Characterization of Y2O3 gate dielectric on n-GaAs substrates

Physical and electrical properties of sputtered deposited Y₂O₃ films on NH₄OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y₂O₃ on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 10¹² eV⁻¹ cm⁻²). The results show that the deposition of Y₂O₃ on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y₂O₃/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10⁻⁶ A cm⁻² at a V_FB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y₂O₃ films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y₂O₃/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.     

Crystal field energy levels of the laser crystal Gd3Ga5O12: Nd

The crystal field energy levels of laser crystal Gd₃Ga₅O₁₂: Nd³⁺ are calculated using the diagonalization (of energy matrix) method. From the calculations, the 93 observed crystal field energy levels are explained reasonably and the root-mean-square (r.m.s.) deviation σ(≈25.6 cm⁻¹) and the scalar crystal-field strength parameter Nv (≈3847 cm⁻¹) are obtained. The results are discussed.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

Oxygen exchange kinetics of La0.58Sr0.4Co0.2Fe0.8O3 at 600 °C in dry and humid atmospheres

The time-dependent degradation of the oxygen exchange kinetics of the solid oxide fuel cell cathode material La_0.58Sr_0.4Co_0.2Fe_0.8O_3 − δ (LSCF) is investigated at 600 °C. Special emphasis is placed on systematic long-term dc-conductivity relaxation measurements (t > 1000 h) in dry as well as in humidified atmospheres in order to obtain representative trends for the application of LSCF in intermediate-temperature SOFCs. The determination of the chemical surface exchange coefficient k_chem of oxygen is combined with investigations of the elemental surface compositions and depth profiles of fresh and degraded samples by X-ray photoelectron spectroscopy (XPS), providing further insight into the mechanisms of degradation. The slow decrease of k_chem by a factor of 2 during exposure of the sample to a dry O₂-Ar reference atmosphere for 1000 h at 600 °C can be ascribed to an enrichment of La and Sr in correlation with an elevated oxygen concentration within about 30-35 nm depth. The interpretation of the XPS core level spectra indicates the formation of SrO and La₂O₃ secondary phases in this zone. The subsequent treatment in a humidified atmosphere for 1000 h results in a pronounced initial decrease of k_chem by an additional factor of 10, followed by a time dependent decay of about 15% kh^− 1. A Sr-rich silicate layer of about 10 nm thickness is identified by XPS as the major cause of the degradation in humidified atmosphere. The evidence of Si-poisoning over the whole sample surface could also be confirmed by post-test SEM analysis. In addition, indications of a re-structuring of the sample surface during the degradation are shown. These results indicate, that with LSCF as a cathode in ambient (humid) air in SOFC stacks containing various Si-sources, such as glass or glass-ceramic seals, and thermal insulation materials a significant decrease of the surface oxygen exchange coefficient can occur, even at temperatures as low as 600 °C. In order to prevent a severe Si-induced degradation, dry air should be used as an oxidant. However, even in dry atmosphere a minor decrease of k_chem can occur during long-term operation due to changes in the relative cation and oxygen content at the surface.     

EDXRF measurements on gold diffusion-doped Bi1.8Pb0.35Sr1.9Ca2.1Cu3Oy

Gold (Au) diffusion in superconducting Bi_1.8Pb_0.35Sr_1.9Ca_2.1Cu₃O_y was investigated over the temperature range 500-800 °C by the energy dispersive X-ray fluorescence (EDXRF) technique. It is found that the Au diffusion coefficient decreases as the diffusion-annealing temperature decreases. The temperature dependences of Au diffusion coefficient in grains and over grain boundaries are described by the relations D₁=6.7×10⁻⁵exp(−1.19 eV/k_BT) and D₂=9.7×10⁻⁴exp(−1.09 eV/k_BT), respectively. The diffusion doping of Bi-2223 by Au causes a significant increase of the lattice parameter c by about 0.19%. For the Au-diffused samples, dc electrical resistivity and transport critical current density measurements indicated the critical transition temperature increased from 100 to 104 K and the critical current density increased from 40 to 125 A cm⁻², in comparison with those of undoped samples. From scanning electron microscope (SEM) and X-ray diffraction (XRD) measurements it is observed that Au doping of the sample also improved the surface morphology and increased the ratio of the high-T_c phase to the low-T_c phase. The possible reasons for the observed improvement in microstructure and superconducting properties of the samples due to Au diffusion are also discussed.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

