Characteristics of hydrogenated silicon thin film deposited by RF-PECVD using He–SiH4 mixture

Nanocrystalline silicon thin films (nc-Si:H) were deposited using He as the dilution gas instead of H₂ and the effect of the operating pressure and rf power on their characteristics was investigated. Especially, operating pressures higher than 4 Torr and a low SiH₄ containing gas mixture, that is, SiH₄(3 sccm)/He(500 sccm) were used to induce high pressure depletion (HPD) conditions. Increasing the operating pressure decreased the deposition rate, however at pressures higher than 6 Torr, crystallized silicon thin films could be obtained at an rf power of 100 W. The deposition of highly crystallized nc-Si:H thin film was related to the HPD conditions, where the damage is decreased through the decrease in the bombardment energy at the high pressure and the crystallization of the deposited silicon thin film is increased through the increased hydrogen content in the plasma caused by the depletion of SiH₄. When the rf power was set at a fixed operating pressure of 6 Torr, HPD conditions were obtained in the rf power range from 80 to 100 W, which was high enough to dissociate SiH₄ fully, but meantime low enough not to damage the surface by ion bombardment. At 6 Torr of operating pressure and 100 W of rf power, the nc-Si:H having the crystallization volume fraction of 67% could be obtained with the deposition rate of 0.28 nm/s.     

Optimization of n nc-Si:H and a-SiNx:H layers for their application in nc-Si:H TFT

The n-type doped silicon thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) technique at high and low H₂ dilutions. High H₂ dilution resulted in n⁺ nanocrystalline silicon films (n⁺ nc-Si:H) with the lower resistivity (ρ ∼0.7 Ω cm) compared to that of doped amorphous silicon films (∼900 Ω cm) grown at low H₂ dilution. The change of the lateral ρ of n⁺ nc-Si:H films was measured by reducing the film thickness via gradual reactive ion etching. The ρ values rise below a critical film thickness, indicating the presence of the disordered and less conductive incubation layer. The 45 nm thick n⁺ nc-Si:H films were deposited in the nc-Si:H thin film transistor (TFT) at different RF powers, and the optimum RF power for the lowest resistivity (∼92 Ω cm) and incubation layer was determined. On the other hand, several deposition parameters of PECVD grown amorphous silicon nitride (a-SiN_x:H) thin films were changed to optimize low leakage current through the TFT gate dielectric. Increase in NH₃/SiH₄ gas flow ratio was found to improve the insulating property and to change the optical/structural characteristics of a-SiN_x:H film. Having lowest leakage currents, two a-SiN_x:H films with NH₃/SiH₄ ratios of ∼19 and ∼28 were used as a gate dielectric in nc-Si:H TFTs. The TFT deposited with the NH₃/SiH₄∼19 ratio showed higher device performance than the TFT containing a-SiN_x:H with the NH₃/SiH₄∼28 ratio. This was correlated with the N−H/Si−H bond concentration ratio optimized for the TFT application.     

Preferred growth of nanocrystalline silicon in boron-doped nc-Si:H Films

Preferred growth of nanocrystalline silicon (nc-Si) was first found in boron-doped hydrogenated nanocrystalline (nc-Si:H) films prepared using plasma-enhanced chemical vapor deposition system. The films were characterized by high-resolution transmission electron microscope, X-ray diffraction (XRD) spectrum and Raman Scattering spectrum. The results showed that the diffraction peaks in XRD spectrum were at 2θ≈47° and the exponent of crystalline plane of nc-Si in the film was (2 2 0). A considerable reason was electric field derived from dc bias made the bonds of Si-Si array according to a certain orient. The size and crystalline volume fraction of nc-Si in boron-doped films were intensively depended on the deposited parameters: diborane (B₂H₆) doping ratio in silane (SiH₄), silane dilution ratio in hydrogen (H₂), rf power density, substrate's temperature and reactive pressure, respectively. But preferred growth of nc-Si in the boron-doped nc-Si:H films cannot be obtained by changing these parameters.     

