Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Effects of Ga concentration on structural and electrical properties of screen printed-CIGS absorber layers on polyethylene terephthalate

Copper indium gallium diselenide (CIGS) films were deposited as an absorber layer on polyethylene terephthalate (PET) substrates by a screen printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. The melting point of PET substrate is 254.9 °C; the average transmission in the visible (400 nm–800 nm) for PET substrates is greater than 85%. Effects of Ga content of the CIGS absorber layer on structural and electrical properties of the CIGS films were studied. The lattice parameters, a and c for all CIGS films were decreased with increasing Ga content. At room temperature, Hall mobility and charge-carrier concentration of the CIGS films varies from 97.2 to 2.69 cm² V⁻¹ s⁻¹ and 9.98×10¹⁶ to 3.23×10¹⁸ cm⁻³, respectively.     

Polymer films with multilayer low-E coatings

The paper presents the experimental results on depositing a multilayer low-emissivity (low-E) coating with oxide–metal–oxide structure on polyethylene terephthalate (PET) and polyethylene (PE) films by magnetron sputtering. The TiO₂/ZnO:Ga/Ag/ZnO:Ga/TiO₂ coating on the PET film with high water-resistance and capability to be used outside of sealed double-glazed panes was proposed. The optimal thickness of coating layers was experimentally determined. The coating with the optimal structure has 82% transmittance over the visible spectrum and 91% reflection over the infrared spectrum. The window with a PET film and low-E coating was investigated in terms of heat engineering. It was revealed that heat transfer resistance increased up to 0.73 m² °C W⁻¹ for the windows with a PET film and low-E coating. Heat transfer resistance of the windows without a polymer film was 0.38 m² °C W⁻¹. The water-resistant ZnO:Ga/Ag/ZnO:Ga/SiO₂ coating on a PE film with 77% transmittance and 91–92% reflection in the IR range was proposed to be used as greenhouse covering material. The possibility of using the PE film with a low-E coating to reduce heat loss in greenhouses and enhance yielding capacity was demonstrated.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

Synthesis and characterization of nanostructured magnetoresistive Ni doped ZnO films

We report a method to produce magnetic nanostructured semiconductor films based in ZnO doped with Nickel to control their magnetic properties. The method is based on a combined diffusion–oxidation process within a controlled atmosphere chamber to produce a uniform distribution of Ni ions in the ZnO films (ZnO:Ni). The synthesis of ZnO:Ni films is reported as well as the magnetoresistive characteristics, the used method yields films with reproducible and homogeneous properties. The films were also characterized structurally by X-Ray Diffraction (XRD) and Raman spectroscopy, and by Hall–van der Pauw measurements. The XRD measurements confirm the nanocrystalline films character. The films resulted of n-type conductivity with electron concentrations of ~10²⁰ cm⁻³ in average and carrier mobilities of 5 cm²/V s. The Magnetoresistance (MR) behavior of the films at 300 K shows negative changes of ΔR~0.5% in accordance with the usual literature reports on samples produced by other methods.     

Fabrication of Ag nanoparticle/ZnO thin films using dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with photoreduction method and its application

We report a novel method to grow silver nanoparticle/zinc oxide (Ag NP/ZnO) thin films using a dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with a photoreduction method. The crystalline quality, optical properties, and electrical characteristics of Ag NP/ZnO thin films depend on the AgNO₃ concentration or Ag content and annealing temperature. Optimal Ag NP/ZnO thin films have been grown with a AgNO₃ concentration of 0.12 M or 2.54 at%- Ag content and 500 °C- rapid thermal annealing (RTA); these films show orientation peaks of hexagonal-wurtzite-structured ZnO (002) and face-center-cubic-crystalline Ag (111), respectively. The transmittance and resistivity for optimal Ag NP/ZnO thin films are 85% and 6.9×10⁻⁴ Ω cm. Some Ag NP/ZnO transparent conducting oxide (TCO) films were applied to InGaN/GaN LEDs as transparent conductive layers. The InGaN/GaN LEDs with optimal Ag NP/ZnO TCO films showed electric and optical performance levels similar to those of devices fabricated with indium tin oxide.     

N-doped ZnO based fast response ultraviolet photoconductive detector

We report a study on the fabrication and characterization of ultraviolet photodetectors based on N-doped ZnO films. Highly oriented N-doped ZnO films with 10 at.% N doping are deposited using spray pyrolysis technique onto glass substrates. The photoconductive UV detector based on N-doped ZnO thin films, having a metal–semiconductor–metal (MSM) configuration are fabricated by using Al as a contact metal. I–V characteristic under dark and UV illumination, spectral and transient response of ZnO and N-doped ZnO photodetector are studied. The photocurrent increases linearly with incident power density by more than two orders of magnitude. The photoresponsivity (580 A/W at 365 nm with 5 V bias, light power density 2 μW/cm²) is much higher in the ultraviolet region than in the visible.     

