Recent situation of industrial implementation of Cat-CVD technology in Japan

Efforts of industrial application of Cat-CVD technology are surveyed. Recent movement of industrial implementation is also reviewed by showing examples in Japanese industry. Cat-CVD technology is originally developed as a new tool for fabricating semiconductor devices, however, recently, use of the technology is attempted in various fields such as chemical, mechanical and bio-technical engineering. It is shown that Cat-CVD has high feasibility as a fundamental technology of modern industries.     

New application of Cat-CVD technology and recent status of industrial implementation

Recent progress in application of Cat-CVD (Hot Wire CVD) technology is overviewed, along with recent status of industrial implementation of this technology. Although the use of Cat-CVD technology in factories has not been open to the public, the technology appears to fit for the fabrication of ultra-high frequency devices of compound semiconductors, compound semiconductor lasers, solar cells, and formation of coating films for other devices. The issues for practical use of this technology are also discussed, together with promising future of this Cat-CVD technology.     

Recent progress of Cat-CVD research in Japan—bridging between the first and second Cat-CVD conferences

We review the recent progress of Cat-CVD research in Japan since the 1st Cat-CVD conference in Kanazawa in 2000. Some groups, including ours, succeeded in realizing large-area deposition of amorphous silicon (a-Si) of approximately 1 m size, and thin film transistors (TFTs) with a mobility over several 10s of cm² V⁻¹ s⁻¹ are fabricated using Cat-CVD polycrystalline silicon (poly-Si) films. Extensive studies of in situ cleaning methods revealed that a high rate of chamber cleaning is possible in Cat-CVD systems. Solar cell research is now carried out within the New Energy and Industrial Technology Development Organization (NEDO) project, and the study of Cat-CVD Si₃N₄ films prepared at lower than 100 °C is now a Japan Science and Technology Corporation (JST) project to use them as coatings on organic devices. The feasibility of Cat-CVD for various applications has been widely demonstrated, along with further understanding of the fundamental mechanism of the Cat-CVD process.     

Application of Cat-CVD for ULSI technology

The ULSI technology has been following Moore's law into the sub-100 nm era, although several challenging technical issues must be resolved. This paper describes possible application of Cat-CVD for ULSI technology beyond the 45 nm node. Especially, Cat-CVD SiN film for a transistor gate sidewall and/or a pre-metallic liner layer, and removal of photo resist (ash) by Cat-induced hydrogen atoms in the interconnect structure with an extreme low-k material are mainly discussed.     

Formation of low-resistivity poly-Si and SiNx films by Cat-CVD for ULSI application

In this paper, bulk-Si metal–oxide–semiconductor field effect transistors (MOSFETs) are fabricated using the catalytic chemical vapor deposition (Cat-CVD) method as an alternative technology to the conventional high-temperature thermal chemical vapor deposition. Particularly, formation of low-resistivity phosphorus (P)-doped poly-Si films is attempted by using Cat-CVD-deposited amorphous silicon (a-Si) films and successive rapid thermal annealing (RTA) of them. Even after RTA processes, neither peeling nor bubbling are observed, since hydrogen contents in Cat-CVD a-Si films can be as low as 1.1%. Both the crystallization and low resistivity of 0.004 Ω·cm are realized by RTA at 1000 °C for only 5 s. It is also revealed that Cat-CVD SiN_x films prepared at 250 °C show excellent oxidation resistance, when the thickness of films is larger than approximately 10 nm for wet O₂ oxidation at 1100 °C. It is found that the thickness required to stop oxygen penetration is equivalent to that for thermal CVD SiN_x prepared at 750 °C. Finally, complementary MOSFETs (CMOSs) of single-crystalline Si were fabricated by using Cat-CVD poly-Si for gate electrodes and SiN_x films for masks of local oxidation of silicon (LOCOS). At 3.3 V operation, less than 1.0 pA μm⁻¹ of OFF leakage current and ON/OFF ratio of 10⁷–10⁸ are realized, i.e. the devices can operate similarly to conventional thermal CVD process.     

