Search

In this work, the optical properties of thin-film α-Ga2O3 are examined and contrasted with those of β-Ga2O3 thin films grown on similar substrates. Thin films of α-Ga2O3 were synthesized employing mist chemical vapor deposition (mist CVD) on double-side polished c-plane sapphire. Optical properties were studied through absorbance, photoluminescence (PL), and photoluminescence excitation (PLE). Absorbance measurements showed spectra consistent with that previously reported in the literature, with Eg ~ 5.19 eV for α-Ga2O3. Despite an absorption edge laying at higher energies, the PL spectra in α-Ga2O3 films yield similar features to those of metal-organic chemical vapor deposition (MOCVD) grown β-Ga2O3 thin-films. In both cases, when excited above the band gap, the PL spectra consist of UV, UV′, blue and green broad bands. As the excitation photon energy was varied, the relative intensity of these PL bands changed. This is attributed to a non-uniform defect concentration distribution across the sample depth. With smaller concentration of defects associated with blue and green emission in the bulk compared to the surface in the α-phase films.

Thermoelectrics (TEs) are an important class of technology that harvest electric power directly from heat sources. When designing both high performance and environmentally friendly TE materials, the pseudo-cubic structure has great theoretical potential to maximize the dimensionless figure of merit ZT. The TE multinary single crystal with a pseudo-cubic structure paves a new path toward manipulating valley degeneracy and anisotropy with low thermal conductivity caused by short-range lattice distortion. Here, we report a record high ZT = 1.6 around 800 K realized in a totally environmentally benign p-type Na-doped Cu2ZnSnS4 (CZTS) single crystal. The exceptional performance comes from a high power factor while maintaining intrinsically low thermal conductivity. The combination of the pseudo-cubic structure and intrinsic properties of the CZTS single crystal takes advantage of simple material tuning without complex techniques.

The photovoltaic performance of CdTe solar cells is mainly limited by low doping and short minority carrier lifetime. Group-V element doping and Se-alloying have a significant impact on tuning these fundamental CdTe properties. In this paper, we report the growth of p-type As-doped, Cd-rich CdTe1−xSex single crystals using metallic Cd as the solvent in the traveling-heater method. The structural and electrical properties of CdTe1−xSex are examined for different Se concentrations. CdTe1−xSex single crystals (0 ≤ x ≤ 0.5) with zincblende structure indicate homogeneous composition. The 1017 cm−3 As-doping activation efficiency can be maintained at close to 50% for x ≤ 0.2. Se alloying leads to bulk minority carrier lifetime exceeding 30 ns for samples doped near 1017 cm−3. These results help us to overcome the current roadblocks in device performance.

Recent advances in design and processing technology have made possible commercialization of polycrystalline (px)-CdTe as a photovoltaic absorber. Grain boundaries (GBs) are the most prominent struc...

Ultra-fast thermal annealing of semiconductor materials using a laser can be revolutionary for short processing times and low manufacturing costs. Here we investigate Cu–In–Se thin films as precursors for CuInSe2 semiconductor absorber layers via laser annealing. The reaction mechanism of laser annealed metal stacks is revealed by measuring ex situ X-ray diffractograms, Raman spectra and composition. It is shown that the formation of CuInSe2 occurs via the formation of CuxSe/InxSey binary phases as in conventional annealing routes, despite the entirely different annealing time scale. Pre-alloying the Cu and In metals prior to laser annealing significantly enhances the selenisation reaction rate. Laser annealing for six seconds approaches a near phase-pure material, which exhibits similar crystalline quality to the reference material annealed for ninety minutes in a tube furnace. The estimated quasi Fermi level splitting deficit for the laser annealed material is only 60 meV lower than the reference sample, which implies a high optoelectronic quality.

Three-dimensional (3D) semimetals have been predicted and demonstrated to have a wide variety of interesting properties associated with their linear energy dispersion. In analogy to two-dimensional (2D) Dirac semimetals, such as graphene, Cd3As2 has shown ultrahigh mobility and large Fermi velocity and has been hypothesized to support plasmons at terahertz frequencies. In this work, we experimentally 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 (at 0.82 THz). Such spectrally narrow resonances can be understood on the basis of 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 photoinduced carriers in optical pump/terahertz probe experiments. Our results evidence that the intrinsic 3D nature of Cd3As2 might provide for a very robust platform for terahertz plasmonic applications. Moreover, the long momentum scattering time as well as large kinetic inductance in Cd3As2 also holds enormous potential for the redesign of passive elements such as inductors and hence can have a profound impact in the field of RF integrated circuits.

