Physical properties of transparent conducting indium doped zinc oxide thin films deposited by pulsed DC magnetron sputtering

Transparent conducting In-doped (1at.%) zinc oxide (IZO) thin films are deposited on glass substrate by bipolar pulsed DC magnetron sputtering. We have investigated the effect of pulse frequency on the physical properties of the IZO films. A highly c-axis oriented IZO thin films were grown in perpendicular to the substrate. At optimal deposition conditions, IZO films with a smoothest surface roughness of ～3.6 nm, a low-resistivity of 5.8?×?10^?3 Ωcm, and a high mobility of 14 cm/Vs were achieved. The optical spectra showed a high transmittance of above 85% in the UV–visible region and exhibited the absorption edge of near 350 nm. In micro-Raman, we observed the three phonon modes of host ZnO, which are E ₂ ^low, E ₂ ^high, and A ₁ modes, and the three additional modes. The origin of three additional modes is attributed to the host lattice defect due to the effect of In dopant and increasing the pulse frequency.     

Tailoring the structural and optical properties of RF magnetron sputtered ZnO/graphene thin films by annealing temperature

Abstract

ZnO and ZnO/Graphene thin films were deposited on Cu substrate using a low pressure chemical vapor deposition (LPCVD) and the magnetron sputtering method. The impacts of graphene layer growth and annealing temperature on the optical properties ZnO and ZnO/Graphene thin films were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), X-ray photoelectron spectroscopic (XPS), and photoluminescence (PL) measurements respectively. XRD and SEM results reveal that all the thin films preferred the crystalline [001] orientation along the c-axis direction, which were vertical grown on substrate surface. By comparing the results and analysis of their structure, morphology, chemical bonding and optical property, it is proved that using Graphene as a buffer layer can improve the crystal quality of ZnO thin films. For the annealed ZnO/graphene nanostructures, the area ratio of UV and visible emission region of ZnO/graphene thin films increase with increasing the annealing temperature, reaches a maximum at 500?°C and then starts decreasing with further increase in annealing temperature, which indicating that the controllable ZnO/Graphene thin films have the higher crystallization quality at the annealing temperature of 500?°C. Our results demonstrate that for high quality ZnO/graphene thin films deposition, decreasing the defect concentration should be preferable to simply applying the proper annealing temperature, which might have promising applications for various UV photodetectors devices.     

Blueshift of absorption edge and photoluminescence in Al doped ZnO thin films

ABSTRACT

Pure and Al doped ZnO thin films are fabricated on quartz substrates by sol–gel method, and then analyzed by X-ray diffraction (XRD), transmittance spectra, and photoluminescence (PL) measurements respectively. XRD results reveal that all the thin films have a preferential c-axis orientation. With the increase of Al doping, however, the peak position of the (002) plane is shifted to a low 2θ value. On the other hand, the data of spectrometer transmittance are obtained, with which the band gap energies of Al doped ZnO films are calculated by a linear fitting method. The band gap is found to be broadening, and the absorption edge has an obvious blueshift to the shorter wavelength with increasing dopant concentration. PL measurement is also conducted, and deep-level (DL) emission and near band edge (NBE) emission are observed in pure ZnO thin films. But DL emissions are depressed when Al is doped into thin films. And the peak of NBE emission has a blueshift to the region of higher photon energy as the Al concentration increases, a performance which tallies with observations through the optical transmittance data. The study demonstrates that the blueshift of optical properties in the ZnO:Al films, can nevertheless be easily manipulated and managed by controlling dopant concentration, a big plus to the said films in their applications in broadband UV photodetectors with highly tunable wavelength resolution.     

Spectroscopic ellipsometric determination of optical properties of V-Al co-doped ZnO films by rf magnetron sputtering

Zn_0.9?xV_0.1Al_xO aerogel nanopowders were prepared in thin film form on glass substrates using a rf magnetron sputtering system. The films were characterized by Scanning electron microscopy (SEM) and X-ray diffraction technique (XRD). The XRD results indicate that all the films have c-axis preferred orientation due to self-texturing mechanism. The ellipsometric spectra of the films were recorded in the photon energy range of 1 eV–5 eV. The SE spectra were analyzed with an appropriate model to accurately determine the thickness and optical constants of the ZnO:(V,Al) thin films. The profiles of refractive index and extinction coefficient with photon energy were extracted. The refractive index of the ZnO:(V,Al) film is decreased from 2.14 to 2.07 with increasing Al concentration and then is increased to 2.19 for x?=?0.04. A maximum band gap energy of ~3.57 eV was obtained for x?=?0.02. The optical band gaps of the films were found to vary from 3.57 eV to 3.41 eV, with Al content. It is evaluated that the optical constants of the ZnO:(V,Al) films can be controlled by Al content.     

