CIRP Annals - Manufacturing Technology 57 (2008) 601–620

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CIRP Annals - Manufacturing Technology

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Direct writing technology—Advances and developments

K.K.B. Hon (1)a,*, L. Li (1)b, I.M. Hutchings c
a
Department of Engineering, University of Liverpool, Liverpool 69 3GH, UK
b
School of Mechanical, Aerospace and Civil Engineering, University of Manchester, UK
c
Department of Engineering, University of Cambridge, Cambridge, UK

A R T I C L E I N F O A B S T R A C T

Keywords: Direct writing (DW), also known as digital writing or digital printing, is a family of flexible multi-length
Deposition scale processes for the deposition of functional materials to form simple linear or complex conformal
Miniaturization structures on a substrate. This paper provides an overview of key DW technologies and their process
Direct writing
characteristics under a unified classification system. In DW, a variety of mechanisms and energy modes
such as inkjet, laser, mechanical pressure and tips are used to create material transfer to produce features
from the nm to the mm range. This new group of additive on-demand processes complements existing
manufacturing methods especially in product miniaturization and geometrical footprint reduction due to
its conformal writing capability. The range of materials is exceptionally wide, ranging from metallics,
ceramics, dielectrics and polymers to biomaterials. The thickness of the layer ranges from a monolayer of
molecules to hundreds of micrometres. As DW is a scalable process, it is capable of high-throughput
volume production, especially in microelectronics. Industrial applications have been expanding and
numerous niche examples are given to illustrate meso-, micro- and nano-scale applications. Finally,
challenges for its future development are also discussed.
ß 2008 CIRP.

1. Introduction  A range of technologies, possibly in reconfigurable short produc-

tion runs, of two- or three-dimensional functional structures using
There is a trend for modern products to become more multi- processes that are compatible with being carried out directly on to
functional and compact, with a higher expectancy of quality and potentially large complex shapes [25].
reliability and a shorter life-cycle. There are increasing pressures to  Fabrication methods that employ a computer-controlled trans-
reduce materials content, energy consumption during manufac- lation stage, which moves a pattern-generating device, e.g. ink
ture and operation and to present a smaller carbon footprint to deposition nozzle or laser writing optics, to create materials with
meet the requirements of sustainable development. To deal with controlled architecture and composition [57].
the forces of competition, globalisation and regulation, one
effective approach is to develop new technologies and to innovate
While such definitions describe some of the essential properties
new solutions.
of DW processes, they are unable to distinguish DW from some of
Manufacturing technology has been under accelerated con-
the well-established rapid prototyping processes such as Fused
tinuous improvement over the past few decades; typical examples
Deposition Modelling, 3D printing or Object printing. A more
include high-speed machining [98,108], creep feed grinding
precise and accurate definition is therefore required for DW: direct
[33,116], superplastic forming [21,36] and an entirely new family
writing denotes a group of processes which are used to precisely
of layer-based manufacturing techniques under the generic name
deposit functional and/or structural materials on to a substrate in
of rapid prototyping and manufacturing [55]. It is only recently
digitally defined locations. DW is distinguished from conventional
that an emerging new family of ‘direct writing (DW) technologies’
RP in terms of the following characteristics:
has become more prominent.
Direct writing is not a single process but a diverse, versatile and
 The track width ranges from sub-microns to millimetres.
multi-length scale group of process technologies. Direct writing is
 The range of materials deposited can include metals, ceramics
also known as direct printing and digital writing. Numerous
and polymers, electronically and optically functional materials as
definitions have been proposed:
well as biological materials including living cells.
 The substrate is an integral part of the final product.
 Any techniques or process capable of depositing, dispensing or
processing different types of materials over various surfaces
following a preset pattern or layout [87]. With integrated laser positioning feedback, the topology of the
substrate could be flat, curvilinear, round, flexible, irregular or
inflatable. Based on the above definition, all RP processes are
* Corresponding author. outside the scope of this paper.

0007-8506/$ – see front matter ß 2008 CIRP.

