High temperature metal-induced crystallization of r.f. sputtered amorphous Si thin films

R.f. sputter-deposited amorphous Si (a-Si) films have been found to exhibit an interconnected fine structure of low and high density regions. The porosity decreases as the film thickness increases in agreement with results for evaporated a-Ge previously published by Donovan. At an annealing temperature of 800°C, a-Si films crystallize by the relatively slow diffusionless growth of crystallites nucleated within the a-Si matrix. Similar a-Si films containing a buried layer 30 Å thick of Al in an a-Si/Al/a-Si structure exhibited greatly enhanced nucleation and crystallization rates. Crystallite growth in these films occurred by two separate mechanisms both involving the precipitation of crystalline Si from an Al + Si liquid region. The first growth mechanism was observed during the early stages of crystalline formation in which crystalline islands grew around isolated liquid regions. Later, Al + Si liquid boundary layers were established between crystalline Si and a-Si regions, and further crystallization occurred by the motion of this boundary layer.     

Deposition and structural characterization of poly-Si thin films on Al-coated glass substrates using hot-wire chemical vapor deposition

The growth of polycrystalline Si films onto Al-coated Corning 7059 glass substrates using hot-wire chemical vapor deposition (HW-CVD) was investigated. The crystalline fraction, grain structure and average grain size of the films were compared as a function of the growth rate and the Si/Al thickness ratio. Micrometre-size Si grains were achieved with a Si/Al ratio of 2 and Si thickness of 2 μm at a growth rate of 1 μm h⁻¹. It was found that the films had a bimodal grain size distribution, which included nanocrystalline Si, and that the growth of micrometre-size crystallites does not continue as the thickness of Si film increases. At a growth rate of 5 μm h⁻¹, films are similar to those grown on glass with an average grain size less than 60 nm and crystalline fraction of 75%.     

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.     

A parametric study of AlN thin films grown by pulsed laser deposition

High quality AlN thin films were grown at 200–450°C on sapphire substrates by laser ablation of Al targets in nitrogen reactive atmosphere. The nitrogen pressure was varied between 10⁻³ and 10⁻¹ mbar. The reactive gas pressure during irradiation and the temperature of the substrate were found to essentially influence the quality of the layers. X-ray diffraction analysis evidenced the formation of highly orientated layers for a very restrictive set of parameters. Other analysis techniques, like X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, optical transmission spectroscopy have been used to evidence the good stoichiometry and purity of the films. The characteristics of these films were compared with those of AlN thin films deposited in similar experimental conditions, on Si (100) and Si (111) substrates.     

TiN/Si3N4纳米晶复合膜的微结构和强化机制

采用高分辨透射电子显微镜对高硬度的TiN/Si3N4纳米晶复合膜的观察发现,这类薄膜的微结构与Veprek提出的nc-TiN/a-Si3N4模型有很大不同：复合膜中的TiN晶粒为平均直径约10nm的柱状晶,存在于柱晶之间的Si3N4界面相厚度为0.5～0.7nm,呈现晶体态,并与TiN形成共格界面.进一步采用二维结构的TiN/Si3N4纳米多层膜的模拟研究表明,Si3N4层在厚度约＜0.7nm时因TiN层晶体结构的模板作用而晶化,并与TiN层形成共格外延生长结构,多层膜相应产生硬度升高的超硬效应.由于TiN晶体层模板效应的短程性,Si3N4层随厚度微小增加到1.0nm后即转变为非晶态,其与TiN的共格界面因而遭到破坏,多层膜的硬度也随之迅速降低.基于以上结果,本文对TiN/Si3N4纳米晶复合膜的强化机制提出了一种不同于nc-TiN/a-Si3N4模型的新解释.     