Coverage properties of silicon nitride film prepared by the Cat-CVD method

The coverage properties of silicon nitride (Si₃N₄) films prepared by the catalytic chemical vapor deposition (Cat-CVD) technique were systematically studied. By increasing the catalyzer–substrate distance, the coverage was improved from 46 to 67% on a 1.0-μm line and space pattern. The etching rate of Cat-CVD Si₃N₄ film measured using 16BHF solution was independent of the deposited position of the micro-patterns deposited, and was approximately 3 nm/min, one order of magnitude lower than that of plasma-enhanced CVD (PE-CVD) Si₃N₄ film. This means that Cat-CVD Si₃N₄ films are denser than PE-CVD Si₃N₄ films, and that the quality at the side wall is equivalent to that on the top surface. That is, Cat-CVD Si₃N₄ films show a passivation effect, which was excellent, even at the side wall of micro-patterns. These results suggest that Si₃N₄ films prepared by Cat-CVD are suitable for the passivation films in microelectronic devices having a step configuration, such as TFT-LCDs and ULSIs.     

Future prospect of remote Cat-CVD on the basis of the production, transportation and detection of H atoms

The future prospect of remote Cat-CVD, in which the decomposition and the deposition chambers are separated, is discussed on the basis of the absolute density measurements of H atoms. It is now well recognized that uniform deposition is possible on a large area without plasma damages by Cat-CVD. However, we may not overlook the demerits in Cat-CVD. One of the demerits is the poisoning of the catalyzer surfaces by the material gases, both temporary and permanent. One technique to overcome this problem is remote Cat-CVD. The question is how to separate the decomposition and deposition areas. If the separation is not enough, there should be back diffusion of the material gases, which will poison the catalyzers. If the separation is too tight, radicals may not effuse out from the decomposition chamber. These problems are discussed and it is shown that SiO₂ coating to reduce the radical recombination rates on walls is promising. The possibility of the polytetrafluoroethene coating by Cat-CVD is also discussed.     

Precursor Cat-CVD a-Si films for the formation of high-quality poly-Si films on glass substrates by flash lamp annealing

Amorphous Si (a-Si) films with lower hydrogen contents show better adhesion to glass during flash lamp annealing (FLA). The 2.0 µm-thick a-Si films deposited by plasma-enhanced chemical vapor deposition (PECVD), containing 10% hydrogen, start to peel off even at a lamp irradiance lower than that required for crystallization, whereas a-Si films deposited by catalytic CVD (Cat-CVD) partially adhere even after crystallization. Dehydrogenated Cat-CVD a-Si films show much better adhesion to glass, and are converted to polycrystalline Si (poly-Si) without serious peeling, but are accompanied by the generation of crack-like structures. These facts demonstrate the superiority of as-deposited Cat-CVD a-Si films as a precursor material for micrometer-thick poly-Si formed by FLA.     

AlGaN/GaN HEMTs passivated by Cat-CVD SiN Film

We demonstrate the excellent performance of a 140 W AlGaN/GaN HEMT in the C-band, which is passivated by a Cat-CVD SiN film. The interface trap density of the AlGaN surface passivated by Cat-CVD film after NH₃ treatment is 3 × 10¹² cm^− 2, which is the smallest of investigated deposition techniques. The lowest interface trap density achieved by the Cat-CVD technique makes it possible to operate the AlGaN/GaN HEMT in the C-band. We clarify that the Cat-CVD technique is necessary for developing future amplifiers.     

Advantage of plasma-less deposition in Cat-CVD to the performance of electronic devices

Advantage of plasma-less deposition in catalytic chemical vapor deposition (Cat-CVD) is demonstrated in performance of amorphous-silicon (a-Si) thin-film transistors (TFTs), by comparing with a-Si TFTs fabricated by plasma-enhanced CVD (PECVD). Cat-CVD a-Si TFTs show 2 or 3 orders of magnitude lower off-current than PECVD ones. Exposure of Cat-CVD TFTs to an argon or a hydrogen plasma severely increases their off-current, while the off-current recovers by chemically etching the plasma-damaged surface layer. It is concluded that PECVD damages the a-Si surface to a depth of several tens of nm, whereas Cat-CVD induces no serious damage to the film surface and therefore induces no deterioration of electrical properties.     