We report on the anisotropy of the terahertz permittivity of β-Ga 2 O 3 through terahertz transmission measurements in single crystals of (010) and (-201) orientation. The electromagnetic wave propagation in this anisotropic crystal is best described with an orthogonal set of eigenmodes, i.e., polarization eigenvectors, wherein each eigenmode possess a distinct refractive index. Polarization-dependent transmission measurements were carried out to ascertain the nature of the eigenmodes and their directions with respect to the crystal axes.

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., 18 pages, 3 figures

Exfoliated gallium oxide (Ga2O3) has been reported as an ultrathin channel material in field-effect transistors. Unlike in 2D materials with van der Waals forces between stacked layers, weak bonding in β-Ga2O3 along the (100) direction enables mechanical exfoliation. The thickness of these exfoliated films has been limited to tens to hundreds of nanometers. Here we summarize our latest work, which followed the process developed by Carey et al., enabling us to attain ~2 nm thick Ga2O3 films over a large surface area (< 1 mm2). The films are characterized using optical microscopy, AFM, XPS, Raman spectroscopy, photoluminescence (PL), and TEM. Optical microscope images showed color changes to the film upon annealing. AFM revealed the film thickness to be as thin as 2 nm over areas << 1 mm2. XPS and Raman spectra revealed characteristic signatures of β-phase Ga2O3. Characteristic PL of Ga2O3 was seen in all samples with overall intensity of luminescence increasing after annealing, attributed to increased crystallinity and grain size. Changes in PL after annealing are associated with an increase in oxygen interstitials and a decrease in oxygen vacancies. Lastly, TEM analysis revealed the film as β-phase Ga2O3 polycrystalline. Overall, our results demonstrate that annealing of thin films obtained from oxide printing of liquid metal Ga is a non-expensive and straightforward process that can lead to β-Ga2O3 films that are nanometer-thin over wafer-scale areas.

Thermoelectrics (TEs) are an important class of technologies for harvesting electric power directly from heat sources. To design high performace TE materials, valleytronics has great theoretical potential to maximize a dimensionless figure of merit ZT but has not yet been demonstrated experimentally. Pseudocubic structure approach based on valleytronics paves a new path to manipulate valley degeneracy and anisotoropy with low thermal conductivity caused by short-range lattice distortion. Here, we report a record high ZT = 1.6 around 800 K, realized in totally enviromentally benign Na-doped Cu2ZnSnS4 (CZTS) single crystal. The exceptional performance comes from a high power factor while maintaining intrinsically low thermal conductivity. The results demonstrate that valleytronics is a new strategy and direction in the TE field, which takes advantage of simple material nature tuning without complex techniques.

We report a volume defect behavior in CdTe crystals grown by the travelling heater method (THM), involving dislocation clustering and grain nucleation. Spurious grain nucleation events occur within a specific radial zone in the crystal where the growth interface is planar. These grains were characterized by Laue x-ray diffraction and were found to have the same angle of misorientation to the bulk, with exception of an in-plane rotation. The grains were connected to columnar dislocation clusters that were aligned parallel to the growth axis of the crystal and were evidently linked to the planar region of the growth interface. Simulation of the growth process was used to investigate the effects of solvent zone convection and interface curvature with different rotational rates. The observed defect behavior was attributed to the effect of melt convection on the interface shape and instability. Evidence of faceting on the growth interface and its correlation with spurious grain nucleation is shown. These findings highlight the importance of interface engineering in THM growth of high quality CdTe single crystals.

We report polarization dependent photoluminescence studies on unintentionally-, Mg-, and Ca-doped β-Ga2O3 bulk crystals grown by the Czochralski method. In particular, we observe a wavelength shift of the highest-energy UV emission which is dependent on the pump photon energy and polarization. For 240 nm (5.17 eV) excitation almost no shift of the UV emission is observed between E||b and E||c, while a shift of the UV emission centroid is clearly observed for 266 nm (4.66 eV), a photon energy lying between the band absorption onsets for the two polarizations. These results are consistent with UV emission originating from transitions between conduction band electrons and two differentially-populated self-trapped hole (STH) states. Calcuations based on hybrid and self-interaction-corrected density functional theories further validate that the polarization dependence is consistent with the relative stability of two STHs. This observation implies that the STHs form primarily at the oxygen atoms involved in the original photon absorption event, thus providing the connection between incident polarization and emission wavelength. The data imposes a lower bound on the energy separation between the self-trapped hole states of ~70–160 meV, which is supported by the calculations.

