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Rutile Germanium Dioxide (r-GeO$_2$) has been identified as an ultrawide bandgap (UWBG) semiconductor recently, featuring a bandgap of 4.68 eV, comparable to Ga$_2$O$_3$ but offering bipolar dopability, higher electron mobility, higher thermal conductivity, and higher Baliga's figure of merit (BFOM).These superior properties position GeO$_2$ as a promising material for various semiconductor applications. However, the epitaxial growth of r-GeO$_2$, particularly in its most advantageous rutile polymorph, is still at an early stage. This work explores the growth of r-GeO$_2$ using metal-organic chemical vapor deposition (MOCVD) on an r-TiO$_2$ (001) substrate, utilizing tetraethyl germane (TEGe) as the precursor. Our investigations reveal that higher growth temperatures significantly enhance crystalline quality, achieving a full width at half maximum (FWHM) of 0.181 degree at 925 degree C, compared to 0.54 degree at 840 degree C and amorphous structures at 725 degree C. Additionally, we found that longer growth durations increase surface roughness due to the formation of faceted crystals. Meanwhile, adjusting the susceptor rotation speed from 300 RPM to 170 RPM plays a crucial role in optimizing crystalline quality, effectively reducing surface roughness by approximately 15 times. This study offers a foundational guide for optimizing MOCVD growth conditions of r-GeO$_2$ films, emphasizing the crucial need for precise control over deposition temperature and rotation speed to enhance adatom mobility and effectively minimize the boundary layer thickness., Comment: 20 pages, 5 figures, 3 tables

Rutile Germanium Dioxide (GeO2) has been recently theoretically identified as an ultrawide bandgap (UWBG) semiconductor with bandgap 4.68 eV similar to Ga2O3 but having bipolar dopability and ~2x higher electron mobility, Baliga figure of merit (BFOM) and thermal conductivity than Ga2O3. Bulk crystal growth is rapidly moving towards making large sized native substrates available. These outstanding material properties position GeO2 as a highly attractive UWBG semiconductor for various applications. However, the epitaxial growth in the most advantageous polymorph (rutile), ensuring controlled phase, pristine surface/interface quality, precise microstructure, and optimal functional properties, is still in its infancy. In this work, we explored growth of GeO2 by metal-organic chemical vapor deposition (MOCVD) on both C- and R-plane sapphire. Utilizing tetramethylgermane (TMGe) as a precursor, we have investigated the influences of different parameters on the film properties, including growth temperature, chamber pressure, TMGe flow rate, oxygen flow rate, shroud gas flow rate, and rotation speed. The total pressure emerged as a crucial parameter while growth attempts at low total pressure resulted in no films for a wide range of temperatures, precursor flow rate, argon flow rates, and susceptor rotation rate. A phase diagram, derived from our experimental findings, delineates the growth windows for GeO2 films on sapphire substrates. This study serves as a pioneering guide for the MOCVD growth of GeO2 films., Comment: 22 pages, 14 Figures

In ultrawide bandgap (UWBG) nitride and oxide semiconductors, increased bandgap (Eg) correlates with greater ionicity and strong electron-phonon coupling. This limits mobility through polar optical phonon scattering, localizes carriers via polarons and self-trapping, broadens optical transitions via dynamic disorder, and modifies the breakdown field. Herein, we use polarized optical transmission spectroscopy from 77-633 K to investigate the Urbach energy (Eu) for many orientations of Fe- and Sn-doped \b{eta}-Ga2O3 bulk crystals. We find Eu values ranging from 60-140 meV at 293 K and static (structural defects plus zero-point phonons) disorder contributes more to Eu than dynamic (finite temperature phonon-induced) disorder. This is evidenced by lack of systematic Eu anisotropy, and Eu correlating more with X-ray diffraction rocking-curve broadening than with Sn-doping. The lowest measured Eu are ~10x larger than for traditional semiconductors, pointing out that band tail effects need to be carefully considered in these materials for high field electronics. We demonstrate that, because optical transmission through thick samples is sensitive to sub-gap absorption, the commonly-used Tauc extraction of bandgap from transmission through Ga2O3 greater than 1-3 micro meter thick is subject to errors. Combining our Eu(T) from Fe-doped samples with Eg(T) from ellipsometry, we extract a measure of an effective electron-phonon coupling indicating increases in weighted 2nd order deformation potential with temperature and a larger value for E parallel b than E parallel c. The large electron-phonon coupling in beta-Ga2O3 suggests that theories of electrical breakdown for traditional semiconductors need expansion to account not just for lower scattering time but also for impact ionization thresholds fluctuating in both time and space., Comment: 21 pages, 7 figures, 1 table

