Cirp Annals - Manufacturing Technology

CIRP Annals - Manufacturing Technology 60 (2011) 735755
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CIRP Annals - Manufacturing Technology

jou rnal homep age : ht t p: // ees .e lse vi er . com /ci r p/ def a ult . asp
Laser nano-manufacturing State of the art and challenges

Lin Li (1)a,*, Minghui Hong b, Michael Schmidt (3)c, Minlin Zhong d, Ajay Malshe (2)e,
Bert Huis intVeld (3)f, Volodymyr Kovalenko (1)g
a
Laser Processing Research Centre, School of Mechanical, Aerospace and Civil Engineering, The University of Manchester, M13 9PL, UK
Department of Electrical and Computer Engineering, National University of Singapore, Singapore
Photonic Technologies, FAU Erlangen-Nuremberg, Germany
d
Department of Mechanical Engineering, Tsinghua University, China
e
Department of Mechanical Engineering, University of Arkansas, USA
f
Department of Mechanical Engineering, University of Twente, The Netherlands
g
National Technical University of Ukraine, Ukraine
b
c
A R T I C L E I N F O
A B S T R A C T
Keywords:
Laser
Nano manufacturing
Material
This paper provides an overview of advances in laser based nano-manufacturing technologies including
surface nano-structure manufacturing, production of nano materials (nanoparticles, nanotubes and
nanowires) and 3D nano-structures manufacture through multiple layer additive techniques and nanojoining/forming. Examples of practical applications of laser manufactured nano-structures, materials and
components are given. A discussion on the challenges and outlooks in laser nano-manufacturing is
presented.
2011 CIRP.
1. Introduction
2. Laser fabrication of surface nano-structures
The need for nano-manufacturing is dictated not only by the

requirement of increasingly sophisticated devices and structures
with novel properties but also by the trend of decreasing
component sizes, material usages and energy consumption of
products. To meet the demand for product miniaturization and
nano-material and structures enabled novel functionality, a logical
step is to achieve the desired nano precision and resolution
through the development and wide implementation of nanofabrication technologies [78,119]. Nano-scale manufacture refers
to the production of structures, materials and components with at
least one of lateral dimensions between 1 nm and 100 nm
including surface and sub-surface patterns, 3D nano structures,
nanowires, nanotubes and nanoparticles. Lasers have provided
important opportunities in the realisation of nano- manufacturing.
This paper reviews the progress in the development of laser
based nano-manufacturing technologies and associated sciences in
order to understand the state of the art and challenges. Fig. 1 shows
the scope of the paper with three main areas of focus: (1) laser
fabrication technologies for surface and subsurface nano structures including near eld and far eld techniques, (2) laser
synthesis of nano materials including nanoparticles, nanowires
and nanotubes, (3) laser fabrication of 3D nano structures and
devices primarily based on additive or bottom-up nano-manufacturing techniques. Their industrial applications and scientic/
technological challenges are discussed.
2.1. Diffraction limits to laser beams
* Corresponding author.
0007-8506/$ see front matter 2011 CIRP.
doi:10.1016/j.cirp.2011.05.005
Laser materials processing has been successfully applied in

industry for several decades for cutting, welding, drilling, cleaning,
additive manufacturing, surface modication and micro-machining. In most cases, the feature size and resolution of machining are
above 1 mm. One of the reasons for the limited resolution is the
diffraction limit of the laser beams in the far eld (where the target
surface from the optical element is greater than the optical
wavelength) governed by:
d
l
2n sin a
(1)
where d is the minimum beam spot diameter, l is the laser

wavelength, n is the refractive index of the medium of beam
delivery to the target material and a is the beam divergence angle.
The best theoretical resolution is therefore around half of the laser
wavelength. For most high power engineering lasers the optical
wavelengths are within 248 nm10.6 mm. Therefore, there are
considerable challenges to achieve nano-scale (100 nm) resolution in direct laser fabrication of surface structures.
To improve the fabrication resolution a number of approaches
have been considered including the use of high numerical aperture
optics and shorter wavelength light sources. For example, deep
ultra-violet (DUV, ArF 193 nm) laser sources have been used in
producing lines of 130 nm and 90 nm lithography (32 nm and
45 nm with optics immersed a high refractive index liquid). To
achieve smaller surface patterning feature sizes, F2 lasers of
157 nm wavelength and extreme ultraviolet (EUV) Xe or Sn plasma
systems with a 13 nm wavelength are used for nanolithography.
However, these sources are costly, low output power and unstable
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L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755
Fig. 1. Illustration of the scope of the paper.
in light intensity. Strong absorption of the UV light by air molecules

requires the nanolithography to be carried out in a vacuum or dry
high purity N2 gas protection chamber. How to overcome the
optical diffraction limit with stable UV or visible, IR light sources is
attracting much research interests in the world. Near eld optics
utilizing evanescent waves at the close proximity (within the
length of the light wavelength) from the focusing optics have been
recently applied for laser based nano-fabrications beyond the
diffraction limits. In addition, femto second pulsed lasers have
been used to achieve far eld nano-resolution fabrication based on
ablation threshold setting of the Gaussian beam prole of the
lasers and non-linear light absorption effects. Laser radiation on
scanning probe tips for nano-fabrication is not included in this
paper as it was reported elsewhere [111]. In the following sections,
recent developments in near eld laser nano-fabrication techniques, far eld femto second laser nano-fabrication and laser
induced self-organising nano-ripple formations are summarised.
2.2. Scanning near eld photolithography (SNP) using laser coupled
near eld scanning optical microscopy (NSOM)
SNP is based on the coupling of a laser beam (e.g. a frequency
doubled argon ion laser at l = 244 nm) with an optical bre based
Near-eld Scanning Optical Microscope (NSOM, rst demonstrated
in 1992) with a very ne tip (typically 50 nm) and very close (10
20 nm) tip to target surface distance. A high resolution (beyond
diffraction limit) evanescent energy eld generates at the tip and
decays exponentially with increasing distance. The nanometer
distance between the tip and target ensures that the evanescent
wave arrives at the target surface with sufcient energy density. The
patterned photo-resist is further treated by chemical etching, plasma
etching or UV light radiation to create nano-scale patterns on the
substrate. The technique was rst reported by Lo and Wang in 2001
to demonstrate 128 nm resolution fabrications [100]. Sun and Legget
from Shefeld University, UK [172,173] selectively oxidized a
strongly bound self-assembled nanolayer (SAM) photo resist on a
gold substrate using the SNP technique (the terminology of SNP was
rst proposed in 2002) followed by chemical etching to realise 20
55 nm resolution in surface patterning. This is matching the
resolution by electron beam lithography but without the use of a
vacuum chamber.
The technique was further developed by scientists at Singapore
Data Storage Institute and National University of Singapore, using a
frequency-doubled Ti:Sapphire femto-second laser at l = 400 nm,
coupled into an NSOM bre probe to achieve 20 mm resolution
surface patterning on a UV photo resist (around 40120 nm
thickness) spin coated on a Si substrate for data storage
applications [21,56,9395,217]. The laser etched depth was 20
100 nm. The tip/sample distance was regulated by a tuning-forkbased shear-force feedback. Typical writing speed is 812 mm/s.
In the coupled laser and NSOM nano-fabrication technique, the
probe-to-sample distance is a critical parameter to control both the
nano-feature size and shape. At a small probe diameter and probeto-substrate distance, the NSOM overcomes the traditional far-eld
diffraction limit and can be used to obtain sub-wavelength-size
patterns. Fig. 2 shows an example of nano-line arrays created at
different incident laser powers. In addition, higher writing speed
leads to shorter exposure time and thus lower exposure dose,
resulting in a narrower line width and shallower depth. Considering
that there is a melting threshold of the NSOM tip metal coating, a low
power (<1 mW) laser source is typically used to avoid damaging the
Fig. 2. Nano-lines created by the coupled fs laser/NSOM SNP technique at different

incident laser powers [55].
NSOM tip. For the photo-resist exposure process, exposure energy

dose is another important parameter, which is decided by exposure
UV light energy and exposure time. The high resolution of the SNP
technique is comparable to electron beam lithography. Furthermore,
as the nano-features can be fabricated in air, with a multi-NSOM
bre tip design, parallel nanolithography can be realised for high
speed surface nano-structuring. The drawbacks of the technique
include the requirement of high precision nano-distance control
between the bre tip and the target, and potential contamination or
damage to the bre tip. If the target surface is rough (>50 nm Rz)
then it is difcult to apply the technique for uniform pattern writing.
A recent development has enabled a nano-second laser NSOM
technique (200 nm probe diameter) to be applied for direct
fabrication of nano-scale features on Si without the use of
subsequent photo or chemical etching [165].
2.3. Nano ridge aperture (bowtie) beam transmission enhanced nanofabrication
The amount of light transmission through a small aperture of an
object depends on the aperture size, da, relative to the wavelength,
l, of the light source. For an aperture smaller than the laser
wavelength, light transmission is restricted. For example, for a
circular aperture, the transmission efciency is on the order of (da/
l)4 due to the optical diffraction effect [11]. Researchers in Perdue
University, USA, found that, with a specic aperture geometry such
as a bowtie or H, high energy laser beams can be delivered through
the aperture with much less attenuation than a circular aperture
and the energy is sufcient to produce nano-scale patterns on a
surface through contact lithography [29,226]. The enhancement
was found to be due to near eld surface plasmonic effect [29,227].
Fig. 3a shows a typical bowtie aperture used for nano-fabrication.
The aperture was made of atomic force microscope cantilever
probe (Si3N4 coated with an Al lm) with the gold coating removed
from the back side and the bowtie geometry milled using a focused
ion beam. The aperture had 180 nm 180 nm outline dimension
and a 30 nm gap. When a laser beam of 800 nm wavelength and
50 fs pulse width at 1.57.9 mW power passed through the
aperture, lines with widths down to 62 nm and 2 nm depth were
produced on a photoresist material at a scanning speed of 2.5 mm/s
as shown in Fig. 3b. The distance between the bowtie aperture tip
and the target surface was 30 nm. The laser beam intensity at the
tip of the bowtie aperture was found 39.8 times that of the
incoming beam due to plasmonic enhancement. As this phenomenon only occurs at the near eld, some researchers also classify
this technique as the NSOM based nano-fabrication.
2.4. Optically trapped micro-sphere assisted nano-writing (OTAN)
Scientists at Princeton University recently developed a laser
nano-patterning technique based on laser tweezers [118]. A
Fig. 3. Nano bowtie aperture (a) and nano surface patterns produced by
transmitting a laser beam through it (b) [29].
Fig. 4. Illustration of laser trapped micro-sphere nano-patterning. (a) Experimental

set up and (b) an example of optically trapped micro-sphere nano writing. The scale
bars on the larger picture and the zoomed-in pictures are 2 mm and 250 nm,
respectively [118].
transparent sphere (polystyrene) was held by a focused continuous

wave laser beam (converted to a Bessel beam using an axicon lens) as
in a typical laser tweezers setup in a liquid environment. At the same
time, another pulsed laser (355 nm wavelength, 15 nm pulse length,
15 nJ8 mJ pulse energy) passes through the sphere and produces a
focused energy spot at the bottom of the sphere based on the near
eld evanescence wave effect. By traversing the sphere over a
surface, nano-scale patterns have been generated. Due to the
balance of the laser beam radiation pressure with the electrostatic
repulsion from the target surface [211], which develops due to ionic
groups on the surfaces, the distance between the sphere and the
target surface can be maintained constant even for a curved surface
without any additional feedback control systems. Fig. 4 shows a
typical process set up and an example of a nano-pattern fabricated
using the technique. Arbitrary patterns with the line width around
100 nm were demonstrated with 15 nm feature size variation. The
scientists at the Princeton group further developed the technique by
splitting the sphere trapping beam into multiple beams using beam
splitters to hold and move several micro-spheres (0.763 mm
diameters) simultaneously, while ring a pulsed power beam to
them. Such a system enabled them to write a number of parallel
nano-patterns on a polyimide lm coated on a glass substrate [118].
An advantage of the technique compared with other near eld direct
writing techniques is that for OTAN there is no need for distance
control and it can work on rough surfaces [186]. A limitation of the
technique is that it can only operate in a liquid environment.
737
interaction with materials, the laser interaction time (1015

