Effect of N2O/SiH4 flow ratios on properties of amorphous silicon oxide thin films deposited by inductively-coupled plasma chemical vapor deposition with application to silicon surface passivation

Silicon oxide (SiO_x) thin films have been deposited at a substrate temperature of 300 °C by inductively-coupled plasma chemical vapor deposition (ICP-CVD) using N₂O/SiH₄ plasma. The effect of N₂O/SiH₄ flow ratios on SiO_x film properties and silicon surface passivation were investigated. Initially, the deposition rate increased up to the N₂O/SiH₄ flow ratio of 2/1, and then decreased with the further increase in N₂O/SiH₄ flow ratio. Silicon oxide films with refractive indices of 1.47-2.64 and high optical band-gap values (>3.3 eV) were obtained by varying the nitrous oxide to silane gas ratios. The measured density of the interface states for films was found to have minimum value of 4.3 × 10¹¹ eV⁻¹ cm⁻². The simultaneous highest τ_eff and lowest density of interface states indicated that the formation of hydrogen bonds at the SiO_x/c-Si interface played an important role in surface passivation of p-type silicon.     

A spectroscopic study into the decomposition process of titanium isopropoxide in the nitrogen-hydrogen 100 kHz low-pressure plasma

Optical emission spectroscopy was employed for the study of the nitrogen-hydrogen and nitrogen-hydrogen-titanium (IV) isopropoxide mixtures in the 100 kHz low pressure capacitively coupled discharge. High-energy species were identified in the plasma phase. The behavior of the excited species versus the gas composition has also been investigated. The optical actinometry technique was applied in order to evaluate the N₂, CH, CO, CN, N, C and the H relative concentrations versus the hydrogen concentration in reactive mixtures. The effect of the hydrogen concentration in the nitrogen-hydrogen mixture on the decomposition processes of titanium isopropoxide was investigated. The plasma temperature (the H excitation temperature, the CN, N₂ and N₂⁺ vibrational temperatures and the N₂⁺ rotational temperature) as well as the electron number density were determined here. The temperature magnitudes (T_exc≈5700-7400 K, T_vib(CN)≈4700-8100 K, T_vib(N₂)≈2700-3050 K, T_vib(N₂⁺)≈1500-1600 K and T_rot(N₂⁺)≈660-890 K) indicated a very significant deviation from the LTE state.     

Oxidation of carbon monoxide over Cu- and Ag-NaY catalysts with aqueous hydrogen peroxide

A novel oxidation reaction of CO with aqueous H₂O₂ over Cu-NaY (2-15 wt%) and Ag-NaY (5-15 wt%) catalysts has been achieved at low temperatures (55-70 °C) using a flow mode system. The employed catalysts were prepared by the incipient wetness impregnation of NaY zeolite (Si/Al = 5.6, surface area = 910 m²/g) with an aqueous solution of known concentrations of copper acetate and silver nitrate. Solids were subjected to thermal treatment at 300-450 °C prior to catalytic measurements unless subjected to subsequent reduction with hydrogen at 350 °C. The physicochemical characterization of the catalysts was probed using X-ray diffraction (XRD), FT-IR and combined thermal analyses TGA-DrTGA. The XRD data indicated that, the Ag particles have an ordered location in the sodalite cavity and the center of a single six-ring. The FT-IR data also proved the presence of a new peak at 1385 cm⁻¹ that is assigned to Ag-coordinated with the framework.A slow induced oxidation of CO (induction period, t_ind) took place at the initial stage of the CO oxidation reaction after which the reaction obeyed first-order kinetics. The utilized metal ions are proposed to be reduced to lower oxidation states such as Cu⁺ and Ag⁰ during the first period of reaction, t_ind, where the reaction proceeded favorably on such sites. Such argument was evidenced by carrying out the oxidation reaction over H₂-reduced Cu10-NaY and Ag10-NaY catalysts. The reduction caused a decrease in the t_ind, giving an evidence that the lower oxidation states Cu⁺ and Ag⁰ are the active sites in the studied oxidation reaction. The enhancement in catalytic activity was interpreted in terms of the facile adsorption of CO on the low oxidation state species.     

