Room-temperature UV-ozone assisted solution process for zirconium oxide films with high dielectric properties

A facile, low-cost, and room-temperature UV-ozone (UVO) assisted solution process was employed to prepare zirconium oxide (ZrO_x) films with high dielectric properties. ZrO_x films were deposited by a simple spin-coating of zirconium acetylacetonate (ZrAcAc) precursor in the environment-friendly solvent of ethanol. The smooth and amorphous ZrO_x films by UVO exhibit average visible transmittances over 90% and energy bandgap of 5.7 eV. Low leakage current of 6.0 × 10⁻⁸ A/cm² at 3 MV/cm and high dielectric constant of 13 (100 Hz) were achieved for ZrO_x dielectrics at the nearly room temperature. Moreover, a fully room-temperature solution-processed oxide thin films transistor (TFT) with UVO assisted ZrO_x dielectric films achieved acceptable performances, such as a low operating voltage of 3 V, high carrier mobility of 1.65 cm² V⁻¹ s⁻¹, and on/off current ratio about 10⁴–10⁵. Our work indicates that simple room-temperature UVO is highly potential for low-temperature, solution-processed and high-performance oxide films and devices.     

Silicon carbide films from polycarbosilane and their usage as buffer layers for diamond deposition

Thin films of polycarbosilane (PCS) were coated on a Si (100) wafer and converted to silicon carbide (SiC) by pyrolyzing them between 800 and 1150 °C. Granular SiC films were derived between 900 and 1100 °C whereas smooth SiC films were developed at 800 and 1150 °C. Enhancement of diamond nucleation was exhibited on the Si (100) wafer with the smooth SiC layer generated at 1150 °C, and a nucleation density of 2 × 10¹¹ cm^− 2 was obtained. Nucleation density reduced to 3 × 10¹⁰ cm^− 2 when a bias voltage of − 100 V was applied on the SiC-coated Si substrate. A uniform diamond film with random orientations was deposited to the PCS-derived SiC layer. Selective growth of diamond film on top of the SiC buffer layer was demonstrated.     

Ionic conductivity of Mn2+ doped dense tin pyrophosphate electrolytes synthesized by a new co-precipitation method

Mn²⁺-doped Sn_1−xMn_xP₂O₇ (x = 0–0.2) are synthesized by a new co-precipitation method using tin(II)oxalate as tin(IV) precursor, which gives pure tin pyrophosphate at 300 °C, as all the reaction by-products are vaporizable at <150 °C. The dopant Mn²⁺ acts as a sintering aid and leads to dense Sn_1−xMn_xP₂O₇ samples on sintering at 1100 °C. Though conductivity of Sn_1−xMn_xP₂O₇ samples in the ambient atmosphere is 10⁻⁹–10⁻⁶ S cm⁻¹ in 300–550 °C range, it increases significantly in humidified (water vapor pressure, pH₂O = 0.12 atm) atmosphere and reaches >10⁻³ S cm⁻¹ in 100–200 °C range. The maximum conductivity is shown by Sn_0.88Mn_0.12P₂O₇ with 9.79 × 10⁻⁶ S cm⁻¹ at 550 °C in ambient air and 2.29 × 10⁻³ S cm⁻¹ at 190 °C in humidified air. It is observed that the humidification of Sn_1−xMn_xP₂O₇ samples is a slow process and its rate increases at higher temperature. The stability of Sn_1−xMn_xP₂O₇ samples is analyzed.     

Defect chemistry of a high-k ‘Y5V’ (Ba0.95Eu0.05)TiO3 ceramic

The influence of the sintering temperature (T_s) on the structure, dielectric and valence-state properties of (Ba_1−xEu_x)TiO₃ (x=0.05) ceramics was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electron paramagnetic resonance (EPR), Raman spectroscopy, and dielectric temperature measurements. An increase in T_s can increase the solubility limit of Eu in BaTiO₃. When the T_s was increased to 1450 °C, a high-k ‘Y5V’ (ε′_RT=8500) ceramic (C-BE5T) with a single-phase cubic structure was obtained. The dielectric peak shifted rapidly toward lower temperatures with increasing T_s at a rate of −0.46 °C/K. A symmetric (200) XRD peak, exaggerated grain growth (5.6 μm), a mixed valence of Eu²⁺/Eu³⁺, an asymmetric main Raman band at 2494 cm⁻¹ and a weak sharp band at 1516 cm⁻¹ in the high-wavenumber region are characteristics of cubic symmetry of C-BE5T. The formation of a solid solution of C-BE5T and defect chemistry are discussed.     

