Low-temperature plasma processing for Si photovoltaics

There has been a recent rapid expansion of the range of applications of low-temperature plasma processing in Si-based photovoltaic (PV) technologies. The desire to produce Si-based PV materials at an acceptable cost with consistent performance and reproducibility has stimulated a large number of major research and research infrastructure programs, and a rapidly increasing number of publications in the field of low-temperature plasma processing for Si photovoltaics. In this article, we introduce the low-temperature plasma sources for Si photovoltaic applications and discuss the effects of low-temperature plasma dissociation and deposition on the synthesis of Si-based thin films. We also examine the relevant growth mechanisms and plasma diagnostics, Si thin-film solar cells, Si heterojunction solar cells and silicon nitride materials for antireflection and surface passivation. Special attention is paid to the low-temperature plasma interactions with Si materials including hydrogen interaction, wafer cleaning, masked or mask-free surface texturization, the direct formation of p-n junction, and removal of phosphorus silicate glass or parasitic emitters. The chemical and physical interactions in such plasmas with Si surfaces are analyzed. Several examples of the plasma processes and techniques are selected to represent a variety of applications aimed at the improvement of Si-based solar cell performance. © 2014 Elsevier B.V.

Low-temperature plasmas in carbon nanostructure synthesis

Plasma-based techniques offer many unique possibilities for the synthesis of various nanostructures both on the surface and in the plasma bulk. In contrast to the conventional chemical vapor deposition and some other techniques, plasma-based processes ensure high level of controllability, good quality of the produced nanomaterials, and reduced environmental risk. In this work, the authors briefly review the unique features of the plasma-enhanced chemical vapor deposition approaches, namely, the techniques based on inductively coupled, microwave, and arc discharges. Specifically, the authors consider the plasmas with the ion/electron density ranging from 10^10 to 10^14 cm−3, electron energy in the discharge up to ∼10 eV, and the operating pressure ranging from 1 to 10^4 Pa (up to 105 Pa for the atmospheric-pressure arc discharges). The operating frequencies of the discharges considered range from 460 kHz for the inductively coupled plasmas, and up to 2.45 GHz for the microwave plasmas. The features of the direct-current arc discharges are also examined. The authors also discuss the principles of operation of these systems, as well as the effects of the key plasma parameters on the conditions of nucleation and growth of the carbon nanostructures, mainly carbon nanotubes and graphene. Advantages and disadvantages of these plasma systems are considered. Future trends in the development of these plasma-based systems are also discussed.

Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.

Rapid, simultaneous activation of thin nanowire growth in low-temperature, low-pressure chemically active plasmas

Multiscale numerical modeling of the species balance and transport in the ionized gas phase and on the nanostructured solid surface complemented by the heat exchange model is used to demonstrate the possibility of minimizing the Gibbs-Thompson effect in low-temperature, low-pressure chemically active plasma-assisted growth of uniform arrays of very thin Si nanowires, impossible otherwise. It is shown that plasma-specific effects drastically shorten and decrease the dispersion of the incubation times for the nucleation of nanowires on non-uniform Au catalyst nanoparticle arrays. The fast nucleation makes it possible to avoid a common problem of small catalyst nanoparticle burying by amorphous silicon. These results explain a multitude of experimental observations on chemically active plasma-assisted Si nanowire growth and can be used for the synthesis of a range of inorganic nanowires for environmental, biomedical, energy conversion, and optoelectronic applications.

Minimizing the Gibbs–Thomson effect in the low-temperature plasma synthesis of thin Si nanowires

An advanced combination of numerical models, including plasma sheath, ion- and radical-induced species creation and plasma heating effects on the surface and within a Au catalyst nanoparticle, is used to describe the catalyzed growth of Si nanowires in the sheath of a low-temperature and low-pressure plasma. These models have been used to explain the higher nanowire growth rates, low-energy barriers, much thinner Si nanowire nucleation and the less effective Gibbs–Thomson effect in reactive plasma processes, compared with those of neutral gas thermal processes. The effects of variation in the plasma sheath parameters and substrate potential on Si nanowire nucleation and growth have also been investigated. It is shown that increasing the plasma-related effects leads to decreases in the nucleation energy barrier and the critical nanoparticle radius, with the Gibbs–Thomson effect diminished, even at low temperatures. The results obtained are consistent with available experimental results and open a path toward the energy- and matter-efficient nucleation and growth of a broad range of one-dimensional quantum structures.