Diffusion of native defects such as vacancies and their interactions with impurities are fundamental in semiconductor crystal growth, device processing, and long-term aging of equilibration and transient diffusion of vacancies are rarely investigated. We used aluminum-gallium oxide/gallium oxide superlattices (SLs) to detect and analyze transient diffusion of cation vacancies during annealing in O2 at 1000-1100 C. Using a novel finite difference scheme for the diffusion equation with time- and space-varying diffusion constant, we extract diffusion constants for Al, Fe, and cation vacancies under the given conditions, including the vacancy concentration dependence for Al. indicate that vacancies present in the substrate transiently diffuse through the SLs, interacting with Sn as it also diffuses. In the case of SLs grown on Sn-doped beta-gallium oxide substrates, gradients observed in the extent of Al diffusion indicate that vacancies present in the substrate transiently diffuse through the SLs, interacting with Sn as it also diffuses. In the case of SLs grown on (010) Fe-doped substrates, the Al diffusion is uniform through the SLs, indicating a depth-uniform concentration of vacancies. We find no evidence in either case for the introduction of gallium vacancies from the free surface at rates sufficient to affect Al diffusion down to ppm concentrations, which has important bearing on the validity of typically-made assumptions of vacancy equilibration. Additionally, we show that unintentional impurities in Sn-doped gallium oxide such as Fe, Ni, Mn, Cu, and Li also diffuse towards the surface and accumulate. Many of these likely have fast interstitial diffusion modes capable of destabilizing devices over time, thus highlighting the importance of controlling unintentional impurities in beta-gallium oxide wafers., Comment: 11 pages, 4 figures, references a supplimental which will be submitted seperately

The low symmetry of monoclinic $\beta$-Ga$_2$O$_3$ leads to elaborate intrinsic defects, such as Ga vacancies split amongst multiple lattice sites. These defects contribute to fast, anisotropic Ga diffusion, yet their complexity makes it challenging to understand dominant diffusion mechanisms. Here, we predict the 3D diffusivity tensors for Ga interstitials (Ga${_i^{3+}}$) and vacancies (V${_{Ga}^{3-}}$) via first principles and direct solution of the master diffusion equations. We first explore the maximum extent of configurationally complex ''$N$-split'' Ga interstitials and vacancies. With dominant low-energy defects identified, we enumerate all possible elementary hops connecting defect configurations to each other, including interstitialcy hops. Hopping barriers are obtained from nudged elastic band simulations. Finally, the comprehensive sets of (i) defect configurations and their energies and (ii) the hopping barriers that connect them are used to construct the master diffusion equations for both Ga${_i^{3+}}$ and V${_{Ga}^{3-}}$. The solution to these equations yields the Onsager transport coefficients, i.e. the components of the 3D diffusivity tensors $D_{{Ga}_i}$ and $D_{V_{Ga}}$ for Ga${_i^{3+}}$ and V${_{Ga}^{3-}}$, respectively. It further reveals the active diffusion paths along all crystallographic directions. We find that both Ga${_i^{3+}}$ and V${_{{Ga}}^{3-}}$ diffusion are fastest along the $c$-axis, due to 3-split defects that bridge neighboring unit cells along the $c$-axis and divert diffusing species around high-energy bottlenecks. Although isolated Ga${_i^{3+}}$ diffuse faster than isolated V${_{Ga}^{3-}}$, self-diffusion of Ga is predominantly mediated by V$_{Ga}^{3-}$ due to the higher V$_{Ga}^{3-}$ defect concentration under most thermodynamic environments.