1013 s) is shorter than the time for electrons to pass the energy to
the lattice (around 1011 s). As a result, the material remains cool
while absorbing the laser energy. The use of ultra-short pulse
durations of the fs laser pulses restricts the heat diffusion, and
improves surface roughness, and also minimizes damage to the
adjacent areas. Due to the above mentioned advantages, fs lasers
are used for writing couplers [120], waveguide ampliers [162],
diffraction gratings and memory bits [24]. To achieve nano-scale
resolution, the tip of Gaussian beam is used (setting the laser
uence low enough so that only the tip of laser beam is above the
ablation or phase change threshold of the material). In this way, far
eld laser nano-fabrication beyond diffraction limit can be
realised. Typical pulse energy of fs laser nano-fabrication is
between 0.1 and 100 mJ and power densities above 1 TW/cm2.
Tight focusing of the light by a high NA telecentric lens is
essential for fs laser nanofabrication. Another advantage of
telecentric lens is that every successive scanning beam is parallel
to the optical axis. Due to this, the beam is incident normally on the
entire surface area and symmetrical features can thus be written.
Minimal variation in laser focus energy and accuracy of focal spot/
sample scanning ensure fabrication with high precision. The
charge-coupled device (CCD) camera assists in optical adjustment
and in situ fabrication monitoring [236].
Three critical factors that govern the fs laser writing mechanism
are chemical nonlinearity, material nonlinearity, and optical
nonlinearity. When a high power density from a fs laser is
incident on a target surface, photons are absorbed by either onephoton absorption (OPA), two-photon absorption (TPA), or the
multi-photon absorption (MPA). Photon absorption caused by fslaser beam irradiation leads to different processes such as
ionization, electron excitation, and phase transitions. The electrons
are agitated and their oscillatory energy is converted into thermal
energy of the plasma by collisions with ions by the linear damping
mechanism referred to as inverse Bremsstrahlung heating. This
raises the temperature and the laser energy is absorbed by the
plasma by OPA. These phenomena can occur only in a localized
region around the focal point due to the high peak intensity. The
separation between the high energetic electron cloud and the
positively charged ions in the bulk causes a high voltage (known as
Dember voltage) close to the surface which results in the repelling
of materials in a process known as Coulomb Explosion. For this
reason, the fs laser processing is also termed as cold laser processing
and it is possible to write features even in transparent materials
[109,121,126]. In summary, the formation of nano-features is
attributed to the interaction between the fs laser beam and laserinduced electron plasma and matter [159]. Two photon absorption
mechanisms are illustrated in Fig. 5 [84]. In the gure, S0, S1, and S2
are ground state, one-photon allowed and two-photon allowed
excited states, respectively. The incident light frequencies are v1
and v2 while the uorescent emission frequency is v3.
It should be noted that in standard optical lithography, the
materials respond to light excitation to the rst order effect. For
TPA and MPA in fs laser writing, the response is limited to two and
higher orders and the square light intensity is also narrower than a
linear one. This makes the photon energy of TPA less than that of
2.5. Femtosecond (fs) laser direct writing

The process involved in the formation of nano-scale features by
fs lasers is different from the conventional lasers. In fs laser
Fig. 5. Schematic energy diagram of a TPA process [84] (reproduced with

permission from Elsevier).
738
Fig. 6. Nanofeatures developed in (a) amorphous silica [57] (reproduced with

permission from Elsevier), (b) urethane acrylate resin, SCR 500 [176] (reproduced
with permission from the Optical Society of America), (c) commercial resin, SCR 500
[180] (reproduced with permission from American Institute of Physics), (d) glass
[193], (e) TeO2 [158], (f) photoresist thin lm [94], (g) CVD diamond surface [136]
(reproduced with permission from American Institute of Physics).
OPA. As a consequence, the volume involved in beam-material

interaction reduces and this leads to better resolution in writing
the features. The volume in which this energy is absorbed is less
than the third order of the laser wavelength (l3) and hence high
spatial resolution of the writing process (100 nm) beyond the
optical diffraction limit is possible [176].
For nanoscale writing, it is essential that the laser energy
penetrates into the bulk material without any signicant losses. For
this purpose, a light source with near-infrared wavelength (such as
l = 800 nm) is selected for surface, sub-surface and in-bulk writing.
Due to the high transient power density, fs lasers can excite a wide
range of materials and induce irreversible processes such as
photopolymerisation, photoisomerization, and photoreduction.
Femtosecond lasers have numerous advantages over longer
pulsed lasers for materials processing [179,195197] due to which
they have been used for writing nano-features in a wide variety of
materials such as metals, polymers and ceramics. Examples of the
material, and dimensions of the nanofeatures (100 nm) written
by fs lasers are presented in Table 1 and Fig. 6.
2.6. Micro-lens array for fabricating periodic nano-structures
Periodic nanostructures are useful for plasmonic structures,
photonic crystals, high density data storage, miniaturized radio
frequency (RF) oscillators and optical gratings. Micro-lens array
(MLA) lithography is a laser-based technique being developed for
rapid fabrication of large-scale periodic nanostructures. MLA
consists of a series of miniaturized lenses of identical sizes and
focal lengths, typically arranged hexagonally or squarely packed.
When used in a typical optical system, an MLA can focus an
incident light beam to form a series of parallel light spots in the
focal plane.
Downscaling of the diameter, D, and the focal length, f, of a lens

improves its optical performance [52]. For a xed F number F = f/D,
the diffraction-limited resolution is given by dx lF2 which is
independent of the lens scale. However, the wave aberrations
which describe the deviation of the actual wave front from a
perfect spherical wave front, are less for smaller lenses for the
same F number and wavelength. On the other hand, small lenses
have a shorter focal length [200].
The early studies of micro-lens array based photolithography
were for the manufacturing of periodic micro-scale features
[58,200]. As the micro-lens array production technology improves,
the size of micro-lenses get smaller and so are the feature sizes. For
example, scientists at Singapore Data Storage Institute and National
University of Singapore used an 800 nm wavelength, 100 fs laser to
irradiate a 30 nm-thick GeSbTe layer sputtered onto a polycarbonate
substrate. It created thousands of eld emission transistor structures
in a few minutes with a gate line width of 200 nm. In addition, using
an alkaline solution to etch the material after laser radiation,
nanostructures down to 55 nm on the thin lm were produced [96].
To achieve further reduction in feature sizes, they manufactured a
micro lens array on a quartz substrate with a diameter and pitch of
1 mm each, which consists of 2500 2500 (6.25 million) lenses
covering an area of 5 mm 5 mm. UV light-sensitive photoresist
irradiated by a 248 nm wavelength, 23 ns pulse width KrF excimer
laser through the MLA created nano-dots as small as 78 nm in
diameter, at a resolution of one-third the operating wavelength [92].
Fig. 7 shows an example of periodic patterns produced by a microlens array system.
A critical requirement of the micro-lens array lithography
fabrication technology is that the lens must be horizontal to the
target surface within the entire radiated area to ensure the beams
are vertical to the surface so that the feature sizes are identical. The
lens to target surface is also needed to be controlled precisely. For a
non-at surface, it is difcult to fabricate uniform nano-structures
using this technique.
2.7. Far eld laser interference lithography (LIL)
Laser-interference lithography is a large-area, maskless, and
noncontact nanofabrication technique suitable for repeatable
structures such as periodic lines and 2D shapes. It is based on
the interference of two or more coherent light beams that form a
horizontal standing-wave pattern. The minimum spacing, dL,
between the lines is determined by the laser wavelength, l, and
angle, a, between the laser beams as in:
dL
(2)
2n sina=2
This interference pattern is then recorded on the exposed

photoresist. Laser-interference lithography can be used to
fabricate micro- and nano-surface structures in large areas. By
overlapping exposures at different angles, various patterns (e.g.
circular, square, and hexagonal geometry) can be produced.
Table 1
Examples of nano-features written by fs lasers.
Base material
Nano-features
References
Copper thin lm
Amorphous silica
Urethane acrylate resin, SCR 500
Glass
TeO2
SiO2
Bulk aluminium
Lithium niobate
CVD diamond surface
AAO matrix (Au deposited into anodized aluminium oxide)
Commercial resin, SCR 500
Gallium nitride
Silica glass
TiO2
Pits of 75 nm
Gratings of 15 nm width
Wires of 65 nm lateral width at central portion
Hillocks of 4070 nm height
Voids of 30 nm width
Stripes of 20 nm width
Irregular nanoentities with average size of 100 nm
Thick layer of 100 nm
Ripples with periodicity of 50100 nm
Nanorods of diameter 2040 nm and length of 50 nm
Lines with width of 23 nm
Craters of depth varying from 26 to 40 nm
Wires of width of 15 nm and holes of 20 nm diameter
Ripples with depth of 100 nm
[195]
[57]
[177]
[193,194]
[158]
[159]
[170]
[24,109,110,169]
[136]
[147]
[180]
[126]
[70]
[23]
739
Fig. 10. A typical optical conguration for Lloyds mirror interferometer laser
interference lithography, where u = a/2 [112].
Fig. 7. Large area micro/nanostructures fabricated by laser MLA [92].
Examples include nano-cone arrays on NiCr alloy (Fig. 8) and Au/

Ag bi-metallic plasmonic structures on quartz substrates. Using
this approach, after only a few minutes of UV light exposure,
followed by photoresist development and chemical etching,
periodic nano-lines and nano-dot arrays can be created over a
centimetre scale area.
To further improve the resolution, immersion laser interference
lithography was developed at Max-Planck Institute of Microstructure Physics, Germany [18]. This is to increase n in Eq. (2) by
introducing a Littrow prism and water as the immersion liquid. In
this case, n = 1.51. Line patters with a period less than 100 nm and a
width of 45 nm were demonstrated with a 244 nm wavelength
laser (Fig. 9).
Another way of increasing the resolution is by reducing the

laser wavelength, such as the use of an extreme ultraviolet laser
source (e.g. an A+8 laser at a 46.9 nm wavelength). A great
advantage of this method is the increase of ablation depth to over
120 nm on Si based photo-resist [112]. By combining an EUV laser
and Lloyds mirror interferometer (Fig. 10), nanostructures of
60 nm feature size were produced on PMMA (Fig. 11). The ablation
depth is 2030 nm. Also lines with 95 nm width were produced on
Au substrates using the technique by the same group. A drawback
of the EUV technology is that the process will need a vacuum
chamber to operate due to the use of EUV system which can easily
ionize gases if it is operated in non-vacuum conditions.
2.8. Near eld interference lithography
Near eld interference lithography is based on evanescent
(non-propagating) wave or surface plasmon wave interferences.
The purpose is to defeat the diffraction limit of the lasers to
fabricate smaller nano-structures.
Evanescent interferometric lithography (EIL) or evanescent
near eld optical lithography (ENFOL), or evanescent wave
interference lithography (EWIL) was rst demonstrated using a
mercury arc lamp in 1999 by Blackie et al. at University of
Canterbury, New Zealand [3,14]. Laser based evanescent wave near
eld lithography using total internal reection (TIR) was rst
reported in 2006 by Martinez-Anton of University Complutense
Madrid, Spain [115]. A typical TIR conguration is shown in Fig. 12
with two intersecting beams at an angle to enable the total
reection to occur to create periodic evanescent waves. The prism
Fig. 8. A nano-cone structure fabricated by laser interference lithography (height

