Article pubs.acs.

org/JACS

Size- and Orientation-Selective Si Nanowire Growth: Thermokinetic Eects of Nanoscale Plasma Chemistry
Hamid Mehdipour and Kostya (Ken) Ostrikov*,
Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, New South Wales 2070, Australia and Plasma Nanoscience @ Complex Systems, The University of Sydney, New South Wales 2006, Australia
S Supporting Information *

ABSTRACT: A multiscale, multiphase thermokinetic model is used to show the eective control of the growth orientation of thin Si NWs for nanoelectronic devices enabled by nanoscale plasma chemistry. It is shown that very thin Si NWs with [110] growth direction can nucleate at much lower process temperatures and pressures compared to thermal chemical vapor deposition where [111]-directed Si NWs are predominantly grown. These ndings explain a host of experimental results and oer the possibility of energy- and matter-ecient, size- and orientation-controlled growth of [110] Si NWs for next-generation nanodevices.

1. INTRODUCTION Owing to their fascinating semiconducting, chemical, and biocompatibility properties as well as the eective quantum connement in two dimensions, inorganic NWs (NWs) are exceptional candidates for a variety of applications ranging from eld eect transistors (FETs) and lasers to biosensors and energy conversion and storage devices.16 The NW response in nanoscale applications critically depends on their elemental composition, structural, and morphological properties. Despite many years of intense research and a number of established applications of NWs, the problem of eective control of the structural and morphological parameters, such as the NW length, diameter, and the growth direction, still remains unsolved. The as-grown NW networks commonly contain a mix of thick and thin NWs grown along dierent directions. Therefore, versatile nanoscale synthesis approaches are required to produce suciently long NWs with narrowed distributions of diameters and orientations. For example, selective growth of thin Si NWs along [110] direction is highly warranted for next-generation high-speed, high-density FET nanoelectronic devices3,7,8 at nanodevice-friendly temperatures while maintaining their structural integrity. This approach to thinning Si NWs is quite dierent compared to oxidizing their outer surfaces (followed by the removal of the outer oxide layer) recently studied using molecular dynamics (MD) simulations.9 The [110]-oriented Si NWs have attracted an enormous recent interest as viable building blocks of the future nanoelectronic devices because of the very high hole and electron mobilities, compared to [100] and [111] Si NWs.8,1012 These features are required for high-speed FETs with the advanced on-current capability, very low functional
2013 American Chemical Society

response delay,4 and highly tunable conductance of the quantum tunnel barrier.7 Also, a much higher gure of merit is expected for [110] NWs because of their large band gap (which increases further as the NWs get thinner)13 and lower thermal conductivity.12 A combination of these factors makes the [110]-oriented thin NWs very promising building blocks of the future sensing and nanoelectronic devices. However, it is very challenging to grow thin Si [110] NWs at low temperatures and pressures using conventional neutral gasbased approaches. In this case, thermal production of building units (BUs) is insucient while more and more BUs are expelled out as the catalyst nanoparticle (CNP) size decreases.14 This is why no Si NW nucleation takes place or thicker [111]-oriented Si NWs predominantly nucleate when Au CNPs with a broad size distribution are used.14 To overcome this adverse eect, the catalyst temperature and the gas pressure have to exceed the critical values,15 which can be as high as 800 C16 and 100 Torr,17 respectively. However, kinking and other growth defects are frequently observed under high-pressure conditions.15,18,19 High temperatures, on the other hand, lead to unwanted coalescence of small CNPs and loss of control of the NW size and orientations. Moreover, large amounts of energy and matter are unnecessarily wasted. More advantageous features, applications, and challenges in thermal growth of [110] NWs are summarized in the Supporting Information (SI). Recent plasma-enhanced chemical vapor deposition (PECVD) experiments showed that even a short low-density plasma exposure leads to the growth of high-density arrays of
Received: November 8, 2012 Published: January 8, 2013
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dx.doi.org/10.1021/ja3110279 | J. Am. Chem. Soc. 2013, 135, 19121918

ARTICLE

Kinetics of Low-Pressure, Low-Temperature Graphene Growth: Toward Single-Layer, Single-Crystalline Structure

Hamid Mehdipour and Kostya (Ken) Ostrikov* CSIRO Materials Science and Engineering, Plasma Nanoscience Centre Australia (PNCA), P.O. Box 218, Lindeld, New South Wales 2070, Australia, and Plasma Nanoscience @ Complex Systems, School of Physics, University of Sydney, New South Wales 2006, Australia

ABSTRACT Graphene grown on metal catalysts with low carbon solubility is a

highly competitive alternative to exfoliated and other forms of graphene, yet a singlelayer, 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 eective 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 lowenergy electron diraction 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 dierent combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantied. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive eective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.
KEYWORDS: graphene . elementary surface processes . nucleation . graphene coverage

wing to its exceptional mechanical, electronic, chemical, and optical properties, single-layer graphene is highly promising for high-frequency nanoelecronics,13 biosensing,4 exible electronics,5 and a plethora of other applications.6,7 However, several requirements both in terms of the material quality and the fabrication technique need to be met to materialize these promises. Metal-catalyzed chemical vapor deposition (CVD) has recently been widely accepted as a viable approach toward graphene synthesis.819 Indeed, it combines the advantages of highquality, large-area graphene lms with the possibility to produce them at relatively low temperatures directly in the specied device locations or transfer to other (e.g., exible) substrates depending on the envisaged applications.
MEHDIPOUR AND OSTRIKOV

Ultimately, the graphene lm should have a single-layer, single-crystalline, and defectfree structure over the entire catalyst surface. However, this is extremely dicult to achieve, especially when using metal catalyst layers with low solubility of carbon.20 In this case, graphene islands nucleate and grow by surface attachment of carbon atoms and form graphene grains. These grains have dierent orientations and form grain boundaries when stitched together.21 Moreover, since carbon atoms are mostly produced by catalytic decomposition on the metal surface, it becomes increasingly dicult to complete the monolayer as the surface coverage increases. Hydrogen-assisted dissociation of hydrocarbon precursors has been shown to be very eective for ensuring a continued supply of carbon atoms under these and also many other carbon-starving
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* Address correspondence to kostya.ostrikov@csiro.au. Received for review September 8, 2012 and accepted October 19, 2012. Published online October 19, 2012 10.1021/nn3041446
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COMMUNICATION

