Particuology 19 (2015) 1–13

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Particuology
journal homepage: www.elsevier.com/locate/partic

Invited review

Recent advances in inkjet printing synthesis of functional

metal oxides
Xiaonao Liu a,b,∗∗ , Tzyh-Jong Tarn b , Fenfen Huang a , Jie Fan a,∗
a
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
b
Department of Electrical and Systems Engineering, Washington University, St. Louis, MO 63130, USA

a r t i c l e i n f o a b s t r a c t

Article history: Inkjet printing (IJP) synthesis has emerged as a useful technique for the fabrication of functional metal
Received 21 February 2014 oxides in the fields of nanotechnology and materials science. In this paper, we will review the fundamental
Received in revised form 30 April 2014 state-of-the-art principles of the special ink formulations used for IJP synthesis of functional metal oxides
Accepted 7 May 2014
and the applications of these oxides.
© 2014 Published by Elsevier B.V. on behalf of Chinese Society of Particuology and Institute of Process
Keywords:
Engineering, Chinese Academy of Sciences.
Inkjet printing
Metal oxide
Catalysis
Sensor
Ink

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Inkjet functional ink properties requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Ink compositions for IJP synthesis of metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Liquid carrier medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Metal species precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Colloidal suspensions of metal oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Metal salt solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Colloidal nanoparticles based on sol–gel chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Applications for IJP synthesis of metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Introduction

Metal oxides, and particularly multi-component metal oxides,

have been studied as promising solid-state materials for a wide
∗ Corresponding author. Tel.: +86 571 87952338.
∗∗ Corresponding author at: Department of Chemistry, Zhejiang University,
variety of applications in the fields of nanotechnology (Brosseau,
Hangzhou 310027, China.
Youssef, Talbot, & Konn, 2003; Devan, Patil, Lin, & Ma, 2012) and
E-mail addresses: jfan@zju.edu.cn, liuxiaonao@gmail.com (X. Liu), materials science (Bisquert et al., 2008; Jiang et al., 2012) because of
jfan@zju.edu.cn (J. Fan). their unique chemical, physical and mechanical properties. These

