Catalytic growth and characterization of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

β-Ga₂O₃ nanowires have been synthesized using Ga metal and H₂O vapor at 800 °C in the presence of Ni catalyst on the substrate. Remarkable reduction of the diameter and increase of the length of the Ga₂O₃ nanowires are achieved by separation of Ga metal and H₂O vapor before they reach the substrate. Transmission electron microscopy analyses indicate that the β-Ga₂O₃ nanowires possess a single-crystalline structure. Photoluminescence measurements show two broad emission bands centered at 290 nm and 390 nm at room temperature. Received: 27 June 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +886-6/234-4496, E-mail: wujj@mail.ncku.edu.tw     

Fabrication and characteristics of N-doped β-Ga2O3 nanowires

Undoped and N-doped  β-Ga₂O₃ nanowires (NWs), using NH₃ as the dopant source, were successfully fabricated by the CVD method on Si substrates. The microstructure, morphology, element composition and carrier concentration of the samples were characterized by XRD, SEM, TEM, and EDX. The results revealed that well-aligned undoped NWs were perpendicular to the substrates. Comparing with undoped β-Ga₂O₃ NWs, the morphology of N-doped β-Ga₂O₃ NWs showed a significant change and they were randomly oriented relative to the substrates. As the NH₃ flow was increased, the microstructure of the sample presented a lot of branched-like and trumpet-shaped structures. Simultaneously, a rougher surface has been attained. PL spectrum measurements showed that N-doped β-Ga₂O₃ NWs had ultraviolet (UV), blue and green emission peaks because of the N-doped process. Furthermore, micro-scale undoped β-Ga₂O₃/N-doped β-Ga₂O₃ homojunction structures were fabricated. The I–V property of the fabricated N-doped β-Ga₂O₃ microwire and β-Ga₂O₃/N-doped β-Ga₂O₃ microwire homojunction were compared. I–V results testified that N-doped β-Ga₂O₃ NWs showed p-type conductivity.     

Broadband infrared luminescence from transparent glass–ceramics containing Ni<Superscript>2+</Superscript>-doped <Emphasis Type="BoldItalic">β</Emphasis> -Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals

Transparent Ni²⁺-doped β-Ga₂O₃ glass–ceramics were synthesized. The nanocrystal phase in the glass–ceramics was identified to be β-Ga₂O₃ and its size was about 3.6 nm. It was confirmed from the absorption spectra that the ligand environment of Ni²⁺ ions changed from the trigonal bi-pyramid fivefold sites in the as-cast glass to the octahedral sites in the glass–ceramics. The broadband infrared emission centering at 1270 nm with full width at half maximum (FWHM) of more than 250 nm was observed. The fluorescence lifetime was about 1.1 μs at room temperature. The observed infrared emission could be attributed to the ³ T _2g (³ F )→³ A _2g (³ F ) transition of octahedral Ni²⁺ ions. It is suggested that the Ni²⁺-doped transparent β-Ga₂O₃ glass–ceramics with broad bandwidth and long lifetime have a potential as a broadband amplification medium. PACS 42.70.-a; 42.70.Ce; 81.40.Tv     

Synthesis and characterization of β-Ga2O3 nanorods

A novel method was applied to prepare β-Ga₂O₃ nanorods. In this method, β-Ga₂O₃ nanorods have been successfully synthesized on Si(1 1 1) substrates through annealing sputtered Ga₂O₃/Mo films under flowing ammonia at 950 °C in a quartz tube. The as-synthesized nanorods are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR). The results show that the nanorod is single-crystalline Ga₂O₃ with monoclinic structure. The β-Ga₂O₃ nanorods are straight and smooth with diameters in the range of 200-300 nm and lengths typically up to several micrometers. The growth process of the β-Ga₂O₃ nanorods is probably dominated by conventional vapor-solid (VS) mechanism.     

Multinuclear MAS NMR Investigation of Sol-Gel and Ball-Milled Nanocrystalline Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

⁷¹Ga magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to characterize the structural evolution of nanocrystalline Ga₂O₃ samples prepared by sol-gel and ball-milling techniques. ²⁹Si and ²⁷Al MAS NMR have also been used to characterize silica and alumina Zener pinning phases. ⁷¹Ga NMR parameters are reported for the α- and β-Ga₂O₃ phases, and more tentatively for the δ-Ga₂O₃ phase. By simulating the octahedrally coordinated gallium NMR line of β-Ga₂O₃ using Gaussian distributions in χ_Q, the extent of disorder in the Ga₂O₃ crystallites has been quantified. The ball-milled samples contain much more inherent disorder than the sol-gel samples in the nano-phase, which was observed from simulations of the ⁷¹Ga MAS NMR spectra. The silica pinning phase produced highly crystalline and densely aggregated nanocrystalline Ga₂O₃, as well as the smallest nanocrystal sizes. Authors' address: Mark E. Smith, Department of Physics, University of Warwick, Coventry CV4 7AL, UK     

