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1. Structural and electrical properties of thick κ -Ga 2 O 3 grown on GaN/sapphire templates

   https://doi.org/10.1063/5.0091653  

   Polyakov, A. Y. ; Nikolaev, V. I. ; Pechnikov, A. I. ; Stepanov, S. I. ; Yakimov, E. B. ; Scheglov, M. P. ; Shchemerov, I. V. ; Vasilev, A. A. ; Kochkova, A. A. ; Chernykh, A. V. ; et al ( June 2022 , APL Materials)

   Thick (23 µm) films of κ-Ga 2 O 3 were grown by Halide Vapor Phase Epitaxy (HVPE) on GaN/sapphire templates at 630 °C. X-ray analysis confirmed the formation of single-phase κ-Ga 2 O 3 with half-widths of the high-resolution x-ray diffraction (004), (006), and (008) symmetric reflections of 4.5 arc min and asymmetric (027) reflection of 14 arc min. Orthorhombic κ-Ga 2 O 3 polymorph formation was confirmed from analysis of the Kikuchi diffraction pattern in electron backscattering diffraction. Secondary electron imaging indicated a reasonably flat surface morphology with a few (area density ∼10 3  cm −2 ) approximately circular (diameter ∼50–100 µm) uncoalesced regions, containing κ-Ga 2 O 3 columns with in-plane dimensions and a height of about 10 µm. Micro-cathodoluminescence (MCL) spectra showed a wide 2–3.5 eV band that could be deconvoluted into narrower bands peaked at 2.59, 2.66, 2.86, and 3.12 eV. Ni Schottky diodes prepared on the films showed good rectification but a high series resistance. The films had a thin near-surface region dominated by E c − 0.7 eV deep centers and a deeper region (∼2 µm from the surface) dominated by shallow donors with concentrations of ≤10 16  cm −3 . Photocurrent and photocapacitance spectra showed the presence of deep compensating acceptors with optical ionization energies of ∼1.35 and 2.3 eV, the latter being close to the energy of one of the MCL bands. Deep level transient spectroscopy revealed deep traps with energies near 0.3, 0.6, 0.7, 0.8, and 1 eV from the conduction band edge. The results show the potential of HVPE to grow very thick κ-Ga 2 O 3 on GaN/sapphire templates. 

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2. Electrical properties of α-Ga 2 O 3 films grown by halide vapor phase epitaxy on sapphire with α-Cr 2 O 3 buffers

   https://doi.org/10.1063/5.0090832  

   Polyakov, Alexander ; Nikolaev, Vladimir ; Stepanov, Sergey ; Almaev, Alexei ; Pechnikov, Alexei ; Yakimov, Eugene ; Kushnarev, Bogdan O. ; Shchemerov, Ivan ; Scheglov, Mikhail ; Chernykh, Alexey ; et al ( June 2022 , Journal of Applied Physics)

   We report on growth and electrical properties of α-Ga₂O₃films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr₂O₃buffers predeposited on sapphire by magnetron sputtering. The α-Cr₂O₃buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr₂O₃bandgap and a sharp MCL line near 700 nm due to the Cr⁺intracenter transition. Ohmic contacts to Cr₂O₃were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga₂O₃films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at E_Cof 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr₂O₃buffer indicated the presence of two face-to-face junctions, one between n-Ga₂O₃and p-Cr₂O₃, the other due to the Ni Schottky diode with n-Ga₂O₃. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga₂O₃system.

    

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3. Unassisted Water Splitting Using a GaSb x P (1− x ) Photoanode

   https://doi.org/10.1002/aenm.201703247  

   Martinez‐Garcia, Alejandro ; Russell, Harry B. ; Paxton, William ; Ravipati, Srikanth ; Calero‐Barney, Sonia ; Menon, Madhu ; Richter, Ernst ; Young, James ; Deutsch, Todd ; Sunkara, Mahendra K. ( February 2018 , Advanced Energy Materials)

   Here, unbiased water splitting with 2% solar‐to‐hydrogen efficiency under AM 1.5 G illumination using new materials based on GaSb_0.03P_0.97alloy is reported. Freestanding GaSb_xP_1−xis grown using halide vapor phase epitaxy. The native conductivity type of the alloy is modified by silicon doping, resulting in an open‐circuit potential (OCP) of 750 mV, photocurrents of 7 mA cm⁻²at 10 sun illumination, and corrosion resistance in an aqueous acidic environment. Alloying GaP with Sb at 3 at% improves the absorption of high‐energy photons above 2.68 eV compared to pure GaP material. Electrochemical Impedance Spectroscopy and illuminated OCP measurements show that the conduction band of GaSb_xP_1−xis at −0.55 V versus RHE irrespective of the Sb concentration, while photocurrent spectroscopy indicates that only radiation with photon energies greater than 2.68 eV generate mobile and extractable charges, thus suggesting that the higher‐laying conduction bands in the Γ 1 valley of the alloys are responsible for exciton generation.

    

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4. Electrical and Structural Properties of Two-Inch Diameter (0001) α-Ga 2 O 3 Films Doped with Sn and Grown by Halide Epitaxy

   https://doi.org/10.1149/2162-8777/ac9edb  

   Nikolaev, V. I. ; Polyakov, A. Y. ; Stepanov, S. I. ; Pechnikov, A. I. ; Yakimov, E. B. ; Chernykh, A. V. ; Vasilev, A. A. ; Shchemerov, I. V. ; Kochkova, A. I. ; Guzilova, L. ; et al ( November 2022 , ECS Journal of Solid State Science and Technology)

   Two-inch diameter α -Ga 2 O 3 films with thickness ∼4 μ m were grown on basal plane sapphire by Halide Vapor Phase Epitaxy (HVPE) and doped with Sn in the top ∼1 μ m from the surface. These films were characterized with High-Resolution X-ray Diffraction (HRXRD), Scanning Electron Microscope (SEM) imaging in the Secondary Electron (SE) and Micro-cathodoluminescence (MCL) modes, contactless sheet resistivity mapping, capacitance-voltage, current-voltage, admittance spectra, and Deep Level Transient Spectroscopy (DLTS) measurements. The edge and screw dislocations densities estimated from HRXRD data were respectively 7.4 × 10 9 cm −2 and 1.5 × 10 7 cm −2 , while the films had a smooth surface with a low density (∼10 3 cm −2 ) of circular openings with diameters between 10 and 100 μ m. The sheet resistivity of the films varied over the entire 2-inch diameter from 200 to 500 Ω square −1 . The net donor concentration was ∼10 18 cm −3 near the surface and increased to ∼4 × 10 18 cm −3 deeper inside the sample. The deep traps observed in admittance and DLTS spectra had levels at E c −0.25 eV and E c −0.35 eV, with concentration ∼10 15 cm −3 and E c −1 eV with concentration ∼10 16 cm −3 . 

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5. RTD Light Emission around 1550 nm with IQE up to 6% at 300 K

   https://doi.org/10.1109/DRC50226.2020.9135175  

   Brown, E. R. ; Zhang, W-D. ; Fakhimi, P. ; Growden, T. A. ; Berger, P.R. ( June 2020 , IEEE Device Research Conference (DRC), Columbus, OH (June 22-24, 2020))

   Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at  = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around  = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at  =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). 

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