Influence of Mn dopant concentration on film thickness,structural, morphological,compositional and optical properties of zinc oxide thin films

Thin films of zinc oxide (ZnO) and manganese doped zinc oxide (ZnO:Mn) have been prepared on glass substrates by the method of successive ionic layer adsorption reaction (SILAR) technique. X-ray diffraction pattern revealed that the prepared films found to exhibit hexagonal structure with preferential orientation along (101) plane. Scanning electron microscopic analysis showed the appearance of needle shaped flower like grains for ZnO and ZnO:Mn. The value of band gap is found to be in the range between 3.01 and 3.26 eV. Photoluminescence spectroscopic analysis showed that increase in value of peak intensity is observed for ZnO:Mn than ZnO.     

Influence of annealing on ZnO films grown by metal–organic chemical vapor deposition

Zinc oxide (ZnO) films were deposited on silica glass substrates using metal–organic chemical vapor deposition (MOCVD) with diethyl zinc (DEZn) as the Zn precursor and ethanol as the oxygen source. Annealing was performed at 600°C for 1 h in air. The X-ray diffraction (XRD) patterns of the samples show sharp diffraction peaks for ZnO (0002), which indicates that the films are highly c-axis oriented. The films were also characterized by measuring the optical transmission spectrum, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The XPS spectra showed that the ZnO films changed from O-rich to Zn-rich after being annealed.     

A selective ethanol gas sensor based on spray-derived Ag–ZnO thin films

A simple and cost-effective spray pyrolysis technique was employed to synthesize silver-doped zinc oxide (Ag–ZnO) thin films on the glass substrates from aqueous solutions of zinc acetate and silver nitrate precursors at 450 °C. The effects of Ag doping on structural, morphological, and gas-sensing properties of films were examined. The X-ray diffraction spectra of the Ag–ZnO films showed the polycrystalline nature having hexagonal crystal structure. Scanning electron microscopy (SEM) images of the pure ZnO films revealed the uniform distribution of the spherical grains (~80 nm size). Tiny Ag nanoparticles are clearly visualized in the SEM of Ag–ZnO films. The investigation of the effect of Ag doping on the gas-sensing properties of the Ag–ZnO revealed that the 15 % Ag-doped ZnO sample has the highest gas sensitivity (85 %) and excessive Ag doping in ZnO degraded the gas sensitivity. A possible mechanism of Ag–ZnO-based sensor sensitivity to the target gas is also proposed.     

Effect of Al concentrations on the electrodeposition and properties of transparent Al-doped ZnO thin films

Al-doped zinc oxide (AZO) thin films are prepared on polycrystalline fluorine-doped tin oxide-coated conducting glass substrates from nitrates baths by the electrodeposition process at 70 °C. The electrochemical, morphological, structural and optical properties of the AZO thin films were investigated in terms of different Al concentration in the starting solution. It was found that the carrier density of AZO thin films varied between ?3.11 and ?5.56 × 10²⁰ cm^?3 when the Al concentration was between 0 and 5 at.%. Atomic force microscopy images reveal that the concentration of Al has a very significant influence on the surface morphology and roughness of thin AZO. X-ray diffraction spectra demonstrate preferential (002) crystallographic orientation having c-axis perpendicular to the surface of the substrate and average crystallites size of the films was about 33–54 nm. With increasing Al doping, AZO films have a strong improved crystalline quality. As compared to pure ZnO, Al-doped ZnO exhibited lower crystallinity and there is a shift in the (002) diffraction peak to higher angles. Due to the doping of Al of any concentration, the films were found to be showing >80 % transparency. As Al concentration increased the optical band gap was also found to be increase from 3.22 to 3.47 eV. The room-temperature photoluminescence spectra indicated that the introduction of Al can improve the intensity of ultraviolet (UV) emission, thus suggesting its greater prospects in UV optoelectronic devices. A detailed comparison and apprehension of electrochemical, optical and structural properties of ZnO and ZnO:Al thin films is done for the determination of optimum concentration of Al doping.     