Multilayer based interferential-plasmonic structure: metal cluster 3D grating combined with dielectric mirror

This paper reports strong deep-ultraviolet and visible photoluminescence (PL) of the GaN nanoparticles depending on the conversion time from Ga₂O₃ to GaN. Monoclinic β-Ga₂O₃ nanoparticles with a diameter of approximately 2.5–5.0 nm were fabricated prior to conversion to GaN. The Ga₂O₃ nanoparticles were converted to GaN in the tube furnace with NH₃ flow at 900°C for 10, 30, 60, and 120 min. Depending on the conversion time, the converted GaN nanoparticle size became bigger with the increase of the conversion time. The characteristic GaN x-ray diffraction (XRD) peaks became bigger when the conversion time increased. The PL intensity drastically increased with the increase of the conversion time. The spectra profile completely overlapped for GaN samples converted for 10, 30, and 60 min, with the maximum peak at 390 nm. However, the PL spectrum slightly narrowed and red-shifted with the maximum peak at 400 nm for the GaN nanoparticles converted for 120 min.     

Optical characteristics of highly ordered gallium oxide nano-islands on GaAs

A periodic array of Ga oxide islands was obtained by annealing the highly ordered Ga nano-droplets on GaAs surface at 400°C under an oxygen atmosphere for 7 hours. These Ga oxides are a mixture of α-Ga₂O₃ and β-Ga₂O₃ confirmed by Raman spectroscopy study. Enhanced optical transmission of GaAs with such ordered Ga oxide nano-islands was obtained. Both dielectric and dimensional confinement effects were considered in analysis of the electromagnetic characteristics of the nanostructured materials. Finite-difference time-domain method was used to numerically study the light transmission through the patterned Ga oxide on GaAs surface. Based on the calculated results, the light transmission enhancement is attributed to the formation of the ordered nano Ga oxides.     

Fabrication and characterization of β-Ga2O3 optical nanowires

Monoclinic gallium oxide (β-Ga₂O₃) nanowires with lengths of tens of micrometers and diameters ranging from 100 to 250 nm are synthesized using simple physical evaporation based on vapor–liquid–solid (VLS) mechanism. The as-synthesized straight β-Ga₂O₃ nanowires show excellent diameter uniformity and sidewall smoothness, making them suitable for optical wave-guiding. Light from a fiber taper is launched into the nanowire by means of evanescent coupling. Measured propagation loss of the nanowire at 633 nm wavelength is on the order of 10 dB/mm. Favorable mechanical strength of these nanowires for elastic bending is also observed. Our results suggest that β-Ga₂O₃ nanowires are promising building blocks for micro- and nanophotonic circuits and devices.     

Synthesis of <Emphasis Type="Italic">β</Emphasis>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires as a broadband emitter

High-density monoclinic β-Ga₂O₃ nanowires were synthesized by a vapor transport method with controlled ambient oxygen. The structures and morphology were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM). X-ray diffraction and HR-TEM analysis indicate that the as-grown β-Ga₂O₃ nanowires are single crystals with monoclinic structure. Intense four-band emissions covering the range from ultraviolet (UV) to visible were observed in photoluminescence (PL) spectra at room temperature. The main emission bands of deep blue (3.04 eV) to green (2.37 eV) for β-Ga₂O₃ nanowires were adjusted by controlling the partial pressure of oxygen. This work demonstrates a low-cost and facile process for optoelectronics applications.     

Photoluminescence and Photoacoustic Spectroscopies of Fe3+ in the LiGa5O8–LiGaSiO4–Li5GaSi2O8 System

This report is devoted to the study of the low and room temperature photoluminescence and photoacoustic spectroscopy of the Fe³⁺ impurity ion in the LiGa₅O₈–LiGaSiO₄–Li₅GaSi₂O₈ system. The sample was obtained by solid-state reaction between β-Ga₂O₃, Li₂CO₃, SiO₂ and appropriated quantities of Fe₂O₃. It was investigated by X-ray diffraction to determine the formed phases and through photoluminescence, excitation and photoacoustic spectroscopy measurements. The broad absorption and emission bands in the visible and near-infrared spectral regions presented by that system constitute the motivation for this study. More specifically, the luminescence occurs over a large interval of wavelengths, between 400 nm and 800 nm.     