doi:10.1016/j.cirp.2008.09.006
602 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 1. Publications with ‘direct writing’, ‘inkjet’, ‘rapid prototyping’ in their titles based on ISI Compendex database.
Research efforts have been building up in the past decade as
more new applications have been developed in the biological,
medical, optical and electronics areas. Fig. 1 shows the number of
publications with the term ‘direct writing’ in their title since 1990.
While Fig. 1 shows the general trend of the growing importance of
DW, it may not provide a complete picture of the scientific
advances in DW as a number of publications on DW processes do
not have that term in their title. For instance, there are over 400
articles alone on dip-pen lithography and this is not wholly
reflected in Fig. 1 [76]. Although there is no published data on the
market impact of DW, it is estimated that the market for printable
electronics alone will generate over US$7 billion in 2010 [58].
2. Classification of direct writing
Direct writing is a generic term covering a number of processes
using radically different methods for material transfer on to a
substrate. It is an unusual technology as it covers a vast length scale
from tens of nm to several mm in terms of line width. Based on the
mechanism of materials transfer, DW methods can be grouped
under the headings shown in Fig. 2.
Droplet-based DW can be subdivided into two groups: inkjet
and aerosol. Inkjet technology is the most mature form of DW
technology and has two modes: continuous and drop-on-demand
(DOD). The continuous mode can be further subdivided into binary
deflection, multiple deflection, Hertz and microdot. Drop-on-
demand can be realized by thermal, piezoelectric, electrostatic and
acoustic techniques [52]. The earliest form of inkjet printer
appeared in the mid-1970s. At present, thermal and piezoelectric
drop-on-demand inkjet methods are the most popular. In aerosol
jets, unlike inkjet systems, the driving force is based on a gas to
provide the kinetic energy for the deposition of materials.
Energy beam-based DW refers to deposition of materials by
laser or ion beams. Although electron beam direct writing appears
often in the literature, it is usually used in a material-subtractive
sense rather than the definition adopted in this paper. Laser-based
Fig. 2. Classification of direct writing methods.
DW deposits, transfers or consolidates a strip of material through
the action of a high-energy laser beam. This can be further sub-
divided into four groups based on the precursors, i.e. solid, liquid,
gas or cell. As laser DW is highly versatile, several processes have
been developed for each type of precursor as summarised in
Section 4.2 with nine processes in the group. Focussed ion beam
(FIB) DW requires a precursor gas and its resolution is nearly two
orders of magnitude better than laser albeit with a slower writing
speed.
Flow-based DW requires high precision micro-dispensing
technology which could be in the form of a precision pump as
the case of the nScrypt process or extrusion for the MicroPen.
Usually, the delivery of the flowable material is through a very
small orifice or a needle. This kind of DW system is able to cope
with materials over a wide range of viscosities from 0.5 to
1,000,000 mPa s. Unlike inkjet where the ink is discretized as
individual droplets, the delivery of material for flow-based DW is
continuous.
Tip-based DW is a nanomanufacturing method represented by
two processes. In dip-pen lithography, molecules diffuse on to a
substrate in an ordered pattern through the micro-capillary action
between the tip and the surface. Alternatively, a micro-pipette can
be used, as in the case of MicroPen. The properties of the meniscus
formed between the tip and the surface are highly significant for
direct writing by this method.
A map summarising the capabilities of a few representative DW
processes is given in Fig. 3. It is evident that DW processes can be
divided into two broad categories based on the range of feature size
that can be produced, i.e. nano-scale and micro- to meso-scale. This
is because direct writing is not a single discipline subject and
employs numerous different mechanisms of materials deposition.
With such a vast range of length scale, DW technology offers huge
application potential as described in Section 8 of this paper.
An overall summary of the basic process characteristics of
direct writing techniques discussed in this paper is given in
Appendices A and B.
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 3. Representative direct writing technology capabilities.
3. Droplet-based direct writing
3.1. Inkjet-based direct writing: basic principles
Inkjet printers have become very familiar over the past 30 years
in the context of small office and home (SOHO) applications. The
rapid development of this technology followed the earlier
introduction of inkjet printing in an industrial context for in-line
date coding and marking of products, and is now being followed by
the progressive use of similar technologies in the manufacturing of
products themselves, both in the large-scale printing of text and
graphics, and also in the controlled digital deposition of structural
and functional materials: direct writing. The evolution of these
applications of inkjet technologies is illustrated schematically in
Fig. 4.
Inkjet-based direct writing involves the formation and deposi-
tion of a sequence of droplets of liquid material, often called an ink
or fluid. After deposition this material usually becomes solid, by
the evaporation of a solvent, chemical changes (e.g. through the
cross-linking of a polymer) or through cooling (e.g. by crystal-
lization or vitrification). Subsequent processing steps, such as
sintering, may also be involved. The impact process and the
development of a solid product will be discussed later; we shall
here focus on the formation and control of the liquid drops.
There are two different methods most commonly used to
generate drops in inkjet printing, termed continuous inkjet (CIJ)
and drop-on-demand [DOD]. In CIJ a continuous stream of ink
drops is generated from a nozzle by exciting the natural tendency
of a continuous liquid jet to break-up under surface tension forces.
Each drop is then individually steered (deflected) to write spots on
the substrate. Drops that are not selected in this way are fed into a
gutter and recycled. Simple CIJ systems use single nozzles, but
systems also exist with multiple nozzles. In DOD individual
nozzles, usually in an array containing a large number of nozzles,
are individually addressed to generate a single drop of ink on-
demand, by inducing a transient pressure pulse in a chamber
behind the nozzle. The drops then travel in straight lines from the
nozzle to deposit on the substrate.
Other methods of drop generation are possible, including the
use of an electric field to draw out a liquid from a nozzle (forming
Fig. 4. Evolution of applications of inkjet printing [68].
603
Fig. 5. Composite image showing the break-up of a continuous liquid jet travelling
from left to right. The nozzle is located to the left of the stream in the upper image
and the lower image is a continuation of the upper image.
a so-called Taylor cone which then breaks up into a stream of very
small droplets) but are not commonly employed in commercial
systems [6]. The processes of CIJ and DOD printing are described in
more details and then compared in the following sections.
3.2. Continuous inkjet printing
A stream of liquid emerging from a nozzle is unstable and will
tend to break-up into drops under the action of surface tension.
This phenomenon is known as the Plateau–Rayleigh instability.
The growth of a disturbance in the jet diameter occurs most rapidly
when its wavelength l is about 4.5 times the diameter d of the
stream. In a CIJ printer, this natural break-up is stimulated and
enhanced by the application of a periodic disturbance to the fluid,
at a frequency v=l where v is the jet velocity. The diameter of the
resulting drops is close to 2d. Fig. 5 shows the break-up of a
continuous inkjet travelling from left to right. A typical commercial
CIJ printing system might have a jet diameter of 60 mm and a jet
velocity of 20 m/s, giving drops about 120 mm in diameter and
requiring a drive frequency of about 75 kHz.
In a typical CIJ printhead, shown schematically in Fig. 6, the jet
is generated by pumping the liquid into a chamber from which it
emerges through a nozzle, and the modulating disturbance is
provided by a piezoelectric transducer in contact with the ink or
the nozzle. An alternative method of stimulating the jet break-up is
by the use of a small heating element very close to the nozzle
outlet, fed with a periodic electric current.
In most CIJ systems the drops are deflected electrostatically, as
shown in Fig. 6. The charging electrode surrounds the jet at the
point at which it separates into drops, and the application of an
electrical potential to this electrode induces an electrical charge on
each drop as it leaves the stream. The liquid requires enough
electrical conductivity for this charge to pass along the intact
stream from the nozzle. By varying the potential of the charging
electrode, the charge carried by each drop can be controlled and
varied. The drops then pass through a region of steady electric field
and are deflected sideways to an extent determined by the
magnitude of their charge. Uncharged, and therefore undeflected,
Fig. 6. Schematic illustration of the principle of operation of a continuous inkjet
system.
604 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
drops pass into a gutter from which they are recycled, while
charged drops will be ‘steered’ to strike the substrate at a range of
possible positions.
By using a fluid with appropriate properties of which the most
important are surface tension and viscosity, and optimizing the
frequency and amplitude of the modulation, it is possible to
arrange that the satellite drops which often form between the main
drops and are clearly seen in the top-right area of Fig. 5 recombine
with the main drops, which are present in a very regular and
repeatable sequence.
By deflecting the drops and moving the substrate appro-
priately, a pattern of droplets can be written on to the substrate.
More complex CIJ systems can employ nozzles fed with different
inks, for example to print four-colour graphics at high speeds, and
commercial systems also exist which use linear arrays of many
hundreds of nozzles.
3.3. Drop-on-demand printing
In the DOD method drops of ink are only ejected from the
system when they are required to be printed, and there is
therefore no need to recycle unused liquid. The liquid is ejected
from an ink cavity in response to a trigger signal, as shown
schematically in Fig. 7, through the generation of a pressure pulse
by an actuator.
There are two common types of actuator. The thermal DOD
(or bubble-jet) method is widely used in home and small-office
printers; rapid transient heating of the ink by a small electrical
heating element located in the ink cavity close to the nozzle
creates a short-lived bubble of vapour which drives a jet of ink
out of the nozzle. The bubble then collapses, drawing ink from
the reservoir to refill the cavity, and the process can be repeated.
More common in industrial inkjet systems is the use of a
piezoelectric element which changes the internal volume of the
cavity on the application of an electric field, and generates
pressure waves which in turn eject ink from the nozzle and then
refill the cavity. Since thermal DOD involves the vapourisation of
a small volume of the ink, this places significant restrictions on
the materials which can be jetted by this method; they must be
relatively volatile, or at least have a volatile component. There
are no such restrictions for the piezoelectric DOD method.
Printheads for both methods of DOD typically contain tens,
hundreds or even thousands of separate nozzles, fed by a single
ink manifold but each individually addressable. A typical set of
drops and jets ejected from an industrial printhead is shown in
Fig. 8.
Once the jet emerges from the nozzle, surface tension causes it
to form a main drop followed by a long ligament which may
collapse into one or more smaller satellite drops, as seen in Fig. 8.
As in CIJ, the surface tension and rheological properties of the
liquid strongly influence the formation of drops and ligaments; in
an ideal system the ink will have formed a single drop by the point
at which it impacts the substrate, typically at a stand-off distance
of 0.5–1 mm, but this is sometimes not achieved.
Fig. 7. Schematic illustration of the principle of operation of a drop-on-demand
printhead.
Fig. 8. High-speed photograph of jets ejected downwards from a linear array of
nozzles (located at the top of the image). The jets were ejected in three groups, and
the image shows progressive collapse of the ligaments behind the main drops into a
series of satellites.
3.4. Comparison of commercial CIJ and DOD systems
Although inkjet technology is currently undergoing rapid
development, with perhaps ten patent applications being filed
worldwide each day, it is useful to summarise some of the current
similarities and differences between the various methods of drop
generation.
A fundamental difference between CIJ and DOD methods lies in
the repetition rate, and hence material throughput, which can be
achieved from a single nozzle. In CIJ a continuous jet of liquid
leaves the nozzle, and the drops form by collapse of the jet at a
well-defined spacing, so that the centre spacing of the drops is
about 2.3 times their diameter; jet and drop formation represent
continuous processes. In DOD, in contrast, the process of jet
ejection and drop formation involves the sequential, discrete steps
of fluid ejection and cavity replenishment, with a maximum
frequency of operation governed by the timescale of these events.
In a typical DOD system the minimum spacing achievable between
drops ejected in a continuous sequence might be about 20 times
the drop diameter.
Generally, CIJ systems operate with fluids of lower viscosity
than DOD, and at a higher drop velocity, as summarised in Table 1,
and tend to require larger quantities of fluid for pumping and
recirculation, but certain DOD nozzle arrays also circulate the fluid
through the nozzle manifold to improve reliability. Although early
CIJ systems used single or small numbers of nozzles, while DOD
typically employed tens or hundreds, both are now capable of
addressing many hundreds of nozzles and there is significant
convergence of the technologies. There is a current trend to
increase drop generation rates in DOD; other recent developments
include the ability to generate drops of variable size, in CIJ by
varying a thermal stimulus applied at the nozzle, and in DOD by
using a complex drive waveform which produces a stream of
micro-drops which merge into a single drop before striking the
substrate.
The dominant forces which control the behaviour of liquid jets
and drops arise from inertia, viscosity and surface tension. In
comparing and analysing jetting and break-up phenomena, it is
useful to describe the conditions in terms of appropriate dimension-
Table 1
Comparison of performance and fluid mechanical parameters for typical
commercial CIJ and DOD systems.
Parameters CIJ DOD
Drop velocity (m/s) 10–20 5–10
Drop diameter (mm) 10–150, typically 120 10–150, typically 50
Drop volume (pL) 0.5–2000 0.5–2000
Fluid viscosity (mPa s) 2–10 10–100
Reynolds no. (Re) 100–1000 2–50
Weber no. (We) 500–1500 50–150
Ohnesorge no. (Oh) 0.03–0.2 0.1–1
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
less groups. The Reynolds number Re, defined by Re = rDV/h,
describes the ratio between inertial and viscous forces in a fluid with
dynamic viscosity h and density r, at a velocity V and a characteristic
length D, usually taken to be the jet or drop diameter. The Weber
number We, where We = rDV2/s and s is the surface tension,
describes the ratio between kinetic energy and surface energy: i.e.
between inertial and surface forces. It is sometimes more useful to
consider the value of the Ohnesorge number Oh which describes the
relative importance of viscous and surface forces, where Oh = We1/2/
Re = h/(rsD)1/2.
It has been suggested that DOD printing of a fluid is practical
only if Oh lies within the range between about 0.1 and 1 [113]. For
Oh > 1 viscous dissipation in the fluid prevents drop ejection,
while for Oh < 0.1 multiple drops form rather than a single well-
defined drop. The criterion for ‘jettability’ of a fluid thus involves
both its viscosity, which must fall within the limits indicated in
Table 1, and also the Ohnesorge number which should lie in the
range 1 > Oh > 0.1. For non-Newtonian fluids which are of
increasing interest as applications of inkjet printing become
wider, still other dimensionless groups can be used to incorporate
the effects of viscoelasticity, such as the Weissenberg number
Wi = TV/D where T is the characteristic relaxation time of the fluid.
3.5. Drop impact phenomena
A wide range of behaviour is possible when a liquid drop strikes
a solid surface, as reviewed by Yarin [122]. For the conditions
applicable to inkjet printing and summarised in Table 1, both
gravitational and fluid compressibility effects can be neglected.
The dynamics of drop spreading can be characterized primarily by
the Weber and Ohnesorge numbers, as shown in Fig. 9 adapted
from Schiaffino and Sonin [97]. The value of We determines the
origin of the driving force for spreading, while Oh describes the
force that resists spreading. The conditions for inkjet printing lie in
a regime where, at least for the earlier stages of impact, inertial
forces dominate and viscous forces are weak. As the spreading
liquid comes to rest, however, capillary (surface tension) forces
become more important.
Splashing is generally undesirable if precise drop placement
and deposition is required. The threshold for splashing to occur
during impact depends on the condition of the surface, and can be
expressed in terms of a dimensionless group K = We Oh2/5 [122].
For impact on a surface which is already wet with a liquid film of
thickness h, and where H = h/D, the condition for splashing has
been empirically determined as
K > 2100 þ 5880H1:44 (1)
for 0.1 < H < 1 and Oh > 7  103 [20]. For impact on a dry and
non-absorbent surface the critical value of K depends on the
roughness of the surface, expressed in dimensionless form as
Fig. 9. Schematic diagram adapted from Schiaffino and Sonin showing four regimes
of behaviour for a liquid drop on impact, based on the values of Weber and
Ohnesorge numbers [97]. Typical ranges of values for drop-on-demand (DOD) and
continuous (CIJ) inkjets are shown.
605
Fig. 10. Schematic representation of the spreading of a liquid drop with time. The
axes represent the non-dimensional diameter of the drop d* and the non-
dimensional time t* after impact [after 95]. The labelling of the axes is approximate.
R = (roughness amplitude)/D, and splashing is found to occur for
K > 649 þ 3:76R0:63 (2)
A line is plotted in Fig. 9 for K = 1000 which approximates to
these two conditions. Splashing will be favoured for conditions
above and to the left of this line, i.e. by a larger drop, higher impact
velocity, lower fluid surface tension, lower viscosity or a rougher
substrate. It will occur more readily under the usual conditions for
CIJ printing than for DOD.
Fig. 10 shows the four stages of development of the diameter of
a liquid drop after impact on to a solid surface [95]. The three
curves in the figure illustrate the behaviour for liquids which wet
the surface well (curve A), and poorly (curve C); an intermediate
case is also shown as curve B. The axes represent the diameter of
the deposit in non-dimensional form d* (where d*, often referred to
as the spreading factor, is defined as the contact zone diameter
divided by D), and the time after impact made non-dimensional by
using the impact velocity V and the initial drop diameter D (t* = Vt/
D). Four phases can be identified. In the initial kinematic phase the
drop has its initial spherical shape, truncated by the plane of the
surface, and the contact circle increases according to a power law
with d*  t*1/2. This phase of the impact is completely described by
the impact velocity and initial diameter. In the next phase, beyond
t*  0.1, the spreading depends most strongly on the viscosity of
the liquid, with less effect of surface tension; less viscous liquids
attain larger diameter drops than more viscous liquids, although
towards the end of this phase (say for t*  1) the role of surface
tension becomes more important. During the spreading phase the
diameter is constantly increasing. After this phase (from t*  2) the
effects of surface tension, and in particular of the contact angle
between the liquid and the surface, play a major role. Depending
on the wettability of the surface and the balance between inertial
and viscous forces up to this point, the contact angle at the end of
the spreading phase may be greater or less than the appropriate
(advancing or receding) equilibrium value; the drop may therefore
continue to expand, or retract, during the relaxation phase, as
shown in Fig. 10. For longer times (t* > 10) and if the surface is
