Electrical, optical, and magnetic properties of Sn doped α-Ga2O3 thin films
Journal of Applied Physics (2016)
Wide-bandgap semiconductors (WBG) are expected to be applied to solid-state lighting and power devices, supporting a future energy-saving society. Here we present evidence of p-type conduction in the undoped WBG β-Ga2O3. Hole conduction, established by Hall and Seebeck measurements, is consistent with findings from photoemission and cathodoluminescence spectroscopies. The ionization energy of the acceptor level was measured to be 1.1eV above the valence band edge. The gallium vacancy was identified as a possible acceptor candidate based on thermodynamic equilibrium Ga2O3 (crystal) – O2 (gas) system calculations (Kroger theory) which revealed a window without oxygen vacancy compensation. The possibility of fabricating large diameter wafers of β-Ga2O3 of p and n type nature, provides new avenues for high power and deep UV-optoelectronic devices.
Oxides represent the largest family of wide bandgap (WBG) semiconductors and also offer a huge potential range of complementary magnetic and electronic properties, such as ferromagnetism, ferroelectricity, antiferroelectricity and high-temperature superconductivity. Here, we review our integration of WBG and ultra WBG semiconductor oxides into different solar cells architectures where they have the role of transparent conductive electrodes and/or barriers bringing unique functionalities into the structure such above bandgap voltages or switchable interfaces. We also give an overview of the state-of-the-art and perspectives for the emerging semiconductor β- Ga2O3, which is widely forecast to herald the next generation of power electronic converters because of the combination of an UWBG with the capacity to conduct electricity. This opens unprecedented possibilities for the monolithic integration in solar cells of both self-powered logic and power electronics functionalities. Therefore, WBG and UWBG oxides have enormous promise to become key enabling technologies for the zero emissions smart integration of the internet of things.
Here, we report the analogy of an extremely stable topological-like ultra-wide bandgap insulator, a solid that is a pure insulator in its bulk but has a metallic conductive surface, presenting a two-dimensional conductive channel at its surface that challenges our current thinking about semiconductor conductivity engineering. Nominally undoped epitaxial β-Ga2O3 thin films without any detectable defect (after a range of state-of-the-art techniques) showed the unexpectedly low resistivity of 3 × 10−2 Ωcm which was found to be also resistant to high dose proton irradiation (2 MeV, 5 × 1015cm−2 dose) and was largely invariant (metallic) over the phenomenal temperature range of 2 K up to 850 K. The unique resilience and stability of the electrical properties under thermal and highly ionizing radiation stressing, combined with the extended transparency range (thanks to the ultra-wide bandgap) and the already known toughness under high electrical field could open up new perspectives for use as expanded spectral range transparent electrodes (e.g., for UV harvesting solar cells or UV LEDs/lasers) and robust Ohmic contacts for use in extreme environments/applications and for novel optoelectronic and power device concepts.
While there are several n-type transparent semiconductor oxides (TSO) for optoelectronic applications (e.g. LEDs{,} solar cells or display TFTs){,} their required p-type counterpart oxides are known to be more challenging. At this time{,} the n-type TSO with the largest bandgap (∼5 eV) is Ga2O3 that holds the promise of extending the light transparency further into the deep ultraviolet. In this work{,} it is demonstrated that strongly compensated Ga2O3 is also an intrinsic (or native) p-type TSO with the largest bandgap for any reported p-type TSO (e.g. NiO{,} SnO{,} delafossites{,} oxychalcogenides). The achievement of hole mobility in excess of 10 cm2 V−1 s−1 and (high temperature) free hole concentrations in the ∼1017 cm−3 range challenges the current thinking about achieving p-type conductivity in Ga2O3 being “out of the question”. The results presented in this paper therefore further clarify that p-type Ga2O3 is possible{,} although more research must be conducted to determine what are the real prospects for Ga2O3 solar blind bipolar optoelectronics and ultra-high power electronics based on p–n homojunctions.
