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Int. J. Nanotechnol., Vol. 4, No. 6, 2007

Recent developments in single-crystal inorganic

nanotubes synthesised from removable templates
Guozhen Shen*, Yoshio Bando
and Dmitri Golberg
Nanoscale Materials Center,
National Institute for Materials Science,
Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan
Fax: +81-29-851-6280
E-mail: shen.guozhen@nims.go.jp
E-mail: gzshen@ustc.edu
E-mail: Bando.yoshio@nims.go.jp
E-mail: Golberg.dmitri@nims.go.jp
*Corresponding author
Abstract: Since Sumio Iijima identified the hollow Carbon Nanotubes (CNTs)
in the early 1990s, there have been significant research efforts to synthesise
inorganic nanotubes of various solids. Generally, the formation of tubular
nanostructures requires layered, anisotropic, or pseudo-layered crystal
structures. Inorganic nanotubes, which typically do not possess such structures,
are usually synthesised using template-based methods. However, these
nanotubes are either amorphous, polycrystalline or exist only in ultrahigh
vacuum. Recently, an epitaxial casting method using removable ZnO
nanowires as templates has been developed to synthesise single-crystal GaN
nanotubes. This opens up an exciting field of research on the synthesis
of single-crystal nanotubes with non-layered or non-anisotropic structures.
In this paper, we review recent research activities on single-crystal inorganic
nanotubes synthesised using removable templates via vapour phase methods
based on similar epitaxial casting concepts. The applications and nanodevices
that have been built using these novel inorganic nanotubes are also presented.
Keywords: semiconductors; nanotubes; sulphides; phosphides; chemical
vapour deposition; CVD; templates.
Reference to this paper should be made as follows: Shen, G., Bando, Y. and
Golberg, D. (2007) Recent developments in single-crystal inorganic nanotubes
synthesised from removable templates, Int. J. Nanotechnol., Vol. 4, No. 6,
pp.730749.
Biographical notes: Guozhen Shen received a BS Degree in Chemical
Education from Anhui Normal University in 1999, and a PhD Degree in
Chemistry (with Professor Yitai Qian) from University of Science and
Technology of China, and then he worked as a Postdoctoral Researcher at
Hanyang University, Korea. He joined National Institute for Materials Science
as a postdoctoral researcher in 2005. His most recent research interests include
fabrication of semiconductor nanowires, nanotubes, and 1-D heterostructures;
nanoelectronics, and devices applications of semiconductor nanowires like
Field Effect Transistors (FET) for biosensing. He has authored and co-authored
over 80 journal papers, eight review papers and book chapters, and holds three
issued Japan patents.

Copyright 2007 Inderscience Enterprises Ltd.

Recent developments in single-crystal inorganic nanotubes synthesised

731

Yoshio Bando obtained a PhD Degree in Inorganic Chemistry from Osaka

University. He is currently director-general of International Center for Young
Scientists, Fellow of National Institute for Materials Science (NIMS), group
leader of Nanomaterials Synthesis and Analysis Group, NIMS, and Professor of
University of Tsukuba. He has published over 400 original papers in
international journals.
Dmitri Golberg obtained a PhD Degree in Solid State Physics from Bardin
Central Institute for Ferrous Metallurgy, Moscow, Russia in 1990. He is
currently a Nanotube Group leader within NIMS. His research interests include
synthesis, electron microscopy analysis and physicochemical property studies
of boron nitride, boron carbonitride, various metal oxide, carbide, boride,
phosphide, nitride, sulphide and selenide nanotubes, metal filled nanotubes,
diverse nanowires and nanobelts, and nanostructure formation, and phase
transitions under non-equilibrium conditions at the nanoscale. He has authored
over 250 original papers in international journals and more than 70 Japanese
patents.

