Transition between amorphous and crystalline phases of SiC deposited on Si substrate using H3SiCH3

This paper presents a study of the transition between amorphous and crystalline phases of SiC films deposited on Si(1 0 0) substrate using H₃SiCH₃ as a single precursor by a conventional low-pressure chemical vapor deposition method in a hot-wall reactor. The microstructure of SiC, characterized by X-ray diffraction and high-resolution transmission electron microscopy, is found to vary with substrate temperature and H₃SiCH₃ pressure. The grain size decreases with increasing MS pressure at a given temperature and also decreases with reducing temperature at a given MS pressure. The deposition rates are exponentially dependent on the substrate temperature with the activation energy of around 2.6 eV. The hydrogen compositional concentration in the deposited SiC films, determined by secondary ion mass spectrometry depth profiling, is only 2.9% in the nanocrystalline SiC but more than 10% in the amorphous SiC, decreasing greatly with increasing deposition temperature. No hydride bonds are detected by Fourier transform infrared spectroscopy measurements. The chemical order of the deposited SiC films improves with increasing deposition temperature.     

Low-temperature RPCVD of Si,SiGe alloy,and Si1−yCy films on Si substrates using trisilane (Silcore)

Si homo-epitaxial growth by low-temperature reduced pressure chemical vapor deposition (RPCVD) using trisilane (Si₃H₈) has been investigated. The CVD growth of Si films from trisilane and silane on Si substrates are compared at temperatures between 500 and 950 °C. It is demonstrated that trisilane efficiency increases versus silane's one as the surface temperature decreases. Si epilayers from trisilane, with low surface roughness, are achieved at 600 and 550 °C with a growth rate equal to 12.4 and 4.3 nm min⁻¹, respectively. It is also shown that Si_1−xGe_x layers can be deposited using trisilane chemistry.     

Nucleation and grain growth in as deposited and ion implanted GeTe thin films

The crystallization dynamic of amorphous GeTe 50 nm thick films deposited on a SiO₂/Si substrate by RF magnetron sputtering, either ion implanted by Ge⁺ ions or not, has been analyzed in situ by optical microscopy during annealing in the 143-155 °C temperature range. Raman spectroscopy has been also performed in as deposited, ion implanted (i.i.) and melt quenched (m.q.) amorphous samples to compare the local order among the different amorphous structure. Nucleation and growth rates, for i.i. and as deposited samples, have been observed and directly compared by optical microscopy in a region of about 5 × 10⁴ μm². From these data, the activation energy and pre-exponential terms of each process have been calculated. The nucleation rate and growth velocity of the i.i. films increased by a factor thirteen and a factor three with respect to the as deposited samples. This evidence, in agreement with Raman spectroscopy data, suggests that implantation, providing kinetic energy by collision cascade, induces a local atomic rearrangement towards more relaxed amorphous states. As a result the crystallization kinetic is enhanced by the reduction of wrong bonds formed during sputter deposition, a process which occurs far from equilibrium conditions.     

Electrical, structural and optical properties of SnO2 thin films prepared by spray pyrolysis

This study investigated the effect of the substrate temperature on the structural, optical, morphological, and electrical properties of undoped SnO₂ films prepared by a spray deposition method. The films were deposited at various substrate temperatures ranging from 300-500 °C in steps of 50 °C and characterized by different optical and structural techniques. X-ray diffraction studies showed that the crystallite size and preferential growth directions of the films were dependent on the substrate temperature. These studies also indicated that the films were amorphous at 300 °C and polycrystalline at the other substrate temperatures used. Infrared and visible spectroscopic studies revealed that a strong vibration band, characteristic of the SnO₂ stretching mode, was present around 630 cm⁻¹ and that the optical transmittance in the visible region varied over the range 75-95% with substrate temperature, respectively. The films deposited at 400 °C exhibited the highest electrical conductivity property.     

Low temperature Si homo-epitaxy by reduced pressure chemical vapor deposition using dichlorosilane,silane and trisilane

Dichlorosilane (DCS), silane and trisilane have been investigated as Si precursors for low temperature (<700 °C) Si reduced pressure chemical vapor deposition. DCS and silane are limited to growth temperatures higher than 600–650 and 500 °C, respectively. At lower temperatures, absence of either Cl or H desorption from the surface impedes Si growth with acceptable growth rate (>5 Å/min). Trisilane permits the growth of Si at lower temperatures below 350 °C due to a specific growth mechanism enhancing H desorption. Layers grown at temperatures lower than 500 °C are defective, irrespective of the carrier gas, pressure and precursor flow used.     