Dependence of the a-Si:H defect density of states on the magnetic field profile of an electron cyclotron resonance microwave plasma

The magnetic field profile of an electron cyclotron resonance microwave plasma was systematically altered to determine subsequent effects on a-Si:H film quality. The mobility gap deep density N_D deposition rate and light-to-dark conductivity were determined for the a-Si:H films. By variation of the magnetic field profile N_D could be altered by more than an order of magnitude, from 1 × 10¹⁶ to 1 × 10¹⁷ cm⁻³ at 0.7 mTorr and 1 × 10¹⁶ to 5 × 10¹⁷ cm⁻³ at 5 mTorr as determined by junction capacitance techniques. Two deposition regimes were found to occur for the conditions of this study. Highly divergent magnetic fields resulted in poor quality a-Si:H, while for magnetic field profiles defining a more highly confined plasma, the a-Si:H was of device quality and relatively independent of the magnetic field configuration. The data is interpreted as a consequence of silane depletion for highly divergent magnetic field profiles.     

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.     

Growth of columnar aluminum nitride layers on Si(111) by molecular beam epitaxy

Single crystalline aluminum nitride (AlN) thin films are deposited by molecular beam epitaxy (MBE) using thermally evaporated aluminum and RF-plasma excited nitrogen gas. In this paper we report on films grown on Si(111) at substrate temperatures of 800° with growth rates between 65 and 350 nm h⁻¹. All layers consist of hexagonal and exactly c-axis oriented AlN crystals with column-like structure. For the smoothest layers surface roughness (rms) around 1 nm is obtained. In the XRD-spectra (ω-scan) we have achieved a minimum FWHM of 0.4° (=25′) for the AlN(00.2) reflex. At maximum growth rates (350 nm h⁻¹) for AlN a transition zone of about 200 nm is formed with high defect density compared to the subsequent growth. For lower growth rates (65 nm h⁻¹) no transition zone exists. Application of a substrate nitridation leads to a partial loss of epitaxial relation between AlN layer and Si(111)-substrate.     

Atomic-layer doping in Si by alternately supplied PH3 and SiH4

Atomic-layer doping of P in Si epitaxial growth by alternately supplied PH₃ and SiH₄ was investigated using ultraclean low-pressure chemical vapor deposition. Three atomic layers of P adsorbed on Si(100) are formed by PH₃ exposure at a partial pressure of 0.26 Pa at 450°C. By subsequent SiH₄ exposure at 220 Pa at 450°C, Si is epitaxially grown on the P-adsorbed surface. Furthermore, by 12-cycles of exposure to PH₃ at 300–450°C and SiH₄ at 450°C followed by 20-nm thick capping Si deposition, the multi-layer P-doped epitaxial Si films of average P concentrations of 10²¹ cm⁻³ are formed. The resistivity of the film is as low as 2.4×10⁻⁴ Ω cm. By annealing the sample at 550°C and above, it is found that the resistivity increases and the surface may become rough, which may be due to formation of SiP precipitates at 550°C and above. These results suggest that the epitaxial growth of very low-resistive Si is achieved only at a very low-temperature such as 450°C.     

Molecular dynamics study of the mechanical behavior of nickel nanowire: Strain rate effects

We present the analysis of uniaxial deformation of nickel nanowires using molecular dynamics simulations, and address the strain rate effects on mechanical responses and deformation behavior. The applied strain rate is ranging from 1 × 10⁸ s⁻¹ to 1.4 × 10¹¹ s⁻¹. The results show that two critical strain rates, i.e., 5 × 10⁹ s⁻¹ and 8 × 10¹⁰ s⁻¹, are observed to play a pivotal role in switching between plastic deformation modes. At strain rate below 5 × 10⁹ s⁻¹, Ni nanowire maintains its crystalline structure with neck occurring at the end of loading, and the plastic deformation is characterized by {1 1 1} slippages associated with Shockley partial dislocations and rearrangements of atoms close to necking region. At strain rate above 8 × 10¹⁰ s⁻¹, Ni nanowire transforms from a fcc crystal into a completely amorphous state once beyond the yield point, and hereafter it deforms uniformly without obvious necking until the end of simulation. For strain rate between 5 × 10⁹ s⁻¹ and 8 × 10¹⁰ s⁻¹, only part of the nanowire exhibits amorphous state after yielding while the other part remains crystalline state. Both the {1 1 1} slippages in ordered region and homogenous deformation in amorphous region contribute to the plastic deformation.     

