GOX 2022 Session AC-MoP: Advanced Characterization Techniques Poster Session

Monday, August 8, 2022 5:15 PM in Room Jefferson 1 & Atrium
Monday Evening

Session Abstract Book
(342KB, Oct 9, 2022)
Time Period MoP Sessions | Topic AC Sessions | Time Periods | Topics | GOX 2022 Schedule

AC-MoP-1 Advanced Defect Characterization in b-Ga2O3 Without the Arrhenius Plot
Jian Li (NCKU); Adam Neal, Shin Mou (Air Force Research Laboratory, Materials and Manufacturing Directorate, USA); Man Hoi Wong (University of Massachusetts Lowell)

Defect is one of the issues that limit the present performance of β-Ga2O3 devices. For example, several defects have been observed at 0.6, 0.8. and 1.1 eV below the conduction band edge of β-Ga2O3, which are considered to affect doping compensation, leakage current, and threshold stability in transistors. Conventional detection of β-Ga2O3 defects (in various forms such as Hall, conductivity, admittance spectroscopy, and deep-level transient spectroscopy (DLTS)) is accomplished by inspecting the electrical charge response, which is based on the Arrhenius behavior of the carrier emission rate from a defect determined by the activation energy Ea and the attempt-to-escape frequency ν0. All thermally activated electrical charge response measurements are conventionally analyzed by the Arrhenius plot procedure, where one fits the Arrhenius plot of ln(ν) versus T-1 to a line and extract Ea from the slope and ν0 from theintercept. Improvement of the measurement expediency for extracting Ea and ν0 is desirable to understanding their physiochemical origins and devising mitigation strategies in β-Ga2O3 material and device engineering.

We investigate a ~0.8 eV defect in β-Ga2O3 using a technique that offers substantial improvement over the conventional DLTS technique, specifically in the analytical processing of electrical signal and the extraction of Ea and ν0. The technique bypasses both the rate-window treatment and the Arrhenius plot. First, only the raw capacitance transients in the time domain are needed, which can be readily acquired by general-purpose instruments such as impedance analyzers and lock-in amplifiers. Next, the capacitance transients are projected between the temperature and time domains, as well as to the Ea and ν0 domains. Extraction of Ea and ν0 is accomplished by matching the projected and experimental capacitance transients to each other. The efficient utilization of information from the 2D temperature-time domain allows operation in a smaller temperature/voltage range and extraction of the temperature and electric-field dependence of Ea and ν0.

AC-MoP-2 Infrared-Active Phonon Modes and Static Dielectric Constants of Orthorhombic LiGaO₂
Teresa Gramer, Megan Stokey, Rafal Korlacki, Mathias Schubert (University of Nebraska - Lincoln)

Li2O-Ga2O3 is an oxide system of broader interest. LiGaO2 (LGO) and multiple phases of Ga2O3 (GO) are ultra-wide bandgap metal oxides for future electronic and optoelectronic applications [1], and both LGO, which is orthorhombic, and the orthorhombic phase of GO are expected to be piezoelectric due to the lack of inversion symmetry [1]. While both GO and LGO have recently been identified to most likely trap holes which makes the achievement of sufficient p-type conductivity difficult [2], LGO is particularly promising as a substrate for heteroepitaxial growth of GaN due to very small lattice mismatch (<1%), and a composite LGO/β-GO substrate has also been demonstrated [3]. Here, we provide a thorough study of the fundamental optical and phonon mode properties of high-quality single-crystals of LGO using generalized spectroscopic ellipsometry in combination with hybrid-level density functional theory calculations to investigate the optical properties in the mid- to far-infrared spectral range. From this, all 33 infrared-active pairs of transverse and longitudinal optical phonon modes are observed. We derive the anisotropic midband gap indices of refraction and static dielectric constants.

