Film growth mechanism of photo-chemical vapor deposition

The photo-chemical vapor deposition (CVD) of SiO₂ and SiN _x were investigated using 185 nm light of a low pressure mercury lamp. The film thickness deposited on the substrate was the function of the distance from the substrate to the light source and its relation was investigated by changing the reaction pressure. From these investigations, the space migration length of the active species was estimated, which was, at the processing pressure of 400 Pa, 10–20 mm. This migration length was confirmed by a model calculation. The step coverage of the film was investigated by the use of a two-dimensional capillary cavity. It was shown that the thickness decayed exponentially with the depth in the cavity. The decay constant did not show temperature dependence. From this result, the surface migration of the active species produced by photo-CVD was reported. To confirm this migration we presented a substrate-size effect of photo-CVD, which became obvious when the substrate size became smaller than the space migration length of the active species. From these results, the film growth mechanism of photo-CVD was discussed.Main parts of this paper were presented at the Material Research Society Fall Meeting at Boston 1987     

The properties of boron carbide/silicon heterojunction diodes fabricated by Plasma-Enhanced Chemical Vapor Deposition

p-n heterojunction diodes have been fabricated from boron carbide (B_1–x C _x ) and n-type Si(111). Boron carbide thin films were deposited on Si(111) using Plasma-Enhanced Chemical Vapor Deposition (PECVD) from nido-pentaborane (B₅H₉) and methane (CH₄). Composition of boron carbide thin films was controlled by changing the relative partial pressure ratio between nido-pentaborane and methane. The properties of the diodes were strongly affected by the composition and thickness of boron carbide layer and operation temperatures. Boron carbide/silicon heterojunction diodes show rectifying properties at temperatures below 300° C. The temperature dependence of reverse current is strongly dependent upon the energy of the band gap of the boron carbide films.     

LCVD of copper: Deposition rates and deposit shapes

Laser chemical vapor deposition of copper has been performed under a variety of conditions. The results are interpreted using the kinetic model of Ehrlich and Tsao. We find that the kinetics of the process are limited by the rates of surface reactions and not by diffusion of reactant molecules to the surface. Furthermore, we find that deposit shapes are quite sensitive to laser intensity and scan rate.     

Synchrotron-radiation-induced deposition of boron and boron carbide films from boranes and carboranes II: Nido-2,3-diethyl-2,3-dicarbahexaborane

Boron-carbon thin films have been successfully deposited on Si (111) from the synchrotron radiation induced decomposition of the nido-2,3-diethyl-dicarbahexaborane, (CH₃CH₂)₂C₂B₄H₆. There are indications that molecular precursor states to complete dissociation exist, and that dissociation is the rate limiting step. As with deposition of boron from decaborane, there is an activation barrier to dissociation of diethylcarborane on Si (111). The composition of the growing film, as determined by the boron to carbon ratio, is strongly dependent upon the boron concentration at the surface of the substrate. The boron concentration of the film increases with increasing film thickness.Part one appeared in [1]     

Bistable growth in laser chemical vapor deposition

This is the first report on the observation of a bistability in laser-CVD. The effect is demonstrated for silicon deposition from silane by means of Ar⁺-laser radiation.     

Selective vapor phase etching of SiGe by HCl in a RPCVD reactor

Chemical vapor phase etching of epitaxial SiGe by HCl was investigated using a single wafer reduced pressure CVD (RPCVD) system. For the sample preparation, patterning and dry etching were performed on the Si substrate with SiGe buried layers to open the sidewalls of the buried SiGe layers. The etchrate of the lateral direction was measured. The etchrate of SiGe is increasing with increasing SiGe thickness saturating at SiGe thicknesses higher than ∼25 nm. This result could be caused by diffusion effects of molecules in the narrow trenches during the etching. At the same SiGe thickness, the etchrate of SiGe is increasing with increasing etching temperature. B doping does not affect the etchrate of SiGe. P doping is increasing and C doping is decreasing the etchrate. Facet formation of the etchfront of Si and SiGe depends on initial surface orientation. These results enable improved process controllability of the etching process using doped layers for different applications.     