Plasma-Enabled Graded Nanotube Biosensing Arrays on a Si Nanodevice Platform: Catalyst-Free Integration and In Situ Detection of Nucleation Events
Shailesh Kumar, Hamid Mehdipour, and Kostya (Ken) Ostrikov*
Despite numerous widespread applications of carbon nanotubes (CNTs) as building blocks and functional elements of a very large number of advanced nanomaterials and nanodevices, several pressing issues impede materializing their full potential.[14] Firstly, ultimately direct CNT integration into the presently dominant silicon nanodevice platforms requires metal and oxide catalyst nanoparticle-free growth on Si to minimize inevitable electron transport losses in electronic applications.[5] Secondly, without catalyst nanoparticles, it is extremely challenging to achieve graded morphological and structural properties of the nanotube arrays, which are vital for virtually any area/sitespecic functional responses in nanoelectronics, energy conversion, and sensing applications.[6,7] The problem of production of morphologically and structurally graded CNT arrays directly on Si and without any catalyst (addressed as the catalyst-free graded nanotube growth (CFGNG) problem throughout) still remains unsolved. Thirdly, although catalyst-free growth of CNTs on Si has previously been reported, the mechanisms of such nucleation still remain essentially unclear.[810] In the past, real-time in situ studies[1114] have led to major breakthroughs in the establishing now commonly accepted mechanisms of catalyst-assisted nucleation of CNTs and other one-dimensional nanostructures. However, these studies were inevitably conducted under ultrahighvacuum (UHV) conditions during high-resolution transmission electron microscopy (HR-TEM). These conditions are very far away from the real world of laboratory and commercial nanofabrication facilities, typically operated at pressures at least 56 orders of magnitude higher.[1518] Therefore, how to reveal the mechanisms of catalyst-free CNT nucleation on a real Si device platform in situ (hence, avoiding seemingly inevitable UHV microscopy) also remains a major challenge (referred to as the resolution of nucleation events (RNE) problem). Here, we report on a simple and practically viable solution to both of these problems. We demonstrate that linear arrays of vertically aligned CNTs (VACNTs) can be produced by directly
Dr. S. Kumar, H. Mehdipour, Prof. K. Ostrikov Plasma Nanoscience Centre Australia (PNCA) CSIRO Materials Science and Engineering P.O. Box 218, Lindeld, NSW 2070, Australia E-mail: Kostya.Ostrikov@csiro.au H. Mehdipour, Prof. K. Ostrikov Plasma Nanoscience @ Complex Systems School of Physics University of Sydney NSW 2006, Australia

DOI: 10.1002/adma.201203163

exposing thin linear features written on a Si wafer to nonuniform plasmas. The morphological and structural properties of such arrays can also be graded along the gradient of the plasma density. This is possible to achieve for arbitrary lengths and orientations of the linear features with respect to the center of the spatially localized plasma discharge. We also demonstrate the viability of this approach for nanodevice integration by revealing excellent performance of the catalyst-free VACNT arrays with graded properties in electron eld emission and protein-sensing devices. As such, this simple approach is generic, solves the catalyst-free graded nanotube growth problem and can be used to produce virtually any patterns of linear arrays of VACNTs with variable and graded morphology and structure, without any catalyst or complex nanofabrication. To solve the RNE problem, here we reveal an elegant way of visualizing the CNT nucleation events in situ under realworld conditions of the above plasma-enabled CNT growth on a real Si nanodevice platform. Indeed, when a linear feature is written along the direction of the plasma density gradient, we were able not only to produce VACNT arrays with gradually decreasing lengths away from the plasma but also to identify precisely the furthest spots where the nanotube nucleation was still possible. In this way, it was also possible to disperse the CNT nuclei and short nanotubes (according to their sizes) along the microscopic features. This offers a powerful in situ approach for fundamental studies of nucleation events under conditions of real nanofabrication processes. In addition, we used multiphase, multiscale modeling to explain the essentially catalyst-free nucleation and growth of carbon nanotubes directly on silicon features under the conditions of our experiments. Plasma-Enabled Direct Growth on Si: Figure 1 shows that length-graded CNT arrays can be grown by directly exposing the linear features written on catalyst-free Si wafers to CH4 + N2 plasmas. No external heating was used and the surface temperature of 800850 C was achieved merely through the surface exposure to the plasma. The nanotubes grow directly on Si nanofeatures (NFs) produced on the inner surface of the linear features and appear to be longer where the plasma density is higher. When the nanofeatures are in contact with uniform plasmas (near the center of the plasma discharge), vertically aligned CNTs with a uniform length are produced (Figure 1a,d).[19] The nanotubes also show a uniform structure and thickness as conrmed by micro-Raman spectroscopy and transmission electron microscopy (TEM) (see Supporting Information, Section S1). When the linear features are shifted away from the discharge center where the plasma is nonuniform, the nanotubes tend to be shorter and shorter as the plasma density decreases (Figure 1b). At some distance, the

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ARTICLE

SWCNT Networks on Nanoporous Silica Catalyst Support: Morphological and Connectivity Control for Nanoelectronic, Gas-Sensing, and Biosensing Devices
Zhao Jun Han, Hamid Mehdipour,, Xiaoguang Li,, Jun Shen, Lakshman Randeniya, Hui Ying Yang, and Kostya (Ken) Ostrikov,,*

Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, New South Wales 2070, Australia, Complex Systems, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia, Shanghai Key Laboratory of Special Articial Microstructure Materials and Technology, Tongji University, Shanghai, P. R. China, and Singapore University of Technology and Design, 20 Dover Drive, 138682, Singapore ingle-walled carbon nanotubes (SWCNTs) are one-dimensional nanomaterials with unique electrical, thermal, mechanical, and optical properties.1 SWCNT networks, which consist of interconnected randomly oriented or aligned nanotubes,2,3 have many advantages in nanodevice applications compared to assemblies of individual nanotubes, such as long-term stability, reproducibility, scalability, and low cost.4 This makes the SWCNT networks (SWCNTNs) among the most attractive materials for applications ranging from thin-lm transistors (TFTs), transparent conducting layers, photovoltaic solar cells, to biosensors and drug/ protein/gene delivery systems.58 Among a variety of structural and morphological parameters, the nanotube density is the key factor that determines the network performance. For example, by varying the nanotube density, one can optimize the optical transparency and electrical resistivity in nano- and optoelectronic applications.4,9 Performance of SWCNTN-based TFTs and biosensors have also been intimately related to the nanotube density.2,10 However, higher nanotube densities do not necessarily lead to better device performance as the primary factor is the nanoscale electronic connectivity within the networks.11 The morphological and connectivity factors are thus strongly interlinked, yet it remains largely unknown which SWCNT network arrangements yield the optimum electrical conduction. The electron transport through the networks is determined by the nanotube nanotube and nanotubemetal interactions.12,13 In networks of randomly oriented SWCNTs, a high intertube contact resistance
HAN ET AL.

ABSTRACT Eective control of morphol-

ogy and electrical connectivity of networks of single-walled carbon nanotubes (SWCNTs) by using rough, nanoporous silica supports of Fe catalyst nanoparticles in catalytic chemical vapor deposition is demonstrated experimentally. The very high quality of the nanotubes is evidenced by the G-to-D Raman peak ratios (>50) within the range of the highest known ratios. Transitions from separated nanotubes on smooth SiO2 surface to densely interconnected networks on the nanoporous SiO2 are accompanied by an almost two-order of magnitude increase of the nanotube density. These transitions herald the hardly detectable onset of the nanoscale connectivity and are conrmed by the microanalysis and electrical measurements. The achieved eective nanotube interconnection leads to the dramatic, almost three-orders of magnitude decrease of the SWCNT network resistivity compared to networks of similar density produced by wet chemistry-based assembly of preformed nanotubes. The growth model, supported by multiscale, multiphase modeling of SWCNT nucleation reveals multiple constructive roles of the porous catalyst support in facilitating the catalyst saturation and SWCNT nucleation, consistent with the observed higher density of longer nanotubes. The associated mechanisms are related to the unique surface conditions (roughness, wettability, and reduced catalyst coalescence) on the porous SiO2 and the increased carbon supply through the supporting porous structure. This approach is promising for the direct integration of SWCNT networks into Si-based nanodevice platforms and multiple applications ranging from nanoelectronics and energy conversion to bio- and environmental sensing.
KEYWORDS: single-walled carbon nanotubes . nanonetworks . nanoscale electrical connectivity . porous catalyst support . graphene layer

and a low carrier mobility are expected because of the strong electron scattering and high Schottky barriers. Conversely, when the nanotubes are aligned or the network morphology is optimized, much higher electrical conductance and carrier mobility can be achieved.14,15 The SWCNT networks are commonly fabricated by sophisticated processes based on
VOL. 6

