Ni-silicide precursor for gate electrodes

Ni-silicide film was deposited at a low temperature of 160 °C by CVD using a Ni(PF₃)₄/Si₃H₈ gas system. Injecting Si₃H₈ during the Ni deposition does not affect the deposition rate, but the step-coverage quality deteriorates at high growth temperatures. At high growth temperatures, the Ni/Si ratio of the film deposited on the sidewall varies as the distance from the open area increases. High step-coverage quality and a constant Ni/Si ratio independent of the location of the deposition are strongly required to fabricate a three-dimensional device. These requirements were achieved with this CVD by depositing the Ni-silicide film below 180 °C.     

Properties of hetero-structured SiCX films deposited by hot-wire CVD using SiH3CH3 as carbon source

The hetero-structured SiC_X films have been deposited by hot-wire CVD using SiH₃CH₃ as the carbon source gas. Although the carbon source gas ratio and filament temperature in the deposition using SiH₃CH₃ were smaller than those using C₂H₆, the carbon content in the sample deposited using SiH₃CH₃ was similar to that deposited using C₂H₆. The optical energy gap in the sample deposited using SiH₃CH₃ was larger than that deposited using C₂H₆. The sample deposited using SiH₃CH₃ under optimized condition showed a wide optical energy gap of 1.99 eV and a large dark conductivity of 15.1 S/cm. The p-type sample deposited using SiH₃CH₃ under the optimized condition has been used as a window layer material in p-i-n a-Si:H based solar cells.     

Titanium Interlayer Mediated Epitaxy of CoSi2 on Si1−xGex

Titanium Interlayer Mediated Epitaxy (TIME) has been shown to promote the formation of epitaxial CoSi₂ on Si (100). Similarities between Si and Si_1−xGe_x alloys have motivated a study of whether the TIME process could be successful in forming epitaxial CoSi₂ on Si_1−xGe_x. Titanium layers of varying thickness were deposited as interlayers between a Co layer and c-Si/Si_0.8Ge_0.2 grown epitaxially onto Si (100) to investigate their role in the formation of epitaxial CoSi₂ on Si_1−xGe_x alloys. The effect of Ti interlayer thickness on the orientation of CoSi₂ to the Si_1−xGe_x substrate, and the conditions under which a polycrystalline CoSi₂ film has been formed have been studied. It was found that Ti was beneficial in promoting epitaxy to the substrate in all cases. The experimental results indicate that with a Ti interlayer thickness of ∼ 50 Å, the formation of epitaxial CoSi₂ adjacent to the substrate was achieved, and pinhole formation was minimized. It was also observed that for increased interlayer thickness, Ti reacted with Si to form a titanium silicide.     

Growth studies and characterization of silicon nitride thin films deposited by alternating exposures to Si2Cl6 and NH3

We deposited silicon nitride films by alternating exposures to Si₂Cl₆ and NH₃ in a cold-wall reactor, and the growth rate and characteristics were studied with varying process temperature and reactant exposures. The physical and electrical properties of the films were also investigated in comparison with other silicon nitride films. The deposition reaction was self-limiting at process temperature of 515 and 557 °C, and the growth rates were 0.24 and 0.28 nm/cycle with Si₂Cl₆ exposure over 2 × 10⁸ L. These growth rates with Si₂Cl₆ are higher than that with SiH₂Cl₂, and are obtained with reactant exposures lower than those of the SiH₂Cl₂ case. At process temperature of 573 °C where the wafer temperature during Si₂Cl₆ pulse is 513 °C, the growth rate increased with Si₂Cl₆ exposure owing to thermal deposition of Si₂Cl₆. The deposited films are nonstoichiometric SiN, and were easily oxidized by air exposure to contain 7-8 at.% of oxygen in the bulk film. The deposition by using Si₂Cl₆ exhibited a higher deposition rate with lower reactant exposures as compared with the deposition by using SiH₂Cl₂, and exhibited good physical and electrical properties that were equivalent or superior to those of the film deposited by using SiH₂Cl₂.     

Epitaxial growth of Fe3Si/CaF2/Fe3Si magnetic tunnel junction structures on CaF2/Si(111) by molecular beam epitaxy

The Fe₃Si(24 nm)/CaF₂(2 nm)/Fe₃Si(12 nm) magnetic tunnel junction (MTJ) structures were grown epitaxially on CaF₂/Si(111) by molecular beam epitaxy (MBE). The 12-nm-thick Fe₃Si underlayer was grown epitaxially on CaF_2/Si(111) at approximately 400 °C; however, the surface of the Fe₃Si film was very rough, and thus a lot of pinholes are considered to exist in the 2-nm-thick CaF₂ barrier layer. The average roughness (Ra) of the CaF₂ barrier layer was 7.8 nm. This problem was overcome by low-temperature deposition of Fe and Si at 80 °C on CaF₂/Si(111), followed by annealing at 250 °C for 30 min to form the Fe₃Si layer. The Ra roughness was significantly reduced down to approximately 0.26 nm. A hysteresis loop with coercive field H_c of approximately 25 Oe was obtained in the magnetic field dependence of Kerr rotation at room temperature (RT).     