Fabrication of transparent ceria films by spray deposition without post firing

Most of the existing methods of crystalline ceria (CeO₂) films preparation consume much time and cost. Here we describe a straightforward and relatively cost-effective method of CeO₂ films preparation that involves direct spray deposition process on glass substrates at moderate temperatures (300–400 °C) using cerium acetate precursor in mixture of water and ethanol. X-ray diffraction analysis of obtained films revealed that they were polycrystalline, at least for a certain extent, with cubic fluorite structure and showed the existence of nanocrystallites. Scanning electron microscopic analysis showed that the films were crack-free and consists of nanocrystalline(<10 nm) ceria. Furthermore, the film showed high transparency in the visible and near-infrared region with calculated optical band gap (E _g) value of 3.06–3.08 eV. The film formation mechanism to obtain the transparent film has also been proposed.     

Effects of Mg doping concentration on the band gap of ZnO/Mg x Zn1−x O multilayer thin films prepared using pulsed laser deposition method

Epitaxial ZnO/Mg _x Zn_1-x O multilayer thin films (x?=?0~0.15) were prepared on c-Al₂O₃ substrates by pulsed laser deposition and their crystallinity and optical properties were investigated using X-ray diffraction, TEM, and UV-Vis spectroscopy. ZnO/Mg _x Zn_1-x O multilayer thin films were grown by stacking alternate layers of ZnO and Mg _x Zn_1?x O with laser fluence of 3 J/cm², repetition rate of 5 Hz, substrate temperature of 600 °C, and oxygen partial pressure of 5?×?10^–4 Torr. The thickness of individual ZnO and Mg _x Zn_1?x O layers was maintained at 3 and 6 nm, respectively, and the total thickness of the films was kept in 300 nm. X-ray diffraction results showed that the multilayer thin films were grown epitaxially on c-Al₂O₃ substrates with an epitaxial orientation relationship of $\left. {\left( {0001} \right)\left[ {10\bar 11} \right]_{{\text{multilayer}}} } \right\|\left( {0001} \right)\left[ {10\bar 11} \right]_{{\text{Al}}_{\text{2}} {\text{O}}_{\text{3}} } $ . Cross-sectional TEM micrographs showed alternating layers of bright and dark contrast, indicating the formation of ZnO/Mg _x Zn_1?x O multilayer thin films. The 2θ value of Mg _x Zn_1?x O (0002) peak increased from 34.30° at x?=?0 to 34.67° at x?=?0.15 with increasing Mg doping concentration in the multilayer thin films. The absorption edge in the UV-Vis spectra shifted to shorter wavelength from 360 at x?=?0 to 342 nm at x?=?0.15 and the band gap energy increased from 3.27 eV at x?=?0 to 3.54 eV at x?=?0.15.     

The optical constant of ZnSe/SiO2 composite thin films investigated by spectroscopic ellipsometers

In this paper, ZnSe/SiO₂ composite thin films was prepared by sol–gel process. X-ray diffraction results indicate the phase structure of ZnSe particles embedded in SiO₂ composite thin films is sphalerite (cubic ZnS). The dependence of ellipsometric angle ψ with wavelength λ of ZnSe/SiO₂ composite thin films was investigated through spectroscopic ellipsometers. The optical constant, thickness, porosity and the concentration of ZnSe/SiO₂ composite thin films were fitted according to Maxwell-Garnett effective medium theory. The thickness of ZnSe/SiO₂ composite thin films was measured through surface profile.     

