Characterization of non-stoichiometric Ga2O3-x thin films grown by radio-frequency powder sputtering

We report the synthesis and characterization of non-stoichiometric Ga₂O_3-x thin films deposited on sapphire (0001) substrates by radio-frequency powder sputtering. The chemical and electronic states of the non-stoichiometric Ga₂O_3-x thin films were investigated. By sputtering in an Ar atmosphere, the as-grown thin films become non-stoichiometric Ga₂O_2.7, due to the difference in sputtering yield between Ga and O species of the Ga₂O₃ target. The electronic states of the thin films consist of ~85% Ga³⁺ and ~15% Ga¹⁺, corresponding to Ga₂O₃ and Ga₂O, respectively. The films have the electrical characteristics of a semiconductor, with electrical conductivity of approximately 5.0 × 10^-4 S cm^-1 and a carrier concentration of 4.5 × 10¹⁴ cm^-3 at 300 K.     

Gallium oxide films deposition by RF magnetron sputtering; a detailed analysis on the effects of deposition pressure and sputtering power and annealing

In this study, gallium oxide (Ga₂O₃) thin films were deposited on sapphire and n-Si substrates using Ga₂O₃ target by radio frequency magnetron sputtering (RFMS) at substrate temperature of 300 °C at variable RF power and deposition pressure. The effects of deposition pressure and growth power on crystalline structure, morphology, transmittance, refractive index and band gap energy were investigated in detail. X-ray diffraction results showed that amorphous phase was observed in all the as-deposited thin films except for the thin films grown at low growth pressure. All the films showed conversion to poly-crystal β-Ga₂O₃ phase after annealing process. When the deposition pressure increased from 7.5 mTorr to 12.20 mTorr, change in the 2D growth mode to 3D columnar growth mode was observed from the SEM images. Annealing clearly showed formation of larger grains for all the thin films. Lower transmission values were observed as the growth pressure increases. Annealing caused to obtain similar transmittance values for the thin films grown at different pressures. It was found that a red shift observed in the absorption edges and the energy band gap values decrease with increasing growth pressure. For as-deposited and annealing films, increasing sputtering power resulted in the increase refractive index.     

Structural,optical and morphological evolution of Ga2O3/Al2O3 (0001) films grown at various temperatures by pulsed laser deposition

This study systematically investigated the structural, optical, and morphological evolution of Gallium oxide (Ga₂O₃) films deposited at different substrate temperatures on Al₂O₃(0001) using pulsed laser deposition (PLD). The thickness of the Ga₂O₃ films was standardized in order to eliminate its effect on the film properties. The effect of substrate temperature from room temperature to 600 °C on the film's transmittance, crystalline structure, chemical composition and surface morphology, was explored. The plasma species generated during the deposition of the PLD process were monitored and analyzed employing in situ optical emission spectroscopy. The deposition rate of the films decreased with increasing substrate temperature. X-ray photoelectron spectroscopy was used to detect both Ga³⁺ and Ga ⁺ oxidation states in all prepared films, which indicated substoichiometric Ga₂O₃ films deficient in oxygen. The percentage of non-lattice oxygen decreased with increasing substrate temperature. At optimal condition, mono-crystaline β-Ga₂O₃ was produced with a high visible and near-infrared transmittance, large grain size and smooth surface, which is suitable for the application in high-performance power electric devices and photoelectronic devices.     

Influence of substrate temperature on the properties of (AlGa)2O3 thin films prepared by pulsed laser deposition

(AlGa)₂O₃ thin films were deposited on (0001) sapphire substrates by pulsed laser deposition at different substrate temperatures. The influence of substrate temperature on surface morphology, optical properties, and crystal quality has been systematically investigated by atomic force microscope, transmission spectra, X-ray diffraction, and Raman spectroscopy. The results reveal that all the (AlGa)₂O₃ films have smooth surface and high transmittance. The (AlGa)₂O₃ film with the good crystal quality can be obtained at a substrate temperature of 400 °C. Our results provide an experimental basis for realizing the Ga₂O₃-based quantum well.     

