Deposition rates of titanium nitride plates prepared by chemical vapour deposition of TiCl4+NH3 system

Titanium nitride plates (TiN_x,x = 0.74–1.0, about 2 mm thick maximum) were prepared by chemical vapour deposition (CVD) using TiCI₄, NH₃ and H₂ as source gases. The effects of CVD conditions, i.e. gas molar ratio (m _N/Ti = NH₃/TiCI₄) and deposition temperature (T_dep), on deposition rates and surface morphology were examined, and the deposition mechanism of the CVD-TiN_x plates was discussed. The relationship between m_N/Ti and deposition rates showed a maximum peak at certainm _N/Ti, and this maximum peak shifted to lowerm _N/Ti with increasing_{T dep}. The activation energy for the formation of CVD-TiN_x plates was about 80 kJ mol^–1 in the lower temperature range. The decomposition reaction of NH₃ gas could be associated with the rate-controlling step. At higher temperatures, the diffusion process may be the rate-controlling step, and a large amount of powder (mainly NH₄Cl) was formed in the gas phase. The highest deposition rate obtained in the present work was 1.06×10^–7 ms^–1 (0.38 mmh^–1) atT _dep = 1773 K andm _N/Ti = 0.87.     

Density and deposition rate of chemical-vapour-deposited boron nitride

A study is made on the density and deposition rate characteristics of chemical-vapour-deposited boron nitride (CVD-BN) plates synthesized by use of the BCl₃-NH₃-H₂ system at a deposition temperature (T _dep) of 1200 to 2000°C and a total gas pressure (P _tot) of 5 to 60 torr. At aP _tot of 5 torr, all the CVD-BN plates synthesized at eachT _dep above 1300°C had a density greater than 2.O g cm^–3, and thus showed no noticeable dependence onT _dep. Over theP _tot range from 10 to 60 torr. on the other hand, the density of the plates reached the maximum of 2.08g cm^–3 at aT _dep of 2000° C. AsT _dep was lowered, the density decreased down to a minimum of 1.40 g cm^–3 The deposition rate varied with bothT _dep andP _tot and showed a maximum value under a certainP _tot at a givenT _dep. The value ofP _tot where the deposition rate becomes maximum changed depending on theT _dep. The maximum deposition rate was 0.6 mm h^–1 for the CVD-BN plates when the density was less than 2.0 g cm^–3, and 0.4 mm h^–1 when the density was above 2.0 g cm^–3 The effects of deposition conditions on the characteristics of density and deposition rate are discussed in terms of the structure and deposition mechanism.     

Preparation of SiB4±x and SiB6 plates by chemical vapour deposition of SiCl4 + B2H6 system

SiB_4±x and SiB₆ plates were prepared by chemical vapour deposition (CVD) using SiCl₄, B₂H₆ and H₂ gases under the conditions of deposition temperatures (T _dep) from 1323–1773 K, total gas pressures (P _tot) from 4–40 kPa and B/Si source gas ratio (m _B/Si=2B₂H₆/SiCl₄) from 0.2–2.8. The effects of CVD conditions on the morphology, structure and composition of the deposits were examined. High-purity and high-density SiB_4±x and SiB₆ plates about 1 mm thick were obtained at the deposition rates of 71 and 47 nm s⁻¹, respectively. The lattice parameter, composition and density of CVD SiB_4±x plates were dependent on their non-stoichiometry. The lattice parameter,a, was 0.6325 nm, butc ranged from 1.262–1.271 nm.The B/Si atomic ratio ranged from 3.1–5.0, and the density ranged from 2.39–2.45×10³ kg m⁻³. The CVD SiB₆ plates showed constant values of lattice parameters (a=1.444 nm,b=1.828 nm,c=0.9915 nm), composition (B/Si=6.0) and density (2.42×10³ kg m⁻³), independent of CVD conditions.     

Preferred orientation of TiB2 plates prepared by CVD of the TiCl4 + B2H6 system

Titanium diboride (TiB₂) plates (about 1 mm maximum thickness) were prepared by chemical vapour deposition (CVD) using a TiCl₄, B₂H₆ and H₂ system at deposition temperatures,T _dep of 1323–1773 K. The B/Ti atomic ratio in the deposits was 2, and the composition is strictly stoichiometric. Chlorine was not detected. The measured lattice parameters werea=0.3029 nm andc=0.3229 nm. Density is in close agreement with the theoretical value (4.50 g cm⁻³). Preferred orientation of the CVD TiB₂ plates varies mainly with total gas pressures,P _tot. AtP _tot=4 kPa the (1 0 0) plane and atP _tot=40 kPa the (1 1 0) plane is preferably oriented parallel to the substrates. The effect ofP _tot on the preferred orientation is discussed thermodynamically, and explained by supersaturation in the gas phase.     