[1] A review of band structure and material properties of transparent conducting and semiconducting oxides: Ga2O3, Al2O3, In2O3, ZnO, SnO2, CdO, NiO, CuO, and Sc2O3, Joseph A. Spencer, Alyssa L. Mock, Alan G. Jacobs, Mathias Schubert, Yuhao Zhang, and Marko J. Tadjer , Applied Physics Reviews 9, 011315 (2022)

[2] Self-trapped holes and polaronic acceptors in ultrawide-bandgap oxides, John L. Lyons, Journal of Applied Physics 131, 025701 (2022)

[3] Composite substrate LiGaO2 (0 0 1) β-Ga2O3 (1 0 0) fabricated by vapor transport equilibration, Jungang Zhang, Changtai Xia, Shuzhi Li, Xiaodong Xu, Feng Wu, Guangqing Pei, Jun Xu, Shengming Zhou, Qun Deng, Wusheng Xu, Hongsheng Shi, Mater. Lett. 60. 3073-3075. (2006)

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AC-MoP-3 Spectroscopic Ellipsometry Optical Analysis of Zinc Gallate at Elevated Temperatures
Emma Williams (University of Nebraska-Lincoln, USA); Matthew Hilfiker, Ufuk Kilic, Yousra Traouli Traouli, Nate Koeppe, Jose Rivera, Assya Abakar, Megan Stokey, Rafal Korlacki (University of Nebraska - Lincoln); Zbigniew Galazka (Leibniz-Institut für Kristallzüchtung); Mathias Schubert (University of Nebraska - Lincoln)

Zinc gallate (ZnGa2O4) is shown to be a promising alternative to gallium oxide. This is due to the material’s larger bandgap of 5.27(3) eV, compared to that of β-Ga2O3 (5.04 eV), which is linked to a higher Baliga’s figure of merit. [1,2] ZnGa2O4 also contains an isotropic structure, which is advantageous compared to both the monoclinic β-phase and uniaxial α-phase of Ga2O3 in simplifying device design. [2,5] Additionally, ZnGa2O4 growth has rapidly developed to where bulk single crystals can be melt-grown with controllable n-type conductivity. [4]

In this work, the optical properties of ZnGa2O4 are modeled using a spectroscopic ellipsometry approach at temperatures between 22°C and 600°C, where material properties drastically change in elevated temperatures. At each 50°C interval a Cauchy dispersion equation is applied to the transparent region of the data where the refractive index and high-frequency refractive index is derived. Furthermore, a critical point model is implemented across the spectral range of 1 eV to 6.5 eV. This allows for the determination of the bandgap, which is found to red-shift linearly with temperature with a slope of -0.72(4) meV K-1, resulting from the thermal expansion of the lattice. [3] The linear decrease in the bandgap energy when exposed to increasing elevated temperatures is in congruence with behavior shown by common wide bandgap metal oxides. In particular, the reduction of bandgap width as a function of temperature is comparable to that of the ultrawide bandgap material β-Ga2O3, further justifying ZnGa2O4 as a suitable high-power device material. [2,3]


[1] M. Hilfiker et al. Appl. Phys. Lett. 118, 132102 (2021).

[2] A. Mock et al. Appl. Phys. Lett. 112, 041905 (2018).

[3] M. Hilfiker et al. Appl. Phys. Lett. 120, 132105 (2022).

[4] Z. Galazka et al. APL Materials 7, 022512 (2019).

[5] S. J. Pearton et al. Appl. Phys. Lett. 5, 011301 (2018).

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AC-MoP-4 The Electron Spin Hamiltonian for Fe3+ in Monoclinic β-Ga2O3
Steffen Richter (Lund University); Sean Knight, Philipp Kühne (Linköping University); Mathias Schubert (University of Nebraska - Lincoln); Vanya Darakchieva (Lund University)

Large interest in Ga2O3 originates from the possibility to build devices with high breakdown voltage. Understanding electronic defects is essential to utilize the material. As β-Ga2O3 is monoclinic, the effect of the low symmetry needs to be studied. Electron (paramagnetic) spin resonance (EPR) spectroscopy gives access to local site symmetry of spin-carrying defects. Deploying THz ellipsometry [1], we can measure high-field EPR at arbitrary variable frequency by reflection a free beam [2]. This allows true distinction of anisotropic g-factor and zero-field spin splitting, and hence examining the local site symmetry of electronic defects.

