Evolution of crystallization and its effects on properties during pyrolysis of Si–Al–C–(O) precursor fibers

The high-temperature resistant Si–Al–C–(O) fibers were prepared through polymer-derived method using continuous polyaluminocarbosilane (PACS) fibers. Evolutions of the crystallization during the pyrolysis of the Si–Al–C–(O) precursor fibers were investigated by a series analysis. The structure of the fibers transforms from organic state to inorganic state and the crystalline phases appear during the pyrolysis. The β-SiC crystallite size increases when the temperature is higher than 1,300 °C. At the same time, the α-SiC appears. At 1,600 and 1,800 °C, the grain size of β-SiC of the fibers is 15.4 and 22.1 nm, respectively. The growth of β-SiC and the appearing of α-SiC have a great influence on the properties of the fibers. The change of the tensile strength of the pyrolysis products is divided into three stages with the growth of the crystal. The tensile strength of the Si-Al-C fibers is higher than 1.9 GPa.     

Effect of Si target sputtering power on diffusion barrier properties of Ta–Si–N thin films

Abstract

Ta–Si–N thin films and Cu/Ta–Si–N thin films were deposited on p type Si(111) substrates by magnetron reactive sputtering. Then the films were characterised by four point probe sheet resistance measurement, AFM, SEM and XRD respectively. According to the XRD results, the authors found that the crystallisation of Ta nitrides in Ta–Si–N/Si thin films is suppressed effectively when fabricated by a high Si target sputtering power. As the Si target power varies, the failure temperature of Cu/Ta–Si–N/Si is changed. The sample fabricated by the Si target power of 200 W fails after 800°C rapid thermal annealing and it has the highest failure temperature. The investigation of failure mechanism shows that Cu atoms diffuse through grain boundaries or amorphous structure of the Ta–Si–N barrier, and react with Si to form Cu–Si phase. And it causes the failure of the barrier.     

Role of precursor chemistry on synthesis of Si–O–C and Si–O–C–N ceramics by polymer pyrolysis

In this study, the role played by polymer precursor chemistry on the nature of the pyrolyzed product was examined. Variables examined included extent of conjugation of the precursor, differences between a homopolymer and co-polymer, linear and cyclic structures, siloxanes and silazanes and between vinyl and phenyl containing silanes. Results indicate increasing the vinyl content of the precursor increases the amount of free carbon in the pyrolyzed product. The introduction of an aryl group in the silane decreased yield and lastly there was no change in the yield when a silazane was used instead of a silane, however, the composition of the silazane precursor ceramic is rich in nitrogen while a silane precursor ceramic is rich in carbon.     

Effect of B content on thermal stability of nanocomposite Ti–B–N thin films

Abstract

Ti–B–N thin films with different B contents were deposited on Si (100) at room temperature, followed by vacuum annealed at 400, 600, 800 and 1000°C for 1 h respectively. Effect of boron content on thermal stability was investigated using X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy and nanoindentation measurements. The results indicated that incorporation of B into TiN produced a nanocomposite structure, which had a positive effect on microstructure stability. A high B content resulted in an elevated recrystallisation temperature. The hardness stability was not consistent with that of microstructure, and depended on phase configuration and composition. The films with a high as deposited hardness showed high hardness stability. Excessive or lack of amorphous phase decreased hardness stability. The residual stress value was decreased with increasing annealing temperature owing to recovery of amorphous matrix, and crystallisation of amorphous phase made its direction transform from compression to tension.     

Growth and optical properties of Sn–Si nanocomposite thin films

The growth and optical properties of nanocomposite thin films comprising of nanocrystalline Sn and Si are reported. The nanocomposite films are produced by thermal annealing of bilayers of Sn and Si deposited on borosilicate glass substrates at various temperatures from 300 to 500 °C for 1 h in air. X-ray diffraction reveals that the as-deposited bilayers consist of nanocrystalline Sn films with a crystallite size of 30 nm, while the Si thin films are amorphous. There is onset of crystallinity in Si on annealing to 300 °C with the appearance of the (111) peak of the diamond cubic structure. The crystallite size of Si increases from 5 to 18 nm, whereas the Sn crystallite size decreases with increase in annealing temperature. Significantly, there is no evidence for any Sn–Si compound, and therefore it is concluded that the films are nanocomposites of Sn and Si. Measured spectral transmittance curves show that the films have high optical absorption in the as-deposited form which decreases on annealing to 300 °C. The films show almost 80 % transmission in the visible-near infrared region when the annealing temperature is increased to 500 °C. There is concomitant decrease in refractive index from 4.0, at 1750 nm, for the as-deposited film, to 1.88 for the film annealed at 500 °C. The optical band gap of the films increases on annealing (from 1.8 to ~2.9 eV at 500 °C). The Sn-Si nanocomposites have high refractive index, large band gap, and low optical absorption, and can therefore be used in many optical applications.     

