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.     

Preparation and evaluation of Cu2ZnSnS4 thin films by sulfurization of E---B evaporated precursors

By sulfurization of E---B evaporated precursors, CZTS(Cu₂ZnSnS₄) films could be prepared successfully. This semiconductor does not consist of any rare-metal such as In. The X-ray diffraction pattern of CZTS thin films showed that these films had a stannite structure. This study estimated the optical band gap energy as 1.45 eV. The optical absorption coefficient was in the order of 10⁴cm⁻¹. The resistivity was in the the order of 10⁴ Ω cm and the conduction type was p-type. Fabricated solar cells, Al/ZnO/CdS/CZTS/Mo/Soda Lime Glass, showed an open-circuit voltage up to 400 mV.     

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.     

Electrochemical deposition of Zn3P2 thin film semiconductors on tin oxide substrates

Zn₃P₂ semiconductor thin films were prepared by electrodeposition technique form aqueous solutions. The deposition mechanism was investigated by cyclic voltammetry technique. Crystal structure, morphology and composition of as deposited and annealed Zn₃P₂ thin films grown on SnO₂/glass substrates were determined by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. X-ray diffraction data indicated the formation of Zn₃P₂ as the predominant phase for both as-deposited and annealed films. The compositions of the deposited films were controlled by the bath temperature, deposition potential and Zn/P ratio in the solution.The dark current–voltage measurements of SnO₂/Zn₃P₂/C devices indicated a rectifying behavior and a reverse saturation current density of 1.7×10⁻⁷ A/cm², which is in good accordance with that obtained from films prepared using vacuum technique. Also, the capacitance–voltage measurements showed that the number of interface states and the built in potential are in the order of 5×10⁻⁹ cm⁻³ and 0.85 V, respectively. These preliminary results for Zn₃P₂ thin films reveal that, this semiconductor material can be used for solar cell applications.     

Investigation of photoelectrochemical characteristics of n-type Cu2O films

n-Cu₂O photoelectrodes are obtained by immersing a copper plate in a CuSO₄(10⁻³ M) and HCl (10⁻³ M) solutions. Samples are characterized with XRD and SEM measurements. It is found that Cu²⁺ ions and the copper substrate are essential to obtain n-type photoresponses from Cu₂O. Photocurrent action spectra are investigated with various Cu₂O amounts formed on the copper substrate, made from two different methods. Photoluminescence (PL) measurements of the samples prepared by the two methods are examined. Time development of the photocurrent is investigated in KI(10⁻² M)+I₂ (10⁻⁴ M) and trisodium citrate solutions.     

Synthesis and characterization of aluminum-doped CdO thin films by sol–gel process

Aluminum-doped cadmium oxide (CdO:Al) thin films are deposited on glass substrates by the sol–gel dip-coating method, taking cadmium acetate dihydrate as the precursor material. Aluminum nitrate has been taken as a source of Al-dopant. XRD pattern reveals the good crystallinity of CdO thin films. SEM micrograph showed the presence of faceted crystallites. Optical study shows 40–85% transparency with a bandgap value lying in the range 2.76–2.52 eV, depending upon the Al content in the films. Optimum percentage of Al was 5.22 for a maximum room temperature conductivity of 2.81×10³ (Ω cm)⁻¹. Hall measurement confirmed that the material is of n-type, with mobility and carrier concentrations lying in the range 413–14.7 cm²/V s, and 3.4×10¹⁹–8.11×10²⁰ cm⁻³, when percentage of Al varies in the range 1.32–7.24.     

Scanning tunneling microscopy of electrodeposited CuInSe2 nanoscale multilayers

We have investigated the electrochemical deposition of modulated thin films based on the Cu_xIn_2−xSe₂ system. CuInSe₂ is a leading alternative to silicon for use in thin film photovoltaic solar cells due to its optical absorption and electrical characteristics. Alternating layers of two different compositions based on the Cu_xIn_2−xSe₂ system were potentiostatically deposited. These nanometer-scale layers are used to form reduced-dimensionality structures such as superlattices that can be used in concentrator solar cells. We have used X-ray diffraction, energy-dispersive spectroscopy, and scanning tunneling microscopy to characterize our asdeposited thin films. The ability of the scanning tunneling microscope to resolve the individual nanoscale layers of our multilayered thin films is shown and is used to determine modulation wavelengths.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Investigations on ZnxCd1−xO thin films obtained by spray pyrolysis

Zn_xCd_1−xO thin films were prepared on glass substrates by spray pyrolysis technique. The precursor solutions were obtained by varying the concentration of Zn(NO₃)₂·6H₂O and Cd(NO₃)₂·4H₂O in bi-distilled water. The structural properties have been studied using X-ray diffraction spectra. All the structures include the basic compounds, i.e. ZnO and CdO. The orientation and the crystalline phases of the deposited films were specified. With the addition of Zn to the precursor solution, we can observe the preferential orientation of the CdO in the [2 0 0] direction. The electrical measurements were performed using method of four contacts. Thin films transmittances, in the 1.5–4.3 eV range, for different compositions have been measured and the optical gaps have been determined. The variations are explained considering the gaps of the two pure films. The influence of increased Cd concentration in the films on the structural, electrical and optical properties is investigated in this study.     

