United States

Abstract Body: Zinc germanium nitride (ZnGeN2) is the II-IV-N2 analogue of GaN which has a band gap (Eg) very close to that of GaN (~3.4 eV) and a lattice mismatch of &lt;0.1% with GaN [1]. Based on first principles calculations, the predicted valence band offset (VBO) of ZnGeN2 with GaN can be as high as 1.4 eV, [2] which provides great opportunities to design high efficiency InGaN/ZnGeN2 heterostructure quantum wells for visible light emitters [1]. However, there has been no report on the experimentally determined VBO at the ZnGeN2/GaN heterointerface, due to the lack of availability of high quality materials. In this work, we have experimentally determined the VBOs of ZnGeN2 and a 94% ZnGeN2 – 6% GaN alloy ((ZnGe)0.94Ga0.12N2) with GaN using Kraut’s method. The VBO between two materials A and B are determined using the core energy levels (ECL) in bulk A, bulk B and at the A/B heterointerface and the position of the valence band maxima (VBM) in bulk A and bulk B. X-ray photoemission spectroscopy (XPS) was used to measure the ECL and VBM values. To determine the VBO between ZnGeN2 and GaN, a GaN/c-sapphire template, a 16-nm-thick ZnGeN2 film and a 2-nm-thick ZnGeN2 layer grown on GaN template were used as the bulk GaN, bulk ZnGeN2 and ZnGeN2/GaN heterostructure, respectively. ZnGeN2 films were grown on GaN/c-sapphire templates via metalorganic chemical vapor deposition (MOCVD) [3,4]. By using the measured Zn 3d (Ge 3d) core levels from ZnGeN2 and the Ga 3d core levels from GaN, the VBO of ZnGeN2 with GaN was extracted to be 1.45±0.15 eV (1.65±0.15 eV). These values are comparable to the values predicted from first-principles calculations using explicit interface calculations [2]. Similarly, the VBO of (ZnGe)0.94Ga0.12N2 with GaN was determined. The samples used include a GaN/c-sapphire template as bulk GaN, a 20-nm-thick (ZnGe)0.94Ga0.12N2 films as bulk (ZnGe)0.94Ga0.12N2 and a 3-nm-thick (ZnGe)0.94Ga0.12N2 film as the (ZnGe)0.94Ga0.12N2/GaN heterostructure. These samples were grown on GaN/c-sapphire templates via MOCVD. The experimentally extracted VBO of (ZnGe)0.94Ga0.12N2 with GaN was 1.29±0.15 eV. Assuming a linear dependence of the VBO with composition x of (ZnGe)1-xGa2xN2, the predicted VBO of (ZnGe)0.94Ga0.12N2 from the theoretically calculated VBO of ZnGeN2 would be 1.32 eV. Thus, the experimentally measured VBO results agree well with the theoretically predicted values. The conduction band offsets were derived using the determined VBO values and the energy band gap Eg of the materials. The band gaps of ZnGeN2 and (ZnGe)0.94Ga0.12N2 were estimated from the inelastic energy loss features of N 1s peaks in the XPS spectra of 16-nm-thick ZnGeN2 and 20-nm-thick (ZnGe)0.94Ga0.12N2 samples. The Eg values determined by this method were 3.0±0.2 eV for ZnGeN2 and 3.1±0.2 eV for (ZnGe)0.94Ga0.12N2. The lower values of Eg as compared to the predicted band gap values (~3.4 eV) can be due to the presence of disorder in the cation sublattice. In conclusion, the valence band offsets of MOCVD-grown (ZnGe)1-xGa2xN2 with GaN, with x = 0 and 0.06 were determined experimentally using XPS. The measured VBO values are comparable to the predicted values from first-principles calculations. The results from this study will expand device designs based on pure III-nitrides to III-nitrides/II-IV-N2, which can potentially address key challenges in III-nitride based electronic and optoelectronic device technologies. This work is supported by the U.S. DOE (DOE SSL: DE-EE0008718) and by the NSF (DMREF: SusCHeM: 1533957). References 1. L. Han, K. Kash, and H. Zhao, J. Appl. Phys., 120, 103102 (2016). 2. A. P. Jaroenjittichai, S. Lyu, and W. R. L. Lambrecht, Phys. Rev. B., 96, 079907(E) (2017). 3. M. R. Karim, B. H. D. Jayatunga, M. Zhu, R. A Lalk, O. Licata, B. Mazumder, J. Hwang, K. Kash, H. Zhao, AIP Adv. 10, 065302 (2020). 4. B. H. D. Jayatunga, M. R. Karim, R. A. Lalk, O. Ohanaka, W. R. L. Lambrecht, H. Zhao, and K. Kash, Cryst. Growth Des., 20, 189 (2020).

