Oxidation study of polycrystalline InN film using in situ X-ray scattering and X-ray photoemission spectroscopy

Oxidation process of polycrystalline InN films were investigated using in situ X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS). The films were grown by dc sputter on sapphire (0001) substrates and were oxidized in air at elevated temperatures. The XRD data showed that the structure of the films changed to the bixbyite In₂O₃ (a = 10.11 Å) above 450 °C. Chemical configurations of the sample surfaces were investigated using high-resolution XPS. For the non-intentionally oxidized InN film, XPS analysis on the In 3d peak and the N 1s main peak at 396.4 eV suggests that indium and nitrogen are bound dominantly in the form of InN. An additional peak observed at 397.4 eV in the N 1s photoelectrons and the O 1s peaks indicate that the InN film surface is partly oxidized to have InO_xN_y configuration. After oxidation of the InN film at elevated temperature, the O 1s spectrum is dominated by In₂O₃ peak, which indicates that the structure is stable chemically with In₂O₃ configuration at least within the XPS probing depth of a few nm.     

Characterization of wurtzite indium nitride synthesized from indium oxide by In-115 MAS NMR spectroscopy

Wurtzite indium nitride (w-InN) powders synthesized from the reaction of indium oxide (In₂O₃) with ammonia were characterized by ¹¹⁵In magic-angle spinning (MAS) NMR spectroscopy and nitrogen analyzer. The powders were not a single phase of w-InN but a mixture of w-InN and In-incorporated w-InN. The incorporation of In metal in InN lattice due to thermal decomposition caused the ¹¹⁵In MAS NMR peak of w-InN to be downfield shifted and might be responsible for the increase in the band gap of w-InN.     

Initial stages of the cubic-InN growth with the technique of the pre-deposition of indium

The initial stages of the cubic indium nitride film growth at 350 °C were studied using low-pressure metal-organic chemical vapor deposition. The technique of the pre-deposition of indium was applied, that is, a layer of indium was first deposited on sapphire surface before the growth of InN. X-ray diffraction and X-ray photoelectron spectroscopy show that the pre-deposition of indium is able to promote the growth of InN films, and meanwhile, suppress the indium aggregation in the as-grown films. Atomic force microscopy images of InN films indicate that the pre-deposition of indium not only enhances the density of nucleate sites, but also facilitates the coalescence among the InN islands. The free energy calculations reveal that the pre-deposited indium atoms preferentially react with NH and N radicals after NH₃ introduction, which leads to the formation of InN on the sapphire surface. The preferentially formed InN is then supposed to be responsible for the above phenomena.     

Synthesis and characterization of indium nitride nanowires by plasma-assisted chemical vapor deposition

High-quality indium nitride (InN) nanowires were synthesized in a high temperature furnace on Au-coated Si substrates through the reaction of indium metal vapor with highly reactive nitrogen radicals generated by N₂ plasma. Highly-reactive nitrogen radicals provided a wide process window for the synthesis of InN nanowires by lowering the process temperature to avoid the decomposition of InN. X-ray diffraction, transmission electron microscopy and Raman spectra further showed that the as-synthesized InN nanowires were perfect single crystallites of wurtzite structure with the growth direction along [110].     

Characterisation of molecular nitrogen in ion-bombarded compound semiconductors by synchrotron-based absorption and emission spectroscopies

We have studied formation of molecular nitrogen under low-energy nitrogen bombardment in a range of compound semiconductors by synchrotron-based X-ray photoelectron spectroscopy (XPS) around N 1s core-level and near-edge X-ray absorption fine structure (NEXAFS) around N K-edge. We have found interstitial molecular nitrogen, N₂, in all samples under consideration. The presence of N₂ produces a sharp resonance in low-resolution NEXAFS spectra at around 400.8 eV, showing the characteristic vibrational fine structure in high-resolution measurements. At the same time, a new peak, shifted towards higher binding energies, emerges in all N 1s photoemission spectra. We have found a shift of 7.6 eV for In-based compounds and 6.7 eV for Ga-based compounds. Our results demonstrate that NEXAFS and core-level XPS are complementary techniques that form a powerful combination for studying molecular nitrogen in compound semiconductors, such as GaSb, InSb, GaAs, InN, GaN or ZnO.     

Formation of embedded indium nitride and indium oxide nanoclusters in silica samples sequentially implanted with indium and nitrogen ions

This article discusses the formation of embedded indium nitride (InN) nanoclusters (NCs) in silica matrix through sequential implantation of 890?keV In²⁺ and 140?keV N⁺ ions. The implanted samples were subjected to post-implantation annealing at 500°C in nitrogen atmosphere. Investigations carried out on the implanted samples using glancing incidence X-ray diffraction, high-resolution transmission electron microscopy and Raman spectroscopy gave clear evidence for the formation of InN nanoclusters. Alongside with InN NCs, we also notice the presence of indium oxide nanoclusters in the sample.     