Influence of annealing condition on the properties of sputtered hafnium oxide

Hafnium oxide thin films were deposited on p-type (1 0 0) silicon wafers by reactive dc magnetron sputtering. Prior to the deposition of HfO₂ films, a thin Hf film was deposited. Sputtered HfO₂ thin films deposited at room temperature remain amorphous at T<650°C and orthorhombic phases were observed above 650 °C. The monoclinic phase which is a stable HfO₂ polymorphic form appeared after annealing above 800 °C. Capacitance equivalent thickness values decreased and leakage characteristics are improved by the Hf interlayer and O₂ settlement process. The decrease of accumulation capacitance values upon annealing is due to the growth of an interfacial layer upon post-annealing. The flat band voltage (V_FB) shifts negatively due to positive charge generated during post-annealing.     

Nanocrystalline TiO2 films studied by optical, XRD and FTIR spectroscopy

We report the deposition of thin titanium dioxide films on Si(1 0 0) and silica glass at low temperatures between 200 and 350 °C by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) with 222 nm radiation. The composition and optical properties of the films deposited have been studied using a variety of standard characterisation methods. A strong absorption peak around 438 cm⁻¹, corresponding to Ti-O stretching vibration, was observed by Fourier transform infrared spectroscopy for different deposition temperatures. Nanostructured films on Si wafers were observed by atomic force microscopy while X-ray diffraction results showed that crystalline TiO₂ layers could be formed at deposition temperatures as low as 210 °C. The deposition kinetics and influence of the substrate temperature on the film are discussed. The activation energy for this photo-CVD process at temperatures between 200 and 350 °C was found to be 0.435 eV. This is much lower than the value (E_a=5.64 eV) obtained by conventional thermal CVD. The thicknesses of the films grown, from several nanometers to micrometers can be accurately controlled by changing the number of drops introduced by the injection liquid source. Under optimum deposition conditions, refractive index values as high as 2.5 and optical transmittance of between 85% and 90% in the visible region of the spectrum can be obtained.     

1H-1,2,3-triazole,a promising precursor for chemical vapor deposition of hydrogenated carbon nitride

Well-crystallized hydrogenated carbon nitride thin films have been prepared by microwave plasma enhanced chemical vapor deposition (MWPECVD). 1H-1,2,3-triazole+N₂ and Si (1 0 0) were used as precursor and substrate, respectively. Substrate temperature during the deposition was recorded to be 850 °C. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photo-electron spectroscopy (XPS) analyses. The plasma compositions were checked by optical emission spectroscopy (OES). XRD observation strongly suggests that the films contain polycrystalline carbon nitride with graphitic structure of (1 0 0), (0 0 2), (2 0 0) and (0 0 4). XPS peak quantification reveals that the atomic ratio of the materials C:N:O:Si is 32:41:18:9. X-ray photo-electron peak deconvolution shows that the most dominant peak of C (1s) and N (1s) narrow scans correspond to sp² hybrid structure of C₃N₄. These observations indicate that 1H-1,2,3-triazole favors the formation of hydrogenated carbon nitride with graphitic phase by CVD method and thus is in good agreement with XRD results. SEM of surface and OES of plasma also support the formation of polycrystalline carbon nitride films from 1H-1,2,3-triazole+N₂ by CVD.     

Annealing effects of highly homogeneous a-Si1−xCx:H

We report the effect of annealing on the properties of amorphous hydrogenated silicon carbide thin films. The samples were deposited onto different substrates by plasma enhanced chemical vapor deposition at temperatures between 300 and 350 °C. The gaseous mixture was formed by silane and methane, at the ‘silane starving plasma regime’, and diluted with hydrogen. Rutherford backscattering and Fourier transform infrared spectrometry were used, respectively, to determine the atomic composition and chemical bonds of the samples. The film’s structure was analyzed by means of X-ray absorption fine structure and X-ray diffraction. For temperatures higher than 600 °C, amorphous silicon carbide films annealed under inert atmosphere (Ar or N₂) clearly changed their structural and compositional properties due to carbon loss and oxidation, caused by the presence of some oxygen in the annealing system. At 1000 °C, crystallization of the films becomes evident but only stoichiometric films deposited on single crystalline Si[1 0 0] substrates presented epitaxial formation of SiC crystals, showing that the crystallization process is substrate dependent. Films annealed in high-vacuum also changed their structural properties for annealing temperatures higher than 600 °C, but no traces of oxidation were observed or variations in their silicon or carbon content. At 1200 °C the stoichiometric films are fully polycrystalline, showing the existence of only a SiC phase. The XANES signal of samples deposited onto different substrates and annealed under high-vacuum also show that crystallization is highly substrate dependent.     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