Aluminum-induced crystallization of amorphous silicon films deposited by hot wire chemical vapor deposition on glass substrates

Aluminum-induced crystallization of amorphous silicon films is discussed. Amorphous Si films were deposited by hot wire chemical vapor deposition onto Al coated glass substrates at 430 °C. Complete crystallization of a-Si films was achieved during a-Si deposition by controlling Al and Si layer thicknesses. The grain structure of the poly-Si films formed on glass substrate was evaluated by optical and electron microscopy. Continuous poly-Si films were obtained using Al layers with a thickness of 500 nm or less. The average grain size was found to be 10-15 μm, corresponding to a grain size/thickness ratio greater than 20.     

Effect on thickness of Al layer in poly-crystalline Si thin films using aluminum(Al) induced crystallization method

The polycrystalline silicon (poly-Si) thin films were prepared by aluminum induced crystallization. Aluminum (Al) and amorphous silicon (a-Si) layers were deposited using DC sputtering and plasma enhanced chemical vapor deposition method, respectively. For the whole process Al properties of bi-layers can be one of the important factors. In this paper we investigated the structural and electrical properties of poly-crystalline Si thin films with a variation of Al thickness through simple annealing process. All samples showed the polycrystalline phase corresponding to (111), (311) and (400) orientation. Process time, defined as the time required to reach 95% of crystalline fraction, was within 60 min and Al(200 nm)/a-Si(400 nm) structure of bi-layer showed the fast response for the poly-Si films. The conditions with a variation of Al thickness were executed in preparing the continuous poly-Si films for solar cell application.     

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cm s⁻¹ on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cm s⁻¹ on n- and p-type silicon.     

Self-assembled growth and magnetotransport investigations on strained Si/SiGe multilayers on vicinal (113)-Si surfaces

We have reported on the growth and magnetotransport properties of modulation p-doped Si_1−xGe_x quantum wells on strained multilayers of 2.5 nm Si_1−xGe_x/10 nm Si on vicinal (113) Si surfaces. Owing to the strong step-bunching properties of the (113) Si surface, both the Si_1−xGe_x and the Si layers exhibited a regular pattern of large steps. Low-temperature magnetotransport measurements revealed a hole density (6–9×10¹¹ cm⁻²) independent of direction, whereas a pronounced mobility anisotropy was found. The mobility (1000–2000 cm²/Vs) was approximately two times higher along the [33-2] direction compared to a perpendicular [−110] direction. This is attributed to anisotropic hole scattering caused by anisotropic shear strain which is always present in strained layers on (113) Si. No influence of the large regular steps, whose direction is given by the direction of the substrate miscut, on the mobility was found.     

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.     

The crystalline properties of nitrogen doped hydrogenated microcrystalline silicon thin films

The crystalline properties of nitrogen doped hydrogenated microcrystalline silicon thin films deposited by plasma enhanced chemical vapor deposition were studied. Gas phase doping density in the order of 10⁻² and 10⁻¹ leads to changes in the crystalline properties of the films. Raman scattering signals indicate that nitrogen doping causes a more significant reduction in crystallite size than does an increase in SiH₄ concentration. In addition, the size reduction occurs with a less significant increase in amorphous fraction volume than in the case of SiH₄ concentration increase. The N in the Si crystalline induces disorder or stress as a result of the higher electronegativity and smaller atomic size of N compared to Si. Thus, the crystallite size reduction is thought to occur to reduce the disorder in crystalline grain induced by doped nitrogen.     

Investigation of the nucleation mechanism in bias-enhanced diamond deposition on silicon and molybdenum

Polycrystalline diamond films were deposited on Si and Mo substrates in a microwave plasma-enhanced chemical vapour deposition reactor employing bias-enhanced nucleation. The deposition process was subdivided into two consecutive steps: the pretreatment (bias-enhanced nucleation) and the diamond growth step. To investigate the nucleation process we kept the deposition parameters during the diamond growth step constant and only changed the parameters during the pretreatment. The methods employed to analyze the deposited films after the pretreatment step were electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy.

