW₁₂O₄₀], silicotungstic acid (STA): H₄[SiW₁₂O₄₀], phosphomolybdic acid (PMA): H₃[PMo₁₂O₄₀]) and isopolyacids (IPA) (tungstic acid (TA): H₂WO₄ and molybdic acid (MA): H₂MoO₄) for different deposition times. The chemical, morphological, structural and optical properties of the films have been determined. The composition in sulphur and in cadmium of the films’ surface and volume was determined for various HPA and IPA used in the deposition bath. The HPA and IPA which give the thickest film with the biggest grain size were deduced. The optical transmission at 400 nm of CdS films deposited with STA at short time (20 min) (50%) is higher than those of CdS deposited at longer time (6 h) (7%). The optical transmission of CdS deposited with STA at short time is higher (50%) than that of CdS deposited without STA (20%). The performances of heterojunctions CdS/CdTe solar cells fabricated from CdS films deposited with and without STA and CdTe films deposited without STA have been determined. It was shown that the CdS/CdTe heterojunction solar cells fabricated from CdS films deposited with STA exhibited better photon collection efficiency and solar cell efficiency (η=6%) than CdS/CdTe heterojunction solar cells fabricated from CdS films deposited without STA (η=3.3%).     

Optimized chemical bath deposited CdS layers for the improvement of CdTe solar cells

CdS layers grown by chemical bath deposition (CBD) are treated in different ways to improve the performance of CdS/CdTe solar cells. It has been found that the open circuit voltage of the CdS/CdTe solar cell increases when the CBD CdS is annealed with CdCl₂ before the deposition of CdTe by close spaced sublimation (CSS). A thin CBD CdS (∼80 nm) with bi-layer structure can significantly improve the short circuit current of the CdS/CdTe solar cells.     

Electrochemical deposition of thin ZnTe films as a contact for CdTe solar cells

ZnTe films doped with Cu were deposited by an electrochemical method for the first time directly onto CdTe/CdS/ITO/glass substrates to form a low resistance contact to CdTe. The depositions were carried out in an aqueous solution of ZnCl₂, TeO₂ and CuCl₂ or CuSO₄ in which the substrate was externally short circuited to a Zn counter electrode to complete an electrochemical cell. Single phase films 50 nm to 300 nm thick were obtained for specific pH and TeO₂ concentrations and bath temperature. Complexing the Cu²⁺ with triethanolamine (TEA) allowed reproducible deposition of p-type ZnTe:Cu films. ZnTe/Cu/CdTe/CdS solar cells fabricated using this method have achieved AM1.5 efficiencies of 8.7%.     

CdTe/CdS Solar cells on flexible molybdenum substrates

Development of CdTe/CdS solar cells on flexible metallic substrates is highly interesting due to the light weight and flexible nature of the solar modules. We have deposited CdTe films onto flexible molybdenum substrates using close-spaced sublimation technique and the CdTe/CdS junction was developed by depositing a thin layer of CdS onto the CdTe substrate from a chemical bath. The devices were characterized by Current–voltage (I–V) and photocurrent spectroscopy techniques. Prior to the deposition of the transparent conducting layer, the devices were annealed in air at different temperatures and found that the devices annealed at 400°C have better photovoltaic parameters. The efficiency of a typical device under 60 mW cm⁻² illumination was estimated as 3.5%.     

Semiconductor thin films by chemical bath deposition for solar energy related applications

In this paper we present the basic concepts underlying the chemical bath deposition technique and the recipes developed in our laboratory during the past ten years for the deposition of good-quality thin films of CdS, CdSe, ZnS, ZnSe, PbS, SnS, Bi₂S₃, Bi₂Se₃, Sb₂S₃, CuS, CuSe, etc. Typical growth curves, and optical and electrical properties of these films are presented. The effect of annealing the films in air on their structure and composition and on the electrical properties is notable: CdS and ZnS films become conductive through a partial conversion to oxide phase; CdSe becomes photosensitive, SnS converts to SnO₂, etc. The use of precipitates formed during deposition for screen printing and sintering, in polymer composites and as a source for vapor-phase deposition is presented. Some examples of the application of the films in solar energy related work are presented.     