* Address correspondence to kostya.ostrikov@csiro.au. Received for review December 19, 2011 and accepted June 10, 2012. Published online June 10, 2012 10.1021/nn302020a
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Article pubs.acs.org/JACS

Nanoscale Plasma Chemistry Enables Fast, Size-Selective Nanotube Nucleation

Kostya (Ken) Ostrikov*,, and Hamid Mehdipour,,

Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindfield, New South Wales 2070, Australia, and Plasma Nanoscience @ Complex Systems, School of Physics, The University of Sydney, New South Wales 2006, Australia Department of Physics, Faculty of Basic Science, University of Mazandaran, P. O. Box 47416-1467, Babolsar, Iran
S Supporting Information *

ABSTRACT: The possibility of fast, narrow-size/chirality nucleation of thin singlewalled carbon nanotubes (SWCNTs) at low, device-tolerant process temperatures in a plasma-enhanced chemical vapor deposition (CVD) is demonstrated using multiphase, multiscale numerical experiments. These effects are due to the unique nanoscale reactive plasma chemistry (NRPC) on the surfaces and within Au catalyst nanoparticles. The computed three-dimensional process parameter maps link the nanotube incubation times and the relative differences between the incubation times of SWCNTs of different sizes/chiralities to the main plasma- and precursor gas-specific parameters and explain recent experimental observations. It is shown that the unique NRPC leads not only to much faster nucleation of thin nanotubes at much lower process temperatures, but also to better selectivity between the incubation times of SWCNTs with different sizes and chiralities, compared to thermal CVD. These results are used to propose a time-programmed kinetic approach based on fastresponding plasmas which control the size-selective, narrow-chirality nucleation and growth of thin SWCNTs. This approach is generic and can be used for other nanostructure and materials systems.

1. INTRODUCTION Chirality-selective synthesis of single-walled carbon nanotubes (SWCNTs) at low, nanodevice-tolerable temperatures, while minimizing precursor atom consumption, still remains a major science challenge on the way of their widespread applications in nanoelectronics, information processing and storage, renewable energy, environmental, biomedical, and other technologies.15 Despite almost two decades of research, the underlying mechanisms of this still elusive ability still remain essentially unclear, mostly because of the very large number of the process- and catalyst-specific parameters and effects involved. These effects are related to the process temperature, delivery and loss of precursor species, formation of the initial nuclei and SWCNT caps, as well as defect incorporation during the nucleation or growth stages; these phenomena are commonly studied quite separately.611 This is the reason unifying strategies to resolve this challenge based on the understanding of the nanotube nucleation and growth kinetics in its entirety are highly warranted. Catalyst nanoparticle (CNP) supersaturation with carbon, graphene monolayer (GML) formation, and bending, followed by the stable cap formation and lifting off from the CNP surface is commonly recognized as the most important chiralitydetermining stage.12,13 The completion of this stage is heralded by the onset of the diameter-selective photoluminescence emission (PLE) and is quantified by the incubation time ti.1416 This time is different for nanotubes of different sizes and chiralities. Therefore, by precisely controlling the supply of carbon atoms and energy to catalyst nanoparticles of different
Published XXXX by the American Chemical Society

sizes, it is plausible to achieve time-resolved nucleation of the nanotubes of only the desired thickness and chirality.17,18 However, this is extremely difficult to achieve in practice for several reasons. First, reliable experimental data on the SWCNT incubation times is very limited because of its process- and nanotube-specific nature and measurement complexity.2,13,15 This is the reason predictive numerical modeling to elucidate the effects of the catalyst and process parameters on ti of the nanotubes of different sizes is indispensable and is carried out in this work. Second, selective growth of SWCNTs with narrow size/chirality distributions poses several significant challenges.15,19 Indeed, as the growth continues beyond the incubation time of the nanotubes of the desired size/chirality range, SWCNTs of many other sizes/ chiralities may also nucleate and grow after their respective incubation times elapse. This is the reason the incubation times should be as short as possible and the relative differences between the incubation times of the nanotubes of different sizes/chiralities should be as large as possible. In this case, it may be possible to quickly adjust the process conditions to continue the growth of the as-nucleated SWCNTs of the desired sizes/chiralities while disabling the nucleation of other nanotubes. The incubation times can be reduced by increasing the substrate temperatures and/or precursor gas pressures.15 However, given the already very high temperatures required
Received: November 17, 2011

dx.doi.org/10.1021/ja210813s | J. Am. Chem. Soc. XXXX, XXX, XXXXXX

ARTICLE

Thin Single-Walled Carbon Nanotubes with Narrow Chirality Distribution: Constructive Interplay of Plasma and GibbsThomson Eects
Kostya (Ken) Ostrikov#,* and Hamid Mehdipour# Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, New South Wales 2070, Australia, and Plasma Nanoscience @ Complex Systems, School of Physics, University of Sydney, New South Wales 2006, Australia. #Both authors made equal contributions to this work. wing to their fascinating mechanical, electronic, chemical, and other properties, single-walled carbon nanotubes (SWCNTs) are presently among the most attractive building blocks of a variety of nanodevices for energy conversion and storage, environmental and biomedical sensing and imaging, drug delivery, bioscaffolding in regenerative medicine, gene, protein, and DNA targeting, cellular control, gas separation, water purication, and integrated nanoelectronic curcuitry, to mention just a few.14 The response of SWCNTs in applications critically depends on the distributions of their lengths, thicknesses, and chiralities, which determine the properties of the nanotube arrays. Despite almost two decades of intense research, the problem of eective control of these parameters still remains unsolved and the as-grown nanotube arrays commonly contain a mix of thick and thin, semiconducting, and metallic nanotubes as well as a large variety of chiral structures. Sophisticated postsynthesis chemical separation protocols are required to separate the SWCNTs by their chirality and metallicity.5 However, the problem of direct growth of very thin nanotubes with narrow size, diameter, and chirality distributions directly in the specied device locations and at device-tolerable process temperatures still remains. Recent results suggest that this control can be improved by tailoring arrays of catalyst nanoparticles (e.g., size/position uniformity, alloying/layering, and lattice space) and understanding atomic processes on catalyst surfaces with imperfections as well as the transient nucleation and relaxation dynamics.68 This, mostly catalyst-related, approach is presently believed to be the
OSTRIKOV AND MEHDIPOUR

