Electrochemically deposited gallium oxide nanostructures on silicon substrates

We report a synthesis of β-Ga₂O₃ nanostructures on Si substrate by electrochemical deposition using a mixture of Ga₂O₃, HCl, NH₄OH, and H₂O. The presence of Ga³⁺ ions contributed to the deposition of Ga₂O₃ nanostructures on the Si surface with the assistance of applied potentials. The morphologies of the grown structures strongly depended on the molarity of Ga₂O₃ and pH level of electrolyte. β-Ga₂O₃ nanodot-like structures were grown on Si substrate at a condition with low molarity of Ga₂O₃. However, Ga₂O₃ nanodot structures covered with nanorods on top of their surfaces were obtained at higher molarity, and the densities of nanorods seem to increase with the decrease of pH level. High concentration of Ga³⁺ and OH^- ions may promote the reaction of each other to produce Ga₂O₃ nanorods in the electrolyte. Such similar nature of Ga₂O₃ nanorods was also obtained by using hydrothermal process. The grown structures seem to be interesting for application in electronic and optoelectronic devices as well as to be used as a seed structure for subsequent chemical synthesis of GaN by thermal transformation method.     

Recent progress of Ga2O3-based gas sensors

In recent years, gas sensors fabricated from gallium oxide (Ga₂O₃) materials have aroused intense research interest due to the superior material properties of large dielectric constant, good thermal and chemical stability, excellent electrical properties, and good gas sensing. Over the past decades, Ga₂O₃-based gas sensors experienced rapid development. The long-term stable Ga₂O₃-based gas sensors for detecting oxygen and carbon monoxide have been commercialized and renowned with extremely good gas sensing characteristics. Recent pioneering studies also exhibit that the Ga₂O₃-based gas sensors possess great potentials in applications of detecting nitrogen oxides, hydrogen, volatile organic compounds and ammonia gases. This article presents recent advances in gas sensing mechanism, device performance parameters, influence factors, and applications of Ga₂O₃-based gas sensors. The impacts of influence factors, doping, material structure and device structure on the performance of gas sensors are discussed in detail. Finally, a brief overview of challenges and opportunities for the Ga₂O₃-based gas sensors is presented.     

Plasma etching properties of various transparent ceramics

The etching properties of four types of transparent ceramics: sapphire (a single crystalline α-Al₂O₃), γ-AlON (γ-aluminum oxynitride), Mg-spinel (MgAl₂O₄), and Y₂O₃, as well as a polycrystalline opaque Al₂O₃ were examined using an inductively coupled plasma etcher under an incident plasma power of 2,000 W for up to 3 h. The transparent γ-AlON and opaque Al₂O₃ showed significant surface morphological changes, whereas sapphire, Mg-spinel, and Y₂O₃ revealed a relatively smooth surface upon etching. However, direct correlation between the surface morphological change and the degree of etching could not be drawn because sapphire showed a uniform surface etching despite its significant mass loss. Even though Y₂O₃ was found to be more plasma-resistant than Al₂O₃, overall, Mg-spinel was the most feasible transparent material for monitoring window application in a semiconductor processing chamber because of its minimal degree of erosion (≤0.4g/m²) and the transmittance change (≤2%) upon 3 h of fluorocarbon (CF₄) plasma etching.     

Effect of ZnO and TiO2 doping on the sintering behavior of Y2O3 ceramics

Full densification of Y₂O₃ is challenging and requires a very high sintering temperature (above 1700 °C). In this study, the effect of ZnO and TiO₂ dopants on its densification was investigated, showing that both dopants lowered the sintering temperature and improved the process. Moreover, ZnO promoted the grain growth, while TiO₂ inhibited it; hence, the ZnOTiO₂ co-doping and the change in the ZnO/TiO₂ ratio allowed the control of the sintered body microstructure while maintaining high densification. Since Y₂O₃ has a higher plasma erosion resistance than conventional Si-based materials, the plasma dry etching resistance of the sintered Y₂O₃ was also evaluated and found superior due to the improved densification and controlled grain size of the doped samples.     

