Physical and chemical properties of silicon carbonitride nanocrystalline films

Nanocrystalline transparent films SiC_xN_y were obtained by plasma-enhanced chemical deposition within the temperature range 473–1173 K from low pressure gas phase from a mixture of hexamethyldisilazane vapor, ammonia, and helium. Physical chemical properties of the films obtained were studied by IR and Raman spectroscopy, ellipsometry, X-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron spectroscopy and synchrotron radiation powder diffaction. Voltage-capacity and voltage-current measurements were also made. The dependence of chemical and phase composition of the films on deposition conditions was determined, and the formation of approximately 2 nm sized spherical nanocrystals within the films was established. The nanocrystals are formed by a phase similar to usual α-Si₃N₄, with silicon atoms partially substituted by carbon ones.     

XANES and XPS characterization of hard amorphous CSixNy thin films grown by RF nitrogen plasma assisted pulsed laser deposition

Amorphous carbon silicon nitride thin films were grown on (100) oriented silicon substrates by pulsed laser deposition (PLD) assisted by an RF nitrogen plasma source. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the hard amorphous thin films by XPS in dependence on the composition of the mixed graphite / Si₃N₄ PLD target. The universal nanohardness was measured to be at maximum load force of 0.1 mN up to 23 GPa for thin CSi_xN_y films with reference value of 14 GPa for single crystalline silicon. X-ray photoelectron spectroscopy (XPS) of CSi_xN_y film surfaces showed a clear correlation of binding energy and intensity of fitted features of N 1s, C 1s, and Si 2p peaks to the composition of the graphite / Si₃N₄ target and to nitrogen flow through the plasma source, indicating soft changes of binding structure of the thin films due to variation of PLD parameters. Auger electron spectroscopy (AES) of Si KL₂₃L₂₃;¹D Auger transition gave a detailed view of bonding structure of Si in the CSi_xN_y films. The intensity of π* and σ* resonances at the carbon K-edge X-ray absorption near-edge structure (XANES) of the CSi_xN_y films measured at BESSY I corresponded to the nanohardness of the CSi_xN_y films, thus giving insight into chemical binding structure of superhard amorphous materials.     

X-ray photoelectron and auger spectroscopic study of the chemical composition of BC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> films

X-ray photoelectron and Auger spectroscopy are used to investigate the chemical composition of BC _x N _y films synthesized by PECVD from different initial gas mixtures in the temperature range 473–723 K. Main principles and features of the film formation are found. It is shown that the chemical composition of BC _x N _y films significantly depends on the synthesis parameters, which enables targeted control of their physical properties. The obtained data are discussed.     

From organosilicon precursors to multifunctional silicon carbonitride

Films of silicon carbonitride of variable composition are prepared by the method of plasmochemical decomposition of tetramethyldisilazane, hexamethyldisilazane, and hexamethylcyclotrisilazane in the mixture with helium in the temperature range of 373–973 K. The chemical composition of the low temperature films (373–673 K) is described by the formula SiC _x N _y O _z :H, whereas that of high temperature films, by the formula SiC _x N _y . The films of silicon carbonitride are found to be a nanocomposite material containing an amorphous part and nanocrystals, whose structure is close to the phase α-Si₃N₄. Films of the composition SiC _x N _y O _z :H are promising as low-k interlayer dielectrics in ultra-large scale integrated circuits of new generation, as well as protecting antireflective coatings and light-emitting diodes.     

X-ray spectroscopic study of the electronic structure of boron carbonitride films obtained by chemical vapor deposition on Co/Si and CoO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Si substrates

Boron carbonitride films are synthesized by chemical vapor deposition from a mixture of triethylamine borane and ammonia on a metallic or oxidized cobalt sublayer sprayed over Si(100) substrates. Scanning electron microscopy shows that the surface of a BC _x N _y /Co/Si sample has a homogeneous fine-grained structure; filamentous entities are found on the surface of the BC _x N _y /CoO _x /Si sample. The electronic structure of the films is investigated by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). An analysis of the spectra shows that BC _x N _y films are composed of graphite and hexagonal boron nitride (h-BN) regions and complex BC _x N _y O _z components with B-C, N-C, B-O, N-O, and C-O bonds. The deposition of the BC _x N _y film on the oxidized Co sublayer results in an increase in the number of C-O, N-O, B-O, and C-N bonds and a decrease of the graphite and h-BN components and in the number of C-B bonds. The XPS data are used to estimate the surface elemental composition of the BC _x N _y /CoO _x /Si sample. It is found that the film consists of 66 at.% graphite component and 3 at.% h-BN; the proportion of complex C_0.46B_0.11N_0.05O_0.38 components is 31 at.%.     