Comparison of a-Si TFTs fabricated by Cat-CVD and PECVD methods

We investigate the characteristics of amorphous silicon thin film transistors (a-Si TFTs) fabricated by plasma-enhanced chemical vapor deposition (PECVD) and catalytic CVD (Cat-CVD), and their stability under bias and temperature (BT) accelerated stress. The Cat-CVD a-Si TFTs have off-leak current as small as 10^− 14 A, and a smaller threshold voltage shift under the BT stress. The superiority in off-leak current and stability is observed in the Cat-CVD a-Si TFTs fabricated at both 320 °C and 180 °C. The high performance and stability of the Cat-CVD a-Si TFTs will enable to use low-cost glass substrates and result in a cost reduction of TFT fabrication.     

Hydrophobic properties of polytetrafluoroethylene thin films fabricated at various catalyzer temperatures through catalytic chemical vapor deposition using a tungsten catalyzer

Using the catalytic chemical vapor deposition (Cat-CVD) method, polytetrafluoroethylene (PTFE) thin films were fabricated on Si(100) substrates at various catalyzer temperatures, using a tungsten catalyzer, and Fourier transform infrared (FTIR) spectroscopy and X-ray photoemission spectroscopy (XPS) were used to confirm the fabrication of the films. An atomic-force microscope (AFM) and a scanning electron microscope (SEM) were employed to study the correlation between the wettability and surface morphology of the samples. It was found that the wettability of the PTFE thin films fabricated via Cat-CVD is strongly correlated with the sizes of the film surfaces' nanoprotrusions, and that superhydrophobic PTFE thin-film surfaces can be easily achieved by controlling the sizes of the nanoprotrusions through the catalyzer temperature. The comparison of the wettability values and surface morphologies of the films confirmed that nanoscale surface roughness enhances the hydrophobic properties of PTFE thin films. Further, the detailed analysis of the films' surface morphologies from their AFM images with the use of the Wenzel and Cassie models confirmed that the nanoscale surface roughness enhanced the hydrophobic property of the PTFE films. Further, the variations of the wettability of the PTFE thin films prepared via Cat-CVD are well explained by the Cassie model. It seems that the increase in the trapping air and the reduction of the liquid-solid contact area are responsible for the superhydrophobicity of the PTFE thin films prepared via Cat-CVD.     

Effect of hydrogen on SiNx films deposited by Cat-CVD method

This study is aimed at improving the characteristics of silicon nitride (SiNx) film deposited by catalytic chemical vapor deposition (Cat-CVD) method. Cat-CVD method can deposit SiNx films that have low hydrogen content and high density at low temperature without any plasma damage to substrates. Usually silane (SiH₄) and ammonia (NH₃) are used for source gases. Then adding hydrogen (H₂) gas to source gases makes characteristics of Cat-CVD SiNx improved. When using H₂ gas, hydrogen content in SiNx film becomes lower and electronic reliability becomes higher.     

GaN-based FETs using Cat-CVD SiN passivation for millimeter-wave applications

We have found that SiN passivation by catalytic chemical vapor deposition (Cat-CVD) can significantly increase an electron density of an AlGaN/GaN heterostructure field-effect transistor (HFET). This effect enables thin-barrier HFET structures to have a high-density two-dimensional electron gas and leads to suppression of short-channel effects. We fabricated 30-nm-gate Al_0.4Ga_0.6N(8 nm)/GaN HFETs using Cat-CVD SiN. The maximum drain current density and extrinsic transconductance were 1.49 A/mm and 402 mS/mm, respectively. Current-gain cutoff frequency and maximum oscillation frequency of the HFETs were 181 and 186 GHz, respectively. These high-frequency device characteristics are sufficiently high enough for millimeter-wave applications.     

Fabrication of PTFE thin films by dual catalytic chemical vapor deposition method

Dependence of catalyzing materials on deposition of polytetrafluoroethylene (PTFE = ”Teflon” in commercial) films by catalytic chemical vapor deposition (Cat-CVD) method is investigated. It has been clarified that Ni-containing catalyzers has a catalyzing effect that can decompose hexafluoropropylene-oxide (HFPO) to form PTFE films. A novel method named Dual Cat-CVD is also proposed. In the method, carbonized and fluorinated surface of Ni-containing catalyzer is removed and refreshed using atomic hydrogen generated by additionally introduced tungsten (W) catalyzer in the same chamber. This Dual Cat-CVD method enables to recover the deposition rate of PTFE films drastically.     

