CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited and chemical bath deposited precursors

We have fabricated 13.7%- and 7.3%-efficient CuIn_1−xGa_xSe₂ (CIGS)-based devices from electrodeposited and chemical bath deposited precursors. As-deposited precursors are Cu-rich films and polycrystalline (grain size is very small) in nature. Only preliminary data is presented on chemical bath deposited precursors. Additional In, Ga, and Se were added to the precursor films by physical evaporation to adjust the final composition to CuIn_1−xGa_xSe₂. Addition of In and Ga and also selenization at high temperature are very crucial to obtain high efficiency devices. Three devices with Ga/(In+Ga) ratios of 0.16, 0.26, and 0.39 were fabricated from electrodeposited precursors. The device fabricated from the chemical bath deposited precursor had a Ga/(In+Ga) ratio of 0.19. The films/devices have been characterized by inductive-coupled plasma spectrometry, Auger electron spectroscopy, X-ray diffraction, electron-probe microanalysis, current-voltage characteristics, capacitance–voltage, and spectral response. The compositional uniformity of the electrodeposited precursor films both in the vertical and horizontal directions were studied. The electrodeposited device parameters are compared with those of a 17.7% physical vapor deposited device.     

CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited precursor films

We have developed an electrodeposition bath based on a buffer solution so that the stability of the electrodeposition process is enhanced and no metal oxides or hydroxides precipitate out of solution. The buffer-solution-based bath also deposits more gallium in the precursor films. As-deposited precursors are stoichiometric or slightly Cu-rich CuIn_1−xGa_xSe₂. Only a minimal amount of indium was added to the electrodeposited precursor films by physical vapor deposition to obtain a 9.4%-efficient device.     

Improved electrochromic films of NiOx and WOxPy obtained by spray pyrolysis

Electrochromic films of NiO_x and WO_xP_y were produced by the spray pyrolysis technique. The nickel-oxide-based coatings were obtained from both an alcoholic solution of nickel nitrate and aqueous solution of the mixture nickel nitrate/cobalt nitrate. Coatings obtained from alcoholic solutions showed a noticeable contrast of optical transmittance from fully bleached to colored state. X-ray diffraction analysis showed a slight crystallization in NiO_x after electrochemical treatment: one diffraction peak for as-deposited films turned to three diffraction peaks for electrochemical treated samples. Coatings obtained from aqueous solution of mixture nickel nitrate/cobalt nitrate showed an optimized electrochromic behavior at a Ni:Co proportion of 90:10. At this condition an optical contrast of 50% is found. X-ray diffraction showed that these samples comprised a phase mixture of Co₃O₄ and NiO.WO_xP_y samples were obtained from polytungsten gel in which H₃PO₄ was added. We found that for 8.3 at% of P:W, the electrochromism was optimized. Pyrolytic coatings of WO_xP_y show superior behavior than those of WO_x obtained by spray pyrolysis, both in optical contrast and durability.     

Solar cells with Cu(In1−xGax)S2 thin films prepared by sulfurization

By rapid thermal processing of Cu/In/GaS precursors, good-quality CuIn_1–xGa_xS₂ films are synthesized. By suppressing the formation of In-rich hillocks, we could obtain homogeneous CuIn_1–xGa_xS₂ surfaces. A conversion efficiency of 12% has been achieved using a relatively low (1.2) Cu/In ratio.     

Impact of substrate roughness on CuInxGa1−xSe2 device properties

In comparison to the traditional use of glass substrates, CuIn_xGa_1−xSe₂ (CIGS) deposited onto metal substrates offers improved device cooling under concentration, economical large-scale roll-to-roll processing, and applicability towards lightweight as well as flexible products. However, unlike glass, metal foils tend to exhibit rough surfaces. This study quantifies the effect of substrate roughness on CIGS device performance. Several substrate types with differing average roughnesses were examined. The frequencies of the surface features contributing to roughness are also examined via several different analytical techniques. Devices were prepared and characterized on steel foils, Mo foil, and glass.     

Metal/CdTe/CdS/Cd1−xZnxS/TCO/glass: A new CdTe thin film solar cell structure

The potential of CdTe/CdS/Cd_1−xZn_xS structure as an alternative to CdTe/CdS structure in photovoltaic application has been demonstrated. The unoptimized solar cell structure grown on transparent conducting oxide coated soda lime glass of 3 mm thickness with no antireflection coating yielded a 10% efficiency. This efficiency is the highest ever recorded in any Cd_1−xZn_xS film containing CdTe solar cells.     

