Search

Gallium oxide (Ga2O3) is a promising semiconductor for next-generation high-power electronics due to its ultra-wide bandgap and high critical breakdown field. To utilize its unique electrical properties for real-world applications, an accurate description of its electronic structure under device-operating conditions is required. Although the majority of first-principles models focus on the ground state, temperature effects govern the key properties of all semiconductors, including carrier mobility, band edge positions, and optical absorption in indirect gap materials. We report on the temperature-dependent electronic band structure of β-Ga2O3 in a wide temperature range from T = 0 to 900 K using first-principles simulations and optical measurements. Band edge shifts from lattice thermal expansion and phonon-induced lattice vibrations known as electron–phonon renormalization are evaluated by utilizing the quasi-harmonic approximation and the recently developed “one-shot” frozen phonon method, respectively. Electron–phonon effects and thermal expansion together induce a substantial temperature-dependence on the bandgap, reducing it by more than 0.5 eV between T = 0 and 900 K, larger than that observed in other wide bandgap materials. Key implications, including an increase in carrier concentrations, a reduction in carrier mobilities due to localization of band edge states, and an ∼20% reduction in the critical breakdown field, are discussed. Our prediction of temperature-dependent bandgap matches very well with experimental measurements and highlights the importance of accounting for such effects in first-principles simulations of wide bandgap semiconductors.

In this work, we quantify electronic and ionic contributions to conductivity in the bulk and depletion widths of back-to-back sputtered Pt Schottky contacts on single crystals of β-Ga2O3. We also demonstrate asymmetric changes to these contacts induced by DC bias at temperatures as low as 200 °C, which has obvious bearing on the performance and reliability of devices. Crystals, which were unintentionally doped, doped with Zr donors, and doped with Mg acceptors, were characterized from room temperature to 900 °C. Electrochemical impedance spectroscopy, current–voltage (IV), capacitance–voltage, and the Wagner DC polarization method were employed to characterize changes in conductivity, doping, and built-in potentials with temperature and bias. This work demonstrates that ionic conductivity can be on-par with electronic conductivity in multiple circumstances in bulk crystal samples and leads to changes in Schottky contacts with an applied bias. While it has not been demonstrated that these phenomena are endemic to all melt-grown β-Ga2O3 crystals and epitaxially grown layers were not investigated, these results highlight the importance of understanding and controlling ionic conductivity and defect reactions involving impurities and native defects to enable reliable and long-lived β-Ga2O3 power devices.

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.

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.

Unintentional doping and doping limits in semiconductors are typically caused by compensating defects with low formation energies. Since the formation enthalpy 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 allows populations of charged defects to be modified in ways impossible at thermal equilibrium. We demonstrate that in the presence of excess carriers, the rates of carrier capture and emission involving a defect charge transition level determine the admixture of electron and hole quasi-Fermi levels involved in the formation enthalpy of non-zero charge defect states. To understand the range of possible responses, we investigate the behavior of a single donor-like defect as functions of extrinsic doping and charge transition level energy. We find that that excess carriers will increase the formation enthalpy of compensating defects for most values of the charge transition level in the bandgap. Thus, it may be possible to use non-equilibrium carrier concentrations to overcome limitations on doping imposed by native defects. Cases also exist in which the concentration of defects with the same charge polarity as the majority dopant is either left unchanged or actually increases. This surprising effect arises when emission rates are suppressed relative to the capture rates and is most pronounced in wide bandgap semiconductors. We provide guidelines for carrying out experimental tests of this model.

Group-V element doping is promising for simultaneously maximizing the hole concentration and minority carrier lifetime in CdTe for thin film solar cells, but there are roadblocks concerning point defects including the possibility of self-compensation by AX metastability. Herein, we report on doping, lifetime, and mobility of CdTe single crystals doped with As between 1016 and 1020 cm−3 grown from the Cd solvent by the travelling heater method. Evidence consistent with AX instability as a major contributor to compensation in samples doped below 1017 cm−3 is presented, while for higher-doped samples, precipitation of a second phase on planar structural defects is also observed and may explain spatial variation in properties such as lifetime. Rapid cooling after crystal growth increases doping efficiency and mobility for times up to 20–30 days at room temperature with the highest efficiencies observed close to 45% and a hole mobility of 70 cm2/Vs at room temperature. A doping limit in the low 1017/cm3 range is observed for samples quenched at 200–300 °C/h. Bulk minority carrier lifetimes exceeding 20 ns are observed for samples doped near 1016 cm−3 relaxed in the dark and for unintentionally doped samples, while a lifetime of nearly 5 ns is observed for 1018 cm−3 As doping. These results help us to establish limits on properties expected for group-V doped CdTe polycrystalline thin films for use in photovoltaics.