Perovskites based on methylammonium lead halides, CH3NH3PbX3 (X = Cl, Br, I), have emerged as one of the most promising materials in solar cell technology. Although the photovoltaics field has witn...

The degradation of methyl-ammonium lead iodide (MAPbI3) upon exposure to air is a potentially limiting effect for large scale MAPbI3 photovoltaic production. Here, we report a systematic study on effects of air-exposure on the structural and optical properties of MAPbI3 thin films. The X-ray diffraction studies indicate a shrinking volume of MAPbI3 upon air-exposure as the material decomposes back to its precursors, methyl amine (CH3NH2) and lead iodide (PbI2). However, the photoluminescence (PL) yield and carrier lifetime measured with time-resolved photoluminescence, show an increasing trend upon air-exposure. These phenomena can be explained by self-passivation of MAPbI3 grains by PbI2 layer that reduces the number of non-radiative recombination centres at the grain boundaries. However, this process is not self-limiting and it eventually leads to a film that has completely reverted back to its precursor state. It is shown that this conversion of MAPbI3 film back to its precursors is also accelerated by exposure to laser illumination. Furthermore, we report unusual variation of PL intensity on a shorter time scale of a few seconds in all the films used for the experiment. The variations are found to follow different trends in the encapsulated samples as compared to the un-encapsulated samples. We propose that the decomposition followed by the ionic diffusion through film is responsible for such unusual behaviours.

We report the growth of p -type As-doped, Cd-rich CdTe single crystals using metallic Cd as the solvent in the traveling-heater method. We investigate the growth process from Cd solution in terms of the solid-liquid interface shape and the effects of As incorporation on p -type doping. The resulting CdTe crystals have Cd-rich composition which enhances p -type doping. The As doping efficacy was measured for As concentrations by the combination of inductively coupled plasma mass spectrometry, capacitance-voltage measurements. The p -type doping concentration varied from 6 × 10 15 to 8 × 10 16 cm −3 with increasing As concentration, with an apparent doping limit just below 10 17 cm −3 .

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 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

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.

Spread spectrum time domain reflectometry (SSTDR) can be used to measure complex impedances in live electrical systems by evaluating the shape and magnitude of the reflected signature. A range of capacitors or inductors can be identified, but above and below this range, they cannot be distinguished from open or short circuits. This range depends on the frequency band of the reflectometry system and characteristic impedance of the transmission line. This can be used to characterize changes in complex impedance for the purpose of fault detection in complex loads, such as PV panels and systems.

The process for growing very large CdTe grains on MZO has been explored with the CdCl2 treatment performed for 1-30 minutes for varying film thicknesses and deposition methods.. Large grain growth occurred for thick films after 15 min. at 450°C. The minority lifetime also increased according to room temperature photoluminescence. The activation of the grain growth during the CdCl2 treatment is explained using the CdTe-CdCl2 phase diagram with preferential grain growth for Te rich grain boundaries explained by the Cd-Te-Cl Ternary phase diagram

We investigate the effects of high-rate and high total doses of 60Co gamma rays on the current–voltage (IV) characteristics of GaN p+n diodes grown by metal-organic chemical vapor phase epitaxy on Ga-face (0001) sapphire and hydride vapor phase epitaxy freestanding GaN substrates. We show that diodes grown on sapphire undergo more permanent changes upon irradiation at doses up to 3900 kGy than those grown on freestanding GaN. By combining diode and circular transfer length method measurements, we show that the p-type contact interface and adjacent p++ Mg-doped layer are sensitive to irradiation. In initial experiments, diodes grown on sapphire exhibited p-type contacts with Schottky characteristics, while those on freestanding GaN were Ohmic. Serendipitously, we identified and subsequently irradiated a freestanding sample with a pre-irradiation spatial gradient of p-contact Schottky vs Ohmic behavior across the die. This sample allowed the root cause of induced change to be identified as differences in the p++ contacting layer. We show that the p-type contact's pre-irradiation Schottky behavior is predictive of diodes' IV characteristics changing significantly upon gamma-ray irradiation. Further, we observe that the IV curves of diodes on freestanding GaN recover fully over several weeks at room temperature to be indistinguishable from pre-irradiation. IV curves from diodes on sapphire do not fully recover; we thus hypothesize that interactions between radiation-induced point defects and threading dislocations affect the evolution of radiation damage.

