In2O3, an n‐type semiconducting transparent transition metal oxide, possesses a surface electron accumulation layer (SEAL) resulting from downward surface band bending due to the presence of ubiquitous oxygen vacancies. Upon annealing In2O3in ultrahigh vacuum or in the presence of oxygen, the SEAL can be enhanced or depleted, as governed by the resulting density of oxygen vacancies at the surface. In this work, an alternative route to tune the SEAL by adsorption of strong molecular electron donors (specifically here ruthenium pentamethylcyclopentadienyl mesitylene dimer, [RuCp*mes]2) and acceptors (here 2,2′‐(1,3,4,5,7,8‐hexafluoro‐2,6‐naphthalene‐diylidene)bis‐propanedinitrile, F6TCNNQ) is demonstrated. Starting from an electron‐depleted In2O3surface after annealing in oxygen, the deposition of [RuCp*mes]2restores the accumulation layer as a result of electron transfer from the donor molecules to In2O3, as evidenced by the observation of (partially) filled conduction sub‐bands near the Fermi level via angle‐resolved photoemission spectroscopy, indicating the formation of a 2D electron gas due to the SEAL. In contrast, when F6TCNNQ is deposited on a surface annealed without oxygen, the electron accumulation layer vanishes and an upward band bending is generated at the In2O3surface due to electron depletion by the acceptor molecules. Hence, further opportunities to expand the application of In2O3in electronic devices are revealed.
Effect of Au/HfS 3 interfacial interactions on properties of HfS 3 -based devices
X-ray photoemission spectroscopy (XPS) has been used to examine the interaction between Au and HfS 3 at the Au/HfS 3 interface. XPS measurements reveal dissociative chemisorption of O 2 , leading to the formation of an oxide of Hf at the surface of HfS 3 . This surface hafnium oxide, along with the weakly chemisorbed molecular species, such as O 2 and H 2 O, are likely responsible for the observed p-type characteristics of HfS 3 reported elsewhere. HfS 3 devices exhibit n-type behaviour if measured in vacuum but turn p-type in air. Au thickness-dependent XPS measurements provide clear evidence of band bending as the S 2p and Hf 4f core-level peak binding energies for Au/HfS 3 are found to be shifted to higher binding energies. This band bending implies formation of a Schottky-barrier at the Au/HfS 3 interface, which explains the low measured charge carrier mobilities of HfS 3 -based devices. The transistor measurements presented herein also indicate the existence of a Schottky barrier, consistent with the XPS core-level binding energy shifts, and show that the bulk of HfS 3 is n-type.
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- Award ID(s):
- 2044049
- NSF-PAR ID:
- 10393121
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 24
- Issue:
- 22
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 14016 to 14021
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
Epitaxial growth of κ-phase Ga 2 O 3 thin films is investigated on c-plane sapphire, GaN- and AlN-on-sapphire, and (100) oriented yttria stabilized zirconia (YSZ) substrates via metalorganic chemical vapor deposition. The structural and surface morphological properties are investigated by comprehensive material characterization. Phase pure κ-Ga 2 O 3 films are successfully grown on GaN-, AlN-on-sapphire, and YSZ substrates through a systematical tuning of growth parameters including the precursor molar flow rates, chamber pressure, and growth temperature, whereas the growth on c-sapphire substrates leads to a mixture of β- and κ-polymorphs of Ga 2 O 3 under the investigated growth conditions. The influence of the crystalline structure, surface morphology, and roughness of κ-Ga 2 O 3 films grown on different substrates are investigated as a function of precursor flow rate. High-resolution scanning transmission electron microscopy imaging of κ-Ga 2 O 3 films reveals abrupt interfaces between the epitaxial film and the sapphire, GaN, and YSZ substrates. The growth of single crystal orthorhombic κ-Ga 2 O 3 films is confirmed by analyzing the scanning transmission electron microscopy nanodiffraction pattern. The chemical composition, surface stoichiometry, and bandgap energies of κ-Ga 2 O 3 thin films grown on different substrates are studied by high-resolution x-ray photoelectron spectroscopy (XPS) measurements. The type-II (staggered) band alignments at three interfaces between κ-Ga 2 O 3 and c-sapphire, AlN, and YSZ substrates are determined by XPS, with an exception of κ-Ga 2 O 3 /GaN interface, which shows type-I (straddling) band alignment.more » « less