40 nm and width 30 nm) [152].
Fig. 11. Two dimensional nano patterns on PMMA produced by EUV laser
interference lithography using Lloyds mirror interferometer with two exposures at
different angles, (a) dots with 60 nm FWHM feature size and a period of 150 nm, (b)
regular shapes dots, (c) elongated dots [112].
Fig. 9. Photoresist patterns created by immersion laser interference lithography. (a)

Low magnication and (b) high magnication images of the pattern; the width of the
resist lines is 43. 4 nm. (c) Silver lines after evaporation of 15 nm Ag and lift-off [18].
Fig. 12. Illustration of a typical TIR optical conguration to generated evanescent

waves through interference of tow intersecting beams [115].
740
was irradiated with split 405 nm wavelength laser beams. Periodic

surface relief gratings of around 100 nm period were produced on
photoresists using this technique [115].
More complicated 2D nano-structures can be fabricated using
multiple (more than 2) beam interference through polarization
tuning, based on TIR evanescence wave near eld lithography, as
demonstrated by Chua and Murukeshan [22]. The photoresist in
optical contact with the TIR prism (rectangular) has a lower
refractive index than the prism. Patterns of 70 nm feature size had
been produced using this method (Fig. 13). A drawback of this
method is that the depth is shallow due to the non-propagating
nature of the evanescent wave. The energy transmission through
the masks is also very low.
Surface Plasmon Interference Lithography (SPIL) is another near
eld lithographic technique developed recently to improve energy
transmission and fabrication depth over the evanescent wave
lithography. It is based on energy eld enhancement by the
interaction of light with surface Plasmon (SP, collective electron
oscillation) waves induced around the nano-scale metallic structures and a dielectric interface. If the metallic mask is very thin (e.g.
50 nm), surface Plasmon waves can be generated on both surfaces,
even the structures are not through the full thickness of the metallic
lm. The enhancement, through the coupling between the surface
plasma waves and the evanescent waves, can be several orders of
magnitude in intensity compared with the incoming beam. The
wavelength of the excited surface Plasmon wave is shorter than that
of the exciting laser at the same frequency. Therefore higher
resolution is expected. The wavelength of the exciting laser, l(i,j),

needs to match the materials and the structures of the mask. Their
relationships can be found from [168]:
a
li; j q
2
i j
ed em
ed em
(3)
where a is the metallic mask periodic nanostructure period, ea and

em are the dielectric constants of the mask metal and the
surrounding dielectric medium, respectively and i, j are mode
indices. For example, a UV light can excite surface Plasmon waves
on Al with a nanostructure period of 220 nm. A green or blue light
can excite surface Plasmon waves on a silver mask with a period of
400500 nm. A larger period allows longer exciting wavelengths.
The SPIL technique for the fabrication of periodic surface
nanostructures was rst reported independently by two separate
groups (University of California in USA and RIKEN in Japan) in 2004
[103,168] using an Al or a silver mask. An example of a typical
conguration for the SPIL technique is shown in Fig. 14. For an
80 nm thick Al mask of 20 nm diameter holes and 220 nm period
(fabricated using a focused ion beam) and 30 nm spacer (PMMA)
and irradiated with an arc lamp with a peak intensity at 365 nm,
90 nm periodic structures were produced on a photoresist [168].
The RIKEN group fabricated periodic 100 nm lines using a silver
mask radiated with a 436 nm light. They termed the method as
SPRINT (Surface Plasmon Resonance Interference Nanolithography
Technique) and proposed to use imperforated metallic marks
which have corrugated surfaces on both sides of the metallic mask.
The illuminated side collects the light and induces the SP waves on
the other side of the target material through SP coupling.
Sreekanth et al. at Nanyang Technological University of Singapore
compared standard far eld laser interference lithography, near eld
evanescent wave lithography and the SPLIT techniques in nano
fabrication of period surface structures [167]. They found that that
the SPIL technique can produce deeper features than the evanescent
wave lithography technique and both near eld lithography
techniques have a better resolution than the far eld lithography
technique. Fig. 15 shows an example of periodic dot arrays fabricated
on a Si wafer using the SPIL technique with a UV Argon ion laser at
364 nm wavelength, which has a 82 11 nm feature size,
164 11 nm period and an average height of 180 nm [167].
2.9. Contact particle lens array nano-fabrication (CPLA)
This technique is based on the use of transparent micro
spherical particles spread onto the target surface by self-assembly
Fig. 13. Two dimensional features fabricated using evanescent wave interference
lithography generated by TIR of four p-polarized incident beams. (a) Theoretical
inverse positional photoresist development rate at the interface between the prism
and photoresist, (b) SEM image of hexagonal arrayed 2D features. Inset: Enlarged
region showing the peak (P), valley (V) and saddle (S) regions (top right), (c) AFM
image of the nano-structures [22].
Fig. 14. A typical process conguration for SPIL and an optical mask, (A) schematic
drawing of the SPIL set up and (B) an Al mask for the SPIL experiment (fabricated
using FIB) with a hole size of 160 nm and a period of 500 nm [168].
Fig. 15. An AFM image of periodic nanodot array produced on Si by SPIL technique,
using an Al mask and a UV argon ion laser [167].
to form a mono-layer. Due to laser light intensity enhancement

near the contact area between particles and the substrate, high
resolution patterning can be realised. For example, for a 266 nm
laser and a 500 nm particle, light intensity can be enhanced up to
50 times. Light enhancement increases as particle diameter
increases and light wavelength decreases. However, to increase
particle size results in a larger focused energy eld spot area thus
reducing fabrication resolution. Meanwhile, due to the nature of
particle materials, there is a limit on the laser wavelengths. For
example, a 157 nm F2 excimer laser light is strongly absorbed by
most of optical materials and even air. Therefore, in order to obtain
a smaller light enhancement region, a small particle size needs to
be selected with the content of a weaker light enhancement effect.
This technique can be applied to achieve surface nano-patterning
on different functional material substrates directly without the use
of lithographic procedures.
The phenomena of light induced surface damages through
micro- and nano-particles were known in late 1900s in the process
of laser cleaning of particles from a surface. Kawata et al. at Shizuka
University in Japan used the phenomenon for high resolution
optical microscopy by producing topographical changes on a
polymer surface [71] using very small (50100 nm) optically
transparent spheres. Lu and his colleagues at National University of
Singapore and Data Storage Institute rst explicitly reported the
use of microspheres as a tool for laser nano patterning on Si
substrates [102]. They used 0.5 mm silica spheres to fabricate
100 nm hillocks on Si with a 248 nm KrF excimer laser.
The use of self-organised hexagonally closed packed monolayer
microspheres for laser nano-patterning on large areas was rst
reported by Hasegawa et al. of Toyota Central R&D Laboratory in
Japan in 2001 [50]. They generated 95 nm structures on a polymer
surface using Ar+ laser radiation (488 nm) to self-organised
polystyrene spheres.
Muenzer et al. of University of Konstanz, Germany [125] were
among the early researchers who demonstrated nano-holes (below
100 nm in diameter and <10 nm in depth) generation on glass and
silicon (without photoresists) using polystyrene microspheres
radiated with a laser beam. They applied Mie theory to calculate
the near eld intensity (electrical vector) enhancement effect of an
800 nm wavelength laser irradiated polystyrene micro-sphere.
They found that the energy eld is not focused beyond a distance,
df, from the sphere in air [125]:
df r
2n
2n 1
741
Fig. 16. SEM image of nano-hole arrays formed on a GST thin lm surface after one
pulse of KrF excimer laser irradiation at a laser uence of 5.8 mJ/cm2.
Fig. 16 shows an example of using the CPLA technique for the

fabrication of hole arrays on a Ge2Sb2Te5 (GST)/Al thin lm surface
by Singapore Data Storage Institute and National University of
Singapore. Closely packed colloidal monolayer of 1 mm polystyrene particles were used. A KrF excimer laser was applied to
irradiate the sample. After one pulse of KrF excimer laser
irradiation at laser uence of 5.8 mJ/cm2, bowl-shaped nano-holes
of a uniform diameter of 120 nm were produced.
By using a different medium, such as water or a chemical
solution between particles and the targets, the focal length of the
micro-particles can be signicantly increased [44,218]. Thus subsurface patterning in glass and reversed patterns (such as nanobumps) on Si had been produced. By scanning a focused laser beam
over the particle lens, non-periodic nano-patterns could be
fabricated [140].
Microsphere near-eld nanostructuring is robust and allows
the large scale production of nanostructures. Yet, the exibility of
feature geometries had been limited to holes or pits only until a
new approach was proposed and demonstrated by researchers at
The University of Manchester, UK to produce periodic lines, curves
and arbitrary patterns using an angular scanning particle lens array
technique [45,46,89]. Fig. 17 shows a typical process conguration
in the angular scanning particle lens array nano-patterning
technique and Fig. 18 shows an example of the complex patterns
fabricated using the technique without the use of any masks and
several million identical patterns were generated simultaneously
on a 1 cm 1 cm area [89]. A drawback of the method and other
particle lens array based techniques is that the uniformity of the
patterns is not excellent due to the variation of beam intensity at
each point and possibility of non-monolayer particles at some
locations.
To overcome the problems of non-monolayer particles and on
curved or hydrophobic surfaces, researchers at The University of
Manchester, UK, have recently developed a particle lens transport
system to allow the reuse of the particles and also for patterning on
curved or hydrophobic surfaces [76]. The method is based on lifting
(4)
where n is the refractive index of the sphere and r is the radius of

the sphere. When the microsphere size is below the light
wavelength, two focusing peaks were found and double spots
were generated on a surface of a substrate. For practical
applications of the technique, the microsphere diameter is
normally greater than the laser wavelength.
Fig. 17. Illustration of scanning angled beam particle lens array nano fabrication
technique [45].
742
Fig. 18. Nano start array (several million simultaneously over 10 mm 10 mm area
(a), a section of 5 mm 5 mm area (b)). A single nano star from the array [89].
off a monolayer micro-particle array self-assembled on a at glass

substrate, using a transparent ribbon and transporting it to the
target surface to be patterned. The method is illustrated in Fig. 19.
It has been applied successfully for nano-patterning on a Ti tube
and on a hydrophobic Si surface without pre-treatments.
Metallic nano-particles (e.g. Ag, Ag) have been used, instead of
transparent micro-spheres, to generate smaller nano-patterns
through Plasmon enhanced near-eld effects [86,123,129].
2.10. Laser induced periodic surface structures (LIPSS)
Laser induced periodic surface structures (LIPSS) also referred
to as ripples are frequently observed. The rst observation of ripple
formation on a surface after laser irradiation was made in 1965
[13], which is 5 years after the demonstration of the rst laser.
LIPSS formation comprises the growth of wavy surfaces that can
occur on a wide variety of materials. LIPSS consist of wavy surfaces
with periodicity equal or smaller than the wavelength of the laser
radiation. The ripple period varies with the laser uence applied.
The orientation of ripple formation is normally related to the
polarization direction of the laser light for material excitation.
When linearly polarized laser light is applied, most ripples are
oriented perpendicular to the polarization direction whereas ne
ripples with an orientation parallel to the polarization direction are
seen as well. When circular polarized laser light is applied ripples
without a specic orientation are observed.
By laser processing at intensity below the ablation threshold of
the materials, regular surface structures can be obtained with
uniform sizes at the nanometer scale. Nanometer grooves in
Fig. 19. Illustration of a exible particle lens array transport system for
nanofabrication on a curved surface [76].
synthetic single-crystal CVD diamond have been made with

