Carbon Nanotubes Based Thin Films: Fabrication, Characterization and Applications

40 Adv. Mater. Sci.
36 (2014) 40-61
Rev. L. Fu and A. M. Yu
CARBON NANOTUBES BASED THIN FILMS:

FABRICATION, CHARACTERIZATION AND APPLICATIONS
L. Fu1 and A. M. Yu1,2

1
Faculty of Life and Social Sciences, Swinburne University of Technology, Hawthorn VIC 3122, Australia
2
College of Chemical and Environmental Engineering, Hubei Normal University, 435002, China
Received: May 25, 2013
Abstract. Composite thin films based on carbon nanotubes have received immense attention
which is attributed to their distinct mechanical, thermal, optical and structure properties. Depending
on the film compositions and preparation methods, carbon nanotube based thin films can be
tuned for various applications in many fields. In this comprehensive review paper, we overview
the recent methods for the fabrication of carbon nanotube based thin films and the versatile
techniques for film characterization. Applications of carbon nanotube based thin films and their
devices are also reviewed. The remaining issues that impede the practical applications of thin
films are pointed out to enlighten their future research.
1. INTRODUCTION times to the copper [6]. Moreover, the thermal con-

ductivity of an individual nanotube can reach 3500
Carbon nanotubes (CNTs) have triggered enormous
W m-1K-1 [7,8]. Due to their unique mechanical, elec-
world-wide interest since it was discovered in 1991
trical, and thermal properties, CNTs have emerged
by Iijima [1]. CNTs are built from sp2 carbon units
as novel nanometric materials which have promis-
and present a seamless structure with hexagonal
ing applications in many areas.
honeycomb lattices [1,2]. Basically, there are two
CNTs-related commercial activity has grown sub-
types of CNTs: Single-walled carbon nanotubes
stantially during the past decade. Recently, 2D net-
(SWCNTs) and multi-walled carbon nanotubes
works of CNT incorporated thin films, either CNTs in
(MWCNTs) [1-3]. SWCNTs are single graphene rolls
random networks, aligned arrays or anything in be-
with diameters of 0.8 to a few nanometers while
tween, have attracted a great deal of attention. For
MWCNTs are concentric grapheme tubes that can
example, 2D conductive CNT films display excel-
have diameters from a few to more than a hundred
lent mechanical flexibility, stretchability, and opti-
nanometers. Many theoretical and experimental
cal transparence. Such films have been used for
works have revealed the outstanding properties of
conductive electrodes, and as artificial muscles [9].
CNTs. Their stiffness and strength are phenomenal.
The 3D aligned CNT arrays with properly engineered
Experimental results shows that CNTs have the
surfaces have been explored as dry adhesive tapes
N f Xz d Uf] fd W RaaciZ Re V]j)IERP ,-Q; c
or biomimic gecko feet [10,11]. Incorporating other
comparison, the stiffest conventional carbon fibres
functional materials with CNTs could either improve
R UX] RddW Z
Sc VdYRgVN f Xz d Uf] fd W0(( ER
the film property or greatly extend the range of ap-
and 70 GPa, respectively. The electrical properties
plication, such as battery electrodes, field emitter,
of CNTs are depended on the arrangement of the
antifouling films, antimicrobial, nanoelectronics and
graphene. They could be either semiconductors or
nanoscale sensors.
excellent conductors which have conductivity 1000
Corresponding author: A.M. Yu, e-mail: [email protected]
u*(),6Ug
R TVUHe
fUj8V e
Vc8 Ae
U
Carbon nanotubes based thin films: fabrication, characterization and applications 41
In this review, we begin by describing the vari- solvent. Surface treatment was also employed to
ous common fabrication techniques for preparing increase the conductivity of films. For example, 70%
CNTs based thin films. We then highlight the estab- HNO3 treatment removes the surfactants from the
lished experimental techniques for characterization CNTs surface resulting in the increase in inter-tube
of CNTs based thin films, exposing an array of its conductance. 99% SOCl2 treatment has the effect
unique properties. Finally, we discuss how each of doping on the CNTs surface, which enhance the
particular property can be exploited for potential overall conductance of the film.
applications. Two basic strategies are employed to prepare
CNTs based composite films by spray-coating
2. FABRICATION METHODS FOR method. A one-step molding process that gives well-
PREPARING CARBON NANOTUBE formed morphology, involves using a pre-mixed so-
BASED THIN FILMS lution of dispersed CNTs and the aqueous solution
of incorporated material. On the other hand, depos-
CNTs based thin films have been prepared by vari- iting CNTs and material separately by spray-coat-
ous techniques. In this section, we will focus on ing technique is the secondary way to form CNTs
introducing common techniques for coating and based composite films due to the difference in den-
decorating CNTs films. Last but not least, direct film sities and sizes between two materials.
growth using chemical vapor deposition (CVD) is
also discussed. 2.2. Dip-coating
2.1. Spray-coating Dip-coating is a facile solution based surface coat-
ing method providing great potential to scale up for
Spray-coating involves spraying CNTs dispersion largescale coating and does not require sophisti-
onto a heated substrate where every sprayed drop- cated apparatus. Essentially, the substrate is im-
let reaches the hot substrate surface and under- mersed into the CNTs based dispersion at a con-
goes pyrolytic decomposition, consequently forms stant speed and remains inside for a period of time
a thin layer of CNTs film. The excess solvent and then starts to be pulled up. The pull up process
byproducts escape to the air through the vapor needs a constant speed on carrying out to avoid
phase. The major advantage of spray-coating pro- any jitters. A thin layer of dispersion will be picked-
cess is the ability of forming large area and thick up with the substrate and a thin film forms after the
films. Various substrates can be used for spray- drying process (Fig. 1a). The amount of captured
coating CNTs including glass, quartz, silicon wafer, dispersion depends on several factors: the disper-
ITO, FTO which made this method suitable for a sion viscosity, immersion time, pull-up speed (usu-
large range of device fabrication [12]. ally faster withdrawal gives thicker coating layer)
Surfactants such as sodium dodecyl sulfate and the interaction between the dispersion and sub-
(SDS) [13] and sodium dodecylbenzene sulfonate strate. The quality of the thin film is also affected by
(SDBS) [14] are commonly added to form uniform the drying process. One drawback of the dip-coat-
CNTs water dispersion to be used in the ing technique is that the fabrication process occurs
spraycoating process. Another approach to form well at both sides of the substrate, which may restrict
dispersed CNTs is to disperse CNTs into organic its application.
solvents such as anhydrous ethanol. Low speed The simple operation process has been used for
centrifugation is usually carried out after the disper- fabricating CNTs/polymer composite films. Li et al.
sion procedure to separate the bundles as sedi- [15] reported the utilization of dip coating method
ments. It is worth nothing that the stability of the for fabricating transparent and conductive SWCNTs/
thin film made by spray-coating method is strongly polyvinyl butyral (PVB) composite film. The thick-
affected by the substrate used. Films are easy to ness of the SWCNTs/PVB composite film can be
peel off when the nanotube adhesion to substrate is tuned by varying the concentration and quantity of
weak. In this case, substrates could be modified to SWCNTs/PVB ethanol dispersion. Other polymers
enhance the interaction with CNTs. Schindler et al. like polystyrene, polyurethane elastomers [16] and
[13] recently demonstrated that coating a layer of poly(methyl methacrylate) (PMMA) [17], were also
polyimide or 3-aminopropyl triethoxysilan by self- used for forming thin films with CNTs using the dip-
assembly on glass substrate prior to CNTs deposi- coating method.
tion could increase the sheet resistance by 10%. Introducing surfactants such as Triton X-100 and
This pre-coating also facilitates the evaporation of SDS would improve the dispersibility of CNTs for
42 L. Fu and A. M. Yu
Fig. 1. Schematic diagrams of thin film preparation using (a) dip-coating and (b) spin-coating.
dip-coating. To improve the adhesion between sub- Similar with dip-coating process, spin-coating is
strate and film, pretreatment of substrate is neces- also a good method for preparing CNTs-polymer
sary. Aminopropyltriethoxysilane is usually used for composite films. The addition of surfactant to en-