Growth,doping and characterization of epitaxial thin films and patterned structures of AlN,GaN, and AlxGa1−xN

Advancements in the doping of GaN and Al_xGa_1−xN thin films, and the growth of GaN and Al_xGa_1−xN structures on patterned heterostructure substrates via metalorganic vapor phase epitaxy are reported. The acceptor-type behavior of Mg-doped GaN films grown in N₂ diluents is presented. Net ionized impurity concentrations up to 8×10¹⁸ cm⁻³ and Hall mobilities up to ≈14 cm² V⁻¹ s⁻¹ were measured for Mg-doped films grown in N₂ in the as-grown condition. Donor and acceptor doping of Al_xGa_1−xN alloys was performed. Acceptor doping of Al_xGa_1−xN for x≤0.13 and donor doping for x≤0.58 were achieved for films deposited at 1100 °C. Lateral epitaxial overgrowth of GaN and Al_xGa_1−xN layers was investigated. The growth and coalescence of GaN and Al_xGa_1−xN stripes patterned in SiO₂ and/or SiN_x masks deposited on GaN, including aligned second lateral epitaxial overgrowth on initial laterally overgrown GaN layers, are discussed.     

Correlation between infrared,THz and microwave dielectric properties of vanadium doped antiferroelectric BiNbO4

Terahertz (THz) transmissivity and infrared (IR) reflectivity spectra of orthorhombic microwave (MW) ceramics Bi(Nb_1−xV_x)O₄ (0.002 < x < 0.032) were measured between 4 and 3000 cm⁻¹ (0.09–90 THz) at room temperature. A well underdamped mode, presumably the ferroelectric soft mode, was observed at 25 cm⁻¹. Complex permittivity spectra obtained from the fits to our data were extrapolated down to the MW range and compared with the dielectric data near 5 GHz. The linear extrapolation of dielectric losses from THz down to the MW range is in agreement with the experimental MW losses. Addition of 3.2% of vanadium reduces the sintering temperature to 850 °C and the dielectric properties (ɛ′ = 42.2, Q·f = 14,000 GHz, τ_f = +10 ppm/°C) remain at a level satisfactory for MW applications. Somewhat lower MW losses were observed in a sample sintered in the N₂ atmosphere.     

The effect of calcium on the properties of SmBa1−xCaxCoCuO5+δ as a cathode material for intermediate-temperature solid oxide fuel cells

The effect of calcium on the properties of SmBa_1–xCa_xCoCuO_5+δ (x = 0.0–0.3) as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is evaluated systematically. Samples exhibit a highly crystalline double perovskite phase, and their cell volumes decrease as x is changed from 0.0 to 0.3. The oxygen content and average thermal expansion coefficient (TEC) of SmBa_1–xCa_xCoCuO_5+δ decreases as the calcium content increased. An average TEC of as low as 15.3 × 10⁻⁶ °C⁻¹ is obtained for SmBa_0.7Ca_0.3CoCuO_5+δ. The area specific resistances at 700 °C decrease by approximately 50% when the calcium content is increased from x = 0.0 (0.173 Ω cm²) to x = 0.3 (0.086 Ω cm²). The maximum power densities of SmBa_1−xCa_xCoCuO_5+δ-based single cells at 800 °C increase from 635 mW cm⁻² (x = 0.0) to 939 mW cm⁻² (x = 0.3).     