femtosecond pulses [160]. Grooves are perpendicular to the
direction of the laser polarization and are 40 nm wide, 500 nm
deep, and have an average spacing of 146 7 nm. Originally ripples
were only considered as laser induced surface damage of optical
components [137]. In recent years it was realised that rippled surfaces
have interesting properties and that large areas can be covered with
continuous patterns by overlapping short laser pulses. Ripples are
formed when certain energy densities are applied [146]. Outside this
process window other surface features are created. For example,
below the uence threshold for forming of ripples on metals, small
spheres are formed. These spheres or bubbles have diameters in the
range of 1090 nm. When the energy input is increased, for instance,
by applying a lower processing speed, the periodic patterns transform
into more chaotic structures [39]. The height of ripples is in the
nanometer region, varying from amplitude of about 10 nm [59] to
values above 100 nm. Large area aligned nano-ripples can be realised
by aligning the ripples between each laser scanning tracks [47].
Ripples on surfaces as a result of laser radiation are reported on
a variety of materials. Most studies are carried out for ripple
formation on metals and semiconductors as well as dielectrics,
such as glass and diamond, ceramics and even polymers show
periodic structures. In the 1970s and 1980s nanosecond pulses
were used and in the 1990s and the rst decade of this century ps
and fs pulses became available for micro/nano ripple or periodic
structure formation. Fig. 20 shows an example of nano-scale ripple
formation on alloy steel with fs laser radiation. The nano sized
bubbles with diameters in the range 20100 nm were found on top
of the ne ripples.
Although LIPSS have already been observed for more than 45
years a complete understanding of the origin and growth
mechanism of ripples is still missing. The physical processes on
a time scale of nanoseconds and longer are reasonably well
understood; thermal processes like surface vapourisation, heterogeneous boiling and homogeneous boiling are described [15]. The
question is what happens on a time scale of femto and pico seconds
within the optical penetration depth.
A commonly accepted explanation is that the driving force for
ripple forming originates from the interference of the incident and
reected or refracted laser light with the scattered or diffracted
light near the interface. Scattering of the incident light is supposed
to be caused by microscopic roughness of the surface, by defects or
by spatial variations in the dielectric constant. The interference
between the different waves could lead to an inhomogeneous
energy input to the electron system which, together with positive
feedback mechanisms, can cause ripples.
Fig. 20. Helium microscopy (SHIM) image of ne ripples with lateral sizes of 172 nm
oriented parallel to the polarization direction formed with fs laser pulses on alloyed
steel [59].
The intensity of the scattered waves depends on the laser

parameters and the type of material. If the material possesses an
optically active mode near the laser frequency, it is assumed that
the scattered light can directly excite a real surface electromagnetic wave (SEW) [91]. Such SEWs or surface polaritons are waves
travelling along the interface between two media. If there is no
optically active mode near the laser frequency, ripples are
supposed to form if one of the diffracted waves propagates close
to the surface. The periodicity of ripples depends on the laser
uence, number of pulses, wavelength, the angle of incidence and
the polarization of the laser beam.
3. Laser manufacturing of nano materials
Nano-materials have unique physical and chemical properties.
They are building blocks of nano-devices in the bottom-up
fabrication approach. Various laser based methods have been
developed for the manufacture of nano-materials. This paper limits
to the review of nanoparticle, nanotube and nanowire manufacture by lasers.
3.1. Laser manufacture of nanoparticles
Nanoparticles (NPs) have specic properties that are different
from their bulk materials. Due to their special thermodynamic,
chemical and optical properties [192], nanoscale particles are of
special interest for both basic research and technological application. The high ratio of surface to bulk atoms features nanoparticles
with unique physical and chemical properties, creating a new class
of materials between bulk material and single atoms [79,157,185].
NPs can be in the form of metal, ceramic, semiconductor,
composite, core-shells and polymers.
Nanoparticles can be manufactured by several approaches. Nonlaser based techniques for the fabrication of NPs are based on
chemical reduction, solgel colloidal chemistry, gas phase decomposition, combustion, electrical discharge and mechanical grinding
[4,49]. These methods are easily scalable and therefore applicable for
large scale NP fabrications. However, they are restricted in material
variety and the dispersability of the nanoparticles in liquid media.
Furthermore, for many applications purication steps are required
to remove chemical by-products [48,49] and the quality and purity
of particles produced by these traditional approaches are not
sufcient. Therefore, in the last two decades laser based approaches
for NP generation have been developed. The laser based NP
manufacture techniques are dominated by laser ablation of solid
targets (in a gas, vacuum or liquid environment) [20].
Among the earlier researchers to investigate laser based
nanoparticle generation were Henglein and co-workers [51]. They
used a pulsed ruby laser with a wavelength of l = 694 nm to ablate
thin gold lms to produce gold nanoparticles. Furthermore, they
focused the laser into an aqueous solution with suspended
microscale particles which also led to the formation of colloids,
nanoparticles dispersed in liquid media. The size of the gained
particles varied between 5 and 15 nm [31,51].
A common choice of the laser source was a Q-switched Nd:YAG
laser or a diode pumped solid state laser (DPSS) with pulse lengths
of some nanoseconds and pulse energies of some ten milijoules.
With such a system it was possible to generate silver particles with
sizes of around 20 3 nm [128,161]. To reduce the particle size
Prochazka et al. added chlorides to the water in which the ablation
took place. Thereby, the formation of larger colloidal particles could
be prevented and the average particle size decreased (<11 nm, silver).
This approach, however, modied the silver surface by chloride
anions and also decreased the stability of the resulting colloid.
Another way to reduce the particle sizes without the above
mentioned disadvantages was explored by Prochazka and co-workers. They additionally irradiated the generated colloidal suspension
with the same pulsed laser which led to fragmentation of the larger
particles. The average diameters also went down to 1113 nm for
silver colloids [143]. The inuence of the wavelength and the laser
743
uence was later evaluated by Tsuji et al., who used the primary,
second and third harmonic (wavelength l = 1064 nm, 532 nm,
355 nm) of a Nd:YAG laser with pulse lengths around 59 ns. They
found that the particle size decreased with reducing wavelength and
reached average diameters of 12 nm for copper and silver particles
[187189]. Similar results were obtained by Mafune and co-workers
who also used a Nd:YAG laser with a pulse duration of t = 10 ns and a
wavelength of l = 532 nm and obtained particle diameters of 10 nm
for silver and 8 nm for gold colloids [104107].
Tsuji et al. were among the rst to fabricate NPs using a
femtosecond laser. Although the particle formation efciency was
lower compared to nanosecond laser pulses, they found that with
the femtosecond laser the particle size distribution was much
narrower [190]. Later research by Barcikowski et al. showed that the
size of nanoparticles generated with femtosecond lasers was mostly
determined by the pulse overlap and uence for different materials
(Ti, Ag, Au, Co) [8]. Most of the recent work has been carried out with
femtosecond lasers on different substrate materials in both aqueous
and gaseous media [48,49,98,134,174,175].
Pulsed laser ablation for the nano-materials synthesis has the
advantages of synthesizing pure nano-materials and a wide scope
of nano-material compositions as target materials can be changed
and combined easily.
A typical setup of laser ablation in liquid is shown in Fig. 21.
Inside a liquid, high power and short pulse laser ablation induced
plasma cannot move freely. There are strong interactions between
plasma species and water molecules. High temperature and high
pressure plasma is conned inside a small volume and increases
the collision probabilities among species atoms and liquid
molecules. Typical nanoparticle size and their distributions are
much bigger than those synthesized in a vacuum. However, pulsed
laser ablation in liquid for NP synthesis has the advantages of being
simple and lower system cost with higher yields. To avoid the
nano-material oxidation and aggregation, chemical surfactant can
be added into the liquid during the nano-materials synthesis.
Pulsed laser ablation synthesis of nano-composites in a liquid
can be achieved with different material targets immersed inside
water. An example is Ag deposited TiO2 nano-particles synthesized
by 1064 nm/7 ns Nd:YAG laser ablation. Ag and Ti metal plates
(99.5% pure) are used for the laser ablation in water one after the
other. Nano-composites with 30 nm TiO2 and 10 nm Ag nanoparticles can be synthesized after several minutes of the laser
irradiation. TiO2 is one of the most widely studied semiconductors
for heterogeneous photo-catalysts. It is also one of the promising
candidates for photo-anode materials, which can split water in
solar energy conversion cells. However, the effect of photocatalysts is reduced for the photo-generated electronhole
recombination and the TiO2 electrodes suffer from low solar
energy conversion efciencies less than 4%. Deposition of noble
metals, such as Ag, Au and Pt, on TiO2 surface is one of the effective
methods to reduce electronhole recombination in the photocatalytic process due to the formation of the Schottky barriers at
each Ag/TiO2 contact region. With this approach, the absorption
capability of photo-catalysts can be enhanced. The noble metal
creates conditions for additional absorption band at visible light
Fig. 21. Schematic diagram of nano particle generation by laser ablation in liquid.
744
spectra due to the surface plasmon resonance (SPR) effect. It gives

an opportunity to extend the spectral range of the response of TiO2
photo-anode to a much longer wavelength. Ag deposited TiO2
nano-particles possess a special peak at 400450 nm due to surface
plasmon resonance (SPR) in the free electron metal inclusion. This
nano-composite synthesis by simple pulsed laser ablation in water
can extend the absorption range to the visible wavelength as
compared to pure TiO2 nano-particles, which promotes TiO2
photo-anode properties greatly.
NP generation by laser ablation in liquid provides high purity
materials. However, the NP production rate is a few mg/h. A number
of measures have been taken to improve the productively. Sajti et al.
at Laser Zentrum Hannover studied the effect of water lm thickness
and pulse separation and found that if the water lm thickness is
reduced from 8 mm to 2.5 mm, the NP production rate can be
increased by 350% for Al2O3 NP generation using a 18.5 W Qswitched Nd:YLF laser at 2060 ns pulse width and a scanning speed
of 501400 mm/s [150]. While the NP productivity increases almost
linearly with the pulse energy below a certain energy level, the
ablation efciency saturates above certain pulse energy level (2 mJ)
due to phase explosion [150]. At constant pulse energy, separating
the pulses from overlapping increases the ablation rate by over 300%
compared with the pulse overlapping condition. This is primarily
because with high pulse overlaps, laser beam interacts with the high
density vapour plume, plasma and cavity bubbles causing beam
scattering. At the optimum condition, 1.3 g/h was achieved. Another
way of achieving high productivity is by the use of continuous wave
lasers as demonstrated by Khan et al. and Abdolvand et al. of The
University of Manchester for the generation of TiO2, NiO and g-Al2O3
nanoparticles [1,74,75]. The high average energy of the bre laser
used and a larger ablation area by keyhole generation enabled high
production rate. An example of TiO2 nanoparticles generated using
this method is shown in Fig. 22. A review of NP generation by laser
ablation methods is given by Semaltianos [154].
NP generation by solid/liquid interaction is different from laser
ablation in liquid in that the nanoparticles are not generated from
the solid target materials, but from the liquid (by thermally induced
chemical decomposition or reduction) or a mixture of the elements
from the liquid and the solid target. For example, using laser heating
of a Cu plate inside silver nitrate solution allows the production of Ag
nanoparticles, not Cu, and the Ag particle size (23 nm) was found
much smaller than that by the standard wet chemical processes
(>10 nm) [142]. If a Cu target is heated by a laser beam in Ni nitrate
solution, Ni and Ni oxide NPs are produced [142]. Another example is
the generation of diamond NPs by laser heating of a polycrystalline
graphite sheet in acetone solution [214].
NP generation by laser pyrolysis of gases is another effective
method which involves the use of a laser (typically a focused
continuous wave CO2 laser beam due to its favourable wavelength
at 10.6 mm for good absorption by most gases) to decompose a gas
mixture at high temperatures. The collected gas/fume/particle
mixture can contain NPs. For example, FeSi NPs of 1520 nm size
were produced by a CO2 laser pyrolysis of Fe(CO)5/SiH4 mixture in
Ar [114]. Fe(CO)5 dissociates at 250 8C. The NP size distribution was
found to be markedly narrower than the conventional thermal
process. Si NPs of 310 nm were produced by CO2 laser pyrolysis of
Fig. 22. TiO2 nano particles generated by continuous wave laser ablation in liquid [1].
a SiH4/He gas mixture [19]. A high production rate (250500 g/h)