ABSTRACT Multiscale, multiphase numerical modeling is used to explain the mechanisms of

eective control of chirality distributions of single-walled carbon nanotubes in direct plasma growth and suggest eective approaches to further improvement. The model includes an unprecedented combination of the plasma sheath, ion/radical transport, species creation/loss, plasmasurface interaction, heat transfer, surface/bulk diusion, graphene layer nucleation, and bending/lift-o modules. It is shown that the constructive interplay between the plasma and the GibbsThomson eect can lead to the eective nucleation and lift-o of small graphene layers on small metal catalyst nanoparticles. As a result, much thinner nanotubes with narrower chirality distributions can nucleate at much lower process temperatures and pressures compared to thermal CVD. This approach is validated by a host of experimental results, substantially reduces the amounts of energy and atomic matter required for the nanotube growth, and can be extended to other nanoscale structures and materials systems, thereby nearing the ultimate goal of energy- and matter-ecient nanotechnology.
KEYWORDS: single-walled carbon nanotubes . plasma nanoscience . chirality control . graphene layer

most promising solution. However, very recent results on the eective plasma-based control of the SWCNT chirality and sizes915 suggest that several other factors such as the process pressure and temperature, precursor gas composition, and the rates, duration, and selectivity of precursor supply strongly aect the distributions of the nanotube chirality and sizes on the same catalyst patterns. This is why a clear understanding of the SWCNT nucleation mechanism in its entirety is required, including carbon species production, delivery to the catalyst, surface and vapor transport, energy/matter exchange processes, and catalyst supersaturation, followed by graphene layer nucleation and lift-o. Many techniques such as classical molecular dynamics (MD), Monte Carlo (MC), density functional theory (DFT), gasphase species production, surface kinetic
VOL. 5

* Address correspondence to kostya.ostrikov@csiro.au. Received for review August 12, 2011 and accepted September 9, 2011. Published online September 09, 2011 10.1021/nn2030989
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Plasma effects in semiconducting nanowire growth

Kostya (Ken) Ostrikov,*ab Dong Han Seo,ab Hamid Mehdipour,a Qijin Chengab and Shailesh Kumara
Received 22nd June 2011, Accepted 25th August 2011 DOI: 10.1039/c1nr10658a Three case studies are presented to show low-temperature plasma-specic effects in the solution of (i) effective control of nucleation and growth; (ii) environmental friendliness; and (iii) energy efciency critical issues in semiconducting nanowire growth. The rst case (related to (i) and (iii)) shows that in catalytic growth of Si nanowires, plasma-specic effects lead to a substantial increase in growth rates, decrease of the minimum nanowire thickness, and much faster nanowire nucleation at the same growth temperatures. For nucleation and growth of nanowires of the same thickness, much lower temperatures are required. In the second example (related to (ii)), we produce Si nanowire networks with controllable nanowire thickness, length, and area density without any catalyst or external supply of Si building material. This case is an environmentally-friendly alternative to the commonly used Si microfabrication based on a highly-toxic silane precursor gas. The third example is related to (iii) and demonstrates that ZnO nanowires can be synthesized in plasma-enhanced CVD at signicantly lower process temperatures than in similar neutral gas-based processes and without compromising structural quality and performance of the nanowires. Our results are relevant to the development of next-generation nanoelectronic, optoelectronic, energy conversion and sensing devices based on semiconducting nanowires.

Downloaded by CSIRO Library Services on 09 November 2012 Published on 23 September 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10658A

1. Introduction
Quasi-one-dimensional (1D) structures such as nanowires, nanorods, nanoneedles, and nanotips have found their distinctive place among advanced semiconducting materials. A combination of traditional semiconducting properties intrinsic to the relevant bulk materials and the nanoscale-specic effects makes them a truly unique class of nanomaterials.117 The latter properties include exotic quantum connement effects, highlyunusual carrier generation and transport, outstanding surface reactivity, precisely-tailored electronic band structures, optical polarizability, transmittance, absorption and other attributes, to mention just a few. In some cases the 1D structures feature chemical structures and a variety of properties not shared by their bulk counterparts. This high unusuality can be further enhanced by arranging the 1D nanostructures in various hierarchical, stacked, layered, etc. structures and architectures. The response of semiconducting 1D structures in applications is determined by their elemental composition as well as their

a Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, NSW, 2070, Australia. E-mail: Kostya.Ostrikov@csiro.au; Fax: +61-2-94137200; Tel: +61-2-94137634 b Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, NSW, 2006, Australia This article was submitted as part of a collection highlighting papers on the Recent Advances in Semiconductor Nanowires Research from ICMAT.

structural and morphological properties. Therefore, these properties need to be tailored during the synthesis process. Among a large number of synthesis approaches, Chemical Vapour Deposition (CVD) has proved very effective and is presently one of the most widely accepted and commonly used synthesis routes. A very large number of 1D semiconducting inorganic nanomaterials systems have been synthesized, common examples being single-element (e.g., Si, Ge, etc.), binary (e.g., metal oxides and nitrides, IIIV, IIVI compounds), ternary (metal oxynitrides) and even more complex materials. However, despite very impressive recent successes, there are many signicant issues that need solutions and require versatile and effective nanoscale synthesis processes. In this article, we will discuss three critical issues in semiconductor nanowire growth where application of low-temperature plasma enhanced CVD can be benecial. These issues are related to (i) effective control of nucleation and growth; (ii) environmental friendliness; and (iii) energy efciency, and are the subject of continuouslyincreasing global concern.1,12 One of the current goals of nanotechnology is to address these issues and show not only technological but also societal (e.g., nanosafety) and environmental viability.18 Low-temperature plasma-based nanoscience and nanotechnology is a rapidly emerging eld encompassing a large variety of applications. These applications encompass the more traditional semiconductor structuring and processing for nanoelectronics and a more recent expansion into materials, devices and processes for energy, environment, health care, security, and
Nanoscale, 2012, 4, 14971508 | 1497

This journal is The Royal Society of Chemistry 2012

IOP PUBLISHING Nanotechnology 22 (2011) 315707 (14pp)

NANOTECHNOLOGY doi:10.1088/0957-4484/22/31/315707

Minimizing the GibbsThomson effect in the low-temperature plasma synthesis of thin Si nanowires
H Mehdipour1,2, K Ostrikov2,3 , A E Rider2 and S A Furman2
1 Department of Physics, Faculty of Science, Sahand University of Technology, 51335-1996 Tabriz, Iran 2 Plasma Nanoscience Center Australia (PNCA), CSIRO Materials Science and Engineering, PO Box 218, Lindeld, New South Wales 2070, Australia 3 Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia

E-mail: Amanda.Rider@csiro.au

Received 18 February 2011, in nal form 21 June 2011 Published 7 July 2011 Online at stacks.iop.org/Nano/22/315707 Abstract 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 GibbsThomson 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 GibbsThomson effect diminished, even at low temperatures. The results obtained are consistent with available experimental results and open a path toward the energy- and matter-efcient nucleation and growth of a broad range of one-dimensional quantum structures. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Highly uniform arrays of nanowires (NWs) and other high-aspect-ratio nanostructures hold outstanding promise as components in numerous applications including electron microemitter arrays, nanoelectronic circuitry, biosensors, drug and gene delivery systems, and other nanodevices [114]. For implementation in such devices, a high degree of control over the NW characteristics from the very initial stage of growth is required. Silicon NWs are commonly synthesized using a variety of catalyzed chemical vapor deposition (CVD) [1518], molecular beam epitaxy (MBE) [1921], metalorganic vapor phase epitaxy (MOVPE) [22, 23], high-temperature annealing, and thermal evaporation [2426] techniques. In catalyzed CVD synthesis of NWs, after the formation of a pattern of
0957-4484/11/315707+14$33.00