CuInS2 thin films obtained through the annealing of chemically deposited In2S3-CuS thin films

In this work, we report the formation of CuInS₂ thin films on glass substrates by heating chemically deposited multilayers of copper sulfide (CuS) and indium sulfide (In₂S₃) at 300 and 350 °C in nitrogen atmosphere at 10 Torr. CIS thin films were prepared by varying the CuS layer thickness in the multilayers with indium sulfide. The XRD analysis showed that the crystallographic structure of the CuInS₂ (JCPDS 27-0159) is present on the deposited films. From the optical analysis it was estimated the band gap value for the CIS film (1.49 eV). The electrical conductivity varies from 3 × 10⁻⁸ to 3 Ω⁻¹ cm⁻¹ depending on the thickness of the CuS film. CIS films showed p-type conductivity.     

Dry etching of CuCrO2 thin films

Highly conducting films of p-type CuCrO₂ are attractive as hole-injectors in oxide-based light emitters. In this paper, we report on the development of dry etch patterning of CuCrO₂ thin films. The only plasma chemistry that provided some chemical enhancement was Cl₂/Ar under inductively coupled plasma conditions. Etch rates of ∼500 Å min⁻¹ were obtained at chuck voltages around −300 V and moderate source powers. In all cases, the etched surface morphologies were improved relative to un-etched control samples due to the smoothing effect of the physical component of the etching. The threshold ion energy for the onset of etching was determined to be 34 eV. Very low concentrations (≤1 at.%) of residual chlorine were detected on the etched surfaces but could be removed by simple water rinsing.     

Effects of the substrate temperature on the properties of CuIn5S8 thin films

Structural, optical and electrical properties of CuIn₅S₈ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuIn₅S₈ thin films were carried out at substrate temperatures in the temperature range 100-300 °C. The effects of heated substrate on their physico-chemical properties were investigated using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), optical transmission and hot probe method. X-ray diffraction revealed that the films are strong preferred orientation along the (3 1 1) plane upon substrate temperature 200 °C and amorphous for the substrate temperatures below 200 °C. No secondary phases are observed for all the films. The composition is greatly affected by heated substrate. From the optical transmission and reflection, an important absorption coefficient exceeds 10⁵ cm⁻¹ at 800 nm was found. As increasing the substrate temperature, the optical energy band gap decreases from 1.70 eV for the unheated films to 1.25 eV for the deposited films at 300 °C. It was found that CuIn₅S₈ thin film is an n-type semiconductor at 250° C.     

Effects of vanadium doping on structure and electrical properties of SrBi4Ti4O15 thin films

The effects of vanadium(V) doping into SrBi₄Ti₄O₁₅ (SBTi) thin films on the structure, ferroelectric, leakage current, dielectric, and fatigue properties have been studied. X-ray diffraction result showed that the crystal structure of the SBTi thin films with and without vanadium is the same. Enhanced ferroelectricity was observed in the V-doped SrBi₄Ti₄O₁₅ (SrBi_4−x/3Ti_4−xV_xO₁₅, SBTiV-x (x = 0.03, 0.06, and 0.09)) thin films compared to the pure SrBi₄Ti₄O₁₅ thin film. The values of remnant polarization (2P_r) and coercive field (2E_c) of the SBTiV-0.09 thin film capacitor were 40.9 μC/cm² and 105.6 kV/cm at an applied electric field of 187.5 kV/cm, respectively. The 2P_r value is over five times larger than that of the pure SBTi thin film capacitor. At 100 kHz, the values of dielectric constant and dielectric loss were 449 and 0.04, and 214 and 0.06 for the SBTiV-0.09 and the pure SBTi thin film capacitors, respectively. The leakage current density of the SBTiV-0.09 thin film capacitor measured at 100 kV/cm was 6.8 × 10⁻⁹ A/cm², which is more than two and a half orders of magnitude lower than that of the pure SBTi thin film capacitor. Furthermore, the SBTiV-0.09 thin film exhibited good fatigue endurance up to 10¹⁰ switching cycles. The improved electrical properties may be related to the reduction of internal defects such as bismuth and oxygen vacancies with changes in the grain size by doping of vanadium into SBTi.     