EMC 2021

Experimental Determination of Valence Band Offsets of ZnGeN2 and (ZnGe)0.94Ga0.12N2 with GaN

band offset

ii-iv-n2

zngega2n4

zngen2

mocvd

After two years of virtual conferences, we're excited to host EMC 2022 in person at The Ohio State University in Columbus, Ohio. In addition to cutting-edge technical presentations given in multiple parallel sessions, opportunities to network with colleagues will be present throughout the conference. The size and format of the meeting makes networking easy, whether you have been coming to the conference for many years or are a first-time attendee.

EMC is coordinated with the Device Research Conference (DRC), which will be held the same week, from June 26-29. This recognizes the strong interaction between device and electronic materials research and provides fruitful exchange of information between attendees of both Conferences.

For information on the 80th Device Research Conference, please visit the DRC 2022 website.



EMC 2022

The Electronic Materials Conference (EMC) is the premier annual forum on the preparation, characterization and use of electronic materials. This year’s event will feature a plenary session, topical sessions, a poster session and more.

Abstract Body: Zinc germanium nitride (ZnGeN2) is the II-IV-N2 analogue of GaN which has a band gap (Eg) very close to that of GaN (~3.4 eV) and a lattice mismatch of <0.1% with GaN [1]. Based on first principles calculations, the predicted valence band offset (VBO) of ZnGeN2 with GaN can be as high as 1.4 eV, [2] which provides great opportunities to design high efficiency InGaN/ZnGeN2 heterostructure quantum wells for visible light emitters [1]. However, there has been no report on the experimentally determined VBO at the ZnGeN2/GaN heterointerface, due to the lack of availability of high quality materials. In this work, we have experimentally determined the VBOs of ZnGeN2 and a 94% ZnGeN2 – 6% GaN alloy ((ZnGe)0.94Ga0.12N2) with GaN using Kraut’s method. The VBO between two materials A and B are determined using the core energy levels (ECL) in bulk A, bulk B and at the A/B heterointerface and the position of the valence band maxima (VBM) in bulk A and bulk B. X-ray photoemission spectroscopy (XPS) was used to measure the ECL and VBM values. To determine the VBO between ZnGeN2 and GaN, a GaN/c-sapphire template, a 16-nm-thick ZnGeN2 film and a 2-nm-thick ZnGeN2 layer grown on GaN template were used as the bulk GaN, bulk ZnGeN2 and ZnGeN2/GaN heterostructure, respectively. ZnGeN2 films were grown on GaN/c-sapphire templates via metalorganic chemical vapor deposition (MOCVD) [3,4]. By using the measured Zn 3d (Ge 3d) core levels from ZnGeN2 and the Ga 3d core levels from GaN, the VBO of ZnGeN2 with GaN was extracted to be 1.45±0.15 eV (1.65±0.15 eV). These values are comparable to the values predicted from first-principles calculations using explicit interface calculations [2]. Similarly, the VBO of (ZnGe)0.94Ga0.12N2 with GaN was determined. The samples used include a GaN/c-sapphire template as bulk GaN, a 20-nm-thick (ZnGe)0.94Ga0.12N2 films as bulk (ZnGe)0.94Ga0.12N2 and a 3-nm-thick (ZnGe)0.94Ga0.12N2 film as the (ZnGe)0.94Ga0.12N2/GaN heterostructure. These samples were grown on GaN/c-sapphire templates via MOCVD. The experimentally extracted VBO of (ZnGe)0.94Ga0.12N2 with GaN was 1.29±0.15 eV. Assuming a linear dependence of the VBO with composition x of (ZnGe)1-xGa2xN2, the predicted VBO of (ZnGe)0.94Ga0.12N2 from the theoretically calculated VBO of ZnGeN2 would be 1.32 eV. Thus, the experimentally measured VBO results agree well with the theoretically predicted values. The conduction band offsets were derived using the determined VBO values and the energy band gap Eg of the materials. The band gaps of ZnGeN2 and (ZnGe)0.94Ga0.12N2 were estimated from the inelastic energy loss features of N 1s peaks in the XPS spectra of 16-nm-thick ZnGeN2 and 20-nm-thick (ZnGe)0.94Ga0.12N2 samples. The Eg values determined by this method were 3.0±0.2 eV for ZnGeN2 and 3.1±0.2 eV for (ZnGe)0.94Ga0.12N2. The lower values of Eg as compared to the predicted band gap values (~3.4 eV) can be due to the presence of disorder in the cation sublattice. In conclusion, the valence band offsets of MOCVD-grown (ZnGe)1-xGa2xN2 with GaN, with x = 0 and 0.06 were determined experimentally using XPS. The measured VBO values are comparable to the predicted values from first-principles calculations. The results from this study will expand device designs based on pure III-nitrides to III-nitrides/II-IV-N2, which can potentially address key challenges in III-nitride based electronic and optoelectronic device technologies. This work is supported by the U.S. DOE (DOE SSL: DE-EE0008718) and by the NSF (DMREF: SusCHeM: 1533957). References 1. L. Han, K. Kash, and H. Zhao, J. Appl. Phys., 120, 103102 (2016). 2. A. P. Jaroenjittichai, S. Lyu, and W. R. L. Lambrecht, Phys. Rev. B., 96, 079907(E) (2017). 3. M. R. Karim, B. H. D. Jayatunga, M. Zhu, R. A Lalk, O. Licata, B. Mazumder, J. Hwang, K. Kash, H. Zhao, AIP Adv. 10, 065302 (2020). 4. B. H. D. Jayatunga, M. R. Karim, R. A. Lalk, O. Ohanaka, W. R. L. Lambrecht, H. Zhao, and K. Kash, Cryst. Growth Des., 20, 189 (2020).

technical paper

The Electronic Materials Conference (EMC) is the premier annual forum on the preparation, characterization and use of electronic materials. This year’s event will feature a plenary session, topical sessions, a poster session and more.