substrate treatment as an adhesion promoter by hance the dispersibility is the common strategy
forming an interlayer between CNTs and substrate. during the spin-coating procedure as well. However,
the strong charge repulsion between complexes of
2.3. Spin-coating CNTs and surfactant would prohibit CNTs deposi-
tion onto the substrate. To overcome this problem,
Fabrication of CNTs based thin films using three methods have been proposed. Yim et al. [20]
spincoating method involves depositing a small prepared SWCNTs thin films without surfactant us-
puddle of CNTs based dispersion onto the center of ing multiple spin-coating. Meitl et al. [21] employed
a substrate, then spinning the substrate to high dual spinning to allow SWCNTs to land on the sur-
speed allowing dispersion to spread and cover the face before they meet in dispersion, resulting in a
substrate to form a thin film by centrifugal force (Fig. film of individual SWCNTs. This method can achieve
1b). a desired film thickness without having charge re-
The thickness of film normally relates with the pulsion between the tube-surfactant complexes. The
dispersion viscosity, angular speed and spin time. third method is replacing conventional surfactants
The orientation of CNTs appeared to have an angle by amphiphilic surfactants. Pluronic and Triton-X are
of approximately 45 s C relative to the radial direc- two commercial non-ionic surfactants introduced to
tion of the film, which is independent on the spin the CNTs based dispersion. Jo et al. [22] recently
rare and radial position [18]. The morphology of the reported the use of a lower molecular weight (~2000
thin film is also highly affected by the concentration g/mol) non-inoic surfactant, quinquethiophene ter-
of CNTs [19]. AFM study showed if SWCNTs con- minated poly(ethylene glycol), which can be easily
centration in blended solution is more than 2 wt.%, washed out after deposition.
there is no interconnected phase separation micro- There exist a few drawbacks of spin-coating tech-
structure and no island phase separation appeared nique. Firstly, spin-coating is not suitable for large-
on the film; the carbon nanotubes tend to aggre- scale coating because large substrates cannot be
gate. If the SWCNTs concentration equals to 1 wt.%, spun at a sufficiently high rate to form a uniform
the interpenetrating network phase separation layer. Secondly, the non-uniform distribution of ma-
microstructure can be formed. Nevertheless, terials along the radial direction becomes worst when
when the concentration drops below 0.5 wt.%, re- scaling up the dimension. In addition, for multilayer
sult would only show island phase separation mi- film fabrication, the multiple spin coating process is
crostructure. too cumbersome. Last but not least, the spin-coat-
ing method lacks material efficiency. In a typical followed by sonification. The molar ratio between Si
deposit process, most material is flung off and dis- of SiO2 matrix and C of MWCNTs is 7.5. Films were
posed. deposited by the dip coating method on pre-cleaned
glass substrate then annealed for 20 min at 350 s C.
2.4. Sol-gel method The fabrication method of CNTs-TiO2 is very similar
to CNTs-SiO2. The sol solution contains the mix-
The sol-gel process is a wet-chemical technique ture of titanium butoxide, water, HCl, and ethanol.
widely used for the fabrication of metal oxides ma- Thin films were formed by dipping the substrate into
terials. The underlying principal of sol-gel method is the sol for a few minutes then withdrawn vertically.
the transition of a system from a colloidal sol into a Films can be thickened by multiple dipping [24-26].
solid gel phase. Typically, a solution of the appro- Beyond that, sol-gel method is also appropriate for
priate precursors is formed first, followed by con- incorporating CNTs with other material such as Al2O3
versing into gel state by hydrolysis and condensa- [27], NiO [28,] and WO3 [29].
tion. Sol-gel has been used to incorporate CNTs
into different matrix with the merits of easier com-
position control, better homogeneity, non-vacuum
2.5. Vacuum filtration
process, low processing temperature and low cost Vacuum filtration is a simple method to separate
equipment required. Synthesized precursor solution CNTs composites from solvents and compact into
can be deposited onto substrate by spincoating, films which is achieved based on the different pres-
dip-coating or spray-coating methods and pyrolyzed sures between two sides Buchner funnel. The thin
at a low temperature. Extra steps of drying and sub- film formed is then peeled off from the filter paper
sequent calcinations of the gel are usually carried and subjected to drying process.
out for densification of films and burn out organic Luo et al. [30] were the first to use this approach
residues coming from the solution. CNTs-SiO2 and to fabricate CNTs/Nafion composite films which ex-
CNTs-TiO2 thin films are considered as the two most hibited high conductivity and superhydrophobicity.
successful films fabricated by sol-gel technique. The wettability of the composite film could be con-
Eq. (1) represents the common sol-gel process trolled by varying the filtering rate and the content
to form SiO2 thin film (using silica alkoxydes as ratio between two substances. Functionalization of
starting materials), in which R is an alkyl group. CNTs was also achieved by vacuum filtration. Yao
Eqs. (2) and (3) represent the hydrolysis and con- et al. [31] used octadecylamine for amination of
densation steps of monomeric alkoxysilanes respec- MWCNTs by vacuum filtration method. Introducing
tively. different types of CNTs into vacuum filtration sys-
tem could accomplish film delamination. In addi-
tion, placing metal mash or metal mask above the
Si(OR)4 (4 x )H2 O SiO x (OH)4 2x
4 ROH, (1) filter paperallows the formation of a particular pat-
tern for different applications.
Si-OR H2 O Si-OH ROH, (2) Despite the aforesaid advantages, the thin films
made by vacuum filtration are usually quite thick,
thus may not be preferred for certain applications.
Si-OR HO-Si Si-O ROH. (3)
Furthermore, film transfer is necessary as the
Introducing CNTs into the sol preparation is the first peeled film could not be directly used for device
step of fabrication of CNTs-SiO2 thin films through applications.
the sol-gel method. The most widely-used precur-
sors for silica resource are tetramethoxysilane 2.6. Electrophoretic deposition (EPD)
(TMOS) and tetraethoxysilane (TEOS). The sol
Electrophoretic deposition (EPD) occurs when
preparation is simply mixing precursors with water,
charged particles from a colloidal dispersion move
co-solvent and CNT. The co-solvent is usually metha-
towards an electrode under the constant electric
nol or ethanol, for adjusting viscosity of the sol and
field. Charged CNTs accumulate at the electrode
controlling the thickness of the produced thin films.
during the EPD processes to form a homogeneous
Acidic and basic catalysts are usually added to
and rigid film. One major limitation of EPD is the
accelerate the hydrolysis and condensation pro-
deposition only occurs on conductive surface. Fig.
cess. Berguiga et al. [23] have shown that high qual-
2a shows the schematic diagram of electrophoretic
ity CNTs-SiO2 thin film can be fabricated by mixing
deposition of a CNTs film. The surfactant wrapped
TEOS with HCl, ethanol and functionalized MWCNTs
CNTs possess a negative surface charge.
Fig. 2. (a) Schematic diagram of electrophoretic deposition of a CNT film. (b) A typical pulse-potential
waveform.
The first report on depositing CNTs by EPD pulsepotential waveform. Each circle of pulse con-
method was from Du et al. [32]. They deposited sists of an ON-time and OFF-time during the poten-
MWCNTs from ethanol/acetone dispersion onto a tial or current applied and zero current applied re-
metallic substrate and observed hydrogen evolution spectively. The OFF-time during the pulse elec-
on the cathode, which led to a porous structure of trodeposition discharges the negatively charged layer
the film. Additional EPD after CNTs film deposition and allows the ions to diffuse toward the substrate.
can be employed to deposit nanoparticles into CNTs This method allows synthesis of coatings with con-
film structure or to form a new layer. Alternatively, trolled thickness as well as composition by regulat-
CNTs composite films can be obtained by EPD from ing pulse parameters. It is also able to co-deposit
stable dispersions containing two or more sub- nano and micron sized metal particles onto exist-
stances. The components could also be pre-as- ing films.
sembled to form building blocks in the dispersion Various metals and metallic oxides have been