Dielectric properties of Zr-Sn-Ti-O thin films prepared by pulsed laser deposition

Zr_0.26Sn_0.23Ti_0.51O₂ (ZSTO) films with a dielectric constant of about 40 have been prepared directly on silicon substrates by pulsed laser deposition at 600 °C. TEM observation showed that the as-deposited films are amorphous. Differential thermal analysis showed that the ZSTO films crystallize at about 620 °C. Capacitance-voltage (C-V) characteristics of metal-oxide-semiconductor (MOS) composed of Pt/ZSTO/Si prepared at different deposition temperature have been measured. The EOT of the MOS structures with the same ZSTO physical thickness increased slightly when the deposition temperature increased. The EOT is about 4.2 nm for the 40 nm ZSTO deposited at 600 °C. The leakage current characteristics of ZSTO films for the as deposited, post-annealed in oxygen ambient and post-annealed in nitrogen ambient by rapid thermal annealing have been studied comparatively. The films post-annealed in nitrogen ambient have the lowest leakage current and the as-deposited films have the largest leakage current characteristics. It is proposed that amorphous Zr-Sn-Ti oxide stabilized at 600 °C is a potential dielectric material for dynamic random access memory and high k dielectric gate applications.     

Growth kinetics of SiGe/Si superlattices on bulk and silicon-on-insulator substrates for multi-channel devices

We have studied in reduced pressure chemical vapor deposition the growth kinetics of Si and Si_0.8Ge_0.2 on bulk Si(0 0 1) and on silicon-on-insulator (145 nm buried oxide/20 nm Si over-layer) substrates. For this, we have grown at 650 °C, 20 Torr 19 periods (Si_0.8Ge_0.2 19 nm/Si 32 nm) superlattices on both types of substrates that we have studied in secondary ion mass spectrometry, X-ray diffraction and cross-sectional transmission electron microscopy. The Si and SiGe growth rates together with the Ge content are steady on bulk Si(0 0 1), with mean values around 9.5 nm min⁻¹ and 20.2%, respectively. In contrast, growth rates decrease from ∼9.5 nm min⁻¹ down to values around 7.0 nm min⁻¹ (SiGe) and 6.3 nm min⁻¹ (Si), when the deposited thickness on SOI increases from 0 up to slightly more than 100 nm. They then go back up to values around 8.8–9.0 nm min⁻¹ as the thickness increases from 100 up to 400 nm. They then slowly decrease to values around 8.4–8.6 nm min⁻¹ as the thickness increases from 400 up to 800 nm. The Ge concentration follows on SOI exactly the opposite trend: an increase from 19.9% (0 nm) up to 20.6% (∼100 nm) followed by a decrease to values around 20.1% (400 nm) then a slow re-increase up to 20.4% (800 nm). These fluctuations are most likely due to the following SOI surface temperature variations: from 650 °C down to 638 °C (100 nm), back up to 648 °C (400 nm) followed by a slow decrease to 646 °C (800 nm). These data curves will be most useful to grow on conventional SOI substrates large number of periods, regular Si/Si_0.8Ge_0.2 superlattices that will serve as the core of multi-channel or three-dimensional nano-wires field effect transistors.     

Influence of metal organic and inorganic precursors on spray pyrolyzed ceramic MgO (2 0 0) thin films for epitaxial over layers

The MgO (2 0 0) surface is widely used as a substrate for epitaxial growth of superconducting and ferro-electric films. Highly oriented, single crystalline, extremely flat and transparent MgO films have been successfully deposited on quartz substrates by the chemical spray pyrolysis technique using economically viable metal organic and inorganic precursors under optimized conditions at the substrate temperature of 600 °C. Thermal analysis (TGA/DTA) in the temperature range 30-600 °C with the heating rate of 10 °C/min revealed the decomposition behavior of the precursors and confirmed the suitable substrate temperature range for film processing. The heat of reaction, ΔH due to decomposition of metal organic precursor contributed additional heat energy to the substrate for better crystallization. The intensity of the (2 0 0) peak in X-ray diffraction (XRD) measurements and the smooth surface profiles revealed the dependency of precursor on film formation. The compositional purity and the metal-oxide bond formation were tested for all the films. UV-Vis-NIR optical absorption in the 200-1500 nm range revealed an optical transmittance above 80% and the absorption edge at about 238 nm corresponding to an optical band gap E_g = 5.25 eV. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) micrographs of MgO films confirmed better crystallinity with larger grain size (0.85 μm) and reduced surface roughness (26 nm), respectively.     