Frequently, trends in record AM1.5 power-conversion efficiencies versus time, such as the NREL efficiency chart, are used to analyze the relative merits of different photovoltaic material technologies. However, this approach belies the effort expended in achieving these levels of performance. We introduce cumulative publications as a proxy for total R&D efforts and find surprisingly that silicon, Cu(In,Ga)Se2 (CIGSe), CdTe, and halide perovskite technologies have each followed essentially the same learning curve of 20-24% efficiency within 10,000 publications and a consistent marginal rate of 5% efficiency increase per factor of 10 in publications. While learning spillover from non-PV technologies, cross-pollination from other PV technologies, and hidden commercial effort are not accounted for by this metric, this analysis still yields useful and novel insights into PV technology trajectories. Trajectories below this learning curve have required more total effort per performance and plateaus of efficiency stagnation at large numbers of publications may indicate (but do not guarantee) the existence of fundamental barriers to commercially relevant performance. Lastly, examples to watch are identified for technologies currently exhibiting higher marginal slopes, including some that appeared dormant by this metric in past years.

High-quality dielectric-semiconductor interfaces are critical for reliable high-performance transistors. We report the in-situ metalorganic chemical vapor deposition (MOCVD) of Al$_2$O$_3$ on $\beta$-Ga$_2$O$_3$ as a potentially better alternative to the most commonly used atomic layer deposition (ALD). The growth of Al$_2$O$_3$ is performed in the same reactor as Ga$_2$O$_3$ using trimethylaluminum and O$_2$ as precursors without breaking the vacuum at a growth temperature of 600 $^0$C. The fast and slow near interface traps at the Al$_2$O$_3$/ $\beta$-Ga$_2$O$_3$ interface are identified and quantified using stressed capacitance-voltage (CV) measurements on metal oxide semiconductor capacitor (MOSCAP) structures. The density of shallow and deep level initially filled traps (D$_{it}$) are measured using ultra-violet (UV) assisted CV technique. The average D$_{it}$ for the MOSCAP is determined to be 7.8 $\times$ 10$^{11}$ cm$^{-2}$eV$^{-1}$. The conduction band offset of the Al$_2$O$_3$/ Ga$_2$O$_3$ interface is also determined from CV measurements and found out to be 1.7 eV which is in close agreement with the existing literature reports of ALD Al$_2$O$_3$/ Ga$_2$O$_3$ interface. The current-voltage characteristics are also analyzed and the average breakdown field is extracted to be approximately 5.8 MV/cm. This in-situ Al$_2$O$_3$ dielectric on $\beta$-Ga$_2$O$_3$ with improved dielectric properties can enable Ga$_2$O$_3$-based high performance devices.

We report on the growth and characterization of Ge-doped \b{eta}-Ga2O3 thin films using a solid germanium source. \b{eta}-Ga2O3 thin films were grown using a low-pressure chemical vapor deposition (LPCVD) reactor with either an oxygen or gallium delivery tube. Films were grown on 6 degree offcut sapphire and (010) \b{eta}-Ga2O3 substrates with growth rates between 0.5 - 22 {\mu}m/hr. By controlling the germanium vapor pressure, a wide range of Hall carrier concentrations between 10^17 - 10^19 cm-3 were achieved. Low-temperature Hall data revealed a difference in donor incorporation depending on the reactor configuration. At low growth rates, germanium occupied a single donor energy level between 8 - 10 meV. At higher growth rates, germanium doping predominantly results in a deeper donor energy level at 85 meV. This work shows the effect of reactor design and growth regime on the kinetics of impurity incorporation. Studying donor incorporation in \b{eta}-Ga2O3 is important for the design of high-power electronic devices., Comment: 16 pages,4 figures