before EPD. Zhang et al. [33] reported the deposi- incorporated with CNTs to form composite films by
tion of MnO2-coated CNTs on a flexible graphite pulse electrodeposition technique. Su et al. [35]
sheet (FGS). MnO2 was firstly deposited onto CNTs demonstrated that MWCNTs/Co films could be syn-
by microwave heating method followed by deposit- thesized bypulse reverse current (PRC) electrodepo-
ing the compound onto FGS through EPD method. sition from aqueous bath containing cobalt sulfate
To improve the adhesion of CNTs to substrate and and MWCNTs. Comparing with DC electrodeposi-
increase the deposition rate, charger salts are usu- tion, the composite produced by PRC electrodepo-
ally introduced to the dispersion. The type of salts sition displays higher hardness and better resis-
used determines where (anode or cathode) the depo- tance to wear and corrosion properties. A relatively
sition occurs. As an example, CNTs will be depos- thin and uniform coverage of amorphous RuO2-H2O
ited onto cathode when the dispersion contains nanoparticle layer on CNTs could be obtained by
quaternary ammonium salt and NaOH while CNTs pulse potential electrochemical deposition [36]. The
will be deposited at anode when metal salts are pulse potential cycle has the advantage of being
used. This migration and subsequent deposition of capable of controlling the nucleation and growth of
CNTs is attributed to the preferential adsorption of crystalline RuO2 particles. Our group recently re-
ions in the solution by the CNTs [34]. ported the deposition of Ag nanoparticles onto to
MWCNTs/poly(dimethyldiallylammo-nium chloride)
2.7. Pulse electrodeposition (PDDA) multilayer thin film from AgNO3 solution
using a potentiostatic double pulse deposition
Pulse electrodeposition involves alternating swiftly method [37]. The size, density and morphology of
potential or current to produce a series of pulses of Ag nanoparticles were well controlled by the pulse
equal amplitude, duration and polarity, separated parameters. Ag particle of 10-500 nm with varied
by zero current. Fig. 2b shows the typical density could be electro-generated on MWCNTs/
PDDA surface when a voltage pulse of -600 mV for Firstly, CNTs need to be charged either by strong
particle nucleation and -105 mV for growth were acids oxidation or wrapped by a polyelectrolyte,
applied. The resulting composite film exhibited ex- subsequently alternating adsorption with opposite
cellent electrocatalytic activity for the reduction of charged species to generate films. Our group used
hydrogen peroxide. poly(sodium 4-styrene-sulfonate) (PSS) to wrap
CNTs, to form negatively surface charged PSS-CNTs
2.8. Sputter deposition dispersion then alternating absorption with PDDA
to generated CNTs/polyelectrolyte multilayer thin film
Sputter deposition is a physical vapor deposition [44,45]. For the purpose of forming high quality poly-
method widely used for deposition of certain mate- electrolyte wrapped CNTs dispersion and improves
rials onto existing CNTs film to form composite film. the loading rate during the LbL selfassembly pro-
The underlying mechanism can be described as cess, acid pre-treatment of CNTs is usually carried
plasma ions (commonly use argon) hit the target out during the fabrication process. Wang and co-
with a high energy and consequently atoms are worker [46] recently illustrated MWCNT pre-treat-
ejected from the surface of a target material and ment using 5-aminoisophthalic acid to enhance the
being deposited onto CNTs film. Controlled thin layer dispersibility during the fabrication MWCNTs/poly(p-
can be achieved by sputter elements, alloys, and xylylviologen) (PXV) thin film by LbL self-assembly
compounds onto CNTs film. The disadvantage is the technique. On the other hand, the surface oxidation
deposition is time consuming compared with other inevitably changes the electronic properties of CNTs
methods. by disrupting their conjugated structure. Although
Depositing metal or metal oxide nanoparticles high temperature hydrogen treatment shows the
onto CNTs films have been found a number of appli- ability to reduce the oxidized bonds in treated-CNTs,
cations in different fields. Au, Ag, and Pt but it cannot fully recover the properties of pristine
nanoparticles were deposited at the tips and on the CNTs [47]. To overcome these problems, Tettey et
sidewalls of CNTs by magnetron sputtering per- al. introduced a charge-inducing agent, aerosol OT
formed satisfying electrochemical and (AOT), into this system. The AOT can imparts a
electrocatalytic properties [38-40]. Formation of negative surface charge on MWCNTs and a positive
CNTs with Ni could also be prepared by sputtering surface charge on TiO2, thus unoxidized MWCNT
deposition followed by annealing treatment in an NH3 plays as an electron transporter and significantly
environment, which could be a more cost effective enhanced the photocatalytic activity of TiO2.
alternative for forming non-precious metal catalysts
[41]. CNTs covered with 100 nm BaO/SrO layer has
2.10. Chemical vapor deposition
shown significant improvement in both field and ther-
mionic emission (compared with pure CNTs film, (CVD)
field emission increased by a factor of two, the ther- Chemical vapor deposition (CVD) is a chemical pro-
mionic emission increased by more than four or- cess used to grow thin films. The substrate is ex-
ders) [42]. Sputtering TiO2 onto CNTs thin film then posed to one or more vaporized substances, and
heated at certain degree can form anatase phase the vapor is thermally decomposed or reacted with
CNTs/TiO2 composite films which showed a con- other gases on the substrate surface to form thin
siderable photocatalytic activity [43]. film (Fig. 3). CVD is capable of producing CNTs thin
films on various substrates. CNTs thin film can be
2.9. Layer-by-layer (LbL) selfassembly grown on substrate by simultaneously providing or-
ganometallic and hydro carbon compounds in the
LbL self-assembly technique allows alternate depo-
method of CVD called spray pyrolysis. For the CVD
sition of complementary species on a substrate by
process, catalysts are usually introduced in the
exploiting electrostatic, hydrogen bonding or cova-
growth process to promote the reaction. Ferrocene
lent bonding interactions. Different layers in the thin
(FeCp2) dissolved in benzene [48] and cyclohexane
film overlaps and interpenetrates with adjacent lay-
[49] are commonly used carbon resources.
ers. There are many species capable for deposition
CVD method is used for one-step deposition or
including polyelectrolytes, nanoparticles, proteins,
multiple depositions. Different types of CVD have
enzymes, and many more.
been employed to form different CNTs based com-
CNTs cannot directly assemble with other ma-
posite film. Table 1 summarizes recent CNTs based
terials in a water solution to form LbL films unless
composite thin film generated by CVD method or
its surface has been appropriate functionalized. The
CVD combined with other fabrication techniques.
fabrication process generally involves two steps.
The detailed parameters used are also presented.
Fig. 3. Schematic diagram of typical thin film deposition using CVD method.
A simple CVD method for effective fabrication of ever upon synthesis of CNTs based composite film,
N2-encapsulated CNTs film by pyrolysis of FeCp2 multiple depositions via CVD is another strategy for
and acetonitrile (ACN) has been reported [50]. Batch- incorporating CNTs with other materials. CNTs/dia-
type pyrolysis of catalysts induced flow fluctuation mond thin film deposited on the stainless steels
of the reaction gases which lead to the growth of has been successfully synthesized by hot filament
branched CNTs and rapid extrusion of N2 along the CVD (HFCVD) at 650 s C [52]. 1% and 5% CH4/H2
conical catalyst particles, resulting in the encapsu- volume ratios are supplied for diamond and CNTs
lation of N2 inside the CNTs. Dong et al. [51] devel- growth respectively. Similar method was also re-
oped a one-step process of growing CNTs/graphene ported for the fabrication CNTs/Si thin film through
hybrid thin film onto copper foil (decorated with sili- two-step liquid injection CVD (LICVD) [53]. The first
con nanoparticles) by a CVD method. A graphene step involved in CNTs growth using liquid injection
film grows uniformly on the copper foil and CNTs technique, wherein, m-xylene acts as the carbon
exhibits bamboo-like multiple-wall structure sprout source and FeCp2 serves as the catalyst carried by
out from the Si NPs to form a network on top. How- argon and hydrogen at 770 s C. The second step
Table 1. Summary of recent CNTs based thin films prepared by CVD method.
Thin film type Fabrication Carbon Catalyst Operation Substrate Reference

