Growth and characterisation of electrodeposited ZnO thin films

The electrochemical method has been used to deposit zinc oxide (ZnO) thin films from aqueous zinc nitrate solution at 80 °C onto fluorine doped tin oxide (FTO) coated glass substrates. ZnO thin films were grown between − 0.900 and − 1.025 V vs Ag/AgCl as established by voltammogram. Characterisation of ZnO films was carried out for both as-deposited and annealed films in order to study the effect of annealing. Structural analysis of the ZnO films was performed using X-ray diffraction, which showed polycrystalline films of hexagonal phase with (002) preferential orientation. Atomic force microscopy was used to study the surface morphology. Optical studies identified the bandgap to be ∼ 3.20 eV and refractive index to 2.35. The photoelectrochemical cell signal indicated that the films had n-type electrical conductivity and current-voltage measurements showed the glass/FTO/ZnO/Au devices exhibit rectifying properties. The thickness of the ZnO films was found to be 0.40 μm as measured using the Talysurf instrument, after deposition for 3 min. Environmental scanning electron microscopy was used to view the cross-section of glass/FTO/ZnO layers.     

Chemical bath deposition of textured ZnO thin films in aqueous/ethanolic solution

ZnO thin films have been prepared by chemical bath deposition in aqueous/ethanolic solution. The film texture was successfully controlled by varying the volume ratio of water to ethanol. Films consisting of densely oriented nanorod arrays with the c-axis perpendicular to the substrate were fabricated in aqueous solution. The crystals became increasingly tilted as more ethanol was introduced to the solution, resulting in the cracked nanocolumns and the smoothed crystals. The crystal size was decreased with increasing ethanol content, and granular morphology was obtained in films deposited in ethanolic solution. A gradual evolution of the film texture is possibly due to the inhibited crystal growth in solution with higher ethanol content.     

Perspectives of chlorine doping of ZnO

Thermodynamic analysis for system ZnO:Cl is performed by means of Kröger method of quasi-chemical reactions. We obtained equilibrium concentrations of defects and free carriers as a function of partial pressure of components in gas phase. When Chlorine total concentration of incorporated Chlorine is 10²⁰ cm^− 3 expected concentration of carriers generated is about 5 10¹⁹ cm^− 3, which is almost three orders of magnitude higher than the one of pure ZnO.     

Lattice and internal relaxation of ZnO thin film under in-plane strain

Detailed ab initio density-functional calculations were carried out on the effect of lattice and internal relaxation of ZnO thin film under in-plane strain. It was found that the classical elastic deformation behaves under a restricted joint mechanism including lattice relaxation and internal relaxation. The internal relaxation works to enhance the effect of the in-plane strain on the perpendicular direction and, reduce the residual stress and the strain energy and, thus finally elevate the energetic stability of the resulting structure. By contrast, the free lattice and internal relaxation could consume part of the elastic strain energy to lead to a more stable structure with a degenerated space-group symmetry and no residual stress in any direction. In addition, the free relaxation brings about some different behaviors in many respects relative to the elastic deformation, such as the smaller Poisson ratio, the decreased piezoelectric effect, a “Λ” shaped variety in bandgap at the Γ point and the reduced shift in homogeneity of charge distribution between the two kinds of Zn-O bonds.     

Porous nanostructured ZnO films deposited by picosecond laser ablation

Porous nanostructured polycrystalline ZnO films, free of large particulates, were deposited by picosecond laser ablation. Using a Zn target, zinc oxide films were deposited on indium tin oxide (ITO) substrates using a picosecond Nd:YVO₄ laser (8 ps, 50 kHz, 532 nm, 0.17 J/cm²) in an oxygen atmosphere at room temperature (RT). The morpho-structural characteristics of ZnO films deposited at different oxygen pressures (150–900 mTorr) and gas flow rates (0.25 and 10 sccm) were studied. The post-deposition influence of annealing (250–550 °C) in oxygen on the film characteristics was also investigated. At RT, a mixture of Zn and ZnO formed. At substrate temperatures above 350 °C, the films were completely oxidized, containing a ZnO wurtzite phase with crystallite sizes of 12.2–40.1 nm. At pressures of up to 450 mTorr, the porous films consisted of well-distinguished primary nanoparticles with average sizes of 45–58 nm, while at higher pressures, larger clusters (3.1–14.7 μm) were dominant, leading to thicker films; higher flow rates favored clustering.     

