Plasma enhanced atomic layer deposition of gallium oxide on crystalline silicon: demonstration of surface passivation and negative interfacial charge

Herein we report on the passivation of crystalline silicon by gallium oxide (Ga₂O₃) using oxygen plasma as the oxidizing reactant in an atomic layer deposition (ALD) process. Excess carrier lifetimes of 2.1 ms have been measured on 1.75 Ω cm p‐type silicon, from which a surface recombination current density J₀ of 7 fA cm^–2 is extracted. From high frequency capacitance‐voltage (HF CV) measurements it is shown that, as in the case of Al₂O₃, the presence of a high negative charge density Q_tot/q of up to –6.2 × 10¹² cm^–2 is one factor contributing to the passivation of silicon by Ga₂O₃. Defect densities at midgap on the order of ～5 × 10¹¹ eV^–1 cm^–2 are extracted from the HF CV data on samples annealed at 300 °C for 30 minutes in a H₂/Ar ambient, representing an order of magnitude reduction in the defect density compared to pre‐anneal data. Passivation of a boron‐diffused p⁺ surface (96 Ω/□) is also demonstrated, resulting in a J₀ of 52 fA cm^–2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Measurement of the third‐order nonlinear optical susceptibility χ(3) for the 1002‐cm–1 mode of benzenethiol using coherent anti‐Stokes Raman scattering with continuous‐wave diode lasers

The components of the third‐order nonlinear optical susceptibility χ⁽³⁾ for the 1002‐cm^–1 mode of neat benzenethiol have been measured using coherent anti‐Stokes Raman scattering with continuous‐wave diode pump and Stokes lasers at 785.0 and 852.0 nm, respectively. Values of 2.8 ± 0.3 × 10^–12, 2.0 ± 0.2 × 10^–12, and 0.8 ± 0.1 × 10^–12 cm·g^–1·s² were measured for the xxxx, xxyy, and xyyx components of |3χ⁽³⁾|, respectively. We have calculated these quantities using a microscopic model, reproducing the same qualitative trend. The Raman cross‐section σ_RS for the 1002‐cm^–1 mode of neat benzenethiol has been determined to be 3.1 ± 0.6 × 10^–29 cm² per molecule. The polarization of the anti‐Stokes Raman scattering was found to be parallel to that of the pump laser, which implies negligible depolarization. The Raman linewidth (full‐width at half‐maximum) Γ was determined to be 2.4 ± 0.3 cm^–1 using normal Stokes Raman scattering. The measured values of σ_RS and Γ yield a value of 2.1 ± 0.4 × 10^–12 cm·g^–1·s² for the resonant component of 3χ⁽³⁾. A value of 1.9 ± 0.9 × 10^–12 cm·g^–1·s² has been deduced for the nonresonant component of 3χ⁽³⁾. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of Y incorporation in TaON gate dielectric on electrical performance of GaAs metal–oxide–semiconductor capacitor

In this study, GaAs metal–oxide–semiconductor (MOS) capacitors using Y‐incorporated TaON as gate dielectric have been investigated. Experimental results show that the sample with a Y/(Y + Ta) atomic ratio of 27.6% exhibits the best device characteristics: high k value (22.9), low interfacestate density (9.0 × 10¹¹ cm^–2 eV^–1), small flatband voltage (1.05 V), small frequency dispersion and low gate leakage current (1.3 × 10^–5A/cm² at V_fb + 1 V). These merits should be attributed to the complementary properties of Y₂O₃ and Ta₂O₅:Y can effectively passivate the large amount of oxygen vacancies in Ta₂O₅, while the positively‐charged oxygen vacancies in Ta₂O₅ are capable of neutralizing the effects of the negative oxide charges in Y₂O₃. This work demonstrates that an appropriate doping of Y content in TaON gate dielectric can effectively improve the electrical performance for GaAs MOS devices.

Capacitance–voltage characteristic of the GaAs MOS capacitor with TaYON gate dielectric (Y content = 27.6%) proposed in this work with the cross sectional structure and dielectric surface morphology as insets.     