X-ray absorption spectroscopy study of thermally annealed Cu–Al–O thin films

Cu–Al–O thin films are deposited on (0001) sapphire substrates by radio-frequency sputtering using an Al–Cu mosaic target. The Cu/Al atomic ratio of as-deposited Cu–Al–O films is measured to be 1.1. After deposition, the Cu–Al–O films are annealed at 600, 800, and 1000 °C, respectively, for 1 h in a N₂ atmosphere. The film crystal structure, electronic structure, valence band, and electrical properties are studied. The as-deposited films are amorphous and films annealed at 600 °C contain the crystallized CuO phase; the structure becomes crystallized CuAlO₂ after annealing at 800 °C and 1000 °C. The 800 °C annealed film grows along the (00l) plane. The crystallization decreases with the growth of the (012) and (018) planes for films annealed at 1000 °C. The resistivity values of the 800 °C and 1000 °C annealed films were measured as 1.07 Ω-cm and 864.01 Ω-cm, respectively. The lower resistivity of the 800 °C annealed film is attributed to preferred (00l) growth orientation and a reduction of the energy band gap.     

Structural and chemical stability of Ta–Si–N thin film between Si and Cu

Thermal stability and barrier performance of reactively sputter deposited Ta–Si–N thin films between Si and Cu were investigated. RF powers of Ta and Si targets were fixed and various N₂/Ar flow ratios were adopted to change the amount of nitrogen in Ta–Si–N thin films. The structure of the films are amorphous and the resistivity increases with nitrogen content. After annealing of Si/Ta–Si–N(300 Å)/Cu(1000 Å) structures in Ar–H₂ (10%) ambient, sheet resistance measurement, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and Auger electron spectroscopy (AES) were employed to characterize barrier performance. Cu₃Si and tantalum silicide phase are formed at the same temperature, and the interdiffusion of Si and Cu occurs through the local defect sites. In all characterization techniques, nitrogen in the film appears to play an important role in thermal stability and resistance against Cu diffusion. A 300 Å thick Ta₄₃Si₄N₅₃ barrier shows the excellent barrier property to suppress the formation of Cu₃Si phase up to 800°C.     

Preparation and characterization of pyrolytically deposited (Co–V–O and Cr–V–O) thin films

The metal acetylacetonates of vanadium, cobalt and chromium were prepared from commercial reagents. The corresponding metal acetylacetonates were mixed in desired ratio and deposited on soda lime glass substrate by metal organic chemical vapor deposition technique. Mixed oxides thin films with atomic composition Co_0.31V_1.37O₅ and Cr_0.5V₂O₅ were obtained. A combination of Rutherford backscattering spectroscopy and energy-dispersive X-ray fluorescence was used for the transition element identification and atomic compositional study of the thin films. The thickness of the Co–V–O and Cr–V–O thin films was 166 and 127 nm, respectively. The optical spectra of the films were obtained using a Pye Unicam SP8-400 spectrophotometer in the ultraviolet/visible region. The result of the spectral analyses gave the optical bandgap energy of the materials. The temperature dependence of the electrical resistivity measured using the Van der Pauw method indicated that the materials are semiconducting. Their activation energy was obtained from plots of the natural logarithm of conductivity vs. the reciprocal of temperature. The sign of the thermopower shows that both materials are p-type semiconductors.     