well wetted by the liquid, the drop continues to expand with a
diameter proportional to t*1/10 [107]. In practical applications of
inkjet printing, the first three stages of drop spreading shown in
Fig. 10 last only a few tens of microseconds.
3.6. Aerosol jet direct writing
Instead of using individual liquid ink droplets as the media for
direct writing, Optomec have developed a focused aerosol beam
which is now marketed under the name M3D which stands for
Maskless Mesoscale Material Deposition. An overview of the M3D
system is given in Fig. 11 and its operation consists of three steps.
Firstly, the liquid material is placed into an atomizer, creating
a dense aerosol of micro-droplets from 1 to 5 mm in diameter.
606 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 11. Schematic diagram of M3D aerosol jet direct writing system [38].
Aerosolized liquid particles as small as 20 nm have also been
achieved. The choice of the atomization technique depends on the
ink parameters. Inks with a low viscosity of between 0.7 and
30 mPa s and containing small particles (<50 nm) can be ultra-
sonically atomized. For inks with viscosities between 1 and
2500 mPa s, a pneumatic atomizer is used [38]. Inks can be based
on solutions, nanoparticle suspensions or precursor materials and
can contain metals, alloys, ceramics, polymers, adhesives or even
biomaterials. Secondly, the aerosol is carried by a carrier N2 gas flow
to the deposition head. Finally, within the aerosol head, the aerosol is
aerodynamically focused using a flow guidance deposition head,
which creates an annular flow of sheath gas to collimate the aerosol.
The high velocity co-axial flow is sprayed onto a substrate creating
features from 5 to 150 mm using standard equipment. Recently new
nozzle configurations have been developed which allow a maximum
line width of 5 mm. The ability to write feature sizes through three
orders of magnitude shows the versatility of this process.
The writing speed is up to 200 mm/s and the volumetric
deposition rate is up to 0.25 mm3/s with a single nozzle. The
system can handle a wide range of materials with a viscosity from
0.7 to 2500 mPa s. Once the materials are deposited, they are
usually post-cured to achieve densification and/or chemical
decomposition to produce desired electrical and mechanical
properties. The post-processing can be done either thermally in
a furnace or by an infrared laser depending upon the deposition
material and substrate combination being used [81,92]. Polymeric
materials have also been post-processed in the M3D system using
integrated UV-curing. M3D is scalable for high-throughput volume
production with a multi-nozzle configuration.
Akhatov et al. found that in the focused aerosol beam, seven
forces interact between a particle and the carrier gas flow, i.e. the
Stokes drag force, which represents a steady viscous drag force; the
Basset force, which represents a non-steady viscous drag force;
virtual mass force, which represents the inertia of the fluid around
a particle added to that particle; fluid pressure gradient force;
gravity force; the Magnus force, which represents a steady lift force
of a viscous fluid on a rotating particle; and the Saffman force,
which represents a steady lift force induced by the local shear flow
of a viscous fluid [2]. Based on theoretical and experimental
studies, it was concluded that the Stokes force and Saffman force
have significant effects on the collimation of the aerosol beam with
an exit velocity of the order of 100 m/s.
Aerosol DW has been used in a wide range of applications, for
instance, micro-electronics: conformal interconnect, direct-die
attachment, ceramic moulded interconnect device component,
embedded resistors, inductor coils, platinum electrodes; repair:
PCB trace repair, flat panel display repair. Active development for
biological applications is being made. In a niche application, Horteis
et al. demonstrated high volume printing of collector lines on solar
cells using highly solid loaded silver inks exceeding 70 wt.% [42]. The
aerosol printed seed layer is 40 mm wide with a height of 1.5 mm on
silicon substrate. For this volume production application, Optomec
has developed a high throughput 40-nozzle Aerosol Jet deposition
head that prints a solar cell every 2.5–3 s [38].
A very wide range of materials has been used for aerosol DW,
covering all the material groups described in Section 7. M3D is
applicable for biomanufacturing because the droplet size is of the
order of a few femto-litres. Therefore, the kinetic energy is so small
that it will not destroy living cells due to their tiny mass.
4. Energy beam-based direct writing
4.1. Laser direct writing
Laser direct writing (LDW) refers to the creation of 1D to 3D
features by laser-induced deposition of metal, ceramics, semi-
conductors, polymer, composites and biomaterials without the use
of masks or lithographic methods. LDW was introduced in the early
1980s with pioneering work from Lawrence Livermore National
Laboratory and AT&T Bell Laboratories to enable the fabrication of
micro-electronic circuits with 1–2D features. The technology was
further developed in the 1990s, e.g. with critical contributions
from the Max Plank Institute in Germany and the US Naval
Research Laboratory, to enable the creation of 3D features for
wider applications including photonic crystals and MEMs. Since
the late 1990s LDW has become more mature and new
applications, particularly in the biomedical sector, have been
actively investigated by the wider scientific communities and
industries. In this section, the basic characteristics of major laser
direct writing techniques and the mechanisms of feature forma-
tion and material transfers are presented.
4.2. Laser direct writing technologies and their characteristics
Laser direct writing can be carried out in a number of ways
including depositing from gaseous, liquid and solid precursors and
material transfers. The techniques involve either laser-induced
chemical/electrochemical or physical reactions that lead to the
deposition of a material on to the substrate.
4.2.1. Laser chemical vapour deposition (LCVD)
LCVD for direct writing of 2D features was first demonstrated in
the early 1980s. An argon ion laser with 514.5 nm wavelength of
less than 2 W power is focused using an optical microscope lens to
a spot less than 2 mm in diameter. A reaction chamber is filled with
a gas precursor containing the elements to be deposited, e.g. silane
for depositing Si. The laser beam scans over a substrate target at a
0.5–5 mm/s scanning speed. The hot target dissociates the gas
locally and a thin layer, normally less than 1 mm thick, of solid such
as Si is then deposited onto the surface. Repeated scans of the
surface allow multiple layers to be deposited. Typical line width is
2–3 times larger than the laser beam diameter. As an example,
McWilliams et al. deposited Si and W on SiO2 coated wafer to
manufacture MOSFET with little post-process treatment required
[64]. The deposition rate is gas transport limited, and it is therefore
a slow process. Foulon and Stuke deposited Al lines using
trialkylamine alane precursors, (C2H5)3NAlH3 (TEAA) and
(CH3)3NAlH3 (TMAA), on Si, GaAs and Al2O3 substrates [31]. It
was found that the thermal decomposition of the precursor gas
started at temperatures in excess of 300 K. Surface nucleation
occurs within the first 0.01–0.1 s followed by Al growth. The rate of
crystallite growth is greater than the rate of nucleation, leading to
an increase of surface roughness with the line thickness. Uniform
Al lines of 7 mm wide and 0.7 mm thick were grown at 300 mm/s
scanning rate and a power density of 1.55 MW/cm2.
LCVD can be applied to producing not only 2D but also 3D
structures. Lehmann and Stuke deposited 3D aluminium oxide
rods from a mixture of oxygen and trimethylamine alane
((CH3)3NAlH3) gas precursor by two orthogonal Ar laser beams
split from a single laser [54]. With 0.2–20 mW power focused to a
spot of 3 mm, Al2O3 rods of 3–20 mm diameter were produced. A
growth rate of 80 mm/s can be achieved. The technique was later
applied to the fabrication of 3D photonic band-gap microstructures
with an Al2O3 growth rate up to 100 mm/s [114] and 3D electrical
cages for trapping particles [106]. An example of diamond-like
carbon micro-coils produced from ethylene gas precursor using
LCVD is shown in Fig. 12 [118].
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 12. A diamond like carbon micro-coil produced using LCVD. (a) Schematic
illustration of the deposition process. (b) A deposited sample [118].
The deposition rate in LCVD is dependent on a number of factors
including gas pressure, laser power density and scanning speed.
The deposition rate generally increases with the gas pressure of the
precursor materials (linearly), laser power density (linearly) and is
inversely proportional to the scanning speed. In a low-pressure
static reactor, the diffusion-limited axial growth rate is inversely
proportional to the induced reaction zone size. Thus for a very
small focused laser beam spot, the local diffusion of species to the
reaction is enhanced. The LCVD deposition rate is found to be many
orders of magnitude greater than for standard CVD. For a Gaussian
beam profile, the thickness of a deposited film can be estimated
from [118]:
pffiffiffiffi
pR0 rt
hðvs ; t Þ ¼ pffiffiffiffi
pr þ 2ðvs tÞ
where hðvs ; tÞ is the thickness of the deposited film, R0 is the
diffusion-limited axial growth rate, r is the laser beam radius, t is
time and vs is the scan velocity. In addition, the grain size increases
with deposition thickness [31].
4.2.2. Laser-enhanced electroless plating (LEEP)
Laser-enhanced electroless plating was first reported by von
Gutfeld et al. in the early 1980s [110]. With this method, the
substrate is submerged in a chemical solution containing the
metallic ions required for the deposition. A focused laser beam
irradiates the substrate surface causing a local temperature rise.
This temperature is high enough to decompose the liquid causing
deposition of a metallic layer on the substrate. This can then be
followed by electroplating or electroless plating to increase the
deposition thickness as the new deposition is attracted to the
conducting features created by the laser. The technique is currently
limited to writing 1D and 2D features. For example, Srivastva et al.
reported selective depositing of nickel on an alumina substrate
using a XeCl excimer laser at 308 nm wavelength [104]. Saturated
R grade nickel acetate solution was circulated over the surface of
the alumina substrate. The substrate was then irradiated with the
laser beam at 10–110 mJ pulse energy at 10–100 Hz repetition
rate. Visible Ni layers were formed at energies of 40–60 mJ/pulse at
a frequency of 100 Hz, and a scan rate of 200–300 mm/s. Laser
irradiation resulted in both deposition of metal and etching of the
substrate. The laser deposited layer had a thickness of 0.3–0.6 mm,
which was then brought to 3 mm by electroless plating in a Ni–B
bath.
The electrochemical conditions necessary for an electroless
plating process to take place are [13]:
(i) The reducing potential of the reductant must be less than that
of the reducing potential of the metal.
(ii) The metal must have enough catalytic activity for the anodic
reaction to take place at a reasonable rate.
In LEEP, a laser-induced temperature rise in the substrate
enhances the local chemical reaction, causing the redox reaction to
take place and metal to be deposited. The reducing agent needs
to be chosen such that reduction takes place at an elevated
607
temperature but not at ambient so that spatially selective laser
deposition can take place.
Another example is the deposition of copper wires on Si
substrate using LEEP, with a Ar+ laser (414.5 nm wavelength) that
is better than IR beams for transmitting through the copper
formate Cu(HCOO)2 and CuSO4 precursors. Thermal decomposition
of copper formate can be expressed as [13]
CuðHCOOÞ2 ! Cu þ H2 O þ CO þ CO2 (4)
Since Cu is easily oxidised in water, it cannot be reduced from
aqueous solution of copper formate in the absence of a proper
reducing agent. Glycerol was used as a reagent to reduce the
copper and to prevent oxidation of the metal. The final deposit was
mainly copper with some traces of carbon contamination. Line
width increased with dwell time and laser power. Typical line
width was 2–12 mm and thickness of 0.25–1.2 mm, with a laser
power of 1–3 W and a scanning rate of 0.1–0.8 mm/s. It is worth
noting that the deposition rate of 80 mm/s was about five orders of
magnitude faster than that of conventional electroless plating.
Deposited Cu from CuSO4/glucose has a minimum resistivity of
3.6 mV cm, approximately twice the resistivity of pure copper
(1.68 mV cm) [13]. Aluminium features can be deposited on a Si
substrate by laser scanning of a liquid precursor, triisobutylalu-
minium (TIBAL) using an Ar+ laser at 0.2–0.9 W, focused to a 3-mm
spot size, and at a scanning speed of 0.2–5 mm/s. Aluminium lines
of 0.8–1.1 mm thick and 3 mm in width were produced [53].
4.2.3. Laser enhanced or activated electroplating
(3)
Laser-enhanced electroplating was first reported by von Gutfeld
et al. in the late 1970s and early 1980s with 1000 times faster
deposition rate than normal electroplating due to the increased
local temperature [91,111]. In the early 1990s Lawrence Livermore
National Laboratory developed a laser-assisted electroplating
technique, using a 12 W Ar+ laser with 105 to 2.5  106 W/cm2
power density to melt and alloy the top a-Si coating layer with an
Au film below to enable the laser scanned lines to be conductive.
This is followed by electroplating. Only the exposed conductive
features can be plated. The laser writing speed can reach 110 mm/s
[65]. This method is limited to 1D and 2D features. The
electroplating rate is typically 100 times greater than electroless
deposition rates. This technique is however, a two-stage process.
The University of Manchester developed a direct, single step
process of laser-activated multiple layer electroplating [117]. A
laser beam, e.g. a frequency-doubled diode pumped solid state
laser, Nd: YVO4, with 532 nm wavelength, 20–70 ns pulse width,
scans over a substrate surface such as stainless steel covered with
CuSO4 electrolyte solution with the plating voltage set just below
the deposition threshold, i.e. so that no deposition occurs without
the assistance of the laser beam. A typical set-up is shown in
Fig. 13. As the laser beam scans the surface, there is a local
temperature rise which promotes the deposition rates by up to
1000 times. Typically each scan results in 1 mm deposition
thickness as shown in Fig. 14. Multiple scans would allow thicker
Fig. 13. A typical set-up for laser-activated electroplating for direct writing Cu on a
stainless steel substrate [117].
608 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 14. An example of Cu deposited on stainless steel (multiple layers) by laser-
activated electroplating, at various laser scan rates. (a) 100 mm/s, (b) 200 mm/s and
(c) 300 mm/s [117].
2D to 3D structures to be built.
CuSO4 þ H2 O ! Cu þ ð1=2ÞO2 þ H2 SO4
4.2.4. Laser consolidation of thin solid films
This method, started in the early 1980s, is based on photo-
thermal (pyrolitic) decomposition of solid films of metallo-organic
precursors, i.e. a metal-containing ink. A metal-containing screen
ink is spin-coated on to a substrate followed by baking in an oven
to remove excess solvent. The typical coating thickness is 0.1–
2.5 mm. The surface is then patterned by a laser (typically a
continuous wave Ar+ laser, focused to 0.8–1.5 mm beam spot, up to
20 W, scan speed 100–2000 mm/s), normally in air to allow the
burning off of carbon in the organic binder. The metallic particles
are sintered or fused to form a continuous feature. The unexposed
and partially exposed material is then removed by dissolving it in a
chemical solution such as dichloromethane chromic/sulphuric
acid. A continuous patterned metal film is then formed on the
substrate. For example, gold lines of 0.1–0.7 mm height can be
produced from ink with a thickness of 1–2.8 mm on quartz
substrates and palladium is deposited on a Si substrate from
palladium acetate precursor [34,35]. Due to exothermic reactions
of the organic binder, two thermal fronts are formed which can
lead to periodic line structures under certain conditions. This
method is limited to the formation of 1–2D single layer patterns
due to the inconveniences of adding additional layers at the same
location. It has an advantage over the LCVD method in terms of
materials design, process control and safety. The processing can
often be carried out in air. However, post-processing to remove
untreated materials is required. Precursors must meet certain
requirements to be of practical use. These include:
a. Homogeneous film formation.
b. High metal content, i.e. sufficient to form continuous metal
features.
c. To allow complete volatilisation of organic components at
decomposition temperatures low enough to prevent substrate
damage.
d. Either the film or the substrate must have enough optical
absorption at the laser wavelength to initiate decomposition of
the metallo-organic film.
A variation of the technique was applied by the University of
Manchester for the colour marking of tiles and glass by laser fusing
of a layer of coloured enamels as shown in Fig. 15.
4.2.5. Laser-induced forward transfer (LIFT)
LIFT employs a laser beam to transfer a thin film from an
optically transparent support onto a substrate placed 25–100 mm
below and in parallel to it. LIFT was first demonstrated by Bohandy
Fig. 15. Laser direct writing for depositing coloured enamels on ceramic tiles.
et al. in 1980s to deposit Cu and Ag over silicon and fused silica
using excimer or Nd:YAG lasers [9,10]. The action of the laser pulse
results in vapourisation of a small amount of material that
recondenses on the substrate. LIFT was initially developed to
transfer metals, and was quickly extended to oxides [17,30]. In the
(5) original form, the film material is the same as the deposited
material. Therefore, vapourisation of the film is needed to lift it off
the donor surface and deposit it on to the receiving target. This
limits its applications. A variation of the technique was the matrix
assisted pulsed laser direct write (MAPLE DW) described in the
next section, to overcome some of the difficulties for transferring
materials at lower temperatures.
Further development of the LIFT technology in the 2000s allows
the transfer of biomolecules. This is based on the deposition of a
layer of liquid, containing biomolecules, on a transparent glass
plate which was coated with a thin layer of optically absorbent
material, e.g. Ti [100,119]. A pulsed laser heats the absorbent
material and projects a tiny amount of liquid solution containing
the biomolecules onto a solid substrate. For example, a 50–65 mm
array of double-stranded DNA from salmon sperm was deposited
on to poly-L-lysine coated slides [29]. A similar method reported by
Barron et al. was known as biological laser printing (BioLP) [5]. It
can deposit proteins, DNA, scaffolding materials, prokaryotic and
eukaryotic cells, with low volume transfers. It removes direct
interaction of the laser with the biological material. As the laser
absorption depth or skin depth is between 2.2 and 10.5 nm which
is well within the metal film, 99.9% of non-reflected light is
absorbed within the metal film. Thermal penetration into the
liquid is less than 400 nm into the biolayer. As thermal
vapourisation of the solid film takes place, the first 5% of material
nearest the interlayer is affected. Cells are mixed with 0.1 vol.% of
sodium dodecyl sulphate (SDS) and 50 vol.% glycerol.
A great advantage of the technique is high speed and high
resolution. The deposited spot size has 9.3% standard deviation,
Fig. 16. LIFT for direct write deposition of biomolecules. (a) Experimental set-up. (b)
Deposited droplets containing ETS2 human genes [19].
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
comparable to commercial grade piezo-tip and solid pin arrayers.
Diameter is half that from commercial grade arrayers. 3D human
osteosarcoma cells were printed using this method. The droplet
volume displays a linear dependence on the laser pulse energy
[18]. An example of the typical set-up and laser deposited ETS2
human genes is shown in Fig. 16.
It is possible that the sacrificial layer is a polymer material such
as polyimide for transferring biomedical materials. Droplets of
biomedical materials can be deposited at different laser fluences
that can cause the polymer film to change geometry, melt,
vapourise and rupture, ejecting different size of biomedical
droplets on the target surface. The droplet diameter is linearly
proportional to the laser pulse energy in this case.
4.2.6. Matrix assisted pulsed laser direct write
MAPLE DW was demonstrated in 1999 by Pique et al. at the US
Naval Research Laboratory [88]. Strictly speaking, MAPLE DW is a
form of LIFT with the difference that a carrier material is used to
absorb the thermal energy from the laser. A laser-transparent disk
such as quartz is coated with an organic binder and the material to
be deposited (such as powders of metal or ceramics or cells). The
coated disk is called the ribbon. This ribbon is placed in close