Direct writing of gold lines by laser-induced chemical vapor deposition

Stripes of gold metal were deposited by focussing an Ar⁺ laser (514nm) onto glass substrates in a heated vacuum cell containing the evaporator and the precursor. MeAuPMe₃, Me₃AuPR₃ (R = Me,Et) were used as precursors. Using MeAuPMe₃ or Me₃AuPEt₃, deposits of high quality were obtained above 40° C and 60° C evaporator temperature, respectively. With Me₃AuPMe₃ the same deposits of gold stripes were possible near room temperature. The stripes were characterized by scanning profilometry, electrical resistivity, SEM and SAM measurements. In general, the stripe resistivity was between 1.5 and 7 times of the bulk metal.     

Thin strain-relaxed SiGe grown by ultrahigh vacuum chemical vapor deposition

Large-scale preparation of thin strain-relaxed SiGe is achieved by combining ion implantation and ultrahigh vacuum chemical vapor deposition. The resulting materials were analyzed by double crystal X-ray diffraction, micro-Raman spectroscopy, and tapping mode atomic force microscope. Results revealed that 100-nm-thick Si_0.7Ge_0.3 layers with the diameter of 125 mm and full strain relaxation are successfully prepared by pre-modifying the Si substrates using 50 keV Ar⁺ ions. The strain relaxation is also disclosed to change with both ion species and energy. However, post-modification of SiGe by ion implantation will cause serious damage to the crystal structures, and result in the formation of poly-crystal SiGe.     

Effect of Al incorporation on the AlGaN growth by metalorganic chemical vapor deposition

The effect of Al incorporation on the AlGaN growth by metalorganic chemical vapor deposition is investigated. With the increase of trimethylalluminum (TMAl) flux, the crystal quality becomes worse, and the epilayer surface becomes rougher. An interesting phenomenon is that the growth rate of AlGaN decrease with increasing TMAl flux, which is opposite to the AlN growth rate dependence on the TMAl flux. All these effects are attributed to the different properties of Al atoms due to the higher bond strength of Al-N compared with Ga-N, which lead to lower surface mobility and stronger competitive ability of Al atoms during the growth. The enhancement of the surface mobility of Al is especially important for improving the quality of AlGaN.     

New types of periodic structures in laser-induced chemical vapor deposition

New types of periodic structures that occur in laser-induced chemical vapor deposition have been investigated, mainly for polycrystalline Si deposited on glass substrates covered with a thin amorphous Si layer. These periodic structures, which are believed to be a general phenomenon in pyrolytic laser-induced processing, limit the resolution obtainable in direct writing of patterns.On leave from Fudan University, Department of Electronic Engineering, Shanghai, People's Republic of China     

Deposition of thin rhodium films by plasma-enhanced chemical vapor deposition

Thin films of rhodium have been prepared starting from dicarbonyl-2.4-pentadionato-rhodium(I), Rh(CO)₂C₅H₇O₂, by plasma enhanced CVD. The dependence of the deposition rate and film properties on substrate temperature, partial pressure of the organometallic and on hydrogen has been studied. Metal contents of 100% and thin-film resistivities as low as 5 times the bulk resistivity of rhodium have been achieved.     

Process characterization and mechanism for laser-induced chemical vapor deposition of a-Si : H from SiH4

The dependence of a-SiH film deposition by laser-induced decomposition of SiH₄ on the different process variables is studied. The gas phase temperature in the beam center, produced by CO₂ laser irradiation in parallel configuration, is estimated using a simple energy balance model. The surface temperature is measured with high accuracy employing a Ni sensor (250°–400 °C). The deposition rate and film properties such as the hydrogen content and the optical energy gap are determined as a function of these parameters. The production of H₂ (10%), Si₂H₆ (2%), and Si₃H₈ in the gas phase during laser irradiation is proved by a mass spectrometric analysis. The chemical reaction processes induced in the gas phase and at the surface are discussed. A mechanism explaining the main features of the complicated chemistry involved is developed.     

