Chemical vapour deposition of molybdenum carbides: aspects of phase stability

Thin films of different molybdenum carbides (δ-MoC_1−x, γ′-MoC_1−x and Mo₂C) have been deposited from a gas mixture of MoCl₅/H₂/C₂H₄ at 800°C by CVD. The H₂ content in the vapour has a strong influence on the phase composition and microstructure. Typically, high H₂ contents lead to the formation of nanocrystalline δ-MoC_1−x films while coarse-grained γ′-MoC_1−x is formed with an H₂-free gas mixture. This phase has previously only been synthesized by carburization of Mo in a CO atmosphere and it has therefore been considered as an oxycarbide phase stabilized by the presence of oxygen in the lattice. Our results, however, show that γ′-MoC_1−x films containing only trace amounts of oxygen can be deposited by CVD. Stability calculations using a FP-LMTO method confirmed that the γ′-MoC_1−x phase is stabilized by oxygen but that the difference in energy between e.g. δ-MoC_0.75 and oxygen-free γ′-MoC_0.75 is small enough to allow the synthesis of the latter phase in the absence of kinetic constraints. Annealing experiments of metastable δ-MoC_1−x and γ′-MoC_1−x films showed two different reaction products suggesting that kinetic effects play an important role in the decomposition of these phases.     

Optical and electrical properties of p-type AgInSnxS2−x (x = 0–0.04) thin films prepared by spray pyrolysis

AgInSn_xS_2−x (x = 0–0.2) polycrystalline thin films were prepared by the spray pyrolysis technique. The samples were deposited on glass substrates at temperatures of 375 and 400 °C from alcoholic solutions comprising silver acetate, indium chloride, thiourea and tin chloride. All deposited films crystallized in the chalcopyrite structure of AgInS₂. A p-type conductivity was detected in the Sn-doped samples deposited at 375 °C, otherwise they are n-type. The optical properties of AgInSn_xS_2−x (x < 0.2) resemble those of chalcopyrite AgInS₂. Low-temperature PL measurements revealed that Sn occupying an S-site could be the responsible defect for the p-type conductivity observed in AgInSn_xS_2−x (x < 2) thin films.     

Highly conductive microcrystalline silicon carbide films deposited by the hot wire cell method and its application to amorphous silicon solar cells

Microcrystalline silicon carbide (μc-Si_1−xC_x) films were successfully deposited by the hot wire cell method using a gas mixture of SiH₄, H₂ and C₂H₂. It was confirmed by Fourier transform infrared and X-ray diffraction analyses that the films consisted of μc-Si grains embedded in a-Si_1−xC_x tissue. The p-type μc-Si_1−xC_x films were deposited using B₂H₆ as a doping gas. A dark conductivity of 0.2 S/cm and an activation energy of 0.067 eV were obtained. The p-type μc-Si_1−xC_x was used as a window layer of a-Si solar cells, in which the intrinsic layer was deposited by photo-chemical vapor deposition, and an initial conversion efficiency of 10.2% was obtained.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

High-resolution and analytical transmission electron microscopy of epitaxial YBa2Cu3O7−x thin films and YBa2Cu3O7/PrBa2Cu3O7 superlattices

Transmission electron microscopy (TEM) studies of epitaxial YBa₂Cu₃O_7−x thin films and YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices are summarized. High-resolution imaging of cross-sections and plan views and energy-dispersive X-ray microanalysis and electron energy loss spectroscopy in the transmission electron microscope were the methods applied. In the first section results on YBa₂Cu₃O_7−x thin films With varying oxygen stoichiometry deposited onto SrTiO₃ are discussed. Then, YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices deposited onto SrTiO₃ and MgO are investigated. Finally, an interface analysis of high-quality YBa₂Cu₃O_7−x thin films deposited onto sapphire with yttrium-stabilized zirconia buffer layers is presented.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Fabrication of a-Si1−xCx:H thin films for solar cells by the Cat-CVD method using a carbon catalyzer

We propose a new approach to fabrication of hydrogenated amorphous silicon carbide (a-Si_1−xC_x:H) thin films for solar cells by the catalytic chemical vapor deposition (Cat-CVD) method using a carbon catalyzer, which is more stable than tungsten or tantalum. It was found that by using the carbon catalyzer, undoped and boron-doped a-Si_1−xC_x:H films were easily obtained from a SiH₄, CH₄ and B₂H₆ mixture without any change in the catalyzer surface, even after deposition for longer than 30 h.     

Effects of oxygen partial pressure on lead content of PLZT thin films produced by excimer laser deposition

Excimer laser ablation has been used to produce thin films of lanthanum-modified lead zirconate titanate (PLZT), or Pb_1−xLa_x(Zr_1−yTi_y)_1−x/4O₃. PLZT is an interesting class of materials since it has a wide range of compositionally dependent electro-optical properties and strong non-linear optical characteristics. PLZT thin films of 7/0/100, 28/0/100 and 0/0/100 compositions have been deposited onto crystalline Si100 and amorphous fused silica substrates. Effects of oxygen backfill pressure on the Pb:(Ti + La) ratios were investigated. The results indicate that controlling the oxygen backfill pressure during laser deposition strongly influences the stoichiometry and crystal structure of PLZT thin films.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Influence of disorder on electronic structure and magnetic properties in Fe-rich Fe–Si alloys

We present the results of ab initio calculations of the spin-polarized electronic structure of disordered bcc and fcc Fe_1 − xSi_x alloys from dilute solid solutions of Si on iron up to FeSi intermetallic compound composition (x=0.01..0.5) and ordered intermetallic phases FeSi in B20 structure and Fe₃Si in DO₃ structure. The self-consistent calculations were performed with the coherent potential approximation within the Korringa–Kohn–Rostoker method (KKR–CPA) for disordered case and by using the tight-binding linear muffin–tin orbital (TB LMTO) method for intermetallic compounds. In the last case the supercell approach has been utilized in order to take into account the structural defects for this ordered phase. In particular, we have performed a series of calculations in the BCC Fe_1 − xSi_x alloys with x=0.01, 0.015, 0.1, 0.15, 0.25.     

