Towards ultra-thin CdTe solar cells using MOCVD

A study was made on very thin CdTe absorber < 1 µm layers to investigate limitations in CdTe collection efficiency. Metal organic chemical vapour deposition (MOCVD) was used to deposit cadmium sulfide (CdS), cadmium zinc sulfide (Cd_0.9Zn_0.1S) and cadmium telluride (CdTe). Improvements in photon collection in the blue, where the absorption length is shorter, have been achieved using a wider band gap Cd_0.9Zn_0.1S ternary alloy to replace CdS as the window layer. Solar cell capacitance simulator (SCAPS) modelling software [M. Burgelman, P. Nollet, S. Degrave, Thin Solid Films, 361-362 (2000) 527-532] has been used to calculate device parameters as a function of the absorber layer thickness (controlled by in situ using laser reflectometry). One feature of the MOCVD grown devices is the apparent absence of pin-holes, demonstrated by growth of an ultra-thin absorber (200 nm) with conversion efficiency of nearly 4%.     

Microstructural features of cadmium telluride photovoltaic thin film devices

In order to study the microstructure of cadmium telluride (CdTe) photovoltaic thin film solar cells, manufactured by an in-line manufacturing process, Scanning Electron Microscopy characterization (SEM) and X-ray diffraction (XRD) characterization were performed. SEM measurement showed that no substantial changes in the grain structure of CdTe layers occurred during the Cadmium Chloride (CdCl₂) treatment. No change in the cubic CdTe lattice parameter “a” was observed for the CdCl₂ treated sample. It is inferred that the primary effect of the CdCl₂ treatment in the devices studied is the passivation of grain boundaries and bulk defects. XRD studies show a loss of preferred orientation (as determined from the peak ratios) of planes during the copper compound treatment indicating recrystallization of the grains due to the Cu treatment. Also the Cu treated sample showed decrease in value of the lattice parameter “a”.     

Deposition and properties of CBD and CSS CdS thin films for solar cell application

We deposited cadmium sulfide (CdS) thin films using the chemical-bath deposition (CBD) and close-spaced sublimation (CSS) techniques. The films were then treated in CdCl₂ vapor at 400 °C for 5 min. The CSS CdS films had hexagonal structure, and good crystallinity. The CdCl₂ treatment did not produce major changes, but there was a decrease in the density of planar defects. The untreated CBD CdS films had cubic structure and poorer crystallinity than the CSS films. After the CdCl₂ treatment, these films recrystallized to the hexagonal phase, resulting in better crystallinity and a lower density of planar defects. The conformal coverage and the presence of bulk oxygen are the key issues in making the CBD films more suitable for photovoltaic applications.     

Effects of CdCl2 treatment on the properties of CdS films prepared by r.f. magnetron sputtering

Effects of the thickness of CdCl₂ layer and the annealing on structural and optical properties of sputter-deposited CdS films were investigated. The annealing process of evaporated CdCl₂ was carried out by heating the sample in air at 350-500 °C for 20 min. As the thickness of the CdCl₂ increases, the (002) peak of CdS becomes weak and the other peaks of CdS increases. Especially, for 200 nm CdCl₂, the preferential orientation of the (002) plane disappears and the c-axis of the CdS film tends to orient parallel to the substrate. As the CdCl₂ layer is thicker, the grains are enlarged significantly. The improvement of optical properties of CdS films with thicker CdCl₂ layer might be successfully employed in achieving better conversion efficiencies in solar cells.     

Effect of CdCl2 annealing treatment on thin CdS films prepared by chemical bath deposition

In order to study the CdS recrystallization mechanism, a comparative study was carried out on thin films prepared by chemical bath deposition. The CdS films were annealed in air with or without a CdCl₂ coating layer. In-situ Raman spectra obtained during the annealing showed that both the air- and the CdCl₂-annealing did not cause rearrangement of the neighboring atoms in the CdS clusters below ~ 300 °C. CdS thin film was partially oxidated to CdO and CdSO₄ on the cluster surface when annealed in air. The oxides and the sulfur stoichiometric deficiency prevented the clusters to coalesce at higher temperatures. Coating thin CdS film with a thin CdCl₂ layer protected it from oxidation during annealing in air and promoted formation of Cl_S and V_Cd point defects in CdS. The anti-oxidation was attributed to the incorporation of a significant amount of Cl into CdS to form the Cl_S, which prevented the oxygen in-diffusion and chemical bonding during the annealing. The anti-oxidation at the CdS nano-crystalline surface and the point defects formed in the CdS promoted coalescence of the neighboring clusters without the need of long-range redistribution of the atoms. Large CdS grains with good crystalline quality formed through recrystallization during the CdCl₂ heat treatment, which provided the solid basis for the subsequent CdTe growth and high efficient CdS/CdTe solar cell fabrication.     

