Temperature-dependent properties of nc-Si thin films synthesized in low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas

Silicon thin films were synthesized simultaneously on single-crystal silicon and glass substrates by lowpressure, thermally nonequilibrium, high-density inductively coupled plasma-assisted chemical vapor deposition from the silane precursor gas without any additional hydrogen dilution in a broad range of substrate temperatures from 100 to 500 °C. The effect of the substrate temperature on the morphological, structural and optical properties of the synthesized silicon thin films is systematically studied by X-ray diffractometry, Raman spectroscopy, UV-vis spectroscopy, and scanning electron microscopy. It is shown that the formation of nanocrystalline silicon (nc-Si) occurs when the substrate temperature is higher than 200 °C and that all the deposited nc-Si films have a preferential growth along the (111) direction. However, the mean grain size of the (111) orientation slightly and gradually decreases while the mean grain size of the (220) orientation shows a monotonous increase with the increased substrate temperature from 200 to 500 °C. It is also found that the crystal volume fraction of the synthesized nc-Si thin films has a maximum value of ∼69.1% at a substrate temperature of 300 rather than 500 °C. This rather unexpected result is interpreted through the interplay of thermokinetic surface diffusion and hydrogen termination effects. Furthermore, we have also shown that with the increased substrate temperature from 100 to 500 °C, the optical bandgap is reduced while the growth rates tend to increase. The maximum rates of change of the optical bandgap and the growth rates occur when the substrate temperature is increased from 400 to 500 °C. These results are highly relevant to the development of photovoltaic thin-film solar cells, thin-film transistors, and flat-panel displays.

Nanopowder management and control of plasma parameters in electronegative SiH4 plasmas

The nanopowder management and control of plasma parameters in electronegative SiH4 plasmas were discussed. The spatial profiles of electron and positive/negative ion number densities, electron temperature and charge of the fine particles were obtained. It was found that management of powder charge distribution is also possible through control of the external parameters.

Magnetic-field-enhanced synthesis of single-wall carbon nanotubes in arc discharge

The ability to control the properties of single-wall nanotubes (SWNTs) produced in the arc discharge is important for many practical applications. Our experiments suggest that the length of SWNTs significantly increases (up to 4000 nm), along with the purity of the carbon deposit, when the magnetic field is applied to arc discharge. Scanning electron microscopy and transmission electron microscopy analyses have demonstrated that the carbon deposit produced in the magnetic-field-enhanced arc mainly consists of the isolated and bunched SWNTs. A model of a carbon nanotube interaction and growth in the thermal plasma was developed, which considers several important effects such as anode ablation that supplies the carbon plasma in an anodic arc discharge technique, and the momentum, charge, and energy transfer processes between nanotube and plasma. It is shown that the nanotube charge with respect to the plasma as well as nanotube length depend on plasma density and electric field in the interelectrode gap. For instance, nanotube charge changes from negative to positive value with an electron density decrease. The numerical simulations based on the Monte Carlo technique were performed, which explain an increase in the nanotubes produced in the magnetic-field-enhanced arc discharge. © 2008 American Institute of Physics.

Equilibrium and relaxation of particulate charge in fluorocarbon plasmas

Charging of micron-size particulates, often appearing in fluorocarbon plasma etching experiments, is considered. It is shown that in inductively coupled and microwave slot-excited plasmas of C4F8 and Ar gas mixtures, the equilibrium particle charge and charge relaxation processes are controlled by a combination of microscopic electron, atomic (Ar+ and F+), and molecular ion (CF+ 3, CF+ 2, and CF+) currents. The impact of molecular ion currents on the particulate charging and charge relaxation processes is analyzed. It is revealed that in low-power (<0.5 kW) microwave slot-excited plasmas, the impact of the combined molecular ion current to the total positive microscopic current on the particle can be as high as 40%. The particulate charge relaxation rate in fluorocarbon plasmas appears to exceed 108 s-1, which is almost one order of magnitude higher than that from purely argon plasmas. This can be attributed to the impact of positive currents of fluorocarbon molecular ions, as well as to the electron density fluctuations with particle charge, associated with electron capture and release by the particulates.