We correct three labeling errors, one in Fig. 4(a), and the other two in Section 3.2 of the manuscript text [Opt. Mater. Express 9, 826 (2019)10.1364/OME.9.000826].

We report on the growth and characterization of Ge-doped β-Ga2O3 thin films using a solid germanium source. β-Ga2O3 thin films were grown using a low-pressure chemical vapor deposition reactor with either an oxygen or a gallium delivery tube. Films were grown on 6° offcut sapphire and (010) β-Ga2O3 substrates with growth rates between 0.5 and 22 μm/h. By controlling the germanium vapor pressure, a wide range of Hall carrier concentrations between 1017 and 1019 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 and 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 β-Ga2O3 is important for the design of high-power electronic devices.

In this work, we use photoluminescence spectroscopy (PL) to monitor changes in the UV, blue, and green emission bands from n-type (010) Ga2O3 films grown by metalorganic vapor phase epitaxy 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 the 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 activation energy for the generation of non-radiative defects of 1.34 eV in the bulk but 2.53 eV near the surface. We also deduce activation energies for the green emission-related defects of 1.20 eV near the surface and 2.21 eV at low temperatures and 0.74 eV at high temperatures through the films, whereas the blue-related defects have activation energy in the range 0.72–0.77 eV for all depths. Lastly, we observe hillock surface morphologies and Cr diffusion from the substrate into the film for temperatures above 1050 °C. These observations are consistent with the formation and diffusion of V Ga 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.

We investigate the impact of high-dose gamma-ray irradiation on the electrical performance of Ga-polar and N-polar GaN-based p–n diodes grown by metalorganic chemical vapor deposition. We compare the current density–voltage (J–V), capacitance–voltage (C–V), and circular transfer length method characteristics of the p–n diodes fabricated on Ga-polar and N-polar orientations before and after irradiation. The relative turn-on voltage increases for the Ga-polar diodes with an increasing irradiation dose, while it increases initially and then starts to decrease for the N-polar diodes. The p-contact total resistance increases for Ga-polar and decreases for N-polar samples, which we attribute to the formation of point defects and additional Mg activation after irradiation. The J–V characteristics of most of the tested diodes recovered over time, suggesting the changes in the J–V characteristics are temporary and potentially due to metastable occupancy of traps after irradiation. X-ray photoelectron spectroscopy and photoluminescence measurements reveal the existence of different types of initial defects and surface electronic states on Ga-polar and N-polar samples. Gallium vacancies (VGa) are dominant defects in Ga-polar samples, while nitrogen vacancies (VN) are dominant in N-polar samples. The presence of a higher concentration of surface states on Ga-polar surfaces than N-polar surfaces was confirmed by calculating the band bending and the corresponding screening effect due to opposite polarization bound charge and ionized acceptors at the surface. The difference in surface stoichiometry in these two orientations is responsible for the different behavior in electrical characteristics after gamma-ray interactions.

Laser annealing can reduce the annealing time required to form Cu(In,Ga)(S,Se)2 (CIGSe) thin films for use in thin film photovoltaics to a single second timescale, if not faster. In this work, we use microstructural characterization coupled with modeling of the optical and thermal properties to understand the laser annealing of three types of electrodeposited precursor stacks for the CIGSe parent compound CuInSe2. The precursor films are: stacked elemental layers Cu/In/Se, stacked binary selenides In2Se3/Cu2−xSe, and a single layer of coelectrodeposited Cu–In–Se. Conceptually, these stacks are ordered in terms of decreasing stored chemical and interfacial potential free energy, consideration of which predicts that the formation of large grained CuInSe2 from the stacked elemental layers would be the most exothermic and thus most rapid process. However we find that microstructural details of the electrodeposited films such as void fraction present in the stacked binary selenides dramatically alter the heat and mass flow. Additionally, modeling of the optical absorption within the elemental stacked precursor suggests extremely localized heating at the In/Se interface resulting in significant Se loss. Despite its lower chemical potential energy, the coelectrodeposited CuInSe2 precursor's more uniform optical absorption of near-bandgap light coupled with its compact, low void fraction microstructure of nano-sized grains results in the most optimal recrystallization and compositional homogenization via interdiffusion. Furthermore this annealed layer formed a working device with a short circuit current density of 23 mA cm−2. This combined modeling and experimental investigation underscores the need to consider practical micro- and nanostructure-dependent properties as well as the optical absorption and not simply thermodynamics when designing accelerated two step deposition and annealing processes for compound semiconductors.