http://dx.doi.org/10.1016/j.partic.2014.05.001
1674-2001/© 2014 Published by Elsevier B.V. on behalf of Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences.
2 X. Liu et al. / Particuology 19 (2015) 1–13
oxides have been widely used, not only as supporting or active
species in catalysis (Fan, Liu, & Huang, 2013; Jackson & Hargreaves,
2009; Li & Shen, 2012; Wachs, 2005), but also as a basis for the
fabrication of electronic devices (Lokhande, Dubal, & Joo, 2011;
Meyer et al., 2012; Sun, Thompson, & Nishida, 2007), solar cells
(Jose, Thavasi, & Ramakrishna, 2009), and chemical sensors (Sun
et al., 2012; Wang, Yin, Zhang, Xiang, & Gao, 2010). Because of the
specific characteristics or properties of metal oxides, such as parti-
cle sizes, structures, and compositional variables, that are required
for different applications, a high-yield and reproducible synthesis
method for the production of these metal oxides is required. Inkjet
printing (IJP) is regarded as one of the most promising techniques
for the creation of functional metal oxides on various substrates
because it has an automatically controlled printing scheme with
precise and flexible droplet volumes, it provides a homogeneous
mix at the molecular level in the liquid state, and it offers rapid
mass production.
In 1997, Schultz and co-workers reported the first example of
use of an inkjet delivery system to form a library of phosphors
based on rare-earth-activated metal oxides (de Gans & Schubert,
2003). Since then, the research interest in IJP fabrication of metal
oxides has increased significantly, as clearly demonstrated by more
than 200 scientific publications on the subject over the past decade.
These publications mainly focus on two aspects: (1) formation of
uniform thin films for electronic devices, energy storage and gas
sensor applications, and (2) high-throughput fabrication of a com-
plex metal oxide library for the optimization and discovery of new
functional materials. The aim of this review is to introduce the IJP
technique to recent graduates or researchers who are not familiar
with this technique. We will therefore not offer in-depth explana-
tions of the following inkjet printing fundamentals here: (1) drop
generation, (2) drop interaction with the substrate, and (3) drying
of the drops to form a solid. These processes are obviously very
important to the fabrication of high-quality ceramic, polymer, and
metal components, and several excellent reviews are available that
cover these aspects (Calvert, 2001; Derby, 2011; Singh & Sariciftci,
2006; Singh, Haverinen, Dhagat, & Jabbour, 2010; Tekin, Smith, &
Schubert, 2008).
This review summarizes the major advances in nano-ink formu-
lations for the generation of new solid-state materials during the
period from 2008 to 2013, including progress made in the combina-
torial discovery and optimization of inorganic and heterogeneous
catalysts, the development of sensors, and other applications of
these materials. The vast majority of industrial IJP equipment is
designed for use with inks for graphics applications and is not com-
patible with metal oxide inks. For the aforementioned electronic
applications, the formulation of jettable inks, which are composed
of a liquid carrier medium, metal oxide precursors and other addi-
tives, is the most critical step. These jettable functional inks are
designed to have chemical and physical properties that are similar
to those of standard inkjet inks to further enhance the compatibil-
ity of these inks with the print-head system and the drop ejection
morphology when using a stable system.
Inkjet functional ink properties requirements
We begin with a brief introduction to IJP technology. Inkjet
printers operate in either continuous or drop-on-demand (DOD)
modes. In the continuous mode (Fig. 1(a)), the ink is pumped
through a nozzle to form a liquid jet. Uniformly spaced and sized
droplets are obtained by periodic perturbation of the jet, leading
to surface tension-driven jet break-up. Continuous IJP has been
widely used in the industrial coding, marking and labeling markets,
where speed is essential. Compared with the continuous mode,
the DOD mode offers smaller drop sizes, greater accuracy and
fewer restrictions on the properties of the ink. The DOD mode is
the dominant technique for the fabrication of functional materials.
An acoustic pulse that is generated thermally or piezoelectrically
ejects the ink droplets from a reservoir through a nozzle. In a ther-
mal DOD inkjet printer or a bubble jet (Fig. 1(b)), a heat resistor
is applied to raise the ink temperature to the bubble nucleation
temperature, which then produces a vapor bubble and forces an
ink droplet out of the nozzle. However, control of the variable ink
temperature presents a major challenge to the stability of the ink
formulation, particularly for a chemical solution system. In addi-
tion, thermal DOD is largely restricted to aqueous systems and
therefore imposes severe restrictions on the selection of the metal
oxide precursors. Piezoelectric DOD IJP (Fig. 1(c)), however, relies
on the deformation of a piezoelectric membrane to generate an
acoustic pulse. Without the need for temperature variation, piezo-
electric DOD is in principle suitable for use with a wider variety of
solvents, and is thus the best option for combinatorial purposes.
In the printing process, to avoid the agglomeration of ink
components that would clog the print head reservoir, the inkjet
solutions used for the fabrication of functional metal oxide mate-
rials should have properties such as particle size, viscosity, surface
tension, and density that are equivalent to those of standard inkjet
printer inks. The general property requirements for fluids to be used
in inkjet printers are listed in Table 1 (Blazdell, Evans, Edirisinghe,
Shaw, & Binstead, 1995; Dong, Carr, & Morris, 2006; Mott, Song, &
Evans, 1999; Oezkol, Ebert, & Telle, 2010). Among these properties,
the viscosity and the surface tension must be carefully controlled
and adjusted, because they strongly affect the fluid dynamics of
the droplets. Inks with high viscosity reduce the droplet ejection
speed, leading to aggregation and agglomeration of the inks in the
print head channels. However, high surface tension makes drop
generation difficult and it becomes easy to form satellite droplets
rather than a single drop of ideal size. If the surface tension of the
ink is too low, it can lead to pollution of the droplets that makes
liquid ink drip toward the substrate at random during the printing
process. Several excellent reviews have been published in recent
years that can help readers to better understand the principles of
ink formulation (Derby, 2010; Duineveld et al., 2002; Sun et al.,
1997).
The fluid rheological requirements for printable inks are deter-
mined by the physics and the fluid mechanics of the drop
generation process (Maier, Stöwe, & Sieg, 2007; Martin, Hoath, &
Hutchings, 2008). The behavior of fluids can be represented by the
Reynolds, Weber, and Ohnesorge numbers (Re, We, Oh):
v˛
Re = , (1a)

v2 ˛
We = , (1b)

