Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

Low temperature UV/ozone oxidation formation of HfSiON gate dielectric

Physical and electrical properties of hafnium silicon oxynitride (HfSi_xO_yN_z) dielectric films prepared by UV ozone oxidation of hafnium silicon nitride (HfSiN) followed by annealing to 450 °C are reported. Interfacial layer growth was minimized through room temperature deposition and subsequent ultraviolet/ozone oxidation. The capacitance–voltage (C–V) and current–voltage (I–V) characteristics of the as-deposited and annealed HfSi_xO_yN_z are presented. These 4 nm thick films have a dielectric constant of 8–9 with 12 at.% Hf composition, with a leakage current density of 3×10⁻⁵ A/cm² at V_fb+1 V. The films have a breakdown field strength >10 MV/cm.     

Crystallization by excimer laser annealing for a-Si:H films with low hydrogen content prepared by Cat-CVD

Crystallization by excimer-laser annealing (ELA) for hydrogenated amorphous silicon (a-Si:H) films with low hydrogen content (C_H) prepared by catalytic chemical vapor deposition (Cat-CVD) was systematically studied. From optical microscopy images, no hydrogen bubbling was observed during ELA, even without a dehydrogenation process. As the laser energy density was increased to 300 mJ cm⁻², the full width at half-maximum of the Raman signal from the crystalline phase decreased to approximately 4 cm⁻¹. This value is almost equal to or even smaller than that reported for polycrystalline Si (poly-Si) films prepared from plasma-enhanced CVD (PECVD) a-Si:H films by ELA so far. The average grain size, estimated from scanning electron microscopy, was approximately 500 nm for C_H of 1.3 at.%. On the other hand, the grain size of poly-Si films prepared from PECVD a-Si:H films with a dehydrogenation process was only 200 nm. The technique using Cat-CVD films is expected to be used for fabrication of low-temperature high-mobility thin-film transistors.     

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.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

Effect of hydrogen radical on growth of μc-Si in hetero-structured SiCx alloy films

The changes of the crystallinity of μc-Si phase are studied in samples deposited with hydrogen dilution ratio, H₂/SiH₄, from 9.0 to 19.0 by hot-wire CVD (Cat-CVD). In the samples deposited at filament temperature, T_f, of 1850 °C, the crystalline fraction and the crystallite size of μc-Si phase increased with increasing the H₂/SiH₄. The carbon content, C/(Si+C), was almost constant. In the XRD patterns, the intensity of Si(1 1 1) peak decreased and that of Si(2 2 0) peak increased with increasing the H₂/SiH₄. In the samples deposited at T_f of 2100 °C with H₂/SiH₄ over 11.4, the μc-Si phase was not formed and the C/(Si+C) increased. The growth mechanism of μc-Si in hetero-structured SiC_x alloy films is discussed.     

Polycrystalline silicon prepared by metal induced crystallization

Growth of large-grain polycrystalline silicon has been demonstrated using silicide-mediated crystallization of amorphous silicon (a-Si) by a pulsed rapid thermal annealing (RTA). The Ni atoms in concentration of 4.6×10¹²/cm² on the a-Si surface were heated at 700 °C in the RTA system for 10 s, ten times with 60 s intervals between the heat pulses. The Ni atoms on a-Si aggregate together, forming NiSi₂ precipitates. The crystallization proceeds from the NiSi₂ nuclei until the neighboring crystallites collide and forms distinct grain boundaries. It was found that 3.6×10⁷ Ni atoms form a seed for metal induced crystallization and the grain size was 40 μm when the Ni density was 4.6×10¹²/cm² on the a-Si. The grain size increases with decreasing metal density on a-Si.     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

Preparation of SiO2 thin films using the Cat-CVD method

Using the catalytic chemical vapor deposition (Cat-CVD) method, a-Si and SiN_x films have been the main focus of studies. SiO₂ films have not been studied because of the limited life of catalysts such as tungsten or molybdenum in an oxidative atmosphere. In this report, we describe oxide film preparation using an iridium catalyst. We determined the most appropriate catalyst material for the oxide film process by exposing heated materials in tetraethoxysilane (TEOS) or O₂ gas. As the result, it was confirmed that the Ir catalyst works in a slow oxidative atmosphere. Using the Ir catalyst, SiO₂ films were deposited in two gas combinations: TEOS and N₂O, and SiH₄ and N₂O. Although the SiO₂ film processed with the combination of TEOS and N₂O was stoichiometric, its breakdown voltage is not sufficient. The SiO₂ film processed with the combination of SiH₄ and N₂O showed good electrical property.     

