A study of the chemical bond types in films deposited from bis(trimethylsilyl)-ethylamine by PECVD

Silicon carbonitride films are synthesized by plasma enhanced chemical vapor deposition from bis(trimethylsilyl)ethylamine and helium or ammonium mixtures. The structure of chemical bonds in the films is studied by X-ray photoelectron and IR spectroscopy. The data on the main types of bonds present in silicon carbonitride films deposited under different synthesis conditions are obtained. It is shown that the use of ammonia at a low deposition temperature provides the synthesis of films with a simultaneous formation of Si-C, Si-N, and C-N bonds. The main bonds in films obtained from a bis(trimethylsilyl)ethylamine and helium mixture are Si-C and Si-N. The chemical structure of films obtained at high synthesis temperatures is close to SiC _x regardless of the type of the additional gas used.     

Superconductivity of some transition metal compounds

Single crystals of niobium carbonitride were made by zone melting growth methods and single crystals of γ-NbN and δ-NbN by zone annealing crystal growth. The crystals are nonstoichiometric in contrast to the niobium carbonitride or niobium nitride prepared in reaction with nitrogen gas and niobium-niobium carbide mixtures and niobium metal, respectively. The transition temperature for superconductivity (T_c) decreases with increasing deviation from stoichiometry, and a determination of T_c is a nondestructive determination of this deviation. An instrument using the Wheatstone bridge principle is described and T_c values are listed for some nonstoichiometric single crystals of niobium carbonitride and niobium nitride.     

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.     

Investigations of radiative lifetimes in the 3p5p configuration of neutral silicon

Lifetimes for the³ S ₁,³ P _{0, 1, 2} and³ D _{1, 2, 3} states in the 3s ²3p5p configuration of silicon have been determined using stepwise dye laser excitation and time resolved detection. A comparison is made with theoretical values, calculated using multi-configuration Hartree-Fock wavefunctions. Laser-evaporation was used to produce free silicon atoms by focusing a Nd: YAG laser on a rotating silicon target.     

SNMS and XRD investigations of laser deposited YSZ buffer layers

Summary Secondary Neutral Mass Spectrometry (SNMS) and X-Ray Diffraction (XRD) were used to find optimum parameters for the in-situ pulsed laser deposition of ZrO₂/Y₂O₃ (YSZ) buffer layers on silicon (100) substrates. Homogeneous and nearly stoichiometric concentration depth profiles were found by SNMS for the laser deposited YSZ films. A peak of the SiO intensity during profiling of the YSZ/Si interface points to a SiO₂ intermediate layer. An increasing Y-deficit of the YSZ films was found by decreasing the laser energy density at the target. Epitaxial growth of the YSZ thin films was observed at an oxygen partial pressure lower than 10^–3 mbar, a substrate temperature of 600–800°C and a laser energy density at the target of about 8 J/cm².     

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.     

Amorphous silicon carbonitride thin‐film coatings produced by remote nitrogen microwave plasma chemical vapour deposition using organosilicon precursor

Amorphous silicon carbonitride (a‐SiCN) films were produced by remote nitrogen plasma chemical vapour deposition (RP‐CVD) from bis(dimethylamino)methylsilane precursor. The effect of substrate temperature (T _S) on the kinetics of RP‐CVD, chemical structure, surface morphology and some properties of the resulting films is reported. The T _S dependence of film growth rate implies that RP‐CVD is an adsorption‐controlled process. Fourier transform infrared spectroscopic examination revealed that an increase in T _S from 30 to 400°C involves the elimination of organic moieties from the film and the formation of Si─C and Si─N network structure. The films were characterized in terms of their surface roughness and basic physical and optical properties, such as density and refractive index, respectively. Reasonably good relationships between the structural parameters represented by relative integrated intensity of infrared absorption bands from the Si─C and Si─N bonds (controlled by T _S) and the film properties are determined. Due to their small surface roughness, high density and high refractive index, the a‐SiCN films produced at T _S ≥ 350°C would seem to be useful protective coatings for metals and optical devices.     