Introduction

Since the identification of Carbon Nanotubes (CNTs) in 1991 by Iijima [1], there have
been enormous research efforts to synthesise various kinds of CNTs and to test their
unique functions such as hydrogen storage, field-emission displays, field-effect
transistors, diodes, sensors, and actuators [26]. To date, CNTs have successfully been
synthesised using a variety of methods, such as arc-discharge, laser vapourisation,
hydrocarbon pyrolysis, solvothermal methods, and Chemical Vapour Deposition (CVD)
[712]. In addition to CNTs, there have also been great research endeavours to fabricate
nanotubes of other solids. Some layered inorganic solids similar to graphite, in which the
atoms are covalently bonded to form two-dimensional layers that are stacked together
through van der Waals interactions, such as WS2, MoS2, and NiCl2 can also be rolled up
to form seamless nanotubes. In fact, the formation of tubular nanostructures generally
requires a layered or anisotropic crystal structure. Pioneered by the work on WS2
nanotubes in 1992 by Tenne et al. [13], inorganic nanotubes have been synthesised from
a wide range of compounds possesing layered or anisotropic structures, such as MoS2
[14], TiS2 [15], ZrS2 [16], HfS2 [16], BN [17], VOx [18], NiCl2 [19], NbSe2 [20,21], NbS2
[22], TaS2 [22], Bi [23], Se [24], Te [25], Bi2S3 [26] and Sb2S3 [27].
Synthesis of inorganic nanotubes that do not have a layered crystal structure has also
attracted considerable attention. Recent reports indicated that under appropriate
experimental conditions, geometrically closed, concentric nanotubes could also form.
However, compared with layered compounds, formation of nanotubes from solid
materials without layered structures requires much more effort to bring together the
atoms or small particles into hollow tubular structures. As a result, templates like CNTs,
and porous membranes (AAO etc.) are usually needed to assist the growth into cylinder
tubes. Another method relies on thin film rolling of lamellar precursors. Many kinds of
inorganic nanotubes have been synthesised from non-layered inorganic materials using
the so-called template-assisted methods, such as TiO2 [28], SiO2 [29,30], Al2O3 [31],
SrAl2O4 [32], In2O3/Ga2O3 [33], ZrO2 [34] and metals [35,36]. However, typically, all the
produced nanotubes are either amorphous, polycrystalline or exist only in ultrahigh

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G. Shen, Y. Bando and D. Golberg

vacuum. In fact, the growth of single-crystal hollow nanotubes would be more

advantageous for potential practical applications in nanoscale electronics,
optoelectronics, and biochemical sensing. Thus the synthesis of single-crystal nanotubes
with non-layered structures still remains a challenging task.
Goldberger et al. [37] reported on the synthesis of single-crystal GaN nanotubes by
epitaxial casting, in which hexagonal ZnO nanowires had served as templates for
epitaxial overgrowth of thin GaN sheaths. The ZnO nanowire template were then
subsequently removed by thermal reduction and evaporation with formation of GaN
nanotubes [37]. This work has opened up an exciting new field of research on the
synthesis of single-crystal nanotubes with nonlayered or non-anisotropic structures.
In this paper, we review the recent research activities and breakthroughs with respect to
single-crystal inorganic nanotubes synthesised using removable templates via vapour
phase methods based on similar epitaxial casting concepts. Firstly, the synthetic
concepts are introduced. Then the inorganic nanotubes synthesised through these
approaches are surveyed based on two different sub-concepts of the template-based
methods: the physical templating and chemical templating. Finally, the applications and
nanodevices that have been built using these novel inorganic nanotubes are highlighted.

Synthesis concepts

There are many kinds of methods developed for the vapour-phase syntheses of
single crystal inorganic nanotubes. Templating against pre-existing nanostructures
(e.g., nanowires, nanobelts) in the vapour phase processes is one of the most recently
adopted techniques. It represents a straightforward and efficient route towards
single-crystal nanotubes.
In such process, the first step is either pre-formation or in situ formation of easily
removable 1-D nanostructures in vapour phase conditions. These 1-D nanostructures are
used as templates for the next deposition of target material coatings to finally form 1-D
core/shell nanostructures. In the last step, by choosing a proper etching technique,
the inner core nanowires are removed, which resulted in the formation of single crystal
nanotubes.
To this end, two different strategies have been developed, namely, the physical
templating and chemical templating approaches, as indicated in Figure 1. In the physical
templating approach, a 1-D single crystal nanostructure serves as a substrate for the
epitaxial growth of another composite to obtain core/shell nanowires containing sharp
structural and compositional interfaces. Selective etching of the inner nanostructures
leads to the formation of single crystal nanotubes with well-controlled inner and outer
diameters. In the chemical templating method, a 1-D single-crystal nanostructure serves
as not only a substrate, but also reacts with proper chemical reagents to be partially or
completely converted into the target nanotubes.