proximity of about 25–100 mm and parallel to the acceptor
substrate. The pulsed laser is focused through the transparent disk
on to the matrix coating. When a laser pulse strikes the coating, a
fraction of the polymer decomposes into volatile by-products
which repel the powders to the acceptor substrate. In MAPLE DW,
the material to be transferred is not vapourised, because the laser
fluences required to decompose the photo-sensitive polymer are
below the ablation threshold of the powders. By avoiding the
vapourisation of the depositing material, complex compounds can
be transferred without modifying their composition, phase and
functionality [123]. Also there is little heating of the substrate.
Each pass would deposit <1 mm layer. Multiple passes are required
to deposit thicker layers. Typical materials include Ag and BaTiO3.
Line widths of 50–200 mm have been deposited with a beam spot
size of 25–100 mm. A deposition speed up to 500 mm/s has been
claimed. Due to the low temperature of the transferred materials,
the substrates can be polymer materials. Large numbers of
applications use this technique, mainly driven by the work of
the US Naval Research Laboratory. Examples include micro-
capacitors, interconnects, phosphor displays, coplanar resistors
[15,16], laminated band pass filters, inductors, resistors and on
separate layers [125], Li-ion micro-batteries [115], Ag2O for
primary alkaline cells and LiMn2O4 deposition for secondary Li-
ion cells [86]. An example of a spiral inductor is shown in Fig. 17.
For transfer of biomedical materials, an aqueous-based
biological support is used. The water in the biological support
absorbs the UV light, causing some of the liquid at the interface to
be vapourised and resulting in the ejection of the remaining
material. 99% of the laser light passes through the liquid, raising
the possibility that the laser light could also damage the biological
material [84]. The number of cells transferred to the substrate can
Fig. 17. A spiral inductor deposited by the MAPLE DW technique [125].
609
Fig. 18. A schematic of laser backward transfer [70].
be altered through the concentration prior to the formation of the
film on the transparent support [94]. Based on this method,
polymers, enzymes, proteins, tissues, etc. have been successfully
transferred on to various substrates [120]. Micro-contact printing
and lithography techniques are limited to 2D and resolution of less
than 100 mm. Laser direct writing has allowed cell and tissue
structures to be formed in 3D with a better resolution.
4.2.7. Laser-induced backward transfer
For optically transparent substrates, laser-induced backward
transfer can be used to deposit various materials including metallic
and metal oxides. The University of Manchester has demonstrated
laser direct writing of conducting SnO2 films on to a glass substrate,
by placing the substrate on top with a 20–100 mm gap above a Sn
powder bed. The laser beam passes through the glass and melts/
vapourises, some of the metal and deposits the vapour/molten
material on the back surface of the glass. A schematic of the process
is shown in Fig. 18 and an example of laser direct write deposited
SnO2 on glass is shown in Fig. 19. This example was processed in air
without a specific reaction chamber. An advantage of the process is
the capability of depositing very thin (<50 nm) layers of materials
that can be fused on to the substrate as the laser would start to be
absorbed at the coating substrate interface. A disadvantage of the
process is the restriction of the substrates to optically transparent
materials.
4.2.8. Multi-photon polymerisation
By tightly focusing a pulsed laser beam, non-linear photo-
chemistry can be obtained, within a three-dimensionally defined
focal volume of photo-sensitive acrylate polymers, to enable
complex topographical structures to be fabricated with sub-
micrometer resolution. This has been achieved through multi-
photon absorption by the materials to cause solidification. By the
use of a femtosecond laser scanning in 3D using micro-stages,
plastic model animals, interlocking buildings [46], and micro-
scopic words can be produced [4]. Laser Zentrum Hannover has
Fig. 19. SnO2 grids deposited on glass with a film thickness 50 nm at 30 mm/s
scanning rate.
610 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 20. A micro-Venus produced by two-photon polymerisation [99].
demonstrated the fabrication of 3D micro-objects by two-photon
polymerisation with a femtosecond laser, as shown in Fig. 20 [99].
Ti–sapphire lasers have also been used to direct write 3D
protein microstructures, including low-profile arches and long
aspect ratio cables [39]. The possibility of photo-fabricating 3D-
defined matrixes from biomaterials such as proteins opens
opportunities for creating sophisticated cellular interfaces that
could enable cell growth in three dimensions or restrict diffusion of
analytes secreted from subcellular regions of interest. Pitts and co-
workers first reported the use of multi-photon excitation to
promote protein cross-linking in defined 3D voxels, allowing an
extended protein-based matrix to be created in aqueous environ-
ments by scanning a laser focus through a reagent solution
containing protein and photosensitizer [89]. Kaehr et al. showed
the possibility of activating multi-photon polymerisation through
a low cost frequency-doubled Nd:YAG (532 nm) laser with 3.5 mJ
pulse energy. Two-photon excitation of aromatic amino acids and
bovine serum albumin (BSA) was demonstrated [45].
4.2.9. Laser contact-free trapping and transferring of particles in
solution for 3D direct writing
Laser tweezers can be used to force transparent particles in
solution into the region of maximum light intensity. The
application is limited to cases where the object index of refraction
exceeds that of the surrounding liquid [3]. Laser-guided direct
writing can be realised by using a diode laser beam of 200 mW,
830 nm wavelength, focused using a microscope lens to radially
trap and axially deliver particles to a non-absorbing surface. It is
capable of guiding metal, silicon, polymer, bacteria and animal
cells [78], embryonic chick neurons [77] and multi-potent adult
progenitor cells [75] and endothelial cells [74] to various targets in
2D and 3D formations. The principle employs the unbalanced
momentum of the particles within the non-uniform laser beam
which drives the particles towards the higher energy concentra-
tion of the laser field.
4.3. Discussion of laser direct writing
Although there are many laser direct writing techniques
available, each technique has its advantages and disadvantages
or limitations. LCVD allows 3D structures to be built but very
slowly, although it is much faster than conventional CVD which
builds at a few mm per hour. In most cases, the morphology and
electrical conductivity of the deposited features are inferior to the
bulk material, or the adhesion of the layer to the substrate is poor
and cannot be controlled. Gas phase deposition is limited by the
availability of volatile metal-organic or inorganic materials,
contamination of metal deposits and the need for specialised
reaction chambers. For example, it is difficult to find Cu gas
precursors that would allow sufficiently high vapour pressure.
Although deposition can be carried out on various 2D and 3D forms
of substrates, the technique is not yet able to deposit on to organic
substrates such as polymers and cells. A further drawback of the
technique is the high cost, due to the use of a reaction chamber
associated with vacuum equipment. It is difficult to deposit alloys,
composites and organic materials using the technique.
Laser deposition in a liquid environment has high deposition
rates and excellent adhesion, but is limited to 2D structures only. It
can deposit metals and ceramics, but is not suitable for organic
materials. It does not require vacuum equipment. Therefore it has
lower cost than LCVD. Laser consolidation of solid films allows the
deposition of most metallic and ceramic materials. It is however
limited to applications on 2D surfaces.
Laser backward transfer, although fast in depositing metal and
metal oxides, is limited to optically (to the laser beam) transparent
materials. It would be difficult to deposit 3D structures using this
technique.
LIFT and MAPLE DW allow the building of 3D structures with
the widest range of materials on various substrates. A great
advantage is its capability to deposit biomedical materials at low
temperatures without damaging the cells. It has better thickness
control and allows a near-monolayer coverage that conventional
ink jet technique struggles to achieve. One limitation is the
substrate geometry. In LIFT and MAPLE DW the substrate needs to
be flat and placed parallel to the donor disk.
Multi-photon polymerisation and laser guidance are recent
developments that are mainly suited to organic and biomedical
materials. They offer great flexibility and highest accuracy in
creating 3D structures. They can deliver and grow cells on a 3D
object or substrate. Laser trapping and guided deposition in liquid
is limited to low volume materials and is typically suited to small
particles and cells.
4.4. Focussed ion beam direct writing
In FIB, the ion beam is generated from a liquid gallium source.
The ion beam energy is typically between 10 and 50 keV, with
beam currents varying between 1 pA and 10 nA. When energetic
ions hit a surface, four mechanisms can take place: sputtering of
neutral and ionized substrate atoms, electron emission, displace-
ment of atoms in the solid and emission of phonons. For the DW
mode, the process requires the spraying on the substrate surface of
a precursor gas. For the deposition of W, the organometallic
precursor gas is W(CO)6 [93]. Other precursor gases are available
for the deposition of conductors such as Au, Al, Cu, Mo and Pt, and
insulators such as TEOS, TMCTS/O2, PMCPS/O2 [12,27,124].
The principle of deposition is similar to LCVD except that FIB
offers better resolution but lower deposition rate, typically
0.05 mm3/s. The minimum feature that can be produced under
the conditions used is 80 nm due to particle scattering and
migration of the carbon from the near-surface atmosphere prior to
deposition [73]. The minimum thickness is about 10 nm and aspect
ratios are between 5 and 10.
FIB DW is a well-established tool for the repair of conventional
and phase-shift masks to add missing absorber materials. As
organo-metallic compounds are used for metal deposition, FIB
deposits are not pure because of organic contaminants and Ga+
ions. Due to rather large carbon contents, the resistivity of these
deposits is generally about one to two orders of magnitude higher
than those of pure metal [26].
FIB is a relatively slow process and its applications are restricted
to low volume production, especially repair work [72]. It is capable
of conformal deposition and forming 3D micro-structures which
can be used for hermetic encapsulation for micro-sensors.
5. Flow-based direct writing
5.1. Precision pump method
The common property of processes grouped under flow-based
DW is that they all require a positive mechanical pressure to
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 21. The Smart Pump [59].
achieve precision micro-dispensing through a positive displace-
ment pump, air pressure or extrusion through a syringe. Unlike
inkjet or aerosol jet DW where a line is formed from individual
droplets, flow-based DW is characterized by a continuous flow of
ink, paste or slurries on to the substrate. This group of methods
differs from the fused deposition method (FDM) in two main
respects. Firstly, there is no heating of the material, and secondly,
the volume of flow is much lower, in the order of nL/s. The two
most well-known and established methods are known as nScrypt
and MicroPen, both of which are trademarks.
nScrypt, formed in 2002, is based on Sciperio’s Micro-Dispense
Direct Write (MDDW) technology developed through the DARPA
(US Defence Advanced Research Projects Agency) MICE program
(Mesoscopic Integrated Conformal Electronics) in 2002. The core
technology of the syringe-based DW system is a high precision
micro-dispensing pump with accurately controlled air pressure,
timing, valve opening and dispensing height as shown in Fig. 21.
Dispensing precision is enhanced with an integral suction function
which removes all residual materials sticking on the tip. It is
capable of dispensing very small volumes of material, down to
20 pL, and a range of viscosities from 1 to over 1,000,000 mPa s
[59].
The flowrate is sensitive to the dispensing height for a constant
applied pressure as shown in Fig. 22. In order to maintain line
width consistency and accuracy, the dispensing height must be
maintained at above a certain value which is 50 mm in this case. In
practice, a laser height sensor is employed to either pre-scan or
scan the substrate surface in real-time to create a surface contour
map. The dispensing tip is then controlled to following the contour
map to maintain a constant height throughout the writing process.
The line width is directly dependent on the material, which is
often a slurry paste. Generally, the minimum line width is at least
10 times bigger than the biggest particle size in the specific paste.
nScrypt is able to print any line width between 25 mm and 3 mm.
The tolerance of the line width varies from 3% to 5% for line
widths of 150 and 75 mm, respectively. The maximum writing speed
Fig. 22. The relationship of flow rate and dispensing height [59].
611
Fig. 23. Schematic diagram of MicroPen [121].
is 300 mm/s and the minimum speed can be 0.1 mm/s. The typical
speed is dependent on different material and applications; 50 mm/s is
normally observed [58].
5.2. Syringe and extrusion method
Another form of direct writing based on a micro-capillary tip is
MicroPen which is the trademark of a DW system produced by
OhmCraft Inc. In operation, a flowable material which can be a
liquid or particulate slurry, is loaded into a syringe that is then
connected to the writing head of the MicroPen. A pneumatic ram
compresses the plunger of the syringe and forces the material into
the writing head known as the ‘block’. The writing head consists of
a metal double piston cylinder, an A-frame fluidic pathway and
micro-capillary writing tip. Flowable material fed into the ‘block’ is
pressurized up to 13.8 MPa and dispensed through the writing tip.
The tip traverses perpendicularly on the surface of the substrate
surface without direct contact. A schematic diagram of the
MicroPen set-up is given in Fig. 23 [121].
The MicroPen uses an extrusional method for depositing
material and there are unique writing parameters for each pen
orifice size, writing speed and paste material. The pressure
required must overcome the frictional stresses at the wall and
the capillary force of the orifice as shown by the Benbow equation
[8]:
  D0 4L
P ¼ 2 s y0 þ aV ln þ ðt 0 þ bV Þ (6)
D D
where P is the extrusion pressure, sy0 is the initial tip orifice entry
yield stress, a is the tip orifice entry yield stress velocity factor, V is
the mean writing speed, D0 is the diameter of the chamber before
the tip, D is the diameter of the writing orifice, L is the length of the
tip, t0 is the initial tip entry shear stress, and b is the orifice velocity
factor.
As the height of the pen tip is continuously sensed and its force
can be controlled to tens of microNewtons levels, MicroPenning
enables deposition on extremely soft surfaces with active topologies,
including inflatables such as medical balloons. Any liquid material
whose viscosity ranges between 5 and 500,000 mPa s is a candidate
for MicroPen deposition. The line widths are in the range of 50 mm to
2.5 mm with a height from 1.3 to 250 mm. The system can also
dispense individual dots with a volume as small as 100 nL. For an
orifice of 50 mm, a writing speed of 25.4 mm/s has been used to write
functional silanes [28].
Other simple methods of precision micro-dispensing have been
developed such as the time-pressure needle dispensing system and
pin transfer. The time-pressure needle dispensing system normally
consists of a syringe containing a material which is deposited on to
the substrate via a needle through the action of air pressure on a
mechanical plunger.
Vozzi et al. analysed the time-pressure needle process with
several assumptions [112]. First, the driving pressure is the
predominant force in this system and the other forces such as the
surface tension between the fluid and air, dynamic friction
between the fluid and the glass substrate are negligible. Second,
the flow is laminar and third, the fluid is a Newtonian viscous fluid.
Under such conditions, the flow inside the capillary is given by
612 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Poiseuille’s equation,
pR4S d p
Q¼
8m dz
where Q is the flow of fluid from the needle, Rs is the internal radius
of the tip of the needle, m is viscosity of the fluid, and dp/dz is the
applied pressure gradient.
With further manipulation, the line width a of the direct
writing is given as
pR4S d p
a¼
8mv0 h dz
where v0 is the velocity of substrate with respect to the syringe and
h is the height of the polymer deposited.
Using an air-pressure activated syringe at a pressure of
50 mmHg, DW of poly-L-lactic acid (PLLA) and polycaprolactone
(PCL) with line widths of 10–20 mm was achieved with a needle
of 20 mm internal diameter. It was also reported that the viable
range of polymer viscosity should be within 100–700 mPa s.
Low viscosity solutions leak out of the tip whereas highly viscous
solutions require pressures that may damage the tip and be a
danger to the operator [112].
6. Tip-based direct writing
6.1. Dip-pen nanolithography (DPN)
Dip-pen Nanolithography which is a general nano-scale direct
writing or nano-patterning method, was first demonstrated by
Mirkin’s group at Northwestern University in 1999 [85]. DPN is a
trademark of NanoInk. The vehicle for deposition can include
pyramidal scanning probe microscope tips, hollow tips, and even
tips on thermally actuated cantilevers.
Basically, DPN consists of the dipping of an AFM probe in an
‘ink’. The ink is transferred to the substrate by capillary transport.
Inks such as proteins, polymers, DNA and active enzymes have
been used to create nanometric patterns. Jang et al. presented
Fig. 24. (a) DPN Process with weak surface binding [66]. (b) Deposition of a
monolayer of molecules by DPN.
a theoretical model explaining DPN as a three-step process as
shown in Fig. 24a [44,66]. The three main steps are: molecular
deposition, lateral diffusion on a monolayer of molecules and
(7)
finally termination of diffusion by chemical binding to a substrate.
This will lead to the formation of well-ordered self-assembled
monolayer (SAM) patterns.
The heights of the DPN tips which are the same as for AFM, are
usually about 3–10 mm. The diameter of the end of the tip can be as
small as 10 nm which is a determining factor of the minimum
feature size that could be written on a surface [40]. Hong et al. have
demonstrated patterning of molecular structures of about 10 nm
(8)
via DPN [41]. In the normal DPN process, the tip is in direct contact
with the substrate with a contact force of about 1 nN. However, an
oscillating DW mode is also used with the advantage of reducing
the interaction between the AFM tip and the substrate.
DPN is a scalable, high-throughput, flexible and versatile
method for precision nano-scale pattern formation. In 2006,
Salaita et al. fabricated a massively parallel NDP 2D array with
55,000 tips across a 1 cm2 chip using photo-lithographic techni-
ques. This array was demonstrated to generate 88 million gold dots
with a pitch distance of 400 nm and a diameter of 100  20 nm
[96]. With a throughput rate of 3  107 mm2/h, the 2D array
technique is able to compete with e-beam lithography. DPN is the
only sub-50 nm technique that can directly deposit molecules under
ambient conditions because its environmental process controls
allows precise control over many varieties of ink deposition.
The original DPN technique has been limited by an inability to
turn the ink flow on and off. Existing dip-pens apply ink as long as
they remain in contact with a surface. The thermal DPN (tDPN)
method developed by Sheehan et al. solves that problem by using
easily melted solid inks and a special AFM cantilever with built-in
resistive heater that allows writing to be turned on and off at will
[101,102]. This approach allows the local deposition of molecules
which are not mobile at ambient temperature and controls the rate
at which they are deposited. The cantilever has a heating time in
the range of 1–20 ms and a cooling time in the range of 1–50 ms
and the temperature could reach 700 8C [50].
6.2. Nanofountain pen
Nanofountain pen (NFP) was developed by Espinosa and is
similar to DPN except that the AFM tip is replaced by a cantilevered
nanopipette [49]. The pipette is filled with the solution to be
deposited and the liquid flows to the substrate when the pipette is
placed in contact with the surface, as shown in Fig. 25. NFP has
been used to deposit proteins, active enzymes, DNA and polymers.
Fig. 25. (a) Schematic diagram of the nanofountain pen. (b) SEM of the dispensing
tip [49].
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620 613