ZnO thin films deposited by a CVT technique in closed ampoules

ZnO thin films were prepared on quartz glass, Si (100), and sapphire (001) substrates by a chemical vapour transport (CVT) technique. During the growing processes, the source and substrate temperatures were maintained at 1000 °C and 600 °C, respectively. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements showed that the crystalline qualities of ZnO thin films were sensitively dependent on substrates. ZnO thin film deposited on sapphire substrate exhibited the best morphology with the largest crystallite size of more than 20 μm. Meanwhile, the XRD patterns showed that ZnO thin film deposited on sapphire substrate was strongly c-axis preferred-oriented with high crystalline quality. The optical properties of ZnO thin films were investigated by photoluminescence (PL) spectroscopy at room temperature (RT). The results suggested that the optical properties of ZnO thin films were highly influenced by their crystalline qualities and surface morphologies.     

Preparation and properties of ZnO thin films deposited by sol-gel technique

Zinc oxide (ZnO) thin films were deposited on (100) Si substrates by sol-gel technique. Zinc acetate was used as the precursor material. The effect of different annealing atmospheres and annealing temperatures on composition, structural and optical properties of ZnO thin films was investigated by using Fourier transform infrared spectroscopy, X-ray diffraction, atomic force microscopy and photoluminescence (PL), respectively. At an annealing temperature of 400°C in N₂ for 2 h, dried gel films were propitious to undergo structural relaxation and grow ZnO grains. ZnO thin film annealed at 400°C in N₂ for 2 h exhibited the optimal structure and PL property, and the grain size and the lattice constants of the film were calculated (41.6 nm, a = 3.253 ? and c = 5.210 ?). Moreover, a green emission around 495 nm was observed in the PL spectra owing to the oxygen vacancies located at the surface of ZnO grains. With increasing annealing temperature, both the amount of the grown ZnO and the specific surface area of the grains decrease, which jointly weaken the green emission. Translated from Journal of Lanzhou University (Natural Science), 2006, 42(1): 67–71 [译自: 兰州大学学报 (自然科学版)]     

Effect of Ga doping on micro/structural, electrical and optical properties of pulsed laser deposited ZnO thin films

Undoped and Ga doped ZnO thin films (1% GZO, 3% GZO and 5% GZO) were grown on c-Al₂O₃ substrates using the 1, 3 and 5 at. wt.% Ga doped ZnO targets by pulsed laser deposition. X-ray diffraction studies revealed that highly c-axis oriented, single phase, undoped and Ga doped ZnO thin films with wurtzite structure were deposited. Micro-Raman scattering analysis showed that Ga doping introduces defects in the host lattice. The E₂^High mode of ZnO in Ga doped ZnO thin film was observed to shift to higher wavenumber indicating the presence of residual compressive stress. Appearance of the normally Raman inactive B₁ modes (B₁^Low, 2B₁^Low and B₁^High) due to breaking of local translational symmetry, also indicated that defects were introduced into the host lattice due to Ga incorporation. Band gap of the Ga doped ZnO thin films was observed to shift to higher energy with the increase in doping concentration and is explicated by the Burstein-Moss effect. Electrical resistivity measurements of the undoped and GZO thin films in the temperature range 50 to 300 K revealed the metal to semiconductor transition for 3 and 5% GZO thin films.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

Optical and electrical properties of ZnO films deposited by activated reactive evaporation

ZnO films having good transmittance and conductivity were deposited by activated reactive evaporation of Zn metal on glass and Si substrates at room temperature. Optical constants and thickness of ZnO films deposited under different deposition conditions were determined both by spectroscopic ellipsometry (SE) and spectrophotometry. Structural studies showed that the films exhibited a polycrystalline wurtzite structure with the preferential oriented along the (002) plane. Electrical studies by four probe technique showed that the sheet resistance of the films varied from 10⁶ to 50 Ω/square depending upon the oxygen partial pressure used during deposition, and this sheet resistance value increased with time. The increase in sheet resistance with time was found to be dependent on the surface morphology of the film and on the substrate over which they were deposited.     