The determination of interface state energy distribution of the H-terminated Zn/p-type Si Schottky diodes with high series resistance by the admittance spectroscopy

Analysis of Zn/p-Si Schottky diodes (SDs) with high resistivity has been given by admittance spectroscopy. The importance of the series resistance in the determination of energy distribution of interface states and especially their relaxation time in the SDs with high resistivity has been considered. The effect of the series resistance on capacitance-conductance/frequency characteristics has been given by comparing experimental data with theoretical data. The interface state density N_ss from the admittance spectroscopy ranges from 1.0×10¹² cm⁻² eV⁻¹ in 0.720-E_v eV to 2.03×10¹² cm⁻² eV⁻¹ in 0.420-E_v eV. Furthermore, the relaxation time ranges from 4.20×10⁻⁵ s in (0.420-E_v) eV to 3.20×10⁻⁴ s in (0.720-E_v) eV. It has been seen that the interface state density has a very small distribution range (1.0-2.03×10¹² cm⁻² eV⁻¹) that is ascribed to the predominant termination with hydrogen of the silicon surface after HF treatment.     

Atomic layer deposition of MnO using Bis(ethylcyclopentadienyl)manganese and H2O

Manganese oxide (MnO) atomic layer deposition (ALD) was accomplished using sequential exposures of bis(ethylcyclopentadienyl)manganese (Mn(CpEt)₂) and H₂O. Rutherford backscattering analysis revealed a nearly 1:1 atomic ratio for Mn:O in the MnO ALD films. X-ray diffraction determined that the films were crystalline and consistent with the cubic phase of MnO. Quartz crystal microbalance (QCM) measurements monitored the mass deposition rate during MnO ALD and verified self-limiting reactions for each reactant. Extremely efficient reactions were observed that required reactant exposures of only 3 × 10⁴ L (1 L = 1.33 × 10^− 4 Pa s). X-ray reflectivity (XRR) studies were used to confirm the QCM measurements and determine the film density and film thicknesses. The MnO ALD film density was 5.23 g/cm³. The growth per cycle was investigated from 100-300 °C. The largest MnO ALD growth per cycle was 1.2 Å/cycle at 100 °C and the growth per cycle decreased at higher temperatures. Transmission electron microscopy images observed the conformality of MnO films on ZrO₂ nanoparticles and confirmed the growth per cycle observed by the XRR studies. Fourier transform infrared spectroscopy was used to study the -CpEt? and -OH? surface species during MnO ALD and also monitored the bulk vibrational modes of the growing MnO films. The results allowed a growth mechanism to be established for MnO ALD using Mn(CpEt)₂ and H₂O. Only 54% of the Mn sites are observed to retain the -CpEt? surface species after the Mn(CpEt)₂ exposure. Efficient MnO ALD using Mn(CpEt)₂ and H₂O should be useful for a variety of applications where metal oxides are required that can easily change their oxidation states.     

Superconductivity of p-type diamond (001) and (111) thin films: Ab initio calculations

The surface structure, electronic properties, lattice dynamics, and the electron-phonon coupling for p-doped diamond (001)-(2 × 1) and (111)-(2 × 1) thin films have been extensively investigated using ab initio methods within the virtual crystal approximation. The calculations of p-doped diamond thin films strongly favor dimer reconstruction of diamond surfaces. The physical origin of superconductivity of diamond (001)-(2 × 1), respectively, and (111)-(2 × 1) thin films which is higher than that of bulk diamond is systematically studied. It is showed that surface vibrational modes of diamond (001)-(2 × 1) surfaces give main contributions to superconducting transition temperature T_c, while T_c of diamond (111)-(2 × 1) surfaces is attributed to the combined action of surface and bulk vibrational modes. Therefore, at the highest concentration (13.98 × 10²¹ cm^− 3) T_c ≈ 56.5 K of diamond (111)-(2 × 1) surfaces is about twice as high as that of bulk and diamond (001)-(2 × 1) surfaces.     

Preparation of various DLC films by T-shaped filtered arc deposition and the effect of heat treatment on film properties

Different types of diamond-like carbon (DLC) films (ta-C, a-C, ta-C:H and a-C:H) were prepared on super hard alloy (WC-Co) substrate using a T-shape filtered arc deposition (T-FAD) system. At first, the film properties, such as structure, hydrogen content, density, hardness, elastic modulus, were measured. Ta-C prepared with a DC bias of −100 V showed the highest density (3.1 g/cm³) and hardness (70-80 GPa), and the lowest hydrogen content (less than 0.1 at. %). It was found that the hardness of the DLC film is proportional to approximately the third power of film density. The DLC films were then heated for 60 min in an electric furnace at 550 °C in N₂. Only the ta-C film hardly change its structure, although other films were graphitized. The 200-nm thick ta-C film was then heated for 60 min through the temperature range from 400 to 800 °C in N₂ with 2 vol.% of O₂ and the film structure found to be stable up to 700 °C. The substrate was oxidized at 800 °C, indicating the ta-C film had a thermal barrier function up to that temperature.     