laser pyrolysis of Si3N4, SiC and amorphous Si/N/C nanoparticles of
less than 30 nm diameters was achieved using CO2 laser
decomposition of a low cost organosilane (CH3)Si)2NH and
NH3 at different temperatures with over 93% of the collected
products being desired NPs [90]. Core-shell Fe2O3/organosilicon
NPs was produced by CO2 laser pyrolysis of Fe(CO)5/C2H4,
(NH3)3SiOCH3, Ar gas mixture [141].
NP generation by laser annealing is based on laser heating of
thin (a few nm) metal coatings on a substrate or a template. The
thin lm (a few nm thick) coating process generates an internal
stress. Laser energy delivers thermal energy to the atoms which
after gaining sufcient mobility will cause the lm to break into
spherical particles with minimum internal energy. The internal
dispersion/repulsion force stabilizes the nanoparticles achieving a
uniform distribution. For example a ns pulsed XeCl excimer laser at
308 nm wavelength and a uence of 100300 mJ/cm2 uence was
used to anneal Ag and Au thin lms deposited by pulsed laser
deposition on a SiO2 substrate to produce highly ordered,
monolayer Ag and Au nanoparticles of few tens of nanometers
[61]. Enhanced Raman scattering has been found. Wang et al. used
similar laser annealing technique (Here Ag coating was made by Ebeam evaporation and an KrF excimer laser with 248 nm
wavelength was used for the annealing) to produce Ag nanoparticles on a Si substrate followed by chemical etching to produce
deep holes in Si [213]. The lm thickness controls the particle sizes.
Thinner lm gives smaller particles. Also laser uence is important.
If the laser uence is too high (e.g. >400 mJ/cm2) larger and nonuniform particle sizes were resulted. If the laser uence is too low
(<180 mJ/cm2) NPs did not form. A template can be used to
precisely form the nanoparticles with uniform spacing and sizes
using laser annealing technique (or template dewetting). For
example, Co NPs were formed by laser annealing of Co thin lms
coated on Si wafer with 200 nm period nano inverted pyramid
nano-pits [135]. One particle per pit was formed at 850 8C with
15 nm lm thickness (Fig. 23). The advantage of the technique is
Fig. 23. Example of Co nanoparticles produced by laser annealing of Co thin lms

deposited on a 200 nm spaced hole-array. (a) With 8 nm Co coating thickness and
template G with silicon nitride coating; (b) with 15 nm Co coating thickness and
5 nm Co coating thickness [135].
the production of ordered NP arrays on a surface. The disadvantage

is the need for the preparation of the template.
The main process parameters inuencing the size and
composition of laser generated nanoparticles are the properties
of the applied laser radiation (intensity, pulse length, pulse
overlap, wavelength), the properties of the ablated material
(absorption coefcient, melting and evaporation temperature,
chemical properties) and the properties of the environment
(vacuum, gas atmosphere, liquid medium) [7,8]. Generally the
laser assisted particle generation in a gaseous environment has a
much higher efciency than in liquid medium, whereas smaller
particle sizes with less dispersion can be fabricated in a liquid
environment [8,48]. Barcikowski et al. observed a 10 times higher
efciency for femtosecond particle generation in gaseous environment compared to water. On the other hand in liquid environment
smaller particles showing less size dispersion can be generated [8].
Although femtosecond pulses allow a more efcient particle
generation than picosecond pulses, the latter allows a higher
productivity due to the higher mean laser power of picosecond
laser systems [7]. Furthermore, it was shown that productivity of
laser particle generation in liquid medium can be improved by
applying a liquid ow [7], whereas in gaseous environment
productivity can be increased by a pulse overlap [8]. The so called
airbrushing method combines the high efciency of particle
generation in gas medium with the potential for the generation of
small particles in liquid environment and allows the production of
small particle sizes at a high productivity [8].
3.2. Laser manufacture of nanotubes
Nanotubes have unusual properties. For example, carbon
nanotubes (CNT) have very high tensile strength (e.g. 60 GPa),
high electrical capacity (2000 times of copper), super hydrophobic
and anti-bacteria. As a result, nanotubes, particularly CNT have
been used widely for stain resistant textiles, transparent conductors to replace Indium Tin Oxide (ITO) in LCDs, solar cells,
optical limiting, hydrogen storage, composites, gas sensors,
conducting plastics, anti-bacteria coatings, nano-robots, CO2 ler,
nano-lasers, ultrafast oscillators, eld effect emitters, water proof
paper, and conducting adhesives.
Nanotube manufacture by lasers has been mainly focused on
carbon nanotube production by laser ablation. The rst report of
laser synthesis of CNTs was give by Guo et al. of Rice University,
USA in 1995 [43]. They used a frequency doubled Nd:YAG laser of
67 ns pulse width operating at defocused beam condition (6
7 mm diameter) to ablate a metal/graphite composite. The role of
the bi-metals (e.g. Ni/Pt, Co/Ni, Co/Pt, Co/Cu) is to act as effective
seeds to enable carbon diffusion into them at high temperatures (in
a 1200 8C furnace) after the graphite is vapourised by the laser.
Saturation of diffused carbon in the nano metal particles (also by
laser vapourisation) and subsequent cooling in the argon gas
environment (at 500 Torr pressure), allows the carbon to be
extruded in a tubular form. Both single walled and multiple walled
nano carbon tubes can be produced this way.
To improve beam absorption by the graphite composite, CO2
(10.6 mm wavelength) lasers in either pulsed or a continuous wave
mode can be used. Maser et al. was the rst to report the use of a
CO2 laser for the manufacture of CNTs under similar materials and
environmental conditions as the Nd:YAG laser ablation technique,
but with around 80% beam absorption [64,117]. With a 2 kW CO2
laser 0.2 g/h CNT production rate can be made. This is comparable
to other non-laser techniques for CNT manufacture.
To improve the production rate, streams of graphite microparticles and Co (2.5%), Ni particles (2.5%) were injected into the
1100C furnace for CO2 laser vapourisation. Single walled carbon
nano-tube with 2040% yield from 500 mg of soot in 10 min laser
radiation was achieved at 90 mg/kWh energy input [16].
Atmospheric condition production of CNTs by laser ablation has
been shown possible with the introduction of continuous N2 gas
ow to a heated furnace [77]. Highly ordered and directed growth
745
of carbon nanotubes on a substrate can be achieved by pulsed laser

physical vapour deposition of carbon vapour onto a substrate (e.g.
Si) with nano-sized metal powder coatings, e.g. Co, Fe, even to
grow along/across laser etched micro-groove tracks [183,230]. The
diameters of the CNTs are controlled by the nanoparticle sizes, and
the CNT bre length is controlled by the carbon vapour deposition
time. Aligned CNTs can also be made by pulsed laser deposition of
metallic lms (e.g. Fe, Co, Ni) on a substrate (e.g. Si) followed by
laser annealing/patterning to create nanoparticle catalysts. The
surface is then exposed to a carbon containing organic gas at a high
temperature (9501200 8C) to decompose the gas. The deposition
of the carbon from the gas on substrate surface containing the
metal particle catalyst forms aligned CNTs. Fig. 24 shows an
example of horizontally aligned CNTs produced in this way [38].
The carbon source is not limited to graphite solids. Carbon
containing gases, such as acetylene (C2H2) can be decomposed by
hot metal particles produced by laser ablation of a solid metal
target and the carbon can diffusion into the nano-particles e.g. Ni
325 nm in size. Multi-walled carbon nano-tubes can be produced
by precipitation of the saturated C from the metal nano particles
[69]. The basic mechanism of CNT production using laser chemical
vapour deposition LCVD is illustrated in Fig. 25.
Other carbon containing gases such as propane (C3H8) were also
used to produce carbon nano tubes by laser heating of nano metal
particles (goldpalladium) in this gas environment to produce
multi-walled carbon nano tubes of 550 nm diameter and up to
30 mm in length [82].
It is worth noting that as most CNT manufacture techniques
require metal nano particles as catalysts, metal particles are
imbedded in the carbon nano tubes produced. Furthermore, other
impurities exist, such as graphite particles. Post processing is
normally required to remove these impurities and metal particles,
by centrifugal separation, acid washing (to remove metal
particles), heating (to burn off some carbon particles) and
ultrasonic water washing processes. Wang et al. demonstrated a
catalyst and template free CNT manufacturing technique by laser
ablation of a crystalline graphite target in water [216]. However,
Fig. 24. SEM images of an aligned nanotube bundle grown by pyrolysis of 2-amino4,6-dichloro-s-triazine over a laser-etched (5 mJ per shot) cobalt substrate. (a) Low
magnication of an individual bundle exhibiting aligned nanotubes of uniform
length (around 30 mm), scale bar: 3 mm. (b) Higher magnication showing that the
tubes are of uniform diameter (around 3050 nm), scale bar: 1 mm [38].
746
Fig. 25. Illustration of the mechanism of carbon nano-tube production by laser

ablation of Ni target in a C2H2 gas environment [69].
the uptake and further development of this method has been

limited.
In addition to NCTs, other nanotube materials such as boron
nitride nanotubes (wide band gap semiconductors with superior
chemical inertness at high temperature, grown by laser ablation
[127], BCN nanotubes (by laser ablation [235]), TiO2 nanotubes
(grown on Ti substrate by laser micro-machining and standard
anodization for photo-catalytic applications [212]), leadzirconia
nanotubes (PbZrO3, by pulsed laser vapour deposition on an
anodized aluminium oxide template [163]) have been manufactured successfully.
3.3. Laser manufacture of nanowires and nanorods
Nanowires have specic anisotropic physical and chemical
properties that are signicantly different from their bulk materials.
Laser manufactured nanowires and nanorods are increasingly used
in the microelectronics (e.g. transistors), photonics (e.g. LEDs,
waveguides, nanowire lasers), instrumentation (e.g. gas sensors,
bio-sensors) and energy industries (e.g. solar cells). Various
nanowires and nanorods of semiconductors (e.g. Si, GaA), metal
oxides (e.g. ZnO, SnO2, MgO, CdO, CuO), and metals (e.g. Ag, Au)
have been manufactured by pulsed laser ablation (PLA), pulsed
laser deposition (PLD), laser interference lithography, laser
annealing and laser assisted molecular beam epitaxy (Laser
MBE) techniques. Most of these are based on bottom-up synthesis.
Among the materials, ZnO dominates the nanowire manufacture
research due to its great potentials for applications in the photonic
industry.
Pulsed laser ablation in vacuum or a controlled atmosphere is a
common and established method for nanowire manufacture.
Morales and Lieber were among the rst to report the use of laser
ablation technique to produce nano-scale metallic nanoparticle
seeds for the growth of Si and Ge nanowires, in 1998 [124]. They
are based on vapourliquidsolid (VLS) mechanism (i.e. a vapour
phase material diffuses into the small seed particles to form liquid
catalysts, which allow nanowires to grow from them until they are
cooled down to a solid state. The catalyst particle diameter was,
however, limited to >0.1 mm by conventional VLS). The PLA
approach overcame the limitations in nanowire diameter, and 6
20 nm diameter Si and 39 nm diameter Ge nanowires were
produced [124]. For example, a Si0.9Fe0.1 target was ablated with a
frequency doubled Nd:YAG laser to produce vapour and liquid
phase Si and Fe nano clusters and they were kept in a 1200 8C
environment. The depleted Si then diffuses into Fe and precipitate
upon saturation to grow nanowires until solidication takes place.
Wang et al. at City University, Hong Kong, in the same year,
reported the use of a similar technique but avoided the use of a
metallic nano particle catalyst. They used a mixed SiO2 and Si
powders that were ablated by a pulsed laser. With this method the
yield of nanowire was found to be over 30 times greater than that
with the use of a SixFe system [215]. Fig. 26 shows an example of Si
Fig. 26. Si nanowires produced by PLA technique, (a) bright eld TEM and (b) dark
eld TEM images [215].
nanowires produced by Wang et al. using PLA. Since then several