Morphology and preferred orientation of titanium nitride plates prepared by chemical vapour deposition

Thick titanium nitride (TiN _x ; x = 0.74–1.0) plates (up to 2 mm thick) were prepared by chemical vapour deposition using TiCl₄, NH₃ and H₂ as source gases at a total gas pressure, P _tot, of 4 kPa, deposition temperatures, T _dep, from 1373–1873 K, and NH₃/TiCl₄, m _N/Ti, gas molar ratio from 0.17–1.74. The effects of deposition conditions on morphology, preferred orientation and composition of CVD-TiN _x plates were investigated. Surface morphology changed from faceted to nodular texture with increasing m _N/Ti and T _dep. The faceted and nodular deposits showed columnar and shell-like fracture cross-sections, respectively. The composition (x = N/Ti) increased with increasing m _N/Ti and T _dep below m _N/Ti = 1.0, and was constant above m _N/Ti = 1.0. Three kinds of preferred orientations were observed: (100) orientation at low T _dep, (110) orientation at intermediate T _dep and low m _N/Ti, and (111) orientation at high T _dep and high m _N/Ti. This tendency is discussed thermodynamically, and explained as being due to changes in the degree of supersaturation in the gas phase.     

Preparation of amorphous Si3N4-C plate by chemical vapour deposition

Chemical vapour deposition of a Si-N-C system has been studied by using SiCl₄, NH₃, H₂ and C₃H₈ as source gases at deposition temperatures (T _dep) of 1100 to 1600° C, and total gas pressures (P _tot) of 30 to 100 torr. To control the amount of carbon in these deposits the propane gas flow rate [FR(C₃H₈)] was varied from 0 to 200 cm³ min^–1. Homogeneous plate-like amorphous deposits were successfully prepared atT _dep=1100 to 1300° C,P _tot=30 to 70 torr andFR(C₃H₈)=25 to 100 cm³ min^–1. The deposits were composed of amorphous silicon nitride and carbon and the carbon content increased up to 10 wt% with increasingFR(C₃H₈). The surfaces of the deposits had a pebble-like structure.     

Thermal properties of chemical vapour-deposition SiC-C nanocomposites

The relationship between the thermal properties and the microstructure of chemical vapour-deposition (CVD) SiC-C nanocomposites, covering the entire composition range from SiC to C, was investigated after measuring thermal conductivity and thermal expansion. The samples were prepared under deposition temperatures (T _dep) of 1673 and 1773 K and total gas pressure (P_tot) of 40 kPa. The thermal conductivity of CVD SiC-C nanocomposites decreased as C content increased. For the deposits containing 24.3 to 71 mol % C prepared atT _dep = 1773 K, some parts of the C phase formed a layered structure having its plane parallel to the deposition surface. This arrangement reduced the thermal conductivity in the direction perpendicular to the deposition surface to a much lower value. The CVD C and CVD C-SiC containing < 1.5 mol % SiC showed strong anisotropic thermal expansion. However, the thermal expansion of CVD SiC-C nanocomposites having a C content up to about 70 mol % was isotropic and nearly equal to that of CVD SiC. The low preferred orientation and the low modulus of elasticity of the C phase may be reasons for these results.     

Preparation of Li–Al–O films by laser chemical vapor deposition

Li–Al–O films were prepared on AlN substrates by laser chemical vapor deposition at deposition temperatures (T_dep) of 800–1300 K and molar ratios of Li to Al precursors (R_Li/Al) of 0.1–12. Single-phase α-LiAl₅O₈ films having faceted grains with pyramidal and polygonal shapes were obtained at T_dep = 1107–1280 K and R_Li/Al = 0.1–2.9. Single-phase γ-LiAlO₂ films having pyramidal grains were prepared at T_dep = 984–1238 K and R_Li/Al = 0.9–10.6. Under the conditions of T_dep = 923 K and R_Li/Al = 11.4, single-phase β-Li₅AlO₄ films with a fluffy morphology were deposited. The highest deposition rate of Li–Al–O films was 98 μm h⁻¹ with a mixture of γ-LiAlO₂ and β-Li₅AlO₄ at T_dep = 944 K.     