Processing map to control the erosion of Y2O3 in fluorine based etching plasmas

Due to the increasing number of applications for ceramic components in reactive etching processes, the interest in the specific erosion behavior of highly etch-resistant materials like yttrium oxide (Y₂O₃) has increased in the past years. Despite the large number of investigations already existing in this field, a more general understanding of the erosion mechanisms still lacks due to the limited comparability of these investigations. The huge difference in the kind of etching setups, processing parameters (bias voltage and plasma gas composition), and sample microstructures prevented consistent conclusions so far. To achieve a more general understanding, this study investigates the erosion behavior Y₂O₃ under a broad spectrum of plasma etching parameters. Therefore, the bias voltage is increased from 50 to 300 V and the plasma gas composition is gradually changed from Ar-rich to CF₄-rich compositions. This systematic approach allows to directly correlate the morphology changes caused by plasma erosion with the related plasma etching parameters and enables to better understand their influence on the depth of physical and chemical interactions, surface damage, and etching rate. We discovered three distinct erosion regimes, which exhibit specific erosion characteristics. Using these observations, a schematic processing map for Y₂O₃ was developed, which could help to estimate the severity of the erosion attack dependent on the processing parameters.     

Effects of chemical etching on structure and properties of Y0.5Gd0.5Ba2Cu3O7-z coated conductors

Corrosion resistance is a crucial property to achieve successful superconducting joints of Y_0.5Gd_0.5Ba₂Cu₃O_7-z (YGdBCO) coated conductors (CCs). Cu and Ag metallic layers need to be fully removed from the area of conductor to be joint to allow for a superconducting path across the joint. Therefore, when using a wet etching process to remove the metallic layers, the joint performance can be significantly influenced by the etching conditions. The effects of chemical etching with ammonia water and hydrogen peroxide mixture on crystal structure, surface microstructure and critical current (I_c) of YGdBCO CCs were systematically investigated. We found the set of etching parameters that does not affect conductor performance, leaving the I_c of the YGdBCO conductor unchanged upon etching. However, when the etching conditions are not optimal, decrease in I_c was found and the underlying reasons driving the degradation were investigated. Raman spectroscopy and XRD analysis indicated that the reduced I_c is mainly due to oxygen deficiency in the YGdBCO crystal lattice.     

Passivation effect on the surface characteristics and corrosion properties of yttrium oxide films undergoing SF6 plasma treatment

This study investigates the structures, compositions and fluorocarbon-plasma etching behaviors of yttrium oxyfluoride (YOF) passivation films fabricated on sputter-deposited yttrium oxide (Y₂O₃) by high-density SF₆ plasma irradiation. High-resolution transmission electron microscopy and nano-beam electron diffraction confirmed a YOF passivation film containing multiple phases of (104) and (006) crystal planes was formed on the fluorinated Y₂O₃ surface. X-ray photoelectron spectroscopy revealed few changes in the chemical compositions and surface roughness of the YOF passivation film after fluorocarbon plasma etching, confirming the chemical stability of the SF₆ plasma-treated Y₂O₃ sample. The etching depth was ～20% lower on the SF₆ plasma-treated Y₂O₃ film than on the commercial Y₂O₃ coating. These results showed that the SF₆ plasma-treated Y₂O₃ films have an excellent erosion resistance properties compared to the commercial Y₂O₃ coatings.     

