M. Ting

GaNAsP: An intermediate band semiconductor grown by gas-source molecular beam epitaxy

Dilute nitride GaNAsP thin films were grown via a GaAsP metamorphic buffer on GaP(100) substrate with gas-source molecular beam epitaxy. The compositions of this III-V-V-V compound were determined by channeling Rutherford backscattering spectroscopy and nuclear reaction analysis. Photoreflectance shows two distinctive transitions from the valence band to the split conduction bands due to N incorporation. Photoluminescence and optical absorption show the fundamental bandgap of Ga(N)AsP is largely tailored by the small amount of N. The observed multiband characteristics and the bandgap tunability of GaNAsP are two merits that fit into the intermediate-band solar cell roadmap, and GaNAsP of high crystal quality provides a strong candidate for intermediate band solar cell materials.

Highly mismatched GaN1-xSbx alloys: Synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA.

Growth and characterization of ZnO1−xSx highly mismatched alloys over the entire composition

Alloys from ZnO and ZnS have been synthesized by radio-frequency magnetron sputtering over the entire alloying range. The ZnO1−xSx films are crystalline for all compositions. The optical absorption edge of these alloys decreases rapidly with small amount of added sulfur (x ∼ 0.02) and continues to red shift to a minimum of 2.6 eV at x = 0.45. At higher sulfur concentrations (x > 0.45), the absorption edge shows a continuous blue shift. The strong reduction in the band gap for O-rich alloys is the result of the upward shift of the valence-band edge with x as observed by x-ray photoelectron spectroscopy. As a result, the room temperature bandgap of ZnO1−xSx alloys can be tuned from 3.7 eV to 2.6 eV. The observed large bowing in the composition dependence of the energy bandgap arises from the anticrossing interactions between (1) the valence-band of ZnO and the localized sulfur level at 0.30 eV above the ZnO valence-band maximum for O-rich alloys and (2) the conduction-band of ZnS and the localized oxygen le...

Growth and characterization of highly mismatched GaN1-xSbx alloys

A systematic investigation on the effects of growth temperature, Ga flux, and Sb flux on the incorporation of Sb, film structure, and optical properties of the GaN1−xSbx highly mismatched alloys (HMAs) was carried out. We found that the direct bandgap ranging from 3.4 eV to below 1.0 eV for the alloys grown at low temperature. At the growth temperature of 80 °C, GaN1−xSbx with x > 6% losses crystallinity and becomes primarily amorphous with small crystallites of 2–5 nm. Despite the range of microstructures found for GaN1−xSbx alloys with different composition, a well-developed absorption edge shifts from 3.4 eV (GaN) to close to 2 eV for samples with a small amount, less than 10% of Sb. Luminescence from dilute GaN1−xSbx alloys grown at high temperature and the bandgap energy for alloys with higher Sb content are consistent with a localized substitutional Sb level ESb at ∼1.1 eV above the valence band of GaN. The decrease in the bandgap of GaN1−xSbx HMAs is consistent with the formation of a Sb-derived ba...

Electronic band structure of highly mismatched GaN1−xSbx alloys in a broad composition range

In this letter, we study the optical properties of GaN1−xSbx thin films. Films with an Sb fraction up to 42% were synthesized by alternating GaN-GaSb layers at a constant temperature of 325 °C. The measured optical absorption data of the films are interpreted using a modified band anticrossing model that is applicable to highly mismatched alloys such as GaN1−xSbx in the entire composition range. The presented model allows us to more accurately determine the band gap as well as the band edges over the entire composition range thereby providing means for determining the composition for, e.g., efficient spontaneous photoelectrochemical cell applications.

Electronic band structure of ZnO-rich highly mismatched ZnO1−xTex alloys

We synthesized ZnO1−xTex alloys with Te composition x < 0.23 by using pulsed laser deposition. Alloys with x < 0.06 are crystalline with a columnar growth structure while samples with higher Te content are polycrystalline with random grain orientation. Electron microscopy images show a random distribution of Te atoms with no observable clustering. We found that the incorporation of a small concentration of Te (x ∼ 0.003) redshifts the ZnO optical absorption edge by more than 1 eV. The minimum band gap obtained in this work is 1.8 eV for x = 0.23. The optical properties of the alloys are explained by the modification of the valence band of ZnO, due to the anticrossing interactions of the localized Te states with the ZnO valence band extended states. Hence, the observed large band gap reduction is primarily originating from the upward shift of the valence band edge. We show that the optical data can be explained by the band anticrossing model with the localized level of Te located at 0.95 eV above the ZnO v...

Composition and optical properties of dilute-Sb GaN1−xSbx highly mismatched alloys grown by MBE

In this work the compositional and optical characterization of three series of dilute-Sb GaN1 − xSbx alloys grown with various Sb flux, under N and Ga-rich conditions, are presented. Using wavelength dispersive x-ray microanalysis and Rutherford backscattering spectroscopy it is found that the N-rich samples (Ga flux 2.3 × 10−7 Torr) under the same growth conditions. The optical properties of the Ga-rich samples are measured using room temperature cathodoluminescence (CL), photoluminescence (PL) and absorption measurements. A broad luminescence peak is observed around 2.2 eV. The nature and properties of this peak are considered, as is the suitability of these dilute-Sb alloys for use in solar energy conversion devices.

Effects of native defects on properties of low temperature grown, non-stoichiomtric gallium nitride

The properties of GaN thin films grown by molecular beam epitaxy at temperatures from 80 to 500 °C under a wide range of Ga:N flux ratios are studied. We found that at growth temperatures as low as ~80 °C, GaN films still have a polycrystalline, columnar morphology with c-axis preferred orientation. Soft x-ray absorption and emission and optical absorption measurements on Ga-rich samples suggest the presence of a partially occupied GaN antisite defect band located at ~1.2 eV below the conduction band minimum. P-type conductivity observed in this LTMBE Ga-rich GaN is consistent with transport within this partially occupied defect band.

Highly mismatched GaN1−xSbxalloys: synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA.

Effects of Ni d-levels on the electronic band structure of NixCd1-xO semiconducting alloys

NixCd1-xO has a ∼3 eV band edge offset and bandgap varying from 2.2 to 3.6 eV, which is potentially important for transparent electronic and photovoltaic applications. We present a systematic study of the electronic band structure of NixCd1-xO alloys across the composition range. Ion irradiation of alloy samples leads to a saturation of the electron concentration associated with pinning of the Fermi level (EF) at the Fermi stabilization energy, the common energy reference located at 4.9 eV below the vacuum level. The composition dependence of the pinned EF allows determination of the conduction band minimum (CBM) energy relative to the vacuum level. The unusually strong deviation of the CBM energy observed from the virtual crystal approximation is explained by a band anticrossing interaction between localized 3d states of Ni and the extended states of the NixCd1-xO alloy host. The resulting band structure explains the dependence between the composition and the electrical and optical properties of the allo...