method source temperature
N2-encapsulated CVD ACN FeCp2 0-(x

8 Silica wafer [50]
CNTs
CNTs/Ni rf PECVD CH4 - .-(x
8 Si/Si3N4 [88]
CNTs/Mo CVD + electron- Ethylene Fe /*(x
8 Silicon [108]
beam evaporation
CNTs/((Ti,Al)N) CVD + magnetron Acetylene Fe /((x
8 Silica wafer/ [54]
sputtering high speed
steel
CNTs/Graphene CVD Ethanol - 0((%
1((x8 Copper foil [51]
CNTs/Diamond HFCVD CH4 Stainless .-(x8 Stainless [52]
steels steels
CNTs/GZO ICPCVD + pulsed C2H2 Ni /((x8 Tungsten [55]
laser deposition rod
SWCNTs/V2O5 CVD + hydrolytic FeCp2 Sulphur + ))((x8 Aluminum [124]
deposition FeCp2 foil
SWCNTs/MnO2 CVD + FeCp2 Sulphur + )),(x8 Copper foil [125]
Precipitation FeCp2
CNTs/Si CVD m-xylene FeCp2 //(x
8 Stainless [53]
steel
simply replaces hydrogen with silane gas, and ad- ent materials and mechanisms involved in the pro-
justs temperature to 500 s C for growth of silicon. cesses to end up with thin films. It stands to reason
Capable of producing highly dense and uniform that each type of thin films have different structure
CNTs films with excellent reproducibility and adhe- and properties. Characterization of CNTs based thin
sion at relatively high deposition rate is one of the films not only measures the property of thin film
advantages of CVD. However, it also has limitations which link to a specific application, but also is an
such as the difficulty to deposit multicomponent acceptance test for the fabrication technique. Many
materials with well-controlled stoichiometry using characterization techniques have been developed
multi-source precursors. To producing mechanically for correlating the macroscopic manipulation with
satisfying CNTs composite film, researchers put important properties of thin films at the micro or
enormous efforts to investigate the combination of nanoscale. This section will be devoted to introduce
CVD with other deposition methods. For instance, the common experimental techniques for the char-
CNTs embedded in ((Ti,Al)N) coated film was pre- acterization of CNTs based thin films.
pared combining in-situ CVD growth of CNTs with
magnetron reactive sputtering deposition of a ce- 3.1. Morphology analysis
ramic matrix ((Ti,Al)N) [54]. This combination joins
the advantages between two deposition systems: For the composite thin films, there is a strong inter-
CVD offers the possibility of tailoring the density, relationship between the structure and properties.
individual diameter, length and vertical alignment of The morphology and internal structure of the com-
CNTs, meanwhile magnetron sputtering offers un- posite films is formed during the fabrication step.
paralleled flexibility of thin films with a choice of well- The CNTs represent in the thin film can be one of
defined stoichiometry and structure. Recently, Park the entangled, agglomerated, uniformly dispersed
and coworkers [55] prepared a CNTs and gallium- or aligned states. Furthermore, different materials
doped zinc oxide (GZO) thin film which combined introduced into thin film can dramatically change
inductively coupled plasma-CVD (ICPCVD) with its structure. The size, shape, and distribution of
pulsed laser deposition. each component determined the film properties.
Formation of CNTs based thin films through CVD Therefore, morphology observation is an essential
method is highly related to several parameters in- part for thin film characterization. Scanning elec-
cluding the flow rate of the gaseous species, pres- tron microscopy (SEM), transmission electron mi-
sure of the chamber, temperature and catalyst. croscopy (TEM) and atomic force microscopy (AFM)
Huakang et al. [56] investigated the growth of CNTs are three common techniques used for analyzing
on montmorillonite precursors treated with Fe(NO3)3 thin film morphology.
at 50 s C and 100 s C via CVD of acetylene. The re- SEM has already become a basic technique for
sults showed that CNTs embedded at 100 s C had visualizing the surface morphology of thin films. This
narrower diameter distribution than that formed at method can intuitively distinguish the change be-
50 sC. The concentration of carbon in the precursor tween different films. Figs. 4a and 4b represent the
significantly affects the product yield because high one and six bilayer films of MW CNTs/gold
carbon concentration causes catalyst deactivation. nanoparticles (GNPs) [57]. The six bilayer film
Thus, low carbon concentration in the gas phase is clearly displays higher coverage of MWCNTs and
favored for production of CNTs thin films using CVD GNPs which indicates the successful growth of the
method. In addition, the catalyst density and growth multilayer assembly. Additionally, the difference
time normally affect the density of the thin film. It is between the neat and composite film can also be
noted that CNTs films generated by CVD method determined by SEM. Figs. 4c and 4d show the im-
may have the residual catalyst left which might in- ages of annealed TiO2 and MWCNTs/TiO2 film taken
fluence the properties of devices. Importantly, CVD by the field emission-SEM [58]. Both images dis-
usually requires harsh conditions like high vacuum play a similar surface structure of TiO2 with coarse
and high temperature process. grains of approximately 1 m in size. The MWCNTs
aggregations present at Fig. 4d, suggests that the
MWCNTs/TiO2 hybrid film is successfully formed and
3. TECHNIQUES FOR
the incorporation of MWCNTs does not significantly
CHARACTERIZATION OF CARBON alter the surface area of TiO2.
NANOTUBE BASED THIN FILMS TEM is a powerful imaging technique to charac-
As we described above, there are numerous meth- terize atomic features found in nanostructures. TEM
ods for fabrication of CNTs based thin films, differ- usually provides more detailed structural infomation
deposition method [59]. Compared with the inset