HIGH EFFICIENCY THIN FILM CdS/CdTe SOLAR CELLS†

Cadmium telluride is a most promising thin film photovoltaic material as shown by the higher than 10% efficient CdS/CdTe heterojunction solar cells. In this work, thin film CdS/CdTe solar cells have been prepared using CdS films grown from an aqueous solution and p-CdTe films deposited by metalorganic chemical vapor deposition (MOCVD) and close-spaced sublimation (CSS). The solution-grown CdS films, with high photoconductivity ratios and good optical transmission, are well-suited for optoelectronic devices. The CdTe films deposited by CSS show considerably better microstructure than those by MOCVD because of the higher substrate temperature used in the CSS process. The properties of CdS/CdTe heterojunctions have been studied. Solar cells of 1 cm2 with an AM 1.5 efficiency of 14.6%, verified at the National Renewable Energy Laboratory, have been CdTe films     

ELECTRODEPOSITED CdTe FOR THIN FILM SOLAR CELLS

Large area 300 mm x 300 mm CdS/CdTe solar cells with record efficiencies over 10% have been fabricated using a reproducible, safe and low cost electrodeposition route for CdTe deposition. CdS window layers have been grown using chemical bath deposition which produces uniform adherent films by a cost effective route. Electrical characterization of small area (0.02 cm²) devices confirms that the structure is p-n rather than p-i-n. Module reliability tests show efficiency stability for more than 16,000 hours outside, and very little change using indoor environmental tests.     

CdS thin film post-annealing and Te–S interdiffusion in a CdTe/CdS solar cell

Small area CdTe/CdS solar cells were fabricated using chemical bath deposited CdS and CSS deposited CdTe thin films to investigate the interface properties related to the CdS processing. The effect of post deposition annealing of CdS on the junction properties and the possible interdiffusion at the interface is discussed. The hypothesis of hardening of CdS due to annealing against the diffusion of “S” and “Te” is discussed using the quantum efficiency data in the blue and red regions. Devices prepared using as-deposited CdS films exhibited evidences of higher “S” and “Te” diffusion compared to devices made using CdS films annealed in oxygen. The maximum efficiency of the devices used in this study was 9.8%.     

Influence of CdS growth process on structural and photovoltaic properties of CdTe/CdS solar cells

The morphology of CdS layers grown by chemical bath deposition (CBD) and high vacuum evaporation (HVE) have been investigated. The grains of CBD-CdS are more compact and smooth than those of HVE-CdS. The annealing and CdCl₂ treatment cause grain growth, which is stronger for the CdCl₂ treated samples. The grain-size of the as-deposited CdTe on CBD-CdS is about 5 times larger than of those grown on HVE-CdS. The structural and electrical properties of CdTe/CdS solar cells are strongly dependent on the CdS. The grain size of CdCl₂ treated CdTe layers are similar, irrespective of the transparent conducting oxide substrate and CdS deposition method. The efficiency of solar cells on thin CBD-CdS is low (about 5.6%) because of pin-holes and a large intermixing of CdTe-CdS. The cells on HVE-CdS yield a higher current density despite thicker HVE-CdS as compared to CBD-CdS. The efficiency of solar cells on HVE-CdS is 12.3%.     

Influence of growth and microstructure of chemical deposited CdS films on the electrical properties of CdS/CdTe solar cells

Thin film n-CdS/p-CdTe solar cells were prepared from chemical bath deposited CdS and electrodeposited CdTe layers. The microstructural and some electrical properties of these layers were studied and connection with photovoltaic performance of the cells was shown. Especially, adherence of the CdS films and the quality of heterojunction interface manifesting themselves in the value of the open-circuit voltage U_oc depend on the cadmium precursor used for CdS deposition and on whether pH buffered conditions were applied or not. The number of CdS layers in the cells needed to obtain U_oc of about 700 mV is connected with the CdS deposition conditions.     