Microstructures and dielectric properties of Zn2SnO4 thin films by sputtering from a ZnO doped ceramic target

The dielectric properties of Zn₂SnO₄ thin films with various degrees of ZnO dopant concentration were investigated. Zn₂SnO₄ thin films were prepared using the radio frequency magnetron sputtering. The X-ray diffraction patterns of the 0 and 75 mole % ZnO doped Zn₂SnO₄ thin films revealed that Zn₂SnO₄ is the main crystalline phase, which is accompanied by a little SnO₂ as the second phase. The second phase SnO₂ in specimens vanished when the extent of ZnO additive was increased to 100 mole%. A dielectric constant of 15–40 and a loss factor of 0.10–0.14 of Zn₂SnO₄ thin films were measured at 1 MHz with ZnO dopant concentration in the range of 0–100 mole%.     

Effects of temperature on structural and optical properties of ZnMgO films fabricated by pulsed laser deposition

ZnMgO thin films have been deposited on Si(111) substrates by pulsed laser deposition (PLD) technique at growth temperature from 300 to 700°C in nitrogen ambient of 1.0 Pa. The effects of growth temperature on structural and optical properties of deposited ZnMgO thin films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared absorption (IR) spectra and photoluminescence (PL) spectra. The results of XRD and SEM analyses show that the film fabricated at 400°C possesses good crystallinity with hexagonal wurtzite structure and surface morphology. The Mg has been incorporated into ZnO in the form of substitutional Zn. The IR spectra reveal the typical absorption peaks of ZnMgO. The band-gap values have been obtained from 2.96 to 4.23 eV with increasing growth temperature. The PL spectra show that the highest UV emission is obtained at growth temperature of 600°C, and the obvious blue-shift is observed. This may be assigned as the change of the band-gap due to the increasing incorporation of Mg²⁺ ions with the increasing growth temperature.     

Synthesis of ZnSe nanocrystalline powders by mechanochemical reaction

The ZnSe nanocrystalline powders were synthesized by mechanochemical reaction method. The powders milled at air atmosphere have the second phase ZnO, but that milled above 2 h at high N₂ atmosphere have not second phase ZnO. The phase structure of the ZnSe powder milled for 10 h at N₂ atmosphere is sphalerite structure. The average size of the as-milled and annealed ZnSe nanocrystalline powders is 5.17 and 8.88 nm respectively. The TEM analysis demonstrated that the size of agglomerated ZnSe crystalline is less than 100 nm, but the electron diffraction pattern showed that ZnSe clusters were a polycrystalline structure. The absorption spectrum of ZnSe samples was measured by UV–VIS–NIR Photometer Spectrum. It showed that the absorption edge of the ZnSe nanocrystalline powders by mechanochemical reaction comparing to ZnSe bulk materials had a red-shift. This result can be attributed to the residual stress and lattice aberrance of ZnSe nanocrystalline powders in milling process. The absorption edge of the annealed ZnSe powders was recovered owing to the residual stress was eliminated by annealing for 2 h containing nitrogen.     

Characteristics of ZnO thin film for film bulk acoustic-wave resonators

Highly c-axis-oriented zinc oxide (ZnO) thin films were deposited on Au electrodes by reactive radio frequency (RF) magnetron sputtering and their sputtering pressure on thin film bulk acoustic-wave resonator (FBAR) characteristics are presented. The evolution of the preferred orientation and the surface morphologies of the deposited ZnO films are investigated using X-ray diffraction, scanning electron microscopy, and atomic force microscopy measurement techniques. The result obtained in this study show that the ZnO films prepared using a lower sputtering pressure of 2?×?10^?3 Torr have a strong c-axis orientation, promote smoother surface and higher resonance frequency. The experimental results demonstrate that the fabricated two-port FBAR using the optimum process parameters yields an effective electromechanical coupling constant ( $ k^{2}_{{{\text{eff}}}} $ ) of 2.8%, series quality factor (Q _s) of 436, and a parallel quality factor (Q _p) of 600.     

Effect of Strain Gradation on Luminescence and Electronic Properties of Pulsed Laser Deposited Zinc Oxide Thin Films