We investigate high-quality Na-doped Cu 2 ZnSnS 4 (CZTS) single crystals grown by using the traveling-heater method and the effect of Na doping on the fundamental properties of these crystals. Na-doped CZTS single crystals were obtained from Sn solution at growth temperatures of 850–900 °C and at speeds of 4 mm/day. The crystals have a kesterite structure, as determined by powder X-ray diffraction and Raman measurements. The Hall effect properties such as hole concentration, conductivity, and hole mobility are enhanced with increasing Na concentration. These results reveal that Na improves the electrical properties of CZTS.

Kesterite Cu2ZnSn(S,Se)4 (CZTSSe) is a sustainable material for thin-film photovoltaics with device efficiencies greater than 12% have been demonstrated. Despite similar crystal structure and polycrystalline film microstructures, there is widespread evidence for larger-amplitude potential and bandgap fluctuations in CZTS than in the analogous Cu(In,Ga)Se2 (CIGSe) chalcopyrite material. This disorder is believed to account for a sizable part of the larger open-circuit voltage (VOC) deficit in CZTS devices, yet the detailed origins and length scales of these fluctuations have not been fully elucidated. Herein, we present a transmission electron microscopy study focusing on composition variation within bulk multicrystals of CZTS grown by the travelling heater method (THM). In these slow-cooled, solution grown crystals we find direct evidence for spatial composition fluctuations of amplitude

The quasi-static anisotropic permittivity parameters of electrically insulating beta gallium oxide (β-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 β-Ga2O3 in high-frequency electronic devices.

Homoepitaxial growth of β-Ga 2O 3 using metalorganic vapor-phase epitaxy (MOVPE) on several different crystal orientations has previously been studied, but growth on the ( 2 ¯ 01 ) plane has remained comparatively unexplored. To investigate this, we grew Si-doped and unintentionally doped (UID) homoepitaxial layers simultaneously on Sn-doped ( 2 ¯ 01 ) and ( 010 ) substrates under conditions optimized for ( 010 ) growth. We report herein on results from current–voltage and capacitance–voltage (IV and CV) and deep level transient spectroscopy (DLTS) characterization of Schottky diodes fabricated on these samples. Devices on ( 010 ) display nearly ideal Schottky diode JV and CV behaviors while for ( 2 ¯ 01 ) evidence of complete depletion of >2 μm thickness, UID epilayers are observed. The ( 2 ¯ 01 ) UID diodes exhibited Mott–Gurney space charge-limited transport and were completely depleted even at zero bias. Doping ( 2 ¯ 01 ) samples heavily with Si was sufficient to overcome background compensation and reproduce near-ideal diode behavior. DLTS data from these doped devices show, in addition to typical negative majority-carrier transients, positive transients with a broad energy distribution, possibly indicating traps on structural defects or surface states. An etch pit analysis under SEM revealed intricate structures of the grown layers. Cross-sectional TEM characterization of a ( 2 ¯ 01 ) sample revealed a high density of structural defects within the epitaxial layer, likely stacking faults. Hypotheses for the origins of the compensation in ( 2 ¯ 01 ) β-Ga 2O 3 homoepitaxial MOVPE growth under ( 010 ) growth conditions are discussed; the most likely explanation is the presence of defect states introduced by the stacking faults visible under TEM.

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

Acceptor doping CdTe with group-V elements is promising for increasing the power conversion efficiency of CdTe photovoltaic devices via an increased hole concentration and open circuit voltage (VOC). In past work, we have investigated doping with As in Cd-rich CdTe single crystals grown using the Cd-solvent traveling heater method we have developed. In this study, we compare the doping parameters and stability of hole concentration in the light and dark for P, As, and Sb dopants in crystals cooled very slowly from the growth temperature to approximate thermal equilibrium. In contrast to older reports of a high acceptor ionization energy for Sb, our temperature dependent Hall effect experiments reveal an acceptor ionization energy slightly above 90 meV for Sb doping in the mid 1016 cm−3 range. Room temperature hole concentrations above 1016 cm−3 are observed for P, As, and Sb with each dopant type exhibiting only small changes in hole concentrations over 2 years' time at room temperature. Crystals doped with P, As, or Sb exhibit increased conductivity after above-gap illumination, which decays over periods of minutes to hours depending on temperature. Analysis of the photoconductivity decay reveals a barrier attributed to hole capture of 190–280 meV for the series P, As, and Sb.

