Surface modification and patterning using low-energy ion beams: Si-O bond formation at the vacuum/adsorbate interface.

Modification of hydroxyl-terminated self-assembled monolayer (HO-SAM) surfaces by collision of low-energy (15 eV) hyperthermal Si(CH3)3+ ions is shown to lead to Si-O bond formation and terminal trimethylsilyl ether formation. Modification was verified by in situ mass spectrometry using chemical sputtering with CF3+ ions (70 eV), ex situ secondary ion mass spectrometric analysis (12 kV Ga+ primary ion beam), and through X-ray photoelectron spectroscopy by monitoring Si (2s). The nature of the surface modification was further established by analysis of synthetic SAM surfaces made up of mixtures of the trimethylsilyl-11-mercapto-1-undecane ether and various proportions of the hydroxyl-terminated mercaptan (11-mercapto-1-undecanol). These mixed surfaces, as well as the spectroscopic data, indicate that ca. 30% of the hydroxyl chains are covalently modified at saturation coverage. Analogous surface transformations are achieved using Si(CH3)2F+ and Si(CH3)2C6H5+.     

In-situ synchrotron radiation photoemission spectroscopy study of the initial atomic layer deposition of Al2O3 film on Si(001) substrate

In-situ synchrotron radiation photoemission spectroscopy and X-ray photoemission spectroscopy have been used to investigate the initial stages of Al2O3 growth on a Si(001) substrate by atomic layer deposition (ALD). The core level spectra of Si 2p, O 1s, and Al 2p as well as the valence band spectra were measured at every half reaction in the trimethylaluminum (TMA)-H2O ALD process. The line shape changes and binding energy shifts of the core level spectra reveal that Al2O3 is predominantly formed with a small amount of Si oxide in the initial stages without the formation of Al silicate. All core level spectra were alternately shifted toward higher and lower binding energies sides at every half ALD reaction. This can be explained by the band bending effect induced by different chemical species on the surface during the TMA-H2O ALD reaction. The valence band spectra showed that four cycles of ALD reactions were necessary to complete the electronic structure of the Al2O3 film with a valence band offset of 3.73 eV.     

Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.     

含铍碳化硅陶瓷先驱体聚铍碳硅烷的合成

以氢氧化铍、硫酸和乙酰丙酮为原料合成了乙酰丙酮铍(Be(acac)2).用乙酰丙酮铍和聚碳硅烷在加热的条件下反应一定时间,生成了树脂状的产物.反应中乙酰丙酮铍被消耗,生成产物熔点相对起始聚碳硅烷熔点升高.元素分析表明产物中含有铍元素,凝胶渗透色谱分析表明产物分子量相对起始聚碳硅烷向增大的方向发生变化.傅立叶红外光谱分析表明产物中主要存在如下结构:Si(CH3)2—CH2—,—Si(CH3)·(H)—CH2—.核磁共振1H-NMR分析表明反应物中Si—H键被消耗.根据分析结果推测了反应机理,Si—H键的消耗在产物的形成中起了重要作用.实验与理论分析表明先驱体产物是一种含铍聚碳硅烷,可以命名为聚铍碳硅烷(PBeCS).在1200℃的高温处理下产物作为先驱体可以转化为碳化硅陶瓷,元素分析表明碳化硅陶瓷中含有铍,是含铍碳化硅陶瓷.     

Quantum cascade laser-based measurement of metal alkylamide density during atomic layer deposition

