Gallium oxide (Ga2O3) is emerging as a viable candidate for certain classes of power electronics, solar blind UV photodetectors, solar cells, and sensors with capabilities beyond existing technologies due to its large bandgap. It is usually reported that there are five different polymorphs of Ga2O3, namely, the monoclinic (β-Ga2O3), rhombohedral (α), defective spinel (γ), cubic (δ), or orthorhombic (e) structures. Of these, the β-polymorph is the stable form under normal conditions and has been the most widely studied and utilized. Since melt growth techniques can be used to grow bulk crystals of β-GaO3, the cost of producing larger area, uniform substrates is potentially lower compared to the vapor growth techniques used to manufacture bulk crystals of GaN and SiC. The performance of technologically important high voltage rectifiers and enhancement-mode Metal-Oxide Field Effect Transistors benefit from the larger critical electric field of β-Ga2O3 relative to either SiC or GaN. However, the absence of clear demonstrations of p-type doping in Ga2O3, which may be a fundamental issue resulting from the band structure, makes it very difficult to simultaneously achieve low turn-on voltages and ultra-high breakdown. The purpose of this review is to summarize recent advances in the growth, processing, and device performance of the most widely studied polymorph, β-Ga2O3. The role of defects and impurities on the transport and optical properties of bulk, epitaxial, and nanostructures material, the difficulty in p-type doping, and the development of processing techniques like etching, contact formation, dielectrics for gate formation, and passivation are discussed. Areas where continued development is needed to fully exploit the properties of Ga2O3 are identified.

A review of Ga2O3 materials, processing, and devices

Applications of Phosphorene and Black Phosphorus in Energy Conversion and Storage Devices

Gallium oxide (Ga2O3) is emerging as a viable candidate for certain classes of power electronics with capabilities beyond existing technologies due to its large bandgap, controllable doping, and the availability of large diameter, relatively inexpensive substrates. These applications include power conditioning systems, including pulsed power for avionics and electric ships, solid-state drivers for heavy electric motors, and advanced power management and control electronics. Wide bandgap (WBG) power devices offer potential savings in both energy and cost. However, converters powered by WBG devices require innovation at all levels, entailing changes to system design, circuit architecture, qualification metrics, and even market models. The performance of high voltage rectifiers and enhancement-mode metal-oxide field effect transistors benefits from the larger critical electric field of β-Ga2O3 relative to either SiC or GaN. Reverse breakdown voltages of over 2 kV for β-Ga2O3 have been reported, either with or without edge termination and over 3 kV for a lateral field-plated Ga2O3 Schottky diode on sapphire. The metal-oxide-semiconductor field-effect transistors fabricated on Ga2O3 to date have predominantly been depletion (d-mode) devices, with a few demonstrations of enhancement (e-mode) operation. While these results are promising, what are the limitations of this technology and what needs to occur for it to play a role alongside the more mature SiC and GaN power device technologies? The low thermal conductivity might be mitigated by transferring devices to another substrate or thinning down the substrate and using a heatsink as well as top-side heat extraction. We give a perspective on the materials’ properties and physics of transport, thermal conduction, doping capabilities, and device design that summarizes the current limitations and future areas of development. A key requirement is continued interest from military electronics development agencies. The history of the power electronics device field has shown that new technologies appear roughly every 10-12 years, with a cycle of performance evolution and optimization. The older technologies, however, survive long into the marketplace, for various reasons. Ga2O3 may supplement SiC and GaN, but is not expected to replace them.

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Perspective: Ga2O3 for ultra-high power rectifiers and MOSFETS

After the synthesis of graphene, in the first year of this century, a wide research field on two-dimensional materials opens. 2D materials are characterized by an intrinsic high surface to volume ratio, due to their heights of few atoms, and, differently from graphene, which is a semimetal with zero or near zero bandgap, they usually have a semiconductive nature. These two characteristics make them promising candidate for a new generation of gas sensing devices. Graphene oxide, being an intermediate product of graphene fabrication, has been the first graphene-like material studied and used to detect target gases, followed by MoS2, in the first years of 2010s. Along with MoS2, which is now experiencing a new birth, after its use as a lubricant, other sulfides and selenides (like WS2, WSe2, MoSe2, etc.) have been used for the fabrication of nanoelectronic devices and for gas sensing applications. All these materials show a bandgap, tunable with the number of layers. On the other hand, 2D materials constituted by one atomic species have been synthetized, like phosphorene (one layer of black phosphorous), germanene (one atom thick layer of germanium) and silicone (one atom thick layer of silicon). In this paper, a comprehensive review of 2D materials-based gas sensor is reported, mainly focused on the recent developments of graphene oxide, exfoliated MoS2 and WS2 and phosphorene, for gas detection applications. We will report on their use as sensitive materials for conductometric, capacitive and optical gas sensors, the state of the art and future perspectives.

2D Materials for Gas Sensing Applications: A Review on Graphene Oxide, MoS2, WS2 and Phosphorene

Solar-blind photodetectors are of great interest to a wide range of industrial, civil, environmental, and biological applications. As one of the emerging ultrawide-bandgap semiconductors, gallium oxide (Ga2O3) exhibits unique advantages over other wide-bandgap semiconductors, especially in developing high-performance solar-blind photodetectors. This paper comprehensively reviews the latest progresses of solar-blind photodetectors based on Ga2O3 materials in various forms of bulk single crystal, epitaxial films, nanostructures, and their ternary alloys. The basic working principles of photodetectors and the fundamental properties and synthesis of Ga2O3, as well as device processing developments, have been briefly summarized. A special focus is to address the physical mechanism for commonly observed huge photoconductive gains. Benefitting from the rapid development in material epitaxy and device processes, Ga2O3-based solar-blind detectors represent to date one of the most prospective solutions for UV detection technology towards versatile applications.