Performing deep level transient spectroscopy (DLTS) on Schottky diodes, we investigated defect levels below the conduction band minima (Ec) in Czochralski (CZ) grown unintentionally-doped (UID) and vertical gradient freeze (VGF)-grown Zr-doped beta-Ga2O3 crystals. In UID crystals with an electron concentration of 10^17 cm-3, we observe levels at 0.18 eV and 0.46 eV in addition to the previously reported 0.86 (E2) and 1.03 eV (E3) levels. For 10^18 cm-3 Zr-doped Ga2O3, signatures at 0.30 eV (E15) and 0.71 eV (E16) are present. For the highest Zr doping of 5*10^18 cm-3, we observe only one signature at 0.59 eV. Electric field-enhanced emission rates are demonstrated via increasing the reverse bias during measurement. The 0.86 eV signature in the UID sample displays phonon-assisted tunneling enhanced thermal emission and is consistent with the widely reported E2 (FeGa) defect. The 0.71 eV (E16) signature in the lower-Zr-doped crystal also exhibits phonon-assisted tunneling emission enhancement. Taking into account that the high doping in the Zr-doped diodes also increases the electric field, we propose that the 0.59 eV signature in the highest Zr-doped sample likely corresponds to the 0.71 eV signature in lower-doped samples. Our analysis highlights the importance of testing for and reporting on field-enhanced emission especially the electric field present during DLTS and other characterization experiments on beta-Ga2O3 along with the standard emission energy, cross-section, and lambda-corrected trap density. This is important because of the intended use of beta-Ga2O3 in high-field devices and the many orders of magnitude of possible doping., Comment: 18 pages, 3 figures

The quasi-static anisotropic permittivity parameters of electrically insulating gallium oxide (beta-Ga2O3) were determined by terahertz spectroscopy. Polarization-resolved frequency domain spectroscopy in the spectral range from 200 GHz to 1 THz was carried out on bulk crystals along different orientations. Principal directions for permittivity were determined along crystallographic axes c, and b, and reciprocal lattice direction a*. No significant frequency dispersion in the real part of dielectric permittivity was observed in the measured spectral range. Our results are in excellent agreement with recent radio-frequency capacitance measurements as well as with extrapolations from recent infrared measurements of phonon mode and high frequency contributions, and close the knowledge gap for these parameters in the terahertz spectral range. Our results are important for applications of beta-Ga2O3 in high-frequency electronic devices, Comment: Main Manuscript is 6 pages long with 3 figures and 1 table. The submission also contains a Supplementary Info section

In this work, we use photoluminescence spectroscopy (PL) to monitor changes in the UV, UV', blue, and green emission bands from n-type (010) Ga2O3 films grown by metalorganic vapor phase epitaxy (MOVPE) induced by annealing at different temperatures under O2 ambient. Annealing at successively higher temperatures decreases the overall PL yield and UV intensity at nearly the same rates, indicating the increase in formation of at least one non-radiative defect type. Simultaneously, the PL yield ratios of blue/UV and green/UV increase, suggesting that defects associated with these emissions increase in concentration with O2 annealing. Utilizing the different absorption coefficients of 240 and 266 nm polarization-dependent excitation, we find an overall activation energy for the generation of non-radiative defects of 0.69 eV in the bulk but 1.55 eV near the surface. We also deduce activation energies for the green emission-related defects of 0.60 eV near the surface and 0.89-0.92 eV through the films, whereas the blue-related defects have activation energy in the range 0.43-0.62 eV for all depths. Lastly, we observe hillock surface morphologies and Cr diffusion from the substrate into the film for temperatures above 1050 oC. These observations are consistent with the formation and diffusion of VGa and its complexes as a dominant process during O2 annealing, but further work will be necessary to determine which defects and complexes provide radiative and non-radiative recombination channels and the detailed kinetic processes occurring at surfaces and in bulk amongst defect populations., Comment: 14 pages, 3 figures

