Study of plasma enhanced chemical vapor deposition of ZnO films by non-thermal plasma jet at atmospheric pressure

Plasma enhanced chemical vapor deposition using a non-thermal plasma jet was applied to deposition of ZnO films. Using vaporized bis(octane-2,4-dionato)zinc flow crossed by the plasma jet, the deposition rate was as high as several tens of nm/s. From the results of infrared spectra, the films deposited at the substrate temperature T_sub = 100 °C contained a significant amount of carbon residue, while the films prepared at T_sub = 250 °C showed less carbon fraction. The experimental results confirmed that the plasma jet decomposed bis(octane-2,4-dionato)zinc in the gaseous phase and on the substrate, and that there should be the critical T_sub to form high-quality ZnO films in the range from 100 to 250 °C.     

Growth of silicon carbide thin films by hot-wire chemical vapor deposition from SiH4/CH4/H2

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition from SiH₄/CH₄/H₂ and their structural properties were investigated by X-ray diffraction, Fourier transform infrared absorption and Raman scattering spectroscopies. At 2 Torr, Si-crystallite-embedded amorphous SiC (a-Si_1 − xC_x:H) grew at filament temperatures (T_f) below 1600 °C and nanocrystalline cubic SiC (nc-3C-SiC:H) grew above T_f = 1700 °C. On the other hand, At 4 Torr, a-Si_1 − xC_x:H grew at T_f = 1400 °C and nc-3C-SiC grew above T_f = 1600 °C. When the intakes of Si and C atoms into the film per unit time are almost the same and H radicals with a high density are generated, which takes place at high T_f, nc-3C-SiC grows. On the other hand, at low T_f the intake of Si atoms is larger than that of C atoms and, consequently, Si-rich a-Si_1 − xC_x:H or Si-crystallite-embedded a-Si_1 − xC_x:H grow.     

Growth and characterization of tris(8-hydroxyquinoline)-aluminum molecular films

Various tris(8-hydroxyquinoline)-aluminum (Alq3) molecular solid films were grown on top of indium-tin-oxide (ITO) glass substrates using physical vapor deposition. The effect of changing the growth conditions on the properties of the films was studied. From scanning electron microscopy, an Alq3 planar layer over an ITO-substrate was observed at the initial period, and an Alq3 tubular structure (which becomes dominant at substrate temperature T_sub ≧ 90 °C) was found to nucleate from this layer. From X-ray diffraction, the Alq3 planar layer possesses an amorphous character while the Alq3 tubular layer has a triclinic α-phase structure. Based on an Arrhenius plot of the growth rate versus 1/T_sub, the growth behaviors in various T_sub-regions were discussed to be dominated by adhesion (for T_sub < 90 °C), steric effect (90 °C < T_sub < 150 °C), and re-evaporation (T_sub > 150 °C). Then, from optical transmission and photoluminescence spectra performed on the high crystalline Alq3 films, two signals associated with the optical-bandgap E_g absorption and the gap-state absorption were determined and discussed in terms of the optical properties of the constituent Alq3 molecules. Finally, from a fit of E_g(T) by an effective electron-phonon interaction model, the physical significance of these fitting parameters for the Alq3 molecular solid was investigated.     

Black SiC formation induced by Si overlayer deposition and subsequent plasma etching

Black SiC formation by plasma etching with SF₆/O₂ chemistry is reported. Black SiC was produced by depositing Si overlayer on SiC and then etching the Si/SiC stack sequentially, thus replicating the black Si morphology to SiC. Black SiC is obtained with almost zero reflectance over the wavelengths from 300 nm to 1050 nm. Thicker Si film was advantageous, and it was important to optimize the etch condition considering both the black Si morphology and the flattening effect of SiC.     