Electrodeposited cuprous oxide on indium tin oxide for solar applications

Semiconducting cuprous oxide films were prepared by electrodeposition onto commercial conducting glass coated with indium tin oxide deposited by spraying technique. The cuprous oxide (Cu₂O) films were deposited using a galvanostatic method from an alkaline CuSO₄ bath containing lactic acid and sodium hydroxide at a temperature of 60°C. The film's thickness was about 4–6 μm. This paper includes discussion for Cu₂O films fabrication, scanning electron microscopy and X-ray diffractometry studies, optical properties and experimental results of solar cells. The values of the open circuit voltage V_oc of 340 mV and the short circuit current density I_sc of 245 μA/cm² for ITO/Cu₂O solar cell were obtained by depositing graphite paste on the rear of the Cu₂O layer. It should be stressed that these cells exhibited photovoltaic properties after heat treatment of the films for 3 h at 130°C. An electrodeposited layer of Cu₂O offers wider possibilites for application and production of low cost cells, both in metal–semiconductor and hetero-junction cell structures, hence the need to improve the photovoltaic properties of the cells.     

A new route for fabricating CdO/c-Si heterojunction solar cells

CdO/c-Si solar cells have been made by depositing CdO thin films on p-type monocrystalline silicon substrate by means of the rapid thermal oxidation (RTO) technique using a halogen lamp at 350 °C/45 s in static air. Results on structural, optical, and electrical properties of grown CdO films are reported. The electrical and photovoltaic properties of CdO/Si solar cells are examined. Under AM1 illumination condition, the cell shows an open circuit voltage (V_OC) of 500 mV, a short circuit current density (J_SC) of 27.5 mA/cm², a fill factor (FF) of 60%, and a conversion efficiency (η) of 8.84% without using frontal grid contacts and/or post-deposition annealing. Furthermore, the stability of solar cells characteristics is tested.     

Effect of 8 MeV electron irradiation on electrical properties of CuInSe2 thin films

Radiation damages due to 8 MeV electron irradiation in electrical properties of CuInSe₂ thin films have been investigated. The n-type CuInSe₂ films in which the carrier concentration was about 3×10¹⁶ cm⁻³, were epitaxially grown on a GaAs(0 0 1) substrate by RF diode sputtering. No significant change in the electrical properties was observed under the electron fluence <3×10¹⁶ e cm⁻². As the electron fluence exceeded 10¹⁷ e cm⁻², both the carrier concentration and Hall mobility slightly decreased. The carrier removal rate was estimated to be about 0.8 cm⁻¹, which is slightly lower than that of III–V compound materials.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Optical transmittance and photoconductivity studies on ZnO : Al thin films prepared by the sol–gel technique

Polycrystalline ZnO : Al thin films have been prepared by the (Sol–gel) chemical deposition method. The ZnO : Al thin films are very transparent (90%) in the near UV, VIS and IR regions. The films are oriented along the c-axis ([0 0 2] direction) in the hexagonal structure. It is known that pure ZnO thin films are not chemically stable in corrosive media, but aluminium stabilizes the ZnO system and increases its electrical conductivity. Finally, the ZnO : Al thin films are reasonably stable under storage in air and in reactive atmospheres like O₂, H₂O, H₂ or in weak acids. Dark- and photo-conductivity of the ZnO : Al films are very high (1–100 Ω⁻¹ cm⁻¹), so that they can be used as transparent conductors in solar cells or in electrochromic devices.     

Effect of proton irradiation on electrical properties of CuInSe2 thin films

High-energy proton irradiation (380 keV and 1 MeV) on the electrical properties of CuInSe₂ (CIS) thin films has been investigated. The samples were epitaxially grown on GaAs (0 0 1) substrates by Radio Frequency sputtering. As the proton fluence exceeded 1×10¹³ cm⁻², the carrier concentration and mobility of the CIS thin films were decreased. The carrier removal rate with proton fluence was estimated to be about 1000 cm⁻¹. The electrical properties of CIS thin films before and after irradiation were studied between 80 and 300 K. From the temperature dependence of the carrier concentration in CIS thin films, we found N_D=9.5×10¹⁶ cm⁻³, N_A=3.7×10¹⁶ cm⁻³ and E_D=21 meV from the fitting to the experimental data on the basis of the charge balance equation. After irradiation, a defect level was created, and N_T=1×10¹⁷ cm⁻³ for a fluence of 3×10¹³ cm⁻², N_T=5.7×10¹⁷ cm⁻³ for a fluence of 1×10¹⁴ cm⁻² and E_T=95 meV were also obtained from the same fitting. The new defect, which acted as an electron trap, was due to proton irradiation, and the defect density was increased with proton fluence.     