image of pure SWCNT, it clearly showed that the
bundle of SWCNT were decorated uniformly with
nanoparticles of 2-7 nm. Furthermore, two types of
interaction modes between Ni and SWCNTs were
found: one was Ni located on the fringe of SWCNTs
bundles, where the diameter of SWCNTs was about
1-2 nm and the size of Ni particles was around 5-10
nm, another one was Ni particles insert the space
of thin SWCNTs bundles. In terms of CNTs/poly-
electrolytes composite thin film, TEM plays impor-
tant role in investigating the change of film struc-
ture, which is usually hard to be confirmed by SEM.
Fig. 4. SEM images of (a) 1 bilayer MWCNTs/GNPs
Figs. 5b and 5c are the TEM images of oxidized
thin film. (b) 6 bilayers MWCNTs/GNPs thin film.
MWCNTs and MWCNTs/poly(N,Ndiethylacrylamide)
(c) Pure TiO2 thin film. (d) MWCNTs/TiO2 thin film.
(PDEAAm) composite respectively [60]. It is obvi-
Reprinted from Ref. [57,58], Copyright 2013 with
ous that the diameter of MWCNT/PDEAAm com-
permission from Elsevier.
posite is much thicker than the oxidized MWCNTs.
The surface of oxidized MWCNTs is smooth and
than SEM because it is capable of achieving a point- clear, while the MWCNTs/PDEAAm composite has
to-point resolution down to 0.1 nm. TEM imaging is fuzzy and translucent edges. Those differences prove
particularly important in studying the relationship that a layer of PDEAAm was wrapped on the sur-
between CNTs and composited nanoparticles. Fig. face of MWCNTs. The widespread use of AFM for
5a illustrates the TEM image of SWCNTs/Ni(NiO) characterizing thin film sample is attributed to the
composite deposited onto the cathode by the electro- accurate threedimensional reconstruction of the
Fig. 5. TEM images of (a) SWCNTs/Ni(NiO) composite. (b) Oxidized MWCNTs. (c) MWCNTs/PDEAAm
composite. AFM images of (d) GCE. (e) GC/CoPc. (f) SWCNTs/GC (g) SWCNTs/GC + CoPc. Reprinted
from Ref. [59,60,61], Copyright 2013 with permission from Elsevier.
sample topography with atomic resolution. AFM also SR U zSR UR Ue YVdVT U c UVc UVdRc V
allows imaging of the surface roughness of the clearly seen. When CNTs are incorporated into thin
sample. Figs. 5d-5g show the AFM images of bare films, these characteristic peaks will change which
glass carbon electrode (GCE) (d), cobalt phthalo- gives the information on the structural change. The
cyanine (GC/CoPc) (e), SWCNTs/GC (f) and absorption intensity and band change have also been
SWCNTs/GC + CoPc (g). There are clear differences observed for functionalized CNTs. Yim et al. [20]
in terms of surface roughness values are collected, cVa c e
VUe YVfah c UdYZ W
eW z SR U hYZ TYZdZe Vc%
which confirming the different compositions exist in preted as a signature of CNTs film compression fol-
the hybrid thin films. Fig. 5e gives island-like struc- lowing water evaporation during nitric acid treatment.
ture which indicates the CoPc cluster adsorbed on Wang et al. [46] also reported the small shift of G-
GC electrode. Conversely, SWCNTs observed from band of MWCNTs after isophthalic acid treatment.
Fig. 5f are randomly distributed but completely cov- Besides, a lower in the intensity ratio of D band (ID)
ered the GC electrode surface, when comparing to to G band (IG) implies a better graphite structure
unmodified GC electrode (Fig. 5d). In the case of and a higher degree of graphitization. Additionally,
SWCNTs/CoPc/GC electrode, CoPc is distributed the reduced intensity of G-band in Raman spectra
with a non-uniform island-like structure. On the other can be detected when CNTs based gas sensor af-
hand, the electrical properties of CNTs based thin ter exposing to target gases [63].
film could also be measured by AFM. The electrical FTIR is another widely used spectral technique
properties of single MWCNT from a macroscopic for characterization of CNTs based thin films. FTIR
composite thin film of aligned MWCNTs embedded is often used to confirm the surface modification of
in polymer matrix was studied by Villeneuve et al. CNTs and reveals the chemical structure of the com-
[61] It is the first presentation of the conduction pro- pounds that attached on CNTs. It sometimes also
file of a single vertical CNT. Results also indicate gives extra information on the property change of
only the external sheets are conductive. materials. For example, Fig. 6b shows the FTIR
spectra of polyaniline (PANI), MWCNTs, and
3.2. Spectroscopic characterization MWCNTs/PANI composite [64]. Compared with
PANI, the spectrum of MWCNTs/PANI composite
Spectroscopic analysis techniques are powerful has no new absorption peak occurring, but the
methods for characterizing many aspects of CNTs changes in peak shape and absorption intensity
based thin films, such as the amount of material were observed. Specifically, the peaks at 1205, 1105,
loading during the fabrication process, the chemi- 847, and 1318 cm -1 became wider and stronger.
cal composition in the surface region, elemental There changes are due to the spectra overlapping
composition of thin film, and the identification of CNTs and the interaction between MWCNTs and PANI
modification. There are four common spectroscopic which gives the evidence that PANI is attached to
analysis techniques for characterizing CNTs based the MWCNTs. In addition, the peak at 1105 cm-1 is
thin film: Raman spectroscopy, Fourier-transform a measure of the degree of delocalization of elec-
infrared spectroscopy (FTIR), ultraviolet-visible trons, which is related to the characteristic of the
(UVVis) spectroscopy and X-ray photoelectron spec- conductivity of PANI [65, 66]. The MWCNTs/ PANI
troscopy (XPS). composite has a stronger absorption at 1105 cm-1
Raman spectroscopy is a technique used to eYR afc VE6C hYZ TYZ a] ZVde YRe eYVE6Cz dT %
study the vibrational, rotational, and other low fre- ductivity is improved when attached to MWCNT.
quency modes of a material. It relies on the inelas- UV-Vis spectroscopy is a quantitative measure-
tic scattering, also called Raman scattering of mono- ment of the reflection or transmission properties of
chromatic light. In Raman scattering, the difference a material as a function of wavelength. This absorp-
in energy between the absorbed and reemitted pho- tion spectroscopic technique is very useful in moni-
tons corresponds to the energy required to excite a toring the growth of CNTs based thin film. Fig. 6c
molecule to a higher vibrational energy band. All al- demonstrates the use of UV-Vis spectroscopy to
lotropic forms of carbon are active in Raman spec- study the LbL self-assembly of MWCNTs/PDDA
troscopy. However, the position, width, and relative multilayers thin film. The spectra clearly showed a
intensity of absorption bands are different accord- regular absorbance increase along with the number
ing to the different forms of carbon. The typical of PDDA/MWCNT bilayers which confirmed the
Raman spectroscopy of CNTs are shown in Fig. 6a stepwise formation of MWCNTs/PDDA multilayer film
[62]. The characteristic features of CNT including [37]. In addition, the absorbance data gives the in-
the radial breathing mode (RBM), the D band, G formation on how much of the materials were de-
Fig. 6. (a) Raman spectrum of CNT showing its most characteristic features of radial breathing mode
(RBM), the D band, G band, G' band, and the second order modes. (b) FTIR spectra of MWCNT, PANI, and
MWCNT/PANI composite. (c) UV-vis absorption spectra of PEI/PSS(PDDA/MWCNTs)n (n = 1-13) multi-
layer films on quartz slide. The inset shows the absorbance maximum at 228 nm as a function of bilayer
numbers. (d) XPS spectra (C1s, N1s, and O1s) of pristine CNT and Z-Gly-OSu-functionalized CNT. The inset
figure is the magnified N1s spectra. Reprinted from Ref. [62,64,67,68], Copyright 2013 with permission from
Elsevier.
posited during the assembly process. The inset of shows the XPS spectra of pristine CNTs and the Z-
Fig. 6c represents the absorbance at 228 nm as a Gly-OSu- functionalized CNTs at the peaks of C1s,
function of bilayer numbers, indicating that the ini- N1s, and O1s. The binding energy of C1s peak of pris-
tial growth of the film is slow then it becomes much tine CNTs is located at 284.0 eV. After
faster from the 6th layer with more than double functionalization, two C1s peaks have been found in
amount of the materials being adsorbed in each spectrum. The original peak showed little shift to
deposition cycle. Similar to FTIR, the peak appear- 284.8 eV, additional peak appeared at 288.5 eV,
ance and shape change of UV-Vis spectra is an may respond by N-C=O from the amide bond. N1s
alternative way to determine the compounds that spectra also improved the functionalization happens
added to the CNT [67]. at CNT because there is no peak appear at pristine
Finally, XPS is a powerful surface analytical tech- CNTs, but one new peak at 399.8 eV has been found
nique being capable of collecting the information of in Z-Gly-OSu-functionalized CNTs sample, which
a surface layer (2-5 nm depth), such as composi- can be ascribed to the N atoms of Z-Gly-OSu linker.
tion, chemical states and quantity of an element.
XPS has been successfully used for characterizing 3.3. Thermal analysis
a variety of thin films. Wei and coworkers [68] used
XPS to identify the functionalization of CNTs with Z- The thermal stability of the lms is experimentally
glycine Nsuccinimidyl ester (Z-Gly-OSu). Fig. 6d determined by the threshold temperature during
Fig. 7. (a) TGA thermograms of pure MWNT, pure PVK, and PVK/MWNT under N2 at a heating rate of 20
C/min. Inset Graph of DTG curves of pure MWNT, pure PVK, and MWNTs/PVK nanocomposite solutions.
(b) XRD pattern of heat-treated CNTs-TiO2 hybrid thin film under various temperatures. (c) The voltammetric
response to 1 mM hydrogen peroxide at bare ITO electrode, [PEI/PSS/(PDDA/MWCNT)6] and [PEI/PSS/
(PDDA/MWCNTs)6/Ag NPs] modified ITO electrodes in pH 7.0 PB solution. Scan rate: 50 mV/s. (d) Imped-
ance spectra of electrophoretic deposited ES/PANI and MWCNTs/ES/PANI composite film. Reprinted from
Ref. [37,69,74,77], Copyright 2012 with permission from Elsevier.
annealing at which the lm structure begins to change different ratios of the MWCNTs/PVK composite
and roughen. Some applications of CNTs based thin film upon heating in a nitrogen atmosphere [69]. It
films require working at high temperature condition, is clear seen in the graph that the pure MWCNTs
so the thermal limitation is an important feature of exhibited a high stability showing only a 2% weight
the film. Thermal gravimetric analysis (TGA) and loss after heating to 500 s C. PVK represented lower
derivative thermal gravimetric (DTG) methods are stability which starts degradation at 260 s C. Com-
usually used for testing the thermal stability of CNTs paring MWCNTs/PVK composite films with differ-
based thin film. TGA is based on the measurement ent ratios of MWCNTs, it was observed that the in-
of mass loss of material as a function of tempera- creasing percentage of MWCNTs led to less weight