Structural and optical properties of nc-Si:H thin films deposited by layer-by-layer technique

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films deposited on c-Si and quartz substrates by layer-by-layer (LBL) technique using radio-frequency plasma enhanced chemical vapour deposition system. The effects of rf power on the interlayer elemental profiling, structural and optical properties of the films were investigated by Auger electron spectroscopy, Fourier transform infrared spectroscopy, Raman scattering spectroscopy, X-ray diffraction and optical transmission and reflection spectroscopy. The results revealed that the LBL deposition leads to a formation of different ranges of crystallite sizes of nc-Si corresponds 3–6 and 8–26 nm respectively. LBL deposition also demonstrated a capability to increase the crystalline volume fraction of nc-Si up to 65.3 % with the crystallite size in between 5 and 6 nm, at the rf power in between 80 and 100 W. However, the crystalline volume fraction decreased for the rf power above 100 W due to the growth of nc-Si was suppressed by the formation of SiO₂. In addition, the onset of crystallization of the films deposited on c-Si and quartz substrates are different with increase in the rf power. The effects of rf power on the growth of nc-Si, and the hydrogen content, structural disorder, crystallite size of nc-Si and oxygen diffusion into the LBL layer with the change of optical energy gap under the variation of rf power are also discussed.     

Structural changes of hot-wire CVD silicon carbide thin films induced by gas flow rates

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition in a CH₄ gas flow rate of 1 sccm, and the influence of the gas flow rates of SiH₄ and H₂ gases on the film structure and properties were investigated. In the case of a H₂ gas flow rate below 100 sccm, the SiC:H films obtained in SiH₄ gas flow rates of 3 and 4 sccm were amorphous. On the other hand, when the H₂ gas flow rate was above 150 sccm, SiH₄ gas flow rates of 4 and 3 sccm resulted in a Si-crystallite-embedded amorphous SiC:H film and a nanocrystalline cubic SiC film, respectively. It was found that gas flow rates were important parameters for controlling film structure.     

High rate growth highly crystallized microcrystalline silicon films using SiH4/H2 high-density microwave plasma

The plasma parameter for fast deposition of highly crystallized microcrystalline silicon (μc-Si) films with low defect density is presented using the high-density and low-temperature microwave plasma (MWP) of a SiH₄-H₂ mixture. A very high deposition rate of ∼ 65 Å/s has been achieved at SiH₄ concentration of 67% diluted in H₂ with high Raman crystallinity I_c / I_α > 3 and low defect density of 1-2 × 10¹⁶ cm^− 3 by adjusting the plasma condition. Contrary to the conventional rf plasma, the defect density of the μc-Si films strongly depend on substrate temperature T_s and it increased with increasing T_s despite T_s below 300 °C, suggesting that the real surface temperature at the growing surface was higher than the monitored value. The sufficient supply of deposition precursors such as SiH₃ at the growth surface under an appropriate ion bombardment was effective for the fast deposition of highly crystallized μc-Si films as well as the suppression of the incubation and transition layers at the initial growth stage.     

Low refraction properties of F-doped SiOC:H thin films prepared by PECVD

Low refractive index materials which F-doped SiOC:H films were deposited on Si wafer and glass substrate by low temperature plasma enhanced chemical vapor deposition (PECVD) method as a function of rf powers, substrate temperatures, gas flow ratios (SiH₄, CF₄ and N₂O). The refractive index of the F-doped SiOC:H film continuously decreased with increasing deposition temperature and rf power. As the N₂O gas flow rate decreases, the refractive index of the deposited films decreased down to 1.378, reaching a minimum value at an rf power of 180 W and 100 °C without flowing N₂O gas. The fluorine content of F-doped SiOC:H film increased from 1.9 at.% to 2.4 at.% as the rf power was increased from 60 W to 180 W, which is consistent with the decreasing trend of refractive index. The rms (root-mean-square) surface roughness significantly decreased to 0.6 nm with the optimized process condition without flowing N₂O gas.     

Investigation of optical and compositional properties of thin SiNx:H films with an enhanced growth rate by high frequency PECVD method

Hydrogenated thin silicon nitride (SiN_x:H) films were deposited by high frequency plasma enhanced chemical vapor deposition techniques at various NH₃ and SiH₄ gas flow ratios [R = NH₃/(SiH₄ + NH₃)], where the flow rate of NH₃ was varied by keeping the constant flow (150 sccm) of SiH₄. The deposition rate of the films was found to be 7.1, 7.3, 9 and 11 Å/s for the variation of R as 0.5, 0.67, 0.75 and 0.83, respectively. The films were optically and compositionally characterized by reflectance, photoluminescence, infrared absorption and X-ray photoelectron spectroscopy. The films were amorphous in nature and the refractive indices of the films were varied between 2.46 and 1.90 by changing the gas flow ratio during the deposition. The PL peak energy was increased and the linear band tails become broad with the increase in R. The incorporation of nitrogen takes place with the increase in R.     