Growth of 3C-SiC on Si(111) using the four-step non-cooling process

A modified four-step method was applied to grow a 3C-SiC thin film of high quality on the off-axis 1.5° Si(111) substrate in a mixed gas of C₃H₈, SiH₄ and H₂ using low pressure chemical vapor deposition. The modified four-step method adds a diffusion step after the carburization step and removes the cooling from the traditional three-step method (clean, carburization, and growth). The X-ray intensity of the 3C-SiC(111) peak is enhanced from 5 × 10⁴ counts/s (the modified three steps) to 1.1 × 10⁵ counts/s (the modified four steps). The better crystal quality of 3C-SiC is confirmed by the X-ray rocking curves of 3C-SiC(111). 3C-SiC is epitaxially grown on Si(111) supported by the selected area electron diffraction patterns taken at the 3C-SiC/Si(111) interface. Some {111} stacking faults and twins appear inside the 3C-SiC, which may result from the stress induced in the 3C-SiC thin film due to lattice mismatch. The diffusion step plays roles in enhancing the formation of Si-C bonds and in reducing the void density at the 3C-SiC/Si(111) interface.     

Growth of 3C-SiC on 150-mm Si(100) substrates by alternating supply epitaxy at 1000 °C

To lower deposition temperature and reduce thermal mismatch induced stress, heteroepitaxial growth of single-crystalline 3C-SiC on 150 mm Si wafers was investigated at 1000 °C using alternating supply epitaxy. The growth was performed in a hot-wall low-pressure chemical vapor deposition reactor, with silane and acetylene being employed as precursors. To avoid contamination of Si substrate, the reactor was filled in with oxygen to grow silicon dioxide, and then this thin oxide layer was etched away by silane, followed by a carbonization step performed at 750 °C before the temperature was ramped up to 1000 °C to start the growth of SiC. Microstructure analyses demonstrated that single-crystalline 3C-SiC is epitaxially grown on Si substrate and the film quality is improved as thickness increases. The growth rate varied from 0.44 to 0.76 ± 0.02 nm/cycle by adjusting the supply volume of SiH₄ and C₂H₂. The thickness nonuniformity across wafer was controlled with ± 1%. For a prime grade 150 mm virgin Si(100) wafer, the bow increased from 2.1 to 3.1 μm after 960 nm SiC film was deposited. The SiC films are naturally n type conductivity as characterized by the hot-probe technique.     

Effect of hydrogen on the structure of high-rate deposited SiC on Si by atmospheric pressure plasma chemical vapor deposition using high-power-density condition

Using the atmospheric pressure plasma chemical vapor deposition (AP-PCVD) technique, SiC films were fabricated from the gas mixture of He, H₂, SiH₄ and CH₄ on silicon substrates. High-power-density condition was adopted to sufficiently activate the reactive gas molecules in the plasma. The structure, composition and crystallinity of the films were investigated as functions of the H₂ concentration in the gas mixture and substrate temperature. It was shown that increase in H₂ concentration in the plasma atmosphere reduced the growth temperature of polycrystalline SiC film. As a result, polycrystalline 3C-SiC film of which grain size was of the order of 10 nm could be grown at a substrate temperature of 820 K with a deposition rate of approximately 6.7 nm/s. It was suggested that atomic hydrogen generated with addition of H₂ in the gas mixture considerably affects not only the reaction process at the film-growing surface but also the form of precursors in the atmospheric pressure plasma. The results indicated the possibility of realizing the columnar growth of large 3C-SiC grains on Si substrate when the H₂ concentration and the VHF power were simultaneously increased in the AP-PCVD process.     