Fabrications of SnS thin films and SnS-based heterojunctions on flexible polyimide substrates

The flexible polyimide substrates were utilized to realize the flexibility of SnS thin films and SnS-based heterojunctions. The SnS thin films and ZnO/SnS heterojunctions were deposited on polyimide substrates by magnetron sputtering. The properties of SnS thin films and ZnO/SnS heterojunctions were studied. The experimental results show that the post annealing can enhance the degree of crystallinity of flexible SnS thin films. The annealed SnS thin films present polycrystalline structure with preferential orientation along the (040) plane and grain size of 18 nm. The compositions of as-deposited and annealed flexible SnS thin films are close to the stoichiometry of SnS. The direct band gaps are 1.48 and 1.32 eV for the as-deposited and annealed SnS thin films, respectively. The fabricated flexible ZnO/SnS heterojunctions show rectifying properties with the rectifying ratio of 6.85 and the diode ideal factor of 1.23. The experimental results indicate the feasibility of using polyimide as the substrates of SnS thin films and SnS-based heterojunctions.     

Enhanced acetone detection using Au doped ZnO thin film sensor

Zinc oxide (ZnO) thin films are prepared using sol–gel method for acetone vapor sensing. Zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) was taken as starting material and a stable and homogeneous solution was prepared in ethanol by deliquescing the zinc acetate and distinct amount of monoethanolamine as a stabilizing agent. The prepared solution was then coated on silicon substrates by spin coating method and then annealed at 650 °C for preparing ZnO thin films. The thickness of the film was maintained at 410 nm. The structural, morphological and optical studies were done for the synthesized ZnO thin films. The operating temperature and sensor response is considered to be an important parameter for the gas sensing behavior of any material. Therefore, the present study examined the effect of sensing behavior of 3% v/v gold (Au) doped ZnO thin films as a sensor. The response characteristics of 410 nm ZnO thin film for temperature ranging from 180 to 360 °C were determined for the acetone vapors. The reported study provides a significant development towards acetone sensors, where a very high sensitivity with rapid response and recovery times are reported with lowered optimal operating temperature as compared to bare ZnO nano-chains like structured thin films. In comparison to the bare ZnO thin films giving a response of 63 at an operating temperature of 320 °C, a much better response of 132.3 was observed for the Au doped ZnO thin films at an optimised operating temperature of 280 °C for a concentration of 500 ppm of acetone vapors.     

连续离子层吸附与反应法(SILAR)生长ZnO多晶薄膜的研究

采用连续离子层吸附与反应法(SILAR),以锌氨络离子([Zn(NH₃)₄]²⁺)为前驱体溶液,在玻璃衬底上沉积了ZnO薄膜,以XRD和SEM等手段分析了薄膜的晶体结构和表面、断面形貌,考察了空气气氛下的退火过程对ZnO薄膜晶体结构与微观形貌的影响,并初步探讨了以SILAR方法沉积ZnO薄膜的机理.结果表明,经200次SILAR沉积循环,所得ZnO薄膜为红锌矿结构的多晶薄膜,沿<002>方向择优生长;薄膜表面致密、光滑均匀,厚度约800nm.退火处理使ZnO薄膜氧缺位减少,晶粒沿c轴取向增强;随退火温度升高,锌间隙原子增加;500℃退火时,ZnO薄膜发生再结晶.减小前驱体溶液的[NH₃·H₂O]/[Zn²⁺]比率可提高ZnO薄膜生长速率.     

Effect of complexing agents: investigations on structural,morphological, topographical and optical analysis of copper iron sulphide thin films deposited by chemical bath deposition method

Copper iron sulphide (FeCuS₂) thin films deposited by chemical bath deposition method using ferrous sulphate and copper sulphate as cationic sources and sodium sulphide as anionic source with complexing agents, EDTA and Leishman stain were reported. The structural, optical and morphological studies were carried out using X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV–Visible spectroscopy techniques. The X-ray spectrum reveals that the films are polycrystalline nature and also showed the deposition of cubic phases at room temperature. The SEM images for prepared films have clear morphology influenced by the complexing agents used in deposition process. The result of AFM studies shown that the particles in the film have grain size around ~?60–70 nm and also have almost similar thickness. Based on the optical absorbance spectra the FeCuS₂ film exhibited a high absorbance in the visible region. The absorption edge shifted toward lower wavelength with varying complexing agents. The band gap value obtained was found to be 3.57–3.85 eV. From these results, it is indicated that the prepared films are suitable candidate for solar cell applications.     