Stoichiometric and non-stoichiometric films in the Si–O–N system: mechanical,electrical, and dielectric properties

A novel low-temperature (600–850 °C), chemical vapor deposition method, involving a simple reaction between disiloxane (H₃Si–O–SiH₃) and ammonia (NH₃), is described to deposit stoichiometric, Si₂N₂O, and non-stoichiometric, SiO_xN_y, silicon oxynitride films (5–500 nm) on Si substrates. Note, the gaseous reactants are free from carbon and other undesirable contaminants. The deposition of Si₂N₂O on Si (with (1 0 0) orientation and a native oxide layer of 1 nm) was conducted at a pressure of 2 Torr and at extremely high rates of 20–30 nm min⁻¹ with complete hydrogen elimination. The deposition rate of SiO_xN_y on highly-doped Si (with (1 1 1) orientation but without native oxide) at 10⁻⁶ Torr was ∼1.5 nm min⁻¹, and achieved via the reaction of disiloxane with N atoms, generated by an RF source in an MBE chamber. The phase, composition and structure of the oxynitride films were characterized by a variety of analytical techniques. The hardness of Si₂N₂O, and the capacitance–voltage (C–V) as a function of frequency and leakage current density–voltage (J_L–V) characteristics were determined on MOS (Al/Si₂N₂O/SiO/p-Si) structures. The hardness, frequency-dispersionless dielectric permittivity (K), and J_L at 6 V for a 20 nm Si₂N₂O film were determined to be 18 GPa, 6 and 0.05–0.1 nA cm⁻², respectively.     

Sintering, densification and crystallization of Ca–Al–B–Si–O glass/Al2O3 composites for LTCC application

Ca–Al–B–Si–O glass/Al₂O₃ composites were prepared based on the borosilicate glass powders (D₅₀ = 2.84) and Al₂O₃ ceramic powders (D₅₀ = 3.26), and the sintering, densification, crystallization of samples were investigated. The shrinkage of sample starts to have a sharp increase at 600 °C. The shrinkage of sample starts to have a further rapid increase after the glass softening temperature of about 713 °C. Glass/Al₂O₃ composites can be sintered at 875 °C/15 min and exhibit better properties of a relative density of 98.4 %, a λ value of 2.89 W/mK, a ε _r value of 7.82 and a tan δ value of 5.3 × 10^?4. The interface between glass and Al₂O₃ grains and the interface between anorthite and glass phase depicts a good compatibility according to transmission electron microcopy test. It is the low sintering temperature, high density and good compatibility with Ag electrodes that, guarantee borosilicate glass/Al₂O₃ composites suitable for low temperature co-fired ceramic materials.     

Corrosion behaviour of amorphous Ni–Si thin films on AISI 304L stainless steel

Abstract

Nanoscale Ni – Si thin films are widely used in commercial microelectronic devices because of their promising electrical properties as well as their chemical stability. However, their application in corrosive environment has not been frequently addressed in the literature. In this study, amorphous Ni_0.66Si_0.33, Ni_0.40Si_0.60, and Ni_0.20Si_0.80 thin films are prepared on AISI 304L stainless steel by means of ion-beam sputter (IBS) deposition and their corrosion behaviour is studied using potentiodynamic polarisation measurements. The electrochemical measurements were conducted in 0.05M HCl solution at room temperature. By means of optical interferometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the surface morphology and chemical composition of the thin films were examined before and after the electrochemical measurement. The evaluated results showed that the Ni–Si thin films may exhibit improved corrosion resistance over the 304L substrate provided that Si content is high enough to facilitate the formation of a Si-rich passive film.     

Pyrolytic-grown B–C–N and BN nanotubes

We report the growth of pyrolytic boron–carbon–nitrogen (B–C–N) nanotubes on iron (Fe) and nickel (Ni) catalysts. It was discovered that different catalysts had effect on the elemental compositions of B–C–N nanotubes, which may allow one to tune the transport properties of B–C–N nanotubes in a wide range. A new synthetic route was also developed to generate H₃N:BH₃ as the precursor and yield boron nitride (BN) nanotubes by pyrolysis. The typical growth scenario of multi-wall BN tubes will be discussed.     

Pyrolytic-grown B–C–N and BN nanotubes

We report the growth of pyrolytic boron–carbon–nitrogen (B–C–N) nanotubes on iron (Fe) and nickel (Ni) catalysts. It was discovered that different catalysts had effect on the elemental compositions of B–C–N nanotubes, which may allow one to tune the transport properties of B–C–N nanotubes in a wide range. A new synthetic route was also developed to generate H₃N:BH₃ as the precursor and yield boron nitride (BN) nanotubes by pyrolysis. The typical growth scenario of multi-wall BN tubes will be discussed.     