Structural study of Si1 − xGex nanocrystals embedded in SiO2 films

We have investigated the structural properties of Si_1 − xGe_x nanocrystals formed in an amorphous SiO₂ matrix by magnetron sputtering deposition. The influence of deposition parameters on nanocrystal size, shape, arrangement and internal structure was examined by X-ray diffraction, Raman spectroscopy, grazing incidence small angle X-ray scattering, and high resolution transmission electron microscopy. We found conditions for the formation of spherical Si_1 − xGe_x nanocrystals with average sizes between 3 and 13 nm, uniformly distributed in the matrix. In addition we have shown the influence of deposition parameters on average nanocrystal size and Ge content x.     

Behavior of N atoms after thermal nitridation of Si1 − xGex surface

Behavior of N atoms after thermal nitridation of Si_1 − xGe_x (100) surface in NH₃ atmosphere at 400 °C was investigated. X-ray photoelectron spectroscopy (XPS) results show that N atomic amount after nitridation tends to increase with increasing Ge fraction, and amount of N atoms bonded with Ge atoms decreases by heat treatment in H₂ at 400 °C. For nitrided Si_0.3Ge_0.7(100), the bonding between N and Si atoms forms Si₃N₄ structure whose amount is larger than that for nitrided Si(100). Angle-resolved XPS measurements show that there are N atoms not only at the outermost surface but also beneath surface especially in a deeper region around a few atomic layers for the nitrided Si(100), Si_0.3Ge_0.7(100) and Ge(100). From these results, it is suggested that penetration of N atoms through around a few atomic layers for Si, Si_0.3Ge_0.7 and Ge occurs during nitridation, and the N atoms for the nitrided Si_0.3Ge_0.7(100) dominantly form a Si₃N₄ structure which stably remains even during heat treatment in H₂ at 400 °C.     

Lead-free piezoelectric thin films of Mn-doped NaNbO3-BaTiO3 fabricated by chemical solution deposition

Lead-free piezoelectric thin films of NaNbO₃-BaTiO₃ were fabricated on Pt/TiO_x/SiO₂/Si substrates by chemical solution deposition. Perovskite NaNbO₃-BaTiO₃ single-phase thin films with improved leakage-current and ferroelectric properties were prepared at 650 °C by doping with a small amount of Mn. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ thin films showed slim ferroelectric P-E hysteresis and field-induced strain loops at room temperature. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ films showed remanent polarization values of 6.3 and 6.2 μC/cm², and coercive field of 41 and 55 kV/cm, respectively. From the slope of the field-induced strain loop, the effective piezoelectric coefficient (d₃₃) was found to be 40-60 pm/V.     

Effect of LaNiO3 electrodes and lead oxide excess on chemical solution deposition derived Pb(Zrx,Ti1 − x)O3 films

The effects of LaNiO₃ (LNO) and Pt electrodes on the properties of Pb(Zr_x,Ti_1 − x)O₃ (PZT) films were compared. Both LNO and PZT were prepared by chemical solution deposition (CSD) methods. Specifically, the microstructure of LNO and its influence on the PZT properties were studied as a function of PbO excess. Conditions to minimize the Pyrochlore phase and porosity were found. Remnant polarization, coercive field and fatigue limit were improved in the PZT/LNO films relative to the PZT/Pt films. Additionally, the PZT crystallization temperature over LNO was 500 °C, about ~ 50 °C lower than over Pt. The crystallization temperature reported here is amongst the lowest values for CSD-based PZT films.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by Substituting Mg for Co

The microwave dielectric properties of La(Mg_0.5−xCo_xSn_0.5)O₃ ceramics were examined with a view to exploiting them for mobile communication. The La(Mg_0.5−xCo_xSn_0.5)O₃ ceramics were prepared using the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La(Mg_0.4Co_0.1Sn_0.5)O₃ ceramics revealed that La(Mg_0.4Co_0.1Sn_0.5)O₃ is the main crystalline phase, which is accompanied by small extent of La₂Sn₂O₇ as the second phase. Formation of this Sn-rich second phase was attributed to the loss of MgO upon ignition. Increasing the sintering temperatures seemed to promote the formation of La₂Sn₂O₇. An apparent density of 6.67 g cm⁻³, a dielectric constant (?_r) of 20.3, a quality factor (Q.F.) of 70,500 GHz, and a temperature coefficient of resonant frequency (τ_f) of −77 ppm °C⁻¹ were obtained for La(Mg_0.4Co_0.1Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Effects of TeOx films on temperature coefficients of delay of Love-type wave devices based on TeOx/36°YX-LiTaO3 structures