Crystal structure,characterisation and vibrational study of a mixed compound Cs0.4Rb0.6H2Po4

Abstract

The crystal structure of Cs_1-x Rb _x H₂PO₄, x = 0.6 (CRDP) which crystallises in space group P2₁/m and is isostructural with the monoclinic phase of CsH₂PO₄ (CDP), has been refined at room temperature using single-crystal X-ray diffractometer data. The cell parameters are a = 4.8183(9)å, b = 6.2671(6) å, c = 7.7620(10)å, β= 108.260(10)°, V = 222.58(5)å³, Z = 2, D_x = 3.009g cm^?3. F(000)=187, T = 298(2)K (room-temperature phase), R = 0.0355 and wR = 0.0949 for 654 observed reflections. CRDP contains two crystallography inequivalent hydrogen bonds in the unit cell. The shorter bond (Ko – o = 2.453(7) A) links the phosphate groups into chains running along the b-axis and the longer bond (Ko – o = 2.488(6) A) which is always ordered, crosslinks the chains to form (001) layers. The phase transitions in the mixed Cs_0.4Rb_0.6H₂PO₄ (CRDP) were characterised by differential scanning calorimetry which shows two anomalies at about 293 and 525 K. The Raman and infrared spectra at room temperature were investigated in the frequency ranges 10–3500 and 200–4000 cm^?1 respectively. An assignment of all the bands is given. The bands are in agreement with the monoclinic room-temperature phase implying high dynamical disorder of the acidic proton O-H s–O hydrogen bond.     

Effect of temperature–bias annealing on the hysteresis and subthreshold behavior of multilayer MoS2 transistors

The transfer characteristics (I_D–V_G) of multilayers MoS₂ transistors with a SiO₂/Si backgate and Ni source/drain contacts have been measured on as‐prepared devices and after annealing at different temperatures (T_ann from 150 °C to 200 °C) under a positive bias ramp (V_G from 0 V to +20 V). Larger T_ann resulted in a reduced hysteresis of the I_D–V_G curves (from ～11 V in the as‐prepared sample to ～2.5 V after T_ann at 200 °C). The field effect mobility (～30 cm² V^–1 s^–1) remained almost unchanged after the annealing. On the contrary, the subthreshold characteristics changed from the common n‐type behaviour in the as‐prepared device to the appearance of a low current hole inversion branch after annealing. This latter effect indicates a modification of the Ni/MoS₂ contact that can be explained by the formation of a low density of regions with reduced Schottky barrier height (SBH) for holes embedded in a background with low SBH for electrons. Furthermore, a temperature dependent analysis of the subthreshold characteristics revealed a reduction of the interface traps density from ～9 × 10¹¹ eV^–1cm^–2in the as‐prepared device to ～2 × 10¹¹ eV^–1cm^–2after the 200 °C temperature–bias annealing, which is consistent with the observed hysteresis reduction.

Schematic representation of a back‐gated multilayer MoS₂ field effect transistor (left) and transfer characteristics (right) measured at 25 °C on an as‐prepared device and after the temperature–bias annealing at 200 °C under a positive gate bias ramp from 0 V to +20 V.     

The rate constants of singlet oxygen collision-induced emission at 634 and 703 nm wavelengths

Absolute spectral luminosity from an O₂–O₂(a)-H₂O gas flow formed by a chemical singlet oxygen generator was measured at 600–800 and 1230–1310 nm wavelengths. The results were used to determine the rate constants for O₂(a, 0) + O₂(a, 0) → O₂(X, 0) + O₂(X, 0) + hν (λ = 634 nm) and O₂(a, 0) + O₂(a, 0) → O₂(X, 1) + O₂(X, 0) + hν (λ = 703 nm) collision-induced emission ((6.72 ± 0.8) × 10⁻²³ and (7.17 ± 0.8) × 10⁻²³ cm³/s, respectively).     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

A DFT‐GIAO and DFT‐NBO study of polar substituent effects on NMR 17O chemical shifts in some rigid polycyclic alkanes