metal catalyst nanoparticles (NPs) on a substrate and the addition of the precursor gas (silane gas in this study) into the growth environment, NW growth usually proceeds via the vaporliquidsolid (VLS) growth mode. The VLS growth mode may be described by four main stages [27]: (i) the thermal and/or ion-assisted generation of building units (BUs) on the catalyst surface, (ii) the saturation of the catalyst particles with adatoms which then absorb into the catalyst (followed by the formation of a AuSi alloy), (iii) a fast microscopic stage of nucleation of each Si monolayer (ML) from the liquid phase with constant liquidcatalyst radius rd , (iv) a slow macroscopic stage of NW growth from the vapor phase.
1
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Rapid, simultaneous activation of thin nanowire growth in low-temperature, low-pressure chemically active plasmas
Kostya (Ken) Ostrikovab and Hamid Mehdipour*c
Received 21st January 2011, Accepted 30th March 2011 DOI: 10.1039/c1jm10318k 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-specic 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.
a Plasma Nanoscience Center Australia (PNCA), CSIRO Materials Science and Engineering, PO Box 218, Lindeld, New South Wales, 2070, Australia. E-mail: Kostya.Ostrikov@csiro.au; Fax: +61-294137200; Tel: +61-2-94137634 b Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, NSW, 2006, Australia c Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996 Tabriz, Iran. E-mail: hamid11062@yahoo.com Both authors contributed equally to this work.

1. Introduction
Owing to the rapid development of the nanoscale science and technology, low-dimensional nanostructures such as quantum dots and nanowires have attracted a signicant recent interest for nanoelectronic, optoelectronic, sensing, biomedical and energy conversion applications. These nanostructures have many

Kostya (Ken) Ostrikov is a CEO Science Leader, Australian Future Fellow, and a founding leader of the Plasma Nanoscience Center Australia at CSIRO Materials Science and Engineering. His achievements include the Pawsey (2008) medal of the Australian Academy of Sciences and the Walter Boas (2010) medal of the Australian Institute of Physics, 8 prestigious fellowKostya Ken Ostrikov ships in 6 countries, more than 280 refereed journal papers and 80 plenary, keynote, and invited talks at international conferences. His research on nanoscale control of energy and matter in plasmasurface interactions contributes to the solution of the grand and as-yet unresolved challenge of directing energy and matter at the nanoscale, a challenge that is critical for the development of renewable energy and energy-efcient technologies for a sustainable future.
This journal is The Royal Society of Chemistry 2011

Hamid Mehdipour was born in Dezful, Iran, in 1984. He received the B.S. degree in physics from the University of Mazandaran, Babolsar, Iran, in 2006 and the M.S. degree, in 2009, from the Sahand University of Technology, Tabriz, Iran. His current research is focused on numerical modeling and simulation of plasma-aided fabrication of nanostructures and nanomaterials.
Hamid Mehdipour

J. Mater. Chem., 2011, 21, 81838191 | 8183

Full Paper

Heating and Plasma Sheath Effects in LowTemperature, Plasma-Assisted Growth of Carbon Nanobers
Hamid Mehdipour, Kostya (Ken) Ostrikov, Amanda E. Rider,* Zhaojun Han

Plasma sheath, nanostructure growth, and thermal models are used to describe carbon nanober (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.

H. Mehdipour Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996, Tabriz, Iran K. Ostrikov Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P. O. Box 218, Lindeld, New South Wales 2070, Australia and Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia A. E. Rider Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia and Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P. O. Box 218, Lindeld, New South Wales 2070, Australia Fax: 61 2 9413 7200; E-mail: arider@physics.usyd.edu.au Z. Han Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P. O. Box 218, Lindeld, New South Wales 2070, Australia
Plasma Process. Polym. 2011, 8, 386400 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Introduction
High-aspect-ratio nanostructures[13] have attracted considerable interest recently due to their use as components in many applications such as eld emitter devices, synthetic membranes, reinforced polymer/ceramic nanocomposites, drug and gene delivery systems, nanoelectronic interconnects, hydrogen storage devices, quantum information architectures, sensors, and several other devices.[419] Owing to the many unique properties of reactive plasmas,[2026] carbon-based nanostructures,[2734] such as carbon nanotubes (CNTs) and carbon nanobers (CNFs) can be grown via plasma enhanced chemical deposition (PECVD) in large arrays and feature a greater degree of vertical alignment[15,16,35] compared to nanostructures synthesized in neutral gas-based thermal processes, such as chemical vapor deposition (CVD). Controlled PECVD synthesis takes place in the plasma sheath. Plasma sheaths are formed near plasma-exposed surfaces upon which

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DOI: 10.1002/ppap.201000150

APPLIED PHYSICS LETTERS 98, 033104 2011

Energy and matter-efcient size-selective growth of thin quantum wires in a plasma

K. Ostrikov1,a and H. Mehdipour2
1

Plasma Nanoscience Center Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, New South Wales 2070, Australia and Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia 2 Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996 Tabriz, Iran

Received 28 October 2010; accepted 21 December 2010; published online 18 January 2011 It is shown that plasmas can minimize the adverse Gibbs-Thompson effect in thin quantum wire growth. The model of Si nanowire nucleation includes the unprecedented combination of the plasma sheath, ion- and radical-induced species creation and heating effects on the surface and within an Au catalyst nanoparticle. Compared to neutral gas thermal processes, much thinner, size-selective wires can nucleate at the same temperature and pressure while much lower energy and matter budget is needed to grow same-size wires. This explains the experimental observations and may lead to energy- and matter-efcient synthesis of a broader range of one-dimensional quantum structures. 2011 American Institute of Physics. doi:10.1063/1.3540645 Electron connement in two dimensions, tunability of electronic bands, very high surface-to-volume ratio and chemical reactivity, and unusual bioactivity make inorganic nanowires NWs exceptional candidates for next-generation environmental and biosensors, nanoelectronic, optoelectronic, photonic, biomedical, and energy conversion devices.13 The NWs are synthesized in a vapor-liquid-solid VLS mode of catalyzed chemical vapor deposition CVD, which is critically affected by the Gibbs-Thomson GT effect of a dramatic increase of the nucleation energy barrier as the wires get thinner. This is why synthesis of thin NWs requires very high temperatures, above the acceptable nanofabrication standards. To overcome these barriers, very high levels of supersaturation of building units BUs, Si atoms here in the catalyst nanoparticle NP are also needed, and hence, elevated process pressures. Under such conditions, kinking and other growth defects are observed4 and a very large amount of energy and matter is wasted. The critical radius of a catalyst NP, below which the NW nucleation ceases, is determined by the surface energy at the vapor-liquid interface, and is inversely proportional to the difference in chemical potentials of the Si atoms in the liquid and the solid phases ls,57 which in turn decreases due to the size-dependent GT effect.6,8 Thus, for smaller catalyst NPs the GT effect is stronger and sets the minimum NP diameter which could nucleate a Si monolayer ML at the interface with the substrate. Moreover, ls decreases with decreasing the catalyst temperature and supersaturation of AuSi alloy in the catalyst. This is why the CVD synthesis of very thin NWs is not possible at low-temperature and lowpressure conditions.4 This problem can be mitigated by using nonequilibrium plasmas where one can expect more Si atoms produced on the catalyst surface9 and a much higher supersaturation as well as stronger catalyst heating through plasma-specic surface reactions.10,11 Using the unprecedented combination of models of the plasma sheath, ion- and radical-induced heating and species creation and transport on the surface and within a Au catalyst
a