EMC is coordinated with the Device Research Conference (DRC), which will be held during the same week, from June 20-23. This recognizes the strong interaction between device and electronic materials research and provides fruitful exchange of information between attendees of both Conferences.

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Abstract Body: β-Ga2O3 is well known for its multidimensional functionality, such as deep-UV photodetector, high power electronic device, water splitting, CO2 reduction, gas sensor, etc. Here we are presenting a low cost pulsed laser deposition method to demonstrate nano-columnar β-Ga2O3 thin film on silicon substrate with an average crystallite size of ~9 nm. In-situ anisotropic thermal conductivity during the grow process facilitates the unidirectional columnar growth of β-Ga2O3 thin film, decorated with nanocrystalline surface morphology. With increasing substrate temperature, it shows blue shifting of band edge absorption with decreasing defect density. Luminescence spectra show drastic improvement in intensity (~30 times), which is beneficial for further optoelectronic application.

Realization of Self-Assisted Growth of Nano-Columnar β-Ga2O3 Thin Film on Silicon Substrate

Abstract Body: Digitally-grown AlInAsSb alloys have recently emerged as a platform for high performance short- avalanche photodiodes (APDs) with potential applications in chemical sensing, security, and LIDAR [1,2]. While the impact ionization of APDs grown with a single composition has been shown to be nearly perfectly electron-initiated [2,3], AlInAsSb also enables sophisticated bandgap engineering to create a “staircase” APDs – a solid-state analogue of the photomultiplier tube wherein impact ionization only occurs in spatially-localized, narrow-gap wells [4, 5]. Carrier trapping phenomena in the narrow-gap regions, coupled to non-radiative Shockley-Read-Hall recombination, can reduce the efficiency of impact ionization and reduce the maximum achievable gain in staircase APDs. Unfortunately, due to the miscibility gap associated with conventionally grown AlInAsSb, the carrier lifetime of AlInAsSb materials is largely unknown. Furthermore, the SWIR and MWIR spectral regions spanned by AlInAsSb remain an active area of research for high-performance unity-gain photodiodes and emitters for chemical sensing and security applications; high performance in either class of devices depends critically on the carrier recombination dynamics. Thus, there is a need to measure the carrier lifetime in digitally-grown AlInAsSb to foster improved staircase APD performance, as well as to evaluate AlInAsSb more broadly as a candidate material for SWIR and MWIR detection and emission. Here, we present an investigation of carrier recombination dynamics of SWIR and MWIR AlInAsSb digital alloys with alloy compositions ranging from 0% Al to 30% Al, at temperatures between 77K and room temperature. Bright photoluminescence was observed from all samples at all temperatures, spanning wavelengths from 1.8μm to 5μm. Minority carrier lifetimes were measured from time-resolved photoluminescence ranging from 75ns to 260ns at 77K, and 25ns to 75ns at room temperature. Samples containing more than 0% Al displayed a ‘U’ shaped dependence on the temperature, with the minima occurring around 200K and ranging from 20ns to 50ns. The minority carrier lifetime of the 0% Al sample, however, monotonically increased with decreased temperature. Further characterization and analysis will be presented at the conference. This work was supported by ARO (W911NF-17-1-0065), DARPA (HR0011-20-9-0087), and NSF (ECCS-1926187). [1] S.R. Bank et al., IEEE J. Sel. Top. Quantum Electron. 24, 3800407 (2018) [2] M. Ren et al., … J. C. Campbell, J. Light. Technol. 35, 2380 (2017) [3] Y. Yuan et al., … J. C. Campbell, IEEE Photon. Technol. Lett. 31, 315 (2019) [4] F. Capasso and G. F. Williams, IEEE Trans. Nucl. Sci. 30, 381 (1983) [5] M. Ren et al., … S. R. Bank, Appl. Phys. Lett. 108, 081101 (2016).