Role of Ni–Co co-substitution in improving electrical and dielectric properties of La-based multiferroics nanomaterials

The synthesis of a material having ferroelectric and ferromagnetic properties in the same phase is a challenging task. In the present work, lanthanum based multiferroic materials, with composition La_1−xCo_xFe_1−yNi_yO₃ (where, x=0.0–0.5 and y=0.0–1.0), have been synthesized via sol–gel auto-combustion method. The phase of the synthesized materials was confirmed by the X-ray diffraction (XRD) analysis, while the surface morphology and particle size were determined by the scanning electron microscopy (SEM) analysis. The DC electrical resistivity and activation energy were observed to increase from 2.14×10⁷ to 3.04×10¹⁰ Ω cm and 0.64 to 0.77 eV, respectively with the increase in concentration of substituents. The drift mobility decreases from 3.27×10⁻¹³ to 2.80×10⁻¹⁶ cm² V⁻¹ S⁻¹. The dielectric constant, dielectric loss and dielectric loss factor decrease with the increase in frequency (1 MHz to 3 GHz) and Ni–Co content as well. The electrical and dielectric results are in good agreement with each other. The increase in electrical resistivity and decrease in dielectric parameters make these materials suitable for applications in microwave devices.     

Oxygen ionic transport in SrFe1−yAlyO3−δ and Sr1−xCaxFe0.5Al0.5O3−δ ceramics

The oxygen permeability of mixed-conducting Sr_1−xCa_xFe_1−yAl_yO_3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO₂ gradient of 0.21/0.021 atm vary from 3.7×10⁻¹⁰ mol s⁻¹ cm⁻² to 1.5×10⁻⁷ mol s⁻¹ cm⁻² at 950 °C. The maximum solubility of Al³⁺ cations in the perovskite lattice of SrFe_1−yAl_yO_3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr_1−xCa_xFe_0.5Al_0.5O_3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO₃-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe_0.5Al_0.5O_2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe_0.7Al_0.3O_3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO₂ stability limits of Sr_1−xCa_xFe_1−yAl_yO_3−δ seem essentially independent of composition, varying between that of LaFeO_3−δ and the Fe/Fe_1−γO boundary. Thermal expansion coefficients of Sr_1−xCa_xFe_1−yAl_yO_3−δ ceramics in air are 9×10⁻⁶ K⁻¹ to 16×10⁻⁶ K⁻¹ at 100–650 °C and 12×10⁻⁶ K⁻¹ to 24×10⁻⁶ K⁻¹ at 650–950 °C. Doping of SrFe_1−yAl_yO_3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.     

Microwave dielectric properties of Li2SrTa2(1−x)Nb2xO7 ceramics investigated by Raman spectroscopy

We investigated the crystal structure and microwave dielectric properties of the Li₂SrTa_2(1−x)Nb_2xO₇ (x=0−1.0) compounds using Raman spectroscopy. The Raman spectra clearly exhibit the orthorhombic structure (Cmcm space group) of these compounds. The Raman mode at 800 cm⁻¹ corresponds to the B–O3 (B=Nb and Ta) bond and shifted towards the higher frequency with increase of Nb content. The increase in separation between the two modes at 589 and 596 cm⁻¹ gives an indication of change in the difference between B–O1 and B–O2 bond lengths. The microwave dielectric properties of these compounds were found to be strongly dependent on the BO₆ octahedra. The peak width of A_g (800 cm⁻¹) mode and quality factor (Q×f) is inversely proportional to each other and the shift of this mode is correlated to dielectric constant (ε_r). Further analysis of the Raman modes at 800, 596 and 589 cm⁻¹ (due to the BO₆ octahedra) indicates the enhancement of octahedral distortion with increase in Nb content, which led to increase of temperature coefficient of resonant frequency (τ_ƒ).     

Temperature-stable and high-ɛ dielectric ceramics based on Ag (Nb1−xTax)O3

The dielectric properties of novel dielectric system AgNb_1−xTa_xO₃ (ANT) have been studied in this paper. In this system, the temperature coefficient of capacitance (TCC) can be adjusted to 0 ± 30 × 10⁻⁶/°C by choosing proper molar ratio of Nb⁵⁺ to Ta⁵⁺. When 2 wt% glass is added to the ceramics, the sintering temperature is reduced to 960 °C, which restrains Ag⁺ decomposition in ambient atmosphere. It is noted that the dielectric loss reduces further after adding 2.5 wt% Sb₂O₅. The dielectric properties of the resultant samples are as follows: dielectric constant ɛ ≈ 512, loss tangent tan δ ≈ 5.2 × 10⁻⁴, and TCC ≈ 10 × 10⁻⁶/°C.     