Nanostructured ZrO2 and Zr‐C‐N Coatings from Chemical Vapor Deposition of Metal‐Organic Precursors

Nanocrystalline zirconium carbonitride (Zr‐C‐N) and zirconium oxide (ZrO₂) films were deposited by chemical vapor deposition (CVD) of zirconium‐tetrakis‐diethylamide (Zr(NEt₂)₄) and ‐tert‐butyloxide (Zr(OBu^t)₄), respectively. The films were deposited on iron substrates and characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The Zr‐C‐N films show blue, golden brown or bronze colours, with colour stability depending upon the precursor composition (pure metal amide or mixed with Et₂NH). The deposition temperature showed no pronounced effect on the granular morphology of the Zr‐C‐N films. The XRD data of the films correspond to the formation of carbonitride phase whereas the XPS analyses revealed a strong surface oxidation and incorporation of oxygen in the film. The films deposited using a mixture of Zr(NEt₂)₄ and Et₂NH showed higher N content, better adhesion and scratch resistance when compared to films obtained from the CVD of pure Zr(NEt₂)₄. Subject to the precursor composition and deposition temperature (550‐750 °C), the microhardness values of Zr‐C‐N films were found to be in the range 2.11‐5.65 GPa. For ZrO₂ films, morphology and phase composition strongly depend on the deposition temperature. The CVD deposits obtained at 350 °C show tetragonal ZrO₂ to be the only crystalline phase. Upon increasing the deposition temperature to 450 °C, a mixture of tetragonal and monoclinic modifications was formed with morphology made up of interwoven elongated grains. At higher temperatures (550 and 650 °C), pure monoclinic phase was obtained with facetted grains and developed texture.     

Matrix-free infrared soft laser desorption/ionization

Infrared soft laser desorption/ionization was performed using a 2.94 µm Er : YAG laser and a commercial reflectron time-of-flight mass spectrometer. The instrument was modified so that a 337 nm nitrogen laser could be used concurrently with the IR laser to interrogate samples. Matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization and desorption/ionization on silicon with UV and IR lasers were compared. Various target materials were tested for IR soft desorption ionization, including stainless steel, aluminum, copper, silicon, porous silicon and polyethylene. Silicon surfaces gave the best performance in terms of signal level and low-mass interference. The internal energy resultant of the desorption/ionization was assessed using the easily fragmented vitamin B₁₂ molecule. IR ionization produced more analyte fragmentation than UV-MALDI analysis. Fragmentation from matrix-free IR desorption from silicon was comparable to that from IR-MALDI. The results are interpreted as soft laser desorption and ionization resulting from the absorption of the IR laser energy by the analyte and associated solvent molecules. Copyright © 2004 John Wiley & Sons, Ltd.     

Piezoresistive properties of polycrystalline and crystalline silicon films

The piezoresistive properties of thin polycrystalline and crystalline boron-doped silicon films on thermally oxidized silicon substrates are reported, based on their calculated and measured gauge factors. A simple theoretical model for calculating the longitudinal and transverse gauge factors, including grain size, crystallite orientation and doping dependence, is described. Boron doping concentrations in the range 5 × 10¹⁸ cm⁻³ to 1 × 10²⁰ cm⁻³ have been investigated. Predictions of gauge factors using our model give good agreement with experimental results. Maximum gauge factors of K₁ ≅ 37 and K_t ≅ −9 for polycrystalline silicon with grain sizes of about 120 nm were obtained at doping concentrations of about 1 × 10¹⁹ cm⁻³. In the case of completely crystalline silicon films, the advantages of SOI technology are combined with excellent piezoresistive properties comparable to those of usual piezoresistors in monocrystalline silicon devices.     

Chemical Composition and Structure of Thin Films Produced by Chemical Vapor Deposition

This paper reports results from studies of the chemical composition and structure of semiconducting, dielectric, and metallic films produced from molecular precursors by the chemical vapor deposition method. A study was made of films of zinc sulfides, mixed copper, cadmium, and zinc sulfides, boron nitride, carbonitride, silicon carbonitride, and iridium films. It is shown that the use of metal compounds with different ligands (zinc and manganese) enables production of zinc sulfide films in which manganese ions are uniformly incorporated into the zinc sulfide crystal lattice to substitute zinc at the lattice sites. For the films of simple and mixed cadmium, copper, and zinc sulfides, the film structure depends on the type of substrate. The thin layers of mixed cadmium and zinc sulfides are asubstitution solution with a hexagonal structure. The thin layers of boron nitride produced from borazine exhibit a nanocrystalline structure and are a mixture of cubic and hexagonal phases. Composite layers were produced from alkylamine boranes and their mixtures with ammonia. Depending on synthesis conditions, the layers are mixtures of hexagonal boron nitride, carbide, and carbonitride or pure boron nitride. Using silyl derivatives of asymmetric dimethylhydrazine containing Si—N and C—N bonds in the starting molecule, we produced silicon carbonitride films whose crystal habit belongs to a tetragonal structure with lattice parameters a = 9.6 and c = 6.4 . The iridium films obtained by thermal decomposition of iridium trisacetylacetonate(III) on quartz substrates in the presence of hydrogen have a polycrystalline structure with crystallite sizes of 50 to 500 . A method for determining grainsize composition was proposed, and grain shapes for the iridium films were analyzed. The influence of substrate temperature on the internal microstructure and growth of the iridium films is demonstrated. At the iridium–substrate interface, a transition layer forms, whose composition depends on the substrate material and deposition conditions.     