Table 2
List of some materials used in direct writing applications.

Material class Examples

Alloys Al alloys, Pt–Ru, Ag–Pd, Cu–Ni, Sn–Pb solders

Biomaterials Living neural cell, peptides, proteins, antibodies, DNA oligomers, simple eukaryotic cell, mammalian cells,
Escherichia coli bacteria, enzymes
Ceramics Al2O3, SiO2, PZT, TiO2, ZrO2
Dielectrics Barium titanate, barium strontium titanate, PMN/glass ferrites, polyimide
Food Chocolate
Metals Ag, Al, Au, Cu, In, Pt, Sn
Nanoparticle materials Ag, Au, Cu, BaTiO3, Carbon nanotubes, Fe3O4
Optical materials Silicate glass, Epoxy resin
Oxides YBaCuO, BiSrCaCuO, InOx
Polymers PTF-epoxy + carbon + titanate, biodegradable polymer (PLGA), organic light emitting polymer, conductive polymers
(e.g. PEDOT:PSS, polyaniline), organic semiconductors, UV-curing polymers
Resistors Ag/Pd/glass, ruthenate
Speciality Diamond

Quartz nanopipettes can have an outer diameter of 10 nm and an
inner hole as small as 3 nm. A typical line width is about 40 nm
which is about the size of the smallest virus found in nature. Lewis
et al. demonstrated the DW of a line of 1.15 mm line of cyanide on a
chrome film at a speed of 0.4 mm/s [56]. Deposition of a 20 mm
diameter dot of a fluorescein with a 600 nm aperture pipette was
reported [7]. More recently, Moldovan et al. demonstrated that this
process was scalable with the construction of a linear array of 12
probes producing sub-100 nm features [71].
Hwang et al. showed that the line width Lf produced by NFP
consisted of two components including detailed analysis of each
component:
Lf ¼ Lt þ Ld
Lt is the line width due to the tip and is directly affected by the
acceleration and initial mass of the meniscus. Ld is the additional
line width due to diffusion of ink but can be affected by ambient
conditions such as temperature and humidity [43].
7. Materials
7.1. General properties and types of materials used in direct writing
The provision of high quality and consistent materials is a pre-
requisite for all DW processes. The starting materials, sometimes
termed ink, slurry or paste may consist of combinations of
powders, nano-powders, flakes, surface coatings, organic precur-
sors, binders, vehicles, solvents, dispersants, and surfactants which
require customized chemical and rheological properties. These
materials have applications as conductors, resistors, and dielectrics
and have been developed specifically for very low-temperature
deposition from less than 200–400 8C. Low-temperature proces-
sing will allow fabrication of passive electronic components and
radiofrequency devices with the performance of conventional
thick-film materials, but on low-temperature flexible substrates,
such as plastics, paper and fabrics [87].
For full process control and maintaining repeatability, a long list
of material parameters has to be considered, e.g. viscosity, other
rheological properties, melting temperature, mean particle size,
surface tension, wetting properties, particle size distribution,
particle morphology, specific heat, thermal conductivity, density
emissivity, diffusivity, reflectivity, solids loading, substrate mate-
rial, sintering rate parameter and porosity [87].
Powder is a very common precursor for direct writing and its
properties have a direct influence on the DW product. For spherical
powders, the highest possible packing density is about 74% for the
face-centred cubic or hexagonal close-packed structure. For
random close-packed powders, it is even lower at about 64%
[90,109]. This means that there will be at least 26% voids in the
structure. According to the logarithmic mixing rule for dielectrics,
26% air reduces the effective dielectric constant by almost an order
of magnitude, highlighting the importance of reducing the porosity
in transferred materials [63]. A common approach is to use poly-
dispersed powders so that smaller particles will fill the interstitial
gaps between the larger ones. However, the use of nano-powders
will require special safety considerations due to their high surface
energy and possible toxicity.
A very wide range of substrates have been used in DW, for
instance ceramics, plastics such as PVC, mylar, nylon, polyimide,
PEEK, polystyrene, metals such as 304 stainless steel, aluminium,
copper and nitinol. Some unusual substrates include compliant
medical balloons used in association with the MicroPen [121].
All those materials which are compatible with the substrate and
could form a proper bond with or without post-processing such as
surface curing could be used as materials for DW. In this sense, a
(9) very wide range of materials have been reported as used in DW.
Table 2 shows the various classes of DW materials with some
representative examples. In addition, adhesives, electrolytes,
lubricants, pharmaceuticals, radio-opaque materials and surfac-
tants have also been used for DW applications.
7.2. Materials used in inkjet direct writing
Inkjet technology has been used to deposit a very wide range of
materials, for many different applications, with the only restriction
being that the material must be in liquid form with appropriate
rheological properties at the point of printing. Materials which
have been printed include metals, ceramics and artificial polymers,
as well as various biological materials including living cells.
Possible routes to metallic deposits include the direct deposi-
tion of liquid metals, printing of metallic particles followed by
sintering, and printing of a chemical precursor which is then
further processed to generate the metal. An early application for
the direct printing of liquid metal was to form solder droplets for
chip connection bumps, via filling, connector tracks and rework on
electronic printed circuits [62]. Metals with higher melting points
pose significant challenges for printhead design, and although
piezoelectric drive may still be useful for both CIJ and DOD,
precautions must be taken to isolate the transducer from the high
melt temperature; other actuation methods have also been used,
such as direct pneumatic ejection in DOD printing [14]. The
deposition of aluminium, both pure and alloyed, has been
demonstrated in a droplet-based net-form manufacturing process
in which the drops are generated and deflected by piezoelectric CIJ
technology, with drops 190 mm in diameter being generated at
17 kHz, corresponding to a mass throughput of 1.5 kg/h [61].
Metallic particles suspended in a suitable fugitive liquid can be
printed by inkjet processes, and are used for both structural and
electrical applications. Small particles are generally favoured as the
suspensions are more stable, i.e. the particles do not sediment,
nozzle clogging is avoided and very importantly, the high surface to
volume ratio leads to a lowered sintering temperature. There is
considerable interest in the development of conductive nanoparticle
inks with good properties, oxidation resistance and low sintering
temperatures [82]. Inks based on silver nanoparticles, typically 5–
614 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 26. Application examples of direct writing [25].
50 nm in size, for example can be sintered to form deposits of high
electrical conductivity at temperatures below 300 8C, and even as
low as 150 8C, and are then compatible with many polymer
substrates and other printed polymeric materials [32]. Conductive
inks in which the solvent does not evaporate but cures to form a
binder will lead to lower conductivity, but this is sometimes
desirable, an example being the use of carbon nanotubes in a
polymer matrix for the in situ fabrication of resistors.
Various indirect methods of achieving metallic conductive
deposits by inkjet printing exist. One is to print a precursor, a
solution of a compound of the metal, usually silver, which is then
decomposed by heating. For example, inks based on silver nitrate
and on an organic silver compound have been successfully CIJ
printed and processed to yield conductive metallic deposits [69].
An alternative approach is to print a non-conductive but
chemically active deposit which is then subjected to a secondary
treatment in a low-temperature plating bath of copper ions,
leading to autocatalytic deposition of copper on the printed areas;
excellent conductivity can be achieved and the low process
temperature is a significant advantage for some applications.
Long-chain polymers cannot be printed as they are by inkjet
processes, since even as a melt their viscosity is usually too great,
and alternative routes are needed to produce polymeric deposits
[11]. They can be dissolved or colloidally dispersed to form a latex
in suitable solvents, but even in solution the presence of a small
concentration of high molecular weight polymer may introduce
sufficient viscoelasticity to inhibit good droplet formation [23].
Waxes, with molecular weights of a few hundred Daltons, do form
jettable melts, and can be used for some applications such as mask
printing and rapid prototyping. Common routes to the printing of
polymeric deposits include the use of solvent systems and UV-
curing. Electronically functional polymers, such as conductors
(e.g. conjugated polymers such as PEDOT:PSS and polyaniline),
semiconductors and polymer light-emitting diode (PLED) materi-
als, can be DOD printed in solution. There is major commercial
interest in printing organic semiconductors, for such applications
as display backplanes, and also in fabricating large-area PLED
displays [23]. An important challenge in electronic applications, for
best performance, is to achieve solid deposits which are as flat as
possible. There is a natural tendency for solutes to deposit from
evaporating drops of solution towards the rim of the drop, the
‘coffee stain effect’, and special measures, for example through the
use of mixed solvents, must be taken to reduce this effect.
For structural or optical applications, or to achieve dielectric
properties, thermoset polymers can be cross-linked in situ after
printing, by thermal treatment or often by UV-curing a formula-
ted ink containing a photo-initiator; UV-curing is increasingly
common in graphical printing applications, and can involve a brief
‘pinning’ exposure immediately after printing to arrest migration
of the drop edge, followed by subsequent full curing, perhaps after
further layers of material have been printed.
7.3. Materials used in aerosol jet direct writing
The aerosol is formed from a liquid precursor material and the
droplet size is usually between 1 and 5 mm. The particulate
suspension is dependent on the mode of atomization, i.e. ultrasonic
or pneumatic. For the ultrasonic method, nanoparticle suspensions
and high vapour pressure solvents are used and the range of
viscosity is up to 30 mPa s. For the pneumatic method, nanopar-
ticles can be used in suspension up to a viscosity of 2500 mPa s. The
range of materials that can be deposited is very wide including
metals, alloys, resistors, dielectrics, battery materials, polymers,
adhesives, organic electronics and biomaterials.
It is well known that the physical and mechanical properties of
the DW line are different from the bulk material. As an example,
Marinov and Atanasov applied M3D to deposit a silver ink which
contained 57–62 wt.% of Ag nanoparticles with an average size
smaller than 50 nm. The deposits were then sintered on a hot plate
at 200 8C for 60 min. It was found that the average bulk resistivity
of the conventional M3D lines was 9.2 mV cm compared to bulk
silver of 1.6 mV cm [67].
7.4. Materials used in laser direct writing
Almost any materials can be deposited by laser-based direct
writing. In the 1980s and 1990s, most materials deposited were
inorganic including various metals, semiconductors and ceramics.
Since 2000, more focus has been placed on depositing biomaterials
based on LIFT and MAPLE DW.
Deposition by LCVD from the gas phase normally results in single
element metallic materials such as Al, Si, W and diamond-like
carbon from their gas precursors such as trialkylamine alane
(C2H5)3NAlH3 (TEAA), silane, tungsten hexafluoride WF6 and
ethylene, although it would be possible to deposit metal
oxides, nitrides and carbides, such as Al2O3, SiN, WC, by intro-
ducing O2, N2 gases or gas mixtures in the reaction chamber. Due to
the high temperature of the process, the substrate is normally an
inorganic material such as a metal or metal oxide, ceramic or
semiconductor.
Thin solid film consolidation and backward transfer techni-
ques are applicable to depositing inorganic materials such as
metals, ceramics, composites and semiconductor materials on
inorganic substrates. LEEP allows the deposition of both metallic
and ceramic materials, on both conductive and insulating
substrates. Materials such as Ni, Au, and Pt, can be deposited
from nickel acetate, HAuCl4 and H2PtCl6. Laser-activated electro-
plating is limited to metallic materials only.
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
LIFT and MAPLE DW allow the deposition of most known
materials on to both organic and inorganic substrates due to the
lower temperature operating conditions of the process, through
the introduction of organic binders and sacrificial materials. The
functional materials that have been successfully deposited include
metals and alloys, ceramics, composites, polymers, semiconduc-
tors, cells, and genetic material, e.g. Cu, Au, Ag, Ni, NiCr, YBaCuO,
BiSrCaCuO, Sn, SnO, polypyrrole, BSA, BaTiO3, SrTiO3, Y3Fe5O12,
DNA and eukaryotic cells.
Multi-photon polymerisation mainly uses photo-sensitive
materials such as ORMOCER, although other powder materials
can be embedded into the polymer matrix [99]. The same
technique is able to create protein cross-linking for example in
bovine serum albumin [45]. Laser tweezer and laser-guided
protein cross-linking are suited to small organic and inorganic
particles in a liquid environment.
8. Scope and examples of direct writing applications
Direct writing applications cover very wide sectors of industry
including micro-electronics, MEMS, optics, pharmaceutics and
biomedical engineering because of the multi-length scale from
nano-, micro- to meso-process capabilities. The scope of applica-
tion is also enhanced by the vast range of materials and process
simplicity. In addition, the substrate topologies can be flat, round,
flexible, inflatable, irregular and 3D. An overview of DW products is
shown in Fig. 26.
8.1. Micro-electronics industry
Applications of direct write in the electronic industry includes
embedded devices such as resistors, capacitors, inductors, transis-
Fig. 27. Example of solder bumps (70 mm diameter) deposited by DOD inkjet
printing on to an integrated circuit test substrate [37].
Fig. 28. Inductor fabricated with silver nanoparticle ink by piezo-DOD printing [32].
615
tors, semiconductor ICs and interconnects into the circuit board and
micro-batteries. Other typical DW applications include semicon-
ductor packaging for direct-die attach, flip chip, CSP; solder
bumping, underfilling and encapsulation; high-density traces for
flat panels, solar cells, PCBs [38]. In inkjet DW, both CIJ and DOD
methods have been used to achieve solder drops from tens to
hundreds of micrometres in diameter, with the capability to produce
continuous lines and tracks as well as discrete spheres or dots as
shown for example in Fig. 27. Fig. 28 shows a resonant inductor
printed by DOD with five layers of silver nanoparticle ink.
In laser-based DW, MAPLE DW has been used to fabricate
micro-solenoids and electromagnets and embedded electronic
circuits in polyimide substrates [118]. The 3D circuit occupies
about 1/5 of the foot print and 1/10 of the thickness of a normal
printed circuit board. This represents a volume reduction factor
of 0.1–0.01 [86]. LIFT has been used to fabricate Li- or Li-ion micro-
batteries, which must be electrically insulating, ionically conduct-
ing, and chemically and thermally stable [80]. Laser direct
write using the LIFT technique has enabled the deposition of
thick-film electrodes such as LiCoO2 cathodes and carbon anodes
on metallic collectors. The micro-batteries fabricated in this way
have demonstrated a significantly higher discharge capacity,
power and energy densities than those made by sputter-deposited
thin film techniques. This increased performance is attributed to
the porous structure of the laser-printed electrodes, which
allows improved ionic and electronic transport through the thick
electrodes of about 100 mm without a significant increase in
Fig. 29. (a) Conformal Direct writing of an RF frequency selective pattern. (b) Details
of the silver line pattern [105].
Fig. 30. Prototype ceramic impeller 28 mm in diameter formed by direct DOD inkjet
printing with a suspension of 40 vol.% alumina particles in a wax-based suspension,
followed by sintering [1].
616 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620