¹⁷O NMR shieldings of 3‐substituted(X)bicyclo[1.1.1]pentan‐1‐ols ( 1 , Y = OH), 4‐substituted(X)bicyclo[2.2.2]octan‐1‐ols ( 2 , Y = OH), 4‐substituted(X)‐bicyclo[2.2.1]heptan‐1‐ols ( 3 , Y = OH), 4‐substituted(X)‐cuban‐1‐ols ( 4 , Y = OH) and exo‐ and endo‐ 6‐substituted(X)exo‐bicyclo[2.2.1]heptan‐2‐ols ( 5 and 6 , Y = OH, respectively), as well as their conjugate bases ( 1 – 6 , Y = O^?), for a set of substituents (X = H, NO₂, CN, NC, CF₃, COOH, F, Cl, OH, NH₂, CH₃, SiMe₃, Li, O^?, and NH) covering a wide range of electronic substituent effects were calculated using the DFT‐GIAO theoretical model at the B3LYP/6‐311 + G(2d, p) level of theory. By means of natural bond orbital (NBO) analysis various molecular parameters were obtained from the optimized geometries. Linear regression analysis was employed to explore the relationship between the calculated ¹⁷O SCS and polar field and group electronegativity substituent constants (σ_F and σ_χ, respectively) and also the NBO derived molecular parameters (oxygen natural charge, Q_n, occupation numbers of the oxygen lone pairs, n_o, and occupancy of the C? O antibonding orbital, σ*_CO(occup)). In the case of the alcohols ( 1 – 6 , Y = OH) the ¹⁷O SCS appear to be governed predominantly by the σ_χ effect of the substituent. Furthermore, the key determining NBO parameters appear to be n_o and σ*_CO(occup). Unlike the alcohols, the calculated ¹⁷O SCS of the conjugate bases ( 1 – 6 , Y = O^?), except for system 1 , do not respond systematically to the electronic effects of the substituents. An analysis of the SCS of 1 (Y = O^?) raises a significant conundrum with respect to their origin. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of precursor gas ratio and firing on silicon surface passivation by APCVD aluminium oxide

Using a high throughput, in‐line atmosphere chemical vapor deposition (APCVD) tool, we have synthesized amorphous aluminum oxide (AlO_x) films from precursors of trimethyl‐aluminum (TMA) and O₂, yielding a maximum deposition 150 nm min^–1 per wafer. For p‐type crystalline silicon (c‐Si) wafers, excellent surface passivation was achieved with the APCVD AlO_x films, with a best maximum effective surface recombination velocity (S_eff,max) of 8 cm/s following a standard industrial firing step. The findings could be attributed to the existence of large negative charge (Q_f ≈ –3 × 10¹² cm^–2) and low interface defect density (D_it ≈ 4 × 10¹¹ eV^–1 cm^–2) achieved by the films. This data demonstrates a high potential for APCVD AlO_x to be used in high efficiency, low cost industrial solar cells. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low‐thermal budget flash light annealing for Al2O3 surface passivation

This value is achieved due to a very low interface trap density of below 10¹⁰ eV^–1 cm^–2 and a fixed charge density of (2–3) × 10¹² cm^–2. In contrast, plasma ALD‐grown Al₂O₃ layers only reach carrier lifetimes of about 1 ms. This is mainly caused by a more than 10 times higher density of interface traps, and thus, inferior chemical passivation. The strong influence of the deposition parameters is explained by the limitation of hydrogen transport in Al₂O₃ during low‐thermal budget annealing. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Microstructure and varistor properties of ZnO–V2O5–MnO2 ceramics with Ta2O5 addition

The effect of Ta₂O₅ addition on microstructure, electrical properties, and dielectric characteristics of the quaternary ZnO–V₂O₅–MnO₂ vaistor ceramics was investigated. Analysis of the microstructure indicated that the quaternary ZnO–V₂O₅–MnO₂–Ta₂O₅ ceramics consisted of mainly ZnO grain and minor secondary phases such as Zn₃(VO₄)₂, ZnV₂O₄, TaVO₅, and Ta₂O₅. As the amount of Ta₂O₅ increased, the sintered density increased from 94.8 to 97.2% of the theoretical density (5.78 g/cm³ for ZnO), whereas the average grain size decreased from 7.7 to 6.0 μm. The ceramics added with 0.05 mol% Ta₂O₅ exhibited the highest breakdown field (2715 V/cm) and the highest nonlinear coefficient (20). However, further increase caused α to abruptly decrease. The Ta₂O₅ acted as a donor due to the increase of electron concentration in accordance with the amount of Ta₂O₅. The donor concentration increased from 1.97×10¹⁸ to 3.04×10¹⁸cm^?3 with increasing the amount of Ta₂O₅ and the barrier height exhibited the maximum value (0.95 eV) at 0.05 mol% Ta₂O₅.     