Room-temperature ferromagnetism in silicon oxide/silicon nitride composite films

Room-temperature ferromagnetism has been observed in silicon oxide/silicon nitride composite films formed on Si substrates at different substrate temperatures, and the ferromagnetic properties of the samples have been found to depend on the silicon nitride content of the films. It is proposed that the ferromagnetism is related to the interface states between the silicon oxide particles and silicon nitride particles. The saturation magnetization (M_S) reached its maximum value in the film produced at a substrate temperature of 400 °C. A further study on the magnetic properties of the film has been carried out using first-principles calculations based on the density functional theory. The calculations suggest that the magnetic moments of the film originate from N 2p and Si 2p states in the vicinity of the hetoro-interface.     

Sol–Gel SiO2-ZrO2 Coatings for Optical Applications

SiO₂-ZrO₂ based nanostructured multilayers films have been prepared by sol–gel processing from metallorganic precursors by low temperature inorganic polymerization reactions. Simultaneous gelation of both precursors was realized. Homogeneous and transparent films were obtained at room temperature by dip- and spin-coating on glass and silicon wafer substrates. Samples with successively deposited layers (1–3 layers) and successive thermal treatments have been also studied. Each deposited layer was thermally treated for 1 h at 300°C. The coatings were characterized by XRD, spectroellipsometry (SE), UV-VIS spectroscopy and AFM methods. The influence of substrates, number of coatings and number of thermal treatments on the optical and structural properties of the films was established. The thickness of three deposited SiO₂-ZrO₂ layers is about 496 nm on glass substrates and 413 nm on the silicon wafer substrate. The films deposited on glass are more porous than those deposited on silicon. The properties of optical waveguide prepared from SiO₂-ZrO₂ layers on silicon substrates will be discussed.     

An integrated low-power thin-film CO gas sensor on silicon

An approach to an integrated semiconductor gas sensor is presented. The major reasons considered for developing a semiconductor oxide gas sensor on silicon are the accurate local temperature control of the sensing area and the low level of the heating power required, together with an appropriate integrated structure. Thermal loss measurements show that the integrated gas sensor can operate up to 400 °C with less than 200 mW heating power. Depending on the deposition conditions, catalyst addition or surface conditioning, the SnO_x thin films are known to have an optimal sensitivity to CO between 250 °C and 400 °C. The sensitivity for CO gas and the response time of the device are presented for sputtered thin films of SnO_x, deposited on top of an isolated resistive heater, separated from silicon by a thin thermally-isolating membrane.     

Fabrication of crystallized boron films by laser ablation

Polycrystalline β-rhombohedral boron films mixed with amorphous boron phase have been successfully fabricated on quartz substrates using pulsed laser ablation in a quartz glass tube chamber placed in an electric furnace. The crystallinity of the films strongly depended on the temperature of the furnace and the pressure of background argon gas. High temperature and high pressure in the chamber were suitable for crystallized boron film preparation. The best crystalline films (without B₂O₃ phase formation) were obtained at 1000°C, 100 Pa. XPS measurements demonstrated that the major contaminants were carbon and oxygen, and the atomic ratio of oxygen to boron was 0.05 under the preparation conditions of well-crystallized films. The surface roughness of the films decreased by lowering laser energy to 150 mJ/pulse under the same pressure and temperature conditions.     