internal resistance [48]. LEEP has also been applied to plating of

micro-scale copper wires [13].
The exploitation of conformal electronics is represented by the
direct writing of epoxy loaded Ag on to a glass fibre substrate and
then cured at 120 8C for 10 min using a 24-mm tip on an nScrypt
system. The pattern produced is a band stop periodic structure for
10 GHz as shown in Fig. 29 [105]. Apart from production, DW is
also valuable for the repair of high value micro-electronic parts.
Repair of photomasks by FIB which has a placement accuracy of
less than 75 nm is well established [26]. DW methods such as DPN
and M3D are also applied to the repair of flat panel displays.

8.2. Mechanical engineering

Inkjet printing can be used in rapid prototyping by depositing a

binder fluid on to a ceramic powder bed; ceramic particles can also
be directly deposited by printing a suspension. With an evaporat- Fig. 32. Array of micro-lenses fabricated by DOD inkjet printing from epoxy resin
ing solvent, the maximum concentration of solids which can be [http://www.microfab.com].
achieved in a jettable suspension appears to be low (perhaps
10 vol.%), but demonstrator components have been made by direct
inkjet printing in several ceramics, including zirconia, titania, and
PZT [23]. By using a phase-change ink that solidifies on impact a
much higher solids content, as high as 40 vol.%, can be attained.
Fig. 30 shows an example of an alumina component fabricated in
this way [1].

8.3. Micro-engineering

Inkjet printing can be used to produce ordered 2D arrays of

ceramic particles by a self-assembly process in which the
differential evaporation of mixed solvents plays a critical role, as
shown in Fig. 31 [83]. As this method produces uniform deposits
without segregation, it may be useful in next-generation photonic,
electronic and display devices. As with metallic films, certain
ceramic materials can be produced from printed precursors; an
example is the dielectric ceramic barium strontium titanate which
has been deposited by printing a metal-organic precursor on to a
ceramic substrate, followed by pyrolysis and annealing, to form a
capacitor structure [47].
High-pressure LCVD has been used to produce micro-springs
and coils with fibre diameters of 5–240 mm [118]. Laser DW has
also been applied for the production of 3D micro-cages for electric
trapping of small particles including cells [106]. An unusual
application is the 3D nano-structuring of hybrid materials by two-
photon polymerisation demonstrating micro-art work, such as the
micro-Venus [99].
8.4. Optics
The use of inkjet DW for micro-optics applications is now well
established. For instance, Fig. 32 shows the volume production of
micro-lenses by DOD inkjet printing and Fig. 33 shows the printing
Fig. 31. Two-dimensional array of silica microspheres deposited in suspension by
DOD printing [83].
Fig. 33. Optical waveguide system printed by DOD inkjet on a glass substrate; the
waveguides are 100 mm wide [http://www.microfab.com].
of optical waveguides on a glass substrate by the same process. A
process combining LIFT operating in a vacuum chamber and
chemical treatments in zinc nitrate hexahydrate was used to
deposit and grow nano-ZnO rod arrays on a Si substrate.
Photoluminescence shows strong green-yellow emission centred
at 570 nm [51]. The use of LCVD for the growth of 3D Al2O3 for
photonic band-gap structures has been demonstrated by Wanke
et al. [114]. It has the potential to totally reflect electromagnetic
radiation in a band of frequencies propagating in any direction,
acting as a perfect mirror.
8.5. Biomedical and life sciences
Tissue architecture is complex, characterized by multiple cell
types and matrix components precisely organized in three-
dimensions. Loss of tissue architecture due to trauma or diseases
leads to loss of tissue function. An important advance in tissue
engineering would be the ability to organize multi-cell types in the
well-defined three-dimensional architecture of the native organ, in
essence reconstructing the tissue from its cellular and matrix
components [74]. Laser-guided direct writing has been used to trap
and deliver cells with micrometer resolution on to arbitrary surfaces,
including biological gels. For example, human umbilical vein
endothelial cells have been deposited in two and three dimensions
by laser-guided direct writing [74]. MAPLE DW has been applied to
deposit hydroxyapatite-osteoblast-like cell composites for building
tissue scaffolds. This is known as bioactive ceramic, because it is able
to form strong chemical bonds with adjacent tissues [24]. Osteoblast
cells attach, proliferate and differentiate on these materials. MAPLE
DW has also been used to transfer MG 63 osteoblast cells. DNA has
been deposited using LIFT and MAPLE DW. A scaffold of
5.4 mm  5.4 mm  3.5 mm with a strut thickness of 100 mm
was built in PCL using nScrypt system [60].
Both inkjet and nScrypt methods have been applied to write
fractal antennas on to living creatures. The advantage of fractal
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
Fig. 34. Direct writing of an antenna on to a live ant. The line width of the antenna is
25 mm [58].
antennas is wide bandwidth and size reduction with no loss in
gain. The former process has been applied to a butterfly wing and
the latter application to an ant is shown in Fig. 34. DW will play a
significant role in the integration of materials and devices in high
value new bio-product development. New next-generation pro-
ducts aimed at biological and pharmacological therapies, as well as
smart devices and multi use medical devices are anticipated in the
near future [121].
8.6. Nanomanufacturing
Tip-based DW methods have opened up new nano-scale
applications due to their unique ability to deposit SAM patterns.
Typical applications include: generation of nano-structures with
Au or Si; chemically directed assembly and patterning templates
for either bioactive molecules, e.g. proteins, viruses, etc. or
inorganics, e.g. carbon nanotubes, quantum dots; deposition of
pharmaceuticals, and nano-scale surface feature patterning. New
applications in nano-scale sensors, molecular electronic and
photonic devices are being developed [22,79,103].
9. Challenges in direct writing
There are a number of generic challenges in direct writing
technology. First, there is a strong need to gain deeper under-
standing of the processes with more quantitative process
parameter relationships to be developed. This will produce more
accurate and reliable process modelling leading to eventually
process optimization. Second, improvements in adhesion, surface
finish and resolution of the deposited materials would be
beneficial. Third, faster deposition rates are required to enable
commercialization of some techniques which are still mainly
laboratory-based. Finally, support is needed for the formulation of
the feed materials from a given set of functional performance
criteria. Other specific technical challenges which need to be
overcome include the following examples:
 Measurement of the physical properties of the materials laid
down by direct writing technologies because of the small size
and limited amount of materials available [73].
 The need to maintain edge acuity and elimination of necking at
micro- or nano-level.
 Precision on-off control of droplet-based and tip-based DW
process.
 Scalability for high-throughput production.
 Complexity and control requirements for integration arisen from
large parallel DW system, for instance, in DPN.
For the widely used versatile inkjet-based direct writing
methods, there are many aspects which require further research
and development. Improved models for jet and drop formation,
drop impact and drying/curing would assist with process and
material design. Some intrinsic limitations on fluid properties
617
which result from the processes of jet formation and break-up are
clear, but there is further scope to extend the range of fluids which
can be printed, for example to achieve high concentrations of solid
particles or polymer; better understanding of the printing of non-
Newtonian fluids would be helpful. Conductive inks with lower
cost, which achieve high and stable conductivity deposits with
long lifetimes would find a ready market. There are wide
opportunities for further development of functional optical,
magnetic, optoelectronic and semiconducting materials in forms
amenable to inkjet printing, which is ideally suited to the precise
deposition of very small volumes of special materials. With the
development of new methods of droplet generation, e.g. electro-
static, and better awareness of the process and its capabilities, it is
likely that the applications of inkjet printing in direct-write
manufacturing will become much broader.
In the case of laser-based direct writing, further developments
are necessary to overcome the limitations discussed in Section 4.3.
Commercialization of the laser-based direct writing techniques is
slow due to the high cost of the systems, limitations in depositing
materials and substrate dimensions. To speed up commercializa-
tion, faster deposition rates and reduction of the cost of the
equipment would be desirable. Compared to electron beam and
focused ion beam, the resolution of laser-based direct writing
techniques is diffraction limited and therefore it would be difficult
to achieve a dimensional resolution below 100 nm without major
breakthroughs in the science and technology of lasers and optics.
10. Conclusions
Direct writing is a new class of additive materials processing
techniques which are uniquely characterized by their flexibility,
ability to handle a vast range of materials including living cells,
scalability and exceptional multi-length scale capabilities. Direct
writing employs numerous energy modes and material transfer
mechanisms to deposit functional materials precisely and digitally. It
is the only group of additive materials processing methods which can
cover the length scale from nanometres to millimetres. While a fair
amount of fundamental scientific investigations have been under-
taken, full and accurate process modelling and optimization remain
to be pursued, which will require a multi-disciplinary approach.
The provision of high quality materials of consistent properties
is a pre-requisite for direct writing. Consolidation methods for the
deposited materials to meet functional performance requirements
exist for low temperature deposits but search for more efficient
curing methods still continues. Among the entire group of DW
processes, inkjet DW is the most established followed by laser DW
in terms of industrial applications. New and emerging DW
processes such as flow-based DW have huge application potential.
Tip-based DW offers attractive capabilities of nanomanufacturing
and biomanufacturing. The growth of DW is reflected by the
increasing number of DW systems which range from low-cost to
high-cost, from 1D to 3D and conformal writing.
The benefits of DW are plentiful, particularly in cost reduction
for prototyping and production, process chain simplification
through the reduction of process steps, and greater design freedom
due to its geometrical versatility. As the material is deposited on an
on-demand basis, material wastage is minimal and the impact on
environmental footprint is low. In application, DW has a very wide
application window from prototype evaluation to high-throughput
production. New applications are being announced regularly as
this is still an emerging technology area. Niche applications in
micro-electronics, microsystems packaging, and medical devices
have already been identified.
Key challenges for DW are the development of new design rules,
process modelling and optimization, integration issues for micro-
system applications, metrology and evaluation of functional
performance of DW lines and structures. With increasing develop-
ment in micro- and nano-systems combining biological, electronics,
fluidics and optical functions, DW will play a significant role and will
form a new paradigm in this technology trend.
618 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620

Acknowledgements Khirotdin and Susan Xu of Liverpool University, Dr. Martin Hedges

of Neotech; Dr. Bo Li and Dr. Ken Church of nScrypt Inc.; Tom
The authors would like to acknowledge the contributions from Levesque of NanoInk Inc. and Dr. Graham Martin of Cambridge
the following in the preparation of this paper: Rd Khairilhijra University, Inkjet Research Centre.

Appendix A

Summary of direct writing process characteristics excluding laser-based methods.

Process Methods Mechanisms Line width (Lw) or droplet Deposition rate or Materials
characteristics dia. (Dd) writing speed

Droplet Inkjet continuous Deposition of liquid
droplets, generated by
break-up of continuous jet
Inkjet drop-on- Deposition of liquid
demand droplets, generated
individually when required
Aerosol jet Kinetic bombardment
of atomized droplets
Lw from 20 mm to >5 mm. To 60 mm3/s with Liquid with viscosity
Dd from 10 to 150 mm, a single nozzle 2–10 mPa s; can contain
typically 120 mm small particles
Lw from 20 mm to >5 mm. To 0.3 mm3/s with Liquid with viscosity
Dd from 10 to 150 mm, a single nozzle 10–100 mPa s; can contain
typically 50 mm. small particles
Lw from 5 mm to 5 mm. Dd 0.25 mm3/s with Any materials that can be
from 20 nm to 5 mm a single nozzle atomized plus biomaterials
such as cells

Flow Pump Precision micro-dispensing Lw from 25 mm to 3 mm Max vw is 300 mm/s, Liquid, paste and slurry
pump with suck-back typically 50 mm/s materials up to
action 1,000,000 mPa s
Extrusion Syringe-based and flow Lw from 50 mm to 2.5 mm Typical vw is 25.4 mm/s Liquid, paste and slurry
distribution block materials up to
500,000 mPa s

Tip Dip-pen Molecular deposition via an Lw from 10 nm to a few mm Typical range is Molecule thiol, macromolecule,
nanolithography AFM tip 0.2–5 mm/s nanoparticles
(DPN)
Nanofountain Capillary action of Lw from 40 nm to over Typical vw is about Monomer, nanoparticles
pen (NFP) micro-pipette and the 1.15 mm 0.4 mm/s
substrate

Energy beam Focussed ion Ion-induced deposition of Lw from 80 nm to 20 mm Typical deposition rate Metals and insulators
beam (FIB) precursor gas molecules is 0.05 mm3/s

Appendix B

Summary of laser-based direct writing process characteristics.