Raman fingerprint of chromate,aluminate and ferrite spinels

Synthetic and natural spinel single crystals having compositions closely approaching spinel end‐members ZnCr₂O₄, MgCr₂O₄, FeCr₂O₄, ZnAl₂O₄, MgAl₂O₄, CoAl₂O₄, FeAl₂O₄, MnAl₂O₄, MgFe₂O₄, and FeFe₂O₄ were investigated by Raman spectroscopy in the 100–900 cm⁻¹ range using both the red 632.8 nm line of a He‐Ne laser and the blue 473.1 nm line of a solid‐state Nd : YAG laser. Each end‐member exhibits a Raman fingerprint with at least one peculiar peak in terms of Raman shift and relative intensity. Chromates and ferrites exhibit the most intense A_1g mode at around 680 cm⁻¹, at lower wavenumbers than in the aluminates, in agreement with the heavier atomic mass of Cr and Fe with respect to Al. For aluminate spinels, the most intense and diagnostic peaks in the spectrum are as follows: F_2g(1) at 202 cm⁻¹ for MnAl₂O₄, E_g at 408 cm⁻¹ for MgAl₂O₄, F_2g(2) at 516 cm⁻¹ for CoAl₂O₄, F_2g(3) at 661 cm⁻¹ for ZnAl₂O₄, and A_1g at 748 cm⁻¹ for FeAl₂O₄. Noteworthy, analyzing the A_1g, F_2g(3), and, in particular, the E_g peak positions, it is possible to establish which subgroup a spinel belongs to; moreover, a careful inspection of both position and relative intensity of the same peaks allows the determination of the end‐member type. Copyright © 2015 John Wiley & Sons, Ltd.     

Significantly reduced leakage currents in organic thin film transistors with Mn‐doped Bi2Ti2O7 high‐k gate dielectrics

We report the fabrication of organic thin‐film transistors (OTFTs) with high‐k gate dielectrics of Mn‐doped Bi₂Ti₂O₇ (BTO) films. 3% Mn‐doped BTO films deposited on polymer substrates by pulsed laser deposition at room temperature exhibit low leakage currents of 2.1 × 10^–8 A/cm² at an applied electric field of 0.3 MV/cm, while undoped BTO films show much higher leakage currents of 4.3 × 10^–4 A/cm². Mn doping effectively reduces the number of oxygen vacancies in the films and improves the electrical properties. Low operation voltage and significantly reduced leakage currents are demonstrated in pentacene‐based OTFTs with the Mn‐doped BTO gate dielectrics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Charge transfer reaction of multi-charged oxygen ions with O2

The rate of transfer of electrons from O₂ to O²⁺ and O³⁺ has been measured at energies ? 2 eV using a stored ion technique. The rate for O²⁺ is k = 1.0(0.3) × 10^?9 cm³/s and for O³⁺, k = 2.5(0.3) × 10^?9 cm³/s, compared to calculated Langevin rates of 1.8 × 10^?9 cm³/s and 2.7 × 10^?9 cm³/s respectively.     