A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application

Mn₃O₄ thin films have been prepared by novel chemical successive ionic layer adsorption and reaction (SILAR) method. Further these films were characterized for their structural, morphological and optical properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), field emission scanning electron microscopy (FESEM), wettability test and optical absorption studies. The XRD pattern showed that the Mn₃O₄ films exhibit tetragonal hausmannite structure. Formation of manganese oxide compound was confirmed from FTIR studies. The optical absorption showed existence of direct optical band gap of energy 2.30 eV. Mn₃O₄ film surface showed hydrophilic nature with water contact angle of 55°. The supercapacitive properties of Mn₃O₄ thin film investigated in 1 M Na₂SO₄ electrolyte showed maximum supercapacitance of 314 F g⁻¹ at scan rate 5 mV s⁻¹.     

Silicon MIS diodes with Cr2O3 nanofilm: Optical, morphological/structural and electronic transport properties

In this work we report the optical, morphological and structural characterization and diode application of Cr₂O₃ nanofilms grown on p-Si substrates by spin coating and annealing process. X-ray diffraction (XRD), non-contact mode atomic force microscopy (NC-AFM), ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy were used for characterization of nanofilms. For Cr₂O₃ nanofilms, the average particle size determined from XRD and NC-AFM measurements was approximately 70 nm. Structure analyses of nanofilms demonstrate that the single phase Cr₂O₃ on silicon substrate is of high a crystalline structure with a dominant in hexagonal (1 1 0) orientation. The morphologic analysis of the films indicates that the films formed from hexagonal nanoparticles are with low roughness and uniform. UV-vis absorption measurements indicate that the band gap of the Cr₂O₃ film is 3.08 eV. The PL measurement shows that the Cr₂O₃ nanofilm has a strong and narrow ultraviolet emission, which facilitates potential applications in future photoelectric nanodevices. Au/Cr₂O₃/p-Si metal/interlayer/semiconductor (MIS) diodes were fabricated for investigation of the electronic properties such as current-voltage and capacitance-voltage. Ideality factor and barrier height for Au//Cr₂O₃/p-Si diode were calculated as 2.15 eV and 0.74 eV, respectively. Also, interfacial state properties of the MIS diode were determined. The interface-state density of the MIS diode was found to vary from 2.90 × 10¹³ eV⁻¹ cm⁻² to 8.45 × 10¹² eV⁻¹ cm⁻².     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

Ab initio chemical kinetics for the reactions of HNCN with O(P) and O2

The kinetics and mechanisms of the reactions of cyanomidyl radical (HNCN) with oxygen atoms and molecules have been investigated by ab initio calculations with rate constant prediction. The doublet and quartet state potential energy surfaces (PESs) of the two reactions have been calculated by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on geometries optimized at the CCSD/6-311++G(d, p) level. The rate constants for various product channels of the two reactions in the temperature range of 300-3000 K are predicted by variational transition state and RRKM theories. The predicted total rate constants of the O(³P) + HNCN reaction at 760 Torr Ar pressure can be represented by the expressions k_total (O + HNCN) = 3.12 × 10⁻¹⁰ × T^−0.05 exp (−37/T) cm³ molecule⁻¹ s⁻¹ at T = 300-3000 K. The branching ratios of primary channels of the O(³P) + HNCN are predicted: k₁ for producing the NO + CNH accounts for 0.72-0.64, k₂ + k₉ for producing the ³NH + NCO accounts for 0.27-0.32, and k₆ for producing the CN + HNO accounts for 0.01-0.07 in the temperature range studied. Meanwhile, the predicted total rate constants of the O₂ + HNCN reaction at 760 Torr Ar pressure can be represented by the expression, k_total(O₂ + HNCN) = 2.10 × 10⁻¹⁶ × T^1.28exp (−12200/T) cm³ molecule⁻¹ s⁻¹ at T = 300-3000 K. The predicted branching ratio for k₁₁ + k₁₃ producing HO₂ + ³NCN as the primary products accounts for 0.98-1.00 in the temperature range studied.     