Minority-Carrier Lifetimes in Digitally-Grown AlInAsSb Alloys

Abstract Body: Dilute germanium carbides (Ge:C) are promising optical materials for active silicon photonics since they can be grown directly on Si at temperatures compatible with post-metal CMOS fabrication. Although Ge and diamond-lattice C both have an indirect bandgap, substitution of ~1% C into Ge creates a direct bandgap suitable for lasers and modulators. However, there is disagreement in the literature about whether C creates a true direct bandgap or merely a pseudo-direct bandgap in which symmetry prevents optical emission even at Gamma (k=0). In this work, we studied the effects of strain and defects on the optical properties of Ge:C using ab initio techniques. We find Ge:C is similar to other highly mismatched alloys such as GaAs1-xNx in many ways, but it also presents several curious differences. The Vienna Ab initio Simulation Package (VASP) was used to model 128 atom supercells of Ge:C with different periodicities, as well as 128 atom supercells with a single Ge vacancy. The use of HSE06 hybrid functionals provided good agreement with experiment in both the direct and indirect bandgaps in unstrained Ge. To study whether periodic boundary conditions artificially affected the results, supercell lattice vectors were varied; the center of each supercell might align with the face, edge, or vertex of the next supercell. This changed the spacing between C atoms in different directions, mimicking a random alloy at a far lower computational cost than doubling the supercell sizes. Other groups have reported that the new conduction band edge created by C is dominated by indirect (L) states. We found instead that the conduction band splits into two bands, E- and E+, that are similar to each other (consistent with band anticrossing, BAC) but retain a predominantly Ge Γ character. The optical transitions in Ge:C are comparable with those of the direct bandgap transition (Γ) in Ge. Spectral weights after band unfolding show comparable or more weight at Γ than L for both E+ and E- states. We also ran a few validation jobs with spin-orbit coupling, compressive strain, or harder Ge potentials, and these all showed similar results. In particular, the band-to-band optical transition strength in Ge:C is within a factor of 2 of that in Ge, and it is comparable with common III-V materials currently used for lasers. We found that the pressure dependence of the band structure can be highly misleading when trying to interpret band identities. In particular, the E- band shifts with strain almost identically with the Ge CB L valley, but this is pure coincidence. Instead, the slow shift with strain comes from a carbon “defect” state near EVB+0.79 eV that varies relatively slowly, more or less tracking the vacuum level rather than the conduction band edge, unlike traditional impurity states. Because the C “defect” state is so close to the native Ge direct bandgap (0.80 eV), the splitting in bands is very strong, driving the direct bandgap more than 0.2 meV below the indirect L valley. This agrees with the deep state model of Hjalmarson and Dow and BAC models near Γ. However, BAC fails to explain the bands away from k=0, and it also does not explain the appearance of a third CB state between the E+ and E- bands. In summary, these results strongly support the development of Ge:C as a strongly optically active material for silicon photonics, with a strongly direct bandgap and optical transitions comparable with III-V materials. Furthermore, these strain results offer a route to test the computational models against experiments, using a diamond anvil cell. These tests are currently underway.

Optical Properties and Band Structures of Strained Ge:C

Abstract Body: Investigation of new group IV alloys to find a direct bandgap material that can emit and detect light efficiently has been pursued by Si photonics in the past decades. The integration of optoelectronics on the electronics chips enables high-speed data transfers through emitters and detectors that are compatible with Si technology 1. Although GeSn has been shown as a group IV that can achieve the above-mentioned goals by different groups 2, other alloys of group IV have not been yet fully investigated due to technical challenges such as insolubility, lattice mismatch, unavailability of proper precursor, etc. Theoretical calculations show that SixSn1-x alloys can also be a direct bandgap material like GeSn with the difference of having a larger bandgap due to high direct band edge of Si at 3.2 eV (Γ-valley)3. However, the theoretical study of this material is not well developed. The estimation of Sn concentration needed to achieve direct bandgap varies in the range of 40-60% while the experimentalist are expecting that to be in the 25% range.3 In this paper we have studied both material properties as well as electronic band structure using density functional theory (DFT) calculations. We have adopted generalized gradient approximation- Perdew–Burke–Ernzerhof (GGA-PBE) 4 with Vienna Ab-initio Simulation Package (VASP).5 The 16-atom cubic supercells of Si and Sn, as well as the unit cell, were used in this modeling in order to find the atomic configurations and energetics. The supercells were relaxed for all the atoms with a residual force of less than 5 × 10−5 eV/Å for each atom. A (4×4×4) Monkhorst−Pack mesh of k-points for a periodic 16-atom supercell was adopted to generate the Brillouin zone. We calculated the lattice constant and its formation energy for all compositions using the GGA–PBE exchange-correlation potential considering the structural relaxation of an isotropic stress for the supercell. The change in the lattice follows the Vegard’s law and a slight bowing (=0. 05 Å) is observed across the full range which is close to previously reported values 0.02-0.084 Å 3, 6 . The lattice constants of Si and α-Sn were estimated to be 5.47 and 6.65 Å, respectively. These values are in close agreement with previously reported values of 5.47Å for Si7 and 6.65–6.74 Å for α-Sn 8 using a similar modeling method of GGA–PBE. It is noteworthy that compared to other group IV binary alloys such as SiGe and GeSn, the proposed bowing parameter is slightly lower. The band structure of all compositions of SixSn1-x is calculated for both unit cell and supercell of 16 atoms. The electronic properties of the alloys are affected by the displacement of Si1-xSnx atoms; therefore, structural relaxation of the structures plays an important role in the band structure. These structures were relaxed to a high extent as stated above. Since the GGA-PBE method underestimates the bandgap of SixSn1-x alloys, different methods have been applied to bring the calculations closer to the real bandgap. In our calculations, we have included the valence band offset of SixSn1-x alloys. The valence band offset is attributed to the electronic interaction between the occupied and unoccupied orbitals of Si1-xSnx. Therefore, by considering an Sn dependent valence band offset as well as heavy, light, and split-off hole bands, the calculations are closer to the real bandgaps. More details of the material properties along with the electronic band structure calculations will be presented at the conference. References [1] A. Atabaki et al., Nature 556, 349 2018 [2] A. Mosleh et al. J Electron Mater 43, 938 2014 [3] J. Tolle et al., Appl. Phys. Lett. 89, 231924 2006 [4] J. P. Perdew et al. Physical Review B 46, 6671 1992 [5] G. Kresse et al. Physical Review B 54, 11169 1996 [6] P. Yakibchuk et al. J Physical Studies 23, 2703 2019 [7] SQ Wang et al. J Physics: Cond. Matt. 15, L197 2003 [8] R. Pandey et al. Appl. Phys. Lett. 75, 4127 1999