High mobility In2O3:H transparent conductive oxides prepared by atomic layer deposition and solid phase crystallization

The preparation of high‐quality In₂O₃:H, as transparent conductive oxide (TCO), is demonstrated at low temperatures. Amorphous In₂O₃:H films were deposited by atomic layer deposition at 100 °C, after which they underwent solid phase crystallization by a short anneal at 200 °C. TEM analysis has shown that this approach can yield films with a lateral grain size of a few hundred nm, resulting in electron mobility values as high as 138 cm²/V s at a device‐relevant carrier density of 1.8 × 10²⁰ cm^–3. Due to the extremely high electron mobility, the crystallized films simultaneously exhibit a very low resistivity (0.27 mΩ cm) and a negligible free carrier absorption. In conjunction with the low temperature processing, this renders these films ideal candidates for front TCO layers in for example silicon heterojunction solar cells and other sensitive optoelectronic applications. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

Infrared Laser Spectroscopy of Jet-Cooled C2F6near 10 μm

The ν₅(A_2u) and ν₇(E_u) C–F stretching fundamentals of hexafluoroethane, C₂F₆, have been recorded in a supersonic jet by diode laser absorption spectroscopy. The parallel 5¹_oband is accompanied by five satellite bands, of which three have been assigned to hot bands. A fourth satellite band arises from¹²CF₃¹³CF₃. Transitions satisfying 0 ≤KΔK≤ 7 of the perpendicular 7¹_oband are unperturbed while those having −10 ≤KΔK≤ 7 can be fitted assuming anR_z-Coriolis interaction with a state lying at ν_p= 1256 cm⁻¹. A second localized perturbation affects lines withKΔK≥ 8. The band origins are 1117.10736 (7) cm⁻¹(5¹_o) and 1252.96950 (17) cm⁻¹(7¹_o, 0 ≤KΔK≤ 7), and the rotational constantB₀= 0.0615759 (27) cm⁻¹.     

Band alignment and interfacial properties of atomic layer deposited (TiO2)x(Al2O3)1?x gate dielectrics on Ge

(TiO₂) _x (Al₂O₃)_1−x (x=0.7,0.8,0.9) gate dielectrics were deposited on Ge by atomic layer deposition using trimethylaluminium and Ti isopropoxide. The interfacial properties and band alignment were investigated by means of transmission electron microscopy (TEM) and X-ray photoemission spectroscopy. High-resolution TEM results show that the (TiO₂)_0.8(Al₂O₃)_0.2 film annealed at 500°C is amorphous with sharp interface between (TiO₂)_0.8(Al₂O₃)_0.2 and Ge. The conduction-band offsets are enhanced from 1.04 to 1.40 eV with increasing Al content. Capacitance equivalent thickness of 15.8 ? for (TiO₂)_0.9(Al₂O₃)_0.1 gate dielectrics is achieved with a gate leakage current of 2.70×10⁻⁵ A/cm² at V _g=+1 V.     

Measurement of hyperfine structure in the lines 578.77 nm and 587.04 nm of PrII

The hyperfine structure of the transitions 4f³(⁴I^o)5d ³I₅ ^o–4f³(⁴I^o)6p?⁵I₅ (578.77 nm) and 4f³(⁴I^o)5d ³I₆ ^o–4f³(⁴I^o)6p? (J=5) (587.04 nm) of ¹⁴¹PrII has been measured by collinear laser‐ion‐beams spectroscopy. The magnetic‐dipole constant A and the electric‐quadrupole constant B of the involved levels have been determined.     

Gas‐phase reactions of Cl atoms with hydrochloroethers: relative rate constants and their correlation with substituents' electronegativities

Rate constants for the reactions of Cl atoms with CH₃OCHCl₂ and CH₃OCH₂CH₂Cl were determined at (296 ± 2) K and atmospheric pressure using synthetic air as bath gas. Decay rates of these organic compounds were measured relative to the following reference compounds: CH₂ClCH₂Cl and n‐C₅H₁₂. Using rate constants of 1.33 × 10^?12 and 2.52 × 10^?10 cm³ molecule^?1 sec^?1 for the reaction of Cl atoms with CH₂ClCH₂Cl and n‐C₅H₁₂, respectively, the following rate coefficients were derived: k(Cl + CH₃OCHCl₂) = (1.05 ± 0.11) × 10^?12 and k(Cl + CH₃OCH₂CH₂Cl) = (1.14 ± 0.10) × 10^?10, in units of cm³ molecule^?1 s^?1. The rate constants obtained were compared with previous literature data and a correlation was found between the rate coefficients of some CH₃OCHR¹R² + Cl reactions and ΔElectronegativity of ? CHR¹R². Copyright © 2008 John Wiley & Sons, Ltd.