Enhanced electrical properties of pulsed laser-deposited CuIn0.7Ga0.3Se2 thin films via processing control

Polycrystalline CuIn_0.7Ga_0.3Se₂ thin films were prepared on soda-lime glass substrates using pulsed laser deposition (PLD) with various process parameters such as laser energy, repetition rate and substrate temperature. It was confirmed that there existed a limited laser energy, i.e. less than 300 mJ, to get phase pure CIGS thin films at room temperature. Particularly, even at room temperature, distinct crystalline CIGS phase was observed in the films. Crystallinity of the films improved with increasing substrate temperature as evidenced by the decrease of FWHM from 0.65° to 0.54°. Slightly Cu-rich surface with Cu_2−xSe phase was confirmed to exist by Raman spectra, depending on substrate temperature. Improved electrical properties, i.e., carrier concentration of ∼10¹⁸ cm⁻³ and resistivity of 10⁻¹ Ω cm at higher substrate temperature for the optimal CIGS films are assumed to be induced by the potential contributions from highly crystallized thin films, existence of Cu_2−xSe phase and diffusion of Na from substrates to films.     

CuGaSe2 solar cells prepared by MOVPE

Metal organic vapor-phase epitaxy (MOVPE) is used to prepare epitaxial reference films and solar cells based on CuGaSe₂. Room temperature Hall measurements are performed on epitaxial CuGaSe₂. Conductivities up to 0.7 (Ω cm)⁻¹ were obtained. Highest mobilities of 270 cm²/Vs are observed for near stoichiometric slightly Ga-rich films. Net charge carrier concentration is higher in the Cu-rich grown films than in the Ga-rich films. Solar cells with epitaxial absorber are prepared that reach efficiencies of 3.3%. First polycrystalline solar cells are grown on Mo/glass at reduced substrate temperatures. Under AM1.5 illumination open-circuit voltages up to 740 mV and efficiencies of 2.0% are obtained.     

Effect of selenization pressure on CuInSe2 thin films selenized using co-sputtered Cu-In precursors

CuInSe₂ thin films were formed from the selenization of co-sputtered Cu–In alloy layers. These layers consisted of only two phases, CuIn₂ and Cu₁₁In₉, over broad Cu–In composition ratio. The concentration of Cu₁₁In₉ phase increased by varying the composition from In-rich to Cu-rich. The composition of co-sputtered Cu–In alloy layers was linearly dependent on the sputtering power of Cu and In targets. The metallic layers were selenized either at a low pressure of 10 mTorr or at 1 atm Ar. A small number of Cu–Se and In–Se compounds were observed during the early stage of selenization and single-phase CuInSe₂ was more easily formed in vacuum than at 1 atm Ar. Therefore, CuInSe₂ films selenized in vacuum showed smoother surface and denser microstructure than those selenized at 1 atm. The results showed that CuInSe₂ films selenized in vacuum had good properties suitable for a solar cell.     

Epi-n-IZO thin films/1 0 0 Si, GaAs and InP by L-MBE––a novel feasibility study for SIS type solar cells

High quality epitaxial indium zinc oxide (heavily indium oxide doped) (epi-n-IZO) thin films were optimized by laser-molecular beam epitaxy (L-MBE) i.e., pulsed laser deposition (PLD) technique for fabricating novel iso- and hetero-semiconductor–insulator–semiconductor (SIS) type solar cells using Johnson Matthey “specpure”- grade 90% In₂O₃ mixed 10% ZnO (as commercial indium tin oxide (ITO) composition) pellets. The effects of substrate temperatures, substrates and heavy indium oxide incorporation on IZO thin film growth, opto-electronic properties with 1 0 0 silicon (Si), gallium arsenide (GaAs) and indium phosphide (InP) wafers were studied. As well as the feasibility of developing some novel models of iso- and hetero-SIS type solar cells using epi-IZO thin films as transparent conducting oxides (TCOs) and 1 0 0 oriented Si, GaAs and InP wafers as base substrates was also studied simultaneously. The optimized films were highly oriented, uniform, single crystalline approachment, nano-crystalline, anti-reflective (AR) and epitaxially lattice matched with 1 0 0 Si, GaAs and InP wafers without any buffer layers. The optical transmission T (max) 95% is broader and absolute rivals that of other TCOs such as ITO. The highest conductivity observed is σ=0.47×10³ Ω⁻¹ cm⁻¹ (n-type), carrier density n=0.168×10²⁰ cm⁻³ and mobility μ=123 cm²/V s. From opto-electronic characterizations, the solar cell characteristics and feasibilities of fabricating respective epi-n-TCO/1 0 0 wafer SIS type solar cells were confirmed. Also, the essential parameters of these cells were calculated and tabulated. We hope that these data be helpful either as a scientific or technical basis in semiconductor processing.