ZnO thin films were grown by ablation of a ZnO ceramic target using pulsed excimer laser (KrF) under 1 mTorr oxygen partial pressure over (0001) -Al₂O₃ substrates held at 750_C. Highly c-axis oriented (0002) ZnO films with visible range optical transparency over 80% were obtained. Inhomogeneous distribution of strain in the film growth direction was studied by line shape analysis of X-ray diffraction and broad luminescence features centered on near band edge transition at 3.3 eV. Strain in the film adversely affects optical gain and excitonic threshold of UV emission. Post-growth oxygen annealing of films at 850°C for 1 h reduces strain and associated defects at ZnO film interface with (0001) Al₂O₃ substrate. FWHM of X-ray rocking curves show corresponding lowering from 12.5 arc min to 9.0 arc min signifying improved ZnO crystal quality. -rocking curves show line features with two superimposed peaks belonging to interfacial layer and bulk ZnO film. Graded strain in ZnO film is related to differently oriented interfacial layer formed at inception stage of film growth. Decrease in conductivity of annealed ZnO films show that O₂-vacancies are primary defects. Formation of strain free (0002) oriented optical quality ZnO films based on combined process of growth in low O₂ pressure and post growth anneal at high O₂ pressure is proposed for UV-optoelectronic applications.     

Electrical and optical properties of fluorine-doped tin oxide (SnOx:F) thin films deposited on PET by using ECR–MOCVD

The electrical, optical, structural and chemical bonding properties of fluorine-doped tin oxide (SnO_x:F) films deposited on a plastic substrate prepared by Electron Cyclotron Resonance–Metal Organic Chemical Vapor Deposition (ECR–MOCVD) were investigated with special attention to the process parameters such as the H₂/TMT mole ratio, deposition time and amount of fluorine-doping. The four point probe method, UV visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic emission spectroscopy (AES), X-Ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the films. Based on our experimental results, the characteristics of the SnO_x:F thin films were significantly affected by the process parameters mentioned above. The amount of fluorine doping was found to be one of the major parameters affecting the surface resistivity, however its excess doping into SnO₂ lead to a sharp increase in the surface resistivity. The average transmittance decreased with increasing film thickness. The lowest electrical resistivity of 5.0?×?10^?3 Ω^.cm and highest optical transmittance of 90% in the visible wavelength range from 380 to700 nm were observed at an H₂/TMT mole ratio of 1.25, fluorine-doping amount of 1.3 wt.%, and deposition time of 30 min. From the XRD analysis, we found that the SnO_x:F films were oriented along the (2 1 1) plane with a tetragonal and polycrystalline structure having the lattice constants, a?=?0.4749 and c?=?0.3198 nm.     

Aging and Annealing Effects of ZnO Thin Films on GaAs Substrates Deposited by Pulsed Laser Deposition

Zinc oxide (ZnO) thin films were deposited on GaAs (100) substrates at different temperatures in the pulsed laser deposition (PLD) system. From the measurements of X-ray diffraction (XRD) at room temperature, 300–500°C were found to be good condition for the crystallization of the thin films. From the photoluminescence (PL) measurements, 500°C was found to be the optimized temperature for its optical property. Samples grown at 100, 200, 300, and 400°C showed near band-edge (NBE) emissions and deep-level emissions. The intensity of deep-level emissions decreased as time goes on, which is believed to originate from oxygen vacancies or zinc interstitials in thin films. While for the sample grown at 500°C, bright NBE emissions were observed at room temperature, and no deep-level emissions observed. This means that the high-optical-quality thin film was grown at 500°C. At the same time, annealing process of ZnO thin films grown at room temperature was carried out in PLD chamber. It was found that the annealing temperature of 600°C has strong effects on its PL. Aging and annealing effects in ZnO thin films grown on GaAs substrates by PLD were observed for the first time.     

INFLUENCE OF DEPOSITION TEMPERATURE AND N2 FLOW RATE ON HIGH QUALITY ZNO THIN FILM DEPOSITED ON SiO2/SI SUBSTRATE BY ULTRASONIC SPRAY PYROLYSIS

ABSTRACT

ZnO thin films were prepared on SiO₂/Si substrate by ultrasonic spray pyrolysis (USP) method using the aqueous solution of zinc acetate dehydrate. X-ray diffraction (XRD) and atomic force microscopy (AFM) were employed to analyze the crystalline and microscopic structure of the films. The properties of ZnO films were investigated with respect to deposition temperature (T_s) and N₂ flow rate (f). The results show that ZnO thin films exhibit hexagonal wurtzite structure and the highly preferential orientation along c-axis under T_s = 320°C and f = 5 L/min deposition condition.     