SiSn Electronic Band Structure Modelling Using Density Functional Theory for Optoelectronic Applications

Abstract Body: The next generation of solid-state power electronics will increasingly utilize the AlxGa1-xN system, benefitting from its large and direct band gap, high switching speed, and high FOM. Formation of selective-area p-type regions is critical for field management and remains a significant challenge for higher-voltage next-generation architectures. Activation of the p-type dopant Mg, especially in the case of ion-implanted AlxGa1-xN, requires temperatures high enough to cause significant diffusion of the dopant, potentially distorting the doped region shape. Microwave annealing has been shown to induce both dopant activation and diffusion, especially for rapid drive-in of B in Si1 Diffusion dynamics induced by microwave annealing can diverge from those suggested by the bulk thermal condition of the sample. This has been attributed to interaction of the microwave beam with ionized defects and dopants in the material, permitting higher diffusion of electrically charged (ionized) species in the lower-temperature bulk2. This makes understanding Mg redistribution in GaN due to microwave annealing in both implanted and in-situ doped material of critical importance to the continued development of selective-area doping. In order to better understand this diffusion and activation behavior, a study was conducted of spatially resolved Mg distribution in in-situ doped and implanted GaN grown by metalorganic chemical vapor deposition (MOCVD) and annealed by gyrotron microwave beam. Annealing conditions between 1160–1410 °C were performed for durations between 30–65 s in total using a quasi-gaussian beam intensity profile and a 2.5 cm beam raster across the sample surface. Low-temperature PL spectra were measured and used as a proxy for acceptor activation before and after annealing of doped GaN. At the locations of PL measurements on samples, depth profiles of [Mg] were taken using dynamic secondary ion mass spectroscopy (D-SIMS). Beyond concentrations of around 1016 cm-3, the intensity of PL bands is not linearly related to the density of acceptors in the material3, however PL spectra have been shown to indicate the presence of conductivity type, provided initial knowledge of the growth condition. The as-implanted [Mg] profile of all samples shows a profile of 1×1019 cm-3 to a depth of 250 nm with a quasi-Gaussian tail. The in-situ doped as-grown [Mg] of 7×1019 cm-3 remains constant from the surface to the p-GaN layer depth of ~120 nm before annealing, and the profile does not appreciably change after annealing. After annealing implanted samples above 1350 °C, diffusion of Mg dopant is observed to vary spatially across the sample, correlating approximately with the beam shape and raster. To understand potential correlation of such diffusion with PL bands, measurements on the same location as SIMS measurement was performed. PL measurements show the characteristic near-band edge (NBE) luminescence at 3.47 eV and Mg-acceptor-related UVL at 3.27 eV in all spectra. In the 2.2–2.4 eV range, either the VN-related GL2 band or the CN-ON-related YL band is dominant. Relative intensity of these bands varies across the sample area, however no correlation of PL activity with Mg diffusion is observed. We show that while PL activity reflects the presence of MgGa and other optically active defects within the laser excitation depth (~92 nm), (anneal-induced) diffusion has no significant impact on [Mg] within this depth, and therefore that diffused Mg deeper in the sample (200–800 nm) does not necessarily impact PL activity. This may be due in part to the upper limit of PL sensitivity to acceptor concentration3. This work was funded by a grant from ARPA-E PNDIODES program, grant #DE-FOA-001691 under the direction of Dr. Isik C. Kizilyalli. [1] Kohli, P., et al. (2002). J. of Electron. Mat., 31(3), 214-219. [2] Booske, J. H., Cooper, R. F., & Dobson, I. (1992). J. Mat. Research, 7(2), 495-501. [3] Reshchikov, M. A., et al. (2017). Scientific reports 7(1), 1-11.