Electrical properties of Ta2O5 films deposited on ZnO

High dielectric constant (high-k) Ta₂O₅films have been deposited on ZnO/p-Si substrate by microwave plasma at 150°C. Structure and composition of the ZnO/p-Si films have been investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) for chemical composition. The electrical properties of the Ta₂O₅/ZnO/p-Si metal insulator semiconductor (MIS) structures were studied using high frequency capacitance-voltage (C-V), conductance-voltage (G-V) and current-voltage (I-V) characteristics. Charged trapping properties have been studied by measuring the gate voltage shift due to trapped charge generation under Fowler-Nordheim (F-N) constant current stressing.     

ZnO基紫外探测器的研究进展

ZnO是一种新型的宽带隙半导体光电材料,可用于制作高性能的紫外探测器,是未来半导体紫外探测器的发展重点.介绍了ZnO基紫外探测器常见的器件结构、探测材料的基本特性和主要制备方法,以及器件近期的研究进展,并扼要分析了其今后的发展方向.     

Roughness evolution in Ga doped ZnO films deposited by pulsed laser deposition

We analyze the morphology evolution of the Ga doped ZnO(GZO) films deposited on quartz substrates by a laser deposition system. The surface morphologies of the film samples grown with different times are measured by the atomic force microscope, and they are analyzed quantitatively by using the image data. In the initial stage of the growth time shorter than 8 min, our analysis shows that the GZO surface morphologies are influenced by such factors as the random fluctuations, the smoothening effects in the deposition, the lateral strain and the substrate. The interface width uw(t) and the lateral correlation length ξ(t) at first decrease with deposition time t. For the growth time larger than 8 min, w(t) and ξ(t) increase with time and it indicates the roughening of the surface and the surface morphology exhibits the fractal characteristics. By fitting data of the roughness w(t) versus deposition time t larger than 4 min to the power-law function, we obtain the growth exponent β is 0.3; and by the height-height correlation functions of the samples to that of the self-affine fractal model, we obtain the value of roughness exponent α about 0.84 for all samples with different growth time t.     

Microstructural and optical properties of Ga-doped ZnO semiconductor thin films prepared by sol-gel process

Transparent thin films of Ga-doped ZnO (GZO), with Ga dopant levels that varied from 0 to 7 at.%, were deposited onto alkali-free glass substrates by a sol-gel process. Each spin-coated film was preheated at 300 °C for 10 min, and then annealed at 500 °C for 1 h under air ambiance. The effects of Ga dopant concentrations on crystallinity levels, microstructures, optical properties, and electrical resistivities of these ZnO thin films were systematically investigated. Photoluminescence spectra of GZO thin films were examined at room temperature. XRD results revealed that the undoped ZnO thin films exhibited a preferred orientation along the (002) plane and that the ZnO thin films doped with Ga showed degraded crystallinity. Experimental results also showed that Ga doping of ZnO thin films could markedly decrease surface roughness, improve transparency in the visible range, and produce finer microstructures than those of undoped ZnO thin films. The most promising films for transparent thin film transistor (TTFT) application produced in this study, were the 3 and 5 at.% Ga-doped ZnO thin films, both of which exhibited an average transmittance of 90.6% and an RMS roughness value of about 2.0 nm.     