Exchange bias in thin-film (Co/Pt)3/Cr2O3 multilayers

We have fabricated exchange-biased Co/Pt layers ((0.3 nm/1.5 nm)×3) on (0 0 1)-oriented Cr₂O₃ thin films. The multilayered films showed extremely smooth surfaces and interfaces with root mean square roughness of ≈0.3 nm for 10 μm×10 μm area. The Cr₂O₃ films display sufficient insulation with a relative low leakage current (1.17×10⁻² A/cm² at 380 MV/m) at room temperature which allowed us to apply electric field as high as 77 MV/m. We find that the sign of the exchange bias and the shape of the hysteresis loops of the out-of-plane magnetized Co/Pt layers can be delicately controlled by adjusting the magnetic field cooling process through the Néel temperature of Cr₂O₃. No clear evidence of the effect of electric field and the electric field cooling was detected on the exchange bias for fields as high as 77 MV/m. We place the upper bound of the shift in exchange bias field due to electric field cooling to be 5 Oe at 250 K.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Influence of [S2O3]/[Sm] on Sm2S3 thin films deposited by liquid phase deposition method on self-assembled monolayers

Sm₂S₃ thin films were prepared on Si (1 0 0) substrates using SmCl₃ and Na₂S₂O₃ as precursors by liquid phase deposition method on self-assembled monolayers. The influence of the molar concentration ratio of [S₂O₃²⁻]/[Sm³⁺] on the phase compositions, surface morphologies and optical properties of the as-deposited films were investigated. The as-deposited Sm₂S₃ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet-visible (UV-vis) and photoluminescence spectrum (PL). Results show that it is important to control the [S₂O₃²⁻]/[Sm³⁺] during the deposition process and monophase Sm₂S₃ thin films with orientation growth along (0 1 1) direction can be achieved when [S₂O₃²⁻]/[Sm³⁺] = 2.0, pH 3.0, with citric acid as a template agent. The as-deposited thin films exhibit a dense and crystalline surface morphology. Good transmittance in the visible spectrum and excellent absorbency of ultraviolet light of the thin films are observed, and the band gap of the thin films first decrease and then increase with the increase of the [S₂O₃²⁻]/[Sm³⁺]. The as-deposited thin films also exhibit red photoluminescence properties under visible light excitation. With the increase of the [S₂O₃²⁻]/[Sm³⁺] in the deposition solution, the PL properties of Sm₂S₃ thin films are obviously improved.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Laser desorption of NO from a thick C60 film

The desorption of NO molecules from a thick C₆₀ film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of E_b = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of T_rot(v″ = 0) = 370 K, T_rot(v″ = 1) = 390 K and T_vib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10⁻¹⁷ cm². Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.     

Low temperature synthesis and superconducting properties of polycrystalline T′-(La,Sm)2CuO4

La_2−xSm_xCuO_4+δ with the Nd₂CuO₄ structure was synthesized by precipitation from fused alkaline hydroxide, CsOH, at 400 °C. The as-sintered polycrystalline samples showed no diamagnetic signal, but after post-annealing in vacuum of ≈10⁻⁸ atm at 650–700 °C, the samples with x = 0.1 and 0.3 exhibited superconductivity at T_c on = 25 K. The volume fraction of the superconducting phase estimated from the slope of the Zero-Field-Cooled magnetization data was over 30% for x = 0.3, which confirmed that the La_1.7Sm_0.3CuO_4+δ is a bulk superconductor.