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.     

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%.     

以钛酸四正丁酯为钛源制备超细Ti粉体

以有机钛源钛酸四正丁酯（Ti（OC₄H₉）₄）与纳米碳黑（C）为反应原料制备超细Ti（C_1-xN_x）粉体。经过计算可知两者理论质量比约为9.4：1,以m（Ti（OC₄H₉）₄）：m（C）=9：1混料,通过溶胶凝胶法制备烧结前驱体。利用高温碳热还原法,在N₂气氛中,分别在不同温度下恒温烧结1 h,直接反应合成超细Ti（C_1-xN_x）粉体。结果发现,随温度升高,x 值逐渐降低,数值区间为0.19~0.72;产物组分中的总碳含量（C_t）逐渐增大,从14.23wt%增大到18.66wt%,游离碳含量（C_f）与氧含量（C_o）均低于0.5wt%;产物平均粒度也呈增大趋势,平均粒度分布区间为220~275 nm。     

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.     

Synthetic Routes to Novel Nanomaterials

Soon after the bulk production of carbon nanotubes was achieved, using arc discharge techniques, other methods involving gas phase processes (i.e. combustion ami pyrolysis of hydrocarbons, laser irradiation of graphite) were developed. Nowadays, it is possible to generate nanotubes and fullerene-related nanostructures from layered materials such as WS₂, MoS₂, BN, BC₂N and BC₃. Recently, a new technique, involving electrolysis of graphite electrodes in molten ionic salts, has been developed which may open up new synthetic routes to nanotubes in the liquid phase. In this paper, possible growth mechanisms for such processes are reviewed and other routes to nanstructures are discussed.     

Preparation and visible-light-driven photoelectrocatalytic properties of boron-doped TiO2 nanotubes

In the present study, chemical vapour deposition (CVD) was applied to dope boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄·2H₂O + NH₄F electrolyte with the goal of improving the photocatalytic (PC) activity under visible light. The undoped TiO₂ nanotubes had a highly self-organized structure. However, after doping through CVD, TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results confirmed that annealing temperature had an influence on the phase structure and boron impurities could retard anatase–rutile phase transition. Diffuse reflectance absorption spectra (DRS) analysis indicated that B-doped samples displayed stronger absorption in both UV and visible range. B-doped TiO₂ nanotubes electrode annealed at 700 °C through CVD showed higher photoelectrocatalytic (PEC) efficiency in methyl orange (MO) degradation than that annealed at 400 °C and 550 °C. MO degradation was substantially enhanced with the increasing applied bias potential. Moreover, there was a synergetic effect between the electrochemical and photocatalytic processes, and the synergetic factor R reached 1.45. B-doped TiO₂ nanotubes electrode showed good stability after 10 times by repeating photoelectrocatalysis of MO.     

Exploring the fracture toughness KIE and KIC of a medium-Strength steel plate using the surface-flaw test

The fracture toughness of a 30 CrMnSiA steel plate of three thicknesses (10,8 and 5 mm) and three widths (110,80 and 56 mm) has been investigated by using surface-flaw method under room temperature. It is not easy to compute the value of K_IE by the maximum applied load. But the values of K_IE and K_IC could be obtained easily, if the computation of the conditional applied load P₁₀ and P₅ based on the relative effective extension Δa/a₀ = 10% and 5% were adopted, together with the conditions of P_max/P₁₀ 1.2 and P_max/P₅ 1.3. The K_R — Δ_a curve, i.e. the resistance-curve described by the parameter K, has been plotted. The values of K_IC and K_IE are then the resistances corresponding to the real extensions of flaws of Δ/a₀ = 2 and 7%, respectively. These values so obtained are in good agreement with the computed values of K_IC and K_IE by using the conditional applied loads. The values of K_IC and K_IE so obtained are also in agreement with the value of K_IC converted from the J-integral and the effective value of K_IE computed by the maximum applied load, respectively.

An approximate relation between K_IC and K_IE has been found to be: K_IC = (0.85˜0.95)K_IE.