Density and deposition rates of amorphous CVD-Si3N4 including carbon

Amorphous Si₃N₄ containing uniformly distributed carbon was prepared by chemical vapour deposition [Am. CVD-(Si₃N₄-C)] using SiCl₄ vapour and NH₃, H₂ and C₃ H₈ gases at deposition temperatures (T _dep) of 1100 to 1300° C and at total gas pressures (P _tot) of 30 to 70 torr. The density of Am.CVD-(Si₃N₄-C) is between 2.80 and 3.00 g cm⁻³, depending upon the deposition conditions. Rate of growth in thickness increases with increasingT _dep andP _tot, and has the largest value of 0.6 mm h⁻¹ atT _dep=1300° C,P _tot=70 torr and propane gas flow rates [FR(C₃H₈)] of 0 to 20 cm³ min⁻. The activation energy of the formation decreases from 38 to 20 kcal mol⁻¹ with increasingP _tot andFR(C₃H₈).     

Synthesis and structure of chemically vapour-deposited boron nitride

Chemically vapour-deposited boron nitride (CVD-BN) plates have been synthesized on a graphite substrate by the reaction of the BCl₃-NH₃-H₂ gas system in a deposition temperature (T _dep) range from 1200 to 2000° C, with a total gas pressure (P _tot) which was varied from 5 to 60 torr. The effects ofP _tot andT _dep on the crystal structure and the microstructure of the CVD-BN plate were investigated. Turbostratic BN(t-BN) was deposited above 10 torr, at anyT _dep in the range investigated. The interlayer spacing (c ₀/2), the crystallite size (Lc) and the preferred orientation (PO) were strongly affected byT _dep. The t-BN obtained at lowT _dep had largec ₀/2 and smallLc andPO. AsT _dep increased,c ₀/2 tended to decrease whereasLc increased and thec-plane of the crystallites became oriented parallel to the deposition surface. At aP _tot of 5 torr, a mixture of t-BN and h-BN (hexagonal BN) was deposited at anyT _dep above 1700° C, and two kinds of t-BN different inc ₀/2 co-deposited at aT _dep below 1600° C. Moreover, it was indicated that r-BN (rhombohedral BN) was included in the deposits obtained at aP _tot of 5 torr and aT _dep of 1500 to 1600° C.     

Stability to moisture for chemically vapour-deposited boron nitride

Chemically vapour-deposited boron nitride (CVD-BN) plates prepared by use of the BCl₃-NH₃-H₂ gas system were investigated as to their stability to moisture. Infrared (IR) spectroscopic measurement, chemical analysis and thermal gravimetric analysis were used in this study. The synthesis conditions of CVD-BN plates have a large influence on their stability to moisture. The stability of CVD-BN plates prepared under a total gas pressure (P _tot) of 10 to 60 torr degraded as the deposition temperature (T _dep) was lowered. The CVD-BN plates with transparent and isotropic properties, which were prepared at below 1400° C and above 10 torr, showed poor stability to moisture, The CVD-BN plates synthesized under 5 torr had high moisture-resistance, even at aT _dep as low as 1400° C. An IR absorption spectral study revealed that the unstable species existing in CVD-BN plans had changed to ammonium borate hydrates by reacting with moisture in the atmosphere. The stability to moisture for CVD-BN plates degraded as the deposition roe was raked, especially for the CVD-BN plates prepared at 1400° C.     

Investigation of the temperature dependence of electron and phonon Raman scattering in single crystal YBa2Cu3O6.952

Detailed Raman-scattering measurements have been performed on high-quality YBa₂Cu₃O_6.952 single crystal (T _c =93 K, T _c =0.3 K). A sharp (FWHM 7.2 cm^–1 at 70 K and 10.0 cm^–1 at 110 K) 340 cm^–1phonon mode has been observed inB _1g polarization. An electronic scattering peak at 500 cm^–1 in theB _1g polarization extends down to 250 cm^–1. These FWHM values determine the upper limit of the homogeneous linewidth of the phonon and electronic excitations. The start of the electronic spectral function renormalization and of the 340 cm^–1 mode anomalies (frequency softening, linewidth sharpening, and intensity increase) have been observed to occur approximately 40 K aboveT _c . The 340 cm^–1 mode Fano shape analysis has been performed and the temperature dependences of the Fano shape parameters have been estimated. All 340 cm^–1 mode anomalies have been explained by the electronic spectral function renormalization.This work was supported by Swedish Natural Sciences Research Council (G.B. and L.B.) and by the National Science Foundation (DMR 91-20000) through the Science and Technology Center for Superconductivity (G.B. and M.V.K.).     