We have synthesized ternary and quaternary diluted II-VI oxides using the combination of O ion implantation and pulsed laser melting. CdO{sub x}Te{sub 1-x} thin films with x up to 0.015, and the energy gap reduced by 150 meV were formed by O{sup +}-implantation in CdTe followed by pulsed laser melting. Quaternary Cd{sub 0.6}Mn{sub 0.4}O{sub x}Te{sub 1-x} and Zn{sub 0.88}Mn{sub 0.12}O{sub x}Te{sub 1-x} with mole fraction of incorporated O as high as 0.03 were also formed. The enhanced O incorporation in Mn-containing alloys is believed to be due to the formation of relatively strong Mn-O bonds. Optical transitions associated with the lower (E{sub -}) and upper (E{sub +}) conduction subbands resulting from the anticrossing interaction between the localized O states and the extended conduction states of the host are clearly observed in these quaternary diluted II-VI oxides. These alloys fulfill the criteria for a multiband semiconductor that has been proposed as a material for making high efficiency, single-junction solar cells.

We present a systematic investigation on the formation of the highly mismatched alloy GaN{sub x}As{sub 1-x} using N{sup +}-implantation followed by a combination of pulsed laser melting and rapid thermal annealing. Thin films of GaN{sub x}As{sub 1-x} with x as high as 0.016 and an activation efficiency of the implanted N up to 50% have been synthesized with structural and optical properties comparable to films grown by epitaxial deposition techniques with similar substitutional N content. The effects of N{sup +} implantation dose, laser energy fluence and rapid thermal annealing temperature on the N incorporation as well as optical and structural properties of the GaN{sub x}As{sub 1-x} films are discussed.

We have studied the wind driven movement of thin perfluoropolyether (PFPE) polymer films on silicon wafers and CNx overcoats using the blow-off technique. The ease with which a liquid polymer film moves across a surface when sheared is described by a shear mobility χS, which can be interpreted both in terms of continuum flow and in terms of wind driven diffusion. Generally, we find that the movement of PFPE films can be described as a flow process with an effective viscosity, even when the film thickness is smaller than the polymer’s diameter of gyration. Only in the special case of sparse coverage of a polymer with neutral end groups is the motion better described by a wind driven diffusion process. The addition of alcohol end groups to the PFPE polymer chain results in strong interactions with the substrate, creating a restricted layer having an effective viscosity an order of magnitude larger than the mobile layer that sits on top of the restricted layer.

Cd-rich composition and group-V element doping are of interest for simultaneously maximizing the hole concentration and minority carrier lifetime in CdTe, but the critical details concerning point defects are not yet fully established. Herein, we report on the properties of arsenic doped CdTe single crystals grown from Cd solvent by the travelling heater method. The photoluminescence spectra and activation energy of 74 ± 2 meV derived from the temperature-dependent Hall effect are consistent with AsTe as the dominant acceptor. Doping in the 1016 to 1017/cm3 range is achieved for measured As concentrations between 1016 and 1020/cm3 with the highest doping efficiency of 40% occurring near 1017 As/cm3. We observe persistent photoconductivity, a hallmark of light-induced metastable configuration changes consistent with AX behavior. Additionally, quenching experiments reveal at least two mechanisms of increased p-type doping in the dark, one decaying over 2–3 weeks and the other persisting for at least 2 month...

We report photomodulation spectroscopy measurements of the pressure dependence of the optical transition in Zn1−yMnyOxTe1−x alloys that is associated with the lowest Γ conduction band (termed E− subband). The pressure-induced energy shift of the E− transition is nonlinear and much weaker as compared to the change of the direct band gap of Zn0.88Mn0.12Te. The weak pressure dependence of the E− transition can be fully understood based on the band anticrossing model in which the E− subband results from an interaction between the extended ZnMnTe conduction-band states and the localized O electronic states.

The greatest challenge for improving the power conversion efficiency of Cu2ZnSn(S,Se)4 (CZTSSe)/CdS/ZnO thin film solar cells is increasing the open circuit voltage (VOC). Probable leading causes of the VOC deficit in state-of-the-art CZTSSe devices have been identified as bulk recombination, band tails, and the intertwined effects of CZTSSe/CdS band offset, interface defects, and interface recombination. In this work, we demonstrate the modification of the CZTSSe absorber/CdS buffer interface following the deposition of 1 nm-thick Al2O3 layers by atomic layer deposition (ALD) near room temperature. Capacitance-voltage profiling and quantum efficiency measurements reveal that ALD-Al2O3 interface modification reduces the density of acceptor-like states at the heterojunction resulting in reduced interface recombination and wider depletion width. Indications of increased VOC resulting from the modification of the heterojunction interface as a result of ALD-Al2O3 treatment are presented. These results, while ...