CdSe thin films as solar control coatings

CdSe thin films deposited by a physical vapour deposition method were investigated as solar control coatings on architectural glazings. The optical transmittance and the near-normal specular reflectance in the range 0.40−2.40 μm and spectral distribution of reflected and transmitted intesities in the same range showed that CdSe thin films have solar control characteristics comparable to commercially available metallic coatings and other materials such as PbS and Cu_ξS films. The solar control characteristics of CdSe films were found to be dependent on film parameters, including deposition rate and deposition 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.     

Photoelectrochemical behavior of chemically deposited CdSe and coupled CdS/CdSe semiconductor films

Photoelectrochemical effects at chemically deposited CdSe thin films (2000 Å) coupled with as-prepared and air annealed (250°C) CdS films have been investigated by monitoring open-circuit voltage (V_oc) and short-circuit current density (I_sc) at varying incident light intensities and for different heat-treatments temperatures. Two consecutive chemical baths were used in the coupled system. Each bath has been optimized in earlier studies for the deposition of highly photosensitive CdS and CdSe thin films. The photoelectrochemical behavior of single and coupled films was investigated in ferricyanide redox couples. The enhanced short-circuit photocurrent of the as-deposited CdS/CdSe system, despite their lower photosensitivity, indicated that charge separation improved in the coupled system. The role of post-deposition thermal treatments in improving the photoelectrochemical cell characteristics and stability of coupled semiconductors was investigated. Excellent I–V properties were obtained for CdSe and CdS₂₅₀/CdSe photoelectrodes annealed at 280°C. For the coupled system: V_oc=960 mV; I_sc=8.6 mA/cm²; fill factor (ff)=0.53 and cell efficiency (η)=4.2%. The linearity of V_oc/ln(I_L) and I_sc/I_L plots supports the Schottky–Mott model for these interfaces. The stability of the coupled photoanode is superior to that of the CdSe only-film for the initial 3 h.     

Photoluminescence characteristics of CdS layers deposited in a chemical bath and their correlation to CdS/CdTe solar cell performance

In this work, we study CdS films processed by chemical bath deposition (CBD) using different thiourea concentrations in the bath solution with post-thermal treatments using CdCl₂. We study the effects of the thiourea concentration on the photovoltaic performance of the CdS/CdTe solar cells, by the analysis of the I–V curve, for S/Cd ratios in the CBD solution from 3 to 8. In this range of S/Cd ratios the CdS/CdTe solar cells show variations of the open circuit voltage (V_oc), the short circuit current (J_sc) and the fill factor (FF). Other experimental data such as the optical transmittance and photoluminescence were obtained in order to correlate to the I–V characteristics of the solar cells. The best performance of CdS–CdTe solar cells made with CdS films obtained with a S/Cd ratio of 6 is explained in terms of the sulfur vacancies to sulfur interstitials ratio in the CBD–CdS layers.     

Chemically-deposited Te layers improving the parameters of back contacts for CdTe solar cells

A chemical bath process was carried out for the deposition of Te layers on CdTe films grown by the close-space vapor transport technique (CSVT) on conducting SnO₂:F substrates. The Te layers were chemically-deposited on as-grown CdTe films and on previously CdCl₂-treated CdTe ones. After Te deposition, the CdTe films were annealed at temperatures from 200 to 400 °C. The Te layer on top of the CdTe films was studied by Raman Spectroscopy and by Scanning Electron Microscopy. The electrical resistivity of the annealed CdTe films was determined from current versus voltage measurements in a sandwich configuration, employing gold contacts on top of the CdTe modified surface. The results show that the combined effect of the Te layer on CdTe together with previous CdCl₂ treatment improves the electrical properties of CSVT-CdTe films. These results are quite promising for increasing performance of CdS/CdTe solar cells.     