Semiconducting TMDs are promising candidates for THz optoelectronic devices with their ultrafast carrier dynamics and large modulation depths stemming from high photo-induced carrier concentration. In this work, we exploit the ultrafast carrier recombination in photoexcited WSe2 thin films for active THz modulation. The THz absorption was modelled as a sum of a free carrier Drude term and a Lorentzian oscillator for excitonic bound carriers. Based on this, we explore a THz modulator based on a metamaterial structure capacitively coupled to a CVD grown WSe2 film. While the THz absorption upon photoexcitation is strong close to the exciton resonance, the modulation response is limited by free carriers.

Linear energy band dispersion in Dirac semimetals has been associated with strong plasmon coupling in terahertz regime. Graphene, in this regard, has been projected to play crucial role in terahertz optoelectronics due to high carrier mobility and conductivity. However, in the realm of quantum materials, a three-dimension analogue of graphene, Cd 3 As 2 , so called 3D semimetal, has been shown to have carrier mobility and fermi-velocity well exceeding that in graphene. We experimentally demonstrate synthesis of high-quality large-area Cd 3 As 2 thin-films and realization of THz plasmonic structures. The structures exhibit quality factor ~5, at frequency of ~0.7 THz, the highest reported to-date at room temperature in any semiconductor or semimetal. Our results evidence that the 3D nature of Cd 3 As 2 provides for a more robust platform for terahertz applications than what is otherwise possible in graphene.

In this work, we report the different effects of CdCl2 treatment on CdTe films deposited by thermal evaporation onto CdS and MgZnO (MZO) buffer layers. The main finding, which is relevant for understanding recent advances in CdTe device efficiency, is that few- ${\mu}$m thick CdTe films deposited on MZO can be induced to completely recrystallize forming a film consisting of grains that span the film thickness and are up to 30 $\mu$m laterally. On CdS buffer layers, the changes in microstructure with Cl treatment are much less pronounced and the final microstructure is less ideal for thin film photovoltaics. We propose a thermodynamic framework for understanding the microstructural changes during CdCl 2 treatment which can assist in understanding the wide range of behaviors observed across the many CdTe thin film solar cell fabrication procedures.

We report on properties of As doped CdTe single crystals grown from Cd solvent by the travelling heater method.The activation energy of 70 meV derived from temperaturedependent Hall effect are consistent with As Te as the dominant acceptor. Bulk minority carrier lifetimes exceeding 20 ns are observed. We observe persistent photoconductivity, a hallmark of light-induced metastable configuration changes consistent with AX behavior. Cd-rich As-doepd CdTe single crystal was used as absorbing layer in solar cell, and this device can be performed with open-circuit voltage of 900 mV. next.

The effect of Indium (In) doping on CdTe thin film solar cells was investigated. CdTe thin films were deposited using the elemental vapor transport (EVT) technique under various Cd/Te gas phase ratios and In vapor concentrations. TCO/Buffer/n-CdTe/p-ZnTe solar cells have been fabricated and characterized. Indium doping has been found to affect the device performance. Capacitance-voltage (C-V) measurements revealed that net n-type doping increased with In concentration during the EVT deposition. Spectral response (SR) measurements indicated an enhanced carrier collection at higher In concentrations. The open-circuit voltage ($\text{V}_{\mathbf {OC}}$) and fill factor (FF) of the devices was found to increase with increased n-type doping and therefore builtin voltage. To-date n-type CdTe solar cells yielded devices with $\text{V}_{\mathbf {OC}} \quad =$ 730 mV, $\text{J}_{\mathbf {SC}} \quad =$ 20 mA/cm$^{\mathbf {2}} {, \mathbf {FF}} =$textbf 62 % and efficiency near 9 %.

We discuss the optoelectronic property variation between grains and grain boundaries of CdTe polycrystalline thin films using a confocal microscopy system. Single-photon photoluminescence (PL) and time-resolved photoluminescence spectroscopy (PL) is used to map $10 \times 10 \mu \mathrm {m}^{2}$ area at the back surface of CdTe with an optical resolution of 104 nm. TRPL maps show that different grain boundaries have different near-surface lifetimes. Surprisingly, grain-boundaries with high near-surface lifetime are associated with regions of the sample that have low PL yield. This study demonstrates the potential of confocal PL and TRPL mapping to understand carrier lifetime variations in thin films.