We report on the growth and characterization of metalorganic vapor-phase epitaxy-grown \b{eta}-(AlxGa1-x)2O3/\b{eta}-Ga2O3 modulation-doped heterostructures. Electron channel is realized in the heterostructure by utilizing a delta-doped \b{eta}-(AlxGa1-x)2O3 barrier. Electron channel characteristics are studied using transfer length method, capacitance-voltage and Hall measurements. Hall sheet charge density of 1.06 x 1013 cm-2 and mobility of 111 cm2/Vs is measured at room temperature. Fabricated transistor showed peak current of 22 mA/mm and on-off ratio of 8 x 106. Sheet resistance of 5.3 k{\Omega}/Square is measured at room temperature, which includes contribution from a parallel channel in \b{eta}-(AlxGa1-x)2O3., Comment: 22 pages, 4 figures

Currently, Fe doping in the ~10^18 cm-3 range is the most widely-available method for producing semi-insulating single crystalline beta-Ga2O3 substrates. Red luminescence features have been reported from multiple types of Ga2O3 samples including Fe-doped -Ga2O3, and attributed to Fe or N at O. Herein, however, we demonstrate that the high-intensity red luminescence from Fe-doped beta-Ga2O3 commercial substrates consisting of two sharp peaks at 689 nm and 697 nm superimposed on a broader peak centered at 710 nm originates from Cr impurities present at a concentration near 2 ppm. The red emission exhibits two-fold symmetry, peaks in intensity for excitation near absorption edge, seems to compete with Ga2O3 emission at higher excitation energy and appears to be intensified in the presence of Fe. Based on polarized absorption, luminescence observations and Tanabe-Sugano diagram analysis, we propose a resonant energy transfer of photogenerated carriers in beta-Ga2O3 matrix to octahedrally-coordinated Cr3+ to give red luminescence, possibly also sensitized by Fe3+., Comment: 13 pages, 3 figures

This paper reports on the modulation of Schottky barrier heights (SBH) on three different orientations of $\beta$-Ga$_2$O$_3$ by insertion of an ultra-thin SiO$_2$ dielectric interlayer at the metal-semiconductor junction, which can potentially lower the Fermi-level pinning (FLP) effect due to metal-induced gap states (MIGS). Pt and Ni metal-semiconductor (MS) and metal-interlayer-semiconductor (MIS) Schottky barrier diodes were fabricated on bulk n-type doped $\beta$-Ga$_2$O$_3$ single crystal substrates along the (010), (-201) and (100) orientations and were characterized by room temperature current-voltage (I-V) and capacitance-voltage (C-V) measurements. Pt MIS diodes exhibited 0.53 eV and 0.37 eV increment in SBH along the (010) and (-201) orientations respectively as compared to their respective MS counterparts. The highest SBH of 1.81 eV was achieved on the (010)-oriented MIS SBD using Pt metal. The MIS SBDs on (100)-oriented substrates exhibited a dramatic increment ($>$1.5$\times$) in SBH as well as reduction in reverse leakage current. The use of thin dielectric interlayers can be an efficient experimental method to modulate SBH of metal/Ga$_2$O$_3$ junctions., Comment: 8 pages, 10 figures, 2 tables

We report on silicon delta doping of metalorganic vapor-phase epitaxy-grown \b{eta}-Ga2O3 thin films using silane precursor. Delta-doped \b{eta}-Ga2O3 epitaxial films are characterized using capacitance-voltage profiling and secondary-ion mass spectroscopy. Electron sheet charge density in the range of 2.9e12 cm-2 to 8e12 cm-2 with a half width at half maximum ranging from 6.2 nm to 3.5 nm is measured. We also demonstrate a high density (6.4e12 cm-2) degenerate two-dimensional electron gas using a delta-doped \b{eta}-(Al0.26Ga0.74)2O3/\b{eta}-Ga2O3 heterostructure.The total charge could also include a contribution from a parallel channel in the \b{eta}-(Al0.26Ga0.74)2O3 alloy barrier.