Sol‐gel derived TiNb2O7 dielectric thin films for transparent electronic applications

To reduce power consumption of transparent oxide‐semiconductor thin film transistors, a gate dielectric material with high dielectric constant and low leakage current density is favorable. According to previous study, the bulk TiNb₂O₇ with outstanding dielectric properties may have an interest in its thin‐film form. The optical, chemical states and surface morphology of sol‐gel derived TiNb₂O₇ (TNO) thin films are investigated the effect of postannealing temperature lower than 500°C, which is crucial to the glass transition temperature. All films possess a transmittance near 80% in the visible region. The existence of non‐lattice oxygen in the TNO film is proposed. The peak area ratio of non‐lattice oxygen plays an important role in the control of leakage current density of MIM capacitors. Also, the capacitance density and dissipation factor were affected by the indium tin oxide (ITO) sheet resistance at high frequencies. The sample after postannealing at 300°C and electrode‐annealing at 150°C possesses a high dielectric constant (>30 at 1 MHz) and a low leakage current density (<1 × 10^?6 A/cm² at 1 V), which makes it a very promising gate dielectric material for transparent oxide‐semiconductor thin film transistors.     

Effect of oxygen flow ratio on the performance of RF magnetron sputtered Sn-doped Ga2O3 films and ultraviolet photodetector

This work explored the properties of RF magnetron sputtered Sn-doped Ga₂O₃ films grown on sapphire substrates at different oxygen flow ratios from 0.0 to 2.5%. The in situ optical emission spectroscopy was conducted to monitor the plasma radicals generated during the films’ deposition. All the films deposited at room temperature show amorphous structures with some nanoparticles. The deposition rate decreased monotonically with increasing oxygen flow ratio. The proposed conductive mechanism of the films can be mainly attributed to the changes in the ratio of substitutional Sn (Sn⁴⁺ valance state) atoms replacing lattice Ga sites (Ga³⁺ valance state) and the SnO₂ phase in the films. Metal–semiconductor–metal solar-blind photodetectors were developed and analyzed to illustrate the effect of oxygen flow ratio. A high performance photodetector with a low dark current of 1.14 pA, high on/off ratio of 812 and short rise/decay time of 0.05 s/0.12 s was realized at an optimization growth condition. The elaboration of the conductive mechanism and effect of oxygen flow ratio on the performance of Sn-doped Ga₂O₃ films and their photodetectors is crucial for the preparation of high-quality Sn-doped Ga₂O₃ films and its application in optoelectronic devices.     

The sintering behavior,microstructure, and electrical properties of gallium-doped zinc oxide ceramic targets

The properties of sputtering targets have recently been found to affect the performances of sputtered films and the sputtering process. To develop high-quality GZO ceramic targets, the influences of Ga₂O₃ content and sintering temperature on the sintering behavior, microstructure, and electrical properties of GZO ceramic targets were studied.The results showed that the increase in Ga₂O₃ content from 3 wt% (GZO-3Ga) and 5 wt% (GZO-5Ga) not only inhibited the densification but retarded grain growth. During sintering, ZnGa₂O₄ phase formed before 800 °C, and Zn₉Ga₂O₁₂ phase was found after sintering at 1000 °C. Moreover, after sintering at 1200 °C, the number of Zn₉Ga₂O₁₂ precipitates increased at the expense of ZnGa₂O₄ and ZnGa₂O₄ disappearing completely. The relative density, grain size, and resistivity of GZO-3Ga sintered at 1400 °C in air were 99.3%, 3.3 μm, and 2.8 × 10⁻³ Ω cm, respectively. These properties of GZO ceramics are comparable to properties reported in the literature for AZO sintered in air.     

Influence of post-deposition annealing on electrical and optical properties of (Ta2O5)1-x - (TiO2)x thin films,x ≤ 0.08

Tantalum (Ta) and titanium (Ti) metal targets were direct current (DC) magnetron sputtered in the oxygen environment by varying its relative areas to deposit (Ta₂O₅)_1-x- (TiO₂)_x (TTO_x) thin films, with x = 0, 0.03, 0.06, and 0.08, onto the boron-doped p-silicon (1 0 0) and optically polished quartz substrates, at room temperature; and were annealed at 500, 600, 700, and 800 °C, for 1.5 h. The thin films annealed at and above 600 °C show the Ta₂O₅ structure. The leakage current density and capacitance-voltage (C–V) characteristics were measured for TTO_x, x ≤ 0.08, assisted Ag/TTO_x/p-Si metal– oxide– semiconductor (MOS) structures. The leakage current density was found minimum, for the films annealed at 800 °C, for all the prepared TTO_x films, x ≤ 0.08. The minimum leakage current density 1.6 × 10^?8 A/cm², at 3.5 × 10⁵ V/cm electric field, was observed for x = 0.03, annealed at 800 °C, among the prepared compositions. The prepared TTO_0.03 films, annealed at 700 °C show maximum dielectric constant 39, at 1 MHz. The optical parameters, viz., refractive index (n), extinction coefficient (k), and optical band gap (E_g) of the films, with x = 0.03, prepared on quartz substrates, were determined from their optical transmittance plots. The values of n and k of the crystalline films were observed increasing from 2.123 to 2.143, and 0.099 to 0.130, respectively, at 550 nm wavelength; and E_g decreasing from 3.95 to 3.89 eV with the increasing annealing temperature, from 600 to 800 °C. Ohmic emission, in the lower electric field; Schottky and space-charge- limited current conduction mechanisms, in the intermediate to higher electric fields, were generally envisaged from the current-voltage characteristics in the prepared Ag/TTO_0.03/p-Si structures.     