Microwave-Induced Annealing, Its Impact on Mg Diffusion and Photoluminescence Activity in Implanted and In Situ Doped GaN

Abstract Body: Recently, carbon-based electrode, especially graphene, has been introduced to replace the noble metals as a low-cost alternative. In this work, we show that the turn on voltage of the electrochemical reaction can be tuned in a semiconductor-insulator-plasma etched graphene (SIEG) device, especially for hydrogen evolution reaction (HER). By using this structured device, the relative energy level can be shifted to modify the onset potential. Besides, O2 plasma etched graphene was introduced to increase the number of active sites for HER on the surface of the graphene. Figure 1a shows a schematic of the SIEG device. A plasma-etched graphene on an insulator–semiconductor is introduced here. Reactive ion etching (RIE) by oxygen flow method was used to dry etch the graphene to introduce the active reaction sites. Compared to pristine graphene (PG) in Raman Spectroscopy, the ID/IG ratio was increased from ~ 0 to 0.58 from PG to EG shown in Figure 1b, suggesting the disruption of the hexagonal configuration by oxygen plasma etching. The result implies the existence of a higher amount of defect sites due to the introduction of plasma-induced edge defects. Figure 2a shows the HER measurement result of SIEG device in both biased and unbiased conditions. It is noteworthy that the onset potential of HER can shift up to ~0.8 V and 90mA/cm2 current density could be achieved at -0.5V vs RHE at VGr-Si = 1.5V. Figure 2b shows the schematic of the mechanism of catalysis due to hot electrons. The high performance of the device comes from the hot electrons possessing high energy which requires a significantly smaller activation energy barrier to overcome compared to the thermal electrons. Figure 3 shows the mechanism of how hot electrons are introduced into the graphene from the silicon. The applied bias between graphene and silicon shifts the conduction band of silicon relative to the reduction potential of H+/H2 redox couple, injecting carriers from silicon through graphene, while driving the reaction before any scattering happens in the graphene. To clarify this effect of the applied bias, we analyzed the different current components from the system individually. Here we find out that the silicon current is the major current component for chemical reaction (Redox current) when graphene-silicon voltage is applied as shown in Figure 3b. This result shows that the hot electrons from silicon current directly drive the electrochemical reaction, without affecting the graphene current. Figure 4 shows the overlapping of HER current between SIPG and SIEG device. The result shows that the current density of SIEG device at same experimental condition is ~ 2x higher than that of SIPG device. This indicates that the newly introduced active site for the hydrogen ions breaking through the limiting factor of graphene surface area. Electrochemical surface area (ECSA) achieved by cyclic voltammetry measurement also indicates the enhanced electrochemical area of the plasma etched graphene. In conclusion, we demonstrate that a plasma etched graphene based SIEG device can be a promising electrocatalysts candidate. SIEG device is not confined to this certain structure, we could possibly get better results by replacing each component with other materials. Future experiments could explore other redox reactions for carbon dioxide reduction to useful materials, and other 2-D materials with a high density of active sites that transport electrons more efficiently and adsorb more protons on top of the surface to see if high efficiencies can be achieved at lower voltages.

Hot Electron Metal-Free Electrode for Hydrogen Evolution Reaction

Abstract Body: To alleviate the adverse impacts of utilizing fossil fuel reserves on the environment (global warming, greenhouse emissions), extensive research is being devoted to the development of alternative/renewable energy systems, which include: photovoltaics, fuel cells, batteries, etc. Among them, fuel cells are an excellent solution for energy conversion, where proton exchange membrane (PEM) fuel cells have a wide variety of applications. Some of these applications are portable systems, automotive, etc., where an important reaction occurring at the cathode is the oxygen reduction reaction (ORR). At the current stage in fuel cell technology, platinum (Pt)-based materials are the most practical catalysts1, which, undoubtedly, are the prime choice as the cathode catalyst for the electro-reduction of oxygen, but Pt-based catalysts are expensive. To reduce such costs in commercially viable fuel cells, extensive research is focused on developing alternative catalysts. Silver-based catalysts show a comparatively high thermodynamic stability and excellent catalytic activity over a wide pH range. The TMCs (O, S, Se, and especially Se-based chalcogenides) have attracted significant attention since selenium-based cluster compounds work. Selenium-based metal-rich TMCs catalysts exhibit good electrocatalytic activity, which is mainly attributed to selenium because it improves the electronic structure of the metal by preventing the electrochemical oxidation of metals in most transition metal chalcogenides, as seen for the cases of cobalt selenide and ruthenium selenide. Here, we present a high yield, industrially scalable, and the first-time report on the synthesis of silver selenide from silver foil and selenium powder using a two furnace atmospheric pressure-chemical vapor deposition (AP-CVD) system. We grew low temperature, LT-β-Ag2Se on Ag foil in the AP-CVD system using thermal annealing and leading to a hollow fern-like morphology material and its first-ever reported application as an ORR cathode catalyst. The exfoliated β-Ag2Se is characterized using XRD, EDS, HRTEM, AFM, and HRSEM to determine its stoichiometry and its hollow layered fern-like morphology. Differential scanning calorimetry (DSC) further confirms that the final product is the low-temperature phase β-Ag2Se. Electrochemical oxygen reduction reaction (ORR) of exfoliated β-Ag2Se exhibits sharp oxygen reduction current with an onset potential of 0.88 V/RHE under alkaline conditions, indicating the oxygen reduction property of β-Ag2Se. The large value of limiting current (3 mA cm-2) as well as small Tafel slope (68.5 mV dec-1) corroborates β-Ag2Se as a superior layered transition metal chalcogenide cathode material suitable for such energy-related applications (typically fuel cells and/or metal-air batteries). References (1) Ostroverkh, A.; Johánek, V.; Dubau, M.; Kúš, P.; Khalakhan, I.; Šmíd, B.; Fiala, R.; Václavu, M.; Ostroverkh, Y.; Matolín, V. Optimization of Ionomer-Free Ultra-Low Loading Pt Catalyst for Anode/Cathode of PEMFC via Magnetron Sputtering. Int. J. Hydrogen Energy 2019, 44 (35), 19344–19356. https://doi.org/10.1016/j.ijhydene.2018.12.206.