Aluminum doped silicon carbide thin films prepared by hot-wire CVD: Investigation of defects with electron spin resonance

Al-doped p-type μc-SiC:H is prepared in a wide range of HWCVD preparation parameters like Al-doping ratio, deposition pressure, substrate and filament temperatures. We investigate the structural and electrical properties, and focus on identification of paramagnetic defect states by electron spin resonance (ESR). Nominally undoped μc-SiC:H is of a high n-type conductivity (σ_D = 10^− 6-10^− 1 S/cm) and shows a narrow central ESR line (g ≈ 2.003, peak-to-peak linewidth ?H_pp ≈ 4 G) with two pairs of satellites and a spin density N_S = 10¹⁹ cm^− 3. Al-doping results in the compensation of dark conductivity to as low as σ_D = 10^− 11 S/cm and at higher doping concentrations to effective p-type material. Increase of Al-doping results in reduction of crystallinity (I_C^IR), ESR line shifts to g ≈ 2.01 and becomes as broad as ?H_pp ≈ 30 G, not unlike to the resonance of singly occupied paramagnetic valence band tail states in a-Si:H. ESR spectrum of highly crystalline Al-doped μc-SiC:H however has a g-value very close to undoped μc-SiC:H. Electron spin density in compensated material decreases to 5 × 10¹⁷ cm^− 3 before it increases again for the highly doped material.     

First-principle calculations of anomalous spin-state excitation in LaCoO3

We investigate the different spin states of LaCoO₃ employing the state-of-the-art ab initio band structure calculations within a rotationally invariant formulation of local density approximation (LDA) + U approach. The various magnetically ordered spin states of different supercells have been studied, including the low-spin state (LS), intermediate-spin state (IS), high-spin state (HS) Co³⁺ ions, as well as all combinations among these three states. The ground state is correctly predicted to be an insulator nonmagnetic state. Our calculations, together with previous susceptibility measurements for IS excitations in the LS ground state, lead to the conclusion that the nonmagnetic–paramagnetic transition in LaCoO₃ at 90 K is caused by a gradual population of IS Co³⁺ ionic states. Our results show that the first thermally excited spin-state occurs from LS to an LS (Co_LS³⁺ = 87.5%)–IS (Co_IS³⁺ = 12.5%) ordered state, which can be distinguished from the LS–HS or IS state. We find that the mixture of LS–IS, LS–HS, and HS–IS spin states may develop an orbital ordering.     

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

A high electron density (> 10¹¹ cm^− 3) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 Å/s is achieved at a substrate temperature of 150 °C with a high Raman crystallinity and a low defect density of (1-2) × 10¹⁶ cm^− 3. Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H_α/SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity.     

Dielectric response and structure of amorphous hydrogenated carbon films with nitrogen admixture

The optical properties and structure of a-C:H films were modified by addition of nitrogen into the CH₄/H₂ deposition mixture. Three films prepared in capacitively coupled rf discharge were compared: (a) hydrogenated diamond like carbon film with hydrogen content of 34% and indentation hardness of 21.7 GPa, (b) hard a-C:H:N film with nitrogen content of 13% and indentation hardness of 18.5 GPa and (c) soft a-C:H:N film with nitrogen content of 10% and indentation hardness of 6.7 GPa. It is shown how the parametrized density of states model describing dielectric response of electronic interband transitions can be applied to modified a-C:H:N and how it can be combined with correct treatment of transmittance measured in infrared range using additional Gaussian peaks in joint density of phonon states. This analysis resulted in determination of film dielectric function in wide spectral range (0.045-30 eV) and provided also information about the density of states of valence and conduction bands and lattice vibrations.     