Influence of working pressure on the structural,optical and electrical properties of sputter deposited AZO thin films

Highly oriented crystalline aluminum doped zinc oxide (AZO) films were sputter deposited on glass substrates and a systematic investigation on the as deposited and etched films was reported for its further application in silicon thin film solar cell. Influence of the deposition pressure (from 2 to 8 mTorr) and post-annealing temperature (at 400 °C for 5 min) on the structural, optical and electrical properties of the as-deposited and etched samples were analyzed. The optimum condition for its reproducibility and large area deposition is determined and found that the depositions made at 8 mTorr at 200 W having the distance from source to substrate of 9 cm. All the AZO films exhibited a c-axis preferred orientation perpendicular to the substrate and their crystallinity was improved after annealing. From the XRD pattern the grain size, stress and strain of the films were evaluated and there is no drastic variation. Optical transmittance, resistivity, Hall mobility and carrier concentration for the as deposited and etched-annealed films were found to improve from 79 to 82%; 2.97 to 3.14×10⁻⁴ Ω cm; 25 to 38 cm²/V s; 8.39 to 5.96×10²⁰/cm³ respectively. Based on the triangle diagram between figure of merit and Hall mobility, we obtained a balance of point between the electrical and optical properties to select the deposition condition of film for device application.     

Atmospheric plasma deposition of transparent semiconducting ZnO films on plastics in ambient air

Transparent zinc oxide (ZnO) thin films have been successfully synthesized on poly (methyl methacrylate) (PMMA), polycarbonate (PC), and polyethylene terephthalate (PET) substrates by atmospheric plasma deposition in ambient air at room temperature. The structural, optical and electrical properties of the ZnO films as well as their adhesion to the polymer substrates were investigated for various deposition conditions. The film surface exhibited a dome-shaped topography comprised of nanometer-sized grains. The size of both the domes and the grains became larger as the plasma power increased. The visible transmittance increased above 95% with decreasing plasma power. The resistivity exhibited a wide variation in the range of 10²–10⁸ ohm cm. The adhesion energies to PMMA varied from 0.2 to 1.5 J/m² with increasing plasma power. While a finer grain structure achieved with lower plasma power was preferable for higher transmittance, it resulted in lower adhesion to the plastic substrates. The study demonstrated the feasibility of depositing semiconducting transparent ZnO films on polymer substrates at low temperature in ambient air using atmospheric plasma deposition.     

Effects of the substrate temperature and solution molarity on the structural opto-electric properties of ZnO thin films deposited by spray pyrolysis

Zinc oxide (ZnO) was largely studied in various applications such as photovoltaic conversion, optoelectronics and piezoelectric, because of its interesting physical properties (morphological, structural, optical and electrical). The present work deals with the preparation of zinc oxide thin films (ZnO) deposited by the spray pyrolysis method. The starting solution was zinc chloride (ZnCl₂). Effects of solution molarity and substrate temperature on films properties were investigated. All films deposited were characterized by various techniques such as X-ray diffraction for structural characterizations, profilometry for thickness measurements, UV–vis transmission spectrophotometry for optical properties and the four probes conductivity measurements for electrical characterization. The X-ray diffraction (XRD) patterns show that the films deposited are polycrystalline with (0 0 2) plan as preferential orientation. The UV–vis spectroscopy confirms the possibility of good transparent ZnO thin films deposition with an average transmission of about ∼85% in the visible region. However, the measured electrical resistivities of the deposited films were in the order of 10⁴ Ω cm     

Carrier gas and VI/II ratio effects on carbon clusters incorporation into ZnO films grown by MOCVD

Undoped ZnO films were deposited by atmospheric metal-organic chemical vapor deposition (MOCVD) on (0001) ZnO substrate. The films were grown at various partial pressure ratios of oxygen and zinc precursors (VI/II) using either N₂ or H₂ as carrier gas. Micro-Raman scattering was employed to study the effects of carrier gas, VI/II ratio and annealing on carbon impurity incorporation into the ZnO films. Besides the well known phonon modes of ZnO, Raman spectra of the samples grown with N₂ carrier gas show two additional broad peaks, which are ascribed to carbon sp² clusters related modes, spreading in the frequency range 1300–1600 cm^?1 and dominate the Raman spectrum of the sample grown under oxygen deficiency (VI/II=0.25). In addition, a band centered at ～520 cm^?1, considered as some defects related local vibrations, appears in the samples grown with N₂ as carrier gas and its intensity increases when the VI/II ratio decreases. The average cluster size, estimated from the intensity ratio of D over G bands of the carbon sp² clusters, ranges from 16.5 to 19.4 Å. However, in all the samples grown with H₂ as carrier gas, the bands related to carbon sp² clusters and defects, are largely suppressed and the second-order-Raman scattering band (1050–1200 cm^?1) is clearly observed in addition to the bulk ZnO lattice modes. After annealing the samples at 900 °C in oxygen ambient, the crystal quality has been improved for all the samples but the carbon related bands, formed in the as-deposited films grown with the N₂ carrier gas, were only weakened.     