Annealing effects on the structural and optical properties of growth ZnO thin films fabricated by pulsed laser deposition (PLD)

Annealed ZnO thin film at 300, 350, 400, 450 and 500 °C in air were deposited on glass substrate by using pulsed laser deposition. The effects of annealing temperature on the structural and optical properties of annealed ZnO thin films by grazing incident X-ray diffraction (GIXRD), transmittance spectra, and photoluminescence (PL) were investigated. The GIXRD reveal the presence of hexagonal wurtzite structure of ZnO with preferred orientation (002). The particle size is calculated using Debye–Scherrer equation and the average grain size were found to be in the range 5.22–10.61 ± 0.01 nm. The transmittance spectra demonstrate highly transparent nature of the films in visible region (>70 %). The calculation of optical band gap energy is found to be in the range 2.95–3.32 ± 0.01 eV. The PL spectra shows that the amorphous film gives a UV emission only and the annealed films produce UV, violet, blue and green emissions this indicates that the point defects increased as the amorphous film was annealed.     

Synthesis and characterization of zinc stannate thin films prepared by spray pyrolysis technique

The zinc stannate thin films were synthesized by simple and inexpensive spray pyrolysis technique on the glass and fluorine doped tin oxide coated conducting glass substrates. The as deposited films were further annealed at 500 °C temperature for 12 h. The structural optical and morphological characterization of as prepared and annealed films was carried out by XRD, UV–Vis spectroscopy, SEM and AFM techniques respectively. The structural analysis shows that films are polycrystalline and crystallized in cubic inverse spinel crystal structure. SEM studies show that grain size increases after annealing and exhibits spherical morphology. AFM study shows that roughness is higher for the post annealed film. Further the samples were tested for testing their applicability for dye sensitized solar cells. The as prepared, annealed and CNT doped samples exhibits photoconversion efficiencies 2.7, 2.8 and 3.1 % respectively.     

Influence of incorporation of Al3+ ions on the structural, optical and AC impedance characteristics of spin coated ZnO thin films

Aluminium doped zinc oxide thin films were deposited onto glass substrate using spin coating technique. The effects of Al doping on structural, optical and electrical properties of these films were investigated. X-ray diffraction analysis showed that all the thin films were of polycrystalline hexagonal wurtzite structure with (002) as preferential orientation except 2 at.% of Al doped ZnO films. The optical band gap was found to be 3.25 eV for pure ZnO film. It increases up to 1.5 at.% of Al doping (3.47 eV) and then decreased slightly for the doping level of 2 at.% (3.42 eV). The reason for this widening of the optical band gap up to 1.5 at.% is well described by Burstein–Moss effect. The photoluminescence spectra of the films showed that the blue shift and red shift of violet emission were due to the change in the radiative centre between zinc vacancy and zinc interstitial. Variation in ZnO grain boundary resistance against the doping concentration was observed through AC impedance study.     

Influence of annealing temperature on structural,electrical and optical properties of undoped zinc oxide thin films

The undoped zinc oxide thin films were grown on quartz substrate at a substrate temperature of 750 °C by radio frequency magnetron sputtering and post annealed at different temperatures (600–800 °C) for a period of 30 min. The influence of annealing temperature on the structure, electrical and optical properties of undoped ZnO thin films was investigated by X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the thin films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type when the temperature increased from 600 to 800 °C. Electrical and photoluminescence results indicate that native defects, such as oxygen and zinc vacancies, could play an important role in determining the conductivity of these nominally undoped ZnO thin films. The conversion of the conduction type was attributed to the competition between Zn vacancy acceptor and oxygen vacancy and interstitial Zn donors. At an intermediate annealing temperature of 750 °C, the film behaves the best p-type characteristic, which has the lowest resistivity of 12 Ωcm, hall mobility of 2.0 cm²/V s and carrier concentration of 1.5 × 10¹⁷ cm^?3. The photoluminescence results indicated that the Zn vacancy might be responsible for the intrinsic better p-type characteristic in ZnO thin films.     

Post annealing effect on structural and optical properties of ZnO thin films derived by sol–gel route

Zinc oxide thin films have been spun coated on p-Si (100) substrates by sol–gel route. These films were annealed at different annealing temperatures from 300 to 1,000 °C in the oxygen ambient. In this way a suitable annealing temperature window for the sol–gel derived ZnO films exhibiting minimum defects (points and dislocations) and better quality (crystal and optical) was investigated. The structural and optical features of ZnO thin films have been examined by X-ray diffraction, atomic force microscopy, UV–Vis spectroscopy, and photoluminescence spectra. The results revealed that the crystallization in the films initiated at 300 °C, improved further with annealing. All the deposited films exhibited wurtzite phase with c-axis orientations. The variations in the position of characteristic (002) peak, stress, strain and lattice parameters are investigated as a function of annealing temperature. The optical band gap is not significantly affected with annealing as observed by UV–Vis transmission spectroscopy. The Photoluminescence spectra exhibited three luminescence centers. The near band edge esmission was observed in UV region which enhanced with the heat treatment, is an indication of improvement in the optical quality of films. The other two visible emissions are related to native defects in ZnO lattice were appeared only for higher annealing (≥700 °C).     