Precursors or Methods Mechanisms Line width or Deposition rate or Materials
feed material droplet diameter writing speed

Solid Thin film consolidation Melting, fusion onto substrates 10–50 mm 10–2000 mm/s Metals/ceramics on metal/ceramic
substrates
LIFT and MAPLE DW Transfer of material by kinetic 10–100 mm Typically Metals, ceramics, semiconductors,
energy of vapourising organic 3–50 mm/s, polymer, composite, cells, etc.
binders up to 500 mm/s
Backward transfer Physical vapour/liquid 5–200 mm 10–100 mm/s Metals and ceramics on transparent
deposition after laser substrates
irradiation through transparent
medium

Liquid LEEP Thermal decomposition of the 2–12 mm 0.1–80 mm/s Metals and ceramics on inorganic
liquid substrates
Laser-activated Accelerated chemical reaction 0.1–300 mm Typically 0.1–10 m/ Metals on metallic substrates
electroplating by local high temperatures s, up to 2.5 m/s

Gas LCVD Decomposition of gases after 1–20 mm Typically Metals, semiconductors and
vapourisation and 50–200 mm/s, ceramics such as Al, W, Si, Al2O3,
condensation takes place up to 5 mm/s WC

Cells/DNA Trapping-guidance, Momentum balance 0.1–10 mm 10–300 mm/s Cells, small particles in liquid
tweezer
LIFT, BioLP and Laser heating of sacrificial Dd from 30 0.1–10 droplets Cells, polymer, genes, tissue
MAPLE DW material causing, deformation, to 100 mm per second materials, etc. on any substrates
vapour, propelling the liquid
containing biomaterials
 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
References
[1] Ainsley C, Reis N, Derby B (2002) Freeform Fabrication by Controlled Droplet
Deposition of Powder Filled Melts. Journal of Materials Science 37(15):3155–
3161.
[2] Akhatov IS, Hoey JM, Swenson OF, Schulz DL (2008) Aerosol Flow Through a
Long Micro-Capillary: Collimated Aerosol Beam. Microfluidics and Nanofluidics
5(2):215–224.
[3] Ashkin A (1992) Forces of A Single-Beam Gradient Laser Trap on Dielectric
Sphere in The Ray Optics Regime. Biophysics Journal 61(2):569–582.
[4] Baldacchini T, LaFratta CN, Farrer RA, Teich MC, Saleh BE, Naughton MJ,
Fourkas JT (2004) Acrylic-based Resin with Favourable Properties for Three-
dimensional Two-Photon Polymerization. Journal of Applied Physics
95(11):6072–6076.
[5] Barron JA, Wu P, Ladouceur HD, Ringeisen BR (2004) Biological Laser Printing:
A Novel Technique for Creating Heterogeneous 3-dimensional Cell Patterns.
Biomedical Microdevices 6(2):139–147.
[6] Basaran OA (2002) Small-Scale Free Surface Flows with Breakup: Drop
Formation and Emerging Applications. AIChemE Journal 48(9):1842–1848.
[7] Belmont AS, Sokuler M, Haupt K, Gheber LA (2007) Direct Writing of Mole-
cularly Imprinted Microstructures Using a Nanofountain Pen. Applied Physics
Letters 90(19):193101–193103.
[8] Benbow JJ, Oxley E, Bridgwater J (1987) The Extrusion Mechanics of Pastes—
The Influence of Paste Formulation on Extrusion Parameters. Chemical Engi-
neering Science 42(9):2151–2162.
[9] Bohandy J, Kim BF, Adrian FJ (1986) Metal-Deposition From a Supported
Metal-Film Using an Excimer Laser. Journal of Applied Physics 60:1538–1539.
[10] Bohandy J, Kim BF, Adrian FJ, Jette AN (1988) Metal-Deposition at 532-nm
Using a Laser Transfer Technique. Journal of Applied Physics 63:1158–1162.
[11] Calvert P (2001) Inkjet Printing for Materials and Device. Chemical Material
13(10):3299–3305.
[12] Campbell AN, Tanner DM, Soden JM, Stewart DK, Doyle A, Adam E, Gibson M,
Abramo M (1997) Electrical and Chemical Characterization of FIB-Deposited
Insulators. Proceedings of the 23 International Symposium on Testing and Failure
Analysis, 223–230.
[13] Chen QJ, Imen K, Allen SD (2000) Laser Enhanced Electroless Plating of
Micron-Scale Copper Wires. Journal of Electrochemical Society 147(4):1418–
1422.
[14] Cheng SX, Li T, Chandra S (2005) Producing Molten Metal Droplets with a
Pneumatic Droplet-on-Demand Generator. Journal of Materials Processing
Technology 159(3):295–302.
[15] Chrisey DB, Pique A, McGill RA, Horwitz JS, Ringeisen BR, Bubb DM, Wu PK
(2003) Laser Deposition of Polymer and Biomaterial Films. Chemical Reviews
103:553–576.
[16] Chrisey DB, Pique A, Modi R, Wu HD, Auyeung RCY, Young HD (2000) Direct
Writing of Conformal Mesoscopic Electronic Devices by MAPLE DW. Applied
Surface Science 168(1–4):345–352.
[17] Claeyssens F, Klini A, Mourka A, Fotakis C (2007) Laser Patterning of Zn for
ZnO Nanostructure Growth: Comparison Between Laser Induced Forward
Transfer in Air and in Vacuum. Thin Solid Films 515(24):8529–8533.
[18] Colina M, Duocastella M, Fernadez-Pradas JM, Serra P, Morenza JL (2006)
Laser-induced Forward Transfer of Liquids: Study of the Droplet Ejection
Process. Journal of Applied Physics 99(8):084909–084915.
[19] Colina M, Serra P, Fernandez-Pradas JM, Sevilla L, Morenza JL (2005) DNA
Deposition Through Laser Induced Forward Transfer. Biosensors and Bioelec-
tronics 20(8):1638–1642.
[20] Cossali GE, Coghe A, Marengo M (1997) The Impact of a Single Drop on a
Wetted Solid Surface. Experiments in Fluids 22:463–472.
[21] Davies GJ, Edington JW, Cutler CP, Padmanabhan KA (1970) Superplasticity: A
review. Journal of Materials Science 5(12):1091–1102.
[22] De S, Pal A, Pal T (2000) Molecular Photonic Switches Employing Ions and
Nanoparticles of Coinage and Platinum Metals. Langmuir 16(17):6855–6861.
[23] de Gans BJ, Duineveld PC, Schubert US (2004) Inkjet Printing of Polymers: State
of The Art and Future Developments. Advanced Materials 16(3):203–213.
[24] Doraiswamy A, Narayan RJ, Harris ML, Qadri SB, Modi R, Chrisey DB (2006)
Laser Microfabrication of Hydroxyapatite-Osteoblast-like Cell Composites.
Journal of Biomedical Materials Research A 80A(3):635–643.
[25] DTI (2004) Direct Writing: Global Status and Opportunities for the UK in
Advanced Manufacturing-Scoping Study, DTI.
[26] Edinger K (2002) in Pique A, Chrisey DB, (Eds.) Focused Ion Beam for Direct
Writing, in Direct Write Technologies for Rapid Prototyping Applications. Aca-
demic Press, pp. 347–383.
[27] Edinger K, Melngailis J, Orloff J (1998) Study of Precursor Gases for Focused
Ion Beam Insulator Deposition. Journal of Vacuum Science and Technology B
16(6):3311–3314.
[28] Fan H, Reed S, Baer T, Schunk R, López GP, Brinker CJ (2001) Hierarchically
Structured Functional Porous Silica and Composite Produced by Evaporation-
Induced Self-Assembly. Microporous and Mesoporous Materials 44–45:625–
637.
[29] Fernadez-Pradas JM, Colina M, Serra P, Dominguez J, Morenza JL (2004) Laser-
induced Forward Tranfer of Biomolecules. Thin Solid Films 453–454:27–30.
[30] Fogarassy E, Fuchs C, Kerherve F, Hauchecome G, Perriere J (1989) Laser-
Induced Forward Transfer of High-Tc YBaCuO and BiSrCaCuO Superconduct-
ing Thin Films. Journal of Applied Physics 66:457–459.
[31] Foulon F, Stuke M (1993) Argon-ion Laser Direct-Write Al Deposition from
Trialkylamine Alane Precursors. Applied Physics A 56(3):283–289.
[32] Fuller SB, Wilhelm EJ, Jacobson JM (2002) Ink-Jet Printed Nanoparticle
Microelectromechanical Systems. Journal of Microelectromechanical Systems
11(1):54–60.
[33] Furukawa Y, Ohishi S, Shiozaki S (1979) Selection of Creep Feed Grinding
Conditions in View of Workpiece Burning. Annals of the CIRP 28(1):213–216.
619
[34] Gross ME, Appelbaum A, Schnoes KJ (1986) A Chemical and Mechanistic View
of Reaction Profiles in Laser Direct-Write Metallization in Metallo-Organic
Films, Gold. Journal of Applied Physics 60(2):529–533.
[35] Gross ME, Appelbaum A, Gallagher PK (1987) Laser Direct Write Metalliza-
tion in Thin Palladium Acetate Films. Journal of Applied Physics 61(4):1628–
1632.
[36] Hai JT, Gong FZ, Wang XM, Qin XY, Ma TY (1986) Superplastic Precision
Forming of Ti-Alloy Integrated Turbine Disc. Annals of the CIRP 35(1):185–
188.
[37] Hayes DJ, Wallace DB, Cox WR (1999) Micro Jet Printing of Solder and
Polymers for Multi-Chip Modules and Chip-Scale Packages. Proceedings of
the IMAPS International Conference on High Density Packaging and MCMs, .
[38] Hedges M (2008) Private communication, Neotech.
[39] Hill RT, Lyon JL, Allen R, Stevenson KJ, Shear JB (2005) Aqueous Microfabrica-
tion of Bioelectronic Architectures. Journal of the American Chemical Society
127(30):10707–10711.
[40] Hong S, Eby R, Myung S, Lee BY, Rao SG, Jang J (2006) in Samori P, (Ed.) Dip-
pen Nanolithography in Scanning Probe Microscopies Beyond Imaging. Wiley,
pp. 141–174.
[41] Hong S, Zhu J, Mirkin CA (1999) Multiple Ink Nanolithography: Toward a
Multiple-Pen Nano-Plotter. Science 286:523–525.
[42] Hörteis M, Mette A, Richter PL, Fidorra F, Glunz SW (2007) Further Progress in
Metal Aerosol Jet Printing for Front Side Metallization of Silicon Solar Cells.
Proceedings of the 22nd European Photovoltaic Solar Energy Conference, .
[43] Hwang K, Dinh VD, Lee SH, Kim YJ, Kim HM (2007) Analysis of Line Width
with Nano Fountain Pen Using Active Membrane Pumping. Proceedings of the
2nd IEEE International Conference on Nano Micro Engineered and Molecular
Systems, 759–763.
[44] Jang J, Hong S, Schatz GC, Ratner MA (2001) Self-assembly of Ink Molecules in
Dip-Pen Nanolithography: A Diffusion Model. Journal of Chemical Physics
115(6):2721–2729.
[45] Kaehr B, Ertas N, Nielson R, Allen R, Hill R, Plenert M, Shear JB (2006) Direct-
write Fabrication of Functional Protein Matrixes Using a Low-cost Q-
switched Laser. Analytical Chemistry 78(9):3198–3202.
[46] Kawata S, Sun HB, Tanaka T, Takada K (2001) Finer Features for Functional
Microdevices. Nature 412:697–698.
[47] Kaydanova T, Miedaner A, Perkins JD, Curtis C, Alleman JL, Ginley DS (2007)
Direct-write Inkjet Printing for Fabrication of Barium Strontium Titanate-
Based Tunable Circuits. Thin Solid Films 515:3820–3824.
[48] Kim H, Auyeung RCY, Pique A (2007) Laser-printed Thick-film Electrodes for
Solid-State Rechargeable Li-ion Microbatteries. Journal of Power Sources
165(1):413–419.
[49] Kim KH, Moldovan N, Espinosa HD (2005) A Nanofountain Probe with Sub-
100 nm Molecular Writing Resolution. Small 1(6):632–635.
[50] King WP, Kenny TW, Goodson KE, Cross G, Despont M, Durig U, Rothuizen H,
Binnig GK, Vettiger P (2001) Atomic Force Microscope Cantilevers for Com-
bined Thermomechanical Data Writing and Reading. Applied Physics Letters
78(9):1300–1302.
[51] Klinni A, Mourka A, Dinca V, Fotakis C, Claeyssens F (2007) ZnO Nanorod
Micropatterning via Laser-induced Forward Transfer. Applied Physics A
87:17–22.
[52] Le HP (1998) Progress and Trends in Ink-Jet Printing Technology. Journal of
Imaging Science and Technology 42(1):49–62.
[53] Lee HW, Allen SD (1991) High Deposition Rate Laser Direct Writing of Al on Si.
Applied Physics Letters 58(19):2088–2089.
[54] Lehmann O, Stuke M (1994) Three-dimensional Laser Direct Writing of
Electrically Conducting and Isolating Microstructures. Materials Letters
21(2):131–135.
[55] Levy G, Schindel R, Kruth JP (2003) Rapid Manufacturing and Rapid Tooling
with Layer Manufacturing Technologies: State of The Art and Future Per-
spectives. Annals of the CIRP 52(2):589–609.
[56] Lewis A, Kheifetz Y, Shambrodt E, Radko A, Khatchatryan E (1999) Fountain
Pen Nanochemistry: Atomic Force Control of Chrome Etching. Applied Physics
Letters 75(17):2689–2691.
[57] Lewis JA, Gratson GM (2004) Direct Writing in Three Dimensions. Materials
Today 7(7–8):32–39.
[58] Li B (2008) Private Communication, nScrypt.
[59] Li B, Clark PA, Church KH (2007) Robust Direct-Write dispensing tool and