Effect of r.f. sputtering parameters on ZnO films deposited onto GaAs substrates

In order to compensate the piezoelectrical property of GaAs-based material for monolithic integrated acousto-optic circuit applications, a ZnO film with a highly preferred orientation should be deposited. R.f. sputtering was employed to deposit ZnO films with various technological parameters. The optimal conditions to deposit high quality ZnO film onto GaAs-based substrates were deduced and investigated. Low loss surface acoustic wave devices fabricated on ZnO/GaAs wafers were obtained. The total insertion loss measured at a centre frequency of 25.37 MHz was 20 dB.     

High quality ZnO films deposited by radio-frequency magnetron sputtering using layer by layer growth method

Three-layered ZnO films were deposited on Si substrates by radio-frequency magnetron sputtering using layer by layer growth method. The Raman scattering confocal analysis confirms that ZnO film quality is improving at increasing the number of ZnO layers at film deposition.Applied method of deposition was used to realize homoepitaxial growth of ZnO films on c-Al₂O₃, Si, SiN_x/Si, glass and ITO/glass substrates. In order to improve the film quality we increased the number of deposition stages up to 5. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmittance measurements were used to testify the quality of grown five-layered ZnO films. XRD results showed that all five-layered ZnO films have (002) texture. The second order diffraction peak (004) on XRD spectra additionally testifies to the high quality of all five-layered ZnO films. SEM results demonstrated that no defects such as cracks and dislocations caused by interruption of deposition ZnO films were observed. Transmittance measurement results showed that ZnO films deposited on transparent substrates have abrupt absorption edge and high optical transmission in the visible region of the spectrum.     

Structural, electrical and optical properties of ZnO:Al films deposited on flexible organic substrates for solar cell applications

Aluminum doped ZnO thin films (ZnO:Al) were deposited on glass and poly carbonate (PC) substrate by r.f. magnetron sputtering. In addition, the electrical, optical properties of the films prepared at various sputtering powers were investigated. The XRD measurements revealed that all of the obtained films were polycrystalline with the hexagonal structure and had a preferred orientation with the c-axis perpendicular to the substrate. The ZnO:Al films were increasingly dark gray colored as the sputter power increased, resulting in the loss of transmittance. High quality films with the resistivity as low as 9.7 × 10^− 4 Ω-cm and transmittance over 90% have been obtained by suitably controlling the r.f. power.     

Electrical and optical properties of Al-doped ZnO films deposited by hollow cathode gas flow sputtering

Al-doped ZnO (AZO) films were deposited on glass by hollow cathode gas flow sputtering using Zn-Al alloy targets. Sputtering power for all the depositions was fixed at 1500 W. Resistivities of 0.81-1.1 × 10^− 3 Ω cm were obtained for AZO films deposited at room temperature with an O₂ flow from 38 to 50 standard cubic centimetre/minute (SCCM), while static deposition rates were almost constant at 270-300 nm/min. On the other hand, lower resistivities of 5.2-6.4 × 10^− 4 Ω cm were obtained for AZO films deposited at 200 °C with an O₂ flow from 25 to 50 SCCM, while the static deposition rates were almost constant at 200-220 nm/min. Average transmittances in the visible light region were above 80% for both sets of films.     

Effect of surface morphology of metallic zinc films deposited by ion beam sputter deposition on the formation of ZnO nanowires

Metallic zinc film with various surface roughnesses was deposited on Si (100) substrates by ion beam sputter deposition utilizing beam energies at 8, 12 and 16 keV. The surface roughness of the metallic zinc film increased as ion beam energy increased and was found to act as a crucial factor for the formation of ZnO nanowires by subsequent thermal oxidation. ZnO nanowires with diameters of ∼30 nm and average length of ∼1 μm were obtained from 12 to 16 keV ion beam deposited samples while no ZnO nanowires were found on 8 keV ion beam deposited samples. Photoluminescence study of ZnO nanowires exhibits a strong UV emission at 377.2 nm (3.287 eV) with a full-width at half maximum of 95.0 meV and negligible defect related deep level emission. The ZnO nanowires are grown along the [110] direction and the growth mechanism is likely due to a solid state based-up diffusion process. Field-emission measurement shows a turn-on field of 7.9 MV/m and a field enhancement factor β of 691 is achieved.