The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Magnetron-sputtered high performance Y-doped ZnO thin film transistors fabricated at room temperature

In this report, sputtered-grown undoped ZnO and Y-doped ZnO (ZnO:Y) thin film transistors (TFTs) are presented. Both undoped ZnO and ZnO:Y thin films exhibited highly preferred c-axis oriented (002) diffraction peaks. The ZnO:Y thin film crystallinity was improved with an increase of (002) peak intensity and grain size. The electrical properties of ZnO:Y TFTs were significantly enhanced relative to undoped ZnO TFTs. ZnO:Y TFTs exhibited excellent performance with high mobility of 38.79 cm² V⁻¹ s⁻¹, small subthreshold swing of 0.15 V/decade, and high I_on/I_off current ratio of the order of 8.17 × 10⁷. The O_1s X-ray photoelectron spectra (XPS) showed oxygen vacancy-related defects present in the ZnO:Y TFTs, which contributed to enhancing the mobility of the TFTs.     

Properties of high sensitivity ZnO surface acoustic wave sensors on SiO2/(1 0 0) Si substrates

The properties of ZnO/SiO₂/Si surface acoustic wave (SAW) Love mode sensors were examined and optimized to achieve high mass sensitivity. SAW devices A and B, were designed and fabricated to operate at resonant frequencies around 0.7 and 1.5 GHz. The ZnO films grown by pulsed laser deposition on SiO₂/Si demonstrated c-axis growth and the fabricated devices showed guided shear horizontal surface acoustic wave (or Love mode) propagation. Acoustic phase velocity in the ZnO layer was measured in both devices A and B and theoretical and experimental evaluation of the mass sensitivity showed that the maximum sensitivity is obtained for devices with ZnO guiding layer thicknesses of 340 nm and 160 nm for devices A and B, respectively. The performance of the SAW sensors was validated by measuring the mass of a well-characterized polystyrene–polyacrylic acid diblock copolymer film. For the optimized sensors, maximum mass sensitivity values were as high as 4.309 μm²/pg for device A operating at 0.7477 GHz, and 8.643 μm²/pg for device B operating at 1.5860 GHz. The sensors demonstrated large frequency shifts per applied mass (0.1–4 MHz), excellent linearity, and extended range in the femto-gram region. The large frequency shifts indicated that these sensors have the potential to measure mass two to three orders of magnitude lower in the atto-gram range.     

Properties of cobalt-doped zinc oxide thin films grown by pulsed laser deposition on glass substrates

Undoped and cobalt-doped zinc oxide (CZO) polycrystalline piezoelectric thin films (Co: 3, 5 at.%) using a series of high quality ceramic targets have been deposited at 450 °C onto glass substrates using a pulsed laser deposition method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J∕cm²). X-ray diffraction patterns showed that the Co-doped ZnO films crystallize in a hexagonal wurtzite type structure with a strong (0 orientation, and the grain sizes calculated from these patterns decrease from 37 to 31 nm by increasing Co doping. The optical waveguiding properties of the films were characterized by using a prism-coupling method. The distinct M-lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the ZnO films waveguide have been observed. With the aim of study the optical properties of the ZnO films, an accurate refractive index and thickness measurement apparatus was set up, which is called M-lines device. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The optical transmittance spectra showed a good transparency in the visible region. Calculated optical band gap varying from 3.23 to 3.37 eV when the content of Co doping increases from 0 to 5 at.%.     

The effect of deposition conditions on structure properties of radio frequency reactive sputtered polycrystalline ZnO films

Polycrystalline ZnO films were prepared by radio frequency reactive sputtering technique with Zn target on glass wafers under different pressure ratio K (defined as P_O2/(P_Ar+P_O2)) and substrate temperature T_s. X-ray diffraction technique (XRD) was employed to analyze the effect of deposition conditions on the structure of the films. With increase in T_s from room temperature to 400°C, the films appear to have a preferred orientation with the c-axis perpendicular to the substrate. Pressure ratio K has an effect on orientation of the films, which have highly preferred orientation when K=40%. The grain size is in the range 13.2–42.8 nm calculated from XRD data. The packing density, the compressive stress in (0 0 2) plane and the average optical transmittance in visible region of the films deposited under the optimal condition are 97%, −1.06×10⁹ N/m² and 92%, respectively. It is found also that carbon is the main contamination in films observed by X-ray photoelectron spectroscopy. The films are close to stoichiometric relation.     