An in situ gas-phase diagnostic for the metal alkylamide compound tetrakis(ethylmethylamido) hafnium (TEMAH), Hf[N(C(2)H(5))(CH(3))](4), was demonstrated. This diagnostic is based on direct absorption measurement of TEMAH vapor using an external cavity quantum cascade laser emitting at 979 cm(-1), coinciding with the most intense TEMAH absorption in the mid-infrared spectral region, and employing 50 kHz amplitude modulation with synchronous detection. Measurements were performed in a single-pass configuration in a research-grade atomic layer deposition (ALD) chamber. To examine the detection limit of this technique for use as a TEMAH delivery monitor, this technique was demonstrated in the absence of any other deposition reactants or products, and to examine the selectivity of this technique in the presence of deposition products that potentially interfere with detection of TEMAH vapor, it was demonstrated during ALD of hafnium oxide using TEMAH and water. This technique successfully detected TEMAH at molecular densities present during simulated industrial ALD conditions. During hafnium oxide ALD using TEMAH and water, absorbance from gas-phase reaction products did not interfere with TEMAH measurements while absorption by reaction products deposited on the optical windows did interfere, although interfering absorption by deposited reaction products corresponded to only ≈4% of the total derived TEMAH density. With short measurement times and appropriate signal averaging, estimated TEMAH minimum detectable densities as low as ≈2 × 10(12) molecules/cm(3) could be obtained. While this technique was demonstrated specifically for TEMAH delivery and hafnium oxide ALD using TEMAH and water, it should be readily applicable to other metal alkylamide compounds and associated metal oxide and nitride deposition chemistries, assuming similar metal alkylamide molar absorptivity and molecular density in the measurement chamber.     

Atomic layer deposition of SiO2 thin films using tetrakis(ethylamino)silane and ozone

We examined the atomic layer deposition (ALD) of silicon dioxide thin films on a silicon wafer by alternating exposures to tetrakis(ethylamino)silane [Si(NHC2H5)4] and O3. The growth kinetics of silicon oxide films was examined at substrate temperatures ranging from 325 to 514 degrees C. The deposition was governed by a self-limiting surface reaction, and the growth rate at 478 degrees C was saturated at 0.17 nm/cycle for Si(NHC2H5)4 exposures of 2 x 10(6) L (1 L = 10(-6) Torr x s). The films deposited at 365-404 degrees C exhibited a higher deposition rate of 0.20-0.21 nm/cycle. However, they contained impurities, such as carbon and nitrogen, and showed poor film qualities. The concentration of impurities decreased with increasing substrate temperature. It was found that the films deposited in the high-temperature regime (478-514 degrees C) showed excellent physical and electrical properties equivalent to those of LPCVD films.     

Atomic layer deposition of HfO2: Growth initiation study on metallic underlayers

The initial stages of HfO₂ film growth by atomic layer deposition (ALD) on Co, Ta, and Pt thin films have been compared by x-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared spectroscopy. The initial tetrakis-dimethylamido(IV) hafnium (TDMAH) adsorption rate was highest on Co and increased with substrate temperature between 150 °C and 250 °C. The initial adsorption rate of TDMAH on Ta was less than on Co or Pt at the same substrate temperatures. The Ta surface also proved to be more stable with regard to TDMAH decomposition as fluctuations of adsorbed Hf and decomposition products were not observed during ALD cycling. Larger amounts of carbon were observed on Pt after TDMAH exposure compared to Co or Ta, suggestive of decomposition products. The XPS Hf(4f) peak measured after initial exposure of TDMAH on Pt showed evidence of two Hf oxidation states at the surface. It is postulated that the reaction of TDMAH and decomposition by-products with available oxygen or hydroxyl molecules at the surface of the various metal underlayers affected the initial growth of HfO₂.     

Density functional study of silane adsorption onto Si(100) surface

Total energy pseudopotential calculations based on norm-conserving optimized pseudopotential and density functional theory (DFT) with generalized gradient approximation (GGA) have been used to study the possible pathway and corresponding energy barrier for the initial dissociative adsorption of silane (SiH₄) onto Si(100)-(2×2) surface leading to the formation of SiH₃ and H adsorbed on Si(100)-(2×2) i.e. Si(100)-(2×2)(SiH₃:H). Our calculated results found that the formation of Si(100)-(2×2)(SiH₃:H) after the SiH₄ initial adsorption onto Si(100)-(2×2) surface is energetically favorable. Also the energy barrier, which is calculated to be around 0.72 eV (GGA), occurs due to the elongation of Si–H within SiH₄ accompanying the unbuckling of the buckled Si=Si dimer on Si(100)-(2×2) surface. Finally, the reactive sticking coefficient for SiH₄ on Si(100)-(2×2) is calculated to be around 3×10⁻⁶.     