Effects of plasma treatments on structural and electrical properties of methyl-doped silicon oxide low dielectric constant film

In this article, a methyl-doped silicon oxide low k film for use in inter-level dielectric application has been characterized. The structural and electrical properties of films prepared by chemical vapor deposition before and after different etching and photo-resist stripping (PRS) plasma treatments were studied. Structural properties of the low k film with various extents of forming gas and O₂ plasma treatments were reflected by the contents of Si-CH₃ and Si-H bonds. Surface roughness of films with plasma treatments was closely linked to the ratios of the cage- and network-structures of Si-O. Electrical properties of plasma-treated films were dependent on the applications of both etching and PRS plasma chemistries. Forming gas PRS caused the least low k film structural change and electrical deterioration compared with O₂ treatment. Moreover, E_bd of films decreased significantly by CH₂F₂ versus C₄F₈ etch. The best electrical properties of the film was obtained with a leakage current density of < 1 × 10^− 8 A/cm² and a dielectric breakdown strength of ∼3.2 MV/cm after being subjected with C₄F₈ / N₂ / Ar trench etch and forming gas PRS treatment.     

AlGaN/GaN-heterostructures on (111) 3C-SiC/Si pseudo substrates for high frequency applications

We present the realization of high electron mobility transistors (HEMTs) based on AlGaN/GaN heterostructures, which were grown on silicon substrates using an ultrathin SiC transition layer. The growth of AlGaN/GaN heterostructures on 3C-SiC(111)/Si(111) was performed using metalorganic chemical vapour deposition (MOCVD). The 3C-SiC(111) transition layer was realized by low pressure CVD and prevented Ga-induced meltback etching and Si-outdiffusion in the subsequent MOCVD growth. The two-dimensional electron gas (2DEG) formed at the AlGaN/GaN interface showed an electron sheet density of 1.5 × 10¹³ cm^− 3 and a mobility of 870 cm²/Vs. The HEMTs DC and RF characteristics were analysed and showed a peak cut-off frequency as high as 29 GHz for a 250 nm gate length.     

Low-temperature epitaxy of silicon by electron beam evaporation

In this paper we report on homoepitaxial growth of thin Si films at substrate temperatures T_s = 500-650 °C under non-ultra-high vacuum conditions by using electron beam evaporation. Si films were grown at high deposition rates on monocrystalline Si wafers with (100), (110) and (111) orientations. The ultra-violet visible reflectance spectra of the films show a dependence on T_s and on the substrate orientation. To determine the structural quality of the films in more detail Secco etch experiments were carried out. No etch pits were found on the films grown on (100) oriented wafers. However, on films grown on (110) and (111) oriented wafers different types of etch pits could be detected. Films were also grown on polycrystalline silicon (poly-Si) seed layers prepared by an Aluminum-Induced Crystallisation (AIC) process on glass substrates. Electron Backscattering Diffraction (EBSD) shows that the film growth proceeds epitaxially on the grains of the seed layer. But a considerably higher density of extended defects is revealed by Secco etch experiments.     

Superconductivity in carrier-doped silicon carbide

Abstract

We report growth and characterization of heavily boron-doped 3C-SiC and 6H-SiC and Al-doped 3C-SiC. Both 3C-SiC:B and 6H-SiC:B reveal type-I superconductivity with a critical temperature T_c=1.5 K. On the other hand, Al-doped 3C-SiC (3C-SiC:Al) shows type-II superconductivity with T_c=1.4 K. Both SiC:Al and SiC:B exhibit zero resistivity and diamagnetic susceptibility below T_c with effective hole-carrier concentration n higher than 10²⁰ cm^?3. We interpret the different superconducting behavior in carrier-doped p-type semiconductors SiC:Al, SiC:B, Si:B and C:B in terms of the different ionization energies of their acceptors.     

Si-rich a-SiC:H thin films: Structural and optical transformations during thermal annealing

Amorphous hydrogenated silicon-rich silicon carbide (a-Si_0.8C_0.2:H) thin films were prepared by plasma enhanced chemical vapour deposition and were thermally annealed in a conventional resistance heated furnace at annealing temperatures up to 1100 °C. The annealing temperatures were varied and the samples were characterised with Auger electron spectroscopy, glancing incidence X-ray diffraction, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy. As-deposited a-Si_0.8C_0.2:H thin films contain a large amount of hydrogen and are amorphous. When annealing the films, the onset of Si crystallisation appears at 700 °C. For higher annealing temperatures, we observed SiC crystallites in addition to the Si nanocrystals (NCs). The crystallisation of SiC correlates with the occurrence of a strong PL band, which is strongly reduced after hydrogen passivation. Thus PL signal originates from the SiC matrix. Si NCs exhibit no PL yield due to their inhomogeneous size distribution.     