The requirements for the dimensions of specimens are: Thickness of plate: B 1.0(K_IC/σ_0.2)² or 1.25(K_ICσ_0.2)²]; Width of plate: 8 W/B 10, 4 W/2c 5; Effective length: l 2W.     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

Structural characterization of CxByNz (x=0.1 to x=0.2) layers obtained by laser-driven synthesis

C_xB_yN_z layers have been prepared by laser-assisted chemical vapour deposition (CVD) in a gas atmosphere containing C₂H₄, B₂H₆ and NH₃ where the starting composition ratio could vary in a large range. The characterization of these C–B–N materials was made by XRD, EPMA, XPS, optical and scanning electron microscopy. The chemical composition of C–B–N layers tended to a composition C₁B₆N₃ on the line BN–‘B₃C’. The turbostratic structure of C–B–N layers could be influenced and modified as a function of composition. XPS investigations confirmed the single-phase nature and the existence of bonding between all the elements. Some planar structures, containing especially CB₂N groups, were suggested for the ‘unit cell’ of these C–B–N solid solutions, in agreement with EPMA and XPS analysis.     

Molecular beam epitaxy synthesis of Si1−yCy and Si1−x−yGexCy alloys and Ge islands using an electron cyclotron resonance argon/methane plasma

We report the growth of Si_1−yC_y and Si_1−x−yGe_xC_y alloys on Si(001) by electron cyclotron resonance plasma-assisted Si molecular beam epitaxy using an argon/methane gas mixture. Various Si/Si_1−yC_y and Si/Si_1−x−yGe_xC_y multilayers have been grown and characterized principally by X-ray diffraction and Raman spectroscopy. The influence of growth parameters and electron cyclotron resonance plasma source operating conditions on the C substitutional incorporation was studied. Under optimum growth conditions the structures show good structural properties and sharp interfaces with carbon being essentially substitutionally incorporated up to concentrations of 1%. No significant carbon incorporation was measured in films grown under a high methane partial pressure without plasma excitation. Si_1−x−yGe_xC_y layers grown with this technique exhibit the strain compensation and enhanced thermal stability expected for these ternary alloys. Carbon pre-deposition of Si through surface exposure to the argon/methane plasma is shown to act as an antisurfactant on the growth of Ge islands by suppressing the formation of a Ge wetting layer on the surface.     

Preparation and photoelectrochemical properties of Ti1−xVxO2 solid solution thin film photoelectrodes with gradient bandgap

A design of a gradient bandgap Ti_1−xV_xO₂ thin film electrode for wet-type solar cells is provided. The gradient bandgap film electrodes were prepared by heating stacked layers of varying V/Ti ratios using the sol-gel method. A composition gradient was observed for some of the samples by X-ray photoelectron spectroscopy although it was not very large. For the Ti_1−xV_xO₂ film electrodes, conspicuous visible light photoresponse and photoelectrochemical stability were observed. The photocurrent increased with increasing bias potential. However, the photocurrent onset potentials of the Ti_1−xV_xO₂ film electrodes were more positive than those of TiO₂ film electrodes, probably owing to the high surface state density introduced by the diffusion of vanadium ions.     

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.     

Structural characterization of TiNxOy/TiO2 single crystalline and nanometric multilayers grown by LP-MOCVD on (110)TiO2

TiO₂/TiN_xO_y superlattices were grown by Low Pressure-Metal-Organic Vapor Phase Epitaxy (LP-MOVPE) technique at deposition temperatures ranking from 650 to 750°C. The growth was performed on top of TiO₂(110) rutile substrates. Intense peaks observed in the X-rays rocking curves and θ-2θ diffraction patterns show the presence of crystalline epilayers. The TiN_xO_y layers were grown in a (200) cubic structure on the (110) quadratic TiO₂ epilayer structure. Transmission electron microscopy confirmed the XRD results and showed the formation of periodic and well structured epilayers.     

Structural and electrochemical characterization of LiMn2−δVδOy spinels

The spinel phase compounds with the composition of LiMn_2−δV_δO_y were prepared by solid reaction of the mixture of LiNO₃·H₂O, MnCO₃ and NH₄VO₃ powders. Evolution of the crystalline phases of the samples versus the vanadium content was analyzed using X-ray diffraction (XRD) technique, EPR and FT-IR spectroscopes. Cubic spinel is the predominant phase in the powders under heat treatment at 550 °C for 5 h. The valence state of manganese ion changed from +4 to +3 with vanadium substitution for charge compensation. The vanadium substitution of manganese leads the decline in capacity and cyclic behavior of the powders. The electrochemical behaviors relating to the variation of structure corresponding to the vanadium substitution were discussed.     

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.     