Scope and Mechanistic Study of the Coupling Reaction of α, β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C-H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1](1)[propene](0)[cinnamate](-1). A negligible deuterium kinetic isotope effect (k(H)/k(D) = 1.1±0.1) was measured from both (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) and (E)-C(6)H(5)CD=C(CH(3))CONHCH(3) with styrene. In contrast, a significant normal isotope effect (k(H)/k(D) = 1.7±0.1) was observed from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene and styrene-d(10). A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C(6)H(5)CH=CHCO(2)Et with propene ((13)C(recovered)/(13)C(virgin) at C(β) = 1.019(6)), while a negligible carbon isotope effect ((13)C(recovered)/(13)C(virgin) at C(β) = 0.999(4)) was obtained from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene. Hammett plots from the correlation of para-substituted p-X-C(6)H(4)CH=CHCO(2)Et (X = OCH(3), CH(3), H, F, Cl, CO(2)Me, CF(3)) with propene and from the treatment of (E)-C(6)H(5)CH=CHCO(2)Et with a series of para-substituted styrenes p-Y-C(6)H(4)CH=CH(2) (Y = OCH(3), CH(3), H, F, Cl, CF(3)) gave the positive slopes for both cases (ρ = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, Δ H(?) = 20±2 kcal mol(-1) and S(?) = -42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies.     

Atomic layer deposition of an HfO2 thin film using Hf(O-iPr)4

A thin film of hafnium dioxide (HfO₂) was formed on the surface of Si(100) by atomic layer deposition (ALD) using Hf(O-iPr)₄ (Hf(OCH(CH₃)₂)₄, hafnium tetrakis-iso-propoxide) as an Hf source and O₂ as an oxidant. The temperature window of the process was 250–350 °C, which is about 100 °C lower than that of a process using Hf(O-tBu)₄ as a source. This result was in accordance with the decomposition characteristics of the Hf precursor, as investigated by the temperature-programmed decomposition of the compound in an ultra-high vacuum and by thermogravimetric analysis in air. The thickness of a film deposited under the above conditions increased in proportion to the ALD cycles, indicating that the film-growth rate per cycle remained nearly constant during the process. The deposited film consisted of a monoclinic crystal phase included in an amorphous matrix, which was confirmed by X-ray diffraction. The film showed an equivalent-oxide thickness (EOT) of 2.1 nm and a leakage current density of 8.9 × 10^? 6 A/cm² at ? 1 V. The leakage current was three orders of magnitude lower than that of SiO₂ with the same EOT.     

Understanding 'clean-up' of III-V native oxides during atomic layer deposition using bulk first principles models

The use of III-V materials as the channel in future transistor devices is dependent on removing the deleterious native oxides from their surface before deposition of a gate dielectric. Trimethylaluminium has been found to achieve in situ 'clean-up' of the oxides of GaAs and InGaAs before atomic layer deposition (ALD) of alumina. Here we propose six reaction mechanisms for 'clean-up,' featuring exchange of ligands between surface atoms, reduction of arsenic oxide by methyl groups and desorption of various products. We use first principles Density Functional Theory (DFT) to determine which mechanistic path is thermodynamically favoured based on models of the bulk oxides and gas-phase products. We therefore predict that 'clean-up' of arsenic oxides mostly produces As4 gas. Most C is predicted to form C2H6 but with some C2H4, CH4 and H2O. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides to be cleaned-up.     

Ru nanostructure fabrication using an anodic aluminum oxide nanotemplate and highly conformal Ru atomic layer deposition

We fabricated metallic nanostructures directly on Si substrates through a hybrid nanoprocess combining atomic layer deposition (ALD) and a self-assembled anodic aluminum oxide (AAO) nanotemplate. ALD Ru films with Ru(DMPD)(EtCp) as a precursor and O(2) as a reactant exhibited high purity and low resistivity with negligible nucleation delay and low roughness. These good growth characteristics resulted in the excellent conformality for nanometer-scale vias and trenches. Additionally, AAO nanotemplates were fabricated directly on Si and Ti/Si substrates through a multiple anodization process. AAO nanotemplates with various hole sizes (30-100?nm) and aspect ratios (2:1-20:1) were fabricated by controlling the anodizing process parameters. The barrier layers between AAO nanotemplates and Si substrates were completely removed by reactive ion etching (RIE) using BCl(3) plasma. By combining the ALD Ru and the AAO nanotemplate, Ru nanostructures with controllable sizes and shapes were prepared on Si and Ti/Si substrates. The Ru nanowire array devices as a platform for sensor devices exhibited befitting properties of good ohmic contact and high surface/volume ratio.     