Synthesis,characterization, and thermal properties of novel silicon 1,1,3,3-tetramethylguanidinate derivatives and use as single-source chemical vapor deposition precursors

A series of chemical vapor deposition (CVD) precursors have been synthesized by a single-step reaction of 1,1,3,3-tetramethylguanidine and a variety of silicon chlorides. The structures of the 1,1,3,3-tetramethylguanidinate-based compounds were verified by ¹H NMR, ¹³C NMR, XPS, EI-MS, and elemental analysis. The thermal stability, transport behavior, and vapor pressures of these compounds were evaluated by simultaneous thermal analyses (STA). These compounds are highly stable and those in liquid form are very volatile. Silicon carbonitride (SiCN) thin films were prepared by using bis (tetramethylguanidine)-dimethyl-silane as the precursor in helicon wave plasma chemical vapor deposition (HWP-CVD). The properties of the films were investigated by SEM, AFM, and XPS. The results showed that the films have good uniformities, low friction coefficient, and high hardness, enabling the films for fabrication of semiconductor devices.     

Fabrication of hydrophobic fluorinated amorphous carbon thin films by an electrochemical route

A novel electrochemical route for the preparation of hydrophobic fluorinated amorphous carbon (a-C:F) films with nanostructured surfaces on single crystal silicon substrate was reported. The films were investigated in terms of the surface morphology, chemical composition, microstructure and hydrophobic behavior. The results showed that a highly uniform and densely packed bamboo shoot-like nanostructure was obtained without any use of template. The incorporation of fluorine presented mainly in the forms of CF₂ chains and CCF_x (x = 1, 2) in the films. Sessile drop water contact angle measurements showed that the contact angle of a-C:F films deposited by electrochemical route was about 145°, which can be attributed to the lower surface energy of CF_x groups and higher diffusion resistance of the special nanostructured surface to water. Moreover, the related growth mechanism of the resulting films in liquid-phase electrodeposition is discussed as well.     

Surface plasmon resonance on the LB monolayer of solvent-soluble silicon phthalocyanine

Thin films of bis-(p-chlorophenoxy) (tetra-4-nitrophthalocyaninato)silicon, TNPcSi(OPhCl-p)₂, were prepared by using Langmir-Blodgett techniques and the morphology of the film was investigated by AFM (atomic force microscope) analysis. It has been found that the LB films were successfully transferred onto substrates like mica, gold deposited glass, and pure glass with domains aggregated on the substrates. Surface plasmon resonance has been used to investigate the interaction between sulfur dioxide and a monolayer of TNPcSi(OPhCl-p)₂ LB film. It has been found that the monolayer of LB film transferred onto gold deposited glass gave a 0.55° shift of resonant angle and an additional 0.45° shift of resonant angle after exposion in sulfur dioxide\atomospheric ambient for twenty minute. The UV–visible absorption spectrum of the LB films of TNPcSi(OPhCl-p)₂ showed that there is chemical changes in the film after the exposure to the sulfur dioxide ambient. This work has shown a promising application as an optical gas sensor.     

Structure and electrical properties of Pb(Zr<Subscript>0.25</Subscript>Ti<Subscript>0.75</Subscript>)O<Subscript>3</Subscript> thin films on LaNiO<Subscript>3</Subscript>—Coated thermally oxidized Si substrates

Pb(Zr_0.25Ti_0.75)O₃ (PZT25) thin films were prepared on LaNiO₃-coated thermally oxidized silicon substrates by chemical solution deposition method, where LaNiO₃ electrodes were also prepared by a chemical solution deposition technique. The dielectric constant and dielectric loss of the PZT25 thin films were 570 and 0.057, respectively. The remanent polarization and coercive field were 20.11 μC/cm² and 60.7 kV/cm, respectively. The PZT25 thin films on LaNiO₃-coated thermally oxidized silicon substrates showed improved fatigue characteristics compared with their counterparts on plantium-coated silicon substrates.     

Tapered copolymers of styrene and 4-vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

Well-defined polystyrene homopolymers with surface-adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end-functionalization and subsequent hydrosilylation with triethoxysilane. Grafting-to performance of polymers with various molecular weight (M_n = 3000–14,000 g mol⁻¹) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4-vinylbenzocyclobutene (4-VBCB) and styrene, followed by epoxide end-functionalization and triethoxysilane modification (M_n = 4000–14,000 g mol⁻¹). The copolymers were characterized by ¹H-NMR, THF-SEC, and matrix-assisted laser desorption and ionization time-of-flight mass spectrometry. In situ ¹H-NMR kinetic studies in cyclohexane-d₁₂ provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer (r_s = 2.75, r_4-VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting-to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 181–192