Study of CuInSe2 thin films prepared by electrodeposition

Thin films of p-type CuInSe₂ prepared by a one-step electrodeposition method have been studied by constructing CdS/CuInSe2 junctions. After the electrodeposition, the CuInSe₂ films were treated either in vacuum or in Ar. Cells of the form CdS (high σ)/CdS (low σ)/CuInSe₂ were then fabricated for studying the electrodeposited films. Measurements were specifically carried out to determine the diffusion length of minority carriers in the p-type CuInSe₂. It was found that the minority carrier diffusion length in CuInSe₂ films treated in Ar was generally greater than that for films treated in vacuum under similar conditions. A small area cell (active area 0.11 cm²) with a conversion efficiency of about 7% (under 125 mW/cm² illumination) has been fabricated.     

Polymer impinged CdS/CuInSe2 solar cell

In the present paper we report, effect of conjugated polymer (polyaniline) impinging in nanostructured CdS/CuInSe₂ heterojunction thin film solar cell. The heterojunction architecture for the solar cell is achieved by sandwiching the conjugated conducting polymer in n and p type of wide band gap semiconducting material by multilayer chemical deposition methods onto the ITO coated glass substrate at room temperature. The obtained multilayer thin film heterojunction of ITO/CdS/Polymer/CuInSe₂/Ag has been characterized for structural, compositional, optical and solar cell characteristics by illuminating it to 100 mW/cm² intensity light source. The X-ray diffraction pattern (XRD) confirms formation of CdS/CuInSe₂ phase while on polymer impinging the crystallite size observed to be increased from 13 to 19 nm. The compositional analysis by energy dispersive X-ray spectra (EDAX) supports presence of expected elements in the heterojunction. The energy band gap calculated from absorbance spectra shows significant shift in its value from polymer and CdS/CuInSe₂ band gap. I–V analysis shows increase in conversion efficiency from 0.26 in CdS/CuInSe₂ to 0.55% in CdS/Polymer/CuInSe₂ heterojunction upon illumination.     

Preparation and characterization of thin films of electrodeposited CdTe semiconductors

Thin films of CdTe semiconductors were prepared by electrodeposition technique in aqueous solutions. The deposition mechanism was investigated by cyclic voltammetry. The potential regions for the formation of the n-CdTe and p-CdTe films were determined. The structure, composition and morphology characteristics of as-deposited thin films of CdTe grown on SnO₂/glass and CdS/SnO₂/glass were investigated by XRD, EDAX and SEM techniques. The optical properties were measured to determine the absorption coefficient and band gap values. The as-deposited CdTe films grown on SnO₂/glass contained free Te while those grown on CdS/SnO₂/Glass did not contain this phase. The CdTe has the cubic structure with strong (111) orientation. The EDAX analysis showed a nearly stiochiometric Cd:Te ratio. The band gap has a value of 1.48 eV, which is in a good accordance with those reported in the literature. The effect of annealing at 350 and 400°C after CdCl₂ treatment on the structure and morphology was also examined.     

CdTe solar cell degradation studies with the use of CdS as the window material

We present in this work the degradation effects with time in thin film CdTe/CdS solar cells, where the CdS and CdTe layers are deposited by chemical bath deposition (CBD) and close space vapor transport (CSVT), respectively. The CdS thin films were grown from different baths by varying the S/Cd ratio. The variation of the S/Cd ratio allowed us to control the morphology and the density of defects, thus giving rise to better quality CBD CdS films. Depending on the S/Cd ratio an improvement of the morphology and capacitance signal was observed, these factors have also an influence on the open-circuit voltage, short-circuit current density, fill factor and conversion efficiency of the solar cell. The variation with time of these parameters in our devices was tracked during a period of 3 years measured directly on the exposed back contact regions (CdTe/Cu/Au). A discussion on the deterioration of the photovoltaic (PV) performance of the solar cells is presented in correlation with the local environmental conditions. This particular environment has contamination, and represents another type of stress for standard PV operations. These conditions reduce the mean life time of solar cells beyond short periods; this can be of interest for PV community.