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) Ga0.98Mn0.02P and compared it to that of an undoped GaP reference sample, using hard x-ray photoelectron spectroscopy (HXPS) and hard x-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimentaldata,aswellastheoreticalcalculations,tounderstandtheroleoftheMndopantintheemergenceof ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between Ga0.98Mn0.02P and GaP in both angle-resolved and angle-integrated valence spectra. The Ga0.98Mn0.02P bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host GaP crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations and a prior HARPES study of Ga0.97Mn0.03As and GaAs [Gray et al., Nat. Mater. 11, 957 (2012)], demonstrating the strong similarity between these two materials. The Mn 2p and 3s core-level spectra also reveal an essentially identical state in doping both GaAs and GaP.

I–III–VI 2 chalcopyrite compound Cu(In x , Ga 1− x )Se 2 (CIGS) single crystal were successfully grown by traveling heater method (THM). The powder X-ray diffraction (XRD) pattern of the CIGS showed preferred orientations of (112), (220) and (312) planes, confirming the chalcopyrite structure. In Raman spectra, the A 1 mode peaks expected for CIGS were observed, and no secondary phases were observed. The full-width at half-maximum (FWHM) of the X-ray rocking curve (XRC) for the (112) oriented CIGS single crystal is 103 arcsec. The composition of the CIGS single crystal was homogeneous and the stoichiometric ratio of CIGS was found to be slightly Cu-poor, In-rich, Ga-rich and Se-poor. The good-quality single-phase CIGS single crystals can be obtained from these results.

One industrially relevant fabrication method for CuInSe2 absorber layers begins with electrodeposition, which is highly resource efficient and easily up-scalable, followed by a high temperature annealing step. Commonly a furnace is used for annealing, although it is possible to reduce the duration of this step by 2–3 orders of magnitude using laser heating. Past work demonstrated that rastering a 1064 nm, continuous wave, neodymium-doped yttrium aluminium garnet laser beam over an electrodeposited precursor film with 1 s dwell time, promoted CuInSe2 formation, grain growth, and gave a photovoltaic device with 1.6% power conversion efficiency. However, this device showed inhomogeneous current collection correlating approximately to the Gaussian flux profile of the laser beam. This work demonstrates how deviations in the incident laser flux on the precursor lead to local temperature variation in the film. The temperature affects the rates of atomic diffusion, grain growth and chemical reactions, with the hottest region having the largest crystallites and a stoichiometric and constant composition through the film depth. Spatially resolved photoluminescence yield shows a positive correlation to the temperature profile caused by the Gaussian flux. It is expected that with a homogeneous laser beam flux, spatial variations in absorber layer properties would be eliminated, leading to uniform device properties.

Despite the many similarities between Cu2ZnSn(S,Se)4 (CZTSSe) and Cu(In,Ga)(S,Se)2 materials and device architecture, open questions remain about the optimal surface preparation steps for CZTSSe absorbers, including whether differences exist for absorber layers deposited by different methods. In this work, we investigate KCN etching and NH4OH treatment as surface preparation methods for the absorber/CdS interface for two-stage processed CZTSSe and co-evaporated CZTSe absorber layers. Ambient-exposed, thus oxidized and contaminated, thin film absorbers are utilized to examine the effectiveness of these surface preparation methods and to elucidate their effects on device performance. Topography and surface potential images simultaneously obtained by Kelvin probe force microscopy (KPFM) show the existence of an overlayer on the ambient-exposed absorbers. Moreover, KPFM results also demonstrate that although NH4OH treatment removes much of the overlayer from the CZTSSe surface, KCN etching removes the overlayer completely. In addition, differences in the deposited CdS layer and depletion region width result depending on the surface preparation method, with the NH4OH-treated solar cells having narrower depletion region. This is reflected in device results in which KCN-etched solar cells outperform their NH4OH-treated counterparts due to increases in external quantum efficiency at long wavelengths and in open circuit voltage. KPFM measurements also demonstrate that grain boundaries (GBs) in the KCN-etched two-stage processed CZTSSe thin films are either negatively charged or neutral. On the other hand, KCN etching makes the surface almost equipotential in the co-evaporated CZTSe thin film by causing disappearance of positively charged GBs that existed before etching.