solutions for micro meso-scale manufacturing and packaging. Proceedings of
the International Conference on Manufacturing Science and Engineering, .
[60] Li B, Roy TD, Smith CM, Clark PA, Church KH (2007) A Robust True Direct-Print
Technology for Tissue Engineering. Proceedings of the International Conference
on Manufacturing Science and Engineering, .
[61] Liu Q, Orme M (2001) On Precision Droplet-Based Net-Form Manufacturing
Technology. Proceedings of the IMechE Part B Journal of Engineering Manufac-
ture 215(10):1333–1355.
[62] Liu Q, Orme M (2001) High Precision Solder Droplet Printing Technology and
The State-of-The-Art. Journal of Materials Processing Technology 115:271–283.
[63] McNeal ME, Jang SJ, Newnham RE (1996) Particle Size Dependent High
Frequency Dielectric Properties of Barium Titanate. Proceedings of the IEEE
International Symposium on Applied Ferroelectrics, vol. 2, 837–840.
[64] McWilliams BM, Herman IP, Mitlitsky F, Hyde RA, Wood LL (1983) Wafer-
scale Laser Pantography: Fabrication of n-Metal-Oxide-Semiconductor Tran-
sistors and Small-scale Integrated Circuits by Direct-write Laser-Induced
Pyrolytic Reactions. Applied Physics Letters 43(10):946–948.
[65] Malba V, Bernhardt AF (1992) Laser Surface Modification for Selective
Electroplating of Metal: A 2.5 m/s Laser Direct Write Process. Applied Physics
Letters 60(7):909–911.
[66] Manandhar P, Jang J, Schatz GC, Ratner MA, Hong S (2003) Anomalous Surface
Diffusion in Nanoscale Direct Deposition Processes. Physical Review Letters
90(11):1155051–1155054.
620 K.K.B. Hon et al. / CIRP Annals - Manufacturing Technology 57 (2008) 601–620
[67] Marinov V, Atanasov Y (2006) Improved Direct Write Technology for High
Frequency Interconnects on Flexible Substrates. Proceedings of the 39th IMAPS
International Symposium on Microelectronics, .
[68] Martin GD, Hoath SD, Hutchings IM (2008) Inkjet Printing—The Physics of
Manipulating Liquid Jets and Drops. Journal of Physics Conference Series
105:012001.
[69] Mei J, Lovell MR, Mickle MH (2005) Formulation and Processing of Novel
Conductive Solution Inks in Continuous Inkjet Printing of 3-D Electric Cir-
cuits. IEEE Transactions of Electronics Packaging Manufacturing 28(3):265–273.
[70] Mir-Hosseini N, Schmidt MJJ, Li L (2005) Growth of Patterned Thin Metal
Oxide Films on Glass Substrate from Metal Bulk Sources Using a Q-switched
YAG Laser. Applied Surface Science 248:202–208.
[71] Moldovan N, Kim KH, Espinosa HD (2006) A Multi-Ink Linear Array of
Nanofountain Probes. Journal of Micromechanics and Microengineering
16:1935–1942.
[72] Morgan JC (1998) Focused Ion Beam Mask Repair. Solid State Technology
41:61–67.
[73] Nagel DJ (2002) in Pique A, Chrisey DB, (Eds.) Technologies for Micrometer and
Nanometer Pattern and Material Transfer, in Direct Write Technologies for Rapid
Prototyping Applications. Academic Press, pp. 557–701.
[74] Nahmias Y, Schwartz RE, Verfaillie CM, Odde DJ (2005) Laser-guided Direct
Writing for Three-dimensional Tissue Engineering. Biotechnology and Bioen-
gineering 92(2):129–136.
[75] Nahmias YK, Gao BZ, Odde DJ (2004) Dimensionless Parameters for the
Design of Optical Traps and Laser Guidance Systems. Applied Optics
43(20):3999–4006.
[76] NanoInk (2008) www.nanoink.net/BasicResearch.htm.
[77] Odde DJ, Renn MJ (1999) Laser-guided Direct Writing for Applications in
Biotechnology. Trends in Biotechnology 17:385–389.
[78] Odde DJ, Renn MJ (2000) Laser-guided Direct Writing of Living Cells. Bio-
technology and Bioengineering 67(3):312–318.
[79] Ogawa T, Kobayashi K, Masuda G, Takase T, Maeda S (2001) Electronic
Conductive Characteristics of Devices Fabricated with 1,10-Decanedithiol
and Gold Nanoparticles Between 1-Mm Electrode Gaps. Thin Solid Films
393(1):374–378.
[80] Ollinger M, Kim H, Sutto T, Pique A (2006) Laser Printing of Nanocomposite
Solid-State Electrolyte Membranes for Li Micro-batteries. Applied Surface
Science 252(23):8212–8216.
[81] Optomec (2008) M3D 300 Data sheet.
[82] Park BK, Kim D, Jeong S, Moon J, Kim JS (2007) Direct Writing of Copper
Conductive Patterns by Ink-Jet Printing. Thin Solid Films 515(19):7706–7711.
[83] Park J, Moon J (2006) Control of Colloidal Particle Deposit Patterns within
Picoliter Droplets Ejected by Inkjet Printing. Langmuir 22:3506–3513.
[84] Parkinson WH, Yoshino K (2003) Absorption Cross-section Measurements of
Water Vapour in the Wavelength Region 181–199 nm. Chemical Physics
294(1):31–35.
[85] Piner RD, Zhu J, Xu F, Hong SH, Mirkin CA (1999) Dip-Pen Nanolithography.
Science 283:661–663.
[86] Pique A, Arnold CB, Kim H, Ollinger M, Sutto TE (2004) Rapid Prototyping of
Micropower Sources by Laser Direct-write. Applied Physics A 79:783–786.
[87] Pique A, Chrisey DB (2002) Direct-Write Technologies for Rapid Prototyping
.Applications: Sensors, Electronics and Integrated Power Sources. Academic Press
[88] Pique A, Chrisey DB, Auyeung RC, Fitz-Gerald J, Wu HD, McGill RA, Lakeou S,
Wu PK, Nguyen V, Duignan M (1999) A Novel Laser Transfer Process for Direct
Writing of Electronic and Sensor Materials. Applied Physics A 69(1):S279–
S284.
[89] Pitts JD, Campagnola PJ, Epling GA, Goodman SL (2000) Submicron Multi-
photon Free-form Fabrication of Proteins and Polymers: Studies of Reaction
Efficiencies and Applications in Sustained Releases. Macromolecules
33(5):1514–1523.
[90] Pouliquen O, Nicolas M, Weidman PD (1997) Crystallization of Non-Brownian
Spheres under Horizontal Shaking. Physical Review Letters 79(19):3640–3643.
[91] Puippe JC, Acosta RE, von Gutfeld RJ (1981) Investigation of Laser-enhanced
Electroplating Mechanisms. Journal of Electrochemical Society 128(12):2539–
2545.
[92] Renn MJ, Marquez G, King BH, Essien M, Miller DW (2002) in Pique A, Chrisey
DB, (Eds.) Flow- and Laser-Guided Direct Write of Electronic and Biological
Components, in Direct Write Technologies for Rapid Prototyping Applications.
Academic Press, pp. 475–492.
[93] Reyntjens S, Puers R (2001) A review of Focused Ion Beam Applications in
Microsystem Technology. Journal of Micromechanics and Microengineering
11:287–300.
[94] Ringeisen BR, Chrisey DB, Pique A, Young HD, Modi R, Bucaro M, Jones-
Meehan J, Spargo BJ (2002) Generation of Mesoscopic Patterns of Viable
Escherichia coli by Ambient Laser Transfer. Biomaterials 23:161–166.
[95] Rioboo R, Marengo M, Tropea C (2002) Time Evolution of Liquid Drop Impact
onto Solid, Dry Surfaces. Experiments in Fluids 33:112–124.
[96] Salaita K, Wang Y, Fragala J, Vega RA, Liu C, Mirkin CA (2006) Massively
Parallel Dip-Pen Nanolithography with 55000-Pen Two-Dimensional Arrays.
Angewandte Chemie International Edition 45:7220–7223.
[97] Schiaffino S, Sonin AA (1997) Molten Droplet Deposition and Solidification at
Low Weber Numbers. Physics of Fluids 9(11):3172–3187.
[98] Schulz H, Moriwaki T (1992) High Speed Machining. Annals of the CIRP
41(2):637–643.
[99] Serbin J, Chichkov BN, Houbertz R (2003) Three-dimensional Nanostructur-
ing of Hybrid Materials by Two-Photon Polymerization. Proceedings of SPIE
5222:171–177.
[100] Serra P, Fernandez-Pradas JM, Berthet FX, Colina M, Elvira J, Morenza JL
(2004) Laser Direct Writing of Biomolecule Microarrays. Applied Physics A
79:949–952.
[101] Sheehan PE, King WP, Laracuente AR, Yang M, Whitman LJ (2006) Thermal
Dip Pen Nanolithography. Chemical Biochemical Research NRL Review 1–2.
[102] Sheehan PE, Whitman LJ, King WP, Nelson BA (2004) Nanoscale Deposition of
Solid Inks via Thermal Dip Pen Nanolithography. Applied Physics Letters
85(9):1589–1591.
[103] Shipway AN, Katz E, Willner I (2000) Nanoparticle Arrays on Surfaces for
Electronic, Optical, and Sensor Application. ChemPhysChem 1(1):18–52.
[104] Srivastva PB, Boose CA, Kolster BH, Harteveld C, Meinders B (1991) Selective
Metallisation of Alumina by Laser. Surface and Coatings Technology 46:131–
138.
[105] Sidhu J (2004) Case study-Conformal Electronics, BAE Systems Report.
[106] Stuke M, Mueller K, Mueller T, Hagedorn R, Jaeger M, Fuhr G (2005) Laser-
Direct-Write Creation of Three-dimensional OREST Microcages for Contact-
Free Trapping, Handling and Transfer of Small Polarizable Neutral Objects in
Solution. Applied Physics A 81(5):915–922.
[107] Tanner LH (1979) The Spreading of Silicone Oil Drops on Solid Surfaces.
Journal of Physics D Applied Physics 12:1473–1484.
[108] Tlusty J (1993) High Speed Machining. Annals of the CIRP 42(2):733–738.
[109] Torquato S, Truskett TM, Debenedetti RG (2000) Is Random Close Packing of
Spheres Well Defined? Physical Review Letters 84(10):2064–2067.
[110] von Gutfeld RJ, Acosta RE, Romankiw LT (1982) Laser-Enhanced Plating and
Etching: Mechanisms and Applications. IBM Journal of Research and Devel-
opment 26(2):136–144.
[111] von Gutfeld RJ, Tynan EE, Melcher RL, Blum SE (1979) Laser Enhanced
Electroplating and Maskless Pattern Generation. Applied Physics Letters
35:651–653.
[112] Vozzi G, Previti A, De Rossi D, Ahluwalia A (2002) Microsyringe-Based
Deposition of Two-Dimensional and Three-Dimensional Polymer Scaffolds
with a Well-Defined Geometry for Application to Tissue Engineering. Tissue
Engineering 8(6):1089–1098.
[113] Wang T, Derby B (2005) Ink-jet Printing and Sintering of PZT. Journal of the
American Ceramic Society 88(8):2053–2058.
[114] Wanke MC, Lehmann O, Muller K, Wen Q, Stuke M (1997) Laser Rapid Proto-
typing of Photonic Band-Gap Microstructures. Science 275(5304):1284–1286.
[115] Wartena R, Curtright AE, Arnold CB, Pique A, Swider-Lyons KE (2004) Li-ion
Micro-batteries Generated by a Laser Direct-write Method. Journal of Power
Sources 126(1):193–202.
[116] Webster J, Brinksmeier E, Heinzel C, Wittmann M, Thoens K (2002) Assess-
ment of Grinding Fluid Effectiveness in Continuous-Dress Creep Feed Grind-
ing. Annals of the CIRP 51(1):235–238.
[117] Wee LM, Li L (2005) Multiple Layer Laser Direct Writing Metal Deposition in
Electrolyte Solution. Applied Surface Science 247(1):285–293.
[118] William K, Maxwell J, Larsson K, Boman M (1999) Freeform Fabrication of
Functional Microsolenoids, Electromagnets and Helical Springs Using High-
pressure Laser Chemical Vapour Deposition. Proceedings of the 12th IEEE
International Conference on Micro Electro Mechanical Systems (MEMS 99), 232–
237.
[119] Wu PK (2001) The Deposition, Structure, Pattern Deposition and Activity of
Biomaterial Thin-Films by Matrix-assisted Pulsed Laser Evaporation (MAPLE)
and MAPLE Direct Write. Thin Solid Films 398:607–614.
[120] Wu PK, Ringeisen BR, Krizman DB, Frondoza CG (2003) Laser Transfer of
Biomaterials: Matrix-assisted Pulsed Laser Evaporation (MAPLE) and MAPLE
Direct Write. Review of Scientific Instrumentation 74(4):2546–2557.
[121] www.micropen.com, 2008.
[122] Yarin AL (2006) Drop Impact Dynamics: Splashing, Spreading, Receding,
Bouncing. . .. Annual Review of Fluid Mechanics 38:159–192.
[123] Young D, Auyeung RCY, Pique A, Chrisey DB, Dlott DD (2001) Time-resolved
Optical Microscopy of a Laser-based Forward Transfer Process. Applied
Physics Letters 78:3169–3171.
[124] Young RJ, Puretz J (1995) Focused Ion Beam Insulator Deposition. Journal of
Vacuum Science and Technology B 13(6):2576.
[125] Zhang C, Liu D, Mathews SA, Graves J, Shaefer TM, Gilbert BK, Modi R, Wu HD,
Chrisey DB (2003) Laser Direct-write and Its Application in Low Temperature
Co-fired Ceramic (LTTC) Technology. Microelectronic Engineering 70(1):41–49.