Biomimetic synthesis of the arachidic acid/Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>S nanocomposite films

Ag _x Cd _y S nanoparticles were obtained in arachidic acid (AA) monolayer containing Ag⁺ and Cd²⁺ under H₂S flow. The AA/Ag _x Cd _y S monolayers were deposited onto solid substrate to prepare LB films. The UV-vis spectrum showed that the LB film exhibited notable quantum-size effect. The small-angle X-ray diffraction revealed periodic structure of the LB films. The molar ratio of Ag to Cd in AA/Ag _x Cd _y S film was ca. 1 : 5 as measured by the XPS. TEM and FTIR spectroscopy showed that the head-groups of arachidic acid molecules controlled formation of Ag _x Cd _y S nanoparticles in the monolayer.     

Physicochemical Properties and Structure of SiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>:Fe Films Grown From a Gas Mixture of Ferrocene,Hydrogen and 1,1,3,3,5,5-Hexamethylcyclotrisilazane

Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and EXAFS spectroscopy are used to study the composition and structure of SiC_xN_y:Fe films obtained by chemical vapor deposition (CVD) in the Fe–Si–C–N–H system from a mixture of hydrogen, ferrocene (C₅H₅)₂Fe, and organosilicon compound 1,1,3,3,5,5–hexamethylcyclotrisilazane (HMCTS) C₆H₂₁N₃Si₃. The films are deposited under low pressures (LPCVD) at 1123–1273 K, and their phase composition at 300–1300 K is predicted using thermodynamic modeling. The obtained films are nanocomposites with amorphous matrices containing α-Fe crystallites and carbon clusters with a size of 5–10 nm.     

Oxygen barrier,free volume,and blending properties of polyamide 12/poly (vinyl alcohol) blends

Oxygen permeation rates, average volumes of free‐volume‐cavities (V_f), and fractional free volumes (F_v) of polyamide 12 (PA12)/poly(vinyl alcohol) (PVA) (ie, PA12_xPVA⁰⁵_y, PA12_xPVA⁰⁸_y, and PA12_xPVA¹⁴_y) blend films with varying PVA degrees of polymerization reduced to a minimum value when their PVA contents reached a corresponding optimal value, respectively. The minimum oxygen permeation rates, V_f, and F_v values obtained for the optimal PA12_xPVA^z_y blown films were reduced considerably with decreasing PVA degrees of polymerization. Experimental findings from dynamic mechanical analysis, differential scanning calorimetry, wide angle X‐ray diffraction, and Fourier transform infrared spectroscopy of the PA12_xPVA^z_y blend series suggest that PA12 and PVA in PA12_xPVA^z_y are miscible to some extent at the molecular level when their PVA contents are near and less than the corresponding critical values. The considerably enhanced oxygen barrier properties of the PA12_xPVA^z_y blend films with optimized compositions are attributed to the significantly reduced local free volume characteristics.     

Structure and elemental composition of transparent nanocomposite silicon oxycarbonitride films

Based on thermodynamic simulation on the deposition of condensed phases with the complex composition in the Si–C–N–O–H system in a wide temperature range, using initial gas mixtures of 1,1,3,3-tetramethyldisilazane (HSi(CH₃)₂)₂NH (TMDS), TMDS with a variable mixture of oxygen and nitrogen (O₂+xN₂), a method is developed to obtain SiC _x N _y O _z :H nanocomposite films by the plasma chemical decomposition of this gas mixture in the temperature range of 373-973 K. By FTIR and energy dispersive X-ray spectroscopy the structure of chemical bonds and the elemental composition of the obtained silicon oxycarbonitride films are studied. The in situ composition of the initial gas phase in PECVD processes is examined by optical emission spectroscopy.     

Crystal Structure and Properties of Strontium Phosphate Apatite with Oxocuprate Ions in Hexagonal Channels

Strontium phosphate apatites containing different amounts of copper were prepared by a solid state reaction at 1100 °C or by arc melting above 1600 °C in air. The samples were characterized by X‐ray diffraction, ICP analysis, scanning electron microscopy, IR spectroscopy, MAS—¹H—NMR, diffuse reflectance spectroscopy, and SQUID magnetometry. X‐ray crystal structure determination was carried out for a single crystal obtained from the melt. The compound is formulated as Sr₅(PO₄)₃(CuO₂)_1/3 and has an apatite structure (space group P6₃/m, a = 9.7815(4)Å, c = 7.3018(4)Å, Z = 2) with linear CuO₂^3— ions occupying hexagonal channels. For solid state synthesized samples, Rietveld refinement of powder XRD patterns was performed. The samples obtained at 1100 °C acquire the composition Sr₅(PO₄)₃Cu_xOH_y, with x changing from 0.01 to 0.62 and y < 1—x. The copper content can be increased to x = 0.85 by annealing in argon at 950 °C. The compounds represent a hydroxyapatite in which part of the protons is substituted by Cu⁺ and Cu²⁺ ions. The ions form linear O—Cu—O units which are progressively condensed creating the Cu—O—Cu bridges on increasing copper content. IR and NMR data testify existence of OH groups, non‐disturbed and disturbed by neighboring Cu atoms. In the electron spectra, the samples exhibit absorption bands at 7800‐7900, 14200‐14500 and 17500‐17550 cm^—1, which were assigned to Cu²⁺ d‐electron transitions. By annealing the sample with x = 0.1 in oxygen at 800 °C copper is fully oxidized while retaining in channels in unusual for Cu²⁺ linear coordination.     