Facile and Scalable Ambient Pressure Chemical Vapor Deposition-Assisted Synthesis of Layered Silver Selenide (β-Ag2Se) on Ag Foil as a Possible Oxygen Reduction Catalyst in Alkaline Medium

Abstract Body: Photoelectrochemical (PEC) water splitting is a promising technology for using solar energy to convert water molecules into hydrogen gas. Si’s moderate bandgap, high charge mobility and diffusion length, and extensive technology base enable Si-based photoelectrodes to achieve very good PEC performance with the potential for very low cost. However, Si has poor stability in aqueous solutions, limiting long-term stability of Si photoelectrodes for PEC water oxidation or reduction. Metal-insulator-semiconductor (MIS) photoelectrodes have therefore been widely explored for highly efficient and stable PEC water splitting. However, the insulating oxide that protects the semiconductor layer in an MIS photoelectrode typically must be sufficiently thin – a few nm – to enable carrier transport from the semiconductor to the metal catalyst via tunneling, often degrading photoelectrode stability. In this work, we demonstrate a simple, low cost, and highly scalable method to fabricate MIS photoelectrodes with thick SiO2 insulating layers and localized electrical contacts between the Si absorber and metal catalyst structures. The fabricated photoelectrodes show high efficiency and outstanding stability in aqueous solutions, with photoanode onset potential as low as 0.7 V vs. RHE and saturation current density over 30 mA/cm2 under AM1.5G illumination. Both MIS photoanode and photocathode structures are being explored. In a 7 day stability test, constant photocurrent density was maintained with no apparent degradation in performance. These results demonstrate a low-cost, highly scalable approach for fabrication of efficient and very stable photoelectrodes that is suitable for large-scale commercial fabrication and readily adaptable to a variety of catalyst, insulator, and semiconductor materials.

Low-Cost, Scalable Fabrication of Stable, High Performance Si-Based Metal-Insulator-Semiconductor Photoelectrodes for Solar-Driven Water Splitting

Abstract Body: Ever-increasing energy storage demands for vehicle electrification, consumer electronics, and grid energy storage requires further innovations in their performance and safety. To this end, developing new cathode materials has been the major interest in the Li-ion battery community. While cycling, most conventional cathode materials undergo repeated volume changes during Li-ion insertion/extraction (i.e., cycling), which in turn generates stress to the active material particles [1]. As a result of the tensile stress, particles tend to crack and pulverize, leading to a loss of contact and capacity fading. To address the mechanical instability issue from cathode materials, Dr. Lee et al. [2] developed novel spinel-type Li2Co2-xAlxO4 (where x = 0 – 1.0) as a “zero-strain” cathode material; it has less than 0.02% of the volume change during charge/discharge processes. This low volume change was explained by a suppression of rock-salt to spinel phase transition due to the presence of Al cations located in 16c site in [Li2−yAly]16c[Co2−xAlx−yLiy]16dO4. Actually, operando synchrotron XRD analysis demonstrates no phase transition during cycling [2]. The zero-strain Li2Co2-xAlxO4 cathode can overcome the mechanical instability and offer an extended battery life. On the other hand, electrochemical stability of the Li2Co2-xAlxO4 – electrolyte interface is currently unknown. Although the Al-substitution is an effective approach to stabilize the bulk crystal phase, parasitic reactions occurring at cathode – electrolyte interfaces (CEIs) has been a major issue from different types of spinel materials; e.g., transition metal dissolutions from LiMn2O4 or LiNi0.5Mn1.5O4 [3]. Therefore, it is important to understand the CEI properties of the Li2Co2-xAlxO4 and improving the CEI stability further. In this regard, we examined the effect of LiNbO3 coating on the series of Li2Co2-xAlxO4 (x = 0 – 0.6). The LiNbO3 coating layer can offer a facile Li-ion conduction while passivating the CEI layers. The results show that the LiNbO3 coating enhances the cycle life and rate capabilities of the Li2Co2-xAlxO4 cathodes. Electrochemical impedance spectroscopy (EIS) combined with the distribution of relaxation times (DRT) technique has been studied to identify the improvement mechanisms of the LiNbO3. The aging mechanism of the spinel cathode will be demonstrated by various material characterization and electrochemical analysis. This study will be conducted for conventional Li-ion batteries, but the results will be applicable to all-solid-state batteries via future studies. Reference: [1] D.E. Demirocak, B. Bhushan, J. Power Sources, 280 (2015) 256–262. [2] E. Lee, B.J. Kwon, F. Dogan, Y. Ren, J.R. Croy, M.M. Thackeray, ACS Appl. Mater. Interfaces, 2 (2019) 6170-6175. [3] J.-H. Kim, N.P.W. Pieczonka, Y. Li, ChemPhysChem, 15 (2014) 1940-1954.