Recent developments in single-crystal inorganic nanotubes synthesised

Figure 1

733

Schematic illustration of the removable template method towards single-crystal

nanotubes via a vapour phase process

Physical templating approach

3.1 GaN Nanotubes

Wurtzite GaN, a particularly important IIIV semiconductor with a direct band-gap of
3.4 eV, is one of the most promising semiconductors suitable for designing and
fabricating optoelectronic devices in the violet and blue region, in which Si and
conventional IIIV semiconductors are not applicable. So far, considerable efforts have
been directed towards the synthesis of one-dimensional GaN materials, such as nanorods,
nanowires, and nanobelts [3840]. The well-established methods include a carbon
nanotube confined reaction, arc discharge, laser ablation, sublimation, pyrolysis, and
CVD. However, these methods failed with respect to the synthesis of single-crystal GaN
nanotubes, though they are useful for the fabrication of amorphous or polycrystalline
GaN nanotubes when combined with template-confined techniques.
Synthesis of single-crystal GaN nanotubes was accomplished for the first time using
the epitaxial casting technique. In this technique, arrays of wurtzite ZnO nanowires on
(110) sapphire wafers were utilised as templates for the epitaxial overgrowth of thin GaN
layers in a CVD system. Trimethylgallium and ammonia were used as the precursors
for GaN layers. Figure 2(a) is the SEM image of the ZnO nanowire arrays used as
templates in this process, which were synthesised using a vapour deposition process.
These nanowires grew along the [001] direction and have uniform lengths of 25 m and
diameters of 30200 nm with well faceted hexagonal cross-sections. After coating these
ZnO nanowires with GaN layers, the inner ZnO cores were either chemically etched by
ammonia or thermally reduced at high temperatures. Figure 2(b) shows the SEM image

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G. Shen, Y. Bando and D. Golberg

of the resultant GaN nanotube arrays. It can be seen that the morphology of the initial
nanowire arrays was well preserved. The hollow cavities of these GaN products are
visible in some broken tubes, the inset in Figure 2(b). The studies revealed that all the
synthesised GaN nanotubes are single crystals with the preferred [001] growth directions.
Figure 2

SEM images of the: (a) ZnO nanowire arrays; (b) GaN nanotube arrays and (c,d) TEM
images of arrays of GaN nanotubes with their ZnO nanowire templates partially
removed (from [37], with permission)

For the formation of single-crystal GaN nanotubes using ZnO nanowires as templates,
the most important factor is the perfect epitaxial relationship between wurtzite GaN and
ZnO, which was indeed confirmed while studying the microstructures of GaN nanotubes
with their ZnO nanowire templates partially removed (Figure 2(c) and (d)). As known,
both GaN and ZnO have the wurtzite crystal structures and very similar lattice constants
of: a = 3.249 , c = 5.207 for ZnO and a = 3.189 , c = 5.185 for GaN. Thus it is
easy for GaN to epitaxially coat on the side {110} plane surfaces of ZnO. It is in fact,
a perfect epitaxial casting mechanism.

3.2 Si nanotubes
Due to the key role of silicon in interconnections and basic components for the future
nanoelectronic and especially optoelectronic devices, 1-D Si nanostructures have
recently become of special interest. Different methods including laser ablation, CVD,
oxide-assisted method and solution process have been developed for Si nanowire
fabrication. Though these methods have also been used to make Si nanotubes, all the
obtained Si nanotubes are either polycrystalline or amorphous [4143].
Recently, we developed an efficient CVD process to synthesise single-crystal Si
nanotubes using ZnS nanowires as the removable templates. ZnS and SiO powders were
utilised as the source materials in a vertical induction furnace [44]. The experimental
procedure was as follows: firstly, single-crystalline ZnS nanowires were synthesised from
ZnS powders at 1200C. Then, the reaction temperature was increased to 1450C.

Recent developments in single-crystal inorganic nanotubes synthesised

735

During this step, core/shell ZnS/Si nanowires formed. Finally, the core/shell nanowires
were etched in a HCl solution, which resulted in the removal of inner ZnS cores.
ZnS nanowire templates used in the process have diameters of 2060 nm and
grow along the [0001] directions. Figure 3(a) shows the SEM image of the resultant Si
nanotubes. They have very thin walls and tip-ends either closed or open (Figure 3(b)
and (c)). These Si nanotubes are well-structured single crystals growing along the [111]
direction (Figure 3(d)).
Figure 3

(a) Low-magnification TEM image of Si nanotubes; (b,c) TEM images showing

the thin wall and open tip of a Si nanotube and (d) HRTEM image of a Si nanotube
(from [44], with permission)

The formation of single-crystal Si nanotubes was primarily influenced by the initial

ZnS nanowire templates. In fact, the [0001] grown ZnS nanowire and the [111]
grown Si nanotube have well-defined epitaxial relationships as (111)Si//(111)ZnS and
[111]Si//[111]ZnS, which results in the formation of final single crystal Si nanotubes
in a way similar to single-crystal GaN nanotubes prepared using ZnO as removable
template.