Analysis of electrodeposited CdTe thin films grown using cadmium chloride precursor for applications in solar cells

Deposition of cadmium telluride (CdTe) from cadmium chloride (CdCl₂) and tellurium oxide has been achieved by electroplating technique using two-electrode configuration. Cyclic voltammetry shows that near-stoichiometric CdTe is achievable between 1330 and 1400 mV deposition voltage range. The layers grown were characterised using X-ray diffraction (XRD), UV–Visible spectrophotometry, scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), photoelectrochemical (PEC) cell and DC conductivity measurements. The XRD shows that the electrodeposited CdTe layer is polycrystalline in nature. The UV–Visible spectrophotometry shows that the bandgap of both as-deposited and heat-treated CdTe films are in the range of (1.44–1.46) eV. The SEM shows grain growth after CdCl₂ treatment, while, the EDX shows the effect of growth voltage on the atomic composition of CdTe layers. The PEC results show that both p- and n-type CdTe can be electrodeposited and the DC conductivity reveals that the high resistivity is at the inversion growth voltage (V_i) for the as-deposited and CdCl₂ treated layers.     

In situ X-ray studies of metal organic chemical vapor deposition of PbZrxTi1 − xO3

In situ synchrotron X-ray scattering and fluorescence techniques were used to simultaneously observe the evolution of the strain and composition of a growing crystal surface in real time. Control of the X-ray incidence angle allows us to obtain high surface sensitivity. We studied metal organic chemical vapor deposition (MOCVD) of epitaxial PbZr_xTi_1 − xO₃ (PZT) onto SrTiO₃ (001) substrates under various growth conditions. We observe a strong increase in Zr incorporation as strain relaxation occurs, consistent with the effect of compositional strain on the thermodynamic driving force for growth.     

Characteristics of n-Cd0.9 Zn0.1S/p-CdTe heterojunctions

CdTe thin films were prepared by thermal evaporation under a vacuum of 10⁻⁶ Torr and with a deposition rate of about 60 nm/min. X-ray diffraction studies of the as-deposited films revealed polycrystalline films with cubic structure. The effect of heat treatment with or without CdCl₂ enhances the grain size and improves the crystallinity of the films. Moreover, the activation energy decreases upon heat treatment with or without CdCl₂ for CdTe thin films. The optical spectra of CdTe films show interference oscillations indicating the good optical quality of these films. The calculated energy gap decreases with or without CdCl₂ treatments. The current-voltage and capacitance-voltage characteristics for dark and illuminated three junction cells are measured. By analysing these measurements the different junction parameters are obtained and the effect of CdCl₂ treatment on the performance of the heterojunctions is investigated.     

Study of CSS- and HVE-CdTe by different recrystallization processes

CdTe polycrystalline thin film solar cells are highly scalable devices, showing stable performance and high efficiencies. A recrystallization treatment prior to the back contact deposition is essential for obtaining high efficiencies. Heat treatment in chlorine atmosphere (CdCl₂) promotes grain growth, intermixing between CdS and CdTe layers and passivation of the grain boundaries. An alternative method has been previously introduced on close space sublimated (CSS) CdTe devices, consisting in treating CdTe layers in the presence of a gas belonging to the Freon^© family at 400 °C. In this work, the application of this novel “activation process” on physical vapor deposited stacks is described.A comparison between physical/chemical features of the CdCl₂ and Freon treated layers is also presented.     

Mechanism for CdS electrodeposition from fused salt

Electrodeposition of CdS on a graphite substrate from LiCl-KCl eutectic melt containing CdCl₂ and Na₂SO₃ has been examined. It has been found that the cathodic deposition of CdS onto a graphite substrate occurs in competition with the formation of CdS particles by homogeneous precipitation in the bath. We have proposed as a deposition mechanism that the underpotential deposition of cadmium occurs under the influence of some sulphur species. We have also found that crystals of solid solution of CdS-CdSe are electrodeposited by adding selenium powder in the bath.     