ture. A DTG presents the rate of mass change (dm/ loss, suggesting that the MWCNTs improved the
dt) as a function of temperature. Both data are ob- thermal stability of the composite film. The reason
tained when a substance is heated at a uniform rate of this improvement can be explained in two as-
or kept at constant temperature. pects. Polymer chains near the nanotubes may
The thermal characterization has found that the degrade more slowly, which helps to increase the
adding CNTs could improve the thermal stability of decomposition temperature [70]. Another reason
polymer composite. Fig. 7a shows typical TGA ther- may be due to the higher thermal conductivity of
mograms, which depict the mass losses of MWNTs that facilitates heat dissipation within the
MWCNTs, poly (N-vinyl carbazole) (PVK) film and composite.
The DTG curves can provide information about the electrocatalytic activity of MWCNTs/Ag NPs
the point where significant weight loss occurs. From composite film toward hydrogen peroxide by using
the DTG curves (Fig. 7a insert), it is clearly seen the CV technique [37]. Three-electrode system has
that there is a shift to higher degradation tempera- been used in measurement, including a film modi-
ture for the MWNTs/PVK composite as compared fied ITO electrode as the working electrode, a plati-
with the pure PVK. To accurately identify the degra- num disk as the auxiliary electrode and an Ag/AgCl
dation components and their thermal properties, wire as the reference electrode. Fig. 7c demon-
dynamic rate control method of TGA has been widely strates the electrochemical responses of 1.0 mM
used. Li et al. [71] employed TGA to analyze the H2O2 at bare ITO, (MWCNT/PDDA)6 and (MWCNT/
CNTs/TiO2 composite synthesized by variety pre- PDDA)6/Ag NPs deposited electrodes. We found
cursors. The results showed the composites syn- the redox activity of H2O2 could be enhanced by
thesized bydifferent precursors have quite different MWCNT and further improved in the presence of Ag
thermal properties, which should be attributed to NPs. Beyond that, CV is also used to evaluate the
different morphology, compactness and crystallin- assemble process of multilayer films. The regular
ity of TiO2 coatings as a function of precursor type. change of both the anodic and cathodic peak cur-
rent is an evidence for alternative layers formed on
3.4. X-ray powder diffraction (XRD) electrodes.
Electrochemical impedance spectroscopy (EIS)
XRD is the most popular X-ray scattering technique usually provides detailed information on the imped-
for characterizing the crystallographic structure of ance change of the electrode interface. As a steady
samples. The X-ray diffraction pattern of the CNTs state technique with small potential variation, EIS
sample usually presence of two peaks at 2 = 26s is more reliable than CV for measuring the capaci-
and 43scorresponding to the 002 and 100 reflection tance with minimized effect from noncapacitive Fara-
of the carbon atoms. The functionalization process daic contributions [75]. In a typical impedance spec-
will narrow those peaks due to the loss of amor- trum, a semi-circle part at higher frequency range
phous carbon [72]. XRD is also capable of studying and a straight line part at lower frequency range are
the mean tube diameter, the finite size of the bundles included in the Nyquist plot. The diameter of the
and the diameter dispersity of CNTs. In terms of semi-circle at higher frequency range in the Nyquist
CNT based composites, XRD patterns reveals the plot equals to the electron transfer resistance [76].
CNTs/copolymer composite has a more crystalline The dependence of impedance spectra of the CNTs/
nature than the bare copolymer [73]. Identification conducting polymer composite is considered for
of the crystal phase in certain CNTs based thin film studying the characteristics of lm structures, kinet-
is crucial, such as CNTs/TiO2 thin film as the crys- ics, and mechanisms of charge transfer and ion
tal phase of TiO2 is highly related to its photocata- transport in the CNTs/polymer lm interface. As an
lytic activity. Anatase has the best photocatalytic example, Fig. 7d shows the impedance spectrum
rate in several TiO2 crystal phase because of its of the electrophoretic deposited emeraldine salt
larger band gap energy between valence band and (ES)/PANI and MWCNTs/ES/PANI composite film
conduction band. The amorphous TiO2 can be trans- [77]. The remarkable decrease in the diameter of
formed into anatase or rutile structure according to the semicircle (indicative of charge transfer resis-
the heating temperature. Fig. 7b exhibited XRD pat- tance) was detected in the composite film. The
tern of heat-treated CNTs-TiO2 hybrid thin film under smaller semicircle indicates that the charge trans-
various temperatures, which attest amorphous TiO2 fer resistance for MWCNTs/ES composite film is
was well crystallized eventually into anatase phase much lower than the ES film. Besides this, the pres-
at 450 s C [74]. V TV WBL8CIdT f] UR] d dVc g VRdyT UfTe ZX
Sc Z
UXVdz SVehVV :HR UV] VTecUVdfc WRTV
3.5. Electrochemical characterization
CNTs based thin films offer potential applications 4. APPLICATIONS
as conducting or semiconducting layers in various
4.1. Sensors
types of electronic, optoelectronic, and sensor sys-
tems. Cyclic voltammetry (CV) is the most widely The hollow structure of CNT contributes to a large
used technique for investigating the electrochemi- surface area and volume ratio, which makes it ap-
cal property of CNTs based films, which is performed propriate for physisorption and chemisorption of
by cycling the potential of a working electrode and sensing targets. Various types of thin film sensors
measuring the resulting current. Our group studied have been fabricated and investigated based on
SW CNTs, double-walled carbon nanotubes and water under normal living conditions for appli-
(DWCNTs) and MWCNTs. cations, Naoki Inomata and Fumihito Arai [85] in-
vestigated the temperature coefficients of resistance
4.1.1. Temperature and humidity of single CNT in water, air and vacuum, which are
sensors 0.735x10-3, 0.422 x10-3, and 0.214 x10-3/s C, respec-
tively. Temperature sensor fabricated by the sequen-
Humidity can influence several properties of CNTs tial deposition of thin layers of glue and CNTs
including electrical conductivity, electrical transport nanopowder on a paper substrate reveals that there
property and impedance. There is a relationship is average 10-20% decrease in DC resistance of
between the humidity and the capacitance of a CNTs the sensors during the temperature increase from
film sensor: the capacitance of sensor increases or 20 to 75 s C [86]. Not only that, CNTs based thin film
resistance decreases with increasing humidity level sensor also shows great performance at low tem-
[78,79]. Highly sensitive humidity sensor has been perature. Saraiya et al. [87] reported the prepara-
achieved by fabricating CNTs/PDDA composite films tion of CNTs film on the nickel deposited float glass
on to Si/SiO2 substrate through LbL self-assembly substrate by the ion beam deposition technique.
technique [80]. The resistance of sensor responds The resulting film had more than 600% change in
to humidity from 20% to 98% shows exponentially resistance when the temperature change from 300K
increasing after annealing treatment. The response to 10K.
time of the sensor is around 8 s, and the recovery
time only in 35 s. Poly(ethyleneimine) (PEI) and
4.1.2. Gas sensors
MWCNTs composite films sensor reported by Yu et
al. [81] is capable to respond humidity level even The unique chirality of CNTs contributes to the p-
cross 5-97%, the response and recovery time are 2 type semiconducting property. The conductivity of
s and 30 s respectively. CNTs will change significantly when gas molecules
It is generally known that suitable acid treatment are absorbed [88,89]. CNTs based sensor outper-
is a common method to enhance the solubility of form conventional sensors in terms of large adsorp-
CNTs and forming functional groups to the sidewalls, tive capacity, highly sensitive to small quantities of
like -COOH. The incorporation of functionalized gases at room temperature and quick response time.
CNTs with cationic polyelectrolytes into the multi- Because the physisorption and chemisorption syn-
layer films through LbL self-assembly can form high ergistic effect properties that cause the response
sensitive humidity sensor. The comparison shows time of CNTs based sensors are varying for different
the sensitivity of SWCNTs-COOH/PDDA thin film target gases [90]. For the purpose of enhancing the
sensor is more than 20% higher than SWCNTs/ sensitivity and selectivity, CNTs is often hybrid with
PDDA thin film sensor [82]. This phenomenon may other materials. CNTs mixed with silane shows the
be caused by the high contents of - * transition ability to enhance the selectivity of certain gases
structures exist in SWCNTs-COOH/PDDA thin film and also improve the mechanical adhesion to the
which could help adsorb more water molecules. substrate [91]. In terms of enhancing sensor sensi-
Many mechanical, medical, chemical, agricul- tivity, other sensing materials such as metal oxide
tural, and food industries extensively use tempera- semiconductors are usually chose for incorporation.
ture sensors. CNTs based sensor has been cre- A MWCNTs-doped SnO2 thin film gas sensor was
ated ground on the conductance change response reported by Wei et al. [92] which showed much
to the temperature. The electrical transport of highly higher sensitivity than the pure SnO2 film sensor.
disordered MWCNTs of large outer diameter (~60 The performance of the MWCNTs-doped SnO2 sen-
nm) has been found to be dependent on tempera- sor was based on the change in the barrier height
ture change [83]. As the temperature elevate, the and the conductivity of the MWCNTs/SnO2 sensi-
conductivity of CNTs increases accordingly. This tive layer. When NO2 is absorbed, the depletion layer
conduction mechanism can be explained by the at the p-n junction is modulated. It leads to the fact
Percolation theory [84]. The CNTs based thin film that this type of gas sensor is capable to response
sensor can be assumed as a bulk hetero system, to low concentrations of NO2 down to the ppb range.
CNTs layers are highly sensitive to the change of Synthesis of CNTs-conducting polymer composites
temperature which result by the increasing of inter- sensor also tailor the electronic and mechanical
particles contact areas and intrinsic conductivity of properties based on morphological modification or
the nanoparticles take place as rising temperature. electronic interaction between the two components.
For the purpose of using CNTs based sensors in air For example, a gas sensor based on CNTs/
Table 2. Summary of the sensing properties of various CNT based thin film gas sensors.
Sensor description Target Detection Operation Response Recovery Reference