Three-dimensional (3D) semimetals have been predicted and demonstrated to have a wide variety of interesting properties associated with its linear energy dispersion. In analogy to two-dimensional (2D) Dirac semimetals, such as graphene, Cd3As2, a 3D semimetal, has shown ultra-high mobility, large Fermi velocity, and has been hypothesized to support plasmons at terahertz frequencies. In this work, we demonstrate synthesis of high-quality large-area Cd3As2 thin-films through thermal evaporation as well as the experimental realization of plasmonic structures consisting of periodic arrays of Cd3As2 stripes. These arrays exhibit sharp resonances at terahertz frequencies with associated quality-factors (Q) as high as ~ 3.7. Such spectrally-narrow resonances can be understood on the basis of a large kinetic-inductance, resulting from a long momentum scattering time, which in our films can approach ~1 ps at room-temperature. Moreover, we demonstrate an ultrafast tunable response through excitation of photo-induced carriers in optical pump / terahertz probe experiments. Our results evidence that the intrinsic 3D nature of Cd3As2 provides for a very robust platform for terahertz plasmonic applications. Overall, our observations pave a way for the development of myriad terahertz (opto) electronic devices based on Cd3As2 and other 3D Dirac semimetals, benefiting from strong coupling of terahertz radiation, ultrafast transient response, magneto-plasmon properties, etc. Moreover, the long momentum scattering time, thus large kinetic inductance in Cd3As2, also holds enormous potential for the re-design of passive elements such as inductors and hence can have a profound impact in the field of RF integrated circuits., Comment: 32 pages, 8 figures

Despite numerous studies on three-dimensional topological insulators (3D TIs), the controlled growth of high quality (bulk-insulating and high mobility) TIs remains a challenging subject. This study investigates the role of growth methods on the synthesis of single crystal stoichiometric BiSbTeSe2 (BSTS). Three types of BSTS samples are prepared using three different methods, namely melting growth (MG), Bridgman growth (BG) and two-step melting-Bridgman growth (MBG). Our results show that the crystal quality of the BSTS depend strongly on the growth method. Crystal structure and composition analyses suggest a better homogeneity and highly-ordered crystal structure in BSTS grown by MBG method. This correlates well to sample electrical transport properties, where a substantial improvement in surface mobility is observed in MBG BSTS devices. The enhancement in crystal quality and mobility allow the observation of well-developed quantum Hall effect at low magnetic field., Comment: 22 pages, 6 figures, 1 table

Herein we review the remarkable range of modifications to materials properties associated with photoexcitation of the growth surface during physical vapor epitaxy of semiconductors. We concentrate on mechanisms producing measureable, utilizable changes in crystalline perfection, phase, composition, doping, and defect distribution. We outline the relevant physics of different mechanisms, concentrating on those yielding effects orthogonal to the primary growth variables of temperature and atomic or molecular fluxes and document the phenomenological effects reported. Based on experimental observations from a range of semiconductor systems and growth conditions, the primary effects include enhanced anion desorption, molecular dissociation, increased doping efficiency, modification to defect populations and improvements to the crystalline quality of epilayers grown at low temperatures. Future research directions and technological applications are also discussed.