Structure and properties of ternary manganese nitride Mn3CuNy thin films fabricated by facing target magnetron sputtering

Deposition of Mn₃CuN_y thin films on single crystal Si (1 0 0) at various substrate temperatures (T_sub) by facing target magnetron sputtering is reported. The crystal structure and composition were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results confirmed that the crystalline antiperovskite Mn₃CuN_y thin film with (2 0 0) highly preferred texture had been obtained at T_sub = 180 °C. Furthermore, for the resulting Mn₃CuN_y thin film, it showed different properties compared with the bulk counterpart. There was a paramagnetic to ferrimagnetic transition at 225 K with decreasing temperature. The change of the lattice constant with temperature presented positive thermal expansion behavior and no structural transition was observed. The average linear thermal expansion coefficient (α) is 2.49 × 10⁻⁵ K⁻¹ from 123 K to 298 K. More interestingly, the temperature dependence of resistivity displayed a semiconductor-like behavior, i.e. an obvious monotonous decrease of resistivity with increasing temperature.     

Effect of thermal annealing on the structural and mechanical properties of amorphous silicon carbide films prepared by polymer-source chemical vapor deposition

We report on the effect of thermal annealing on the structural and mechanical properties of amorphous SiC thin films prepared by means of a polymer-source chemical vapor deposition process. The chemical bondings of the a-SiC:H films were systematically examined by means of Fourier transform infrared spectroscopy (FTIR). The film composition was measured by X-ray photoelectron spectroscopy, while X-ray reflectivity measurements were used to account for the film density variations caused by the post-annealing treatments over the 750-1200 °C range. In addition, their mechanical properties (hardness and Young's modulus) were investigated by using the nano-indentation technique. FTIR measurements revealed that not only the intensity of a-SiC absorption band linearly increases but also its position is found to shift to a higher wave number as a result of annealing. In addition, the bond density of Si―C is found to increase from (101.6-224.5) × 10²¹ bond·cm^− 3 accompanied by a decrease of Si―H bond density from (2.58-0.46)× 10²¹ bond·cm^− 3 as a result of increasing the annealing temperature (T_a) from 750 to 1200 °C. Annealing-induced film densification is confirmed, as the a-SiC film density is found to increase from 2.36 to ∼ 2.75 g/cm^− 3 when T_a is raised from 750 to 1200 °C. In addition, as T_a is increased from 750 to 1200 °C, both hardness and Young's modulus are found to increase from 15.5 to 17.6 GPa and 155 to 178 GPa, respectively. Our results confirm the previously established linear correlation between the mechanical properties of the a-SiC films and their bond densities.     

Deposition of new microcrystalline materials, μc-SiC, μc-GeC by HWCVD and solar cell applications

This paper describes at first the present status of solar cell efficiencies prepared by Hot Wire CVD (HW-CVD), and then preparation techniques of μc-3C(cubic)-SiC developed for innovative solar cell applications by using HW-CVD method are presented. For preparing μc-3C-SiC, monomethylsilane (MMS) and hydrogen were used for reactant gases. The high conductivity of 5 S/cm could be achieved for N doped n-type μc-3C-SiC. For p-type, as-grown Al-doped μc-3C-SiC films showed a relatively high resistivity, but on thermal annealing, the conductivity increased to the level of 1 × 10^− 2 S/cm. Monomethylgermane (MMG) and H₂ were used to prepare μc-GeC thin films. μc-GeC thin films with a carbon composition of about 7-8% showed a clear shift of absorption coefficient spectra by 0.44 eV, when compared to crystalline Ge. The pin solar cell structures in which all p,i,n layers consist of μc-SiC have been prepared for the first time. It was found that μc-3C-SiC and μc-GeC are the promising candidates as the next generation thin-film solar cell materials, but at present, the film quality is strictly limited by the residual impurity concentration of filament material Re.     