3.3 IIBVI nanotubes

Group IIBVI semiconductors (ZnS, ZnSe, CdS, CdSe) are of great importance in many
fields. Their common characteristic is a propensity to form a wurtzite crystal structure if
the right conditions are chosen. Significant efforts have been paid to shape IIBVI

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G. Shen, Y. Bando and D. Golberg

semiconductors into 1-D morphologies, such as nanorods, nanowires and nanobelts using
solution and CVD processes, or laser ablation [4548]. However, no success has been
claimed in fabricating single crystal IIB-VI nanotubes using these conventional methods.
The pioneering work by Goldberger et al. [37] on GaN nanotubes has opened up a new
horizon in the synthesis of single-crystal nanotubes and makes it possible to prepare
single crystal IIB-VI nanotubes on a large scale.
The first example is single crystal ZnS nanotubes [49]. These nanotubes were
synthesised in a horizontal high-temperature resistance furnace using ZnS and SnO as the
sources. The reaction temperature was 1150C; N2 was used as a protection gas. Figure 4
shows the typical TEM images of a synthesised ZnS product. It is apparent that all
structures have tubular shapes. Some tubes have uniform diameters and wall thicknesses
along the whole tube, while the others have tapered diameters from ~250 nm to ~50 nm.
These ZnS nanotubes are single crystals with the growth directions parallel to the [120]
crystallographic orientation of a wurtzite ZnS crystal. A common feature of the
synthesised ZnS nanotubes is that all of them are entirely or partially filled with Sn.
It is deduced that the formation of ZnS nanotubes is a Sn nanowire-templated process.
During this process, the first step is the reduction of SnO by carbon to generate Sn, which
resulted in the self-catalyzed growth of Sn nanowires. During the second stage, a thin
layer of ZnS deposited on the surface of Sn nanowires to form a Sn/ZnS core/shell
nanostructure. After evaporation at high temperature the inner Sn nanowires were etched.
As a result single-crystal ZnS nanotubes were formed.
Figure 4

Typical TEM images showing filling characteristics of Sn inside the ZnS nanotubes:
(a) ZnS nanotubes with uniform diameters throughout the whole lengths
and (b) tapered ZnS nanotubes (from [49], with permission)

Similarly, single crystal ZnSe nanotubes/submicrotubes were synthesised, which also

grew along the [120] orientation of a wurtzite ZnSe crystal [50].
CdS and CdSe compounds with crystal structures similar to ZnS or ZnSe are
particularly important. Wurtzite is the most stable structure for CdS and CdSe.
Both materials have many potential applications in optical, electric and optoelectronic
fields. Though many kinds of 1-D CdS or CdSe nanostructures have been fabricated
using VLS or VS processes, single crystal CdS and CdSe nanotubes have never been
obtained using these techniques. The only success was achieved through a physical
templating approach using in situ formed Sn nanowires as the removable templates [51].

Recent developments in single-crystal inorganic nanotubes synthesised

737

The formation of CdS and CdSe nanotubes is generally similar to that of ZnS and
ZnSe ones. In a typical process, CdS or CdSe, SnO, SnO2 and activated carbon powders
were thermally evaporated at high temperature in a horizontal resistance furnace.
The products deposited on graphite wafers in a low temperature region. Figure 5 depicts
a series of SEM images of CdS nanotubes (left-hand-side) and CdSe nanotubes
(right-hand-side). Both CdS nanotubes and CdSe nanotubes have the following features:
parts of them have uniform diameters along the whole lengths and the others have tapered
diameters. All tubes are fully or partially filled with Sn and have large Sn particles
attached to their tips. All the nanotubes are single crystals with the preferred growth
directions along the [001] crystallographic orientations. Similar to single-crystal ZnS
nanotubes, the formation mechanism is a two-step Sn nanowire templated process.
Figure 5

(ae, left) TEM and HRTEM images of CdS nanotubes. (ae, right) TEM and HRTEM
images of CdSe nanotubes (from [51], with permission)