Optical properties of a-(Se70Te30)100−x(Se98 Bi2)x thin films

Measurements of optical constants (absorption coefficient, refractive index, extinction coefficient, real and imaginary part of the dielectric constant) have been made on a-(Se₇₀Te₃₀)_100−x (Se₉₈Bi₂)_x thin films (where x=0, 5, 10, 15 and 20) of thickness 2000 Å in the wavelength range 450–1000 nm. It is found that the optical bandgap decreases with the increase of Se₉₈Bi₂ concentration in the a-(Se₇₀Te₃₀)_100−x(Se₉₈Bi₂)_x system. The value of refractive index (n) decreases, while the extinction coefficient (k) increases with increasing photon energy. The results are interpreted in terms of concentration of localized states varying effective Fermi level.     

Structural and electronic properties of C3N4−nPn (n=0,1,2,3,4)

First principles electronic structure method based on the density functional theory and the local density approximation is used to investigate the structural and electronic properties of C₃N_4−nP_n (n=0,1,2,3,4). It is found that the N-rich compounds energetically favor structures with sp² bonding, while the pseudocubic structure which is characterized by sp³ bonding is preferred by the P-rich compounds. Even though C₃N₄ is a wide-gap semiconductor, the band gap of C₃N_4−nP_n decreases rapidly when N is gradually substituted with P, and the P-rich compounds are predicted to be metallic or narrow-gap semiconductors.     

Growth of high-quality relaxed SiGe films with an intermediate Si1−yCy layer for strained Si n-MOSFETs

High quality and thin relaxed SiGe films were grown on Si (0 0 1) using ultra high vacuum chemical vapor deposition (UHV/CVD) by employing an intermediate Si_1−yC_y layer. The Si_1−yC_y/SiGe bilayer was found to change mechanism of relaxation in the SiGe overlayer. Compared with the samples with a Si layer, the equilibrium critical thickness of top SiGe films with rough surface by introducing an intermediate Si_0.986C_0.014 layer are drastically reduced; this result was attributed to larger tensile stress in the inserted Si_0.986C_0.014 layer. With a 210-nm-thick Si_0.8Ge_0.2 overlayer, this Si_0.8Ge_0.2/Si_0.986C_0.014/Si_0.8Ge_0.2 heterostructure has a threading dislocation density (TDs) less than 1 × 10⁵ cm⁻² and a residual strain of 30%. The root mean square (RMS) of surface roughness for this sample was measured to be about 1.8 nm. In this SiGe/Si_1−yC_y/SiGe structure, C atoms in the intermediate Si layer will improve the relaxation of thin SiGe overlayer, however, the relaxation for the 700-nm-thick SiGe overlayer is independent of the addition of C. The point defects rich Si_0.986C_0.014 layer plays the role to confine the misfit dislocations, which formed at the interface of the top Si_0.8Ge_0.2 and the Si_0.986C_0.014 layer, and blocked the propagation of TDs. Strained-Si n-channel metal-oxide-semiconductor transistors (n-MOSFETs) with a 210-nm-thick Si_0.8Ge_0.2 overlayers as buffer were fabricated and examined. Drain current and effective electron mobility for the strained-Si device with this novel substrate technology was found to be 100 and 63% higher than that of control Si device. Our results show that thin relaxed Si_0.8Ge_0.2 films with the intermediate Si_0.986C_0.014 layer serve as good candidates for high-speed strained-Si devices.     

The Role of Boron Nitride in Graphite Plasma Arcs

Novel graphitic nanostructures (e.g. nanotubes, graphitic onions, polyhedral particles, hemitoroidal nanotube caps and branched nanotubes) are produced by arcing graphite electrodes, containing hexagonal-BN, in inert atmospheres. The introduction of BN or B inside the graphite anode generates long (≤ 20μm) and well graphitised carbon nanotubes exhibiting boron at their tips. High Resolution Electron Microscopy (HRTEM), Scaning Electron Microscopy (SEM), Electron Energy Loss Spectroscopy (EELS) and X-ray powder diffraction studies reveal the production of B₄C crsytals, in addition to little amounts of BC₃ nanotubes. Mass spectrometry (MS) studies over the generated soots indicate high yields of large fullerenes (e.g. C₇₀, C₇₆, and C₈₄) and thermo-Gravimetric analysis (TGA) of the nanostructures show high oxidation resistance.     

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.