different materials have investigated. For example, crystalline
boron nanowires (a high melting point, high hardness material)
were produced by pulsed laser ablating a boron rod doped with Ni/
Co powders placed in a furnace at 1250 8C [234]. Laser ablation of
solid targets in liquid is another way of producing nanowires. This
is similar to nanoparticle generation in liquids by laser ablation.
The difference is that a linearly polarized laser (instead of circular
polarized beam) is used and a chemical capping agent is used to
control the growth direction to form nanowires. The advantage is
the avoidance of the use of a catalyst seed particles, thus better
material purity. Bian et al. showed the use of a linearly polarized
femto second laser ablation of a silver target in deionized water
solution (with the addition of capping agents: sodium citrate and
polyvinylpyrrolidone) to produce silver nanowires [12]. Plasmon
plasmon interactions were identied as the mechanism for the
formation of nanowires by joining nanoparticles. When the laser
beam was circularly polarized only nanoparticles are produced
[12]. Nickel, indium and lead nanowires with 58 nm diameters
were produced by bre laser ablation of metal targets in a liquid
helium environment [37]. Jia et al. showed that the ZnSe nanowire
length by p polarized femtosecond laser ablation of ZnSe wafer in
water is linearly proportional to the number of laser pulses [63].
Pulsed laser deposition, commonly known as PLD, is the most
widely reported and applied laser-based nanowire production
technique on a substrate. It is based on the laser ablation of a target
material (the nanowire formation material) and depositing the
laser generated target material vapour/plasma onto a substrate
that has a layer of nano-particles (e.g. Au) as a catalyst or seed
material. The laser ablated target material vapour/plasma is
deposited on the heated target material coated with seed
nanoparticles that enable the growth of nanowires from them.
The nanowire size and distribution are controlled by the laser
ablation processing parameters, such as laser uence, seeding
nanoparticle size and gas pressure. Highly directional nanowire
arrays can be produced this way. When the substrate surface is
parallel to the target surface, the nanowires usually grow
perpendicular to the substrate surface. When the substrate angle
changes from parallel to other angles, nanowires can grow in a
different orientation or to form an arc shape [156]. A large variety
of materials have been successfully used for nanowire growth by
the PLD technique. These include, for example, ZnO with and
Fig. 27. An SEM image of GaN nanowires fabricated by KrF excimer laser PLD at a
pressure of 106 Torr [132].
without the use of a catalyst [42,54,164,199], SnO2 [99], GaA [237],

MgO [113,229] and DNA [33].
Fig. 27 shows an example of GaN nano-wires synthesized by
248 nm/30 ns KrF excimer laser ablation of a solid GaN target in a
vacuum chamber purged with N2 gas kept at 30 mTorr, deposited
on a 5 nm gold coated sapphire substrate held at 700 8C. Upon
heating, the gold lm breaks into a layer of nanoparticles that act as
the seed material. Single crystal GaN nanowires were grown
uniformly in an area of 2 cm2 at a diameter of 20 nm, length of
5 mm and lattice spacing of 2.8 A [130]. By femtosecond laser
patterning of gold coated substrates, selective growth of the
nanowires can be realised on un-patterned areas [131,132].
Laser interference lithography has been used to combine with
metal assisted etching for nanowire/nanorod manufacture on a
substrate. The method uses standard laser interference lithography
with two exposures at 908 on a photoresist spin coated substrate
(e.g. Si), followed by a thin metal (e.g. Au) lm coating, lifting-off of
the photoresist posts and their metal caps, leaving a metal lm
with a pattern of holes and etching of the sample in a HF/H2O2
solution, Upon immersion, the substrate in direct contact with the
metal is dissolved. Consequently, the metal lm sinks into the
substrate, leaving nanowires at the position of the holes in the
metal lm. Fig. 28 shows an example of Si nanowires of around
65 nm diameter produced using this method [17]. An advantage of
the technique is that the nanowire diameter and length are well
controlled and uniform.
To avoid the use of a catalyst, a number of variations of the PLD
were developed for nanowire growth on a substrate. These include
laser induced forward transfer (LIFT), laser assisted molecular
beam epitaxy (MBE) and use of self-organised nano-polystyrene
(PS) spheres as a template in PLD. In the LIFT technique, PLD is used
Fig. 28. (a) SEM micrograph of silicon nanowires produced using laser interference
lithography combined with metal assisted etching, with a periodicity of p = 244 nm,
a diameter d = 66 nm. The overlay presents the size distribution. (b) and (c) show
the same sample after longer etching time in top view and tilted view, respectively.
Note that the wires in (c) have a length of about 1 mm, corresponding to an aspect
ratio of 1:15. The scale bars are 500 nm [17].
747
to deposit a nano-structured lm of the target material on a glass

substrate at relatively higher gas pressured compared to standard
PLD. This nanostructured lm is then transferred to a substrate
(same material as the target material) by LIFT. Nanowire growth
can be realised without an additional catalyst. For silicon nanowire
growth by LIFT technique, SiO2 nanoparticles formed in PLD were
considered as the nuclei for the nanowire growth [148]. In laser
MBE technique, a nanostructured template such as anodized
aluminium oxide (AAO) is used and laser MBE is used to deposit
target materials (e.g. a metal) onto the AAO surface. Subsequent
elective etching will remove AAO leaving deposited materials as
nanorods or nanowires. For example, nickel nanowires have been
grown using this technique on an aluminium substrate as a surface
for enhanced Raman scattering [233]. In PLD on a mono-layer PS
coated substrate (e.g. Si), PLD deposited target material can grow
on the nano PS particle array template. The subsequent annealing
in a furnace removes the PS and allows highly ordered nanowire
clusters to be adhered to the substrate. Iron oxide nano-wire
columns have been gown on silicon using this method for
applications in eld-emission, superhydrophilicity and photocatalysis [88]. Also nanosphere lithography (NSL) has been combined
with PLD for the deposition of ordered ZnO nanowires on a
sapphire substrate [144].
4. Laser nano-manufacture of 3D structures and devices
To build nano-scale 3D devices and structures, a number of
laser based techniques have been developed including two-photon
polymerisation (TPP), nano-welding and nano-forming. Among
these techniques the TPP technique has been the most widely used.
4.1. Two-photon polymerisation (TPP)
TPP is different from UV photo-polymerisation in stereolithography where the absorption of the laser or UV light is on the
surface of the liquid (although there is a penetration depth), thus to
build up 3D structures, a new layer of liquid needs to be placed for
each layer for standard stereo-lithography. Therefore the layer
thickness in UV light stereo-lithography is limited by the uid layer
thickness which is difcult to reach nano-scale resolution due to
surface tension.
TPP is based on the non-linear effect (reaction rate is
proportional to the square of the radiating light intensity instead
of a linear relationship as in single-photon absorption) of certain
optically transparent polymer or solgel materials (e.g. curable by
a UV light). These materials can absorb two photons simultaneously to allow the liquid polymer or solgel to be solidied at the
beam focus point once the laser uence is above a certain
threshold. Therefore an infrared laser beam, typically, an 800 nm
wavelength femtosecond laser, can transmit through a liquid layer
and scan a pattern inside the transparent polymer or solgel to
solidify the material at the laser beam focus. By controlling the
laser uence, scanning speed and multiple layer scan paths, 3D
features with nano-scale resolution can be built. The reason for the
resolution to be achieved beyond the diffraction limit of the lasers
is because the solidication of the liquid is dependent on the laser
uence which can be set to allow only part (the tip) of a Gaussian
beam to be above the threshold.
For two photon absorption (TPA) to occur, the laser beam
intensity needs to be very high (e.g. >1 TW/cm2). The two photons
need to arrive at very short period of time between each other
(1015 s for simultaneous absorption which involves the excitation
of the polymer molecule to a virtual intermediate energy state
which has a very short life time before the arrival of the second
photon to cause TPA). Therefore most TPP processes are based on
femto-second lasers. A typical process setup for the TPP micro/
nano fabrication is shown in Fig. 29.
The TPA theory was rst proposed in 1931 by Goppert-Mayer
[36] and experimentally demonstrated in 1961 by Kaiser and
Garret [67]. The rst report to demonstrate TPP for 3D
748
LTPP
0s
11=2
s 22 N02 nt L
@
1A
2zR
C
C ln
Fig. 29. A typical process set-up for TPP micro/nano fabrication [155].
microstructure fabrication was given by Maruo et al. of Osaka

University in 1997 using a femtosecond laser [116], although the
concept of using TPP for 3D data storage was proposed in 1989
using two beams [139]. The resolution of TPP was further improved
in the following years and the rst nano-scale (120 nm feature
size) TPP of 3D structures was demonstrated by Kawata et al. of
Osaka University in 2001 with the production of micro-bulls of
10 mm long and 7 mm high [72]. Laser scanning of only the surface
prole of the micro-bull followed by UV curing reduced the
fabrication time from 180 min to 13 min compared with the full
raster scan [72,73,182]. An example of the micro-bulls produced by
the Osaka group by the two different laser scanning methods is
shown in Fig. 30.
The highest resolution of 3D structures has been experimentally achieved in a non-photosensitized resist. However, the widest
processing window is observed in photo-sensitized resists [108].
The heat generated at the focal point of the laser beam was found
to facilitate the TPP process by promoting polymer molecule cross
linkage and electron avalanche ionization [108]. Over the last few
years, Stimulated Emission Depletion (STED), originally used for
microscopy, technique has been adopted for high resolution (e.g. 4
0 nm) lithograph [87]. It is worth noting that, unlike that in
standard stereo-lithography, the TPP technique does not normally
require support structures for overhang features as the liquid
would have enough viscosity to support the structures. The
solidication feature width, dTPP, and depth, LTPP, in TPP processes
can be found from [155]:
s

s 2 N02 nt L
dTPP r 0 ln
(5)
C
Fig. 30. Micro-bulls produced by the TPP method. (a) By raster scanning mode (in
each layer, every point of the geometry on the layer is scanned in straight lines), (b)
by vector mode (only the perimeter or prole of the geometry is scanned) [73].
r0
r0 rth
(6)
(7)
where r0 is laser focal radius; s2 is the effective two-photon cross