Effects of hydrogen gas on properties of tin-doped indium oxide films deposited by radio frequency magnetron sputtering method

Tin-doped indium oxide (ITO) films were deposited at ∼ 70 °C of substrate temperature by radio frequency magnetron sputtering method using an In₂O₃-10% SnO₂ target. The effect of hydrogen gas ratio [H₂ / (H₂ + Ar)] on the electrical, optical and mechanical properties was investigated. With increasing the amount of hydrogen gas, the resistivity of the samples showed the lowest value of 3.5 × 10^− 4 Ω·cm at the range of 0.8-1.7% of hydrogen gas ratio, while the resistivity increases over than 2.5% of hydrogen gas ratio. Hall effect measurements explained that carrier concentration and its mobility are strongly related with the resistivity of ITO films. The supplement of hydrogen gas also reduced the residual stress of ITO films up to the stress level of 110 MPa. The surface roughness and the crystallinity of the samples were investigated by using atomic force microscopy and x-ray diffraction, respectively.     

Development of microcrystalline silicon carbide window layers by hot-wire CVD and their applications in microcrystalline silicon thin film solar cells

Microcrystalline silicon carbide (μc-SiC:H) thin films in stoichiometric form were deposited from the gas mixture of monomethylsilane (MMS) and hydrogen by Hot-Wire Chemical Vapor Deposition (HWCVD). These films are highly conductive n-type. The optical gap E₀₄ is about 3.0-3.2 eV. Such μc-SiC:H window layers were successfully applied in n-side illuminated n-i-p microcrystalline silicon thin film solar cells. By increasing the absorber layer thickness from 1 to 2.5 μm, the short circuit current density (j_SC) increases from 23 to 26 mA/cm² with Ag back contacts. By applying highly reflective ZnO/Ag back contacts, j_SC = 29.6 mA/cm² and η = 9.6% were achieved in a cell with a 2-μm-thick absorber layer.     

Effects of applied power on hydrogenated amorphous carbon (a-C:H) film deposition by low frequency (60 Hz) plasma-enhanced chemical vapor deposition (PECVD)

Hydrogenated amorphous carbon (a-C:H) films were deposited onto glass substrates using low frequency (60 Hz) plasma-enhanced chemical vapor deposition and the effects of the applied power on a-C:H films deposition were investigated. During deposition, the electron temperature and the density of CH₄-H₂ plasma were 2.4-3.1 eV and about 10⁸ cm⁻³, respectively. The main optical emission peak of the carbon species observed in the CH₄-H₂ plasma is shown to be excited carbon CH* at 431 nm. The sp³/sp² ratio, band gap, hydrogen content, and refractive index of a-C:H films gradually increased up to a power of 25 W and then saturated at higher power. This tendency is similar to the variation of plasma parameters with varying applied power, thereby indicating that a strong relationship exists between the properties of the films and the plasma discharge.     

Ni-Al-O diffusion barrier layer for high-κ metal-oxide-semiconductor capacitor

Using amorphous Ni-Al-O (a-Ni-Al-O) thin film as the intermediate layer, poly-crystalline Er₂O₃ thin film was grown on a-Ni-Al-O/Si (p-type) via laser molecular beam epitaxy, forming the Er₂O₃/Ni-Al-O gate stack. It was found that the mean dielectric constant of the Er₂O₃/Ni-Al-O gate stack with an equivalent oxide thickness of 1.5 nm is about 17-23, the interfacial states density is about 3.16 × 10¹² cm⁻² and the stack gate leakage current density is as small as 4.1 × 10^− 6 A/cm². Furthermore, The insertion of the Ni-Al-O thin film between the Er₂O₃ gate dielectric and p-Si substrate prevents the oxygen from being out-diffused, which significantly improved the stability of gate stack, showing that the Er₂O₃/Ni-Al-O gate stack thin film could be used as an ideal gate oxide layer for the future Metal Oxide Semiconductor Field Effect Transistors.     

Study on the homogeneity of hydrogenation for LaFe11.5Si1.5 intermetallic compound

The homogeneity of hydrogen absorption for LaFe_11.5Si_1.5 intermetallic compound was investigated. The hydrides remained NaZn₁₃-type structure when the hydrogenation temperature varied from 423 K to 923 K under 1 atm hydrogen atmosphere. The Differential Scanning calorimetric (DSC) measurements revealed slightly inhomogeneous distribution of hydrogen atoms in the hydrides hydrogenated at a low temperature. The activation before hydrogenating at a higher temperature could improve the homogeneity of hydrogen absorption. Uniform magnetic transition temperature, corresponding to the homogeneous hydrogen absorption, was observed by hydrogenating the compound at 823 K, or at 523 K after activation. The maximum magnetic entropy change ΔS_M (ΔH = 2 T) for the compound hydrogenated at 823 K is about 15.5 J/kg K with the latent heat of 5.12 × 10³ J/kg during the phase transition.     