The use of ultra-wide bandgap transparent conducting beta gallium oxide (β-Ga2O3) thin films as electrodes in ferroelectric solar cells is reported. In a new material structure for energy applications, we report a solar cell structure (a light absorber sandwiched in between two electrodes – one of them – transparent) which is not constrained by the Shockley–Queisser limit for open-circuit voltage (Voc) under typical indoor light. The solar blindness of the electrode enables a record-breaking bulk photovoltaic effect (BPE) with white light illumination (general use indoor light). This work opens up the perspective of ferroelectric photovoltaics which are not subject to the Shockley-Queisser limit by bringing into scene solar-blind conducting oxides.
Which the actual critical electrical field of the ultra-wide bandgap semiconductor β-Ga2O3 is? Even that it is usual to find in the literature a given value for the critical field of wide and ultra-wide semiconductors such as SiC (3 MV/cm), GaN (3.3 MV/cm), β-Ga2O3 (~8 MV/cm) and diamond (10 MV/cm), this value actually depends on intrinsic and extrinsic factors such as the bandgap energy, material residual impurities or introduced dopants. Indeed, it is well known from 1950’s that reducing the residual doping (NB) of the semiconductor layer increases the breakdown voltage capability of a semiconductor media (e.g. as NB−3/4 by using the Fulop’s approximation for an abrupt junction). A key limitation is, therefore, the residual donor/acceptor concentration generally found in these materials. Here, we report that doping with amphoteric Zinc a p-type β-Ga2O3 thin films shortens free carrier mean free path (0.37 nm), resulting in the ultra-high critical electrical field of 13.2 MV/cm. Therefore, the critical breakdown field can be, at least, four times larger for the emerging Ga2O3 power semiconductor as compared to SiC and GaN. We further explain these wide-reaching experimental facts by using theoretical approaches based on the impact ionization microscopic theory and thermodynamic calculations.
The family of spinel compounds is a large and important class of multifunctional materials of general formulation AB2X4 with many advanced applications in energy and optoelectronic areas such as fuel cells, batteries, catalysis, photonics, spintronics, and thermoelectricity. In this work, it is demonstrated that the ternary ultrawide-band-gap (∼5 eV) spinel zinc gallate (ZnGa2O4) arguably is the native p-type ternary oxide semiconductor with the largest Eg value (in comparison with the recently discovered binary p-type monoclinic β-Ga2O3 oxide). For nominally undoped ZnGa2O4 the high-temperature Hall effect hole concentration was determined to be as large as p = 2 × 1015 cm–3, while hole mobilities were found to be μh = 7–10 cm2/(V s) (in the 680–850 K temperature range). An acceptor-like small Fermi level was further corroborated by X-ray spectroscopy and by density functional theory calculations. Our findings, as an important step toward p-type doping, opens up further perspectives for ultrawide-band-gap bipolar spinel electronics and further promotes ultrawide-band-gap ternary oxides such as ZnGa2O4 to the forefront of the quest of the next generation of semiconductor materials for more efficient energy optoelectronics and power electronics.
Ultra-wide bandgap (UWBG) semiconductors and ultra-thin two-dimensional materials (2D) are at the very frontier of the electronics for energy management or energy electronics. A new generation of UWBG semiconductors will open new territories for higher power rated power electronics and deeper ultraviolet optoelectronics. Gallium oxide – Ga2O3 (4.5-4.9 eV), has recently emerged as a suitable platform for extending the limits which are set by conventional (~3 eV) WBG e.g. SiC and GaN and transparent conductive oxides (TCO) e.g. In2O3, ZnO, SnO2. Besides, Ga2O3, the first efficient oxide semiconductor for energy electronics, is opening the door to many more semiconductor oxides (indeed, the largest family of UWBGs) to be investigated. Among these new power electronic materials, ZnGa2O4 (~5 eV) enables bipolar energy electronics, based on a spinel chemistry, for the first time. In the lower power rating end, power consumption also is also a main issue for modern computers and supercomputers. With the predicted end of the Moore’s law, the memory wall and the heat wall, new electronics materials and new computing paradigms are required to balance the big data (information) and energy requirements, just as the human brain does. Atomically thin 2D-materials, and the rich associated material systems (e.g. graphene (metal), MoS2 (semiconductor) and h-BN (insulator)), have also attracted a lot of attention recently for beyond-silicon neuromorphic computing with record ultra-low power consumption. Thus, energy nanoelectronics based on UWBG and 2D materials are simultaneously extending the current frontiers of electronics and addressing the issue of electricity consumption, a central theme in the actions against climate change.
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