The high performance of polycrystalline CdTethin film solar cells is enabled by annealing in the presence of Cl. This process is typically carried out for tens of minutes resulting in reduction of defect states within the bandgap among other beneficial effects. In this work, we investigate laser annealing as a means of rapidly annealing CdTe using a continuous wave sub-bandgap 1064 nm laser. The partial transmission of the beam allows us to monitor the annealing process in-situ and in real time. We find that optoelectronic and structural changes occur through two distinct kinetic processes resulting in the removal of deep defects and twinned regions, respectively. A multilayer optical model including surface roughness is used to interpret both the in-situ transmission as well as ex-situreflectivitymeasurements. These experiments demonstrate beneficial material changes resulting from sub-bandgap laser-driven CdCl2 treatment of CdTe in minutes, which is an important step towards accelerating the processing of the CdTe absorber layer.

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, U.S. Department of Energy, under Contract No. DE-AC03-76SF00098. One of the authors ~M.A.S.! acknowledges support by an NSF graduate research fellowship.

The work at the Lawrence Berkeley National Laboratory was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098. The work at Harvard was supported by NASA Grant No. NAG8-1680. One of the authors ~M.A.S.! acknowledges support from an NSF Graduate Research Fellowship.

Laser processing of polycrystalline CdTe is a promising approach that could potentially increase module manufacturing throughput while reducing capital expenditure costs. For these benefits to be realized, the basic effects of laser irradiation on CdTe must be ascertained. In this study, we utilize surface photovoltage spectroscopy (SPS) to investigate the changes to the electronic properties of the surface of polycrystalline CdTe solar cell stacks induced by continuous-wave laser annealing. The experimental data explained within a model consisting of two space charge regions, one at the CdTe/air interface and one at the CdTe/CdS junction, are used to interpret our SPS results. The frequency dependence and phase spectra of the SPS signal are also discussed. To support the SPS findings, low-temperature spectrally-resolved photoluminescence and time-resolved photoluminescence were also measured. The data show that a modest laser treatment of 250 W/cm2 with a dwell time of 20 s is sufficient to reduce the ef...

The effects of nanosecond pulsed ultraviolet laser annealing on the surface stoichiometry of close-space sublimated polycrystalline thin films are investigated using angle-resolved x-ray photoemission spectroscopy (XPS). The raw data suggest the formation of a Cd-rich surface layer, but this is counter to the expectation based on Cd and Te vapor pressures above CdTe that predicts a Te-rich layer and to direct observation of elemental Te at the surface. In order to explain this apparent discrepancy, we analyze our XPS data in the context of prior reports of lateral segregation of Cd and Te at the surface after pulsed laser treatments with a simple model of angular dependent XPS in the presence of surface roughness. This analysis reveals that a uniform Te layer cannot explain our results. Instead, our analysis suggests that Te enrichment occurs near grain boundaries and that a sub-monolayer Cd layer exists elsewhere. These complex yet repeatable results underscore the challenges in measuring surface stoichiometry to high precision on films relevant for polycrystalline CdTe devices. It also suggests that the Cd and Te vapor pressures above grain boundaries may differ from those above grain interiors and that ohmic contact may be made preferentially at the grain boundaries after pulsed laser annealing.

Cu2ZnSnS4 is a promising low-cost, nontoxic, earth-abundant absorber material for thin-film solar cell applications. In this study, combinatorial coevaporation was used to synthesize individual thin-film samples spanning a wide range of compositions at low (325 °C) and high (475 °C) temperatures. Film composition, grain morphology, crystalline-phase and photo-excitation information have been characterized by x-ray fluorescence, scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and photoluminescence imaging and mapping. Highly textured columnar grain morphology is observed for film compositions along the ZnS-Cu2ZnSnS4-Cu2SnS3 tie line in the quasi-ternary Cu2S-ZnS-SnS2 phase system, and this effect is attributed to structural similarity between the Cu2ZnSnS4, Cu2SnS3, and ZnS crystalline phases. At 475 °C growth temperature, Sn-S phases cannot condense because of their high vapor pressures. As a result, regions that received excess Sn flux during growth produced compositions falling alon...