Polymer nanofiber‐templated fabrication and characterization of gallium oxide nanofibers consisting of granular nanoparticles

Gallium oxide (β‐Ga₂O₃) is an interesting semiconductor that has a wide bandgap and can be used as an optoelectronic material in flat‐panel displays, solar energy conversion devices and optical limiters for UV light. However, it is difficult to fabricate and process Ga₂O₃ nanofibers for actual optoelectronic applications. When the excellent processability of polymeric materials is introduced into the inorganic nanofiber fabrication process, this limitation can be easily overcome. The aim of the research reported was to prepare granular Ga₂O₃ nanofibers utilizing an electrospun polyacrylonitrile nanofiber template combined with sol‐gel technology. Ga₂O₃ nanofibers were successfully fabricated by electrospinning a solution of polyacrylonitrile mixed with gallium nitrate and subsequent calcination. The surface and bulk morphologies of the calcined nanofibers investigated using field‐emission scanning electron microscopy and transmission electron microscopy (TEM) indicated that Ga₂O₃ nanofibers were constructed by the fusion of gallium oxide nanoparticles. TEM bright‐field images combined with selected‐area electron diffraction indicated that the average diameter of the Ga₂O₃ nanofibers produced was ca 55 nm and the crystalline structure was β‐Ga₂O₃ with a monoclinic unit cell. Furthermore, the photoluminescence spectrum of the Ga₂O₃ nanofibers exhibited two strong green emission peaks and one UV emission peak. Copyright © 2010 Society of Chemical Industry     

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.     

Resistive random access memory based on gallium oxide thin films for self-powered pressure sensor systems

The resistive switching (RS) behavior of a gallium oxide (Ga₂O₃) thin film for use in resistive random access memory (RRAM) was investigated. Ta/Ga₂O₃/Pt memory devices exhibited favorable RS behavior, such as a small distribution of switching parameters and switching cycles of more than 3 × 10⁶. X-ray photoelectron spectroscopy and the current transport mechanism indicated that that the RS behavior was attributed to the local variation on the Schottky barrier near the Pt electrode interface due to oxygen vacancies. A hybrid system for self-powered data storage and deletion was built by combining the RRAM device with a commercial Pb(Zr_1-xTi_x)O₃ piezoelectric ceramic as a pressure sensor/power generator. The excellent anti-interference and reuse performance of the system indicated promising potential for the application of this memory device.     

Annealing temperature controlled crystallization mechanism and properties of gallium oxide film in forming gas atmosphere

Gallium oxide (Ga₂O₃) films had been fabricated on Al₂O₃(0001) substrate by employing pulsed laser deposition (PLD) and annealed at different temperatures under forming gas (FG) atmosphere (95% N₂ + 5% H₂). The influence of annealing temperature on the structural, optical, chemical composition, and surface morphological properties of the Ga₂O₃ thin films was investigated comprehensively. The annealing processes with hydrogen gas play a crucial role in the characteristics of Ga₂O₃ thin films. A crystallization mechanism of Ga₂O₃ films controlled by annealing temperature has been proposed firstly and analyzed systematically, which contains three kinds of competitive mechanism, namely the thermal enhanced crystallization, the enhanced H₂ dissociative adsorption on Ga₂O₃ surfaces, and the high-temperature decomposition of Ga₂O₃. Both Ga⁺ and Ga³⁺ oxidation valence states were presented in all samples, which indicated lattice oxygen deficiency in Ga₂O₃ films. The variation of the non-lattice oxygen proportion of Ga₂O₃ films related to the crystallization mechanism firstly increased and then decreased with the increase of annealing temperature. The detailed crystallization mechanism of PLD-Ga₂O₃ films annealed in FG offers a guideline and references for the further fabrication of high-quality Ga₂O₃ films and their applications in high-performance devices.     

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.     

The role of fluorination during the physicochemical erosion of yttria in fluorine-based etching plasmas

A physicochemical mechanism acting between the reactive plasma and the material surface controls the erosion of polycrystalline ceramics in fluorine containing etching plasmas. In this study, a Y₂O₃/YOF composite was exposed to a fluorine etching plasma. Relocalization enables the direct correlation of crystalline orientation with material response. Our study reveals an orientation dependent surface fluorination of Y₂O₃, which controls the etching resistance and morphology formation. Orientations near the low index planes (001), (010) and (100) exhibit the lowest stability due to a homogeneous surface reaction. The presented results help to extend the mechanistic understanding of the plasma-material interaction of Y₂O₃.     