Refraction properties of PECVD of silicon nitride film

Using a neural network, the refractive index of a film deposited in a plasma enhanced chemical vapor deposition is characterized. The deposition process was characterized by a 2^6-1 fractional factorial experiment. Experimental variables and ranges include 20-40 W radio frequency (RF) power, 80-160 Pa pressure, 180-260 sccm SiH₄ flow rate, 1-1.4 sccm NH₃ flow rate, 0-1000 sccm N₂ flow rate, and 200-300°C substrate temperature. To examine the effect of the interaction between variables on the refractive index, a predictive neural network model was constructed. Prediction accuracy was optimized as a function of training factors. Model predictions were certified experimentally. Many complex interactions between the variables not reported previously were revealed. The power effect was transparent only in such plasma conditions as high SiH₄ or NH₃ flow rate. The temperature effect was conspicuous under high pressure. Deposition mechanisms were qualitatively estimated in conjunction with the reported linear dependency of refractive index on SiH/NH ratio.     

Insight into excimer laser crystallization exploiting ellipsometry: Effect of silicon film precursor

The optical diagnostic of spectroscopic ellipsometry is shown to be an effective tool to investigate the mechanism of excimer laser crystallization (ELC) of silicon thin films. A detailed spectroscopic ellipsometric investigation of the microstructures of polycrystalline Si films obtained on SiO₂/Si wafers by ELC of a-Si:H and nc-Si films deposited, respectively, by SiH₄ plasma enhanced chemical vapor deposition (PECVD) and SiF₄-PECVD is presented. It is shown that ellipsometric spectra of the pseudodielectric function of polysilicon thin films allows to discern the three different ELC regimes of partial melting, super lateral growth and complete melting. Exploiting ellipsometry and atomic force microscopy, it is shown that ELC of nc-Si has very low energy density threshold of 95 mJ/cm² for complete melting, and that re-crystallization to large grains of ∼ 2 μm can be achieved by multi-shot irradiation at an energy density as low as 260 mJ/cm² when using nc-Si when compared to 340 mJ/cm² for the ELC of a-Si films.     

Effect of rf power on the growth of silicon nanowires by hot-wire assisted plasma enhanced chemical vapor deposition (HW-PECVD) technique

Silicon nanowires (SiNWs) were synthesized by simultaneous evaporation of Au and Si deposition using H₂ diluted SiH₄. The deposition techniques combined hot-wire (HW) and plasma enhanced chemical vapor deposition (PECVD). Au wires were placed on the filament and heated simultaneously with the activation of the rf plasma for the dissociation of SiH₄ and H₂ gases. Five set of samples were deposited on ITO-coated glass substrate at different rf power varied from 20 to 100 W in an interval of 20 W, keeping other deposition parameters constant. High yield of SiNWs with diameter ranging from 60 to 400 nm and length about 10 μm were grown at rf power of 80 W (power density ~ 1018 mW cm⁻²). Rf power of 100 W (power density ~ 1273 mW cm⁻²) suppressed the growth of these SiNWs. The growth mechanisms of SiNWs are tentatively proposed. The nanocrystalline structure of SiNWs is confirmed by Raman spectra and HRTEM measurement.     

Numerical modeling of SiH4 discharge for Si thin film deposition for thin film transistor and solar cells

Amorphous and microcrystalline silicon thin films are used in solar cells as a multi-junction photovoltaic device. Plasma enhanced chemical vapor deposition is used and high deposition rate of a few nm/s is required while keeping film quality. SiH₄ is used as a precursor diluted with H₂. Electron impact processes give complex interdependent plasma chemical reactions. Many researchers suggest keeping high H/SiH_x ratio is important. Numerical modeling of this process for capacitively coupled plasma and inductively coupled plasma is done to investigate which process parameters are playing key roles in determining it. A full set of 67 volume reactions and reduced set are used. Under most of conditions, CCP shows 100 times higher H/SiH₃ ratio over ICP case due to its spatially localized two electron temperature distribution. Multi hollow cathode type CCP is also modeled as a 2 × 2 hole array. For Ar, the discharge is well localized at the neck of the hole at a few Torr of gas pressure. H₂ and SiH₄ + H₂ needed higher gas pressure and power density to get a multi hole localized density profile. H/SiH₃ was calculated to be about 1/10.     