Fabrication and characterization of amorphous In–Zn–O/SiOx/n-Si heterojunction solar cells

Amorphous In–Zn–O (a-IZO) films were deposited on SiO_x covered n-type Si substrates by using pulsed laser deposition (PLD) technique to form a-IZO/SiO_x/n-Si heterojunction solar cells. The a-IZO films grown at 150 °C with various laser power (250–500 mJ/pulse) exhibit low resistivity (2–3 × 10⁻³ Ω cm) and high transparency (∼80%) in the visible wavelength range. The highest conversion efficiency of the fabricated a-IZO/SiO_x/n-Si solar cells is 2.2% under 100 mW/cm² illumination (AM1.5 condition). The open-circuit voltage, short-circuit current density and fill factor of the best device are 0.24 V, 28.4 mA/cm² and 33.6%, respectively.     

Electrochromic properties of NiOxHy thin films

NiO_xH_y films were prepared by DC magnetron sputtering in H₂/O₂ atmosphere. NiO_xH_y coatings with transparency and high electrochromic efficiency were obtained by changing H₂ content. A 60 nm thick NiO_xH_y film with transmittance of 0.57 (as-deposited state), 0.78 (bleached state) and 0.24 (coloured state) at wavelength of 550 nm was deposited in an atmosphere of H₂(60%)+O₂(40%). Analysis of infrared spectra (60002400 cm⁻¹) showed that the absorption peaks for bleached and colored states are associated with free ‘OH’ and OH stretching vibrations, respectively. XPS Ni2p core level spectra of colored NiO_xH_y film exhibited a peak at 856.2±0.2 eV which is attributed to Ni³⁺. Ni2p core level spectra of the bleached and as-deposited films exhibited two peaks at 856.4±0.2 and 854.6±0.2 eV which are attributed to Ni³⁺ and Ni²⁺.     

Investigation of non-aqueous electrodeposited CdS/Cd1−xZnxTe heterojunction solar cells

Polycrystalline Cd_1−xZn_xTe solar cells with efficiency of 8.3% were grown by cathodic electrodeposition on glass/ITO/CdS substrates using non-aqueous ethylene glycol bath. The deposit is characterised versus the process conditions by XRD and found to possess a preferred (1 1 1) orientation on Sb doping in the electroplating bath. The surface morphology of the deposit is studied using atomic force microscope. The average RMS roughness for the ternary film was higher than that for the binary CdTe. Optical properties of the films were carried out to study the band gap and calculation of molar concentration ‘x’. The effects of Sb doping in CdS/Cd_1−xZn_xTe heterojunctions have been studied. The short circuit current density (c) was found to improve and series resistance (R_s) reduced drastically upon Sb doping. This improvement in J_sc is attributed to an increase in quantum efficiency. The evaluation of solar cell parameters was also carried out using the current–voltage characteristics in dark and illumination. The best results were obtained when 2×10⁻³ M ZnCl₂ along with antimony were present in the deposition bath. Under AM 1.5 conditions the open circuit voltage, short circuit current density, and fill factor of our best cell were V_oc=600 mV, J_sc=26.66 mA/cm², FF=0.42 and efficiency, η=8.3%. The carrier concentration and built-in potential of Cd_1−xZn_xTe calculated from Mott–Schottky plot was 2.72×10¹⁷ cm⁻³ and 1.02 eV.     

Structural and photoluminescence study of the quaternary alloys system CuIn(SxSe1−x)2

The full composition range CuIn(S_xSe_1−x)₂ alloy system has been studied using 40 mm length crystal cuts from 10 mm diameter ingots grown by the classical Bridgman method. X-ray diffraction diffractographs show that the CuIn(S_xSe_1−x)₂ compounds have a chalcopyrite structure for each composition x, they exhibit an expansion on the unit cell characteristics by the tetragonal distortion which depends linearly on the electronegativity of the atoms. The photoluminescence spectra is investigated as a function of various compositions, temperature and excitation intensities. Photoluminescence spectra shows a wide variation in the dominant peak location and an overall blue shift with the increase of sulphur content. Photoluminescence CuInS₂ and CuIn(S_0.72Se_0.28)₂ have been studied in detail.     