3.4 Magnetite nanotubes

Magnetic nanotubes, such as FePb, Fe3O4, and LPMO, may potentially serve as tunable
fluidic channels for tiny magnetic particles, data storage devices in nanocircuits,
and scanning tips for magnetic force microscopes. Single-crystal magnetite (Fe3O4)
nanotubes were synthesised by a three-step process [52]. Single-crystal MgO nanowires
(30100 nm in diameter) were first grown on a gold-coated Si/SiO2 substrate from
Mg3N2 powders by thermal evaporation. Then a layer of Fe3O4 was deposited on these
MgO nanowires using the pulsed laser deposition technique to form the MgO/Fe3O4
core/shell nanowires. Being etched in a (NH4)2SO4 solution at 80C, the inner MgO
nanowires were removed and single-crystal Fe3O4 nanotubes were formed. Figure 5(a)
shows the TEM image of a single Fe3O4 nanotube with an outer diameter of ~30 nm.

G. Shen, Y. Bando and D. Golberg

738

The upper inset SAED pattern clearly indicates that the tube is a single crystal.
Combined with the HRTEM image shown in the lower inset it reveals that the
growth direction was along the [100] orientation. These free-standing Fe3O4 nanotubes
rendered a unique opportunity to investigate the electron transport through Fe3O4 in a
quasi-one-dimensional form.
Similar technique can be extended to synthesise core/shell transition metal oxide
nanowires, such as MgO/YBa2Cu3O6.66, MgO/La0.67Ca0.33MnO3, and PbZr0.58Ti0.42O3
nanowires [53,54]. By efficient selection of proper etching methods, single crystal
transition metal oxide nanotubes, YBa2Cu3O6.66, La0.67Ca0.33MnO3, PbZr0.58Ti0.42O3, are
expected to also form. If these kinds of transition oxide nanotubes can be successfully
synthesised, novel chemical and physical properties, such as high Tc superconductivity,
colossal magnetoresistivity and ferroelectricity are envisaged.

Chemical templating approach

4.1 II3V2 nanotubes

Narrow band gap II3V2 semiconductors are of prime scientific and technological
importance. They may exhibit more pronounced size quantisation effects than the IIVI
or IIIV semiconductors due to their large excitonic radii. However, it is quite difficult to
synthesise one-dimensional II3V2 nanostructures due to the lack of general synthetic
methods. Recently, we obtained single-crystal II3V2 nanotubes using the in situ formed
IIB metal nanowires as removable templates [55]. Single-crystal II3V2 nanotubes
(Zn3P2, Cd3P2) were synthesised at 1350C under ambient pressure in a vertical induction
furnace from a mixture of ZnS (or CdS), P and Mn3P2 powders. Figure 6 gives the typical
SEM images of the synthesised Zn3P2 and Cd3P2 nanotubes. It can be seen that using
the removable template method, in fact, the nanotubes can be obtained on a large scale.
By controlling the experimental conditions, the product morphology can also be well
controlled. For instance, if the reaction temperature was increased, Zn3P2 and Cd3P2
microtubes were synthesised at the expense of nanotubes. When excessive ZnS or CdS
were taken as the source material, hierarchical Zn3P2/ZnS or Cd3P2/CdS heterostructures
were prepared instead.
Figure 6

Low-magnification TEM image of a Fe3O4 nanotube, with SAED pattern and HRTEM
image shown in the upper and lower inset, respectively (from [52], with permission)

Recent developments in single-crystal inorganic nanotubes synthesised

739

Microstructures of the synthesised nanotubes have clearly been verified using HRTEM
imaging. From the low-magnified TEM images, the hollow cavities of the products are
visible (Figure 7(a)(c)). All the nanotubes have very thin walls of ~4050 nm and open
tips (Figure 7(d), (f) and (g)). Both the Zn3P2 and Cd3P2 nanotubes are single crystals
with the preferred growth directions perpendicular to the (101) planes (Figure 8).
The growth of the nanotubes is a three-step process: firstly, metallic Zn or Cd nanowires
were formed through a Vapour-Solid (VS) process via ZnS + C  Zn + CS2 or
CdS + C  Cd + CS2. In the second step, the generated phosphorus (P) gases partially
reacted with these Zn or Cd nanowires to form Zn/Zn3P2 or Cd/Cd3P2 core/shell
nanowires. Finally, the inner Zn or Cd were consumed during evaporation of the coaxial
nanocables, whereas the Zn3P2 or Cd3P2 shell remained intact as the final nanotubes.
Figure 7