Low temperature Solution-Processed ZnO film on flexible substrate

Transparent conductive ZnO films were directly deposited on unseeded polyethersulfone (PES) substrates with a spin-spray method using aqueous solution at a low substrate temperature of 85 °C. All ZnO films were crystalline with wurtzite hexagonal structure and impurity phases were not detected. ZnO films deposited without citrate ions in the reaction solution had a rod array structure. In contrast, ZnO films deposited with citrate ions in the reaction solution had a continuous, dense structure. The transmittance of the ZnO films was improved from 11.9% to 85.3% as their structure changed from rod-like to continuous. After UV irradiation, the ZnO films with a continuous, dense structure had a low resistivity of 9.1×10⁻³ Ω cm, high carrier concentration of 2.7×10²⁰ cm⁻³ and mobility of 2.5 cm² V⁻¹ s⁻¹.     

Enhancing charge transport in copper phthalocyanine thin film by elevating pressure of deposition chamber

Copper phthalocyanine (CuPc)-based thin film transistors were fabricated using CuPc films grown under different deposition pressure (P_dep) (ranging from 1.8 × 10⁻⁴ Pa to 1.0 × 10⁻¹ Pa). The transistor performance highly depended on P_dep. A field-effect mobility of 2.1 × 10⁻² cm²/(V s) was achieved under 1.0 × 10⁻¹ Pa. Detailed investigations revealed that P_dep modulates the molecular packing and orientation of the organic films grown on a SiO₂/Si substrate and influences the charge transport. Furthermore, from a device physics point of view, contact resistance of the fabricated transistors decreased when P_dep increased, which was beneficial in reducing energy consumption.     

Post-annealing modification in structural properties of ZnO thin films on p-type Si substrate deposited by evaporation

Zinc oxide (ZnO) films of thickness ∼380 nm were deposited on p-type Si (1 1 1) substrate maintained at 300 °C under 3×10⁻⁶ Torr by a radio frequency (RF) heating source. Transmission Fourier transform infrared (FTIR) spectrum exhibited a clear Zn–O bond excitation frequency of ∼408 cm⁻¹. X-ray diffraction spectrum demonstrated four peaks (P₁–P₄) at 2θ (deg) ∼36±0.06, 40±0.09, 82±0.17 and 86±0.2, which originated from (1 0 0), (0 0 2), (2 0 1) and (0 0 4) hexagonal planes, respectively. P₂ being the highest intensity peak indicated that the growth of ZnO predominantly occurred along the c-axis i.e. (0 0 2) plane. Micrographs of the samples obtained from scanning electron microscopy (SEM) and atomic force microscopy (AFM) identically displayed scattered nanocrystallites, which grew bigger with the increase of sample annealing temperature (°C) in the range of 400–1000. AFM pictures, in particular, exposed the hexagonal structure of the deposited films along with voids. However, ZnO composition ∼6:1 (Zn:O) as calculated from the energy dispersive spectrum (EDS) revealed that the formation of ZnO was not stoichiometric, rather of Zincsuboxide structure ZnO_x (x<1). Arrhenius plot of the resistivity data yielded a donor level (zinc interstitial and/or Zn–on–O site) with ionization energy E_c–1.26 eV, thereby it supports our measured results, in general.     

Improvement in crystal quality of ZnO film on Si substrate by using a homo-buffer layer

ZnO thin films without and with a homo-buffer layer have been prepared on Si(1 1 1) substrates by pulsed laser deposition (PLD) under various conditions. Photoluminescence (PL) measurement indicates that the optical quality of ZnO thin film is dramatically improved by introducing oxygen into the growth chamber. The sample deposited at 60 Pa possesses the best optical properties among the oxygen pressure range studied. X-ray diffraction (XRD) results show that the films directly deposited on Si are of polycrystalline ZnO structures. A low-temperature (500 °C) deposited ZnO buffer layer was used to enhance the crystal quality of the ZnO film. Compared to the film without the buffer layer, the film with the buffer layer exhibits aligned spotty reflection high-energy electron diffraction (RHEED) pattern and stronger near-band-edge emission (NBE) with a smaller full-width at half-maximum (FWHM) of 98 meV. The structural properties of ZnO buffer layers grown at different temperatures were investigated by RHEED patterns. It is suggested that the present characteristics of the ZnO epilayer may be raised further by elevating the growth temperature of buffer layer to 600 °C.