Standing surface waves in a dust-contaminated large-area planar plasma source

The effect of charged particulates or dusts on surface wave produced microwave discharges is studied. The frequencies of the standing electromagnetic eigenmodes of large-area flat plasmas are calculated. The dusts absorb a significant amount of the plasma electrons and can lead to a modification of the electromagnetic field structure in the discharge by shifting the originally excited operating mode out of resonance. For certain given proportions of dusts, mode conversion is found to be possible. The power loss in the discharge is also increased because of dust-specific dissipations, leading to a decrease of the operating mode quality factor.

Generation of uniform plasmas by crossed internal oscillating current sheets : key concepts and experimental verification

The results of comprehensive experimental studies of the operation, stability, and plasma parameters of the low-frequency (0.46 MHz) inductively coupled plasmas sustained by the internal oscillating rf current are reported. The rf plasma is generated by using a custom-designed configuration of the internal rf coil that comprises two perpendicular sets of eight currents in each direction. Various diagnostic tools, such as magnetic probes, optical emission spectroscopy, and an rf-compensated Langmuir probe were used to investigate the electromagnetic, optical, and global properties of the argon plasma in wide ranges of the applied rf power and gas feedstock pressure. It is found that the uniformity of the electromagnetic field inside the plasma reactor is improved as compared to the conventional sources of inductively coupled plasmas with the external flat coil configuration. A reasonable agreement between the experimental data and computed electromagnetic field topography inside the chamber is reported. The Langmuir probe measurements reveal that the spatial profiles of the electron density, the effective electron temperature, plasma potential, and electron energy distribution/probability functions feature a high degree of the radial and axial uniformity and a weak azimuthal dependence, which is consistent with the earlier theoretical predictions. As the input rf power increases, the azimuthal dependence of the global plasma parameters vanishes. The obtained results demonstrate that by introducing the internal oscillated rf currents one can noticeably improve the uniformity of electromagnetic field topography, rf power deposition, and the plasma density in the reactor.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Electron transport across magnetic field in low-temperature plasmas : an alternative approach for obtaining evidence of Bohm mechanism

A comparative study involving both experimental and numerical investigations was made to resolve a long-standing problem of understanding electron conductivity mechanism across magnetic field in low-temperature plasmas. We have calculated the plasma parameters from experimentally obtained electric field distribution, and then made a 'back' comparison with the distributions of electron energy and plasma density obtained in the experiment. This approach significantly reduces an influence of the assumption about particular phenomenology of the electron conductivity in plasma. The results of the experiment and calculations made by this technique have showed that the classical conductivity is not capable of providing realistic total current and electron energy, whereas the phenomenological anomalous Bohm mobility has demonstrated a very good agreement with the experiment. These results provide an evidence in favor of the Bohm conductivity, thus making it possible to clarify this pressing long-living question about the main driving mechanism responsible for the electron transport in low-temperature plasmas.

Effective control of nanostructured phases in rapid, room-temperature synthesis of nanocrystalline Si in high-density plasmas

An innovative and effective approach based on low-pressure, low-frequency, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to synthesize device-quality nanocrystalline silicon (nc-Si) thin films at room temperature and with very competitive growth rates. The crystallinity and microstructure properties (including crystal structure, crystal volume fraction, surface morphology, etc.) of this nanostructured phase of Si can be effectively tailored in broad ranges for different device applications by simply varying the inductive rf power density from 25.0 to 41.7 mW/cm3. In particular, at a moderate rf power density of 41.7 mW/cm3, the nc-Si films feature a very high growth rate of 2.37 nm/s, a high crystalline fraction of 86%, a vertically aligned columnar structure with the preferential (111) growth orientation and embedded Si quantum dots, as well as a clean, smooth and defect-free interface. We also propose the formation mechanism of nc-Si thin films which relates the high electron density and other unique properties of the inductively coupled plasmas and the formation of the nanocrystalline phase on the Si surface.

Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

High-rate, low-temperature synthesis of composition controlled hydrogenated amorphous silicon carbide films in low-frequency inductively coupled plasmas

It is commonly believed that in order to synthesize high-quality hydrogenated amorphous silicon carbide (a-Si1-xCx : H) films at competitive deposition rates it is necessary to operate plasma discharges at high power regimes and with heavy hydrogen dilution. Here we report on the fabrication of hydrogenated amorphous silicon carbide films with different carbon contents x (ranging from 0.09 to 0.71) at high deposition rates using inductively coupled plasma (ICP) chemical vapour deposition with no hydrogen dilution and at relatively low power densities (∼0.025 W cm -3) as compared with existing reports. The film growth rate R d peaks at x = 0.09 and x = 0.71, and equals 18 nm min-1 and 17 nm min-1, respectively, which is higher than other existing reports on the fabrication of a-Si1-xCx : H films. The extra carbon atoms for carbon-rich a-Si1-xCx : H samples are incorporated via diamond-like sp3 C-C bonding as deduced by Fourier transform infrared absorption and Raman spectroscopy analyses. The specimens feature a large optical band gap, with the maximum of 3.74 eV obtained at x = 0.71. All the a-Si1-xCx : H samples exhibit low-temperature (77 K) photoluminescence (PL), whereas only the carbon-rich a-Si1-xCx : H samples (x ≥ 0.55) exhibit room-temperature (300 K) PL. Such behaviour is explained by the static disorder model. High film quality in our work can be attributed to the high efficiency of the custom-designed ICP reactor to create reactive radical species required for the film growth. This technique can be used for a broader range of material systems where precise compositional control is required. © 2008 IOP Publishing Ltd.

Catalytic probes with nanostructured surface for gas/discharge diagnostics : a study of a probe signal behaviour

Catalytic probes are used for plasma diagnostics in order to quantify the density of neutral atoms. The probe response primarily depends on the probe material and its surface morphology. Here we report on the design, operation and modelling of the response of niobium pentoxide sensors with a flat and nanowire (NW) surfaces. These sensors were used to detect neutral oxygen atoms in the afterglow region of an inductively coupled rf discharge in oxygen. A very different response of the flat-surface and NW probes to the varying densities of oxygen atoms was explained by modelling heat conduction and taking into account the associated temperature gradients. It was found that the nanostructure probe can measure in a broader range than the flat oxide probe due to an increase in the surface to volume ratio, and the presence of nanostructures which act as a thermal barrier against sensor overheating. These results can be used for the development of the new generation of catalytic probes for gas/discharge diagnostics in a range of industrial and environmental applications.

Ways to increase the length of single wall carbon nanotubes in a magnetically enhanced arc discharge

Ability to control the properties of single-wall nanotubes produced in the arc discharge is important for many practical applications. Our experiments suggest that the length and purity of single-wall nanotubes significantly increase when the magnetic field is applied to the arc discharge. A model of a single wall carbon nanotube interaction and growth in the thermal plasma was developed which considers several important effects such as anode ablation that supplies the carbon plasma in an anodic arc discharge technique, and the momentum, charge and energy transfer processes between nanotube and plasma. The numerical simulations based on Monte-Carlo technique were performed, which explain an increase of the nanotubes produced in the magnetic field - enhanced arc discharge.

Reactive species in Ar+H2 plasma-aided nanofabrication : two-dimensional discharge modelling

Understanding the generation of reactive species in a plasma is an important step towards creating reliable and robust plasma-aided nanofabrication processes. A two-dimensional fluid simulation of the number densities of surface preparation species in a low-temperature, low-pressure, non-equilibrium Ar+H2 plasma is conducted. The operating pressure and H2 partial pressure have been varied between 70-200 mTorr and 0.1-50%, respectively. An emphasis is placed on the application of these results to nanofabrication. A reasonable balance between operating pressures and H 2 partial pressures that would optimize the number densities of the two working units largely responsible for activation and passivation of surface dangling bonds (Ar+ and H respectively) in order to achieve acceptable rates of surface activation and passivation is obtained. It is found that higher operating pressures (150-200 mTorr) and lower H2 partial pressures (∼5%) are required in order to ensure high number densities of Ar+ and H species. This paper contributes to the improvement of the controllability and predictability of plasma-based nanoassembly processes.