Iron incorporated on gallium sites can act as compensating acceptor and facilitate semi-insulating material. Here, we investigate the spin Hamiltonian of the neutral Fe3+ state with spin s=5/2. It is characterized by large zero-field splitting that differs for Fe on octahedral Gaii site (preferential) and Fe on tetrahedral Gai site. Different, partially incorrect, reports exist about the nature of the spin Hamiltonian [3,4]. In contrast to standard EPR measurements at X or Q band with limited access to allowed spin transitions, we obtain EPR scans in the frequency range 110-170GHz at magnetic field between 3 and 7T that capture all five resonances for each Fe site at the same time. Modeling the spin Hamiltonian reveals a slight anisotropy of the g-factor and shows that zero-field splitting up to fourth order is relevant. We will discuss how the monoclinic s=5/2 spin Hamiltonian differs from orthorhombic and/or s=3/2 approximations.

[1] P. Kühne et al., IEEE Trans. Terahertz Sci. Technol. 8(3), 257 (2018).
[2] S. Schubert et al., Appl. Phys Lett. 120, 102101 (2022).
[3] R. Büscher et al., Z. Naturforsch. 42a, 67 (1987).
[4] M. L. Meil’man, Sov. Phys. Sol. State 11(6), 1403 (1969).

The supplemental material features exemplary experimental data and the form of the spin Hamiltonian.

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AC-MoP-5 Characterization of (010) β-Ga2O3 to Support Fabrication, Wafer Size Scaleup, and Epi Development
David Snyder (Penn State Applied Research Laboratory)

Efficient wafer size scaleup of quality (010) β-Ga2O3 substrates and epi development require extensive materials characterization. Over the past two years, the Applied Research Laboratory (ARL) Electronic Materials and Devices Department (EMDD) has partnered with Northrop Grumman’s SYNOPTICS division in support of the Air Force Research Laboratory (AFRL)’s initiative to produce 2-inch epi-ready (010) β-Ga2O3 substrates via the Czochralski (Cz) method. As part of this effort, ARL has developed a multitude of techniques specifically for characterizing β-Ga2O3 substrates at various stages of processing. In this poster, we highlight these techniques and describe the rapid feedback loop that ARL enables between those working on crystal growth, substrate fabrication, epi growth, and device processing within the expanding β-Ga2O3 community.

This poster covers defect mapping and identification, surface metrology, and x-ray characterization. Each of these areas provide essential information about the quality of β-Ga2O3 substrates for subsequent epi growth and ultimately device fabrication. We show how etch pit analysis is used to automatically map defects in up to 2-inch wafers in conjunction with the focused ion beam (FIB) approach to prepare cross-sections for imaging the defect structures, including nanopipes. White light interferometry/profilometry and atomic force microscopy (AFM) provide three-dimensional topography information about the wafers, i.e., after polishing, thermal annealing, or free etching. This poster also describes our method for in-situ high-resolution x-ray characterization during fabrication in which a decrease in full-width at half-maximum (FWHM) was correlated with removal amount to optimize β-Ga2O3 polishing. Finally, we discuss how x-ray characterization provides information about curvature and substrate/epi layer quality with grazing incidence x-ray diffraction (GIXRD) being utilized to provide extremely surface-sensitive monitoring.

AC-MoP-6 Photoluminescence Spectroscopy of Cr3+ in β-Ga2O3 and (Al0.1Ga0.9)2O3
Cassandra Remple, Jani Jesenovec, Benjamin Dutton, John S. McCloy, Matthew D. McCluskey (Washington State University)

Alloying β-Ga2O3 with Al2O3 to create (AlxGa1-x)2O3 enables ultra-wide band gap material deep into the UV. Here, photoluminescence (PL) spectra of Cr3+ dopant is compared between monoclinic single crystals β-Ga2O3, and 10 mol.% Al2O3 alloyed with β-Ga2O3, denoted β-(Al0.1Ga0.9)2O3 or AGO. Temperature dependent PL properties were studied for Cr3+ in AGO and β-Ga2O3 from 285 to 16 K. For β-Ga2O3at room temperature, the red-line emission doublet R1 and R2 occurs at 696 nm (1.78 eV) and 690 nm (1.80 eV) respectively along with a broad emission band at 709 nm (1.75 eV). For both AGO and β-Ga2O3 the R1 line increases in intensity with decreasing temperature. This can be explained by the thermal depopulation effect of the R1 state, which occurs with increasing temperature. The R1 and R2 lines of both materials were observed to blue-shift with decreasing temperature. Additional emission lines emerge at lower temperatures, with β-Ga2O3 showing more peaks than AGO. R1 and R2 peak parameters such as energy, intensity, width, and splitting were studied as a function of temperature, with significant differences between the two materials.