Phase composition,structure, and mechanical properties of arc PVD Mo–Si–Al and Mo–Si–Al–N coatings

Using an arc physical vapor deposition process, we have produced nanostructured Mo–Si–Al coatings with a uniform distribution of equiaxed grains 8–12 nm in size and Mo–Si–Al–N coatings with a multilayer structure and a modulation period from 22 to 25 nm. The former coatings consist of MoSi₂ and Mo and the latter consist of Mo2N and amorphous Si₃N₄ and AlN. The hardness of the Mo–Si–Al–N and Mo–Si–Al coatings is 41 and 18 GPa, respectively; they are similar in resistance to elastic deformation; and the Mo–Si–Al–N coating has a considerably higher resistance to plastic deformation. The coatings have roughly identical coefficients of friction (~0.67–0.69 at 20°C and ~0.52–0.56 at 550°C), but the wear resistance of the Mo–Si–Al–N coating is higher by three and two orders of magnitude at 20 and 550°C, respectively. The coatings of the two systems exhibit good adhesion to the substrate and cohesive fracture. Partial wear of the Mo–Si–Al and Mo–Si–Al–N coatings in the course of scratch testing occurs at indentation loads of 80 and 63 N, respectively.     

Hydrothermal synthesis of Zn-doped Ni–Mn–Al–O thin films toward high-performance negative temperature coefficient thermistor

In this study, Zn-doped Ni–Mn–Al–O negative temperature coefficient thermistor (NTC) film with high electrical performance has been demonstrated. XRD, XPS, SEM and electrical measurements were carried out to explore the impact of Zn-doping. The XRD analysis of NiMn_1.8?xAl_0.2Zn_xO₄ films confirmed the cubic spinel crystal phase regardless of x. The SEM image illustrated that the morphology of NiMn_1.8?xAl_0.2Zn_xO₄ is closely related to the Zn doping amount. The XPS showed that the relative molar content of Mn³⁺ and Mn⁴⁺ increased with the increase of Zn doping concentration. Remarkably, the Zn-doped Ni–Mn–Al–O film presented the typical NTC characteristics, and the room temperature resistance (R₂₅) increased with the improvement in Zn doping concentration. Moreover, the thermistor constant B_25/50 remained reasonably high from 4088 to 4272 K. Meanwhile, the aging test showed that the Zn-doped films were more stable, even aging at 150 °C for 500 h.     

Microstructure and mechanical properties of nanolayered W/W–C thin films

The present study reports on the mechanical and structural properties of W/W–C multilayered thin films with bilayer periods Λ ranging from 2.5 to 100 nm. Films were grown by reactive sputtering radio frequency on Si (100) substrate. X-ray diffraction (XRD), grazing incidence X-ray diffraction (GIXRD) and X-ray reflectivity were used to globally characterise the multilayers structure. Hardness and Young modulus have been determined using nanoindentation with a Berkovich tip. The XRD and the GIXRD diagrams revealed the presence of three phases: WC_1−x randomly oriented, W₂C with (100) preferred orientation and W with (110) preferred orientation. An increase in hardness is observed with decreasing period Λ, reaching a maximum value of ~26 GPa at Λ = 2.5 nm.     

Effect of Al and C on structure and mechanical properties of Fe–Al–C alloys

Abstract

Effect of aluminium and carbon content on the microstructure and mechanical properties of Fe–Al–C alloys has been investigated. Alloys were prepared by combination of air induction melting with flux cover (AIMFC) and electroslag remelting (ESR). The ESR ingots were hot forged and hot rolled at 1373 K. As rolled alloys were examined using optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to understand the microstructure of these alloys. The ternary Fe–Al–C alloys containing 10·5 and 13 wt-%Al showed the presence of three phases: FeAl with disordered bcc structure, Fe₃Al with ordered DO₃ structure and Fe₃AlC_0·5 precipitates with L′1₂ structure. Addition of high concentration of carbon to these alloys resulted in excellent hot workability and superior tensile at room temperature as well as tensile and creep properties at 873 K. An increase in Al content from 9 to 13 wt-% in Fe–Al–C alloys containing the same levels of carbon has no significant influence on strength and creep properties at 873 K, however resulted in significant improvement in room temperature strength accompanied by a reduction in room temperature ductility.