Influence of substrate temperature on the microstructure of YSZ films and their application as the insulating layer of thin film sensors for harsh temperature environments

Thin film sensors are employed to monitor the health of hot-section components of aeroengine intelligence (for instance, blades), and electrical insulating layers are needed between the metal components and thin film sensors. For this purpose, the electrical insulation characteristics of an yttria-stabilized zirconia (YSZ)/Al₂O₃ multilayer insulating structure were investigated. First, YSZ thin films were deposited by DC reactive sputtering at various substrate temperatures, and the microstructural features were investigated by scanning electron microscopy and X-ray diffraction. The results indicate that the micromorphology of the YSZ thin film gradually became denser with increasing substrate temperature, and no new phases appeared. The compact and uniform topography of the YSZ thin film improved the insulation properties of the multilayer insulating structure and enhanced the adhesion of the thin film sensors. In addition, the electrical insulation properties of the YSZ/Al₂O₃ multilayer insulating structure were evaluated via insulation resistance tests from 25 to 800 °C, in which the YSZ thin film was deposited at 550 °C. The results show that the insulation resistance of the multilayer structure increased by an order of magnitude compared with that of the conventional Al₂O₃ insulating layer, reaching 135 kΩ (5.1 × 10^?6 S/m) at 800 °C. Notably, the insulation resistance was still greater than 75 kΩ after annealing at 800 °C for 5 h. Finally, the shunt effect of the YSZ/Al₂O₃ multilayer insulating structure was estimated using a PdCr thin film strain gauge. The relative resistance error was 0.24%, which demonstrates that the YSZ/Al₂O₃ multilayer insulating structure is suitable for thin film sensors.     

A new sol-gel route to prepare dense Al2O3 thin films

Anew sol-gel route has been applied to synthetize dense Al₂O₃thin films from aluminum isopropoxide (Al(OPri)₃)as raw precursor material. The results show that, in the solution, acetylacetone (AcAc) and aluminum form a complex compound which effectively suppresses the growth of colloidal particles and makes the sol very stable. Al₂O₃thin films fabricated by spin-coating method and calcined at 500 °C for 3 h possess an amorphous structure and exhibit a highly homogeneous surface texture without evidence of holes or cracks throughout the film. Moreover, the prepared films display a low leakage current and a high transmittance. This new sol-gel route appears to be a highly promising method to synthetize dense Al₂O₃ thin films from Al(OPrⁱ)₃, and could provide a wide range of optical and electric applications.     

Fabrication of Ce:(Gd2Y)(Ga3Al2)O12 scintillator ceramic by oxygen-atmosphere sintering and hot isostatic pressing

A Ce-doped (Gd₂Y)(Ga₃Al₂)O₁₂ ceramic with good performance was fabricated by sintering in an oxygen atmosphere and hot isostatic pressing. The microstructure as well as the optical and scintillation characteristics of the ceramic was investigated. The ceramic exhibited a high transmittance of 78% in the range of 500–800 nm. The radioluminescence intensity of the ceramic reached up to 30 times that of a bismuth germinate single crystal, and the light yield within 750 ns shaping time was approximately 25800 photons/MeV under ¹³⁷Cs γ-ray irradiation.     

Fabrication and characterization of highly transparent ZrO2-doped Tm2O3 ceramics

Highly transparent polycrystalline Tm₂O₃ ceramics were successfully fabricated by vacuum sintering at temperatures from 1650 to 1850 °C for 8 h using commercial Tm₂O₃ and ZrO₂ (1 at%) powders as starting materials. It is the first time that ZrO₂ was reported as a sintering additive to prepare Tm₂O₃ transparent ceramics. The effects of sintering temperature on the optical transmittance and microstructure of Tm₂O₃ transparent ceramics were studied. The desired Tm₂O₃ ceramics with relative density of 99.8% and an average grain size of approximately 9.7 μm were obtained at 1800 °C and the in-line transmittance reached 75% at 880 nm and fluctuated around 80% from 2100 to 2400 nm, respectively. This study demonstrated that Tm₂O₃ transparent ceramics with higher in-line transmittance and smaller grain size could be prepared by using ZrO₂ as sintering additive at a relatively lower vacuum sintering temperature compared to those already reported in open literatures.     

