Deposition of transparent and conductive Al-doped ZnO thin films for photovoltaic solar cells

The effect of the substrate temperature on the optoelectronic properties of ZnO-based thin films prepared by rf magnetron sputtering has been studied. Three different targets (Zn/Al 98/2 at%, ZnO:Al 98/2 at% and ZnO:Al₂O₃ 98/2 wt%) have been investigated in order to compare resulting samples and try to reduce the substrate temperature down to room temperature. From the ZnO:Al₂O₃ target, transparent conductive zinc oxide has been obtained at 25°C with the average optical transmission in the 400–800 nm wavelength range, T = 80–90% and resistivity, = 3−5 × 10⁻³ Ωcm. In Al:Zn0 layers, the spatial distribution of the electrical properties across the substrate placed parallel to the target has been improved by depositing at high substrate temperatures, above 200°C. Besides, owing to diffusion processes of CuInSe₂ and CdS take place at 200°C, an AI:ZnO/CdS/CuInSe₂ polycrystalline solar cell made with the Al:ZnO deposited at 25°C as the transparent conductive oxide, has shown a more efficient photovoltaic response, η = 6.8%, than the one measured when the aluminium-doped zinc oxide has been prepared at 200°C, η = 1.8%.     

Properties of RF sputtered zinc oxide based thin films made from different targets

The effect of deposition parameters on optoelectronic and properties of ZnO based thin films prepared by RF magnetron sputtering have been studied. Different targets (pure Zn, ZnO, Zn---Al (98/2 at 2%), ZnO---Al (98/2 at%), and ZnO---Al₂O₃ (98/2 wt%)) have been investigated to compare resulting samples and establish the best target composition. From reactive sputtering, using a Zn---Al target, transparent conductive zinc oxide has been obtained at 380°C with E_g = 3.25–3.35 eV and = 4.8 × 10⁻⁴ ω cm. Reduction of substrate temperature at 200°C has been possible by nonreactive sputtering from ZnO---Al and ZnO---Al₂O₃ targets. The values of the energy gap and resistivity under these conditions are 3.30–3.35 eV and 1 × 10⁻³ ω can respectively.     

ZnO:F thin films deposited by chemical spray: effect of the fluorine concentration in the starting solution

Conductive and transparent fluorine-doped zinc oxide, ZnO:F, thin films were deposited at 500°C on glass substrates by the chemical spray technique. Two sets of samples were deposited, based on a fresh and a two-day old starting solution prepared from zinc acetyl acetonate and ammonium fluoride dissolved in a mixture of water and alcohol. The electrical, structural, morphological and optical characteristics of the films as a function of the fluorine concentration in the starting solution were studied. Films with a resistivity as low as 2×10⁻² Ω cm, mobility up to 5 cm²/(V s), carrier concentration in the range 1.5–5.7×10²⁰ cm⁻³ and a transmittance in the range 75–90% were achieved with the old solution. Films were polycrystalline, growing preferentially along the (0 0 2) and (1 0 0) directions, depending on the fluorine concentration in the starting solution.     

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.     

Physical properties of ZnO:F obtained from a fresh and aged solution of zinc acetate and zinc acetylacetonate

Fluorine-doped zinc oxide thin films, ZnO:F, were deposited by the spray pyrolysis technique on sodocalcic glass substrates. Two different zinc precursors were used separately, namely, zinc acetate and zinc pentanedionate. The effect of the zinc precursor type, the aging of the starting solution, the substrate temperature and a vacuum-annealing treatment on the electrical, morphological, structural and optical properties was studied, in order to obtain conductive and transparent ZnO:F thin films. The resistivity values of ZnO:F thin films deposited from aged solutions were lower than those films obtained from fresh solutions. The lowest resistivity values of as-grown films deposited at 500 °C, using a two-day aged starting solution of zinc acetate and zinc pentanedionate, were 1.4×10⁻² and 1.8×10⁻² Ω cm, respectively. After a vacuum annealing treatment performed at 400 °C for 30 min a decrease in the resistivity was obtained, reaching a minimum value of 6.5×10⁻³ Ω cm for films deposited from an aged solution of zinc acetate. The films were polycrystalline, with a (0 0 2) preferential growth orientation in all the cases. Micrographs obtained by SEM show a uniform surface covers by rounded grains. No evident change in the surface morphology was observed with the different precursors used. The transmittance of films in the visible region was higher than 80%.     