The local crystal structure and electronic band gap of β-sialons

The electronic properties of β-Si₃N₄ and β-sialons (β-Si_6?z Al _z O _z N_8?z ) solid solutions were characterized using a combination of X-ray emission spectroscopy (XES), X-ray absorption spectroscopy (XAS), and density functional theory (DFT). The electronic structure measurements reveal a single bonding environment for both the Si and Al atoms, which corresponds to a specific nonrandom structural arrangement of the Al–O solute atoms into nanotube-like clusters or channels, running parallel to the c-axis of the β-Si₃N₄ host structure. Compared to an arrangement of alternating Si–N and Al–O slabs (“Dupree model”), lower total energy and overall better agreement to the experimentally observed electronic features confirm this “Al–O nanotube” model for β-sialon originally proposed by Okatov to be closer to the true chemical topology of the β-Si_6?z Al _z O _z N_8?z solid solution series. The β-sialons are shown to be wide band gap semiconductors with the band gap reduction arising from the O p-states moving toward the Fermi level. This band gap reduction provides the ability for direct band gap transitions, which is very important for practical applications. In contrast to the previous observations, both measurement and theory indicate a linear dependence of band gap energy with composition z. The experimental (theoretical) electronic band gaps of β-Si_6?z Al _z O _z N_8?z with z = 0.0, 2.0, and 4.0 as determined by XAS/XES (DFT) are 7.2 ± 0.2 (5.88), 6.2 ± 0.2 (3.45), and 5.0 ± 0.2 (2.39) eV, respectively. The considerable discrepancy between experimental and theoretical values is attributable to the shortcomings of DFT, which often underestimates the electronic band gap energy.     

Oxidation state of chromium in (Na0.5Bi0.5TiO3)(1?x)(BiCrO3)x solid solution; investigated by XAS and impedance spectroscopy

X-ray absorption spectroscopy (XAS) and impedance spectroscopy have been used to study the oxidation state of chromium in (Na_0.5Bi_0.5TiO₃)_(1−x)(BiCrO₃) _x solid solution. XAS measurements reveal that chromium ion occupies the octahedral site in Na_0.5Bi_0.5TiO₃ (NBT). The increase in chromium content increases the distortion in chromium-oxygen octahedral. No shift in the Cr–K edge was observed with increase in chromium content. The XAS measurements suggest that chromium exists either as +3 or +5 state in (Na_0.5Bi_0.5TiO₃)_(1−x)(BiCrO₃) _x . The impedance measurements show a considerable increase in the electrical conductivity with increase in chromium content. The activation energy for conduction mechanism was found to lie between 0.50 and 0.7 eV for all the samples. These measurements indicate that main contribution to the conductivity is because of oxygen defects generated by the incorporation of chromium at B-site of NBT.     

X-ray absorption spectroscopy, simulation and modeling of Si-DLC films

Amorphous silicon-containing diamond-like carbon (Si-DLC) films were deposited on silicon wafers by Ar⁺ Ion Beam Assisted Deposition (IBAD) at various energy conditions. The films were examined with X-ray Absorption Near Edge Structure (XANES) spectroscopy and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The Si K-edge X-ray Absorption Spectroscopy (XAS) results indicate that Si-DLC films have an amorphous structure, where each Si atom is coordinated to four carbon atoms or CH_n groups. This short-range order, where a Si atom is surrounded by four C atoms, was found in all Si-DLC films. The XANES spectra do not indicate Si coordination to oxygen atoms or phenyl rings, which are present in the precursor material. A structural model of Si-DLC is proposed based on XAS findings. Simulated X-ray absorption spectra of the model produced by FEFF8 show a good resemblance to the experimental data.     

Photoelectrochemical properties of nitrogen-doped indium tin oxide thin films prepared by reactive DC magnetron sputtering

Nitrogen-doped indium tin oxide (N-ITO) thin films are deposited on unheated ITO glass substrates in this study. The structural properties of the N-ITO thin films, determined by X-ray diffraction (XRD) and Raman scattering, show that the indium nitride (InN) phase is liable to form in N-ITO films prepared in 20% N₂. A broad XRD peak around 2θ = 33° and Raman peak around 490 cm^− 1 are assigned to the InN phase, but no such peak is observed from the ITO film. Hence, the bandgap is narrowed by N-doping for absorbing light of longer wavelengths of ~ 500 nm. However, under illumination by ultraviolet, the N-ITO film prepared in 20% N₂ exhibits the least photocurrent response, which is less than one third that of the N-ITO catalyst that was doped in 16.4% N₂. This result is attributed mostly to the fact that the valence and conduction band potentials are not positioned properly between the newly formed InN and host ITO phases, rendering inefficient inter-semiconductor electron transfer. Therefore, higher N-doped samples exhibit a lower photocurrent response. Interestingly, the N-ITO film prepared in 16.4% N₂ exhibits the highest photocurrent density of about 165.5 μA/cm² at an applied bias of 1.2 V. This implies that the N-ITO films should be prepared at a low N₂ ratio to ensure a favorable photoelectrochemical activity.     