Microwave dielectric properties of the BaTi5O11 thin film grown on the poly-Si substrate using rf magnetron sputtering

BaTi₅O₁₁ thin films were grown on the poly-Si/SiO₂/Si substrate using rf magnetron sputtering. The BaO-TiO₂ thin film deposited on the poly-Si substrate had an amorphous phase even though the growth temperature was high at 550 °C. The amorphous film was crystallized into the BaTi₅O₁₁ phase when the film was post annealed above 800 °C. The post annealing temperature is one of the most important factors for the formation of the crystalline BaTi₅O₁₁ thin film. The homogeneous BaTi₅O₁₁ thin film was obtained when the film was grown at 550 °C and rapid thermal annealed (RTA) at 900 °C for 3 min. The dielectric constant (ɛ_r) of the BaTi₅O₁₁ film measured at 100 kHz was about 35 and the dissipation factors of all the films were smaller than 4.0%. The dielectric properties of the BaTi₅O₁₁ thin film were also measured at microwave frequencies. For the BaTi₅O₁₁ thin film grown at 550 °C and RTA at 900 °C for 3 min, the ɛ_r of 34–30 and dielectric loss of 0.025 ± 0.005 were obtained at 1–6 GHz.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

The suppression of dark current for achieving high-performance Ga2O3 nanorod array ultraviolet photodetector

Gallium oxide (Ga₂O₃) is a promising candidate for next-generation solar-blind photodetectors (PDs) because of its large bandgap of 4.9 eV. Its single-crystal nanorod structure improves its photoelectric performance, which promotes carrier transformation and separation. However, Ga₂O₃ nanorods fabricated by the hydrothermal method have many oxygen vacancies, which largely enhance the dark current and reduce the on/off ratio of PDs, restricting application of such devices. Therefore, in this paper, dual strategies are applied to reduce the dark current of a metal–semiconductor–metal-structured Ga₂O₃ nanorod PD fabricated by the hydrothermal method. Through these dual strategies, which include annealing treatment and the application of a polymethyl methacrylate (PMMA) coating, the dark current of the PD is reduced from 1.34 × 10^?7 to 2.04 × 10^?9 A at 1 V, resulting in the on/off ratio of the PD reaching as high as 3.24 × 10⁴. Besides, the responsivity and detectivity of the device reach 1.73 A/W and 2.53 × 10¹² Jones respectively, which represents better performance than those of other reported Ga₂O₃ nanorod array PDs. Results have shown that the new strategy adopted can greatly improve the performance of Ga₂O₃-based ultraviolet photodetectors.     

Effects of element chemical states and grain orientation growth of ITO targets on photoelectric properties of the film

A study was carried out to compare element chemical states and grain orientation growth between two ITO targets, which were respectively sintered at 1560 °C (target A#) and 1600 °C (target B#). The lower sintering temperature can be beneficial to increase mass content ratio of In₂O₃ to SnO₂, reduce the production of Sn²⁺ ions and the component of O-In as well as increase oxygen holes, and can also promote grain orientation growth of In₂O₃ and In₄Sn₃O₁₂ phase. Three groups of ITO films were deposited at 230 °C using these targets to investigate the effects of sputtering parameters on the photoelectric properties of ITO films. Under different sputtering pressures, the sheet resistance for target A# has higher sensitivity to low O₂ flow, while target B# displays higher sensitivity to high O₂ flow. In the case of sputtering pressure of 0.5 Pa, ITO films for target A# displays the highest visible transmittance. In addition, annealing process could decrease the sheet resistance and improve the transmittance of ITO films because of its effect on the crystallinity and surface morphology of ITO films.     

Transparent conductive oxide films mixed with gallium oxide nanoparticle/single-walled carbon nanotube layer for deep ultraviolet light-emitting diodes

We propose a transparent conductive oxide electrode scheme of gallium oxide nanoparticle mixed with a single-walled carbon nanotube (Ga₂O₃ NP/SWNT) layer for deep ultraviolet light-emitting diodes using spin and dipping methods. We investigated the electrical, optical and morphological properties of the Ga₂O₃ NP/SWNT layers by increasing the thickness of SWNTs via multiple dipping processes. Compared with the undoped Ga₂O₃ films (current level 9.9 × 10^-9 A @ 1 V, transmittance 68% @ 280 nm), the current level flowing in the Ga₂O₃ NP/SWNT increased by approximately 4 × 10⁵ times and the transmittance improved by 9% after 15 times dip-coating (current level 4 × 10^-4 A at 1 V; transmittance 77.0% at 280 nm). These improvements result from both native high transparency of Ga₂O₃ NPs and high conductivity and effective current spreading of SWNTs.     