Recrystallization behavior,oxygen vacancy and photoluminescence performance of sputter-deposited Ga2O3 films via high-vacuum in situ annealing

Ga₂O₃ films were deposited on Si substrates through radio-frequency magnetron sputtering at room temperature and were annealed in situ in a high-vacuum environment. The as-deposited Ga₂O₃ film exhibited an island-like surface morphology and had an amorphous microstructure, with a few nanocrystalline grains embedded in it. After high-temperature in situ annealing, the films recrystallized and exhibited coalesced surfaces. Because of the thermally driven diffusion of Ga, the interfacial layer between Si and Ga₂O₃ was composed of SiGaO_x. Compared with ex situ annealing in air, in situ annealing in high vacuum is more advantageous because it enhances surface mobility and improves the crystallinity of the Ga₂O₃ films. The higher oxygen vacancy concentration of in situ annealed films revealed that oxygen atoms were easily released from the Ga₂O₃ lattice during high-vacuum annealing. Photoluminescence (PL) spectra exhibited four emission peaks centered in ultraviolet, blue, and green regions, and the peak intensities were significantly enhanced by thermal annealing at >600 °C. This work elucidates the effect of the in situ annealing treatment on the recrystallization behavior, interfacial microstructure, oxygen vacancy concentration, and PL performance of the Ga₂O₃ films, making it significant and instructional for the further development of Ga₂O₃-based devices.     

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.     

Synthesis of tuneable porous hematites (α-Fe2O3) for gas sensing and lithium storage in lithium ion batteries

Tuneable porous α-Fe₂O₃ materials were prepared by using a selective etching method. The structure and morphology of the as-prepared porous hematites have been systematically characterised by X-ray diffraction, field emission scanning electron microscope, and transmission electron microscope. We found that the pore size and pore volume can be controlled by adjusting the etching time during the synthesis process. The porous hematites have been applied for gas sensing and lithium storage in lithium ion cells. The porous α-Fe₂O₃ materials demonstrated a reversible lithium storage capacity of 1269 mAh/g. When used as a sensing material in gas sensors, porous α-Fe₂O₃ exhibited a superior sensitivity towards toxic and flammable gases.     

Phase composition,structural, and plasma erosion properties of ceramic coating prepared by suspension plasma spraying

Y₃Al₅O₁₂ (YAG), Y₂O₃, and Al₂O₃ ceramic coatings were manufactured to investigate the plasma erosion properties. The X‐Ray Diffraction (XRD) analysis confirmed that YAG coating was synthesized successfully by Y₂O₃ and Al₂O₃ mixture suspension using the plasma spraying method. Meanwhile, metastable phases were found in Y₂O₃ and Al₂O₃ coatings due to the quenching in cooling process of melted droplets. The coating surface morphology and microstructure of cross sections were characterized by SEM. The results reveal that coatings are composed by ultrafine splats and exhibit dense lamellar structure. The plasma erosion properties were evaluated at different etching test power under Ar/CF₄/O₂ plasma gas. The experimental results clarify that both of YAG and Y₂O₃ coatings show the better plasma erosion resistance than Al₂O₃ coatings. The formation of fluorination layer surface prevents the coatings from further erosion with plasma gas. Moreover, the etching rate of coatings depended on the fluorination and removing rate of fluoride layer.     