NP, as well of monolayer nucleation at the catalyst-substrate interface, we demonstrate and quantify the reduction of the inuence of the GT effect by the plasma-specic effects, which in turn facilitate the BU supersaturation in the catalyst NP and lower the NW nucleation barriers. This explains and quanties the experimental observations of the nucleation of thin quantum wires at plasma process temperatures and gas pressures substantially lower than in thermal CVD. It is also shown that the difference between nucleation barriers for different NW radii in the plasma-enhanced CVD PECVD is more signicant than in the CVD thus leading to achieve better size selectivity in a broader size range. Let us consider the Au NP-assisted nucleation of a Si nanowire in reactive plasmas of Ar+ H2 + SiH4 gas mixtures.12 The model includes the plasma sheath, Si surface and bulk diffusion into the catalyst, NP heating, and Si ML nucleation modules. Figure 1 shows the Si NW growth on a conducting substrate of thickness d placed on a substrate holder heated externally to temperature Th. A sketch of the top section of the NW is shown in Fig. 1b; it shows the dimensions of a thin two-dimensional Si island nucleated layer, surface SD and bulk BD diffusion of Si species, surface temperature of the catalyst NP Td, and the key neutral and ionic species included in the plasma sheath and Si BU production models. The Si atoms are created on the surface

Electronic mail: kostya.ostrikov@csiro.au.

FIG. 1. Color online Schematics of the NW growth process a. The insets show the scanning electron micrograph SEM and pure-Si elemental composition evidenced by a single peak in EDS spectrum of typical Si nanowires. A sketch of the Au catalyst NP and particle deposition on the NP surface b. Scale bar is 100 nm courtesy of PNCA. 2011 American Institute of Physics

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PHYSICS OF PLASMAS 17, 123708 2010

Structure of the magnetized sheath of a dusty plasma

H. Mehdipour,1 I. Denysenko,2 and K. Ostrikov3
1 2

Department of Physics, Faculty of Science, Sahand University of Technology, Tabriz 51335-1996, Iran School of Physics and Technology, V. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv 61077, Ukraine 3 Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science and Engineering, P.O. Box 218, Lindeld, New South Wales, Sydney 2070, Australia and School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia

Received 8 November 2010; accepted 23 November 2010; published online 9 December 2010 A three-component uid model for a dusty plasma-sheath in an oblique magnetic eld is presented. The study is carried out for the conditions when the thermophoretic force associated with the electron temperature gradient is one of the most important forces affecting dust grains in the sheath. It is shown that the sheath properties the sheath size, the electron, ion and dust particle densities and velocities, the electric eld potential, and the forces affecting the dust particles are functions of the neutral gas pressure and ion temperature, the dust size, the dust material density, and the electron temperature gradient. Effects of plasma-dust collisions on the sheath structure are studied. It is shown that an increase in the forces pushing dust particles to the wall is accompanied by a decrease in the sheath width. The results of this work are particularly relevant to low-temperature plasma-enabled technologies, where effective control of nano- and microsized particles near solid or liquid surfaces is required. 2010 American Institute of Physics. doi:10.1063/1.3526740
I. INTRODUCTION

As a unique multicomponent system, dusty complex plasmas have attracted a major interest in the last few decades. It has been actively studied in laboratory, industrial and astrophysical situations.15 At present, properties of such plasmas, including collective phenomena, dust generation and charging, formation of complex self-organized structures dust crystals, voids, vortices, dust balls, etc., and forces affecting dust particles are reasonably well understood.111 It has also been studied how dust particles affect other plasma particles their densities, spatial distributions, drift velocities, electron energy distribution function, and temperature. In particular, it was shown that the presence of dust particles in laboratory plasmas is usually accompanied by a decrease of the electron density and an increase of the electron temperature.1,12 Dust particles also affect the shape of the electron energy distribution function,1315 as well as the plasma-sheath.16 The presence of dense clouds of dust particles near the wall essentially changes the plasma-sheath behavior and a new dissipative sheath structure can be formed.2 The dust particles can be introduced articially in a plasma-sheath or may appear as the impurity contaminants, which are added by production tools and processes. In plasma-assisted fabrication of microchips, the dust contaminant is a serious threat, and the dust particles must be removed from the plasma environment; otherwise the unwanted contaminant compromises the performance and quality of the microchip. In technologies, where plasma-grown nanoparticles are building units for nanostructures formed on a substrate, the dust particles cross the sheath before their deposition on the substrate. A precise manipulation of these building units in the sheath is required,1723 which is impossible without understanding processes in the dusty sheath.
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The dynamics of the dust component in the plasmasheath, both an isolated grain and a dense cloud of dust particles, has been studied by several authors.2431 Most of the studies have been carried out for the case when an external magnetic eld is absent. Ma and Yu27 showed that there exists a critical velocity for ions similar to the Bohm criterion for two-component plasma entering the sheath, which is a function of dust density. They also found that the potential drop near the wall is small the sheath is wider for intermediate values of dust density than that of the dust-free case, while at large density the potential drop is larger the sheath is narrower. A self-consistent relation between the dust surface potential and ion Mach number at the sheath edge was derived in Ref. 30. Chutov and co-workers32 showed that dust particles due to selective collection of electrons and ions can cause essential change in both electron and ion distribution functions, as well as ion ux into the sheath. A dusty plasma-sheath was also simulated in the presence of two temperature electrons.33 It was shown numerically that trapped dust grains play an important role in sheath modication leading to the formation of triple electric eld structure within the sheath and construction of the sheath.34 The Bohm criterion for the electrostatic sheath in electronegative dusty plasmas, which are composed of electrons, negative and positive ions, as well as dust grains, was investigated in Ref. 35. Mikikian et al.36 measured the dust charge in the sheath in a dc discharge plasma. The inuence of different dust density as well as of the negative bias to the metallic plate on the ion sheath structure was studied experimentally in Ref. 37. Magnetized plasma-sheaths with dust particles have been also intensively studied. It was shown that the equilibrium and levitation of dust particles in a collisional magnetized sheath depends on plasma-neutral collision frequencies
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IOP PUBLISHING Nanotechnology 21 (2010) 455605 (13pp)

NANOTECHNOLOGY doi:10.1088/0957-4484/21/45/455605

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

H Mehdipour1, K Ostrikov2,3 and A E Rider2,3
1 Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996, Tabriz, Iran 2 Plasma Nanoscience Center Australia (PNCA), CSIRO Materials Science and Engineering, PO Box 218, Lindeld, New South Wales 2070, Australia 3 Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia

E-mail: Kostya.Ostrikov@csiro.au

Received 14 July 2010, in nal form 14 September 2010 Published 14 October 2010 Online at stacks.iop.org/Nano/21/455605 Abstract A numerical growth model is used to describe the catalyzed growth of carbon nanobers 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 nanober growth characteristics, such as the growth rate, the effective carbon ux 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 nanober growth at higher temperatures. The conditions under which the carbon nanober 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. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Recently, there has been a very strong and continuously increasing interest in plasma-based synthesis of high-aspect-ratio nanostructures (e.g., nanotubes, nanobers, etc), due to the signicant advantages offered by the low-temperature plasma environments [1, 2]. These nanostructures are promising for energy conversion, microemitter applications, intracellular drug and gene delivery devices, nanoelectronics, reinforced nanocomposites, biosensors, and several others [322]. In the synthesis of carbon nanobers (CNFs) metal catalyst nanoparticles are used both in chemical vapor deposition (CVD) and plasma-enhanced CVD (PECVD) processes [2327]. Due to the ion and radical-assisted processes on the top-most surface of a catalyst particle (which is attached to the tip of CNFs) that are unique to the plasma environments, the carbon nanobers
0957-4484/10/455605+13$30.00

can be synthesized even at low temperatures when the effective catalytic precursor decomposition is not possible via neutral gas-based CVD [4, 7, 11, 28, 29]. These processes include but are not limited to ion-induced dissociation of hydrocarbon molecules, radicals and ions, as well as the interaction of the adsorbed species with incoming hydrogen atoms on the top surface of the catalyst particle in low-pressure reactive plasmas [30] of Ar + H2 + CH4 /C2 H2 gas mixtures [31, 32]. It is known that plasma sheaths (areas with uncompensated surface charge) are formed near the boundaries of plasma-exposed surfaces. Furthermore, in the plasma-aided fabrication of nanostructures, these structures are commonly synthesized on a substrate facing the plasma which is coated with conductive or insulating materials. Therefore, the nanostructures are produced in the plasma sheath (rather than the plasma bulk) where microscopic electric elds near the
1
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PHYSICS OF PLASMAS 17, 083704 2010

The magnetized sheath of a dusty plasma with nanosize dust grains

H. Mehdipour1 and G. Foroutan1,2
1 2

Department of Physics, Faculty of Science, Sahand University of Technology, 51335-1996 Tabriz, Iran Nanostructure Material Research Center, Sahand University of Technology, 51335-1996 Tabriz, Iran and School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia

Received 20 April 2010; accepted 28 July 2010; published online 31 August 2010 The magnetized sheath of a dusty plasma is investigated via numerical simulations of stationary multiuid equations by taking into account the electric, magnetic, gravitational, ion drag, neutral drag, and thermophoretic forces. Dependence of the sheath properties on the characteristics of the magnetic eld and plasma parameters is explored. The sheath dynamics is mainly governed by the electric and ion drag forces and the effect of gravitation is negligible. The sheath demonstrates a nonmonotonic behavior against variations of the magnetic intensity and its angle of incidence. The sheath thickness and the maximum of dust density distribution decrease with increasing the ion to electron density ratio at the sheath edge, but increase with growing electron temperature and the positive temperature gradient of the neutrals. The effects of ion drag are similar to those of the gravitational force as both of them accelerate the dust to the wall. By a suitable conguration of the temperature gradient in the neutral gas, thermophoretic force can be utilized to deposit the building units of nanostructures on a substrate or remove any unwanted contaminant from its neighborhood. 2010 American Institute of Physics. doi:10.1063/1.3480099
I. INTRODUCTION

The investigation of plasma-wall transition is of great importance in different areas such as plasma-aided material processing, plasma probes, and plasma-assisted fabrication of ordered nanostructures.13 Due to the different mobilities of electrons and ions the wall receives more electrons than ions and its potential remains negative with respect to the main body of plasma. This negative potential prevents further escape of the electrons toward the wall and leads to the separation of charges and formation of a sheath layer with a net positive charge near the wall. The scale of the sheath region is typically a few Debye lengths, while the quasineutrality scale is about the typical size of the system. To study the plasma and sheath structures, kinetic and hydrodynamic models are commonly employed. For a detailed consideration of using these models to describe the sheath region of a two component plasma, we refer to Refs. 412. Dust particles are frequently encountered in laboratory plasmas such as processing discharges for etching, sputtering, and ion implantation.1,1318 The dust grains can be the impurity contaminants, introduced into the system by production tools or formed via agglomeration during the course of plasma processing. In plasma-assisted fabrication of microchips, particulate contaminant is a serious threat in the fabrication and must be removed from the processing environment, otherwise the unwanted contaminant compromises the performance and quality of the device. On the other hand, nanosize particles are introduced into plasma as building units for plasma-aided fabrication of different nanostructures. This is because, due to their large electric charge, siteselective and controlled deposition of nanoparticles is conceivable via the sheath electric eld.1927 The dynamics of dust particles in plasma sheath both in the presence and absence of an external magnetic eld has
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been studied by several authors.2844 Ma and Yu34 used a three-uid model with Boltzmann distributed electrons and cold ion and dust uids to describe the electrostatic sheath of a dusty plasma. They found that for small dust particles the sheath potential exhibits a solitonlike proles and the dust density is strongly localized, while for larger dust grains a stratication of the dust density occurs. Davoudabadi and Mashayek41 studied the sheath structure in the presence of an oblique magnetic eld. In their one-dimensional model, the electrons are in thermal equilibrium, while the ions experience a friction force due to collisions with neutrals. They found that the sheath thickness decreases as the strength of the magnetic eld increases and for low-pressures there exist optimums of the magnetic intensities for which the absolute charge on an isolated grain is minimum or maximum. Oscillations were observed in the spatial distribution of the ion velocity and density. Foroutan et al.44 numerically investigated the structure of the magnetized sheath of a dusty plasma with micron size dust particles. Among the forces acting on the dust grains only the electrostatic, magnetic, and gravitational forces were taken into account. It was shown that above a threshold magnetic intensity, some kind of large regular inhomogeneities develops on the spatial prole of the dust particles. The sheath thickness shows nonlinear behavior against variations of the electron temperature and magnetic eld intensity. The present work is mainly motivated by the applicability of self-consistent sheath theory to plasma processing of materials and plasma-aided nanofabrication. The latter is a new and rapidly expanding multidisciplinary research area with continuously increasing importance both in fundamental research and technological applications.3,2427,4554 Unlike conventional two component plasmas, dusty plasmas contain nanosize particles carrying dynamically variable charge, which can be used for deterministic and controlled synthesis
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PHYSICS OF PLASMAS 16, 103703 2009

Simulation study of the magnetized sheath of a dusty plasma

G. Foroutan,1,2 H. Mehdipour,1 and H. Zahed1
1 2

Department of Physics, Faculty of Science, Sahand University of Technology, 51335-1996 Tabriz, Iran School of Physics, The University of Sydney, New South Wales 2006, Sydney, Australia

Received 30 July 2009; accepted 14 September 2009; published online 12 October 2009 Numerical solutions of stationary multiuid equations are used to study the formation and properties of the magnetized sheath near the boundary of a dusty plasma. The impacts of the strength of the magnetic eld, the dust and plasma number densities, and the electron temperature on the sheath structure and spatial distributions of various quantities are investigated. It is shown that for a given angle of incidence of the magnetic eld, there is a threshold magnetic eld intensity above which some kind of large regular inhomogeneities develop on the spatial prole of the dust particles. The sheath thickness, the electron and ion number densities, and the absolute dust charge are strongly affected by the variation in the dust number density. The sheath demonstrates a nonlinear dependence on the electron temperature; as the electron temperature rises, the sheath rst is broadened and the absolute wall potential decreases but then at higher temperatures the sheath becomes narrower and the absolute wall potential increases. 2009 American Institute of Physics. doi:10.1063/1.3243497
I. INTRODUCTION