HighT c of liquid-quenched Bi1.6Pb0.4Sr2Ga2Cu3Ox

AlthoughT _c cannot be found for a liquid-quenched Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_x glassy sample, a highT _c is found after annealing for 24 h at 1100 K. The maximum offset temperature of the superconducting transition is 113.3 K at 2.2 × 10^–2mAmm^–2. The maximumT _{c off} is larger than that (the maximumT _{c off} is 103.4 K at 2.0 × 10^–2 mAmm^–2) of sintered specimens before liquid quenching.     

Study of the defect pyrochlores A(SbTe)O6 (A=K,Rb, Cs,Tl)

By solid-state reaction in air, four deficient pyrochlores A(SbTe)O₆ (A=K, Rb, Cs, Tl) have been prepared as pale polycrystalline powders. A(SbTe)O₆ are cubic with space group Fd¯3m (No. 227),Z=8, anda (nm) values varying from 1.01133(2) (A=K) to 1.01935(4) (A=Cs). The best discrepancyR factors were obtained for A at 32(e) positions andx positional parameters close to 1/8, origin at centre, ¯3m; antimony and tellurium distributed at random at 16(d); oxygen atoms at 48(f), withu positional parameters from 0.421 (A=Tl) to 0.430 (A=Cs). The coordination polyhedron of A has been considered as depending on thex positional parameter. The products of the thermal decomposition of A(SbTe)O₆ were examined by electron microscopy and could be identified as A₃Sb₅O₁₄ (A=Rb, Cs) and a pyrochlore phase that does not contain tellurium (A=Tl). The electric conductivity measurements led to ( ^–1 cm^–1) values between 1.0×10^–9 (A=K) and 9.7×10^–6 (A=Cs) at 773 K.     

Non-contact measurements of thermophysical properties of niobium at high temperature

Four thermophysical properties of both solid and liquid niobium have been measured using the vacuum version of the electrostatic levitation furnace developed by the National Space Development Agency of Japan. These properties are the density, the thermal expansion coefficient, the constant pressure heat capacity, and the hemispherical total emissivity. For the first time, we report these thermophysical quantities of niobium in its solid as well as in liquid state over a wide temperature range, including the undercooled state. Over the 2340 K to 2900 K temperature span, the density of the liquid can be expressed as _L (T) = 7.95 × 10³ – 0.23 (T – T _m)(kg · m^–3) with T _m = 2742 K, yielding a volume expansion coefficient _L(T) = 2.89 × 10^–5 (K^–1). Similarly, over the 1500 K to 2740 K temperature range, the density of the solid can be expressed as _s(T) = 8.26 × 10³ – 0.14(T – T _m)(kg · m^–3), giving a volume expansion coefficient _s(T) = 1.69 × 10^–5 (K^–1). The constant pressure heat capacity of the liquid phase could be estimated as C _PL(T) = 40.6 + 1.45 × 10^–3 (T – T _m) (J · mol^–1 · K^–1) if the hemispherical total emissivity of the liquid phase remains constant at 0.25 over the temperature range. Over the 1500 K to 2740 K temperature span, the hemispherical total emissivity of the solid phase could be rendered as _TS(T) = 0.23 + 5.81 × 10^–5 (T – T _m). The enthalpy of fusion has also been calculated as 29.1 kJ · mol^–1.     