Plasma etching of virtually stress-free stacked silicon nitride films

Stacked silicon nitride films for use in manufacturing of surface micromachined membranes were deposited using custom made plasma-enhanced chemical vapor deposition instrument with silane (SiH₄) and ammonia (NH₃) gas mixture as deposition precursor. Deposition conditions were adjusted by varying substrate temperature and SiH₄ to NH₃ flow ratio and temperature to obtain the required stress related and electrical properties of the membranes. Transmission Fourier transformed infrared spectroscopy and scanning electron microscopy were used to investigate the chemical composition and morphology of the stacked film components. An increase in the SiH₄ to NH₃ flow ratio and a decrease in temperature resulted in a silicon-rich silicon nitride film, as well as an increased silicon oxide concentration. To avoid underetch and sidewall defects, the plasma power density during the plasma etching was changed from 0.5 W/cm² during the etching of both top and bottom layers in a stacked film, to 1.0 W/cm² during the etching of the middle both silicon and silicon oxide rich film. This resulted in an improved overall stacked film sidewall quality and reduced the unwanted underetch.     

Synthesis of nanosize Si–C–N powder in low pressure plasmas

Multicomponent powders based on the B–C–N–Si system are of great interest as starting materials for sintering advanced ceramics and composites with improved properties. The square-wave modulation of the electrical power supplied to low pressure (<100 Pa) radio frequency (rf) plasmas has been shown as a suitable method to produce high purity silicon and binary powders, such as SiC, SiN and BN. The present study investigates the synthesis of silicon carbonitride (SiCN) nanometric powder in a plasma-enhanced chemical vapour deposition reactor, by rf glow discharge decomposition of CH₄, SiH₄ and NH₃ gases at room temperature. The output of the rf source (13.56 MHz) was square-wave modulated at a period of 20 s with plasma-on times between 0.05 and 5 s. Transmission electron microscopy showed that the SiCN nanopowder was amorphous and that the average particle size increased from 9 to 100 nm as the plasma-on period increased. The chemical composition of the powder was analyzed by X-ray photoelectron spectroscopy and elemental analysis. Infrared spectroscopy revealed the presence of Si–C, Si–N, C–N and hydrogenated bonds. The infrared absorptions of hydrogenated bonds decreased as the plasma-on time increased, volume ratio with the increase in particle size.     

Importance of H2 gas for growth of hot-wire CVD nanocrystalline 3C-SiC from SiH4/CH4/H2

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition from SiH₄/CH₄/H₂ and the influence of H₂ gas flow rate (F(H₂)) on the film properties was investigated. The SiH₄ gas flow rate was 1 sccm. At the CH₄ gas flow rate (F(CH₄)) of 1 sccm, nanocrystalline cubic SiC (nc-3C-SiC) grew even without H₂. On the other hand, at F(CH₄) = 2 sccm, amorphous SiC grew without H₂ and nc-3C-SiC grew above F(H₂) = 50 sccm. As F(H₂) was increased, the crystallinity improved both at F(CH₄) = 1 and 2 sccm. However, the mean crystallite size decreased at F(CH₄) = 1 sccm and increased at F(CH₄) = 2 sccm. We discuss growth mechanisms of nc-3C-SiC.     

Electronic properties of silicon nanoneedle structure obtained by RIE for nonvolatile memory applications

Nanotechnology is one of the newly rising technological fields and acquiring the research priorities in these days. Nanostructures found to have high optical gain, and found to be a key element in the nonvolatile memory devices. The major drawback in the formation of nanocrystalline silicon (nc-Si) is the lack of uniformity and low density. Uniform and packed needle like silicon surface with a size of 50 nm and with a depth of 300 nm was established in the present study using a reactive ion etching (RIE) system. SF₆ and O₂ gases were used for the reactive ion etching process. The ratio of gas flow rates during etching was optimized for the anisotropic etching of silicon to generate nanostructures. Surface morphology was investigated after etching using scanning electron microscope (SEM). The sample etched at an SF₆ flow rate of 13 sccm was found to be smooth, but as the SF₆ flow rate increases, we can see the formation of columnar microstructures. For a typical flow of SF₆ with the flow rate of 22 sccm, we found the silicon surface covered by columnar structures with diameters ∼ 50 nm and depth of about 300 nm. Radio Frequency (RF) power, etching time and oxygen flow rate were fixed to 100 W, 15 min and 12 sccm, respectively, during the experiment for all the samples. In order to observe the effect of RF power on the formation of nanoneedle silicon surface, experiments were carried out at different powers (60 W, 80 W and 100 W) and at a constant SF₆ and oxygen flow rates of 22 sccm and 13 sccm. From this study, we formed a deep nanoneedle structured silicon surface at a power of 100 W. Photoluminescence (PL) and capacitance–voltage (C–V) characteristics were recorded on metal-oxide-semiconductor (MOS) capacitors with nanoneedle surface structure of silicon.     