SEM images of the synthesised Zn3P2 nanotubes (upper) and the Cd3P2 nanotubes
(lower). The inset displays a magnified image; that clearly shows a hollow structure

Due to their extremely thin walls, these nanotubes are expected to show size quantisation
effects. This idea was checked during the Cathodoluminescence (CL) measurements.
It is known that a bulk Zn3P2 crystal has an emission at ~802 nm. The synthesised Zn3P2
nanotubes with wall thickness of ~45 nm emit at 796 nm, which is similar to that of bulk
crystal since the wall thickness (45 nm) is much larger than the excitonic radii of Zn3P2.
However, when the wall thicknesses became 20 nm and 10 nm, emissions centred at
711 nm and 491 nm appeared, respectively. These values show notable blue-shifts with
respect to a bulk crystal due to predicted quantisation effects.

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G. Shen, Y. Bando and D. Golberg

4.2 ZnAl2O4 nanotubes

Spinel oxides have the composition AB2O4, where A and B may represent divalent and
trivalent cations, respectively. Spinel oxides have very important technical applications.
For example, iron-containing spinels (ferrites) are well-known magnetic materials.
Strontium aluminate (SrAl2O4) is one of the most studied and most efficient host
materials for long-lasting phosphorescence [56].
The first example of a single crystal spinel nanotube using a removable template is a
ZnAl2O4 nanotube [57]. Fan et al. synthesised single crystal ZnAl2O4 nanotubes using
ZnO nanowires as templates. Single-crystal ZnO nanowires were synthesised using
vapour phase transport methods. Then a thin layer of Al2O3 was deposited on these ZnO
nanowires via atomic layer deposition to form core/shell nanowires. These nanowires
were annealed at 700C and final ZnAl2O4 nanotubes were fabricated.
After annealing, the remained 1-D nanostructures are freestanding, narrow in
diameter (3040 nm) and wall thickness (10 nm) and are hollow from one end to the
other, as shown in Figure 9(a) and (b). The nanotubes are single crystals and most of
them have crystal orientations parallel to the (111) spinel planes. By careful choosing
of ZnO template with different morphology, different kinds of tubular ZnAl2O4
nanostructure can be fabricated. For instance, saw-like branched ZnAl2O4 nanotubes were
synthesised using saw-like ZnO nanowires as templates.
Figure 8

(a)(c) TEM images of Cd3P2 nanotubes; (d,e) HRTEM image of a Cd3P2

nanotube, revealing its single-crystal nature and (f)(h) TEM and HRTEM images
of single-crystal Zn3P2 nanotubes (from [55], with permission)

Recent developments in single-crystal inorganic nanotubes synthesised

Figure 9

741

(a,b) SEM and TEM images of the ZnAl2O4 spinel nanotubes and (c) a branched
ZnAl2O4 spinel nanotube (from [57], with permission)

Single-crystal ZnAl2O4 nanotubes were formed via an interfacial solid-state reaction

between ZnO and Al2O3 involving the Kirkendall effect, which is a classical phenomenon
in metallurgy and was applied to explain the formation of hollow spherical nanocrystals
[58,59]. It is an interesting approach since the Kirkendall effect allows one to develop a
rational design of nanoscale tubular objects based on any appropriate choice of materials
and different reaction properties. It also constitutes a systematic pathway to prepare
single-crystal nanotubes made of diverse range of materials.

4.3 MgAl2O4 nanotubes

Fabrication of single crystal MgAl2O4 nanotubes was based on the scheme shown
in Figure 10 [60]. In this process, reactive MgO nanowires were chosen as templates.
As we have discussed above, a MgO nanowire is a very commonly used epitaxial
substrate for depositing various transition oxides including Fe3O4, YBa2Cu3O6.66,
La0.67Ca0.33MnO3, and PbZr0.58Ti0.42O3 and forming either single crystal nanotubes or
core/shell nanowires. Due to a high reactivity of MgO during spinel syntheses through
the topotaxial solid state reactions, MgO nanowires are assumed to be proper sacrificing
templates for MgAl2O4. A work carried out by Fan et al. [60] did confirm such
assumption. Firstly, single-crystal MgO nanowires were synthesised inside a horizontal
quartz tube furnace using a Mg3N2 powder as the source material. Then using the
precisely controlled atomic layer deposition, a thin layer of ~10 nm Al2O3 was deposited
on the MgO nanowires to form core/shell MgO/Al2O3 nanowires. In order to transform
the core/shell MgO/Al2O3 nanowires into spinel MgAl2O4 nanotubes, the sample was first
annealed at high temperature and then etched in a (NH4)2SO4 solution. The whole process
is depicted in Figure 10.