species level/range temperature time time
MWCNTs-doped CO 50 ppm +((s

8 4s 16 s [26]
TiO2 xerogel
MWCNTs-Al2O3 NH3 6-25 ppm RT* 10 min 20 min [27]
SnO2-arc-dischargeNH3 1 ppm/NH3 RT* - - [63]
SWCNTs O3 20 ppb/ O3
Horizontally aligned H2 200- RT* 8-17 min 2.4-4.5 min [126]
CNTs 16,000 ppm
N-doped SWCNTs NO2 200 ppb )-(s8 25 min 30 min [127]
Pd-decorated MWCNTs H2 350 ppm RT* 150 s 210 s [128]
CNTs/reduced graphene NO2 0.5-10 ppm RT* - - [129]
Polyaniline-MWCNTs NO2 100 ppm RT* 5 min 10 min [130]
Acid modified MWCNTs SF6 0.5-20 ppm RT* - - [131]
WO3/MWCNTs NO2 5 ppm RT* 12 min 15 min [132]
ZnO/SWCNTs NO2 1-1000 ppm *-%
+((s8 5 min 8 min [133]
poly(oanisidine) (POAS) composite offers a sensi- charge of the communication between the target
tivity of approximate 28% compared to a mere 4% biomolecule and the sensor surface. The unique
by CNTs alone for the detection of HCl vapor [93]. physical and chemical properties of nanostructured
This extended detection capability is attributed to CNTs based thin film have paved the way to achieve
the direct charge transfer with electron hopping ef- advanced electrochemical biosensors. For example,
fects on intertube conductivity through physically CNTs could serve as electric conductor and elec-
adsorbed POAS between CNTs. trode modifier in pasty electrodes and oxidase based
Stability in different environment is always a cru- biosensors. Patolsky et al. [96] reported the first
cial aspect for gas sensors. Ceramic materials has study on the aligned reconstitution of a redox glu-
been involved to reinforce the impart stiffness, cose oxidase (GOx) on the CNTs modified electrode
strength, and toughness of CNTs due to its excel- surface. SWCNTs act as nano-connectors between
lent mechanical properties and relatively low den- the active site of the enzyme and the electrode.
sity. Depositing CNTs films onto TLM platform can According to the surface coverage of the GOx-CNT
improve the temperature stability of the sensor due units, the turnover rate of electron transferred to the
to the top layer of platinum. electrode is about 4100 s-1, which is sixfold higher
The major drawback of the gas sensors is its than the active site of GOx to its natural O2 electron
slow and incomplete recovery. Some literature de- acceptor. The experiment also showed that the elec-
picted the recovery time of the senor was approxi- tron transmission velocity was depended on the
mately 10 h [94]. Researchers have put lots of effort length of SWCNT. In addition, the CNTs thin film
to surmount this issue. Valentini et al. [95] have architectures have been studied to develop high
demonstrated that heat treatment at 465-500K sensitive and selective immunosensor. Ou et al. [97]
could significantly reduce the recovery time to 1 h. reported the use of MWCNTs/GNPs/thionine film as
On the other hand, UV treatment could also reduce a label-free amperometric immunosensor for
the recovery time by evicting the absorbed molecules carcinoembryonic antigen (CEA) detection. The
out of the sensor. Except of using external forces, MWCNTs act as a support to the redox mediator
combining CNTs to certain materials can also thionine as well as the conductor to enhance the
shorten the recovery time conspicuously. Table 2 electron transfer of the mediator to the electrode.
summarizes the sensing properties of some recent The results showed the immunosensor was highly
reported CNTs based film gas sensors. sensitive to CEA with a detection limit of 0.01 ng
mL-1 and it could be regenerated 10 times by sim-
4.1.3. Biosensors ply immersing the immunosensor in a stirred 5 M
urea solution for 5 min and washing with water.
Basically, the improvement of biosensor performance
One challenge in biosensor development is that
requires a good signal transducer material which in
the immobilized biomolecules easily denature lead-
ing to the loss of their bioactivity. LbL selfassembly sion efficiency, high power density, and low operat-
technique was found to be able to improve this is- ing temperature. Recent research revealed that the
sue. A DNA biosensor has been fabricated based CNTs can greatly improve the performance of fuel
on the LbL covalent assembly of GNPs and cells by offering a high surface area support to the
MWCNTs-CONH-(CH2)2-SH on the Au electrode Pt nanoparticle catalyst. The use of CNTs also im-
which showed the great stability and reproducibility proves the dispersity of Pt nanoparticles, promotes
to detect singlebase mismatched DNA sequence electron transfer and enhances stability. Girishkumar
[57]. A LbL self-assembly technique combined with and co-workers [104] demonstrated that compared
MWCNTs modification was reported for fabricating with commercial Pt/carbon black catalyst, SWCNTs/
choline sensors [98]. This choline sensor showed a Pt film electrodes exhibit a lower onset potential
linear response in the concentration range between and a higher electron-transfer rate constant for oxy-
5x10-7 and 1x10-4 M and a detection limit of 2x10-7 gen reduction. The accelerated durability test was
M. Except for quick response time, six amperometric carried out in HClO4 solution which showed electro-
measurements for 0.1 mM choline suggest that the chemically active surface area of Pt/carbon black
sensor with MWCNTs has lower relative standard has continuously decrease during the test and fi-
deviation than the sensor without MWCNTs. The nally bellow to SWCNT/Pt after 36 h, even though
long-term storage stability experiments showed the the Pt/carbon black has a higher electrochemically
choline sensor without MWCNTs retained 78.5% of activity surface area than SWCNTs/Pt before the
the initial sensitivity after 1 month while the sensor durability test. The result indicates the SWCNTs
include MWCNTs retained 89.5%. could enhance the stability of the electrocatalyst
for long-term use. However, the scarcity of durabil-
4.2. Energy conversion and storage ity test is carried out in acidic solution which can-
not fully confirm the performance in actual environ-
Solar energy has a great potential as a green en- ment.
ergy owing to its abundance and even distribution Biofuel cells provide new opportunities for the
in nature. Thin film based solar cells has attracted sustainable production of energy from biodegrad-
large interest because of their low fabrication cost able compounds which could serve as power
and high energy conversion performance. Studies sources for implanted devices like pacemakers,
have showed that incorporating CNTs into solar cells sensors, and drug dispensers. The properties of
can significantly improve the photo-conversion effi- CNTs can be used for increasing effective surface
ciency. For example, incorporating MWCNTs into area of electrode, and at same time for the con-
the TiO2 active layer contributes to an outstanding struction of extended conducting networks. Fig. 8a
improvement in the energy conversion efficiency of shows the schematic of anthracene and an-
dye-sensitized solar cells (DSSCs) [58]. This im- thraquinone covalently modied SWCNTs as cath-
provement attributes to the capacity of CNTs to fa- odes for biocatalytic reduction of dioxygen [105].
cilitate the charge transport across the photoactive The outcome reveals that glassy carbon electrode
layer resulting in a reduced rate of charge recombi- covered with arylated SWCNTs and coated with a
nation [99]. CNTs based thin film solar cells poten- layer of Nafion containing laccase was a very effi-
tially offer many advantages beyond the traditional cient cathode in hybrid battery. More than 2 Mw/
DSSCs. As the semiconducting property of CNTs cm2 power densities and 1.5 V open circuit poten-
for photo conversion, solar cells do not need to rely tial was obtained in the experiment that Zn wire was
on dyes [100]. Moreover, Pt is commonly used as used as anode. Fig. 8b briefly illustrates the con-
counter electrode in solar cells which represent an struction of an enzymatic fuel cell based on CNTs
undesirable reliance on noble metals that may re- [106]. The small diameter of CNT allows a close
strict for large scale devices. Another problem with approach to the redox active site of redox enzyme
Pt is the degradation due to contact with electro- for electronic communication, therefore regenerate
lyte [101]. In contrast, the chemical inert of CNTs the biocatalysts during direct electron transfer or
let it become a great candidate as counter elec- act as redox mediators to help electron transfer.
trodes [102,103]. Furthermore, the conducting coat- For instance, fuel cell that has glucose/O2 biofuel
ing is not required for solar cells since CNTs based cell with (MWNTs/thionine/Au NPs)8 GDH film modi-
thin film itself is a transparent conductor which ban- fied ITO electrode as anode and the (MWNTs/PLL/
ishing the need of In coating. laccase)15 lm modied ITO electrode as a cathode
Fuel cells are promising choice for clean energy showed 700 mV open-circuit voltage and 329 mW/
due to its eco-friendly system, high energy conver- cm2 power density at 470 V of the cell voltage [107].
(a) (b)
Fig. 8. Schematic representation of (a) biobattery circuit and (b) enzymatic fuel cell based on CNT. Re-
printed from Ref. [105,106], Copyright 2013 with permission from Elsevier.
CNTs based electrodes have previously been dation of environmental pollutants in aqueous con-
shown to have excellent properties in supercapacitor tamination, wastewater treatment, and air purifica-
applications. For example, the CNTs film with in- tion. There are two mechanisms being discussed
trinsic bottom metal contacts to construct mechani- to explain the CNTs-enhanced photocatalytic activ-
cally bendable, densely aligned CNTs forests was ity of TiO2. The first mechanism was proposed by