In-growth or post-deposition treatment of $Cu_{2}ZnSnS_{4}$ (CZTS) absorber layer had led to improved photovoltaic efficiency, however, the underlying physical mechanism of such improvements are less studied. In this study, the thermodynamics of Na and K related defects in CZTS are investigated from first principle approach using hybrid functional, with chemical potential of Na and K established from various phases of their polysulphides. Both Na and K predominantly substitute on Cu sites similar to their behavior in $Cu(In,Ga)Se_{2}$, in contrast to previous results using the generalized gradient approximation (GGA). All substitutional and interstitial defects are shown to be either shallow levels or highly energetically unfavorable. Defect complexing between Na and abundant intrinsic defects did not show possibility of significant incorporation enhancement or introducing deep n-type levels. The possible benefit of Na incorporation on enhancing photovoltaic efficiency is discussed. The negligible defect solubility of K in CZTS also suggests possible surfactant candidate., Comment: 16 pages, 4 figures

Undesired unintentional doping and doping limits in semiconductors are typically caused by compensating defects with low formation energies. Since the formation energy of a charged defect depends linearly on the Fermi level, doping limits can be especially pronounced in wide bandgap semiconductors where the Fermi level can vary substantially. Introduction of non-equilibrium carrier concentrations during growth or processing alters the chemical potentials of band carriers and thus provides the possibility of modifying populations of charged defects in ways impossible at thermal equilibrium. Herein we demonstrate that, for an ergodic system with excess carriers, the rates of carrier capture and emission involving a defect charge transition level rigorously determine the admixture of electron and hole quasi-Fermi levels determining the formation energy of non-zero charge states of that defect type. To catalog the range of possible responses to excess carriers, we investigate the behavior of a single donor-like defect as functions of extrinsic doping and energy of the charge transition level. The technologically most important finding is that excess carriers will increase the formation energy of compensating defects for most values of the charge transition level in the bandgap. Thus, it may be possible to overcome limitations on doping imposed by native defects. Cases also exist in wide bandgap semiconductors in which the concentration of defects with the same charge polarity as the majority dopant is either left unchanged or actually increases. The causes of these various behaviors are rationalized in terms of the capture and emission rates and guidelines for carrying out experimental tests of this model are given.

In many semiconductors, compensating defects set doping limits, decrease carrier mobility, and reduce minority carrier lifetime thus limiting their utility in devices. Native defects are responsible in many cases, but extrinsic dopants may also act as their own compensation when occupying an alternate lattice site. Suppressing the concentrations of compensating defects during processing close to thermal equilibrium is difficult because formation enthalpies are lowered as the Fermi level moves towards the majority band edge. Excess carriers, introduced for example by photogeneration, modify the formation enthalpy of semiconductor defects and thus can be harnessed during crystal growth or annealing to suppress such defect populations. Herein we develop a rigorous and general model for defect formation in the presence of steady-state excess carrier concentrations by combining the standard quasi-chemical formalism with a detailed-balance description that is applicable for any defect state in the bandgap. Considering the quasi-Fermi levels as chemical potentials, we demonstrate that increasing the minority carrier concentration increases the formation enthalpy for typical compensating centers, thus suppressing their formation. This effect is illustrated for the specific example of native GaSb antisite acceptors in nominally un-doped and extrinsically n-type doped GaSb. The model also predicts reductions in the concentration of ionized scattering centers as well as increased mobility. While our treatment is generalized for excess carrier injection or generation in semiconductors by any means, we provide a set of guidelines for applying the concept in photoassisted physical vapor deposition.

Utilizing three-terminal tunnel emission of ballistic electrons and holes, we have developed a method to self-consistently measure the bandgap of semiconductors and band discontinuities at semiconductor heterojunctions without any prerequisite material parameter. Measurements are performed on lattice-matched GaAs/AlxGa1-xAs and GaAs/(AlxGa1-x)0.51In0.49P single-barrier heterostructures. The bandgaps of AlGaAs and AlGaInP are measured with a resolution of several meV at 4.2 K. For the GaAs/AlGaAs interface, the measured Gamma band offset ratio is 60.4:39.6 (+/-2%). For the GaAs/AlGaInP interface, this ratio varies with the Al mole fraction and is distributed more in the valence band. A non-monotonic Al composition dependence of the conduction band offset at the GaAs/AlGaInP interface is observed in the indirect-gap regime., Comment: 4 pages, 4 figures, submitted to Phys. Rev. Lett.