Highly conducting transparent nanocrystalline Cd1−xSnxS thin film synthesized by RF magnetron sputtering and studies on its optical, electrical and field emission properties

Transparent conducting Cd_1−xSn_xS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates for various tin concentrations in the films. X-ray diffraction studies showed broadening of peaks due to smaller crystal size of the Cd_1−xSn_xS films, and SEM micrographs showed fine particles with average size of 100 nm. Sn concentration in the films was varied from 0% to 12.6% as determined from energy-dispersive X-ray analysis. The room-temperature electrical conductivity was found to vary from 8.086 to 939.7 S cm⁻¹ and corresponding activation energy varied from 0.226 to 0.076 eV. The optimum Sn concentration for obtaining maximum conductivity was found to be 9.3%. The corresponding electrical conductivity was found to be 939.7 S cm⁻¹, and the mobility 49.7 cm² V⁻¹ s⁻¹. Hall measurement showed very high carrier concentrations in the films lying in the range of 8.0218×10¹⁸–1.7225×10²⁰ cm⁻³. The conducting Cd_1−xSn_xS thin films also showed good field emission properties with a turn on field 4.74–7.86 V μm⁻¹ with variation of electrode distance 60–100 μm. UV–Vis–NIR spectrophotometric studies of the films showed not needed the optical band gap energy increased from 2.62 to 2.80 eV with increase of Sn concentration in the range 0–12.6%. The optical band gap was Burstein–Moss shifted, and the corresponding carrier concentration obtained from the shift also well matched with that obtained from Hall measurement.     

Photo atomic layer deposition of transparent conductive ZnO films

Low-resistivity ZnO films were grown by photo atomic layer deposition (photo-ALD) technique using diethylzinc (DEZ) and H₂O as reactant gases. Self-limiting growth was achieved for the temperature range from 105°C to 235°C. It was found that UV light irradiation was very effective to increase the electron concentration of the films and the electron concentration of 5 × 10²⁰ cm⁻³ was achieved even in undoped ZnO. Thus, the resistivity of the films grown with UV irradiation was one order of magnitude less than that grown without UV irradiation. The minimum resistivity of 6.9 × 10⁻⁴Ω cm was obtained by photo- ALD method without any intentional doping.     

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.     

Doping, vacuum annealing, and thickness effect on the physical properties of zinc oxide films deposited by spray pyrolysis

Gallium, aluminum, and indium-doped ZnO (ZnO:Ga, ZnO:Al, and ZnO:In) films have been deposited by the chemical spray method on sodocalcic substrates. The effect of different dopant elements, a post-annealing treatment in vacuum, and the film thickness on the electrical, optical, structural, and morphological properties of the films has been investigated. The best electrical properties were observed in the thickest indium-doped ZnO films; the lowest electrical resistivity was of the order of 10⁻³ Ω cm. In general, the optical transmittance value in the visible spectrum oscillated around of 87% in the thinnest films. The structural and morphological properties of ZnO:Ga and ZnO:Al films are similar, as in both cases the (0 0 2) orientation is dominant on the rest of the peaks, and both surfaces have a rough appearance. In the case of ZnO:In films, the (1 0 1) was the preferential growth orientation, and the surfaces seem to be smoother than the corresponding ZnO:Ga and ZnO:Al films.     

CdO/Cu2O solar cells by chemical deposition

CdO and Cu₂O thin films have been grown on glass substrates by chemical deposition method. Optical transmittances of the CdO and Cu₂O thin films have been measured as 60–70% and 3–8%, respectively in 400–900 nm range at room temperature. Bandgaps of the CdO and Cu₂O thin films were calculated as 2.3 and 2.1 eV respectively from the optical transmission curves. The X-ray diffraction spectra showed that films are polycrystalline. Their resistivity, as measured by Van der Pauw method yielded 10⁻²–10⁻³ Ω cm for CdO and approximately 10³ Ω cm for Cu₂O. CdO/Cu₂O solar cells were made by using CdO and Cu₂O thin films. Open circuit voltages and short circuit currents of these solar cells were measured by silver paste contacts and were found to be between 1–8 mV and 1–4 μA.     

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.     