AC-MoP-7 Surface Relaxation and Rumpling of Sn Doped B-ga2o3(010)
Nick Barrett (CEA Saclay); Alexandre Pancotti (Universidade Federal de Jataí); Tyson Back (AFRL); Wassim Hamouda, Myriam Laccheb, Christophe Lubin, Anthony Boucly (CEA Saclay); Patrick Soukiassian (Université Paris-Saclay); John Boeckl, Donald Dorsey, Shiun Mou, Thaddeus Asel (AFRL); Grégory Geneste (CEA)

We have used X-ray Photoelectron Diffraction (XPD), low-energy electron diffraction (LEED), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) to determine the surface structure, chemistry and interplanar relaxation and rumpling in single crystal, Sn-doped b-Ga2O3 (010). XPD is a powerful technique, which combines information on local chemistry and atomic structure. By measuring the angular anisotropy of core level intensity one can, by comparison with simulations, deduce the local atomic and chemical environment around each type of emitting atom. The XPS measurements show typical spectra for stoichiometric Ga2O3(010). Annealing at 823 K yielded a well-ordered surface with sharp (1x1) low-energy electron diffraction (LEED) pattern. AFM shows unique surface termination with root mean square roughness of 0.1-0.15 nm. The XPD measurements were performed using a laboratory based setup with a monochromatic Al Ka (1486.7 eV) source and a high precision angular manipulator capable of scanning both polar (q) and azimuthal (f) angles. The XPD patterns collected for the Ga 2p3/2 and O 1s emission. Surface interlayer relaxation up to 8% of the bulk interplanar distance and 0.11–0.14 Å rumpling are observed at the β-Ga2O3(010) surface. At the surface, the oxygen atoms shift toward the vacuum with respect to the gallium atoms. The rumpling decreases to zero and and the interplanar distance reaches the bulk value of 1.52 Å by the sixth atomic layer. The surface structure agrees with that predicted by first-principles density functional theory calculations which, in addition, suggest a significant band gap narrowing of ≈1 eV in the surface layer, due to surface states spatially localized on surface oxygen atoms of OII type.

A. Pancotti et al. Phys. Rev. B102, 245306 (2020)

AC-MoP-8 Probing Vacancies and Hydrogen Related Defects in β-Ga2O3 with Positrons and FTIR
Corey Halverson, Marc Weber, Jani Jesenovec, Benjamin Dutton, Cassi Remple, Matthew McCluskey, John McCloy (Washington State University)
β-Ga2O3 is a promising material for power electronics. Ubiquitous hydrogen and vacancies strongly influence the electronic properties of these materials. Methods to detect and characterize them are desirable. Fourier Transform Infrared Spectroscopy (FTIR) and Positron Annihilation Spectroscopies (PAS) both have been use with success. Here, they are applied to investigate the hydrogen content in gallium vacancies particularly in the top 6 micrometers below the surface. A Czochralski grown bulk single crystal is explored before and after repeated annealing in vacuum with the main goal to remove hydrogen from the sample. The hydrogen reduction method was first applied with success on single crystal ZnO samples. β-Ga2O3 is sealed in an evacuated hydrogen-depleted quartz tube together with thin foils of titanium. Before sealing the ampoule, the quartz and the titanium are heated repeatedly to drive out trapped hydrogen. Then β-Ga2O3 is annealed at 850C to 900C for up to 8 days while maintaining the Ti-foil at the other end of the ampoule at room temperature. Depth resolved PAS Doppler broadening data reveal significant reduction in the effective positron diffusion length and small changes in the vacancy sensitive width of the annihilation line (S-parameter). These changes reversed by subsequent annealing in hydrogen. The positron data will be presented and correlated with bulk FTIR measurements on the same sample. This work generously supported by the Air Force Office of Scientific Research under award number FA9550-18-1-0507 monitored by Dr. Ali Sayir.
AC-MoP-9 Evolution of Anisotropy and Order of Band-to-Band Transitions, Excitons, Phonons, Static and High Frequency Dielectric Constants Including Strain Dependencies in Alpha and Beta Phase (AlXGa1-X)2O3
Megan Stokey (University of Nebraska-Lincoln); Rafal Korlacki, Matthew Hilfiker, Teresa Gramer (University of Nebraska - Lincoln); Jenna Knudtson (University of Nebraska-Lincoln); Steffen Richter (Lund University); Sean Knight (Linköping University, Sweden); Alyssa Mock (Weber State University); Akhil Mauze, Yuewei Zhang, Jim Speck (University of California Santa Barbara); Riena Jinno, Yongjin Cho, H. Grace Xing, Debdeep Jena (Cornell University); Yuichi Oshima (National Institute for Materials Science); Elaheh Ahmadi (University of Michigan); Vanya Darakchieva (Lund University); Mathias Schubert (University of Nebraska - Lincoln)