氧流量对热蒸发CVD法生长β-Ga2O3纳米材料的结构及发光特性的影响

用热蒸发CVD法制备了β-Ga₂O₃纳米材料, 并用光致发光(PL)方法研究了其发光特性. Ｘ射线衍射分析显示, 产物为单斜结构的β-Ga₂O₃. 扫描电子显微镜测试表明: 在较小氧流量条件下制备的产物为β-Ga₂O₃纳米带, 宽度小于100nm, 长度有几微米; 较大氧流量时制备出β-Ga₂O₃纳米晶粒结构, 晶粒尺度在80—15 关键词： 光致发光 氧流量 纳米结构 2O₃')" href="#">Ga₂O₃     

Synthesis and characterization of dentate-shaped β -Ga2O3 nano/microbelts via a simple method

Dentate-shaped β-Ga₂O₃ nano/microbelts were synthesized successfully via chemical vapor deposition without any other reaction or catalyzer material. The morphology and crystal structure were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) analytic technologies, respectively. The growth mechanism of the products was discussed assisted by the SEM and TEM images. The photoluminescence properties of the β-Ga₂O₃ nano/microbelts have been investigated with a He–Cd laser (325 nm) at room temperature. PACS 81.05.Hd; 81.07.Bc; 81.10.Bk; 81.15.Gh; 81.70.Fy     

Growth of β-gallium oxide nanostructures by the thermal annealing of compacted gallium nitride powder

Various β-gallium oxide (β-Ga₂O₃) nanostructures such as nanowire, nanobelt, nanosheet, and nanocolumn were synthesized by the thermal annealing of compacted gallium nitride (GaN) powder in flowing nitrogen. We suggest that Ga₂O₃ vapor might be formed by the reaction of oxygen with the gaseous Ga formed by GaN decomposition. The Ga₂O₃ vapor diffuses into voids derived by compacting GaN powder and is supersaturated there, resulting in the growth of Ga₂O₃ nanostructures via the vapor–solid (VS) mechanism. Ga₂O₃ plate-like hillocks and nanostructures were also grown on the surface of a c-plane sapphire placed on the GaN pellet.     

Growth of β-Ga2O3 nanorods by ammoniating Ga2O3/V thin films on Si substrate

This paper reports that/3-Ga2O3 nanorods have been synthesized by ammoniating Ga2O3 films on a V middle layer deposited on Si（111） substrates. The synthesized nanorods were confirmed as monoclinic Ga2O3 by x-ray diffraction,Fourier transform infrared spectra. Scanning electron microscopy and transmission electron microscopy reveal that the grown β-Ga2O3 nanorods have a smooth and clean surface with diameters ranging from 100 nm to 200 nm and lengths typically up to 2μm. High resolution TEM and selected-area electron diffraction shows that the nanorods are pure monoclinic Ga2O3 single crystal. The photoluminescence spectrum indicates that the Ga2O3 nanorods have a good emission property. The growth mechanism is discussed briefly.     

Effect of switching ultrasonic amplitude in preparing a hybrid of fullerene (C60) and gallium oxide (Ga2O3)

In this study, we proposed ‘switching ultrasonic amplitude’ as a new strategy of applying ultrasonic energy to prepare a hybrid of buckminsterfullerene (C₆₀) and gallium oxide (Ga₂O₃), C₆₀/Ga₂O₃. In the proposed method, we switched the ultrasonic amplitude from 25% to 50% (by 5% amplitude per 10 min, within 1 h of ultrasonic irradiation) for the sonochemical treatment of a heterogeneous aqueous mixture of C₆₀ and Ga₂O₃ by a probe-type ultrasonic horn operating at 20 kHz. We found that compared to the conventional techniques associated with high amplitude oriented ultrasonic preparation of functional materials, switching ultrasonic amplitude can better perform in preparing C₆₀/Ga₂O₃ with respect to avoiding titanium (Ti) as an impurity generating from the tip erosion of a probe-type ultrasonic horn during high amplitude ultrasonic irradiation in an aqueous medium. Based on SEM/EDX analysis, the quantity of Ti (wt.%) in C₆₀/Ga₂O₃ prepared by the proposed technique of switching ultrasonic amplitude was found to be 1.7% less than that prepared at 50% amplitude of ultrasonic irradiation. The particles of C₆₀/Ga₂O₃ prepared by different modes of amplitude formed large (2–12 μm) aggregates in their solid phase.Whereas, in the aqueous medium, they were found to disperse in their nano sizes. The minimum particle size of the as-synthesized C₆₀/Ga₂O₃ in an aqueous medium prepared by the proposed method of switching ultrasonic amplitude reached to approximately 467 nm. Comparatively, the minimum particle sizes were approximately 658 nm and 144 nm, using 25% and 50% amplitude, respectively. Additionally, Ga₂O₃ went under hydration during ultrasonic irradiation. Moreover, due to the electron cloud interference from C₆₀ in the hybrid structure of C₆₀/Ga₂O₃, the vibrational modes of Ga₂O₃ were Raman inactive in C₆₀/Ga₂O₃.     