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Review of gallium-oxide-based solar-blind ultraviolet photodetectors

The studies on enhancing the sensitivities of chemical sensors based on two-dimensional (2D) materials have been focused primarily on surface modifications including defect engineering, chemical doping, and incorporation of metal nanoparticles. Exfoliated black phosphorus (BP), which is one of the 2D materials, has attracted considerable attention because it offers higher sensitivity than other 2D materials (e.g., graphene and MoS2). In this study, for the first time, we attempt to increase the performance of BP chemical sensors to their theoretical limit by floating BP flakes on top of electrode posts in order to provide full (both sides) adsorption sites and avoid interface scattering effects. Our suspended BP gas sensors fabricated via dry transfer showed higher sensing performances than the conventional supported BP gas sensors (gas response was increased by approximately 23% at 200 ppm). In addition, faster response and recovery with high reproducibility were observed in suspended BP chemicals sensors than in the supported ones. Our work reveals the full potential of pristine BP-based chemical sensors and paves the way for the next-generation high performance 2D chemical sensors.

Suspended black phosphorus nanosheet gas sensors

We report defect-engineered graphene chemical sensors with ultrahigh sensitivity (e.g., 33% improvement in NO2 sensing and 614% improvement in NH3 sensing). A conventional reactive ion etching system was used to introduce the defects in a controlled manner. The sensitivity of graphene-based chemical sensors increased with increasing defect density until the vacancy-dominant region was reached. In addition, the mechanism of gas sensing was systematically investigated via experiments and density functional theory calculations, which indicated that the vacancy defect is a major contributing factor to the enhanced sensitivity. This study revealed that defect engineering in graphene has significant potential for fabricating ultra-sensitive graphene chemical sensors.

Defect-engineered graphene chemical sensors with ultrahigh sensitivity

We demonstrated the thinning of exfoliated quasi-two-dimensional β-Ga2O3 flakes by using a reactive ion etching technique. Mechanical exfoliation of the bulk β-Ga2O3 by using an adhesive tape was followed by plasma etching to tune its thickness. Since β-Ga2O3 is not a van der Waals material, it is challenging to obtain ultra-thin flakes below a thickness of 100 nm. In this study, an etch rate of approximately 16 nm/min was achieved at a power of 200 W with a flow of 50 sccm of SF6, and under these conditions, thinning of β-Ga2O3 flakes from 300 nm down to ∼60 nm was achieved with smooth morphology. We believe that the reaction between SF6 and Ga2O3 results in oxygen and volatile oxygen fluoride compounds, and non-volatile compounds such as GaFX that can be removed by ion bombardment. The opto-electrical properties were also characterized by fabricating solar-blind photodetectors using the plasma-thinned β-Ga2O3 flakes; these detectors showed fast response and decay with excellent responsivity and selectivity. Our results pave the way for tuning the thickness of two-dimensional materials by using this scalable, industry-compatible dry etching technique.

Tuning the thickness of exfoliated quasi-two-dimensional β-Ga2O3 flakes by plasma etching

We report on the synthesis of wafer-scale (4 in. in diameter) high-quality multi-layer graphene using high-temperature carbon ion implantation on thin Ni films on a substrate of SiO2/Si. Carbon ions were bombarded at 20 keV and a dose of 1 × 1015 cm−2 onto the surface of the Ni/SiO2/Si substrate at a temperature of 500 °C. This was followed by high-temperature activation annealing (600–900 °C) to form a sp2-bonded honeycomb structure. The effects of post-implantation activation annealing conditions were systematically investigated by micro-Raman spectroscopy and transmission electron microscopy. Carbon ion implantation at elevated temperatures allowed a lower activation annealing temperature for fabricating large-area graphene. Our results indicate that carbon-ion implantation provides a facile and direct route for integrating graphene with Si microelectronics.

Wafer-scale synthesis of multi-layer graphene by high-temperature carbon ion implantation

Black phosphorus (BP), especially in its two-dimensional (2D) form, is an intriguing material because it exhibits higher chemical sensing ability as compared to other thin-film and 2D materials. However, its implementation into hydrogen sensors has been limited due to its insensitivity toward hydrogen. We functionalized exfoliated BP flakes with Pt nanoparticles to improve their hydrogen sensing efficiency. Pt-functionalized BP sensors with back-gated field-effect transistor configuration exhibited a fast response/decay, excellent reproducibility, and high sensitivities (over 50%) at room temperature. Langmuir isotherm model was employed to analyze the Pt-catalyzed BP sensors. Furthermore, the activation energy of hydrogen adsorption on Pt-decorated BP was evaluated, which is equal to the change in work function resulting from hydrogen adsorption on the Pt(111) surface. These results demonstrate that Pt-catalyzed BP exhibits a great potential for next-generation hydrogen sensors.

Geonyeop Lee

Papers

Suspended black phosphorus nanosheet gas sensors

Defect-engineered graphene chemical sensors with ultrahigh sensitivity

Tuning the thickness of exfoliated quasi-two-dimensional β-Ga2O3 flakes by plasma etching

Wafer-scale synthesis of multi-layer graphene by high-temperature carbon ion implantation

Platinum-functionalized black phosphorus hydrogen sensors