742

G. Shen, Y. Bando and D. Golberg

Figure 10 Schematics of the fabrication process of MgAl2O4 spinel nanotubes

(from [60], with permission)

After etching, MgAl2O4 nanotubes were obtained, as shown in Figure 11(a). Typical
nanotubes have wall thicknesses of 1112 nm. All these nanotubes are single crystalline
(Figure 11(b)) with a longitudinal direction along the (001) planes of a spinel MgAl2O4
crystal (Figure 11(c)).
Figure 11 HRTEM images of the MgAl2O4 nanotubes, showing their single-crystalline
characteristics (from [60], with permission)

In the regarded process, the tube wall thickness and diameters can be efficiently
controlled through two different ways:

a control in the deposited Al2O3 layer thickness

a control in the diameter of a MgO nanowire template.

4.4 GaN nanotubes

Although single-crystal GaN nanotubes have been synthesised by Goldberger et al. [37]
based on the physical templating method and using ZnO nanowires as the removable
templates, it is still a challenge to find a pathway towards single-crystal GaN nanotube
fabrication using chemical templating [61].

Recent developments in single-crystal inorganic nanotubes synthesised

743

Single-crystal GaN nanotubes using this concept were crystallised via a two-stage
process based on a well-controllable conversion of amorphous gallium oxide (Ga2O)
nanotubes. During the first stage, amorphous Ga2O nanotubes were prepared by
carbon-thermal reduction of Ga2O3 powders under N2 at 1250C. The involved
reactions were Ga2O3 + 2C  Ga2O + 2CO, and 2Ga2O + 4CO  4Ga + C + 3CO2.
These reactions resulted in the formation of Ga-filled amorphous Ga2O nanotubes
(Figure 12(a), (b)). During the second stage, N2 gas was changed to NH3 gas and the
reaction temperature was increased to 1400C. In this stage, the involved reaction
was Ga2O + 2NH3  2GaN + H2O + 2H2. It led to the formation of single-crystal GaN
nanotubes (Figure 12(c) and (d)). The GaN nanotubes have preferred growth direction
along the [101] orientation, which is quite different from GaN nanotubes synthesised
using ZnO nanowires as removable templates. The possible reason may be that the
present GaN nanotubes were formed via a chemical conversion method while the former
GaN tubes were fabricated using epitaxial casting of GaN on ZnO nanowires.
Figure 12 (a,b) TEM images of amorphous Ga2O nanotubes and (c,d) TEM images
of single-crystal GaN nanotubes converted from Ga2O nanotubes (from [61],
with permission)

The regarded single-crystal GaN nanotubes showed different cathodoluminescence

properties compared with a bulk GaN crystal. A green emission centred at 505 nm was
observed for GaN nanotubes, which displays a blueshift of ~40 nm compared with a bulk
GaN crystal. In the templating conversion process, GaN nanotubes were prepared from
Ga2O. Therefore, it was thought that a blueshift may be attributed to some intrinsic point
defects, such as Ga vacancies, or O impurities.