The study on high efficient AlxGa1−xAs/GaAs solar cells

The investigation of Al_xGa_1−xAs/GaAs solar cells is carried out by means of both metalorganic chemical vapor deposition (MOCVD) and liquid-phase epitaxial (LPE) technique. The measurements of illuminated I–V characteristics, dark I–V characteristics and quantum efficiencies were performed for the GaAs solar cells made in author's laboratory. The measuring results revealed that the quality of materials in GaAs solar cell's structures is the key factor for getting high-efficient GaAs solar cells, but the effect of post-growth technology on the performances of GaAs solar cells is also very strong. The 21.95% (AM0, 2×27 cm², 25°C) high conversion efficiency in a typical GaAs solar cell has been achieved owing to improving the quality of materials as well as optimizing the post-growth technology of devices.     

Optical, electrical and structural investigations on Cd1−xZnxSe sintered films for photovoltaic applications

II–VI polycrystalline semiconducting materials have come under increased scrutiny because of their wide use in the cost reduction of devices for photovoltaic applications. Cd_1−xZn_xSe is an important semiconducting alloy because of the tunability of its physical parameters such as band gap and lattice parameters by controlling its stoichiometry. Many more material characteristics of it would be altered and excellently controlled by controlling system composition x.Polycrystalline thin films of Cd_1−xZn_xSe with variable composition (0x1) have been deposited onto ultra-clean glass substrates by sintering process. The optical, structural and electrical transport properties of Cd_1−xZn_xSe thin films have been examined. The optical band gap and optical constants of these films were determined by using double beam spectrophotometer. The DC conductivity and activation energy of the films were measured in vacuum by two-probe technique. The Schottky junction of Cd_1−xZn_xSe with indium was made and the barrier height and ideality factor were determined using current–voltage characteristics. The nature of sample, crystal structure and lattice parameters were determined from X-ray diffraction patterns. The films were polycrystalline in nature having cubic zinc-blende structure over the whole range studied.Sintering is very simple and viable compared to other cost intensive methods. The results of the present investigation will be useful in characterizing the material, Cd_1−xZn_xSe, for its applications in photovoltaics.     

Active solar energy material science thermoelectric properties of nGe-p(InSb)1 ? x(Sn2)x heterostructures

By the method of liquid phase epitaxy, the epitaxial layers of a substitutional solid solution of the (InSb)_{1 − x} (Sn²) _x (1 ≤ x ≤ 0.05) p type of conductivity on nGe substrates were grown from a limited volume of an indium solution melt. It has been found that during the heating of the structure in the dark, an electrical current and voltage are generated in it.     

Properties of CuIn1−xGaxSe2

Polycrystalline bulk samples of CuIn_1−xGa_xSe₂ weregrown with nominal x = 0.15, 0.25 and 0.5. Mobility, conductivity and band gap were measured at room and low temperatures. Mobilities for x = 0.21 were several hundred cm² V⁻¹s⁻¹ at room temperature and for x = 0.15 were 10³ cm² V⁻¹ s⁻¹, all n type. The band gaps were estimated from the spectra of photoelectrochemical cells at room temperature (with 8.5 K photoluminescence estimates shown in brackets), as 1.10 eV (1.14) for x = 0.21, and 1.07 eV (1.093) for x = 0.15. Crystal mechanical properties as regards cracks were not as good as for CuInSe₂, using similar growth techniques.     

Composition, surface topography, structure, Raman, and electrochemical/photoelectrochemical characterisation of CdxHg1−xTe films

Cd-rich Cd_xHg_{1 − x}Te films have been electrodeposited under potentiostatic conditions on conducting glass and Ti substrates from an acidic solution containing the respective ions as Cd²⁺:Hg²⁺:HTeO₂⁺ = 100:1:2. Six films one after another have been prepared from a single electrochemical cell. EDAX analysis of the air annealed films show decreasing Hg content in the deposit as the number of film preparation increases. SEM analysis indicate undulatory surface with Hg-rich clusters at the top surface. XRD analysis indicate the presence of Cd_xHg_{1 − x}Te along with . The Cd_xHg_{1 − x}Te alloy formation have been confirmed from Raman shift measurements which change with composition, x. The as-deposited films are n-type but converts to p-type after air annealing. Spectral response measurements gave band gap values that change with Hg content in the deposit. Band gap values ranging from 1.1 eV to 1.45 eV have been estimated. Photoelectrochemical solar cells using polysulphide electrolyte have been fabricated which gave an open-circuit photovoltage and short-circuit photocurrent, respectively, as 325 mV and 5.5 mA/cm² under 60 mW/cm² intensity of illumination.     