Cu2ZnSn(S,Se)4 (CZTSSe) is an earth-abundant semiconductor with potential for economical photovoltaic power generation at terawatt scales. In this work, we use Raman scattering to investigate phase coexistence in combinatorial CZTS thin films grown at 325 or 470 °C. The surface of the samples grown at 325 °C is rough except for a prominent specularly reflective band near and along the ZnS-Cu2SnS3 (CTS) tie line in the Cu-Zn-Sn-S quaternary phase diagram. All structurally incoherent secondary phases (SnS2, CuS) exist only as surface phases or are embedded as separate grains, whereas the structurally coherent secondary phase CTS coexists with CZTS in the dense underlying film. In films grown at 325 °C, which are kinetically trapped by the low growth temperature, a change is observed in Cu and Sn site occupancy, evidenced by the shift from cubic-CTS in the Cu-rich region (Cu/Sn > 2) to more tetragonal-CTS in the Sn-rich region (Cu/Sn

We have studied the effect of sodium on the electrical properties of Cu2ZnSnS4 (CZTS) single crystal by using temperature dependence of Hall effect measurement. The sodium substitution on the cation site in CZTS is observed from the increasing of unit-cell size by powder X-ray diffraction. Sodium increases the effective hole concentration and makes the thermal activation energy smaller. The degree of compensation decreases with sodium incorporation, thus the hole mobility is enhanced. We revealed that sodium is important dopant in CZTS to control the electrical properties.

Creating an ohmic back contact has long been a problem for making efficient CdTe solar cells. Current devices utilize some combination of preferential chemical etching, buffer layer, and Cu doping with additional cost, time, and complexity added for each step. In this Letter, these processes are eschewed and replaced with a nanosecond pulsed ultraviolet laser treatment. It is shown that this treatment can eliminate the rollover effect seen in photovoltaic current-voltage (J-V) curves that is indicative of a non-ohmic back contact. Transfer length measurements show that a single UV laser pulse can reduce the specific contact resistivity by a factor of 24 versus untreated samples. X-Ray photoemission spectroscopy shows evidence of increased conductivity and of elemental Te created at the surface by laser pulses. Finally, finite element modeling is used to model the laser-sample interaction, which predicts both the temperature and the amounts of Cd and Te lost during a laser pulse.

Native defects are ubiquitous especially in compound semiconductors and dominate the properties of many materials. Applying first principles calculations, we propose a novel strategy to tune native defect populations in Cu2ZnSn(S,Se)4 which is an emerging photovoltaic absorber material. The formation of Cu vacancies (VCu), which are predicted to be shallower acceptors than Cu on Zn antisites (CuZn), can be greatly promoted by compressive strain. Additionally, nonlinearities are found in the strain dependence of the VCu formation energy. Both uniform and non-uniform strains may be present in physical samples implying probable variations in native defect concentrations.

CuInSe2 (CISe) is a prototype material for the I–III–VI chalcopyrites such as Cu(In,Ga)(S,Se)2 (CIGSSe) used as absorber layers in thin film photovoltaic cells. These thin film photovoltaic absorber layers are primarily synthesized by vacuum-based techniques in manufacturing. In this work, we investigate non-vacuum film synthesis by electrochemical deposition of CISe from a single bath followed by continuous wave laser annealing (CWLA) using a 1064 nm laser. We find that parameters exist for near-infrared CWLA which result in structural changes without melting and dewetting of the films. While Cu-poor samples show only about 40% reduction in the full width at half maximum (FWHM) of the respective x-ray diffraction (XRD) peaks, identically treated Cu-rich samples indicate a FWHM reduction of more than 70% in the XRD and Raman scattering data for irradiation at 50 W/cm2. This study demonstrates that an entirely solid-phase annealing path driven by intense illumination exists for chalopyrite phase formation and crystallization from electrodeposited CISe thin films.

We elucidate the dominant physical mechanisms for enhanced light absorption in thin film solar cells with embedded dielectric nanoparticles and conformal surface texturing. A prior work reported enhancement in short-circuit current for such a structure and attributed this gain to increased photon absorption due to Mie scattering by the embedded nanoparticles [S. Nunomura, A. Minowa, H. Sai, and M. Kondo, Appl. Phys. Lett. 97(6), 063507 (2010)]. On the contrary, simulations indicate that absorption gain is categorically dominated by the roughened surface texture that resulted from conformal overgrowth of amorphous silicon above the deposited dielectric nanoparticles.

The temperature-dependent conductivity of Cu2ZnSnS4 (CZTS) thin films prepared by sulfurization of different sputtered ZnS/Cu/Sn stacks and also of the same stack annealed for different times was investigated from 30-300 K. Fitting of the through-thickness conductivity requires a model including Mott variable-range hopping (M-VRH), nearest-neighbor hopping (NNH), and thermionic emission over grain boundary (GB) barriers. The GB barrier height varies sensitively from 50–150 (±5) meV with annealing and especially with [Cu]/([Zn] + [Sn]) ratio but is independent of [Zn]/[Sn] ratio. These results are critical for understanding the behavior of solar cells based on polycrystalline CZTS absorber layers.