X-ray absorption spectroscopy studies of the Ni ion of Li(Ni0.8Co0.15Al0.05)0.8(Ni0.5Mn0.5)0.2O2 with a core–shell structure and LiNi0.8Co0.15Al0.05O2 as cathode materials

Core–shell materials have attracted a great deal of interest since core–shell particles have superior physical and chemical properties compared to their single-component counterparts. The cathode material Li(Ni_0.8Co_0.15Al_0.05)_0.8(Ni_0.5Mn_0.5)_0.2O₂ (LNCANMO) with a core–shell structure was synthesized via a co-precipitation method and investigated as the cathode material for lithium ion batteries. The core–shell particle consisted of LiNi_0.8Co_0.15Al_0.05O₂ (LNCAO) as the core and LiNi_0.5Mn_0.5O₂ as the shell. The cycling behavior between 2.8 and 4.3 V at a current of 0.1 C-rate showed a reversible capacity of ～195 mAh g^?1 with little capacity loss after 50 cycles. Extensive assessment of the electronic structures of the LNCAO and LNCANMO cathode materials was carried out using X-ray absorption spectroscopy (XAS). XAS has been used for structure refinement on the transition metal ion of the cathode. In particular, XAS studies of electrochemical reactions have been done from the viewpoint of the transition metal ion. In this study, Ni K-edge XAS spectra of the charge and discharge processes of LNCAO and LNCANMO were investigated.     

Mechanisms of reactive sputtering of indium I: Growth of InN in mixed Ar-N2 discharges

Optical absorption and emission spectroscopies were used for in situ investigations of process occuring in the plasma and at the electrode-gas interfaces which control the reactive sputter etching of indium targets and the reactive deposition of InN films in mixed Ar-N₂ glow discharges. The sputtering parameters used were a d.c. target voltage of -2.5 kV, a total sputtering pressure P of 30–70 m Torr (4–9.3 Pa), N₂ mol.% C_N2 values of 0–100 and a target-to-substrate separation d of 3–6 cm. Under these conditions no indication of complete nitride formation at the target surface or of sputter ejection of InN molecular species was obtained. Increasing C_N2 at a constant value of P caused a decrease of the target sputtering rate R. This decrease was due primarily to a decrease in the ion current i_T, which was caused by thermalization of low energy electrons in the plasma through excitation of vibrational modes in molecular N₂. Atomic absorption provided a real-time monitor of R over the entire range of sputtering parameters. The optical emission intensity from sputtered indium atoms in the cathode glow was found to increase with C_N2 (even though R decreased) because of enhanced excitation through collisions with N₂ metastable species.The nitrogen concentration in the deposited films, as determined by X-ray photoelectron spectroscopy and X-ray diffraction, was found to depend strongly on C_N2, P_N2 and d. The dependence on d was caused by the position of the growing film surface with respect to the negative glow region where most of the atomic nitrogen was formed through the reaction N₂⁺ + N₂ → N₂ + N⁺ + N In discharges with short mean free paths this is the primary mechanism of nitrogen incorporation since indium does not chemisorb N₂, only atomic nitrogen. InN films grown on glass substrates at about 80°C were found to be polycrystalline n-type semiconductors with a room temperature resistivity of 40 mΩ cm, a carrier concentration of about 5×10¹⁸ cm^-3 and an electron mobility of approximately 20 cm² V^-1 s^-1. The refractive index at a wavelength of 1 μm and the room temperature direct band gap were found to be 2.85 and 1.7 eV respectively.     

Structural, optical and electrical properties of indium nitride polycrystalline films

The structural, optical and electrical properties of InN polycrystalline films on glass substrate are investigated by means of X-ray photoelectron spectroscopy, Raman scattering measurements, X-ray diffraction analysis, optical spectroscopy, and electrical measurements as a function of the inverse of temperature. The absorption edge for the films is most likely due to an impurity band formed by the presence of defects in the material. Such an impurity band, located at 1.6 eV extends itself to about 1.8 eV above the Fermi level, and it is attributed to nitrogen vacancies present in the material. The Raman scattering data also reveal the incorporation of oxygen in the InN films, leading to the formation of the In₂O₃ amorphous phase during the process of sputtering. Additionally, the X-ray photoelectron spectroscopy of the valence band, which is highly desirable to the determination of the Fermi level, confirms the optical gap energy. Furthermore, the X-ray diffraction patterns of the thinner films present broader peaks, indicating high values for the strain between the film lattice and the glass substrate. Finally, first principles calculations are used to investigate the optical properties of InN and also to support the experimental findings.     