Temperature-insensitive dielectric and piezoelectric properties in (1-x)K0.5Na0.5Nb0.997Cu0.0075O3-xSrZrO3 ceramics

Systematic investigation on phase transition, dielectric and piezoelectric properties of (1-x)K_0.5Na_0.5Nb_0.997Cu_0.0075O₃-xSrZrO₃ (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15, abbreviated as KNNC-100xSZ) ceramics was carried out. Due to the coexistence of orthorhombic and tetragonal phase in a wide temperature range, a diffused polymorphic phase transition (PPT) region was achieved in KNNC with x ≥ 0.06. KNNC-12SZ ceramics exhibited high dielectric permittivity (∼1679), low dielectric loss (∼0.02) and small variation (Δe'/ε'_25 °C ≤ 15%) in dielectric permittivity from −78 °C to 237.3 °C. KNNC-6SZ ceramic possessed a high level of unipolar strain (∼0.15%) and maintained a smaller variation of ±12% under the corresponding electric field of 60 kV cm⁻¹ at 10 Hz from 25 °C to 175 °C. d₃₃^*, which was calculated according to the unipolar strain at 60 kV cm⁻¹, was 230 pm V⁻¹ and remained stable below 100 °C. Therefore, our work provided a new promising candidate for temperature-insensitive capacitors and piezoelectric actuators.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

Characterization of vertical Mo/diamond Schottky barrier diode from non-ideal I–V and C–V measurements based on MIS model

In this study, we investigated non-ideal characteristics of a diamond Schottky barrier diode with Molybdenum (Mo) Schottky metal fabricated by Microwave Plasma Chemical Vapour Deposition (MPCVD) technique. Extraction from forward bias I–V and reverse bias C^− 2–V measurements yields ideality factor of 1.3, Schottky barrier height of 1.872 eV, and on-resistance of 32.63 mΩ·cm². The deviation of extracted Schottky barrier height from an ideal value of 2.24 eV (considering Mo workfunction of 4.53 eV) indicates Fermi level pinning at the interface. We attributed such non-ideal behavior to the existence of thin interfacial layer and interface states between metal and diamond which forms Metal-Interfacial layer-Semiconductor (MIS) structure. Oxygen surface treatment during fabrication process might have induced them. From forward bias C–V characteristics, the minimum thickness of the interfacial layer is approximately 0.248 nm. Energy distribution profile of the interface state density is then evaluated from the forward bias I–V characteristics based on the MIS model. The interface state density is found to be uniformly distributed with values around 10¹³ eV^− 1·cm^− 2.     

Electrochemical intercalation of lithium into boron-doped CVD diamond electrodes grown on carbon fiber cloths

Boron-doped diamond electrodes grown on a cloth of graphite fibers have demonstrated as an innovative material electrode for lithium intercalation by electrochemical method. It was studied lithium electrochemical intercalation for samples with different levels of boron doping. Diamond films were grown by hot-filament-assisted chemical vapor deposition technique. Boron was obtained from a source of B₂O₃ dissolved in methanol. The electrochemical characterization was carried out by voltammetry cyclic and charge/discharge curves. The electrolyte used was 1 mol l⁻¹ of LiPF₆ in mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate (1:1:1 wt.). The reference and work electrode were metallic lithium and the cell was assembled a dry-box. The results show that the insertion of lithium Li_x(B_zC_1−z)₆ is reversible and presents specific capacity, which depend on B-concentration. For limits of cut-off potential of 3.0 e 0.01 V vs. lithium we found a reversible specific capacity of 88 mAh g⁻¹ (x∼0.23) for sample with ∼10¹⁸ B cm⁻³ and 43 mAh g⁻¹ (x∼0.11) for sample with 10²¹ B cm⁻³. The voltage vs. capacity presents a hysteresis that increases with decreasing of boron concentration.     