Effect of post annealing on structural and optical properties of ZnO thin films deposited by vacuum coating technique

We report the effect of annealing temperature on structural, electrical and optical properties of polycrystalline zinc oxide thin films grown on p-type silicon (100) and glass substrates by vacuum coating technique. The XRD and AFM measurements confirmed that the thin films grown by this technique have good crystalline hexagonal wurtzite structures and homogenous surfaces. The study also reveals that the rms value of thin film roughness increases from 6 to 16 nm, the optical band gap increases from 3.05 to 3.26 eV and resistivity from 0.3 to 5 Ωcm when the post-deposition annealing temperature is changed from 400 to 600 °C. It is observed that ZnO thin film annealed at 600 °C after deposition provide a smooth and flat texture suited for optoelectronic applications.     

Morphology, optical, and photoelectrochemical properties of electrodeposited nanocrystalline ZnO films sensitized with Cd x Zn1−x S nanoparticles

Nanocrystalline ITO/ZnO films formed by porous zinc oxide microplatelets 1–3 μm in size and 100–200 nm in thickness, which consist of 30–50 nm ZnO crystallites, were sensitized to visible light by Cd _x Zn_1?x S nanocrystals deposited using the method of successive ionic layer adsorption and reaction (SILAR). The composition of Cd _x Zn_1?x S nanocrystals as well as the dependence between molar Cd(II) fraction in the films and the ratio of cadmium and zinc nitrate concentrations in solutions used for the SILAR procedure were determined by a combination of electron, Raman, and energy-dispersive X-ray spectroscopies. The photovoltage observed at illumination of the ITO/ZnO/Cd _x Zn_1?x S heterostructures by white light (λ >400 nm) in aqueous Na₂S solution increases with a decrease of Cd(II) content proportionally to an increment in the conduction band potential of the Cd _x Zn_1?x S nanocrystals. The photocurrent density normalized to the light absorbance of the ITO/ZnO/Cd _x Zn_1?x S films increases by a factor of around four when the conduction band potential of Cd _x Zn_1?x S nanocrystals grows by 220 mV as a result of Cd(II) fraction changing from 1.0 to 0.62–0.67. The results show that Cd _x Zn_1?x S solid solutions are more advantageous sensitizers for the short-wavelength part of the sensitivity window of the liquid-junction solar cells (400–450 nm) than conventionally used cadmium sulfide.     

Preparation of cadmium-doped ZnO thin films by SILAR and their characterization

Cadmium-doped zinc oxide (Cd : ZnO) thin films were deposited from sodium zincate bath following a chemical dipping technique called successive ion layer adsorption and reaction (SILAR). Structural characterization by X-ray diffraction reveals that polycrystalline nature of the films increases with increasing cadmium incorporation. Particle size evaluated using X-ray line broadening analysis shows decreasing trend with increasing cadmium impurification. The average particle size for pure ZnO is 36·73 nm and it reduces to 29·9 nm for 10% Cd:ZnO, neglecting strain broadening. The strong preferred c-axis orientation is lost due to cadmium doping and degree of polycrystallinity of the films also increases with increasing Cd incorporation. Incorporation of cadmium was confirmed from elemental analysis using EDX. The optical bandgap of the films decreases with increasing Cd dopant. The value of fundamental absorption edge is 3·18?eV for pure ZnO and it decreases to 3·11?eV for 10% Cd:ZnO.     

Comparative study of multilayered ZnO/TiO<Subscript>2</Subscript>/ZnO and TiO<Subscript>2</Subscript>/ZnO/TiO<Subscript>2</Subscript> thin films prepared by sol–gel dip coating method

The aim of this research work is to represent the comparative study of ZnO/TiO₂/ZnO (ZTZ) and TiO₂/ZnO/TiO₂ (TZT) thin films deposited by sol–gel dip coating on FTO substrates. After deposition, the films were annealed at 500 °C for 1 h. Structural, surface morphology, optical and electrical properties of these films were studied by X-ray diffractrometer (XRD), Raman spectra, atomic force microscope (AFM), photoluminescence spectra (PL) and four point probe technique respectively. XRD and Raman spectra confirmed the anatase, brookite phases of TiO₂ and cubic phase of ZnO. AFM confirmed the formation of nano particles with average sizes of 18.4 and 47.2 nm of TZT and ZTZ films respectively. According to PL spectra, both the multilayer films slowdown the electron hole recombination rate and enhances the optoelectronic properties of the materials. Also it showed the peaks in the visible region of spectrum. The four point probe results showed that the average sheet resistivity of the films is 450 and 120 (ohm-m) respectively.     