Excellent passivation effect of Cat-CVD SiNx/i-a-Si stack films on Si substrates

We have demonstrated that the surface recombination velocity can be lowered to as low as 1.3 cm/s for n-type c-Si wafers and to 9.0 cm/s for p-type wafers by using amorphous Si (a-Si) and Si nitride (SiN_x) stacked films prepared by catalytic chemical vapor deposition (Cat-CVD). These values are much lower than those of c-Si wafers passivated by same stacked structures formed by low-damage remote plasma-enhanced CVD (PECVD). It is revealed that Cat-CVD a-Si insertion layers play an important role to improve interface quality, and also SiN_x films are also essential for reducing the surface recombination velocity down to such low levels.     

Cat-CVD SiN passivation films for OLEDs and packaging

A Roll-to-roll type catalytic chemical vapor deposition (Cat-CVD) apparatus was developed for the application to flexible organic light-emitting diode (OLED) displays and packaging. Silicon nitride (SiN_x) films were prepared by this roll-to-roll type apparatus at temperatures below 60 °C. It was found that these SiN_x films are highly moisture resistant, and the water vapor transmission rate (WVTR) on plastic substrates could be lowered to 0.01 g/m² day. Roll-to-roll type Cat-CVD is one of the most promising methods for the preparation of barrier films for OLED displays and packaging.     

Carbonized tantalum catalysts for catalytic chemical vapor deposition of silicon films

Catalytic chemical vapor deposition (Cat-CVD) has been demonstrated as a promising way to prepare device-quality silicon films. However, catalyst ageing due to Si contamination is an urgency to be solved for the practical application of the technique. In this study, the effect of carbonization of tantalum catalyst on its structure and performance was investigated. The carbonized Ta catalyst has a TaC surface layer which is preserved over the temperature range between 1450 and 1750 °C and no Si contamination occurs on the catalyst after long-term use. Si film prepared using the carbonized Ta catalyst has a similar crystal structure to that prepared by uncarbonized Ta catalyst. Formation of the TaC surface layer can alleviate the ageing problem of the catalyst, which shows great potential as a stable catalyst for Cat-CVD of Si films.     

Flash-lamp-crystallized polycrystalline silicon films with high hydrogen concentration formed from Cat-CVD a-Si films

We investigate residual forms of hydrogen (H) atoms such as bonding configuration in poly-crystalline silicon (poly-Si) films formed by the flash-lamp-induced crystallization of catalytic chemical vapor deposited (Cat-CVD) a-Si films. Raman spectroscopy reveals that at least part of H atoms in flash-lamp-crystallized (FLC) poly-Si films form Si-H₂ bonds as well as Si-H bonds with Si atoms even using Si-H-rich Cat-CVD a-Si films, which indicates the rearrangement of H atoms during crystallization. The peak desorption temperature during thermal desorption spectroscopy (TDS) is as high as 900 °C, similar to the reported value for bulk poly-Si.     

Development of Cat-CVD apparatus for 1-m-size large-area deposition

Thin film deposition on large-area substrates of 1-m size is demonstrated by catalytic chemical vapor deposition (Cat-CVD) apparatus equipped with a newly developed showerhead catalyzer unit. The arrangement of catalyzer wires for uniform film thickness was determined by simulation, assuming that decomposed species on catalyzers were transported by isotropic thermal diffusion without an influence of the gas flow. A film thickness uniformity of ±7.5% was successfully achieved on a substrate of 400 mm×960 mm at an average deposition rate of 32 nm/min for hydrogenated amorphous silicon (a-Si:H) film. Film thickness uniformity of ±8.6% for a-Si:H film and ±12.3% for silicon nitride film were also successfully obtained on substrates of 680 mm×880 mm size at an average deposition rate of 12.1 and 2.5 nm/min, respectively. These results suggest that Cat-CVD is a promising method for the fabrication of large-area devices such as thin-film-transistor liquid-crystal displays and solar cells.