Growth of GaN on SiC/Si substrates using AlN buffer layer by hot-mesh CVD

GaN films were grown on SiC/Si (111) substrates by hot-mesh chemical vapor deposition (CVD) using ammonia (NH₃) and trimetylgallium (TMG) under low V/III source gas ratio (NH₃/TMG = 80). The SiC layer was grown by a carbonization process on the Si substrates using propane (C₃H₈). The AlN layer was deposited as a buffer layer using NH₃ and trimetylaluminum (TMA). GaN films were formed and grown by the reaction between NH_x radicals, generated on a tungsten hot mesh, and the TMG molecules. The GaN films with the AlN buffer layer showed better crystallinity and stronger near-band-edge emission compared to those without the AlN layer.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

HfO2 etching mechanism in inductively-coupled Cl2/Ar plasma

Etching characteristics and the mechanism of HfO₂ thin films in Cl₂/Ar inductively-coupled plasma were investigated. The etch rate of HfO₂ was measured as a function of the Cl₂/Ar mixing ratio in the range of 0 to 100% Ar at a fixed gas pressure (6 mTorr), input power (700 W), and bias power (300 W). We found that an increase in the Ar mixing ratio resulted in a monotonic decrease in the HfO₂ etch rate in the range of 10.3 to 0.7 nm/min while the etch rate of the photoresist increased from 152.1 to 375.0 nm/min for 0 to 100% Ar. To examine the etching mechanism of HfO₂ films, we combined plasma diagnostics using Langmuir probes and quadrupole mass spectrometry with global (zero-dimensional) plasma modeling. We found that the HfO₂ etching process was not controlled by ion-surface interaction kinetics and formally corresponds to the reaction rate-limited etch regime.     

Textured surface boron-doped ZnO transparent conductive oxides on polyethylene terephthalate substrates for Si-based thin film solar cells

Textured surface boron-doped zinc oxide (ZnO:B) thin films were directly grown via low pressure metal organic chemical vapor deposition (LP-MOCVD) on polyethylene terephthalate (PET) flexible substrates at low temperatures and high-efficiency flexible polymer silicon (Si) based thin film solar cells were obtained. High purity diethylzinc and water vapors were used as source materials, and diborane was used as an n-type dopant gas. P-i-n silicon layers were fabricated at ~ 398 K by plasma enhanced chemical vapor deposition. These textured surface ZnO:B thin films on PET substrates (PET/ZnO:B) exhibit rough pyramid-like morphology with high transparencies (T ~ 80%) and excellent electrical properties (Rs ~ 10 Ω at d ~ 1500 nm). Finally, the PET/ZnO:B thin films were applied in flexible p-i-n type silicon thin film solar cells (device structure: PET/ZnO:B/p-i-n a-Si:H/Al) with a high conversion efficiency of 6.32% (short-circuit current density J_SC = 10.62 mA/cm², open-circuit voltage V_OC = 0.93 V and fill factor = 64%).     

Microanalyses on the hydrogen permeated 70% SiCC films

SiCC films with content of 70% SiC were deposited by rf magnetron sputtering on stainless steel or NaCl substrate followed by argon ion bombardment. Samples were then submitted to hydrogen permeation at 3.23×10⁷ Pa and 500 K for 3 h. Secondary ion mass spectroscopy (SIMS) was used to analyze hydrogen concentration with depth and to check the formation of hydrogen related bonds in the SiCC films with IR measurement. Auger electron spectra (AES) and X-ray photoelectron spectra (XPS) were carried out to check the effects of hydrogen participation on shifts of chemical bonding states of C, Si and O contamination.