The CdTe solar cell back contact interface gets activated by means of thermal annealing. Depending on the back contact (BC) material the annealing time can vary between 20 - 60 minutes. In this study fast contact anneal times - $< 90$ sees - are investigated using a 60 Watt dual diode 808nm laser. Two types of back contacts are used: (a) Cu-Graphite, and (b) MoN/Mo-Cu. Laser power density (LPD) and Cu concentration were varied to study their effect on device performance. Capacitance-voltage characteristics revealed a correlation between LPD and the net doping concentration in CdTe. Higher Cu concentration was found to be detrimental to the device performance, possibly due to excess Cu reaching the CdTe/CdS interface as indicated by secondary ion mass spectroscopy (SIMS) measurements. Solar cells exhibited open-circuit voltage (Voc), short-circuit current (Jsc), and fill-factor (FF) similar to the baseline thermally anneal devices. To-date the LPD was optimized with best cell parameters being: $\mathrm{V_{oc}} ={830} \ \mathrm{mV}, \ \mathrm{J_{sc}} ={22} \ \mathrm{mA/cm}^{2}$, and $\mathrm{FF}=70\%$, for laser anneal time of 90 seconds.

In this paper we study the structural properties of Cu 2 ZnSnS 4 (CZTS) synthesized by cosputtering binary sulfide followed rapid thermal annealing (RTA) as functions of temperature and composition. By annealing identical samples at different temperatures we were able to find the optimum temperature for annealing samples in our RTA furnace. With this information, we annealed samples with a variety of discrete compositions at the optimum temperature to study the compositional differences on the optical, electrical and the structural differences on CZTS thin film crystallization. Samples were evaluated by x-ray diffraction, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Sample rich in Cu tended to form areas of CU 2-x S. It was confirmed that Sn loss during annealing increases with increased annealing temperature. Samples rich in tin before annealing grew larger grains indicating that Sn can also playa role in grain growth.

Photon absorption is a critical process for photovoltaic operation, yet the effect of illumination on semiconductor growth and processing is rarely investigated. In this work we investigate the effect of illumination during the cadmium chloride (CdCl2) annealing treatment of cadmium telluride (CdTe) thin films for photovoltaic applications while keeping the sample temperature constant. Illumination at 808 nm with varying intensity (0, 0.5, 1 and 1.5 W) when incident on CdTe during thermal CdCl2 treatment of CdTe lead to enhancement of grain size and optoelectronic properties of CdTe. However photoassisted etching of the CdTe surface is also observed at illuminations sufficiently low that the sample temperature was barely affected during annealing. Additionally, annealing under high illumination sufficient to drive CdCl2 annealing in the absence of a furnace has no such effect on the CdTe surface. We attempt to reconcile these observations and provide rationale for further experiments.

Cd-rich CdTe single crystals were grown from Cd solvent in the traveling-heater method (THM) rather than the more common Te solvent used for high-resistivity CdTe. The growth process from Cd solution in terms of the solid-liquid interface shape and group- V doping under Cd-rich condition were investigated. Stable, flat solid-liquid interfaces can be obtained by optimizing THM furnace temperature profile. An apparent doping limit in the 1016 to 1017cm−3range which scales weakly with increasing group- V element concentrations in the Cd-rich CdTe samples were indicated from capacitance-voltage measurement. The two-photon excitation time-resolved photoluminescence revealed a bulk lifetime of 20–40 ns.

Larger grain sizes and crystallographic texture in the absorber layer are correlated with performance in polycrystalline inorganic thin film solar cells because they lead to reduced densities of recombination centers and traps at grain boundaries. In this work, we compare the effects of rapid thermal annealing (RTA) and furnace annealing on film morphology, grain growth, and crystallographic texture in Cu2ZnSnS4 (CZTS) thin films deposited on Mo-coated glass by RF cosputtering. Using x-ray diffraction (XRD),scanning electron microscopy (SEM), and electron backscatter diffraction (EBSD), we show that RTA induces significant grain growth and texture without the degradation of the substrate caused in furnace annealing by the high temperatures required for CZTS phase formation. CZTS grains grown in RTA annealed samples were 2–3 times larger than those in furnace-annealed samples. Significantly, this is demonstrated in RTA on sodium-free glass which implies that RTA and similar processing methods may be capable of producing desirable CZTS grain distributions on alternative substrates such as metal foil, plastic, or thin glass.