Rapid progresses are achieved in catalytic CVD (Cat-CVD), often called hot-wire CVD, in the past 3-years NEDO national project in Japan. Cat-CVD technology presents many advantages in thin-film formation processes; high-efficiency of gas use, large-area deposition, no ion bombardment and low-temperature deposition even below 200°C. All of the elemental techniques for the industrially applicable Cat-CVD apparatuses, such as the suppression of the metal contamination, the precise control of the substrate temperature, the life extension of the catalyzer, 1-m size uniform deposition and the chamber cleaning, have been completely developed. Sophisticatedly designed substrate holder with electrostatic chuck and showerhead equipped with catalyzers are both key technologies for these achievements. High reproducibility for film properties is also obtained by controlling the reaction between high-density radicals and chamber walls. Prototype mass-production apparatus for SiNx passivation films in GaAs devices has been already developed and this will be probably the first application of Cat-CVD in industry. These recent movements appear to promise the drastic revolution in semiconductor and flat-panel display industries by introducing Cat-CVD in very near future.

Large grain-size polycrystalline Si (poly-Si) films are obtained on glass substrate by newly developed catalytic chemical sputtering method at low temperatures around 400 C. Si films are also epitaxially grown on (100) single-crystalline Si substrates. In the method Si films are deposited by the chemical transport of SiH4 species generated by the reaction between solid Si target and catalytically generated H atoms. Efficient deposition is realized using the remarkable difference in the etch rate depending on Si target temperatures. That is, SiH4 species are efficiently generated on cooled Si target by atomic-H etching and deposited on substrates with suppressed etching phenomena by heating. Full-width at half maximum of transverse-optical Raman signals originating from crystalline phase for the obtained poly-Si films is narrower than that for poly-Si prepared by excimer-laser annealing. It was noticeable that the grain size exceeds 1 m for the films with a thickness of about 1 m. Growth mode of poly-Si films especially in the initial stage is remarkably changed with a difference in the substrate material. It was found that formation of seed layer enhances the growth of poly-Si films on glass substrate.

This paper reports structural and electrical properties of catalytic-nitrided silicon dioxide (SiO2) films. The surface of SiO2/Si(100) was nitrided at temperatures below 573 K. It was found that the incorporated N atoms are bound to Si atoms and O atoms and located on the top-surface of SiO2. Catalytic-nitrided SiO2 films have small amounts of Si-OH bonds and adequate resistance to boron (B) penetration.

This paper reports a procedure for low-temperature nitridation of silicon dioxide (SiO2) surfaces using species produced by catalytic decomposition of NH3 on heated tungsten in catalytic chemical vapor deposition (Cat-CVD) system. The surface of SiO2/Si(100) was nitrided at temperatures as low as 200°C. X-ray photoelectron spectroscopy measurements revealed that incorporated N atoms are bound to Si atoms and O atoms and located top-surface of SiO2.

This is to review the present understanding on Cat-CVD (catalytic chemical vapor deposition) or hot wire CVD. Firstly, the deposition mechanism in Cat-CVD process is briefly mentioned along with key issues such as the effect of heat radiation and a method to avoid contamination from the catalyzer. Secondly, the properties of Cat-CVD Si-based thin films such as amorphous silicon (a-Si), polycrystalline silicon (poly-Si) and silicon nitride (SiNx) films are demonstrated, and finally, the feasibility of such films for industrial application is discussed.

This is to report the feasibility of ultra-thin silicon nitride (SiNx) films, prepared by catalytic chemical vapor deposition (Cat-CVD) method, as an ultra-thin gate insulator. In the Cat-CVD method, the deposition gases such as a gaseous mixture of silane (SiH4) and ammonia (NH 3) are decomposed by catalytic cracking reactions with a heated tungsten catalyzer placed near substrates, and SiNx films are formed at substrate temperatures around 300°C without using plasma. In the paper, additionally the effect of post-deposited treatments by using NH3-decomposed species or hydrogen (H2)-decomposed species formed by catalytic cracking of NH3 and H2 are also studied. It is found that a small hysteresis loop is seen in the C-V curve of as-deposited Cat-CVD SiNx films and that the leakage currents with thickness of 3nm equivalent oxide thickness (EOT) is slightly larger than that in the conventional thermal SiO2 of similar EOT. However, it is also found that the properties of Cat-CVD SiNx films are drastically improved by the post-deposited H2 or NH3 treatments, that is, the hysteresis loop disappears and the leakage current decreases by three orders of magnitude.

Ultra-thin silicon dioxide films can be formed at temperatures as low as 220°C by direct oxidation of Si, using active oxygen species generated by tungsten catalytic reaction in a catalytic chemical vapor deposition (Cat-CVD) system. The structural and electrical properties of such a films are investigated. It is found that the density of Si atoms in intermediate oxidation states and the density of films determined from etch rate in dilute HF solution were comparable to those of the films by a conventional thermal oxidation at 900°C. The electrical properties, breakdown electric field and leakage current were also comparable to those of thermally oxidized films.

Polycrystalline silicon (poly-Si) films are obtained at temperatures lower than 400°C by catalytic chemical vapor deposition (Catalytic CVD = Cat-CVD) method, often called hot-wire CVD method. Structural properties of the Cat-CVD poly-Si films, deposited with various gas pressures, are studied by Raman scattering spectroscopy and X-ray diffraction technique. It is found that there are two recipes for obtaining device quality poly-Si films, that is, such poly-Si films are obtained at low gas pressure around 1 mTorr or less as already reported, and also at high gas pressure around 0.1 to 1 Torr. It is also found that, in addition to catalyzer temperature, the gas pressure is a key factors to obtain device quality poly-Si films at high deposition rates.

We proposed use of a new CdF2/CaF2 heterointerface for the formation of large conduction band discontinuities to apply quantum effect devices fabricated on Si substrates. Resonant tunneling diodes using this heterointerface on Si were fabricated and negative differential resistance whose P/V current ratio of 24 at highest was observed at room temperature.

Polycrystalline silicon (poly-Si) films are deposited at temperatures lower than 300–400°C by the cat-CVD method. In the method, a SiH4 and H2 gas-mixture is decomposed by catalytic cracking reactions with a heated tungsten catalyzer placed near substrates. Carrier transport, optical and structural properties are investigated for this cat-CVD poly-Si. The films show both large carrier mobility and large optical absorption for particular deposition conditions. The cat-CVD poly-Si films are found to be one of the useful materials for thin film transistors and thin film solar cells.