Optical and photoluminescence properties of Ga doped ZnO nanostructures by sol-gel method

Zinc oxide (ZnO) nanocrystallites with different Ga-doping levels were successfully prepared by spin coating sol?Cgel technique. The morphological properties of Ga doped ZnO films were studied by atomic force microscopy (AFM). Alignment of ZnO nanorods with respect to the substrate depends on the amount of Ga dopant content. The dopant content varies from 1?% to 4?%, based on Ga-doping levels. The optical properties of the ZnO nanocrystallites following Ga-doping were also investigated by UV?CVisible absorption and Photoluminescence spectra. Our results indicate that Ga-doping can change the energy-band structure and effectively adjust the intensity of the luminescence properties of ZnO nanocrystallites. Transmittance spectra of the films indicate that the films have high transparency. The refractive index dispersion was analyzed by single oscillator model developed by Wemple and DiDomenico. The oscillator energy, dispersion energy, high frequency dielectric constant values for the films were determined were calculated and it is found that the optical parameters are changed with Ga-doping content.     

Enhancement of the surface and structural properties of ZnO epitaxial films grown on Al2O3 substrates utilizing annealed ZnO buffer layers

ZnO films were grown on Al₂O₃ (1000) substrates without and with ZnO buffer layers by using radio-frequency magnetron sputtering. Atomic force microscopy images showed that the surface roughness of the ZnO films grown on ZnO buffer layers annealed in a vacuum was decreased, indicative of an improvement in the ZnO surfaces. X-ray diffraction patterns showed that the crystallinity of the ZnO thin films was enhanced by using the annealed ZnO buffer layer in comparison with the film grown on without a buffer layer. The improvement of the surface and structural properties of the ZnO films might be attributed to the formation of the Zn-face ZnO buffers due to annealing in a vacuum. These results indicate that the surface and structural properties of ZnO films grown on Al₂O₃ substrates are improved by using ZnO buffer layers annealed in a vacuum.     

Large area deposition of Pb(Zr,Ti)O<Subscript>3</Subscript> thin films for piezoelectric MEMS devices

Pb(Zr,Ti)O₃ (PZT) thin films deposited on insulating ZrO₂ buffered silicon wafer are intended to be employed for in-plane polarized piezoelectric MEMS devices. Multi-target reactive sputtering system for large area deposition of in-situ crystallized PZT thin films and the ZrO₂ buffer layer has been employed. The interface analysis of multilayer structures by high resolution transmission microscope, X-ray diffraction, optical refraction, and absorption spectra studies has been presented. At a substrate temperature of 520°C and excess lead deposition condition, the formation of a PZT superstructure has been revealed. The substrate temperature of 580°C leads to the crystallization of PZT directly into a single phase perovskite crystal structure. A pronounced Urbach behavior in our PZT thin films has been observed by optical absorption studies. The surface roughness of PZT films deposited on a ZrO₂ buffer layer is much higher than that on conducting platinized silicon wafer.     

The electronic structures for the optical absorption of Hf-O-N thin films

The local structures of Hf-O-N thin films were analyzed using an extended X-ray absorption fine structure (EXAFS) study on Hf L _III-edge and first-principles calculations. Depending on their composition and atomic configurations, Hf₄O₈ (CN: 7.0), Hf₄O₅N₂ (CN: 6.25) and Hf₄O₂N₄(CN: 5.5) were suggested as the local structures of Hf-O-N thin films. The optical band gaps of Hf-O-N thin films were compared with the calculated band gap. And to investigate the optical absorption, the effects of film compositions on the valence bands of Hf-O-N thin films were analyzed by comparing the experimental valence band with the valence band.     

Sapphire orientation dependence of the microstructure of ZnO thin film during annealing

The sapphire orientation dependence of the microstructure of ZnO thin films has been studied in real-time synchrotron X-ray scattering experiments. The ZnO films with a 2400-Å-thick were grown on sapphire (001) and sapphire (110) substrates at room temperature by radio frequency magnetron sputtering. The as-deposited ZnO film on sapphire (001) has the only (002) crystal grains, while that on sapphire (110) has not only (002) crystal grains but (100) and (101) additional grains. The ZnO films were changed into fully epitaxial ZnO (002) grains both on sapphire (001) and sapphire (110) substrates with increasing the annealing temperature to 600^°C. The epitaxial relationships of the ZnO grains were summarized as ZnO (00l)[100]//sapphire (00l)[110] and ZnO (00l)[110]//sapphire (110)[001].