Interfacial reaction and adhesion between SiC and thin sputtered nickel films

Thin sputtered nickel films grown on SiC were annealed in an Ar/4 vol % H2 atmosphere at temperatures between 550 to 1450 °C for various times. The reactivity and the reaction-product morphology were characterized using optical microscopy, surface profilometry, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. The reaction with the formation of silicides and carbon was observed to first occur above 650 °C. Above 750 °C, as the reaction proceeded, the initially formed Ni3Si2 layer was converted to Ni2Si and carbon precipitates were observed within this zone. The thin nickel film reacted completely with SiC after annealing at 950 °C for 2 h. The thermodynamically stable Ni2Si is the only observed silicide in the reaction zone up to 1050 °C. Above 1250 °C, carbon precipitated preferentially on the outer surface of the reaction zone and crystallized as graphite. The relative adhesive strength of the reaction layers was qualitatively compared using the scratch test method. At temperatures between 850 to 1050 °C the relatively higher critical load values of 20–33 N for SiC/Ni couples are formed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Magnetic properties, phase evolution, and microstructure of melt spun Hf-substituted Sm(Co0.97Hf0.03)(x)Cy (x = 5-9; y = 0-0.1) nanocomposites

Magnetic properties, phase evolution, and microstructure of melt spun Hf-substituted Sm(Co0.97Hf0.03)(x)Cy (x = 5-9; y = 0-0.1) ribbons quenched at the wheel speed of 40 m/s are investigated. X-ray diffraction analysis shows that the main phases existed in Sm(Co0.97Hf0.03)(x) ribbons are 1:5 phase for x = 5-5.5; 1:5 and 1:7 phases for x = 6; 1:7 phase for x = 6.5-7.5; 1:7 and 2:17 phases for x = 8; and only 2:17 phase for x = 8.5-9, respectively. For Sm(Co0.97Hf0.03)(x) (x = 5-9) ribbons, the optimum magnetic properties of B(r) = 5.6 kG, (i)H(c)= 15.6 kOe and (BH)(max) = 7.1 MGOe are obtained for Sm(Co0.97Hf0.03)6.5 ribbons. Furthermore, a slight amount of C addition in Sm(Co0.97Hf0.03)(x) ribbons slightly modify phase constitution and effectively refine the grain size from 200-700 nm for C free ribbons to 10-70 nm, strengthening the exchange coupling effect between magnetic grains of the ribbons. As a result, magnetic properties are further improved. The magnetic properties of B(r) = 6.9 kG, (i)H(c) = 9.2 kOe and (BH)(max) = 10.0 MGOe can be achieved for Sm(Co0.97Hf0.03)7.5C0.1 nanocomposites.     

Preparation and Characterization of Sol-gel Derived CH_3SiO_(3/2)-SiO_2 Thick Film

A large size CH3SiO3/2-SiO2 self sustained film with the thickness ranging from 50 to 1000 μm was prepared through sol-gel method by adopting CH3Si(OC2H5)3 and Si(OC2H5) as precursors.In this paper, the preparation processes of this thick film are discussed in detail and XRD technique was adopted for the identification of oligomer solution. Also, IR and AFM techniques were used to investigate the film structure and surface morphology     

Permeation of solvents through disk type rice husk silica membrane modified with alkyl silylation reagents