The nucleation density (N_D) on Si following the complete deposition cycle (pretreatment and diamond growth step) increases considerably from 5 × 10⁸ cm⁻² to 5 × 10¹⁰ cm⁻² with an increase in the substrate temperature during the pretreatment (T_p) in the temperature range from 680 to 750 °C. For T_p ≥ 770 °C continuous films are formed. The structure of the pretreatment deposit undergoes likewise considerable changes: if T_p exceeds 770 °C the appearance of an intense diamond plasmon at 34 eV is observed, indicative of an increase in the concentration of diamond crystallites embedded in an otherwise amorphous carbon matrix. Our experiments suggest that diamond crystallites formed during the pretreatment serve as nucleation centres for the subsequent diamond growth.

The same deposition parameters which result in the formation of a continuous diamond film on Si, yield only low nucleation densities on Mo. An increase in N_D from 6 × 10⁶ cm⁻² to 2 × 10⁸ cm⁻² can be achieved by raising the methane concentration [CH₄] in the gas phase during the pretreatment from 5 to 50% (T_p = 820 °C). The carbon concentration at the surface for the pretreatment deposit, determined by XPS analysis, increases likewise with [CH₄]. According to the EELS analysis the structure of the pretreatment deposit is comparable with disordered graphite or a-C and no diamond plasmon is observed. The high [CH₄] is required to form the Mo-carbide interface and balance the diffusion of carbon into the metal before the a-C layer can be formed.

The formation of nucleation centres during the bias-enhanced nucleation seems under these deposition conditions to proceed via different pathways on Si and Mo. While the nucleation on Si appears to be linked to the formation of diamond nanocrystals during the pretreatment, this is not the case for Mo.     

MBE growth and characterization of buried silicon oxide films on Si(100)

Silicon molecular beam epitaxy (Si-MBE) has been used to produce silicon oxide (SiO_x) films by evaporating Si on a heated Si(100) substrate in an ultra high vacuum system with an O₂ pressure of 10⁻⁶ to 10⁻⁴ mbar. Then the SiO_x films were overgrown with pure Si. The influence of the substrate temperature, the O₂ pressure and the Si deposition rate on the oxygen content in the SiO_x films and on the crystalline quality of the Si top-layer was investigated by Rutherford backscattering spectrometry and ion channeling. Epitaxial growth of the Si top-layer was observed up to a maximum concentration of ≈20 at.% oxygen content in the SiO_x film. Cross-sectional transmission electron microscopy shows that the structure of the SiO_x film changes duringa subsequent annealing procedure. Electron energy loss spectrometry proves that amorphous SiO₂ is formed and the development of holes indicates that the density of the as-grown SiO_x film is much lower than that of SiO₂. The specific for the as-grown SiO_x films was determined by I–V measurements.     

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.     

Optical and structural characterizations of Cu-doped KCl films

The production of highly Cu⁺-doped KCl films and the properties of their 266 nm absorption band, which has an off-center property in doped single crystals, open the possibility of application of these films as ultra-violet optical filters. The investigated films, of approximately 1 μm thickness, were prepared by resistive co-evaporation of KCl and CuCl powders on different substrates of CaF₂, Al₂O₃, SiO₂, KCl and Si. The Cu⁺ concentration, as determined by energy-dispersive X-ray, ranges from 10²⁰ to 10²¹ cm⁻³, for 1–15% CuCl nominal mole percent concentration. Structural and optical properties were investigated through scanning electron microscopy, X-ray diffraction, ellipsometry, optical absorption and transmission. The films are polycrystalline, and the gain size decreases with increasing Cu⁺ impurity concentration, yielding an increase of visible transmission to a limited CuCl concentration. These films show a 6.295 Å lattice parameter with a f.c.c. structure and an index of refraction of 1.53 at 266 nm. When the Cu⁺ concentration is increased, the UV band position remains the same and no clusters are evidenced even to the high 15% CuCl concentration investigated, which differs very much from single crystals samples grown by the Kyropoulos-Czochralski method. For a Cu⁺ concentration of 8×10²⁰ cm⁻³ the film shows a transmission better than 88% at 350 nm wavelength.