Mid-frequency PECVD of a-SiCN:H films and their structural,mechanical and electrical properties

The mid-frequency pulsed plasma enhanced chemical vapour deposition (PECVD) of hydrogenated amorphous silicon carbonitride (a-SiCN:H) was investigated to prove the suitability of these films as a mechanical stiff insulator for the integration of piezoelectric fibres in microstructured aluminium plates. For the a-SiCN:H deposition trimethylsilane (SiH(CH₃)_3; 3MS) and nitrogen in mixture with argon were used. The films were characterised regarding their deposition rate, elastic modulus and hardness (nanoindentation), mechanical stress, elemental composition (ERDA) and electrical insulating properties.The breakdown field strength of μm-thick a-SiCN:H films is in the range of 2–4 MV/cm. At pressures of a few Pa the deposition rate reached values up to 6 μm/h. It is limited by the power absorption in the 100 kHz bipolar-pulsed discharge. Varying the pressure from 2 Pa to 15 Pa has only little influence on the film composition. With increasing pressure during deposition the elastic modulus of the films decreases from about 146 GPa to 100 GPa and the compressive film stress from 1.2 GPa to 0.55 GPa. By reducing the 3MS flow rate from 50 sccm to 10 sccm (at 8 Pa deposition pressure), the carbon and the hydrogen concentrations in the films were reduced by about 10 at. %. The Si-content is only slightly reduced but the N-content is more than tripled. In contrast, the changes in the mechanical film properties are comparatively small. The mechanical properties of a-SiCN:H films are not simply correlated to the stoichiometry but are rather controlled by the ion bombardment during growth.     

Comparative study on dry etching of polycrystalline diamond thin films

The reactive ion etching (RIE) technique was used to etch polycrystalline diamond thin films. In this study we investigate the influence of process parameters (total pressure, rf power, gas composition) of standard capacitively coupled plasma RIE system on the etching rate of diamond films. The surface morphology of etched diamond films was characterized by Scanning Electron Microscopy and the chemical composition of the etched film part was investigated by Raman Spectroscopy.We found that the gas composition had a crucial effect on the diamond film morphology. The use of CF₄ gas resulted in flatter surfaces and lateral-like etching, while the use of pure O₂ gas resulted in needle-like structures. Addition of argon to the reactant precursors increased the ion bombardment, which in turn increased the formation of non-diamond phases. Next, increasing the rf power from 100 to 500 W increased the etching rate from 5.4 to 8.6 μm/h. In contrast to this observation, the rise of process pressure from 80 to 150 mTorr lowered the etching rate from 5.6 down to 3.6 μm/h.     

Influence of gas pressure on low-temperature preparation and film properties of nanocrystalline 3C-SiC thin films by HW-CVD using SiH4/CH4/H2 system

We investigated an influence of gas pressure on low-temperature preparation of nanocrystalline cubic silicon carbide (nc-3C-SiC) films by hot-wire chemical vapour deposition (HW-CVD) using SiH₄/CH₄/H₂ system. X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectra revealed that the films prepared below 1.5 Torr were Si-nanocrystallite-embedded hydrogenated amorphous SiC. On the other hand, nc-3C-SiC films were successfully prepared at gas pressure above 2 Torr. The high gas pressure plays two important roles in low-temperature preparation of nc-3C-SiC films: (1) leading to sufficient decomposition of CH₄ molecules through a gas phase reaction and an increase in the incorporation of carbon atoms into film and (2) promoting a creation of H radicals on the heated filament, allowing the sufficient coverage of growing film surface and a selective etching of amorphous network structure and/or crystalline-Si phase. It was found that total gas pressure is a key parameter for low-temperature preparation of nc-3C-SiC films.     

Low-pressure synthesis and characterization of multiphase SiC by HWCVD using CH4/SiH4

Silicon carbide (SiC) thin films were deposited by low-pressure hot wire chemical vapor deposition (HWCVD) technique using SiH₄ and CH₄ gas precursors with no hydrogen dilution. Spectroscopic and structural properties of the films deposited at various methane flow rate (10-100 sccm) and low silane flow rate of 0.5 sccm were investigated. The use of low methane flow rate resulted in a sharp and intense Si-C peak in the Fourier transform infrared (FTIR) absorption spectra. The XRD spectra of the films showed the formation of SiC crystallites at low methane flow rate. The Raman spectroscopy measurements showed the coexistence of a-Si and SiC phases in the films. Increase in methane flow rate increased the carbon incorporation and deposition rate of the SiC films but also promoted the formation of amorphous Si and SiC phases in the films.