The rhombohedral alpha and monoclinic beta phases of gallium oxide both make promising candidates for ultra-wide bandgap semiconductor technology. Of particular interest are alloyed films and the evolution of anisotropic optical properties with respect to both alloy composition and strain induced effects. Here, we study alpha and beta phase (AlxGa1-x)2O3 via a combined density functional theory and generalized spectroscopic ellipsometry approach across a range of alloying. Infrared-active phonon properties, static dielectric constants and midband gap indices of refraction are quantified.[1,2,3] Strain and alloying effects are shown and compared to previous theoretical works.[4] Band-to-band transitions, excitons, and high-frequency dielectric constants are also investigated in the visible to vacuum-ultra-violet (VUV) spectral range.[5,6,7,8] We identify a switch in band order where the lowest band-to-band transition occurs with polarization along the ordinary plane in α-Ga­­23 whereas for α-Al­2O3 the lowest transition occurs with polarization in the extraordinary direction. With this, we present the most comprehensive picture of optical properties’ evolution along composition and strain currently available.

[1] M. Stokey, et al., Phys. Rev. Materials 6, 014601 (2022)

[2] M. Stokey, et al., Appl. Phys. Lett. 120, 112202 (2022)

[3] The influence of strain and composition on the infrared active phonons in epitaxial β-(AlxGa1-x)2O3 deposited onto (010) β-Ga2O3; M. Stokey, et al., In Preparation

[4] R. Korlacki, et al., Rev. B 102, 180101(R) (2020)

[5] M. Hilfiker, et al., Appl. Phys. Lett. 118, 062103 (2021)

[6]Anisotropic dielectric function, direction dependent bandgap energy, band order, and indirect to direct gap cross over in α-(AlxGa1-x)2O3 (0≤x≤1); M. Hilfiker, et al., Appl. Phys. Lett. XX, XX (2022)

[7] M. Hilfiker, et al., Appl. Phys. Lett. 119, 092103 (2021)

[8] M. Hilfiker, et al., Phys. Lett. 114, 231901 (2019)

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AC-MoP-10 Photoluminescence Mapping of Gallium Oxide and Aluminum Gallium Oxide Epitaxial Films
Jacqueline Cooke, Praneeth Ranga (University of Utah); Jani Jesenovec, John McCloy (Washington State University); Sriram Krishnamoorthy (University of California at Santa Barbara); Michael Scarpulla, Berardi Sensale-Rodriguez (University of Utah)

The mechanisms generating photoluminescence (PL) emissions from gallium oxide (Ga2O3) and aluminum gallium oxide (AGO) have been under intense scrutiny. In general, spectrally-resolved PL is used to characterize the defects leading to radiative recombination processes within a specific material. In this regard, the PL spectra for β-Ga2O3 has generally been deconvoluted in three emission bands: UV, blue, and green. So far, the intense debate in defining the defects and phenomenological explanations of electronic processes that cause Ga2O3 and AGO emissions have only explored point defects as the potential source for the PL emission leaving out whether extended defects could affect PL. Because of the strong electron phonon coupling, emission peak shapes from any defect are expected to be very broad and not have a simple functional peak shape; these attributes make it challenging to fit spectra uniquely. Because of this, there is little chance of directly assigning PL spectral features unambiguously to specific β-Ga2O3 point defects from PL alone.