Preparation and characterization of bowl-like porous ZnO film by electrodeposition using two-dimensional photonic crystal template

A rapid and low-cost method combining electrodeposition with two-dimensional (2D) photonic crystal template technique to prepare large scale bowl-like porous ZnO films is described. The 2D photonic crystal templates were fabricated by self-assembly of monodispersed polystyrene (PS) microspheres on indium-tin-oxide coated glass substrates using spinning coating method. The interstitial spaces among the spheres of the templates were filled with ZnO via electrodeposition from an aqueous solution containing 0.02 M zinc nitrate as electrolyte under a constant potential of ?1.0 V at 65 °C for 10 min. After removal of the PS photonic crystal template, bowl-like porous ZnO film was obtained. The entire process can be accomplished within 30 min. Scanning electron microscopic images showed good homogeneity in morphology, X-ray diffraction spectra demonstrated the wurtzite structure of the obtained ZnO film, and transmission electron microscopy indicated the single-crystallinity of the ZnO. Ultraviolet–visible (UV–vis) spectrophotometer was used to detect the absorption in UV–vis region of the PS template, opal ZnO-PS composite and inverse opal ZnO respectively. Two strong emission bands at 400 and 550 nm were displayed in photoluminescence spectrum.     

Electrical,optical and magnetoresistive behavior of nanostructured ZnO:Cu thin films deposited by sputtering

Copper doped ZnO (ZnO:Cu) nanostructured films with magnetoresistive behavior were produced by growing ZnO/Cu/ZnO arrays at room temperature (RT) by the sputtering technique on corning glass substrates. The arrays were made with two electrical insulating ZnO films of 50 and 105 nm, and a Cu film of 5 nm, both materials were deposited at RT by the RF- and DC-sputtering technique, respectively. The processing method involves two stages that proceed in the course of the growth process, the main one is originated by the non-equilibrium regime of the sputtering technique, and the second is the diffusion-redistribution of the intermediate Cu film towards the neighborhood ZnO layers aided by the nanocrystalline films character. The influence of applying an additional annealing stage to the arrays in N₂ atmosphere at 250 and 350 °C by periods of 30 min were studied. The resistivity of the ZnO:Cu films can be varied from 0.0034 to 2.83 Ω-cm, corresponding to electron concentrations of 1.12?×?10²¹ and 7.85?×?10¹⁷ cm^?3 with carrier mobility of 1.6 and 2.8 cm²/V s. Measured changes on the magnetoresistance behavior of the films at RT were of ?R?~?3% for annealed samples with electron concentration of 1.12?×?10²¹ cm^?3. The X-ray diffraction measurements show that the films are comprised of nanocrystallites with dimensions between 13 and 20 nm in size with preferred (002) orientation. The transmittance of the films in the visible region was of 83% with an optical band gap of ~?3.3 eV for the low-resistivity samples.     

Effect of zinc addition and vacuum annealing time on the properties of spin-coated low-cost transparent conducting 1 at% Ga–ZnO thin films

Abstract

Pure and 1 at% gallium (Ga)-doped zinc oxide (ZnO) thin films have been prepared with a low-cost spin coating technique on quartz substrates and annealed at 500 °C in vacuum ～10^?3 mbar to create anion vacancies and generate charge carriers for photovoltaic application. Also, 0.5–1.5 at% extra zinc species were added in the precursor sol to investigate changes in film growth, morphology, optical absorption, electrical properties and photoluminescence. It is shown that 1 at% Ga–ZnO thin films with 0.5 at% extra zinc content after vacuum annealing for 60 min correspond to wurtzite-type hexagonal structure with (0001) preferred orientation, electrical resistivity of ～9 × 10^?3 Ω cm and optical transparency of ～65–90% in the visible range. Evidence has been advanced for the presence of defect levels within bandgap such as zinc vacancy (V_Zn), zinc interstitial (Zn_i), oxygen vacancy (V_o) and oxygen interstitial (O_i). Further, variation in ZnO optical bandgap occurring with Ga doping and insertion of additional zinc species has been explained by invoking two competing phenomena, namely bandgap widening and renormalization, usually observed in semiconductors with increasing carrier concentration.