Rice husk silica (RHS) which was obtained with thermal treatment of rice husk has the size of approximately 10 micrometer with 4-5 nm pore. RHS can be mold to a disk type membrane. The membrane may have submicron pore originated from the space among the particles, and the nano pores of the rice husk silica (RHS pore). Even it is difficult to adjust the size of the pores, we can suggest that the membrane shows different permeability for the organic/inorganic solvents if the affinity between the surface of the pores and the permeating molecule is changed. In this study, we investigated the permeation of the typical solvents such as water, ethanol and toluene to the RHS membranes sintered at 1100 degrees C, 1150 degrees C and 1200 degrees C and modified with triethoxymethyl silane (CH3)Si(C2H5O)3, diethoxydiemethyl silane (CH3)2Si(C2H5O)2 and ethoxytriemethyl silane (CH3)3Si (C2H5O). The result showed that permeability of original membranes for water (e.g., 1100 degrees C, 2.87 x 10(-3) mol/m2 s Pa) was larger than ethanol (1100 degrees C, 5.51 x 10(-4) mol/m2 s Pa) and toluene (1100 degrees C, 3.09 x 10(-4) mol/m2 s Pa) at the sintering temperatures. For the silane modified membranes, the permeability for water decreased drastically while those for ethanol and toluene increased.     

Cation–Cation Interaction in Complexes of Np(V) Benzoate and Salicylate with N-Containing Molecular Ligands

Radiochemistry - The hydrothermal method was used to obtain two new compounds of Np(V): benzoate [(NpO2)3(py) (C7H5O2)3(H2O)2] (1) and salicylate [(NpO2)(phen)(HOC7H4O2)] (2), where py = pyridine...     

Sintering behaviour of Nb–16Si–25Ti–8Hf–2Cr–2Al alloy powder fabricated by a hydrogenation–dehydrogenation method

The present study investigated the sintering behaviour of Nb–16Si–25Ti–8Hf–2Cr–2Al alloy powders. The alloy powders were produced using ahydrogenation–dehydrogenation method and featured an irregular morphology. Powders sintered at 1500°C and 1600°C exhibited pores in their microstructures, while powders sintered at 1700°C for 4?h were fully densified and poreless. The cast ingot and powders were composed of three phases: Nb_ss, Nb₅Si₃, and Nb₃Si. However, the Nb₃Si phase was not observed, while HfO₂ oxides formed in the sintered compact. The hafnium and oxygen reacted to form an HfO₂ oxide during the high-temperature sintering process. From the result of the thermodynamic calculation, Hf oxide formed after sintering because Hf has the highest driving force for oxidation among the elements constituting the alloy.     

聚乙烯基三苯乙炔基硅烷的制备及热性能分析

为研究聚乙烯基三苯乙炔基硅烷树脂的热性能,以苯乙炔和乙烯基三氯硅烷为原料,运用格利雅反应合成了乙烯基三苯乙炔基硅烷单体,并通过红外(FT-IR)、核磁(1H-NMR,13C-NMR,29Si-NMR)证实了合成产物.以此单体为原料,通过热聚合法制备了聚乙烯基三苯乙炔基硅烷树脂,并采用TGA-DTG研究该聚合物的热分解动力学,计算了相应动力学参数.结果表明:该树脂的热分解温度(Td5%)在550℃左右,800℃时聚合物的残炭率约80%;用Kissinger法和Ozawa法求得的聚合物热分解活化能分别为266.55和236.89 k J/mol;用Crane法求得聚合物的热分解反应级数为0.93,近似为一级反应.     

Features of the behavior of lanthanum and hafnium atoms in silicon

Features of the interaction of lanthanum (La) and hafnium (Hf) atoms in single crystal silicon have been studied using a differential capacitance (deep-level transient spectroscopy) technique. Hf atoms introduced into silicon by diffusion form two deep levels with the ionization energies E _c-0.28 eV and E _v + 0.35 eV. La atoms introduced into silicon in the course of single-crystal growth from melt exhibit no electrical activity. However, the presence of La atoms in silicon increases the efficiency of formation of the impurity levels related to the subsequent diffusion doping with hafnium and, in addition, leads to the stabilization of these levels: the annealing of Hf-related levels proceeds at a much lower rate in Si〈La,Hf〉 than in Si〈Hf〉 crystals.