Plasma etching behavior of yttrium-aluminum oxide composite ceramics

In order to get a general regularity of erosion performance in alumina-strengthened yttria ceramics, High-quality yttrium-aluminum oxide composite ceramics with different alumina/yttria molar ratios were fabricated, and the as-prepared specimens were named Y₂O₃, YAG, YAGA, and Al₂O₃. The erosion behavior of the ceramics was examined and explained. The etching morphologies of the ceramics revealed that the multi-phase composite ceramic (YAGA) was etched selectively, whereas the single-phase ceramics were corroded homogeneously. The weight loss rate of the ceramics after etching was not proportional to the Al₂O₃ content, and it conformed to the percolation theory. As the alumina content in yttrium-aluminum oxide composite ceramics was below the minimum value of percolation transition in two-phase system the erosion resistance of the strengthened composite ceramics demonstrated excellent as well yttria ceramics.     

Porous Si layers—Preparation, characterization and morphology

Porous silicon layers (PSL) of nano- and micro-structures were prepared by metal-assisted electroless etching of silicon in HF-oxidizing agent aqueous solutions. The effect of oxidizing agent and HF content on the characteristics of the formed porous layers was investigated. A thin Pt film was electroless deposited on p-Si〈1 0 0〉 prior to immersion in the etching solution. The properties and morphology of the PSL formed by this method were investigated by electrochemical impedance spectroscopy (EIS) scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) technique. The characteristics of the PSL were found to be affected by the constituents of the etching medium and also, the etching time. Potassium bromate (KBrO₃), potassium iodate (KIO₃), and potassium dichromate (K₂Cr₂O₇) have been used as oxidizing agents. Pt-assisted etching of p-Si for 1 h in an etching solution consisting of 22.0 M HF and 0.05 M of KBrO₃, results in the formation of nano- and micro-pores on the Si surface. The use of 0.05 M KIO₃ or K₂Cr₂O₇ as oxidizing agent has led to the formation of a deposit on the silicon surface. At relatively higher concentration [>0.05 M] of K₂Cr₂O₇ the surface deposit becomes clear and was found to consist of an insoluble passive solid-phase of K₂SiF₆ which increases the film impedance and blocks the porous structure formation. The use of higher concentration [>22 M] of HF in the etching electrolyte is accompanied by an increase in the dissolution rate of the insoluble K₂SiF₆ layer and a decrease in the PSL passivity. The experimental impedance data were fitted to theoretical data according to a proposed equivalent circuit model which accounts for the mechanism of the porous film formation at the Si/electrolyte interface.     

Synthesis of gallium nitride nanostructures by nitridation of electrochemically deposited gallium oxide on silicon substrate

Gallium nitride (GaN) nanostructures were successfully synthesized by the nitridation of the electrochemically deposited gallium oxide (Ga₂O₃) through the utilization of a so-called ammoniating process. Ga₂O₃ nanostructures were firstly deposited on Si substrate by a simple two-terminal electrochemical technique at a constant current density of 0.15 A/cm² using a mixture of Ga₂O₃, HCl, NH₄OH and H₂O for 2 h. Then, the deposited Ga₂O₃ sample was ammoniated in a horizontal quartz tube single zone furnace at various ammoniating times and temperatures. The complete nitridation of Ga₂O₃ nanostructures at temperatures of 850°C and below was not observed even the ammoniating time was kept up to 45 min. After the ammoniating process at temperature of 900°C for 15 min, several prominent diffraction peaks correspond to hexagonal GaN (h-GaN) planes were detected, while no diffraction peak of Ga₂O₃ structure was detected, suggesting a complete transformation of Ga₂O₃ to GaN. Thus, temperature seems to be a key parameter in a nitridation process where the deoxidization rate of Ga₂O₃ to generate gaseous Ga₂O increase with temperature. The growth mechanism for the transformation of Ga₂O₃ to GaN was proposed and discussed. It was found that a complete transformation can not be realized without a complete deoxidization of Ga₂O₃. A significant change of morphological structures takes place after a complete transformation of Ga₂O₃ to GaN where the original nanorod structures of Ga₂O₃ diminish, and a new nanowire-like GaN structures appear. These results show that the presented method seems to be promising in producing high-quality h-GaN nanostructures on Si.