Nanocrystalline Zn1−x−yBexMgyO thin films synthesized by the sol–gel method: structural and near infrared photoluminescence properties

In this paper, we reports on the structural and optical properties of Zn_1?x?yBe_xMg_yO thin films prepared by sol–gel method, which are new materials for optoelectronic and ultraviolet-light-emitting devices. The crystal structure and core level spectra of these films are studied by X-ray diffraction and X-ray photoelectron spectroscopy. Surface morphology of the films is analyzed by scanning electron microscope images and the surface is composed of spherical shaped grains. Micro-photoluminescence shows a near edge band emission and the peak values tuned from 3.26 eV for the undoped to 3.4 eV for the doped ZnO film. Near infrared emission is observed in the region 1.64–1.67 eV for pure and co-doped ZnO films. In micro-Raman spectra, multiple-order Raman bands originating from ZnO-like longitudinal optical (LO) phonons are observed. A Raman shift of about 5–18 cm^?1 is observed for the first-order LO phonon. A comparative study was made on Raman band for BeZnO, MgZnO and BeMgZnO nanocrystals with the LO phonon band of bulk ZnO. The ultraviolet resonant Raman excitation at room temperature shows multi-phonon LO modes up to the fourth order. Deformation energy of all the films is calculated and BeMgZnO film has the minimum deformation energy.     

Optical and mechanical properties of films obtained by plasma decomposition of hexamethyldisilazane

Films of SiC _x N _y H _z composition are obtained by chemical deposition from the vapor phase via the activation of high-frequency discharge plasma (PECVD). The organosilicon compound hexamethyldisilazane, which contains all the atoms needed for the formation of films, is used as our initial material. Physicochemical properties of the films are studied by spectroscopy of surface acoustic waves, measuring the bending of a film-substrate system, ellipsometry, and infrared spectroscopy. Important features of the films?? structure are established. It is shown that at temperatures of deposition below 400°C, films contain chemical bonds of an organic nature, have very low values of density and the Young modulus, and exhibit high levels of elasticity, indicating their polymer-like structure. It is established that at higher temperatures of deposition, films are inorganic composite materials.     

TixNy团簇结构的密度泛函研究

采用杂化密度泛函方法(B3LYP)和有效核势基组预测了Ti_xN_y (x≤3, y≤2)团簇的结构及稳定性, 并分析了可能存在构型的电子结构. 结果表明Ti₂N中体系的自旋多重度由Ti原子决定. Ti₃N中随着N的配位数增加, N的负电荷增加, 平均每个Ti向N提供约0.3个电子. 从Ti₂N₂可能稳定构型分析, 成键数目越多, 能量上越有利, 且Ti—N键的数目的增加, 将削弱N—N间的成键.     

铁和锰的化学状态对 LaFexMnyAl12-x-yO19 催化剂上 N2O 分解的影响

 以共沉淀法制备了 LaFexMnyAl12-x-yO19 六铝酸盐催化剂, 并用 X 射线衍射、扫描电镜、N2 吸附-脱附、紫外-可见漫反射光谱和穆斯堡尔谱对催化剂进行了表征, 考察了催化剂上高浓度 N2O 分解反应的性能. 结果表明, 在所考察的条件下, Mn 比 Fe 更有利于促进六铝酸盐晶相的形成. LaFexAl12-xO19 (x = 0.5, 1) 中 Fe 以 Fe3+位于六铝酸盐尖晶石结构中的四面体位和镜面层结构中的三角双锥位, 其中后者为 N2O 分解的主要活性中心. LaMnyAl12-yO19 (y = 0.5, 1) 中 Mn 优先以 Mn2+进入四面体位, 然后以 Mn3+进入尖晶石结构中的八面体位, 并成为 N2O 分解的主要活性中心.     