Preparation of cadmium telluride nanoparticles from aqueous solutions by sonochemical method

Cadmium telluride nanoparticles with sizes between 8 and 13 nm have been synthesized via a sonochemical route using cadmium sulfate hydrate (CdSO₄·8/3H₂O), cadmium chloride (CdCl₂) and elemental Te as precursors and aqueous solutions of NaOH and EDTA as solvents. The qualitative characterization and estimation of nanoparticle size were carried out by using X-ray powder diffraction (XRD). The morphology of nanoparticles was analyzed by transmission electron microscopy (TEM). Changes of physical and chemical properties of the prepared CdTe nanoparticles at increased temperature were studied by thermal analysis (TGA, SDTA). A probable mechanism for the sonochemical formation of CdTe is proposed.     

Structural study of the initial growth of nanocrystalline CdS thin films in a chemical bath

Nanocrystalline cadmium sulfide CdS thin films with relevance for optical applications were synthesized from aqueous solutions by chemical bath deposition. Grazing incidence X-ray diffraction shows that the films formed on glass or silicon substrates are made up of nanocrystalline particles. About 80% of the particles have a diameter of 5 ± 1 nm. The nanoparticles have either sphalerite or wurtzite structure. The presence of the sphalerite phase is a signature of a highly non-equilibrium state of the nanocrystalline film. Kinetic studies show that the size of the nanocrystals and the relative fraction of the two phases do not depend on the deposition time once it exceeds a duration of 30 min. For longer times, the particle characteristics remain constant while the thickness of the film grows. Thermodynamical analysis of ionic equilibria allows to choose the reaction bath composition for the formation of cadmium hydroxide Cd(OH)₂. The experiments provide strong evidence that the beginning of the deposition of CdS is accompanied by a formation of cadmium hydroxide Cd(OH)₂.     

Study of CdS-sensitized solar cells, prepared by ammonia-free chemical bath technique

In this study, cadmium sulfide (CdS)-sensitized solar cells have been fabricated, where nanoporous titanium oxide (TiO₂) photoelectrode of equal thickness has been prepared on SnO₂:F coated glass substrate using TiO₂ paste. Different amounts of CdS have been deposited by an ammonia-free chemical bath deposition technique with various deposition times. The CdS-sensitized TiO₂ photoelectrodes show polycrystalline nature. The optical measurement reveals that absorbance edge of the CdS-sensitized TiO₂ photoelectrode extends up to 540 nm and the amount of absorbance increases with the enhancement of CdS-deposition time. The CdS solar cell, with deposition time of 12 min, shows impressive photocurrent and moderate solar cell efficiency.     

Organometallic molecular precursors for low-temperature MOCVD of III–V semiconductors

Metal-organic chemical vapor deposition (MOCVD) is a suitable technique for the preparation of III–V epitaxial layers which are used in the fabrication of microelectronic and optoelectronic devices. The usual Ga and As sources for GaAs are Ga(CH₃)₃ and AsH₃, respectively. However, the use of these precursors has some disadvantages including: The toxicity and storage of arsine, stoichiometry control, carbon incorporation and unwanted side reactions. Several groups of researchers have investigated alternative sources for both the group–III and group-V elements. A review of these new organometallic precursors is presented in this paper. However, because group-III and group-V elements form Lewis-acid/base adducts in the MOCVD reactor, we have especially investigated the use of this class of compounds as single starting molecules. Several adducts have been successfully used for the epitaxial growth of GaAs. Moreover, to avoid any stoichiometry loss due to dissociation of the adduct, the properties of organometallic molecules which feature a covalent bond between the group-III and group-V elements have also been investigated. These covalent compounds are probably formed in the MOCVD reactor when alkyl group-V compounds containing acidic hydrogen R_3?nMH_n (M = As, P; n = 1,2) are used. Such new precursors are also briefly reviewed.     

ZnxCd1 − xS as a heterojunction partner for CuIn1 − xGaxS2 thin film solar cells

Zinc cadmium sulfide (Zn_xCd_1 − xS) heterojunction partner layer prepared with chemical bath deposition (CBD) has exhibited better blue photon response and higher current densities due to its higher bandgap than that of conventional cadmium sulfide (CdS) layer for CuIn_1 − xGa_xS₂ (CIGS2) solar cells. CIGS2/Zn_xCd_1 − xS devices have also shown higher open circuit voltage, V_oc indicating improved junction properties. A conduction band offset has been observed by J-V curves at various temperatures indicating that still higher V_oc can be obtained by optimizing the conduction band offset. This contribution discusses the effect of variation of parameters such as concentration of compounds, pH of solution and deposition time during CBD on device properties and composition and crystallinity of film. Efficiencies comparable to CIGS2/CdS devices have been achieved for CIGS2/Zn_xCd_1 − xS devices.     