Tellurium oxide (TeO_x) thin films are prepared on 36°YX-LiTaO₃ substrates by RF magnetron sputtering technique under different deposition conditions. The structures and compositions of the TeO_x films are analyzed by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, which show that the TeO_x films are amorphous and with different ratios of Te to O prepared in different conditions. Then the Love-type wave devices based on TeO_x/36°YX-LiTaO₃ structures are fabricated, and the temperature coefficient of delay (TCD) of the Love-type wave devices are investigated. The results show that, when TeO_x films deposited at suitable deposition conditions, the TCD of the Love-type wave devices are less than that of the shear-horizontal (SH) wave devices fabricated on the bare 36°YX-LiTaO₃ substrates, which demonstrates that the TCD of the TeO_x films is negative. Moreover, the TCD of the devices are strongly dependent upon the preparation conditions and the thicknesses of the TeO_x films. Therefore, the TCD of the Love-type wave devices can be optimized by suitably selecting the preparation conditions and the thickness of TeO_x films.     

Deposition process of Si-B-C ceramics from CH3SiCl3/BCl3/H2 precursor

Si-B-C coatings have been prepared by chemical vapour deposition (CVD) from CH₃SiCl₃/BCl₃/H₂ precursor mixtures at low temperature (800-1050 °C) and reduced pressures (2, 5, 12 kPa). The kinetics (including apparent activation energy and reaction orders) related to the deposition process were determined within the regime controlled by chemical reactions. A wide range of coatings, prepared in various CVD conditions, were characterized in terms of morphology (scanning electron microscopy), structure (transmission electron microscopy, Raman spectroscopy) and elemental composition (Auger electron spectroscopy). On the basis of an in-situ gas phase analysis by Fourier transform infrared spectroscopy and in agreement with a previous study on the B-C system, the HBCl₂ species was identified as an effective precursor of the boron element. H_xSiCl_(4−x), SiCl₄ and CH₄, derived from CH₃SiCl₃, were also shown to be involved in the homogeneous and the heterogeneous reactions generating silicon and carbon in the coating. A correlation between the various experimental approaches has supported a discussion on the chemical steps involved in the deposition process.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_SiH4=0.8 Torr, the resistivity gradually increased, but for P_SiH4=1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Effect of additive gases on the selective etching of ZrOx film using inductively coupled BCl3-based plasmas

In this study, the effect of BCl₃/C₄F₈ gas mixture on the ZrO_x etch rates and the etch selectivities of ZrO_x/Si were investigated and its etch mechanism was studied. The increase of C₄F₈ in BCl₃/C₄F₈ decreased the silicon etch rate significantly and finally deposition instead of etching occurred by mixing C₄F₈ more than 3%. In the case of ZrO_x, the etch rate remained similar until 4% of C₄F₈ was mixed, however, the further increase of C₄F₈ percentage finally decreased the ZrO_x etch rate and deposition instead of etching occurred by mixing more than 6%. Therefore, by mixing 3-4% of C₄F₈ to BCl₃, infinite etch selectivity of ZrO_x/Si could be obtained while maintaining the similar ZrO_x etch rate. The differences in the etch behaviors of ZrO_x and Si were related to the different thickness of C-F polymer formed on the surfaces. The thickness of the C-F polymer on the ZrO_x surface was smaller due to the removal of carbon incident on the surface by forming CO_x with oxygen in ZrO_x. Using 12 mTorr BCl₃/C₄F₈ (4%), 700 W of rf power, and − 80 V of dc bias voltage, the ZrO_x etch rate of about 535 Å/min could be obtained with infinite etch selectivity to Si.     

Composition dependence of optical constants in ferroelectric Ba(Ti1 − x,Nix)O3 thin films by optical transmittance technique

Ba(Ti_1 − x,Ni_x)O₃ ferroelectric thin films with perovskite structure are prepared on fused quartz substrates by a sol-gel process. Optical transmittance measurements indicate that Ni-doping has an obvious effect on the energy band structure of BaTiO₃. It has been found that the refractive index n, extinction coefficient k, and band gap energy E_g of the films are functions of the film composition. The E_g of Ba(Ti_1 − x,Ni_x)O₃ decreases approximately linearly as the Ni content increases, which is attributed to the decline of conduction band energy level with increasing the Ni content. On the other hand, n and k both increase linearly with increasing the Ni content because of the increase of packing density. These results indicate that thin films might have potential applications in BaTiO₃-based thin-film optical devices.     