Surface-Modified Zero-Strain Spinel-Type Li2Co2-xAlxO4 (where x = 0, 0.3, and 0.60) Cathodes for Lithium-Ion Batteries

Abstract Body: Low work function (WF) materials are necessary for energy storage and conversion devices. Scientific literature is full of explorations made in this field with new and emerging technologies applied to different elements with the purpose of creating low work function materials in the bulk and low dimensional regime. Alkali metals and their alloys with tin, cobalt, indium, etc. have been researched very well in batteries and other energy devices. Alkali metals have been shown to effectively aid in reducing the WF of many metals including Pb, Indium, tin, etc. Particular focus has been laid on Sn/Li alloy system where a work function dip up to 1.25 eV has been shown for a stoichiometric ratio of Sn2Li5[1][2]. Of course, this has been demonstrated to occur in the bulk alloys. However, with the purpose of achieving a similar goal in low dimensions (thin films), we are demonstrating for the first time the formation of a thin film of low work function Sn/Li alloy, formed using physical vapour deposition technique (E-Beam and Thermal Evaporation) at Ultra High Vacuum (UHV) conditions. The experiment utilises the high-end NanoESCA facility at the University of Bristol, UK, where the in situ deposition and the characterisation using X – Ray photoemission spectroscopy (XPS), Ultra-Voilet photoemission spectroscopy (UPS), spot profile low energy electron diffraction (Spa-LEED) techniques is carried out.[3]. In the initial experiments, a single crystal Si substrate was heated at a temperature of 800 oC for the removal of contaminants and Sn was deposited using the E beam deposition while Li was deposited using thermal evaporation method on Si substrate. Si surface was found to be terminated with the oxygen atoms. This should be the reason for the further lowering of WF as oxygen has been found to improve the sticking coefficient between the terminating metal species and the substrate surface. In the beginning, the O terminated Si surface was seen to possess a WF of 4.65 eV and a characteristic 2×1 LEED surface pattern which was then lost due to the disordered Sn and Li layers on the surface. However, Sn 3d peak was seen to shift towards the lower binding energy (B.E.) characteristic of the formation of Sn/Li alloy[4]. The WF was seen to lower to 4.15 eV and the surface was seen to become ordered after going through a series of annealing steps i.e., at 200 oC and 300 oC for 1 hour each and then 350 oC for 2 hours. After the 350 oC anneal, the LEED pattern started emerging. However, the Sn 3d peak was shifted to higher B.E. again which demands further analysis in order to find the optimised stoichiometric ratio between S/Li for ultra-low work function demonstration. [1] K. P. Loh, X. N. Xie, S. W. Yang, J. S. Pan, and P. Wu, “A spectroscopic study of the negative electron affinity of cesium oxide-coated diamond (111) and theoretical calculation of the surface density-of-states on oxygenated diamond (111),” Diam. Relat. Mater., vol. 11, no. 7, pp. 1379–1384, Jul. 2002, doi: 10.1016/S0925-9635(02)00014-6. [2] B. B. Alchagirov, R. K. Arkhestov, and F. F. Dyshekova, “Electron work function in alloys with alkali metals,” Tech. Phys., vol. 57, no. 11, pp. 1541–1546, 2012, doi: 10.1134/S1063784212110023. [3] G. Wan, M. Cattelan, and N. A. Fox, “Electronic structure tunability of diamonds by surface functionalization,” J. Phys. Chem. C, 2019, doi: 10.1021/acs.jpcc.8b11232. [4] D.-T. Shieh, J. Yin, K. Yamamoto, M. Wada, S. Tanase, and T. Sakai, “Surface Characterization on Lithium Insertion/Deinsertion Process for Sputter-Deposited AgSn Thin-Film Electrodes by XPS,” J. Electrochem. Soc., vol. 153, no. 1, p. A106, Dec. 2006, doi: 10.1149/1.2133711.

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