Tuning thermal stability and electronic properties of germanium oxide on Ge(001) surface with the incorporation of nitrogen

The application of germanium as a channel material of transistors in near future requires an improved understanding of the interface between germanium and its potential passivation layer. In this study, we study effects of nitrogen incorporation on the thermal stability and electronic properties of GeO_xN_y/Ge interface by using high‐resolution X‐ray photoemission spectroscopy. We find that with the increasing nitrogen concentration in the GeO_xN_y films, the thermal stability can be increased, while the valence band offset with the Ge(001)substrate is decreased. First‐principles calculations further suggest that the unpaired p orbitals of nitrogen atoms induce electronic states near valence band edge, contributing to the reduction of the valence band offset. Our results provide a possibility to tune electronic and thermal properties of GeO_xN_y/Ge interface by controlling nitrogen concentrations during the growth.     

Thermodynamic modeling of the deposition of Si—C—N films from the gas phase during the decomposition of organosilicon compounds

Thermodynamic modeling of the process of chemical vapor deposition (CVD) of SiC_x and SiC_xN_y films from the gas phase was carried out using organosilicon compounds (EtN(SiMe₃)₂, PhN(SiMe₃)₂, and PhSiMe₃) at reactor pressures of 0.01 and 10 Torr in the temperature range of 500–1200 K. It was established that regions of existence of two phase complexes, namely, SiC + Si₃N₄ + C and SiC + C, were present on the CVD diagrams calculated for the EtN(SiMe₃)₂—He and PhN(SiMe₃)₂—He systems. The CVD diagrams calculated for the EtN(SiMe₃)₂—NH₃, PhN(SiMe₃)₂—NH₃, and PhSiMe₃—NH₃ systems have regions of existence of three phase complexes, namely, Si₃N₄ + C, SiC + Si₃N₄ + C, and SiC + C. The composition of the obtained silicon-containing films was calculated.     

Sur quelques voies d'accès aux carbonitrures CxNy. Exemples à la charniére entre chimie moléculaire et chimie du solide

The synthesis of β-C₃N₄, predicted from ab initio calculations, seems difficult owing to the stability of the N₂ molecule easily formed when high temperatures are involved in the preparation process. Using a high pressure process (P = 3 GPa) with organic precursors (5-azacytosine, 2-amino-4,6-dichloro-1,3,5-triazine) without solvent, a brown-orange solid was prepared. X-ray diffraction, infra-red spectroscopy and chemical titration show the formation of carbon nitride compounds C_xN_y. The knowledge of chemical mechanisms reveals new prospects about the synthesis of carbon nitride C₃N₄.     

Synthesis, Characterization and Thermal Decomposition of the Pyridine Adducts of Co, Ni, Cu and Zn Sulfate

Pyridine adducts of Co, Ni, Cu and Zn sulfate were obtained by refluxing the corresponding sulfate with pyridine in chloroform. The compounds were characterized by elemental analysis, X-ray powder diffraction and FTIR spectroscopy. The thermal decompositions (TG/DTG/DTA) of the complexes in the interval 20–1000°C were also studied. The elemental and thermal analysis results revealed that the formulae of the complexes are M₂(SO₄)₂ xC₅H₅NyH₂O, where x=2, 3, 2 and 1 and y=6, 4, 6 and 4 for the Co, Ni, Cu and Zn compound, respectively. The complexes were not found to be isostructural, but certain structural similarities were observed between the Zn and Co compounds. Although the thermal decomposition pathways of the various compounds were quite different and each consisted of several steps, in all cases the dehydration preceded the depyridination. Metal oxide was always obtained as final product. The spectral data are discussed with regard to the thermal behaviour. Appreciably stronghydrogen-bonding and pronounced structural differences relating to the sulfate ions were presumed for the Cu compound. This revised version was published online in July 2006 with corrections to the Cover Date.     

TiO<Subscript>2</Subscript>/TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanocomposite and its acetaldehyde photodecomposition ability

Nitrogen-doped titania was coupled with the commercial titania nanoparticles by mechanical milling in liquid medium. The as-prepared nanocomposites (TiO₂/TiO_2−x N _y ) were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area, UV–Vis spectroscopy, chemiluminescence, and acetaldehyde decomposition activity techniques. When a small amount of nitrogen-doped titania was added into the commercial titania, higher intensity and longer lifetime of ¹O₂ was observed, and the photocatalytic activity was efficiently improved. The TiO_2−x N _y acts as the acceptor of photoinduced holes. The recombination of the electron-hole was effectively depressed by the heterogeneous electron transfer. This could be an effective way to obtain highly active photocatalysts.     

Microwave-assisted hydrothermal synthesis of monoclinic nitrogen-doped titania photocatalyst and its DeNO<Subscript>x</Subscript> ability under visible LED light irradiation

Nitrogen-doped titania (TiO_2−xN_y) nanoparticles with monoclinic phase were successfully prepared by a microwave-assisted hydrothermal process. The obtained TiO_2−xN_y powders showed high specific surface area, fine particle size, and excellent photocatalytic ability for the oxidative destruction of nitrogen monoxide under irradiation of monochromatic LED light with various wavelengths.