section; N0 is the photon ux; n is the number of pulses; (L is pulse
duration; zR is Rayleigh length of the laser; (0 is the initial density of
the polymer, and (th is the threshold density of the polymer.
The materials used for the TPP nano-manufacturing method are
mainly UV curable liquid resins normally used for single photon UV
light stereo-lithography, as well as photoresists and solgels. The
liquid resin or solgel can be mixed with ne metallic or ceramic
powders or metal ion containing liquids (e.g. AgNO3, HAuCl4) to
allow the fabrication of metallic or ceramic 3D structures.
Examples of metallic and ceramic 3D micro/nano structures by
the TPP techniques include silver 3D structures by TPP of Agparticle images followed by the reduction of AgClO4 within a sol
gel matrix [223], production of gold nanoparticle gratings using
TPP of gold ions inside a polyvinyl alcohol (PVA) lm [68],
production of 3D photonic crystals containing TiO2 nanoparticles
by TPP of titanium ion doped urethane acrylate resins [28] and
production of conductive silver and gold 3D micro/nano parts by
TPP of silver nitrate and aqueous solution of tetrachloroauric acid
[181]. Metallic 3D micro/nano parts have also been produced
through electroless plating of the TPP polymer parts [32].
Parallel production of periodic 3D micro/nano structures has
been realised by the use of micro-lens arrays combined with the
TPP technique [32]. A review of micro/nano 3D structure
manufacturing by TPP was given by Lee et al. [84].
4.2. Laser nano-assembly
Assembly of nano-materials for micro/nano product manufacture can be carried out in a number of ways including joining,
welding, deposition, and laser holographic radiation. Optical
tweezers can be applied for the manipulation and positioning of
micro- and nano-components in a liquid environment [6,25,60,66].
Unfortunately, a simple scaling down of macro and micro laser beam
joining techniques is not always successful, mainly, because the
achievable resolution is limited by the optical wavelength of the
applied laser radiation. Furthermore, nano-systems in many cases
behave quite differently compared to their macroscopic counterparts. The optical penetration depth may be on the scale of the
micro-system itself; near-eld effects can lead to eld enhancement
and interference in the proximity of small nanoparticles [129,219].
The high ratio of surface to bulk nano-materials may signicantly
inuence heat conduction and phase transition processes [81] and
surface tension effects can be more pronounced.
Nano-welding technique was applied for the joining of colloid
nanoparticles, nanowires and nanotubes. Gold nanoparticles were
irradiated with ultrashort pico- and femtosecond laser pulses.
Hereby a welding between the particles could be induced.
Wilson et al. demonstrated a method for joining nanoparticles,
nanorods and nanotubes to electrodes by laser induced avalanche
concentration [221]. The high absorption efciency of the nanomaterials generates heat and elevates the temperature of the
surrounding liquid. This produces a localized temperature gradient
which causes a convective ow to form in the solution. There are
also multiple optical forces that have a much shorter range. The
gradient force, the driving force of optical tweezers, acts to pull the
particle into the region of highest optical intensity of the Gaussian
beam. There is also the scattering force, which pushes the particle
in the direction of light propagation. Nano-materials within a few
micrometer ranges from the laser beam spot can be drawn to the
laser beam and fused to a substrate [221]. They have demonstrated
successful joining of CNTs and VO2 nanorods to electrodes using a
25 mW 633 nm HeNe laser. Tanaka et al. showed that when a
749
have negative electrical and magnetic permeabilities. They are

composed of metallic sub-wavelength building blocks (photonic
atoms) that are densely packed on a transparent host [97]. A
photonic crystal (PC) is a dielectric medium in which periodic
microstructures are formed using high refractive index contrast
materials [65,228]. Using TPP direct laser writing (DLW) of
polymeric templates and subsequent metal coating via silver
chemical vapour deposition (CVD) or silver shadow evaporation,
Rill et al. fabricated various photonic metamaterials, e.g. planar
magnetic metamaterial (Fig. 32) and negative-index bianisotropic
photonic metamaterial [149]. Besides, 3D gold-helix photonic
metamaterials [34], three dimensional bi-chiral helical photonic
crystals [184] and 3D invisibility-cloaking structures [30] have also
been produced by employing the TPP DLW technology. Radially
polarized ultrafast laser beams were used in the fabrication of
three-dimensional photonic crystals with the TPP technique in
organicinorganic hybrid materials [62].
5.2. Data storage
Fig. 31. Electrical current assisted laser welding of CNTs; the inset shows the detail
of the joining [35].
linearly polarized Nd:YAG laser beam is used to radiate Ag

nanoparticles in a solution, an arrayed nanoparticle structure can
be formed along the laser polarization due to surface Plasmon
resonance effect [178]. Kuznetsov et al. demonstrated that 2D and
3D structures can be assembled from nanoparticles by laser
induced forward transfer (LIFT) involving a femtosecond laser
melting and ejecting a molten droplet of a thin metal lm coated on
a glass onto a substrate placed closely [80]. Gong et al. at Tsinghua
University, China reported a method of joining carbon nanotubes
by electrical current (104 A/cm) assisted CO2 laser welding [35].
An example of such welded CNTs is shown in Fig. 31.
In micro- and nano-assembly, highest accuracy and resolution
in terms of positioning of the functional components among each
other are necessary. However, due to the increasing complexity of
the micro-systems these accuracy requirements can hardly be
fullled during the whole production chain by means of
conventional methods. The manufacturing strategy involves
assembly of micro-components with relatively larger tolerances
using conventional methods. In a second step the critical parts of
the system are aligned to each other with the required accuracy
using a laser beam. Laser based adjustment techniques have been
used in numerous micro/nano assembly applications as they allow
an easily automatable and contact free-positioning. The temperature gradient mechanism (TGM) in combination with the upsetting
mechanism allows both an angular and transversal micro
positioning [153]. Yet, these techniques have various disadvantages restricting their applicability in a nano-manufacturing
process chain: long cooling cycles of up to 30 s, thermally induced
residual stresses in the actuator after the adjustment procedure,
danger of thermal damage other to components close to the
actuator and restricted applicability for brittle materials [153].
In order to overcome these restrictions, a nano-adjustment
approach, using ultrashort lasers and allowing high alignment
accuracies without undesired thermal effects, called micro
shockwave bending has been developed [9,10,153]. When focusing
an ultrashort laser pulse on a material surface the energy is
absorbed by the free and valence electrons and the material is
transformed in a state of plasma. The rapidly expanding plasma
induces shockwaves leading to a deformation of the substrate if the
plasma pressure exceeds the bulk materials yield stress.
A continuing trend in information storage is the desire for

greater storage capacity within a smaller space. In the past 50
years, the disk drive price per Mbytes has dropped by around
2 million times while its recording density has increased by
100 million times [55]. All of these are attributed to the
development of phase change materials [224] and advanced
precision engineering techniques, which are able to fabricate
functional micro/nanostructures at a lower cost and higher
resolution. As a novel processing means, laser nanofabrication
provides unique advantages over other tools, especially when
combined with other advanced processing methods, playing an
important role in the realisation of high density data storage.
Leen et al. [85] demonstrated the all-optical recording of deeply
subwavelength data bits in phase change material Ge2Sb2Te5 using
an NSOM probe that utilized a C-aperture fabricated through
membrane focused ion beam milling. Using this aperture together
with a voltage pulsed telecom distributed feedback laser
(l = 980 nm) as the laser source, a minimum physical bit size of
53.5 nm 50.2 nm was achieved, indicating a data density of
223 Gbit/in2. Miura et al. [122] reported the recording, readout,
5. Applications of laser manufactured nano-structures and

materials
5.1. Metamaterials and photonic crystals
Metamaterials are man-made materials with negative refractive indexes, commonly known as left-handed materials as they
Fig. 32. SEM micrographs of metamaterial structures by laser 2PP direct writing and
metal vapour deposition. (a) The SiO2 layer between the SU-8 template and the
silver coating. (b) A 3D structure composed of bars. Note that the silver coating
covers the bars all around [149].
750
and erasure of a three-dimensional optical memory using the

valence-state change of samarium ions to represent a bit. A
photoreduction bit of 200 nm diameter can be recorded with a
femtosecond laser. A memory capacity of 1 Tbit could be achieved
with dimensions of 10 mm 10 mm 1 mm with this method.
Metallic nanoparticles are highly suitable for chemical sensing.

Porous particles allow for a diffusion of analyte molecules and
since the metallic cores are conductive they provide a means of
signal transduction [157]. Because of their large surface area, noble
metals such as platinum are utilized as catalysts for numerous
chemical reactions [157].
5.3. Biomedical applications

5.5. Functional surfaces
The applications of laser nano-manufacturing technologies in
the biomedical eld include the fabrication of biochips (e.g.,
bioelectronicchips and biouidic chips), microneedles for transdermal drug delivery, ossicular replacement prostheses, tissue
engineering scaffolds [171].
Venkatakrishnan et al. [198] reported a simple, fast, and
repeatable method for fabricating nano-uidic channels based on
TPP. Here uidic channels up to 110 nm in width between
polymerised parallel ribs were produced in SU-8. Applications of
uidic channels include protein separation and DNA sequencing,
drug delivery, biomolecular sorting, and single molecule detection
[60]. Nicolau et al. [133] proposed a method for protein immobilisation on micro/nanostructures fabricated via laser ablation of a thin
metal layer deposited on a transparent polymer, exhibiting 100 nmrange structures. It has been found that these micro/nanostructured
surfaces translate into a 310 fold amplication of protein
adsorption, as compared to at, chemically homogenous polymeric
surfaces, opening new opportunities for more sensitive protein
arrays, and fundamental studies regarding the interaction of
proteins with nanostructures. Rebollar et al. [145] found the
presence of nanostructures produced by an excimer laser on the
substrates were able to guide cell alignment along denite
directions. This alignment was only observed when the periodicity
is above a critical value that is cell-type specic.
3D microstructured medical devices, including microneedles and
tissue engineering scaffolds, were fabricated by TPP of Ormocer
organic-inorganic hybrid materials [27]. Lu and Chen [101] reported
a nanosphere lithography technology for biodegradable polymers,
by which critical dimension of about 100 nm can be realised.
Although most of current design/fabrication of scaffolds occurs
at scales larger than 100 nm [53,171,231], future development
should strive to incorporate nanoscale features, mimicking the
native extracellular environment. Integration of micrometer and
nanoscale features into designed scaffolds could improve both
mechanical properties through toughening mechanisms and tissue
regeneration through improved control of cell adhesion.
Laser generated polymer nanoparticles can be used as drug
delivery devices to effectively bring the drug to a target site with
minimized side effects [166].
5.4. Sensors
Sensor development is another important application of laser
nano-manufacturing technologies, especially when considering
that sensors can be an essential part to other elds, e.g. biomedical.
The ability to integrate micro-channels for uid transport with
optical elements is attractive for the development of compact and
portable chip-based sensors. By femtosecond laser direct writing
followed by wet chemical etching, micro-uidic channels coupled
with optical waveguides towards an integrated sensing device for
molecular detection were demonstrated [5]. Using TPP in the
organic-inorganic hybrid material ORMOCER, Woggon et al.
fabricated surface gratings with 400 nm periodicity and 40 nm
height modulations, which can be used as an integrating
distributed feedback (DFB) laser [222]. This laser can be integrated
with sensing schemes as a lab-on-a-chip system, so the laser based
sensing schemes may no longer require external laser sources and
the alignment processes connected with them.
Single-walled carbon nanotubes (SWCNTs) with a diameter of
1.2 nm were prepared by pulsed laser ablation (PLA) on an Al2O3
substrate with Pt-electrodes to make a gas sensor, which showed
high sensitivity and rapid response to NOx gas [191].
The surface properties of materials or components, e.g. optical

properties, biomedical properties, wettability and tribological
properties can be dramatically inuenced by the surface structures
and morphologies, particularly at the micro and nano scales. Thus,
various methods have been used for surface modication, among
which laser technology has been proved to be an enabling tool.
Researchers at University of Rochester, USA [201210] transformed highly reective metals (e.g., Au, Ag, Pt, Ti, Cu, Al, etc.) to
either totally absorptive or reecting only a certain colour of light,
creating the so-called black and coloured metals by laser surface
nano-texturing. This technique essentially provides a controllable
modication of optical properties of metals from UV to terahertz,
promising various applications in photonics, plasmonics, optoelectronics, stealth technology, thermal radiation sources, solar energy
absorbers, radiative heat transfer devices, infrared sensing, thermophotovoltaics, biooptical devices, and airborne/spaceborne devices.
Vorobyev et al. [208] applied femtosecond laser blackening
technique directly to a tungsten incandescent lamp lament. They
found that the tungsten lamp was brightened and its emission
efciency was enhanced to approach 100%, which is consistent
with Kirchhoffs law that the emittance of a surface equals its
absorptance in thermal equilibrium [2]. The femtosecond laser
blackening technique was used to modify the surface wetting
properties, inducing liquid running uphill against gravity at an
unprecedented speed of 1 cm/s [209]. By femtosecond laser
formation of 3300 nm papilla structures on poly-dimethylsiloxane (PDMS) superhydrophobicity with a contact angle higher than
1708 as well as sliding angle less than 38 were demonstrated [232].
Added nanoparticles can specically alter the wetting properties of
a surface and therefore lead to so-called self-cleaning effects well
known from the lotus plants [138].
In paints and lacquers, ceramic nanoparticles can be added to
increase the scratch and corrosion resistances and therefore the
durability of the coatings [151]. Many sanitary products like
sunscreens or deodorants contain nanosize particles to increase
the stability and performance of these lotions and creams. Because of
their strong chemical and biological reactivity, silver nanoparticles
can be used as antibacterial coatings on virtually all surfaces from
computer keyboards to medical implants or industrial pipelines
[7,83].
6. Challenges and opportunities in laser nano-manufacturing