Influence of gas ambient on the synthesis of co-doped ZnO:(Al,N) films for photoelectrochemical water splitting

Al and N co-doped ZnO thin films, ZnO:(Al,N), are synthesized by radio-frequency magnetron sputtering in mixed Ar and N₂ and mixed O₂ and N₂ gas ambient at 100 °C. The ZnO:(Al,N) films deposited in mixed Ar and N₂ gas ambient did not incorporate N, whereas ZnO:(Al,N) films grown in mixed O₂ and N₂ gas ambient showed enhanced N incorporation and crystallinity as compared to ZnO:N thin films grown in the same gas ambient. As a result, ZnO:(Al,N) films grown in mixed O₂ and N₂ gas ambient showed higher photocurrents than the ZnO:(Al,N) thin films deposited in mixed Ar and N₂ gas ambient. Our results indicate that the gas ambient plays an important role in N incorporation and crystallinity control in Al and N co-doped ZnO thin films.     

Degradation studies of transparent conducting oxide: a substrate for microcrystalline silicon thin film solar cells

Aluminium doped ZnO films have been developed by RF-magnetron sputtering at 350 °C substrate temperature on glass substrate and commercially available SnO₂-coated glass substrate. The developed ZnO and SnO₂/ZnO films can be used as the substrates of microcrystalline silicon based solar cell. The electrical, optical properties and surface morphologies of ZnO film and SnO₂/ZnO bi-layer films have been investigated and they are compared with the commercially available SnO_2-coated glass substrate. The resistivities of ZnO and SnO₂ films are comparable (10⁻⁴ Ω-cm). Surface morphologies of different transparent conducting oxide coated substrates before and after H-plasma exposure were studied by scanning electron microscopy. The optical transmission of ZnO, SnO₂/ZnO and SnO₂ films are comparable and varies from 85 to 90% in the visible region. The optical transmission reduces drastically to less than 20% in SnO₂ films and for ZnO film it remains almost unchanged after H-plasma exposure. For SnO₂/ZnO film transmission decreases slightly but remains considerably high (80%). The performance of microcrystalline silicon solar cells fabricated on different transparent conducting oxides as substrates (ZnO/glass, SnO₂/glass and ZnO/SnO₂/glass double layer) is investigated in detail.     

Highly efficient photon-to-electron conversion with mercurochrome-sensitized nanoporous oxide semiconductor solar cells

Dye-sensitized solar cells based on nanoporous oxide semiconductor thin films such as TiO₂, Nb₂O₅, ZnO, SnO₂, and In₂O₃ with mercurochrome as the sensitizer were investigated. Photovoltaic performance of the solar cell depended remarkably on the semiconductor materials. Mercurochrome can convert visible light in the range of 400–600 nm to electrons. A high incident photon-to-current efficiency (IPCE), 69%, was obtained at 510 nm for a mercurochrome-sensitized ZnO solar cell with an I⁻/I₃⁻ redox electrolyte. The solar energy conversion efficiency under AM1.5 (99 mW cm⁻²) reached 2.5% with a short-circuit photocurrent density (J_sc) of 7.44 mA cm⁻², a open-circuit photovoltage (V_oc) of 0.52 V, and a fill factor (ff) of 0.64. The J_sc for the cell increased with increasing thickness of semiconductor thin films due to increasing amount of dye, while the V_oc decreased due to increasing of loss of injected electrons due to recombination and the rate constant for reverse reaction. Dependence of photovoltaic performance of mercurochrome-sensitized solar cells on semiconductor particles, light intensity, and irradiation time were also investigated. High performance of mercurochrome-sensitized ZnO solar cells indicate that the combination of dye and semiconductor is very important for highly efficient dye-sensitized solar cells and mercurochrome is one of the best sensitizers for nanoporous ZnO photoelectrode. In addition, a possibility of organic dye-sensitized oxide semiconductor solar cells has been proposed as well as one using metal complexes.     

Performance of double junction a-Si solar cells by using ZnO:Al films with different electrical and optical properties at the n/metal interface

High-quality ZnO:Al films have been prepared by using RF-magnetron-sputtering method with resistivity ranging from 10⁻¹ to 10⁻⁴ Ω cm and transmittance above 90% in visible region. We have fabricated small area (1 cm²) double junction (a-Si/a-Si) solar cells using ZnO/Al and ZnO/Ag as back contact. The conversion efficiency of double junction a-Si solar cell increases from 9.9% to 10.9% by using ZnO/Al back contact and to 11.4% by using ZnO/Ag as back contact. Effect of variation of thickness of i-layer on performance of the cell has also been studied.     