Chemical vapor deposition of diamond

In the recent decade a multitude of diamond thin film production methods has been developed, generally based on chemical vapor deposition processes from thermally or plasma activated gas phases. Diagnostic studies, growth experiments and numerical kinetic investigations have in recent years lead to an improved understanding of the prerequisites of continuous diamond growth and of the chemical processes involved. While the mechanism of carbon incorporation into the diamond surface is not yet known completely, the gas-phase species which are essential in a diamond-growth atmosphere can be narrowed to a small number, whose role in the gas-phase chemistry is quite well known.     

Growth of vertically aligned carbon-nanotube array on large area of quartz plates by chemical vapor deposition

A simple method has been developed for growth of well-aligned carbon nanotubes (CNTs) on nickel-film quartz plates by chemical vapor deposition (CVD) with organic ethylenediamine as a precursor. High-density carbon nanotubes were vertically aligned on a large area of the quartz plates. The height of the nanotube array could be controlled by varying the CVD time. High-resolution transmission electron microscopy analysis revealed that the multiwalled CNTs were composed of crystalline graphitic sheets with a bamboo structure. Received: 28 May 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Room temperature electroluminescence from ZnO/Si heterojunction devices grown by metal-organic chemical vapor deposition

Heterojunction light-emitting diodes with ZnO/Si structure were fabricated on both high-resistivity (p) and low-resistivity (p⁺) Si substrates by metal-organic chemical vapor deposition technology. Fairly good rectifications were observed from the current-voltage curves of both heterojunctions. Ultraviolet (UV) and blue-white electroluminescence (EL) from ZnO layer were observed only from ZnO/p⁺-Si heterojunction under forward bias at room temperature (RT), while strong infrared (IR) EL emissions from Si substrates were detected from both ZnO/p-Si and ZnO/p⁺-Si heterojunctions. The UV and IR EL mechanisms have been explained by energy band structures. The realization of RT EL in UV-visible and IR region on Si substrate has great applicable potential for Si-based optoelectronic integrated circuits.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

(001) textured PbTiO3 thin films grown on redopingn-Si by metalorganic chemical vapor deposition under reduced pressure

(001) textured PbTiO₃ thin films have been deposited on (001) redopingn-Si substrates by metalorgnic chemical vapor deposition (MOCVD) under reduced pressure, and the film ferroelectricity has been measured using the substrate as bottom electrode directly. Besides this investigation, a set of analysis including AFM surface morphology, SEM cross section morphology, electron-probe element analysis, XRD 0-20 scan and high temperature X-ray diffraction have been carried out to study the microstructure and phase transition process of the PbTiO₃ thin film.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

Doping properties of microcrystalline silicon prepared by mercury sensitized photochemical vapor deposition

Conductivity of photo-CVD microcrystalline silicon (c-Si:H) in wide range of dopant gas concentration (10^–53/SiH₄, B₂H₆/SiH₄<10^–2) is investigated. As compared with a-Si:H, the conductivity of the film is improved more than two orders of magnitude by microcrystallization for a wide range of dopant concentration at a deposition temperature of as low as 150°C. This indicates the suitability of photo-CVD for low temperature processing. A conductivity minimum is found at a doping ratio of about B₂H₆/SiH₄=1×10^–5.     

Effect of temperature on growth and structure of carbon nanotubes by chemical vapor deposition

The effect of temperature on growth and structure of carbon nanotubes (NTs) using chemical vapor deposition (CVD) has been investigated. Iron embedded silica was used to grow NTs in large quantity at various temperatures from 600 to 1050 °C with gas pressure fixed at 0.6 and 760 Torr, respectively. The growth and structure of the NTs are strongly affected by the temperature. At low gas pressure, the NTs are completely hollow at low temperature and bamboo-like structure at high temperature. While at high gas pressure, all the NTs are bamboo-like structure regardless of temperature. The diameter of NTs increases significantly with temperature. At low gas pressure the diameter gets bigger by mainly increasing the number of graphene layers of the wall of NTs, whereas at high gas pressure the diameter gets bigger by increasing both the number of graphene layers of the wall and the inner diameter of the NTs. This result indicates that the growth temperature is crucial in synthesizing NTs with different structures. The findings here are important for realizing controlled growth of NTs for their applications in different fields. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 4 March 2002