6.1. Challenges in laser manufacture of surface nano-structures
Laser writing of surface nano-patterns although having great
advantages in cost and operation convenience (in air, instead of
vacuum) compared with the well established focused ion beam
and electron beam techniques, is still in the pre-market state,
largely due to the lack of complete systems incorporating
manipulation, sensing (e.g. nano-imaging) and control. The
electronic industry still aims at the use of EUV technique to
enable far eld super-resolution direct writing of nano-patters for
the next generation integrated circuits. The key challenges for laser
manufacturing of surface nano-structures include:

Better resolution (<10 nm) and tolerance (<1 nm)

Higher processing speed (>0.5 mm/s)
Greater operating distance (>1 mm)
Greater depth of writing (>400 nm)
Larger area (at least 4 in. wafer size)

Higher throughput (matching other techniques)
Integrated with a nano-imaging system
Integrated with a multiple axis positioning system with distance
feedback control
Better surface nish and avoidance of debris
Durable functional surfaces with nano-features

Researchers at Tsinghua University, China demonstrated

durable functional nano-porous surfaces using conventional laser
cladding technique to generate a binary solid solution material
coating on a metallic substrate followed by chemical etching off
one of the more active elements [26,40]. With such an approach,
large area nano-porous surfaces can be produced very economically and the pore sizes can be controlled by the etching and laser
remelting processes. Laser assisted nano-imprinting (LAN) is
another emerging technology that has fund applications in large
area parallel nano-patterning.
An opportunity for laser nano-patterning technique is the
writing of nano-patterns inside a transparent material. Such a
capability is unique to the lasers. Writing of bre Bragg gratings
and micro-uidic channels are already widely applied in industry.
These are mature technologies for micro-scale fabrications. To
enable nano-scale fabrication inside a transparent material by
lasers, near eld techniques are difcult to apply. Therefore,
opportunities and challenges exist to develop far-eld laser superresolution techniques for nanofabrication inside a transparent
material.
6.2. Challenges in laser manufacture of nano-materials
Laser based manufacture of nano-materials has shown advantages in size distribution, material property, geometry, yield and
purity. In particular, laser deposition techniques can allow the
generation and growth of nano-materials at a particular location of
a substrate, making it very exible for device manufacture. The key
challenges in laser manufacture of nano-materials are:
More precise size control (including diameter, length and size
distribution, to within 5 nm)
Higher production rate (>100 g/h)
Lower cost (<$20/g)
Novel material properties
6.3. Challenges in laser manufacture of 3D nano-structures

Laser manufacture of 3D nano-structures is dominated by the
bottom up approach through additive layered manufacture
based on the TPP method. They are reliable and mature, and are
ready for commercial applications. Nano-joining and assembly are
in very early stages of development. Challenges include:
Creating 3D nano-structures of greater range of functional
materials such as metals with good surface nishes (Ra < 5 nm).
Assembly of micro/nano structures of same and different
materials to a higher degree of accuracy that requires nanoscale beam size, beyond the laser diffraction limit.
Material thickness effect, especially if the materials are in
micrometer scales could be an important factor to consider. The
thermal energy by the laser beam may affect the material
geometry and integrity for very small and thin materials as in
micro-electro-mechanical systems (MEMs). Xia and Chou [225]
showed using the principle of self-perfection by liquefaction
(SPEL), an excimer laser could be used for polishing nano-surface
structures reducing their roughness. Laser nano-welding as a new
technique is still in the initial stages and requires further
investigation [41]. Suitable nano-joining technologies are necessary for future nano-manufacturing process chains.
751
6.4. Scientic challenges in laser nano-manufacturing

The greatest dream in laser nano-fabrication is to achieve
diffraction-free far-eld super-resolution for direct writing. A
signicant breakthrough in photonic and physical science is
needed to realise this dream.
The size effect is another important aspect to investigate as
many practical engineering materials have grain sizes in micrometres. Laser nano-patterning will encounter materials grain
uniformity and surface roughness effects. Fundamental studies are
needed to understand how material grain structures affect laser
nano-surface structuring. How would laser radiation affect the
nano-material properties and structures is still a scientic
challenge and further understanding would open opportunities
such as laser processing and modication of functional nanomaterials.
Modelling of laser beam interactions with different media in
nano-scale is a very challenging task, particularly when multiple
phase and multi-scale problems are encountered. Molecular
dynamic modelling and nite difference in time domain (FDTD)
modelling are particularly suitable for micro/nano scale materials
and would be seen to have their increasing applications in
understanding the material behaviours in laser nano-manufacturing. Wang et al. reviewed the theories (e.g. Mie theory, extended
Mie theory, multiple multi-pole) and modelling techniques
including FDTD, nite element and nite integral technique
(FIT) in near eld laser nano-manufacturing [220].
In laser manufacturing of nano-materials, safety is an important
issue. Understanding the hazards of laser ablated nano-materials
and safe handling these materials are challenging tasks that would
require multi-disciplinary research.
7. Conclusion
Laser manufacturing of surface nano-structures is still in the
basic research phase. While the near eld methods can provide
very high resolutions (20100 nm), they are inconvenient to
implement in practice as the optics need to be very close (20 nm
1 mm) to the target material. The far eld techniques have greater
promises if the resolution can be consistently improved comparable to that of electron beams or focused ion beams. A great
advantage of laser fabrication techniques lies in their capability for
parallel writing of periodic patterns. With, for example, particle
lens arrays or micro-lens arrays, millions of identical nanopatterns can be produced simultaneously. A unique opportunity
for laser nano-patterning technique is the capability of writing
nano-patterns and 3D structures inside a transparent material,
which cannot be realised by an E-beam or focused ion beams.
Laser based manufacture of nano-materials has shown advantages in narrow size distribution, excellent material property, yield
and purity. In particular, laser deposition techniques can allow the
generation and growth of nano-materials at a particular location of
a substrate, making them very exible for device manufacture.
Laser ablation in liquid for nanoparticle and nanowire manufacture
is a promising technology that may lead to wide commercial
applications.
Laser manufacture of 3D nano-structures is dominated by the
TPP method. This unique additive manufacturing method inside a
liquid volume is enabled by femto-second pulsed lasers. It is
reliable and mature, and ready for commercial applications.
The commercial applications of laser nano-manufacturing are
growing, particularly in the photonic, electronic, instrumentation
and biomedical industries. The development of fully integrated
systems (laser, optics, manipulation, software, workpiece handling, in-process sensing and control) will boost the practical
applications of laser nano-manufacturing.
Laser nano-manufacturing is a promising and rapidly growing
eld and is relatively new. Many opportunities for research and
development exist. Multi-disciplinary research for laser nano-
752
manufacturing would spark new scientic discoveries and

applications.
Acknowledgements
The authors gratefully acknowledge the support and advices
given by the colleagues in the CIRP (International Academy of
Production Engineering) STC-E (Scientic Technical Committee
Electro-physical and Chemical Processes) for the preparation of
this manuscript for the Keynote presentation at the 61st CIRP
Generally Assembly, Budapest, Hungary 2127 August 2011. The
authors would like to thank, in particular, the following colleagues:
Professor Bert Lauwers (CIRP STC-E Chairman), Professor Masanori
Kunieda (CIRP Fellow), Mr. David Aspinwall (CIRP Fellow), Dr.
Annop Samant, Ms. Heather Daluz-Vieria and Mr. Peixun Fan for
their assistances, technical inputs and advices in preparing this
manuscript.
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CIRP Annals - Manufacturing Technology 60 (2011) 735755

Contents lists available at ScienceDirect

CIRP Annals - Manufacturing Technology

Laser nano-manufacturing State of the art and challenges

2. Laser fabrication of surface nano-structures

The need for nano-manufacturing is dictated not only by the

2.1. Diffraction limits to laser beams

Laser materials processing has been successfully applied in

where d is the minimum beam spot diameter, l is the laser

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

Fig. 1. Illustration of the scope of the paper.

in light intensity. Strong absorption of the UV light by air molecules

Fig. 2. Nano-lines created by the coupled fs laser/NSOM SNP technique at different

NSOM tip. For the photo-resist exposure process, exposure energy

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

Fig. 4. Illustration of laser trapped micro-sphere nano-patterning. (a) Experimental

transparent sphere (polystyrene) was held by a focused continuous

interaction with materials, the laser interaction time (1015

2.5. Femtosecond (fs) laser direct writing

Fig. 5. Schematic energy diagram of a TPA process [84] (reproduced with

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

Fig. 6. Nanofeatures developed in (a) amorphous silica [57] (reproduced with

OPA. As a consequence, the volume involved in beam-material

Downscaling of the diameter, D, and the focal length, f, of a lens

This interference pattern is then recorded on the exposed

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

Fig. 7. Large area micro/nanostructures fabricated by laser MLA [92].

Examples include nano-cone arrays on NiCr alloy (Fig. 8) and Au/

Another way of increasing the resolution is by reducing the

Fig. 8. A nano-cone structure fabricated by laser interference lithography (height

Fig. 9. Photoresist patterns created by immersion laser interference lithography. (a)

Fig. 12. Illustration of a typical TIR optical conguration to generated evanescent

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

was irradiated with split 405 nm wavelength laser beams. Periodic

resolution is expected. The wavelength of the exciting laser, l(i,j),

where a is the metallic mask periodic nanostructure period, ea and

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

to form a mono-layer. Due to laser light intensity enhancement

Fig. 16 shows an example of using the CPLA technique for the

where n is the refractive index of the sphere and r is the radius of

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

off a monolayer micro-particle array self-assembled on a at glass

synthetic single-crystal CVD diamond have been made with

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

The intensity of the scattered waves depends on the laser

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

spectra due to the surface plasmon resonance (SPR) effect. It gives

a SiH4/He gas mixture [19]. A high production rate (250500 g/h)

Fig. 23. Example of Co nanoparticles produced by laser annealing of Co thin lms

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

the production of ordered NP arrays on a surface. The disadvantage

of carbon nanotubes on a substrate can be achieved by pulsed laser

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

Fig. 25. Illustration of the mechanism of carbon nano-tube production by laser

the uptake and further development of this method has been

nanowires produced by Wang et al. using PLA. Since then several

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

without the use of a catalyst [42,54,164,199], SnO2 [99], GaA [237],

to deposit a nano-structured lm of the target material on a glass

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755

microstructure fabrication was given by Maruo et al. of Osaka

where r0 is laser focal radius; s2 is the effective two-photon cross

L. Li et al. / CIRP Annals - Manufacturing Technology 60 (2011) 735755