Gallium-doped ZnO thin films deposited by chemical spray

Gallium-doped zinc oxide (ZnO:Ga) thin films were deposited on glass substrates by the spray pyrolysis technique. The effect of the variation of the [Ga]/[Zn] rate in the starting solution, the substrate temperature as well as the post-annealing treatments on the physical properties was examined. The electrical properties of the films show an improvement with the Ga incorporation and the annealing treatment. All the films were found to be polycrystalline and show a (0 0 2) preferential growth, irrespective of the deposition conditions. The films were of n-type conductivity with an electrical resistivity in the order of 8×10⁻³ Ω cm and optical transmittance higher than 80% in the visible region. These results makes chemically sprayed ZnO:Ga potentially applicable as transparent electrode in photovoltaic devices.     

In situ hydrogen plasma treatment for improved transport of (4 0 0) oriented polycrystalline silicon films

Polycrystalline silicon (poly-Si) films were deposited on glass by very high-frequency (100 MHz) plasma enhanced chemical vapor deposition from a gaseous mixture of SiF₄ and H₂ with small amounts of SiH₄. (2 2 0) oriented films prepared at small SiF₄/H₂ ratios (<30/40 sccm) showed intrinsic transport properties of poly-Si. However, the room temperature dark conductivity (σ_d) of the (4 0 0) oriented film was very high for intrinsic poly-Si, 7.2×10⁻⁴S/cm. This conductivity exhibited a T^−1/4 behavior, suggesting a high defect density at the grain boundaries. It was found that in situ hydrogen plasma treatment successfully produced (4 0 0) oriented poly-Si with a reasonably low σ_d of 4.5×10⁻⁷S/cm and a good photoconductivity of 1.3×10⁻⁴S/cm.     

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.     

Optical and electrical properties of semiconducting WS2 thin films: From macroscopic to local probe measurements

Photosensitive WS₂ thin films are obtained by annealing in presence of a crystallization promoter like Ni or Co. Conventional optical and electrical measurements (conductivity, Hall effect, photoconductivity) are completed by various local probe investigations like scanning tunneling microscopy (STM) and conductive atomic force microscopy (AFM). This thorough study clarifies the respective role of the crystallites and the grain boundaries in the macroscopic measurements and gives information on the properties and on the photovoltaic prospect of the films. The optical properties of the thin films are comparable to those of WS₂ single crystals, with absorption excitonic peaks of same intensity at 1.94 and 2.36 eV. The films show a p-type behavior with a carrier concentration of p10²³ m⁻³ and a Hall mobility of μ_H10×10⁻⁴ m² V⁻¹ s⁻¹ at room temperature. The Hall mobility is thermally activated with an activation energy of 60–90 meV. The photoconductivity spectra show the first indirect transition at 1.35 eV and a decrease of the quantum efficiency at the excitonic-transitions energies. The transport in the film plane is mainly governed by the potential barriers at the grain boundaries. Using a conducting AFM, the crystallite edges are shown to be degenerate semiconductors, while STM current–voltage (I–V) spectroscopy indicates that the flat WS₂ crystallites have a low density of surface states on the basal planes. Submicron solid-state junctions are fabricated on the film by depositing gold electrodes on single WS₂ crystallites (with an electrode surface of 0.2 μm²). Under illumination the p-WS₂/Au micro-junctions show open circuit-voltages of up to 520 mV. The collection of photo-generated carriers is limited by recombination at the grain boundaries.     

Electrical conduction studies of hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on cleaned glass substrates using the hot wall deposition technique under conditions very close to thermodynamical equilibrium with minimum loss of material. The electrical conductivity of the deposited films has been studied as a function of temperature. All the films showed a transition from phonon-assisted hopping conduction through the impurity band to grain-boundary-limited conduction in the conduction/valence band at temperature around 325 K. The conductivity has been found to vary with composition; it varied from 0.0027 to 0.0198 Ω⁻¹ cm⁻¹ when x changed from 0 to 1. The activation energies of the films of different compositions determined at 225 and 400 K have been observed to lie in the range 0.0031–0.0098 and 0.0285–0.0750 eV, respectively. The Hall-effect studies carried out on the deposited films revealed that the nature of conductivity (p or n-type) was dependent on film composition; films with composition x=0 and 0.15 have been found to be p-type and the ones with composition x=0.4, 0.6, 0.7, 0.85 and 1 have been observed to exhibit n-type conductivity. The carrier concentration has been determined and is of the order of 10¹⁷ cm⁻³. The majority of carrier mobilities of the films have been observed to vary from 0.032 to 0.183 cm² V⁻¹ s⁻¹ depending on film composition. The study of the mobility of the charge carriers with temperature in the range of 300–450 K showed that the mobility increased with power of temperature indicating that the type of scattering mechanism in the studied temperature range is the ionized impurity scattering mechanism.