Effect of interdiffusion and impurities on thin film CdTe/CdS photovoltaic junctions

We have used low temperature photoluminescence (PL) to study thin film CdTe/CdS solar cell structures. The devices were produced by close space sublimation (CSS) and have undergone a post-growth treatment, a vital step in increasing device efficiency. The treatment consisted of evaporating a thin layer of CdCl₂ onto the back CdTe surface and heat treating in air at 400 °C for between 10 and 120 min. This produced a range of device efficiencies from 2% to 9%. The efficiency improvements are the result of a complex interaction between the CdCl₂, impurities and sulfur interdiffusion. The structures were prepared for PL by a chemical bevel etching technique which allows the luminescence emission to be studied as a function of depth throughout the sample. The main features in the PL spectra have been identified as being due to the Cl-A center and the Te-dislocation-related Y luminescence band. Using PL we have quantified the S diffusion into the CdTe which has a maximum of 20% at the interface in the most efficient samples. We have also obtained the profiles of recombination and non-radiative recombination centers in the device. We observe correlations between impurity centers and device efficiency which can help explain the effects of the CdCl₂ treatment on the optoelectronic properties of the CdTe/CdS junction.     

SiO2/Cd(OH)2 composite nanotubes prepared by microwave-solvothermal transformation using water-dissolvable KCdCl3 nanowires as precursor and template

Silica/cadmium hydroxide (SiO₂/Cd(OH)₂) composite nanotubes have been successfully synthesized by a microwave-assisted solvothermal method at 100 °C using water-dissolvable KCdCl₃ nanowires as the precursor and template. The KCdCl₃ nanowires are prepared by adding an aqueous solution containing CdCl₂ and KI into anhydrous ethanol at room temperature. The KCdCl₃ nanowires, which are water-dissolvable and can be easily removed by washing with water, act as both the precursor and template for the preparation of SiO₂/Cd(OH)₂ composite nanotubes in an alkaline solution. One of the advantages of this method is that the preparation of SiO₂/Cd(OH)₂ composite nanotubes can well duplicate the shape of the nanowire precursor, and the simplicity and low cost can be achieved. The samples are characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM).     

Template-free non-aqueous electrochemical growth of CdO nanorods

The direct template-free synthesis and characterization of CdO nanorods (NRs) obtained through electrochemical reduction process of molecular oxygen (O₂) in a dimethylsulfoxide solution containing CdCl₂are reported. X-ray diffraction characterization of the NRs shows that the CdO phase was obtained without the presence of any other secondary phases. In agreement with the aspect ratio of a typical nanorod structure, CdO NRs presented average diameters of ca. 170 nm and average lengths of ca. 920 nm. Current results also demonstrate that the employed electrochemical synthesis route favors the growth of NRs with a preferred crystallographic orientation along the [200] axis direction. The synthesized CdO NRs exhibited a n-type semiconductor character with a donor carrier concentration of N_D = 4.3 × 10¹⁹ cm^− 3.     

Progress towards marketable earth-abundant chalcogenide solar cells

Kesterite-related photovoltaic materials are considered a promising alternative to CdTe and Cu(In,Ga)(S,Se)₂ absorbers, primarily because they are not reliant on scarce elements such as indium and tellurium or the heavy metal cadmium. Recently, we reported a performance breakthrough for this materials class, reaching by a simple hydrazine-based deposition technique 9.6% power conversion efficiency for Cu₂ZnSn(S,Se)₄ devices (40% improvement over vacuum-based methods). Here, more detailed characterization for a hydrazine-prepared device shows the potential of this technology for further efficiency improvement. We also present initial device results for Cu₂ZnSn(S,Se)₄ films deposited using a mixed water-hydrazine-based solvent, yielding devices with 8.1% efficiency.     

MOCVD indium sulphide for application as a buffer layer in CIGS solar cells

Indium sulphide has a high potential as a buffer layer material in Cu(In,Ga)Se₂ (CIGS) solar devices. In this work a metal organic vapour deposition (MOCVD) process was investigated for the indium sulphide deposition. Trimethyl-indium and t-butyl-thiol were applied as precursor sources. The films produced with different process conditions were characterised by scanning electron microscopy. We also present the first results of CIGS laboratory cells with an MOCVD indium sulphide buffer layer. The best device showed an efficiency of 12.3% (CdS reference = 13.0%) at a deposition temperature of 300 °C and a deposition time of 20 min, combined with a 5 min post-annealing treatment at 200 °C in air.