The problem of sheath formation at the boundary of a plasma is of fundamental importance in many applications including plasma probes, low-temperature plasma-aided material processing, as well as fusion research.13 Due to the high mobility of the electrons, the wall potential remains negative with respect to the main body of the plasma. A negative potential barrier prevents further escape of the electrons and results in the formation of a positive space-charge sheath, a Debye sheath, shielding the neutral plasma from the negative wall. The typical sheath thickness is a few electron Debye length D, which is usually small compared with the characteristic length of the plasma dened by the typical size of the system. For the electrostatic sheath formation the ions must enter the sheath region at least with ion sound velocity, the so-called Bohm criterion. Numerous publications can be found in the literature devoted to the study of the different properties of sheaths in unmagnetized two component plasmas.412 When an oblique magnetic eld is applied to the plasma, then Chodura13 stated that a magnetic presheath region arises upstream of the Debye sheath, where there is also a signicant electric eld. According to Choduras model, plasma particles pass through three distinct regions on their way toward the wall. The rst one, called plasma presheath, is the quasineutral plasma region where electrons are accelerated along magnetic eld lines due to the electron pressure gradient. Therefore, an electric eld is generated which in turn accelerates the ions along the magnetic eld up to ion sound speed. The second region the Chodura layer is the quasineutral magnetized presheath where the electric eld becomes strong enough to deect the ions from their motion along the magnetic eld lines. The ions enter the Chodura layer when their velocity component in the direction of the magnetic eld reaches the ion sound speed the Chodura criterion. The scale size of the magnetic presheath is the ion
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Larmor radius i. The third region, Debye sheath, is a region of net, positive space-charge density with strong electric eld that directs the ions toward the wall. However, experiments14 do not support Choduras theory suggesting that the Chodura layer is a consequence of the particular mathematical modeling. It was shown in Refs. 15 and 16 that the Chodura layer can be eliminated if ion-neutral collisions are taken into account. For a detailed discussion of the effects of magnetic eld on the sheath structure and the dynamics of electrons and ions we refer to Refs. 1729. A dusty plasma is simply dened as a multicomponent admixture of electrons, ions, and charged dust particles with size ranging from nanometers to micrometers. Dust particles are often observed to be localized in the plasma boundary near solid objects or walls, such as the planetary rings and comets, articial satellites, in the devices for plasma assisted material and chemical processing, plasma discharges, as well as the wall region of hot fusion plasmas.3043 In processing discharges, dust particles can be created due to coagulation of various components with their subsequent transport into the sheath. The dust grain is charged by the collection of the plasma particles electrons and ions owing onto its surface. Since the electron thermal speed is much larger than the ion thermal speed, the grain acquires much more electrons than ions, and as a result its surface potential becomes negative. The grains of a few micrometers in size have hundreds to thousands of elementary charges. In plasma processing reactors negatively charged dust particles appear as contamination to etching, sputtering, and deposition processes. Moreover, the growth of dust grain in discharges offers unique possibilities for powder synthesis and surface modication processes. The sheath containing negatively charged dust particles is, therefore, relevant to plasma-wall interaction in various plasma-aided industrial applications. The problem of plasma-wall transition in the presence of charged dust particles has been investigated by several
2009 American Institute of Physics

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Dust-Plasma Sheath in an ObUque Magnetic Field

G. Foroutan and H. Mehdipour
Physics Department, Faculty of Science, Sahand University of Technology, Tabriz, Iran Abstract. Using numerical simulations of the midti fliud equations the structure of the magnetized sheath near a plasma boundary is studied in the presence of charged dust particles. The dependence of the electron, ion, and dust densities as well as the electrostatic potential, dust charge, and ion normal velocity, on the magnetic field strength and the edge dust number density is investigated. Keywords: Magnetized sheath. Dust grains. Plasma boundary. Sheath thickness, gravitational force PACS: 52.40.Kh,52.27.Lw,52.40.Hf,52.30.Ex

The problem of the plasma sheath in the presence of heavy dust particles has attracted the interest of plasma physicists during past decade [1, 2, 3, 4]. Ma et al. [4] have investigated the motion and distribution of dust particles in the electrostatic sheath of a dusty plasma using multi fluid description. Their results show that a spatial localization of small dusts particles is possible if the gravitational force is negligible compared to the electrostatic force. When the gravitational effects are taken into account, the dust number density shows a multilayer or stratified structure. Very recently [1,2] the dynamics of a dust particle inside a magnetized sheath has been investigated without considering the effect of dust particle on the plasma sheath structure. In this work we investigate numerically the magnetized sheath of a dusty plasma using fluid equations for electrons, ions and dust particles. Our model equations include the effects of the electric, magnetic, pressure, and gravitational forces. The gravitational force for the electrons and ions and also the pressure force for dust particles are neglected. The results of the numerical simulations are represented using dimensionless variables Ne, Ni, Nd, respectively, for the electron, ion, and dust number densities and ^, g^, f/,^, and E, respectively, for the electrostatic potential, average charge of the dusts, the ion velocity component normal to the wall, and the distance from the sheath edge [1]. Figure 1 represents the structure of the plasma sheath both in the presence and absence of the magnetic field. It is seen that the presence of the magnetic field results in decreasing of the sheath thickness and ion normal velocity as well as the enhancement of the magnitude of the average charge on the dusts and ion number density. Close to the wall the maximum in dust density profile increases to very high levels to overcome the positive field from more stronger ion sheath. Increasing the angle of incidence of the magnetic field has similar effects. Figure 2 displays the structure of the magnetized sheath for three different number densities of the dust particles at the sheath edge. Note that the default value is 1 which in dimensional variable is equal to 1.6 x 10^ cm^^. It is found that the sheath thickness increases initially with dust TO number density, but after FIRST reaching a maximum at intermeCREDIT LINE (BELOW) BE INSERTED ON THE PAGE OF EACH PAPER diate densities the EXCEPT thickness decreases with increasing the density. The stratification of THE PAPERS ON PP. xxx xxx and xxx xxx
CPl 041, Multifacets of Dusty Dusty Plasmas Plasmas Fifth Fifth International International Conference Conference on on the the Physics Physics of of Dusty Plasmas Plasmas CP1041, Multifacets of edited by J. J. T. T. Mendona, Mendon^a, D. D. P. P. Resendes, Resendes, and and P. P. K. K. Shukla Shukla edited

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Abstract Submitted for the DPP10 Meeting of The American Physical Society Sorting Category: 9.0.0 (C)

Low-temperature control of plasma-assisted nanober heating HAMID MEHDIPOUR, Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996, Tabriz, Iran, KOSTYA OSTRIKOV, Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, New South Wales 2006, Australia Three model, sheath, growth, and heat models are coupled to investigate the direct dependencies of the carbon nanober growth and heating on the plasma parameters in a low-temperature plasma. Using the models, the eects of variation in the plasma sheath parameters and substrate potential on the plasma heating eects in catalyzed growth of carbon nanober have been investigated. Numerical results have shown that variations in some parameters such as the electron temperature, electron number density, and substrate potential, which change the sheath width, mainly aect the growth rate and carbon nanober heating at low catalyst temperatures and the other parameters such as gas pressure and the ratio of the hydrocarbon/etching gas density to total gas density, change the carbon nanober growth at all temperatures and substantially increases the temperature of catalyst particle, attached to carbon nanober end, respect to the temperature at substrate interface with substrate-holding platform. These results are also consistent with the available experimental results of the selectively control of plasmaassisted nanostructure heating and the catalyzed growth of some highaspect-ratio structures. Hamid Mehdipour hamid11062@yahoo.com Physics Department, Faculty of Science, Sahand University of Technology, 51335-1996, Tabriz, Iran Electronic form version 1.4

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Date submitted: 13 Jul 2010