Annealing temperature-dependent structural and electrical properties of (Ta2O5)1-x - (TiO2)x thin films,x ≤ 0.11

(Ta₂O₅)_1-x- (TiO₂)_x (TTO_x) thin films, with x = 0, 0.03, 0.06, 0.08, and 0.11, were deposited using magnetron direct current (DC) sputtering method onto the P/boron-silicon (1 0 0) substrates by varying areas of Tantalum and Titanium metallic targets, in oxygen environment at ambient temperature. The as-deposited thin films were annealed at temperatures ranging from 500 to 800 °C. Generally, the formation of the Ta₂O₅ structure was observed from the X-ray diffraction measurements of the annealed films. The capacitance of prepared metal– oxide– semiconductor (MOS) structures of Ag/TTO_x/p-Si was measured at 1 MHz. The dielectric constant of the deposited films was observed altering with varying composition and annealing temperature, showing the highest value 71, at 1 MHz, for the TTO_x films, x = 0.06, annealed at 700 °C. With increasing annealing temperature, from 700 to 800 °C, the leakage current density was observed, generally decreasing, from 10^?5 to 10^?8 A cm^?2, for the prepared compositions. Among the prepared compositions, films with x = 0.06, annealed at 800 °C, having the observed value of dielectric constant 48, at 1 MHz; and the leakage current density 2.7 × 10^?8 A cm^?2, at the electric field of 3.5 × 10⁵ V cm^?1, show preferred potential as a dielectric for high-density silicon memory devices.     

Electrical humidity response of sol–Gel processed undoped and alkali-doped TiO2–Al2O3 thin films

Al₂O₃-TiO₂ thin films were prepared by a sol–gel processing. Sols were prepared having different TiO₂/Al₂O₃ molar ratios, i.e., 9:1, 8:2, and 6:4, without and with the addition of 10 at% of K ions. The films were prepared by dipping the substrates (silicon wafers, alkali-free glass or alumina with comb-type Au electrodes) in the sols. The films were fired in air for 1 h at 300, 500, 650 and 800°C. The films were amorphous, at any composition, up to the firing temperature of 500°C. Crystallization of the films was inhibited by larger contents of Al₂O₃ and K. The humidity-sensitive electrical properties of the thin films were studied using d.c. and a.c. measurements. The addition of K dramatically improved the relative humidity response of the films.     

Characterization of Bi2O3 thin films for doping photoluminescent Er3+ ions

Undoped and Er³⁺-doped Bi₂O₃ thin films were sputter-deposited on Si(100) substrates. Sufficiently oxidized Bi₂O₃ films with refractive indices between 2.17?2.23 were obtained at a wavelength of 633 nm; these values are comparable to those of bulk Bi₂O₃ crystals. While the film composition was stable for deposition temperatures between room temperature (RT) and 450 °C, the refractive index steeply decreased above 450 °C and reached 1.4 at 600 °C. The lowering of the optical transmittance spectra indicated aggregation of metallic Bi and darkening of the film. All films exhibited X-ray diffraction patterns of α-Bi₂O₃. The direct and indirect bandgap energies derived from the Tauc plots were 3.4–3.7 eV and 1.9–2.5 eV, respectively, depending on the O₂ flow rate and deposition temperature. Upon excitation of Er³⁺-doped Bi₂O₃ films at 532 nm, Er³⁺ emissions peaking at 1537 and 1541 nm appeared, and the photoluminescence spectra included fine structures reflecting crystal-field splitting. Resonant excitation of Er³⁺ 4f levels and indirect excitation via the defect levels of Bi₂O₃ followed by energy transfer to Er³⁺ contributed to the emission. The films deposited at RT with Er concentrations of 2 at.% had the emission intensity of Er³⁺, but concentration quenching strongly suppressed the Er³⁺ emission because the doped Er³⁺ ions stayed inside the Bi₂O₃ crystals. At deposition temperatures above 400 °C, the concentration quenching was mitigated possibly because out-diffusion of Er³⁺ ions reduced the effective number of Er³⁺ ions in the Bi₂O₃ crystalline domains.