Reprint of "Palladium Ohmic contact on hydrogen-terminated single crystal diamond film"

Contact properties of Palladium (Pd) on the surface of hydrogen-terminated single crystal diamond were investigated with several treatment conditions. 150 nm Pd pad was deposited on diamond surface by thermal evaporation technique, which shows good Ohmic properties with the specific contact resistivity (ρ_c) of 1.8 × 10^− 6 Ω cm² evaluated by Transmission Line Model. To identify the thermal stability, the sample was annealed in Ar ambient from 300 to 700 °C for 3 min at each temperature. As the temperature increased, ρ_c firstly decreased to 4.93 × 10⁻⁷ Ω cm² at 400 °C and then increased. The barrier height was evaluated to be − 0.15 eV and − 0.03 eV for as-deposited and 700 °C annealed sample by X-ray photoelectron spectroscopy analysis. Several surface treatments were also carried out to determine their effect on ρ_c, among which HNO₃ vapor treated sample indicates a lower value of 5.32 × 10⁻⁶ Ω cm².     

Ion implantation and anneal to produce low resistance metal–diamond contacts

Contacts to boron-doped, (100)-oriented diamond implanted with Si or with Si and B were formed and the effects of dose, implantation energy and anneal treatment on the specific contact resistance were examined. Ti/Au contacts on heavily implanted diamond (10¹⁶ Si ions cm⁻², E_i=30 keV or 10¹⁷ Si and B ions cm⁻², E_i=15 keV (Si) and E_i=10 keV (B)) had a specific contact resistance lower than the best contacts produced on unimplanted diamond. A specific contact resistance of (1.4±6.4)×10⁻⁷ Ω cm⁻² was achieved following a 450°C anneal. The results were consistent with a reduction in barrier height brought about by silicide formation. Light silicon implantation (10¹³ ions cm⁻²) or relatively light dual implantation (B, Si<10¹⁶ ions cm⁻²) did not reduce the specific contact resistance. Increasing the diamond conductivity by 4×10⁴ decreased the specific contact resistance by over three orders of magnitude, in agreement with the trend observed by Prins (J.F. Prins, J. Phys. D 22 (1989) 1562).     

Synthesis of BaCeO3 and BaCe0.9Y0.1O3−δ from mixed oxalate precursors

An oxalate precipitation route is proposed for the synthesis of BaCe_1−xY_xO₃ (x = 0 and 0.1) after calcination at 1100 °C. The precipitation temperature (70 °C) was a determinant parameter for producing a pure perovskite phase after calcination at 1100 °C for 1 h. TG/DTA measurements showed that the co-precipitated (Ba, Ce and Y) oxalate had a different thermal behaviour from single oxalates. Despite a simple grinding procedure, sintered BaCe_0.9Y_0.1O_3−δ pellets (1400 °C, 48 h) presented 90.7% of relative density and preliminary impedance measurements showed an overall conductivity of around 2 × 10⁻⁴ S cm⁻¹ at 320 °C.     

Strontium doping effects on the characteristics of solution-processed aluminum oxide dielectric layer and its application to low-voltage-operated indium-gallium-zinc-oxide thin-film transistors

In this paper, we investigated the strontium doping effects on the electrical and physical characteristics of solution-processed aluminum oxide dielectric layer and its application to low-voltage-operated indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs). With an optimized doping concentration of strontium (5 at%) in aluminum oxide (Al₂O₃), an oxide gate dielectric layer having a dielectric constant of ~7 and low leakage current characteristics (~4 × 10⁻⁷ A/cm² at 3 MV/cm) could be achieved by a solution process, which are comparably better than those of pristine Al₂O₃ film. The enhanced dielectric properties from strontium doping can be attributed to the change in the physical properties of Al₂O₃ film incorporated with strontium, providing charge relaxation of defect states in Al₂O₃ film. Also, since the strontium is highly reactive with oxygen, the strontium substitution through a doping leads to more strongly bound structure in an Al₂O₃ film without considerable lattice distortion. Using the strontium-doped aluminum oxide film as a gate dielectric layer, having a thickness less than 10 nm, solution-processed IGZO TFTs operating at ≤ 1 V were demonstrated showing a field-effect mobility of 1.74 ± 1.10 cm²/V s and an on-current level of ~10⁻⁵ A.