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al³⁺-doped γ-Ga₂O₃ nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (D_av = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al₂O₃ or Al deposition. Thus, ultrafine Al³⁺-doped γ-Ga₂O₃ NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga₂O₃-based NPs were 59 nm and 181 m²/g, respectively. Compared with γ-Ga₂O₃, the optical bandgap of the Al³⁺-doped γ-Ga₂O₃ NPs was broadened, and the thermal stability improved, indicating Al³⁺-doping into the γ-Ga₂O₃ lattice. However, the lattice constant of γ-Ga₂O₃ was almost unchanged with or without Al³⁺-doping. Al³⁺ was introduced into the defect sites of Ga³⁺, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.     

Epitaxial gallium oxide on a SiC/Si substrate

Well-textured gallium oxide β-Ga₂O₃ layers with a thickness of ~1 μm and a close to epitaxial layer structure were grown by the method of chloride vapor phase epitaxy on Si(111) wafers with a nano-SiC buffer layer. In order to improve the growth, a high-quality silicon carbide buffer layer ~100 nm thick was preliminarily synthesized by the substitution of atoms on the silicon surface. The β-Ga₂O₃ films were thoroughly investigated using reflection high-energy electron diffraction, ellipsometry, X-ray diffraction, scanning electron microscopy, and micro-Raman spectroscopy. The investigations revealed that the films are textured with a close to epitaxial structure and consist of a pure β-phase Ga₂O₃ with the (\(\overline 2 01\)) orientation. The dependence of the dielectric constant of epitaxial β-Ga₂O₃ on the photon energy ranging from 0.7 to 6.5 eV in the isotropic approximation was measured.     

Ultrafine α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles grown in confinement of in situ self-formed “cage” and their superior adsorption performance on arsenic(III)

Without the addition of surfactants or templates, ultrafine α-Fe₂O₃ nanoparticles were successfully synthesized by a solvent thermal process at low temperature. During the synthesis, in situ self-formed “cage” of crystallized NaCl confined the growth of α-Fe₂O₃ nanoparticles in both the precipitation and solvent thermal processes, resulting in the creation of well-crystallized α-Fe₂O₃ nanoparticles with an average particle size about 4–5 nm and a high-specific surface area of ~162 m²/g. High resolution TEM investigations provided clear evidences of the in situ self-formation of NaCl “cage” during the synthesis and its confinement effect on the growth of α-Fe₂O₃ nanoparticles. The superior performance of these α-Fe₂O₃ nanoparticles on the adsorption of arsenite(III) (As) from aqueous environment was demonstrated with both lab-prepared and natural water samples at near neutral pH environment when compared with previously reported removal effects of As(III) by Fe₂O₃. This unique approach may also be utilized in the synthesis of other ultrafine metal oxide nanoparticles for a broad range of technical applications.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

Electrical properties and emission mechanisms of Zn-doped β-Ga2O3 films

We study the electrical properties and emission mechanisms of Zn-doped β-Ga₂O₃ film grown by pulsed laser deposition through Hall effect and cathodoluminescence which consist of ultraviolet luminescence (UV), blue luminescence (BL) and green luminescence (GL) bands. The Hall effect measurements indicate that the carrier concentration increases from 7.16×10¹¹ to 6.35×10¹² cm⁻³ with increasing a nominal Zn content from 3 to 7 at%. The UV band at 272 nm is not attributed to Zn dopants and ascribed as radiative electron transition from conduction band to a self-trapped hole while the BL band is attributable to defect level related to Zn dopant. The BL band has two emission peaks at 415 and 455 nm, which are ascribed to the radiative electron transition from oxygen vacancy (V_O) to valence band and recombination of a donor–acceptor pair (DAP) between V_O donor and Zn on Ga site (Zn_Ga) acceptor, respectively. The GL band is attributed to the phonon replicas’ emission of the DAP. The acceptor level of Zn_Ga is estimated to be 0.26 eV above the valence band maximum. The transmittance and absorption spectra prove that the Zn-doped β-Ga₂O₃ film is a dominantly direct bandgap material. The results of Hall and cathodoluminescence measurements imply that the Zn dopant in β-Ga₂O₃ film will form an acceptor Zn_Ga to produce p-type conductivity.