Here, a systematic PL study on multiple series of β-Ga2O3 and AGO epitaxial thin films and bulk single crystals is performed. Spectrally-resolved PL, PL intensity mapping, scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM) were used along with literature to show that extended structural defects largely determine the PL emission from many samples of β-Ga2O3 and AGO. Homogeneous films with no extended defects or stacking faults and bulk crystals yield PL emission with a dominant UV peak, while samples of lesser crystalline quality exhibiting stacking faults, rotation domain boundaries, and other such extended defects do not exhibit a UV emission but rather exhibit blue.

Si-doped homoepitaxial (010) β-Ga2O3 samples yield homogeneous crystalline films with a low density of extended defects and an unshifting dominant UV emission in PL. A bulk (-201) β-Ga2O3 sample shows a dominant UV emission while heteroepitaxial and homoepitaxial (-201) β-Ga2O3 films show dominant blue PL emission (due to the films’ poor quality as seen in PL mapping, AFM and SEM). An AGO series shows consistent blue centered PL for AGO grown on both sapphire and β-Ga2O3 (also due to the films’ poor quality as seen in TEM, PL mapping, AFM and SEM). Lastly, an improved (reduced number of extended defects) 10% AGO film grown on (010) bulk β-Ga2O3 show a shift in the PL spectrum with a now UV dominant emission. PL mapping shows that areas of extended defects emit blue PL while the crystal film emits UV PL within the sample.

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AC-MoP-12 Non-Destructive Characterization of Annealed Si-Implanted Thin Film β-Ga2O3
Aine Connolly, Katie Gann (Cornell University); Stephen Tetlak (Air Force Research Laboratory); Vladimir Protasenko (Cornell University); Michael Slocum, Shin Mou (Air Force Research Laboratory); Michael Thompson (Cornell University)

Selective doping by ion implantation is critical for small-scale device fabrication in wide-bandgap materials such as β-Ga2O3, requiring understanding of both lattice damage due to implantation and subsequent lattice recovery during thermal annealing. Carrier activation, mobility, and diffusion are known to be critically coupled to annealing temperature, time and ambient as well as intrinsic and extrinsic film properties. Electrical measurements provide one measure of annealing behavior, but are limited due to the need for direct metal contacts, the intrinsic spatial averaging, and the inability to directly measure lattice recovery or observe associated defects. To address these limitations, we present Raman spectroscopy and photoluminescence (PL) measurements of β-Ga2O3 implanted and annealed samples, evaluating their ability to local carrier activation and lattice recovery non-destructively.

Recent studies of bulk doped β-Ga2O3 [1] have identified additional Raman peaks in samples with carrier concentrations above the Mott criterion. To determine if these peaks are directly linked to carrier activation, we examined a wide range of Si-implanted (5x1019 cm-3) and annealed samples using a laterally localized Raman probe. A peak at 285 cm-1 was observed above the noise floor in several samples, with the intensity increasingly linearly with sheet carrier density (Ns). The effect of the lattice quality (recovery) on the relative intensities of other Raman peaks was also analyzed.

Previous β-Ga2O3 studies suggest that an increase in activated dopants decreases the total PL, due to the higher defect density and the resultant probability of electrons reaching non-radiative recombination centers [2]. PL behavior of the Si-implanted samples was thus measured as a function of lattice recovery with (N2 ambient) and without (O2 ambient) carrier activation. The Pl signal decreased dramatically after implantation, with partial recovery after thermal anneals and lattice damage recovery. Negative correlation was observed between the PL intensity and carrier activation. Correlations between PL and cathodoluminescence were also measured.

[1] Fiedler, A., Ramsteiner, M., Galazka, Z., and K. Irmscher. Raman scattering in heavily donor doped B-Ga2O3. Appl. Phys. Lett. 117, 152107 (2020)

[2] Shimamura, K., Villora, E.G., Ujiie, T., and K. Aoki. Excitation and photoluminescence of pure and Si-doped B-Ga2O3 single crystals. Appl. Phys. Lett. 92, 201914 (2008).

Session Abstract Book
(342KB, Oct 9, 2022)
Time Period MoP Sessions | Topic AC Sessions | Time Periods | Topics | GOX 2022 Schedule