Heating and plasma sheath effects in low-temperature, plasma-assisted growth of carbon nanofibers

Plasma sheath, nanostructure growth, and thermal models are used to describe carbon nanofiber (CNF) growth and heating in a low-temperature plasma. It is found that when the H2 partial pressure is increased, H atom recombination and H ion neutralization are the main mechanisms responsible for energy release on the catalyst surface. Numerical results also show that process parameters such as the substrate potential, electron temperature and number density mainly affect the CNF growth rate and plasma heating at low catalyst temperatures. In contrast, gas pressure, ion temperature, and the C2H2:H2 supply ratio affect the CNF growth at all temperatures. It is shown that plasma-related processes substantially increase the catalyst particle temperature, in comparison to the substrate and the substrate-holding platform temperatures.

Temperature-dependent growth mechanisms of low-dimensional ZnO nanostructures

One-dimensional ZnO nanostructures were successfully synthesized on single-crystal silicon substrates via a simple thermal evaporation and vapour-phase transport method under different process temperatures from 500 to 1000 °C. The detailed and in-depth analysis of the experimental results shows that the growth of ZnO nanostructures at process temperatures of 500, 800, and 1000 °C is governed by different growth mechanisms. At a low process temperature of 500 °C, the ZnO nanostructures feature flat and smooth tips, and their growth is primarily governed by the vapour-solid mechanism. At an intermediate process temperature of 800 °C, the ZnO nanostructures feature cone-shape tips, and their growth is primarily governed by the self-catalyzed and saturated vapour–liquid–solid mechanism. At a high process temperature of 1000 °C, the alloy tip appears on the front side of the ZnO nanostructures, and their growth is primarily governed by the common catalyst-assisted vapour–liquid–solid mechanism. It is also shown that the morphological, structural, optical, and compositional properties of the synthesized ZnO nanostructures are closely related to the process temperature. These results are highly relevant to the development of light-emitting diodes, chemical sensors, energy conversion devices, and other advanced applications.

Ion-assisted precursor dissociation and surface diffusion : enabling rapid, low-temperature growth of carbon nanofibers

Growth kinetics of carbon nanofibers in a hydrocarbon plasma is studied. In addition to gas-phase and surface processes common to chemical vapor deposition, the model includes (unique to plasma-exposed catalyst surfaces) ion-induced dissociation of hydrocarbons, interaction of adsorbed species with incoming hydrogen atoms, and dissociation of hydrocarbon ions. It is shown that at low, nanodevice-friendly process temperatures the nanofibers grow via surface diffusion of carbon adatoms produced on the catalyst particle via ion-induced dissociation of a hydrocarbon precursor. These results explain a lower activation energy of nanofiber growth in a plasma and can be used for the synthesis of other nanoassemblies. © 2007 American Institute of Physics.

Plasma-controlled adatom delivery and (re)distribution: Enabling uninterrupted, low-temperature growth of ultralong vertically aligned single walled carbon nanotubes

Large-scale (∼109 atoms) numerical simulations reveal that plasma-controlled dynamic delivery and redistribution of carbon atoms between the substrate and nanotube surfaces enable the growth of ultralong single walled carbon nanotubes (SWCNTs) and explain the common experimental observation of slower growth at advanced stages. It is shown that the plasma-based processes feature up to two orders of magnitude higher growth rates than equivalent neutral-gas systems and are better suited for the SWCNT synthesis at low nanodevice friendly temperatures. © 2008 American Institute of Physics.

Low-pressure planar magnetron discharge for surface deposition and nanofabrication

Current-voltage characteristics of the planar magnetron are studied experimentally and by numerical simulation. Based on the measured current-voltage characteristics, a model of the planar magnetron discharge is developed with the background gas pressure and magnetic field used as parameters. The discharge pressure was varied in a range of 0.7-1.7 Pa, the magnetic field of the magnetron was of 0.033-0.12 T near the cathode surface, the discharge current was from 1 to 25 A, and the magnetic field lines were tangential to the substrate surface in the region of the magnetron discharge ignition. The discharge model describes the motion of energetic secondary electrons that gain energy by passing the cathode sheath across the magnetic field, and the power required to sustain the plasma generation in the bulk. The plasma electrons, in turn, are accelerated in the electric field and ionize effectively the background gas species. The model is based on the assumption about the prevailing Bohm mechanism of electron conductivity across the magnetic field. A criterion of the self-sustained discharge ignition is used to establish the dependence of the discharge voltage on the discharge current. The dependence of the background gas density on the current is also observed from the experiment. The model is consistent with the experimental results. © 2010 American Institute of Physics.