Morphological changes induced by thermal anneals in NiFe/Ag multilayers; their relation to the resistive and magnetoresistive properties

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.

(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.

The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Anelastic spectroscopy measurements of nanoscale charge and magnetic structures in cuprates and manganites

Many perovskites and perovskite related materials exhibit electronic phase separation phenomena at nanometer scales, which are thought to concur to important electric and magnetic properties, like high-T_c superconductivity or colossal magnetoresistence (CMR). Recent and new anelastic spectroscopy experiments are presented, which supply information on the dynamics of such inhomogeneities in the superconductors of the La_2−xSr_xCuO₄ (LSCO) family and on the magnetic perovskite La_1−xCa_xMnO₃. In La_2−xSr_xCuO₄, a relaxation process at liquid He temperatures is identified as due to the motion of the hole stripes, acting as walls between antiferromagnetic (AF) domains. Another process is identified as the depinning of these stripes from defects in the disordered phase. In La_1−xCa_xMnO₃ a glassy dynamic response below the ferromagnetic (FM) transition is attributed to the insulating nanodomains coexisting with the ferromagnetic background.     

Study of optical constants in CdxSe1−x

Thin films of Cd_xSe_1−x (0<x<1) have been deposited by the vacuum evaporation technique onto ultra clean substrates maintained at 300°C. The optical properties (specially transmission spectra) of these films were studied. The wavelength dependence of refractive index and extinction coefficient of the films along with the variation of these constants with composition was studied.     

Synthesis and humidity sensitive properties of nanocrystalline Ba1−xSrxTiO3 thick films

Nanocrystalline Ba_1−xSr_xTiO₃ (x=0, 0.2, 0.4, 0.6, 0.8 and 1.0) precursors were synthesized using the stearic acid gel method. After the precursors had been calcined at 600–950°C for 0.5–1 h, nanocrystalline powders with the cubic perovskite structure were obtained and these were made into thick films. The powder samples were characterized by differential thermal analysis, X-ray diffraction and transmission electron microscopy, and the thick film samples were characterized by scanning electron microscopy and X-ray diffraction. The humidity-sensitive properties of the nanocrystalline Ba_1−xSr_xTiO₃ thick films were investigated. The results show that these nanocrystalline thick films possess higher humidity sensitivity and lower resistance than those of conventional materials.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

The optical and magneto-optical properties of MnSbBi films

The optical and magneto-optical properties of Mn(Sb_1−xBi_x) films were investigated for incident photons within the energy range from 1.3 to 4.0 eV. The diagonal and off-diagonal optical conductivities were determined from the results of spectroscopic ellipsometry and the polar Kerr effect measurements. A large Kerr rotation angle of about 0.57° was observed at photon energy ω≈2.65 eV for the Mn₅₅Sb₃₆Bi₉ film with an average grain size of 30 nm. The changes of the exchange splitting and the spin–orbit interaction strength are responsible for the strong spectral dependence of the Kerr effect in Mn(Sb_1−xBi_x) nanocrystalline films.     

Characterization of GaN epitaxial layers on SiC substrates with AlxGa1−xN buffer layers

High quality GaN epitaxial layers were obtained with Al_xGa_1−xN buffer layers on 6H–SiC substrates. The low-pressure metalorganic chemical vapor deposition (LP-MOCVD) method was used. The 500 Å thick buffer layers of Al_xGa_1−xN (0≤x≤1) were deposited on SiC substrates at 1025°C. The FWHM of GaN (0004) X-ray curves are 2–3 arcmin, which vary with the Al content in Al_xGa_1−xN buffer layers. An optimum Al content is found to be 0.18. The best GaN epitaxial film has the mobility and carrier concentration about 564 cm² V⁻¹ s⁻¹ and 1.6×10¹⁷ cm⁻³ at 300 K. The splitting diffraction angle between GaN and Al_xGa_1−xN were also analyzed from X-ray diffraction curves.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Epitaxial grown K1−xRbxTiOPO4 films with extremely flat surfaces for waveguiding

We report on epitaxial {1 0 0} K_1−xRb_xTiOPO₄ waveguide films for the visible spectral range grown on KTiOPO₄ substrates by liquid phase epitaxy. Using the m-line technique a refractive index increase of Δn_x≈0.007 and Δn_z≈0.004 for TM and TE polarisation has been determined for a K_0.78Rb_0.22TiOPO₄ film. Optical transmission and nearfield distribution are comparable to conventional ion-exchanged waveguides. Typical attenuation of about 1 dB/cm for both TM and TE polarisation was obtained at λ=532 and 1064 nm. Energy-dispersive X-ray spectrometry reveals solid-solution films with graded rubidium composition profiles. X-ray rocking curve analyses confirm the epitaxial growth process and indicate perfect and relaxed K_1−xRb_xTiOPO₄ films. Atomic force microscopy investigations reveal regular step structures with step heights Δh<1.3 nm resulting in rms-roughness values of ≈0.4 nm.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.