Properties of indium oxide/tin oxide multilayered films prepared by ion-beam sputtering

The preparation and characterization of indium oxide (InO _x )/tin oxide (SnO _y ) multilayered films deposited by ion-beam sputtering are described and compared with indium tin oxide (ITO) films. The structure and the optoelectrical properties of the films are studied in relation to the layered structures and the post-deposition annealing. Low-angle X-ray diffraction analysis showed that most films retained the regular layered structures even after annealing at 500° C for 16 h. As an example, we obtained a resistivity of 6×10^–4 cm and a transparency of about 85% in the visible range at a thickness of 110 nm in a multilayered film of InO _x (2.0 nm)/SnO _y (0.2 nm)×50 pairs when annealed at 300° C for 0.5 h in air. Hall coefficient measurements showed that this film had a mobility of 17 cm² V^–1 sec^–1 and a carrier concentration (electron density) of 5×10²⁰ cm^–3.     

Electron-doped La0.7A0.3CoO3-x Thin Films (A = Ce, Te) Studied by XAS

The local spatial and electronic structure of thin films of perovskite-derived LaCoO_3-x doped with cerium and tellurium is studied by Co K-edge X-ray absorption spectroscopy (XAS). It is shown that both Ce and Te as dopants give the desired electron-doping effect, and that structural disorder plausibly contributes an important part to the differences in magnetic properties when compared to the hole-doped counterparts.     

Structural and optical properties of wurtzite InN grown on Si(111)

We report the structural and optical properties of InN films on Si(111) prepared by ion-beam-assisted filtered cathodic vacuum arc technique. X-ray diffraction and Raman spectroscopy measurements indicated that all the InN films were hexagonal crystalline InN. The InN films deposited at substrate temperature of 475 °C exhibited highly (0001) preferred orientation and texturing (cratered) surface morphology. The oxygen incorporated in the InN films was segregated in the form of amorphous indium oxide or oxynitride phases at the grain boundaries. Photoluminescence emission of ∼ 1.15 eV was observed at room temperature from the InN films.     

Evolution of the mosaic structure in InGaN layer grown on a thick GaN template and sapphire substrate

The In_xGa_1?xN epitaxial layers, with indium (x) concentration changes between 0.16 and 1.00 (InN), were grown on GaN template/(0001) Al₂O₃ substrate by metal organic chemical vapour deposition. The indium content (x), lattice parameters and strain values in the InGaN layers were calculated from the reciprocal lattice mapping around symmetric (0002) and asymmetric (10–15) reflection of the GaN and InGaN layers. The characteristics of mosaic structures, such as lateral and vertical coherence lengths, tilt and twist angle and heterogeneous strain and dislocation densities (edge and screw dislocations) of the InGaN epilayers and GaN template layers were investigated by using high-resolution X-ray diffraction (HR-XRD) measurements. With a combination of Williamson–Hall (W-H) measurements and the fitting of twist angles, it was found that the indium content in the InGaN epilayers did not strongly effect the mosaic structures’ parameters, lateral and vertical coherence lengths, tilt and twist angle, or heterogeneous strain of the InGaN epilayers.     

Piezoelectric coefficient of InN films prepared by radio-frequency sputtering

An interferometric method has been used to measure the piezoelectric coefficient d₃₃ in indium nitride films deposited by radio-frequency sputtering on borosilicate glass coated with gold. This low temperature growth technique has the advantage of being able to produce samples for piezoelectric measurements where the InN film is grown directly on an Au metal back contact, allowing the accurate measurement of the piezoelectric coefficient of the InN layer without any parasitic series resistance. The InN growth conditions are described, and both crystal and optical characterizations of the film are presented. The measured value of the coefficient was found to be 4.0 ± 0.1 pm V^− 1.     

Growth of InN layers on Si (111) using ultra thin silicon nitride buffer layer by NPA-MBE

Indium nitride (InN) epilayers have been successfully grown by nitrogen-plasma-assisted molecular beam epitaxy (NPA-MBE) on Si (111) substrates using different buffer layers. Growth of a (0001)-oriented single crystalline wurtzite-InN layer was confirmed by high resolution X-ray diffraction (HRXRD). The Raman studies show the high crystalline quality and the wurtzite lattice structure of InN films on the Si substrate using different buffer layers and the InN/β-Si₃N₄ double buffer layer achieves minimum FWHM of E₂ (high) mode. The energy gap of InN films was determined by optical absorption measurement and found to be in the range of ~ 0.73-0.78 eV with a direct band nature. It is found that a double-buffer technique (InN/β-Si₃N₄) insures improved crystallinity, smooth surface and good optical properties.