Non-Contact Measurements of the Thermophysical Properties of Hafnium-3 Mass% Zirconium at High Temperature

Several thermophysical properties of hafnium-3 mass % zirconium, namely the density, the thermal expansion coefficient, the constant pressure heat capacity, the hemispherical total emissivity, the surface tension and the viscosity are reported. These properties were measured over wide temperature ranges, including overheated and undercooled states, using an electrostatic levitation furnace developed by the National Space Development Agency of Japan. Over the 2220 to 2875 K temperature span, the density of the liquid can be expressed as _L (T)=1.20×10⁴–0.44(T–T _m ) (kgm^–3) with T _m =2504 K, yielding a volume expansion coefficient _L (T)=3.7×10^–5 (K^–1). Similarly, over the 1950 to 2500 K span, the density of the high temperature and undercooled solid -phase can be fitted as _S (T)=1.22×10⁴–0.41(T–T _m ), giving a volume expansion coefficient _S (T)=3.4×10^–5. The constant pressure heat capacity of the liquid phase can be estimated as C _PL (T)=33.47+7.92×10^–4(T–T _m ) (Jmol^–1K^–1) if the hemispherical total emissivity of the liquid phase remains constant at 0.25 over the 2250 K to 2650 K temperature interval. Over the 1850 to 2500 K temperature span, the hemispherical total emissivity of the solid -phase can be represented as _TS (T)=0.32+4.79×10^–5(T–T _m ). The latent heat of fusion has also been measured as 15.1 kJmol^–1. In addition, the surface tension can be expressed as (T)=1.614×10³–0.100(T–T _m ) (mNm^–1) and the viscosity as h(T)=0.495 exp [48.65×10³/(RT)] (mPas) over the 2220 to 2675 K temperature range.     

Non-Contact Measurements of Surface Tension and Viscosity of Niobium, Zirconium, and Titanium Using an Electrostatic Levitation Furnace

The surface tension and viscosity of liquid niobium, zirconium, and titanium have been determined by the oscillation drop technique using a vacuum electrostatic levitation furnace. These properties are reported over wide temperature ranges, covering both superheated and undercooled liquid. For niobium, the surface tension can be expressed as (T)=1.937×10³–0.199(T–T _m) (mN·m^–1) with T _m=2742 K and the viscosity as (T)=4.50–5.62×10^–3(T–T _m) (mPa·s), over the 2320 to 2915 K temperature range. Similarly, over the 1800 to 2400 K temperature range, the surface tension of zirconium is represented as (T)=1.500×10³–0.111(T–T _m) (mN·m^–1) and the viscosity as (T)=4.74–4.97 ×10^–3(T–T _m) (mPa·s) where T _m=2128 K. For titanium (T _m=1943 K), these properties can be expressed, respectively, as (T)=1.557×10³–0.156(T–T _m) (mN·m^–1) and (T)=4.42–6.67×10^–3(T–T _m) (mPa·s) over the temperature range of 1750 to 2050 K.     

Measurement of the heat capacity of molybdenum (Standard Reference Material) in the range 1500–2800 K

Measurement of the heat capacity of molybdenum (Standard Reference Material 781 of the National Bureau of Standards) in the temperature range 1500–2800 K by a subsecond-duration, pulse-heating technique is described. The results of the measurements on three specimens are in agreement within 0.6%. The heat capacity of molybdenum in the temperature range 1500–2800 K based on the present results is expressed by the following function (standard deviation =0.5%): C _p =–3.0429+4.7215×10^–2 T–2.3139×10^–5 T ²+4.7090× 10^–9 T ³ where T is in K and C _p is in J · mol^–1 · K^–1. The inaccuracy of the reported results is estimated to be not more than 3%.     

Thermophysical Property Measurements of Liquid and Supercooled Iridium by Containerless Methods

Thermophysical properties of equilibrium and supercooled liquid iridium were measured using noncontact diagnostic techniques in an electrostatic levitator. Over the 2300–3000 K temperature range, the density can be expressed as ρ (T)=19.5×10³ − 0.85(T− T_m) (kg·m⁻³) with T_m=2719 K. The volume expansion coefficient is given by 4.4 × 10⁻⁵ K⁻¹. In addition, the surface tension can be expressed as γ (T)=2.23 × 10³ − 0.17(T−T_m)(10⁻³N·m⁻¹) over the 2373–2833 K span and the viscosity as η(T)=1.85 exp [3.0× 10⁴/(RT)](10⁻³Pa·s) over the same temperature range.     

Containerless Property Measurements of Liquid Palladium

Some thermophysical properties of liquid and supercooled palladium were measured using containerless techniques. Over the 1640–1875 K temperature interval, the density could be expressed as (T)=10.66× 10³ –0.77(T–T_m)(kg·m^–3) and the ratio between the isobaric heat capacity and the hemispherical total emissivity could be rendered as (J·mol^–1·K^–1), where T_m=1828 K. The volume expansion coefficient was also determined as 7.2 × 10^–5 K^–1.