Photoconductivity and defect levels in ZnxCd1−xSe with (x=0.5, 0.55) crystals

Gold surface barriers on Zn_xCd_1−xSe alloys have been investigated for composition with x=(0.5, 0.55). The electrical characteristics were studied as a function of air annealing. The common feature of all the Schottky devices was the reduction of reverse bias leakage current after heating in air. Typical measurements of capacitance as a function of bias voltage can provide information on the charge density and diffusion potential. The barrier height was found to increase after air annealing at 200°C for 2 min. The spectral response of the photocurrent and photocapacitance associated with these device layers enable a donor level at 0.13 eV and acceptor levels at 1.08, 1.3 and 1.45 eV below the bottom of the conduction band to be identified. The results are discussed in terms of the effects of oxygen absorption.     

Analysis of the surface condition of Ti4Fe2Ox

The surface conditions of powder compounds Ti₄Fe₂O_x (x = 0.5; 1.0) have been studied by means of the XPS method. As in the case of the alloys, Ti_1.1 Fe, Ti_1.1Fe_0.9Mn_0.1 and Ti_1.1Fe_0.8Cu_0.1Ni_0.1 studied earlier the peculiarities of the XPS O 1s core-level spectra in Ti₄Fe₂O_x are also observed. The peculiarities can be connected with oxygen-containing gas molecules chemisorbed on the alloy surfaces. The dependence of activation temperature upon the type of oxygen-containing structures absorbed on the alloy surfaces has been established. A physical model of the activation process for TiFe-based alloys is proposed. In this model, the surface oxides play an active role in distinction from the segregation model where the oxides play a passive role.     

Characterization and electrochromic properties of CuxNi1−xO films prepared by sol–gel dip-coating

Cu_xNi_1−xO electrochromic thin films were prepared by sol–gel dip coating and characterized by XRD, UV–vis absorption and electrochromic test. XRD results show that the structure of the Cu_x Ni_1−xO thin films is still in cubic NiO structure. UV–vis absorption spectra show that the absorption edges of the Cu_xNi_1−xO films can be tuned from 335 nm (x = 0) to 550 nm (x = 0.3), and the transmittance of the colored films decrease as the content of Cu increases. Cu_xNi_1−xO films show good electrochromic behavior, both the coloring and bleaching time for a Cu_0.2Ni_0.8O film were less than 1 s, with a variation of transmittance up to 75% at the wavelength of 632.8 nm.     

Chemical bath deposition and electrochromic properties of NiOx films

Nickel oxide (NiO_x) thin films were prepared by the chemical deposition method (solution growth) on two kinds of substrates: (1) glass and (2) glass/SnO₂ : F. Films were thermally treated at 200°C for 10 min in atmosphere. The texture, microstructure and composition were examined by optical microscopy, X-ray diffraction patterns (XRD) and X-ray photoelectron spectroscopy (XPS) analysis of the surface layer. The films exhibited anode electrochromism. The optical properties of the bleached and colored state were examined with transmittance spectroscopy in the visible region and reflectance FTIR spectroscopy. An electrochromic test device (ECTD), consisting of SnO₂/NiO_x/NaOH–H₂O/SnO₂, was assembled and tested by cyclic voltammetry combined with a simultaneous recording of the change of transparency at λ=670 nm. The coloration efficiency was evaluated to be 24.3 cm²/C. The spontaneous ex-situ change of coloration with time of the colored and bleached NiO_x/SnO₂/glass was also examined.     

Preparation and characterization of semiconducting Zn1−xCdxSe thin films

The electrodeposition of Zn_1−xCd_xSe polycrystalline semiconducting thin films from aqueous acidic bath without any additives onto tin oxide-coated conducting glass and titanium substrates are described. The influence of deposition parameters on the film formation and deposition mechanism based on cyclic voltammetry is discussed. X-ray diffraction studies showed the polycrystalline wurtzite nature for all the films deposited under the proposed conditions. The optical studies revealed the band gap values in the range between 2.82 and 1.72 eV as the film composition changes from ZnSe to CdSe. It has been observed that the concentration of cadmium salt plays an essential role on the alloy formation. The surface morphological studies and composition analysis were carried out and the results are discussed.