Structural,electrical and optical properties of SnO2 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

SnO₂ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates at different substrate temperatures (500–800 °C) by metalorganic chemical vapor deposition (MOCVD). Structural, electrical and optical properties of the films have been investigated. The films deposited at 500 and 600 °C are epitaxial SnO₂ films with orthorhombic columbite structure, and the HRTEM analysis shows a clear epitaxial relationship of columbite SnO₂(1 0 0)||YSZ(1 0 0). The films deposited at 700 and 800 °C have mixed-phase structures of rutile and columbite SnO₂. The carrier concentration of the films is in the range from 1.15×10¹⁹ to 2.68×10¹⁹ cm⁻³, and the resistivity is from 2.48×10⁻² to 1.16×10⁻² Ω cm. The absolute average transmittance of the films in the visible range exceeds 90%. The band gap of the obtained SnO₂ films is about 3.75–3.87 eV.     

Low-temperature deposition of crystalline silicon nitride nanoparticles by hot-wire chemical vapor deposition

The nanocrystalline alpha silicon nitride (α-Si₃N₄) was deposited on a silicon substrate by hot-wire chemical vapor deposition at the substrate temperature of 700 °C under 4 and 40 Torr at the wire temperatures of 1430 and 1730 °C, with a gas mixture of SiH₄ and NH₃. The size and density of crystalline nanoparticles on the substrate increased with increasing wire temperature. With increasing reactor pressure, the crystallinity of α-Si₃N₄ nanoparticles increased, but the deposition rate decreased.     

Systematic study of various stages during the growth process of diamond-like carbon film by atomic force microscopy

The diamond like carbon (DLC) films have been grown by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) in methane-argon plasma. In PECVD, the plasma sheath potential drop arising due to argon plasma was utilized to grow the DLC film on silicon (100) substrate at low temperature without using any external negative bias voltage. The growth process of the DLC film has been studied completely starting from nucleation to continuous film by atomic force microscopy. It was seen that the DLC film nucleates around surface defects on the substrate and that the film growth occurs by both adatom deposition and coalescence between nucleated islands. Raman spectrum confirms that the DLC film nucleates excessively in sp² hybridized state and that during the growth process the fraction of sp³ CH_x (x = 1 − 3) increases which leads to the amorphous nature of the film. Long range uniformity of the film was identified using scanning electron microscope.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

Growth and characterization of epitaxial Fe0.8Ga0.2/0.69PMN-0.31PT heterostructures

Fe_0.8Ga_0.2 films were deposited on bulk single-crystal (0 0 1) 0.69PMN-0.31PT substrates by DC magnetron sputtering to make magnetoelectric bilayer composites. Films deposited at temperatures below 600 °C were X-ray amorphous. Films deposited at temperatures of 600 °C and higher exhibited a single-crystal (0 0 1) disordered BCC structure. The crystalline FeGa films demonstrate a 45° twisted cube-on-cube epitaxial relationship with the PMN–PT substrates. Heterostructures with an X-ray amorphous FeGa film exhibited zero magnetoelectric response. Heterostructures with a 990 nm epitaxial FeGa film exhibited a large inverse magnetoelectric voltage coefficient of 13.4 (G cm)/V.     

Growth of GaN films on PLD-deposited TaC substrates

GaN films were grown by metal organic chemical vapor deposition on TaC substrates that were created by pulsed laser deposition of TaC onto (0 0 0 1) SiC substrates at ∼1000 °C. This was done to determine if good quality TaC films could be grown, and if good quality GaN films could be grown on this closely lattice matched to GaN, conductive material. This was done by depositing the TaC on on-axis and 3° or 8° off-axis (0 0 0 1) SiC at temperatures ranging from 950 to 1200 °C, and examining them using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The GaN films were grown on as-deposited TaC films, and films annealed at 1200, 1400, or 1600 °C, and examined using the same techniques. The TaC films were polycrystalline with a slight (1 1 1) texture, and the grains were ∼200 nm in diameter. Films grown on-axis were found to be of higher quality than those grown on off-axis substrates, but the latter could be improved to a comparable quality by annealing them at 1200–1600 °C for 30 min. TaC films deposited at temperatures above 1000 °C were found to react with the SiC. GaN films could be deposited onto the TaC when the surface was nitrided with NH₃ for 3 min at 1100 °C and the low temperature buffer layer was AlN. However, the GaN did not nucleate easily on the TaC film, and the crystallites did not have the desired (0 0 0 1) preferred orientation. They were ∼10 times larger than those typically seen in films grown on SiC or sapphire. Also the etch pit concentration in the GaN films grown on the TaC was more than 2 orders of magnitude less than it was for growth on the SiC.