Some of the authors thank for the support of the Center for Nanoscale Systems (CNS) at Harvard University is acknowledged. Harvard-CNS is a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award No. ECS-0335765. K. M. Yu and J. W. Beeman were supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

We measured the magnetic anisotropy of nearly fully relaxed ferromagnetic Ga1−xMnxAs formed by Mn ion implantation followed by pulsed-laser melting (II-PLM) using magnetometry and ferromagnetic resonance. In qualitative terms the material formed by II-PLM exhibits all magnetic anisotropy features commonly found in Ga1−xMnxAs films fabricated by low-temperature molecular beam epitaxy (LT-MBE). Quantitatively, however, the magnetic anisotropy of II-PLM Ga1−xMnxAs is dominated by cubic anisotropy terms, which we attribute to the smaller strain in the II-PLM material due to the absence of Mn interstitials. One should note, however, that II-PLM Ga1−xMnxAs also exhibits a weak but finite uniaxial in-plane magnetic anisotropy similar to that observed in LT-MBE Ga1−xMnxAs, which can be ascribed to the small built-in compressive strain. The similarity between II-PLM and LT-MBE Ga1−xMnxAs clearly points to an intrinsic origin of this property, independent of the method of fabrication. At low temperatures the remnan...

We report the passivation of the Mn acceptors in Ga1−xMnxP upon exposure to a hydrogen plasma. The as-grown films are nonmetallic and ferromagnetic with a Curie temperature of TC=55 K. After hydrogenation the sample resistivity increases by approximately three orders of magnitude at room temperature and six orders of magnitude at 25 K. Furthermore, the hydrogenated samples are paramagnetic, which is evidenced by a magnetization curve at 5 K that is best described by a Brillouin function with g=2 and J=5/2 expected for Mn atoms in the 3d5 configuration. Upon annealing, partial depassivation and a recovery of ferromagnetism are observed. These observations unambiguously demonstrate that the ferromagnetism in Ga1−xMnxP is carrier-mediated similar to Ga1−xMnxAs.

The electronic and magnetic effects of intentional compensation with non-magnetic donors are investigated in the ferromagnetic semiconductors Ga1-xMnxAs and Ga1-xMnxP synthesized using ion implantation and pulsed-laser melting (II-PLM). It is demonstrated that compensation with non-magnetic donors and MnI have similarqualitative effects on materials properties. With compensation TC decreases, resistivity increases, and stronger magnetoresistance and anomalous Hall effect attributed to skew scattering are observed. Ga1-xMnxAs can be controllably compensated with Te through a metal-insulator transition through which the magnetic and electrical properties vary continuously. The resistivity of insulating Ga1-xMnxAs:Te can be described by thermal activation to the mobility edge and simply-activated hopping transport. Ga1-xMnxP doped with S is insulating at all compositions but shows decreasing TC with compensation. The existence of a ferromagnetic insulating state in Ga1-xMnxAs:Te and Ga1-xMnxP:S having TCs of the same order as the uncompensated materials demonstrates that localized holes are effective at mediating ferromagnetism in ferromagnetic semiconductors through the percolation of ferromagnetic 'puddles' which at low temperatures.

We report strong near-infrared absorption peaks in epitaxial films of GaAs and AlAs containing approximately 0.5–5% of the semimetal ErAs. The energy of the resonant absorption peak can be changed from 0.62to1.0eV (2.2–1.4μm) by variation of the ErAs volume fraction and the substrate temperature. We interpret the infrared absorption in terms of transitions across an energy gap caused by a confinement-induced semimetal-semiconductor transition. An effective mass model relates the changes in nanoparticle diameter observed in transmission electron microscopy to the energy gap.

We have measured the X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD)at the Mn L3,2 edges in ferromagnetic Ga1-xMnxP for 0.018

We have investigated the effect of film thickness on the distribution of Mn atoms at various lattice sites in Ga1−xMnxAs thin films. We find that the growth surface acts as a sink facilitating the outdiffusion of Mn interstitials (MnI), and thus reducing its concentration in the film. The outdiffused MnI accumulate on the surface in a surface oxide layer and do not participate in the ferromagnetism of the film. For thin films less than 15 nm thick, no MnI can be detected. Because of the absence of compensating MnI defects, higher TC can be achieved for such extremely thin Ga1−xMnxAs layers. These results agree with our previously suggested Fermi-level-governed upper limit of the TC of III–Mn–V ferromagnetic semiconductors.