Single-step, rapid low-temperature synthesis of Si quantum dots embedded in an amorphous SiC matrix in high-density reactive plasmas

A simple, effective and innovative approach based on low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to rapidly synthesize Si quantum dots (QDs) embedded in an amorphous SiC (a-SiC) matrix at a low substrate temperature and without any commonly used hydrogen dilution. The experimental results clearly demonstrate that uniform crystalline Si QDs with a size of 3-4 nm embedded in the silicon-rich (carbon content up to 10.7at.%) a-SiC matrix can be formed from the reactive mixture of silane and methane gases, with high growth rates of ∼1.27-2.34 nm s-1 and at a low substrate temperature of 200 °C. The achievement of the high-rate growth of Si QDs embedded in the a-SiC without any commonly used hydrogen dilution is discussed based on the unique properties of the inductively coupled plasma-based process. This work is particularly important for the development of the all-Si tandem cell-based third generation photovoltaic solar cells.

Low- and high-temperature controls in carbon nanofiber growth in reactive plasmas

A numerical growth model is used to describe the catalyzed growth of carbon nanofibers in the sheath of a low-temperature plasma. Using the model, the effects of variation in the plasma sheath parameters and substrate potential on the carbon nanofiber growth characteristics, such as the growth rate, the effective carbon flux to the catalyst surface, and surface coverages, have been investigated. It is shown that variations in the parameters, which change the sheath width, mainly affect the growth parameters at the low catalyst temperatures, whereas the other parameters such as the gas pressure, ion temperature, and percentages of the hydrocarbon and etching gases, strongly affect the carbon nanofiber growth at higher temperatures. The conditions under which the carbon nanofiber growth can still proceed under low nanodevice-friendly process temperatures have been formulated and summarized. These results are consistent with the available experimental results and can also be used for catalyzed growth of other high-aspect-ratio nanostructures in low-temperature plasmas.

Increased size selectivity of Si quantum dots on SiC at low substrate temperatures : an ion-assisted self-organization approach

A simple, effective, and innovative approach based on ion-assisted self-organization is proposed to synthesize size-selected Si quantum dots (QDs) on SiC substrates at low substrate temperatures. Using hybrid numerical simulations, the formation of Si QDs through a self-organization approach is investigated by taking into account two distinct cases of Si QD formation using the ionization energy approximation theory, which considers ionized in-fluxes containing Si3+ and Si1+ ions in the presence of a microscopic nonuniform electric field induced by a variable surface bias. The results show that the highest percentage of the surface coverage by 1 and 2 nm size-selected QDs was achieved using a bias of -20 V and ions in the lowest charge state, namely, Si1+ ions in a low substrate temperature range (227-327 °C). As low substrate temperatures (≤500 °C) are desirable from a technological point of view, because (i) low-temperature deposition techniques are compatible with current thin-film Si-based solar cell fabrication and (ii) high processing temperatures can frequently cause damage to other components in electronic devices and destroy the tandem structure of Si QD-based third-generation solar cells, our results are highly relevant to the development of the third-generation all-Si tandem photovoltaic solar cells.

Distribution of ion-current density on substrate between carbon nanotubes grown from low-temperature plasma

Using Monte Carlo simulation technique, we have calculated the distribution of ion current extracted from low-temperature plasmas and deposited onto the substrate covered with a nanotube array. We have shown that a free-standing carbon nanotube is enclosed in a circular bead of the ion current, whereas in square and hexagonal nanotube patterns, the ion current is mainly concentrated along the lines connecting the nearest nanotubes. In a very dense array (with the distance between nanotubes/nanotube-height ratio less than 0.05), the ions do not penetrate to the substrate surface and deposit on side surfaces of the nanotubes.

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.