Atmospheric plasma discharge chemical vapor deposition of SnOx thin films using various tin precursors

A series of 0.2–0.6 μm thick SnO_x films were deposited onto borosilicate and sodalime silica glass substrates by atmospheric plasma discharge chemical vapor deposition at 80 °C. SnO_x films deposited from monobutyltin trichloride contained a large percentage of SnCl₂:2H₂O, and therefore were partially soluble in water. SnO_x coatings deposited from tetrabutyltin were not soluble in water or organic solvents, had good adhesion even at growth rates as high as 2.3 nm/s, had high transparency of  90% and electrical resistivity of 10⁷ Ω cm. As-grown tin oxide coatings were amorphous with a small concentration of SnO₂, SnO and Sn crystalline phases as determined by grazing angle X-ray diffraction and X-ray photoelectron spectroscopy measurements. Upon annealing in air at 600 °C the resistivity of SnO_x films decreased to 5–7 Ω cm. Furthermore, optical and X-ray measurements indicated that SnO_x was converted into SnO₂ (cassiterite) with a direct band gap of 3.66 eV. Annealing of as-grown SnO_x films in vacuum at 340 °C led to formation of the p-type conductor SnO/SnO_x. The indirect band gap of SnO was calculated from the optical spectra to be 0.3 eV.     

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.     

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.     

Electrical properties of silicon nitride films deposited by catalytic chemical vapor deposition on catalytically nitrided Si(100)

Thin film transistor incorporating silicon nitride (SiN_x) films deposited by catalytic chemical vapor deposition (Cat-CVD) on silicon exhibit some problems such as a large-threshold voltage shift and a large hysteresis loop width of the capacitance vs. voltage (C–V) characteristics. In this work, in order to solve these problems, the surface of the silicon substrate is catalytically nitrided before SiN_x deposition. Inserting the nitridation layer, injection-type hysteresis loop of C–V curve is reduced from 1.3 to 0.05 V and large threshold voltage shift to the negative direction is reduced from 4 to 1.8 V.     

Morphological changes induced by thermal anneals in NiFe/Ag multilayers; their relation to the resistive and magnetoresistive properties

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.

(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.

The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

Inductively coupled plasma — plasma enhanced chemical vapor deposition silicon nitride for passivation of InP based high electron mobility transistors (HEMTs)

Silicon nitride thin films have been deposited on InP-based structures at both room and high temperatures in an RF-inductively coupled plasma enhanced chemical vapor deposition (ICP-PECVD) equipment. Metal insulating semiconductor (MIS) diodes have been widely investigated using either SiH₄+NH₃ or SiH₄+N₂ gas phase. I–V measurements conducted on these diodes reveal high resistivity and breakdown electric field even at low deposition temperature (50°C). Double channel (DC) High electron mobility transistors (HEMTs) have been passivated by SiN_x films deposited at room temperature using SiH₄+NH₃ precursors. Passivated devices exhibit a very low drift over a 45 h period of stress under high gate-drain electric field.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

Influence of conventional furnace and rapid thermal annealing on the quality of polycrystalline β-FeSi2 thin films grown from vapor-deposited Fe/Si multilayers

Thin films of polycrystalline β-FeSi₂ were grown on (100) Si substrates of high resistivity by electron beam evaporation of Si/Fe ultrathin multilayers and subsequent annealing by conventional vacuum furnace (CVF) and rapid thermal annealing (RTA) for 1 h and 30 s, respectively, in the temperature range from 600 to 900°C. X-ray diffraction, Raman spectroscopy, spectroscopic ellipsometry, resistivity and Hall measurements were employed for characterization of the silicide layers quality in terms of the annealing conditions. For the silicide layers prepared by CVF annealing, although the grain size increase with increasing the annealing temperature, the optimum temperature to obtain the higher material quality (carrier mobility of the order of 100 cm² Vs⁻¹ and carrier concentration of about 1 × 10¹⁷ cm⁻³) is about 700°C. At higher annealing temperatures, the quality of the material is degraded due to the presence of the oxide Fe₂O₃. In the case of the silicides prepared by RTA, the quality of the material is improved progressively with increasing the annealing temperature up to 900°C.