DC sputter deposition of amorphous indium-gallium-zinc-oxide (a-IGZO) films with H2O introduction

Amorphous indium-gallium-zinc-oxide (a-IGZO) films were deposited by dc magnetron sputtering with H₂O introduction and how the H₂O partial pressure (P_H2O) during the deposition affects the electrical properties of the films was investigated in detail. Resistivity of the a-IGZO films increased dramatically to over 2 × 10⁵ Ωcm with increasing P_H2O to 2.7 × 10^− 2 Pa while the hydrogen concentration in the films increased to 2.0 × 10²¹ cm^− 3. TFTs using a-IGZO channels deposited under P_H2O at 1.6-8.6 × 10^− 2 Pa exhibited a field-effect mobility of 1.4-3.0 cm²/Vs, subthreshold swing of 1.0-1.6 V/decade and on-off current ratio of 3.9 × 10⁷-1.0 × 10⁸.     

Protonic conduction in Ca-doped La2M2O7 (M = Ce, Zr) with its application to ammonia synthesis electrochemically

Complex oxides La_1.95Ca_0.05M₂O_7−δ (M = Ce, Zr) were prepared by sol-gel method and characterized by thermal analysis (TG-DTA), X-ray diffraction (XRD). On the sintered complex oxides as solid electrolyte, the conductivity was measured in various atmospheres, and ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods. The rates of ammonia formation were up to 2.0 × 10⁻⁹ mol s⁻¹ cm⁻² for La_1.95Ca_0.05Zr₂O_7−δ and 1.3 × 10⁻⁹ mol s⁻¹ cm⁻² for La_1.95Ca_0.05Ce₂O_7−δ, respectively, at 520 °C.     

Effect of hydrogen plasma treatment on the surface morphology, microstructure and electronic transport properties of nc-Si:H

Hydrogenated nanocrystalline silicon (nc-Si:H) films, deposited by reactive radio-frequency sputtering with 33% hydrogen dilution in argon at 200 °C, were treated with low-power hydrogen plasma at room temperature at various power densities (0.1-0.5 W/cm²) and durations (10 s-10 min). Plasma treatment reduced the surface root mean square roughness and increased the average grain size. This was attributed to the mass transport of Si atoms on the surface by surface and grain boundary diffusion. Plasma treatment under low power density (0.1 W/cm²) for short duration (10 s) caused a significant enhancement of crystalline volume fraction and electrical conductivity, compared to as-deposited film. While higher power (0.5 W/cm²) hydrogen plasma treatment for longer durations (up to 10 min) caused moderate improvement in crystalline fraction and electrical properties; however, the magnitude of improvement is not significant compared to low-power (0.1 W/cm²)/short-duration (10 s) plasma exposure. The results indicate that low-power hydrogen plasma treatment at room temperature can be an effective tool to improve the structural and electrical properties of nc-Si:H.     

Effect of P on crystallization behavior and soft-magnetic properties of Fe83.3Si4Cu0.7B12 − xPx nanocrystalline soft-magnetic alloys

The P content dependences of the crystallization behavior, thermal stability and soft-magnetic properties of high Fe content Fe_83.3Si₄Cu_0.7B_12 − xP_x (x = 0 to 8) nanocrystalline soft-magnetic alloys were investigated. P addition is very effective in widening the optimum annealing temperature range and refining of bcc-Fe grain size in addition to the increasing of nanocrystalline grain density. Uniform nanocrystalline bcc-Fe grains with average size of about 20 nm and number density of 10²³-10²⁴ /m³ were prepared at around x = 6-8 for the annealed Fe_83.3Si₄Cu_0.7B_12 − xP_x alloys. The coercivity H_c markedly decreases with increasing x and exhibits a minimum at around x = 6-8, while the saturation magnetic flux density B_s shows a slight decrease. Fe_83.3Si₄Cu_0.7B₆P₆ nanocrystalline alloy exhibits excellent soft-magnetic properties with a high saturation magnetic flux density B_s of 1.77 T, low coercivity H_c of 4.2 A/m and high effective permeability μ_e of 11,600 at 1 kHz.