used for supercapacitor which possesses salient Hoffmann et al. [110]. A highenergy photon excites
features include simple fabrication process, great an electron from valence band to the conduction
transfer of charge from the aligned CNTs to the sub- band of anatase. Photogenerated electrons formed
strate and easy integration with a variety of surfaces in the space-charge regions are transferred into the
and morphologies. Kozinda et al. [108] reported a CNTs and holes remain on the TiO2 to take part in
CNTs forest of 5x10 mm2 in area on Au/Kaptont redox reaction. Another mechanism reported by
film showed a specific capacitance of 7.0 mF/cm2. Wang et al. [25] is based on the premise that CNTs
Besides, CNTs also plays important roles in hybrid may enhance TiO2 photocatalytic activity by acting
supercapacitors which combine the electrical double as a photosensitizer. The photogenerated electron
layer capacitive electrode and the pseudo-capaci- is injected into the CB of TiO2, simultaneously a
tive electrode. Electrochemical conducting polymers positive charged hole formed by electron migrating
and metal oxides are usually deposited onto CNTs from TiO2 valence band to CNTs and reduction of
to increase the total capacitance through faradaic the so formed hole by absorbed OH-oxidation.
pseudo-capacitance effects. Zhang et al. [109] dem- CNTs/TiO2 composite films have been tested for
onstrated that the MWCNTs/PANI composite film the photodegradation of various chemicals such as
electrode showed better capacitive characteristics Porcion Red [111], phenol [25] and methylene blue
than the pure PANI electrode. The test obtained [71]. All these studies have revealed that the addi-
specific capacitance of 500 Fg-1 by composited film tion of CNTs could enhance the photocatalytic effi-
even if the content of MWCNTs is only 0.8 wt.%. ciency of TiO2. Tettey and co-worker [111] test the
On account of the presence of MWCNTs, the com- photocatalytic activity of MWCNTs/TiO2 composite
posite films possess more active surface area for thin film and pure TiO2 thin film by degradation of
faradaic reaction, larger SC, as well as having lower Porcion Red under UV irradiation. The
resistance and better cyclic stability. photodegradation results showed that the incorpo-
ration of MWCNTs leads to an approximately 2-fold
4.3. Photocatalytic applications increase in the first order rate constant of photo-
catalytic activity of TiO2. Additionally, the potential
Incorporating CNTs thin films with certain application of antibacterial of CNT/TiO2 thin film has
photocatalysts, especially TiO2 is currently being been recently studied. Akhavan et al. [112] investi-
considered for many applications including degra- gated visible light photoinactivation of Escherichia
coli bacteria on the surface of CNTs-doped TiO2 thin that after milk pasteurization for 5 h, the mass of
lms with various CNTs contents. The antibacterial foulant on CNTs/PTFE coated heat exchanger sur-
activity of the nanocomposite thin lms in the dark face was 70.3% less than that on the uncoated
was enhanced by increasing the CNTs content which surface. The total energy consumption of testing
assigned to the partial bactericidal activity of PHE unit also dropped by 10.2%. Another method
MWCNTs themselves. By increasing the CNTs con- is to form CNTs/enzyme/polymer composite films.
tent from 0 to 40 wt.% and annealed at 450 s C, the In this system, CNTs contribute large surface area
effective band gap energy decreased from 3.3 to to load large amount of enzymes and the high as-
less than 2.8 eV, which indicate the ability of visible pect ratio of CNT helps to retain CNTs/enzyme con-
light absorption of the composite film for photocata- jugates in the matrix. The rate of enzyme proteoly-
lytic processes. All the bacteria are inactivated un- sis was greatly improved, which leads to the elimi-
der the visible light irradiation in 1 h by using an- nation of surface biofouling. Furthermore, CNTs
nealed CNTs-doped (20 wt.%) TiO2 thin lms. In ad- could also enhance the stability of adsorbed pro-
dition, combination of CNTs with other teins [123].
photocatalysts such as ZnO also shows great
photoinactivation effect to bacteria [113]. 5. SUMMARY AND PERSPECTIVE
Although CNTs were discovered over a decade ago,
4.4. Antimicrobial, antifouling the progress of preparation and application of CNTs
applications based thin films was initially hindered by the high
The antibacterial effect of CNTs based thin films is cost. Recent innovations in experimental techniques
not limited to CNTs/TiO2 composite films under the have greatly advanced the development of these
photocatalytic mechanism. Several studies have films. Achievements on synthesis, characterization,
shown that CNT itself has antimicrobial properties and device applications of CNTs based thin films.
against diverse groups of microorganisms since These films can be fabrication by various techniques,
2006 [114-117]. SWCNTs are believed to have stron- each technique described here has its own advan-
ger antimicrobial property than MWCNTs due to a tage and disadvantage. Nevertheless, large-scale
higher aspect ratio and probably some heavy metal preparation of CNTs films, accurately controlling the
residues. Therefore, CNTs based films have been size and thickness and longterm stability are still
explored as antimicrobial coatings. The antibacte- challenges for future research. Furthermore, some
rial property of CNTs/polymer composite film was drawbacks of the fabrication process such as the
investigated by School et al. [118] They tested the high temperature requirement of CVD method, long
effect of SWCNTs/PVK composite films on plank- time process of LbL selfassembly method could
tonic cells and biofilms of Escherichia coli and Ba- restrict the practical implementation of these tech-
cillus subtilis. The results suggested that the niques. It is also noted that some techniques de-
SWCNTs/PVK composite film had antibacterial ac- scribed here still remain at the proof-of-principle
tivity on planktonic cells and biofilms at all concen- stage.
tration levels. Qi et al. [119,120] demonstrated that The advanced characterization techniques de-
immobilization of antimicrobial molecules to scribed in this review are used not only for charac-
MWCNTs via covalent bonding could further improve terizing the property of the sample but also as the
the antimicrobial activity. They found that the competent tools for monitoring the fabrication pro-
MWCNTs/nisin and MWCNTs/cephalexin compos- cess. Through results comparison and fabrication
ite films exhibited superior antimicrobial and anti- process adjustment, the relationship between the
biofilm properties. primary properties, film processing condition and
Antifouling coatings have important application device performance could be established. Using dif-
in food industry and medical instruments. Two gen- ferent techniques allows researchers to complement
eral routes have been used for fabrication of CNTs different results and build up a full understanding of
based antifouling coatings. One is to coat CNTs the film.
onto metal substrates to create superhydrophobic The applications of CNTs based thin films are
surfaces [121]. As an example, Rungraeng et al. multidisciplinary. Among them, CNTs/polymer com-
[122] reported the successful inhibition of milk foulant posite films have been the most widely studied,
by applying the superhydrophobic CNTs/ ranging from small electronic devices to large anti-
polytetrafluoroethylene (PTFE) coating on the sur- fouling films. Recently, CNTs/photocatalyst compos-
face of the plate heat exchanger. Results indicated ite films also attract enormous attention. However,
few applications have yet been advanced to the pro- [14] M. Jeong, K. Lee, E. Choi, A. Kim and S.B.
duction. In addition to the shortage of mature fabri- Lee // Nanotechnology 23 (2012) 505203.
cation techniques, lack of full knowledge on the [15] Y. Li, T. Yu, T. Pui, P. Chen, L. Zheng and
photocatalytic mechanism is also a roadblock to K. Liao // Nanoscale 3 (2011) 2469.
accelerate the extensive application. For instance, [16] V. Bliznyuk, S. Singamaneni, R. Kattumenu
while enhanced photocatalysis of CNTs/TiO2 com- and M. Atashbar // Applied Physics Letters
posites has been achieved for the degradation or- 88 (2006).
ganic pollutants in wastewater and air, the mecha- [17] S.H. Lee, H.T. Ham, J.S. Park, I.J. Chung
nism of synergic effect of CNTs on TiO2 photocata- and S.O. Kim // Macromolecular Symposia
lytic activity is still unclear. Ultimately, the use of 249-250 (2007) 618.
CNTs based thin film represents a challenging but [18] B. Safadi, R. Andrews and E.A. Grulke //
potentially a rewarding opportunity to develop the Journal of Applied Polymer Science 84
next generation of advanced functional materials. (2002) 2660.
[19] W. Ding, V. Koutsos, I. Si and Z. Song //
ACKNOWLEDGMENTS Advanced Materials Research 569, (2012)
15.
The work is partially supported by the National [20] J.H. Yim, Y.S. Kim, K.H. Koh and S. Lee //
Natural Science Foundation of China (Grant number: Journal of Vacuum Science and Technology
21075030). B: Microelectronics and Nanometer
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40 Adv. Mater. Sci.

CARBON NANOTUBES BASED THIN FILMS:

L. Fu1 and A. M. Yu1,2

1. INTRODUCTION times to the copper [6]. Moreover, the thermal con-

Thin film type Fabrication Carbon Catalyst Operation Substrate Reference

N2-encapsulated CVD ACN FeCp2 0-(x

deposition method [59]. Compared with the inset

Sensor description Target Detection Operation Response Recovery Reference

MWCNTs-doped CO 50 ppm +((s

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