Epitaxial growth and exchange coupling of spinel ferrimagnet Ni0.3Zn0.7Fe2O4 on multiferroic BiFeO3

Thin films of the zinc nickel ferrite, Zn_0.7Ni_0.3Fe₂O₄ (ZNFO), were deposited by the RF magnetron sputtering on a number of substrates, including (001) oriented single crystals of LaAlO₃ (LAO) and SrTiO₃ (STO), polycrystalline Pt/Si, and epitaxial films of BiFeO₃ (BFO) and LaNiO₃ (LNO). Except for the films on Pt/Si, the ZNFO films grown on other substrates were epitaxial and their magnetic properties were affected by the heteroepitaxy induced strains. Typically, the coercivity (H_c) was increased with the strain, i.e. H_c varied from 31 Oe for the 150 nm thick polycrystalline films grown on Pt/Si, to 55 Oe and 155 Oe for the 20 nm thick epitaxial films grown on BFO and LAO, respectively. The saturation magnetization of the epitaxial films was reduced accordingly to about 470 emu/cm³ from 986 emu/cm³ in the polycrystalline films. The all-oxide architecture allowed field-annealing to perform at the temperature above the Neel temperature of BFO (~ 370 °C), after which clear exchange bias was observed.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Size reduction in crystal grains in LiNb0.5Ta0.5O3 thin films by controlling nucleation density during thermal plasma spray chemical vapor deposition

Two approaches were applied to thermal plasma spray chemical vapor deposition (TPS CVD) in order to reduce crystal grain size or/and surface roughness of LiNb_0.5Ta_0.5O₃ thin films while retaining the advantages of this method, such as high deposition rate. The first method consists of a two-step deposition, where the nucleation density is controlled in the first step and the film with high crystallinity is deposited in the second step. The surface roughness and grain size could be reduced from 1 nm to 7.7 nm, and from 200-350 nm to 120-180 nm, respectively. In the second approach, employing a one-step TPS CVD process, the conventional precursor was substituted by a double-alkoxide precursor and grain size in the deposited films could be reduced to 50-80 nm. Both approaches adopted in this work permitted to reduce the optical propagation loss.     

Composition dependent thermoelectric properties of sintered Mg2Si1−xGex (x = 0 to 1) initiated from a melt-grown polycrystalline source

Fabrication of Mg₂Si_1−xGe_x (x = 0-1.0) was carried out using a spark plasma sintering technique initiated from melt-grown polycrystalline Mg₂Si_1−xGe_x powder. The thermoelectric properties were evaluated from RT to 873 K. The power factor of Mg₂Si_1−xGe_x with higher Ge content (x = 0.6-1.0) tends to decrease at higher temperatures, and the maximum value of about 2.2 × 10^− 5 Wcm^− 1K^− 2 was observed at 420 K for Mg₂Si and Mg₂Si_0.6Ge_0.4. The coexistence of Si and Ge gave rise to a decrease in the thermal conductivity in the Mg₂Si_1−xGe_x. The values close to 0.02 Wcm^− 1K^− 1 were obtained for Mg₂Si_1−xGe_x (x = 0.4-0.6) over the temperature range from 573 to 773 K, with the minimum value being about 0.018 Wcm^− 1K^− 1 at 773 K for Mg₂Si_0.4Ge_0.6. The maximum dimensionless figure of merit was estimated to be 0.67 at 750 K for samples of Mg₂Si_0.6Ge_0.4.     

Three-dimensional supercapacitors composed of Ba0.65Sr0.35TiO3 (BST)/NiSi2/silicon microchannel plates

Three-dimensional (3D) supercapacitors consisting of Ba_0.65Sr_0.35TiO₃ (BST)/NiSi₂/silicon microchannel plate (MCP) stacked structure have been fabricated. The silicon MCP produced by electrochemical etching is utilized as a backbone of the 3D structure on which a nickel silicide current collector layer and Ba_0.65Sr_0.35TiO₃ dielectric layer are deposited successively by electroless plating and the sol-gel method, respectively. The morphology and structure of the 3D BST/NiSi₂/Si-MCP structure are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) and the electrochemical properties are determined by cyclic voltammetry (CV) and chronopotentiometry. The structure exhibits excellent capacitive behavior with a maximum capacitance of 784 F g⁻¹. After 700 charging/discharging cycles, the C_f decreases slightly with only a 5.7% loss and is stable after more than 700 cycles. The BST/NiSi₂/Si-MCP 3D structure is a potential supercapacitor in industrial applications.