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Chromium-doped SrTiO 3 nanocrystals of perovskite structure type and 45 nm (±15 nm) edge lengths were obtained by hydrothermal synthesis in water from titanium oxide, strontium hydroxide, and chromium( iii ) nitrate. According to XPS, the majority of the surface chromium (68.3%) is present in the 3+ state and the remainder (32.2%) in the 6+ state. Optical spectroscopy confirms a broad absorption at 2.3–2.9 eV from Cr(3+) dopant states, in addition to the 3.2 eV band edge of the SrTiO 3 host. After modification with Pt nanoparticles, Cr-doped SrTiO 3 nanocrystals catalyze photochemical H 2 evolution from aqueous methanol under visible light illumination (>400 nm) and with an apparent quantum yield of 0.66% at 435 nm. According to surface photovoltage spectroscopy (SPS), Cr-doped SrTiO 3 nanocrystals deposited onto gold substrates are n-type and have an effective band gap of 1.75 eV. SPS and transient illumination experiments at 2.50 eV reveal an anomalous surface photovoltage that increases with prior light exposure to values of up to −6.3 V. This photovoltage is assigned to ferroelectric polarization of the material in the space charge layer at the Au/SrTiO 3 :Cr interface. The polarization is stable for 24 h in vacuum but disappears after 12 h when samples are stored in air. The electric polarizability of SrTiO 3 :Cr is confirmed when films are exposed to static electric fields (1.20 MV m −1 ) in a fixed capacitor configuration. The discovery of a ferroelectric effect in Cr-doped SrTiO 3 could be significant for the development of improved photocatalysts for the conversion of solar energy into fuel.more » « less
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We report on growth and electrical properties of α-Ga2O3films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr2O3buffers predeposited on sapphire by magnetron sputtering. The α-Cr2O3buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr2O3bandgap and a sharp MCL line near 700 nm due to the Cr+intracenter transition. Ohmic contacts to Cr2O3were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga2O3films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at ECof 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr2O3buffer indicated the presence of two face-to-face junctions, one between n-Ga2O3and p-Cr2O3, the other due to the Ni Schottky diode with n-Ga2O3. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga2O3system.
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Focused Ga + ion milling of lightly Si-doped, n-type Ga 2 O 3 was performed with 2–30 kV ions at normal incidence and beam currents that were a function of beam voltage, 65 nA for 30 kV, 26 nA for 10 kV, 13 nA for 5 kV, and 7.1 nA for 2 kV, to keep the milling depth constant at 100 nm. Approximate milling rates were 15, 6, 2.75, and 1.5 μm 3 /s for 30, 10, 5, and 2 kV, respectively. The electrical effects of the ion damage were characterized by Schottky barrier height and diode ideality factor on vertical rectifier structures comprising 10 μm epitaxial n-Ga 2 O 3 on n + Ga 2 O 3 substrates, while the structural damage was imaged by transmission electron microscopy. The reverse bias leakage was largely unaffected even by milling at 30 kV beam energy, while the forward current-voltage characteristics showed significant deterioration at 5 kV, with an increase in the ideality factor from 1.25 to 2.25. The I–V characteristics no longer showed rectification for the 30 kV condition. Subsequent annealing up to 400 °C produced substantial recovery of the I–V characteristics for all beam energies and was sufficient to restore the initial ideality factor completely for beam energies up to 5 kV. Even the 30 kV-exposed rectifiers showed a recovery of the ideality factor to 1.8. The surface morphology of the ion-milled Ga 2 O 3 was smooth even at 30 kV ion energy, with no evidence for preferential sputtering of the oxygen. The surface region was not amorphized by extended ion milling (35 min) at 5 kV with the samples held at 25 °C, as determined by electron diffraction patterns, and significant recovery of the lattice order was observed after annealing at 400 °C.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2cp01254e