744

G. Shen, Y. Bando and D. Golberg

Applications and nanodevices

1-D nanostructures have been in the focus of recent extensive studies worldwide
due to their unique physical properties and potential to revolutionise broad areas of
nanotechnology compared with standard bulk crystals. 1-D nanostructures represent the
smallest dimension structure that can efficiently transport electrical carriers. They are
ideally suited to the critical and ubiquitous task of moving and routing charges in
nanoscale electronics and optoelectronics. Furthermore, 1-D nanostructures also exhibit
device functions, and thus can be exploited as both the wiring and device elements for
diverse functional nanosystems [6266].
Similar to nanowires, inorganic nanotubes represent important types of nanometer
scale 1-D structures. Use of removable templates via vapour phase methods makes
it possible to rationally and predictably synthesise single-crystal nanotubes with
controllable chemical composition, diameter, length and doping levels. Thus it is possible
to assemble nanotube devices including field-effect transistors, p-n and light emitting
diodes, complex logic gates and so on.
Electrical transport measurements provide information about the electronic structure
and the behaviours of carriers under electric field in 1-D nanoscale materials.
One powerful configuration for studying electrical transport is a Field-effect Transistor
Setup (FET). Single-crystal Fe3O4 nanotubes synthesised using MgO nanowires as
templates rendered a unique opportunity to investigate the electron transport in a quasi
1-D form [52]. Figure 13 shows the SEM image of a device based on single-crystal
Fe3O4 nanotubes and used for the analysis of carrier transport properties. The device
consists of a Fe3O4 nanotube (~5 m) and four metal electrodes evenly distributed
on the top. Figure 14(a) shows the IV curves recorded at different temperatures
(290, 180 and 77 K). They exhibit rather linear features and the nanotube resistivity
increases monotonically with decreasing temperature. Similar with that of an epitaxial
Fe3O4 film, room temperature resistivity was deduced to 4 102 . Figure 14(b)
demonstrates the magnetoresistance measurement at 77 K. Magnetoresistance was clearly
observed for the Fe3O4 nanotube due to the spin-polarised transport across the structural
domain boundaries.
Figure 13 SEM image of a Fe3O4 nanotube device used in the transport study

Recent developments in single-crystal inorganic nanotubes synthesised

745

Figure 14 Electrical measurements of individual Fe3O4 nanotubes (from [52], with permission)
(for colours see online version)

As another example, the electron transport properties of single-crystal GaN nanotubes are
also highlighted here [37]. Figure 15 displays the temperature-dependent IV curves
recorded on a GaN nanotube. The electrodes (20 nm Ti and 80 nm Au) for the electrical
measurements were fabricated using e-beam lithography and thermal evaporation.
They indicate that the resistances of the GaN nanotube are of the order 10 M at room
temperature, and increase with decreasing temperature.
Figure 15 Temperature dependence IV curves of a GaN nanotube (for colours see online version)

Summary

Synthesis of inorganic nanotubes that do not have a layered crystal structure has attracted
considerable attention in recent years due to their interesting and important properties and
applications in electronics, optoelectronics, drug release and bio-sensing. Compared with
layered compounds, formation of nanotubes from solid materials without layered
structures requires much more effort to bring together the atoms or small particles into

746

G. Shen, Y. Bando and D. Golberg

hollow tubular structures. As a result, templates are usually required to assist the growth
into cylinder tubes. In this paper, a comprehensive survey of work on single-crystal
inorganic nanotubes synthesised from removable templates in the vapour phase processes
was reviewed. Such processes can be divided into two categories: a physical templating
approach and a chemical templating approach. For the physical templating approach,
a good example is single-crystal GaN nanotubes synthesised from ZnO nanowire
templates. In such a process, ZnO nanowire only acts as a substrate for the deposition
of a GaN layer. Other examples contain single-crystal Si nanotubes, IIBVI nanotubes,
and magnetite nanotubes. In the chemical templating approach, preformed or in situ
formed nanowires are used not only as a substrate for the deposition of different
chemicals but they also thoroughly or partially react with the chemicals to form the
target composite nanotubes. Single-crystal nanotubes obtained using such concept
include II3V2 nanotubes, ZnAl2O4 nanotubes, MgAl2O4 nanotubes and GaN nanotubes.
We believe that these templating approaches can be readily extended to produce a variety
of single-crystal nanotubes with different compositions if a proper choice of experimental
conditions and reactants is made.
Single-crystal hollow nanotubes are more advantageous for potential practical
applications in nanoscale electronics, optoelectronics, and biochemical sensing
applications than their polycrystalline or amorphous forms. They represent exciting
systems to probe fundamental questions about localisation of electrical carriers and
optical excitons in one dimension. In this paper, single-crystal nanotube applications
and devices were also demonstrated. For example, the four-probe device based on a
single-crystal Fe3O4 nanotube was fabricated in order to investigate its electron transport
properties. The field-effect transistor based on a single-crystal GaN nanotube was also
prepared and the regarded studies showed that the GaN nanotube resistance increased
with decreasing temperature.
Generally, it is worth noting that further continuing efforts are required to achieve
much better control of single-crystal nanotube syntheses and nanodevice fabrication in
order to uncover novel inorganic nanotube intriguing and exciting functional properties.

Acknowledgements
We thank Dr. D. Chen, Dr. J.Q. Hu, Dr. X.S. Fang, and Dr. C.H. Ye for helpful
discussions.

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