√
We 
Oh = = . (1c)
Re (˛)1/2
Here, , , and  are the density, dynamic viscosity and surface
tension of the fluid, respectively, v is the velocity, and ˛ is a char-
acteristic length. Another useful parameter is the Z number, which
is the inverse of the Ohnesorge number (Oh), is independent of
the fluid velocity and can be used to evaluate the printability of an
inkjet ink. The equation for the Z number is as follows:
1
Z= . (1d)
Oh
Fromm (1984) defined the parameter based on a simple model of
fluid flow in a drop generator with simplified geometry and pro-
posed Z > 2 as the best condition for formation of stable droplets.
 X. Liu et al. / Particuology 19 (2015) 1–13 3

Fig. 1. The principles of ink-jet printing: (a) a continuous mode inkjet printer, (b) a thermal DOD inkjet printer, and (c) a piezoelectric DOD inkjet printer (Maier et al., 2007;
Tekin et al., 2008).

Reis and Derby (2000) extended this result through numerical sim- out of the nozzle, whereas with high Z values, multiple satellite
ulations and showed that optimal droplets can be generated when droplets are generated to accompany a single defined drop. Later,
Z has values in the range between 1 and 10. For an inkjet ink with Jang, Kim, and Moon (2009) reported a printable range of 4 ≤ Z ≤ 14
a low Z value, highly-viscous fluid prevents the drop from coming based on their experimental results (the fluid mixtures used were
4 X. Liu et al. / Particuology 19 (2015) 1–13
Table 1
Fluid properties requirements.
Particle size (␮m)
Continuous inkjet ink <1
Thermal <1
DOD inkjet ink
Piezoelectric <1
ethanol, water and ethylene glycol) by considering characteristics
such as single droplet formability, positional accuracy, and maxi-
mum allowable jetting frequency.
The suitability of a liquid for IJP can be roughly assessed based
on its Z number. However, there are other restrictions on fluid
behavior that impose additional limits on practical drop genera-
tion. Duineveld et al. (2002) proposed a minimum Weber number
value (We = 4), below which there is insufficient fluid flow to over-
come the surface tension and generate a small radius drop. Stow
and Hadfield (1981) observed the onset of splashing that occurred
if a droplet hit the substrate at a velocity above a critical threshold
value when We1/2 Re1/4 > 50. These limitations define the parame-
ter limits for We and Re, within which DOD IJP is actually possible.
The parameters above are therefore very useful for investigation of
the corresponding properties of newly formulated functional inks.
Ink compositions for IJP synthesis of metal oxides
In contrast to the successful research that was performed with
respect to organic materials, IJP synthesis of functional inorganic
materials (metal oxides) has had only sporadic success. To date,
only a handful of inorganic materials have been synthesized by
inkjet printing, primarily because of the difficulty of preparing
inkjet-printable functional ink solutions. The functional inks for IJP
synthesis of metal oxides are colloidal systems that are typically
composed of a metal species precursor (1–30%), a liquid carrier
medium (50–60%) and additives (1–10%). In this section, we will
summarize the required specifications for the metal species pre-
cursors and the liquid carrier.
Liquid carrier medium
There are two main types of ink formulation that are based on
a liquid carrier medium for an IJP: solvent-based (non-aqueous-
based) inks and aqueous-based (or water-based) inks. The liquid
carrier medium determines the basic properties of the ink (e.g.,
viscosity, surface tension, density), and dissolves or disperses the
metal species precursor.
Aqueous-based inks have either single or multiple metal col-
loidal nanoparticles or metal precursor solutions that are dissolved
in water. Typically, aqueous-based inks have lower viscosities and
higher surface tensions than the corresponding solvent-based sys-
tems (Dondi, Blosi, Gardini, & Zanelli, 2012). Their properties can
also be modified to match the requirements of different inkjet
printers by addition of co-solvents, including glycols, glycerin,
alcohols, and surfactants. There are three main advantages to
water-based inks: (i) the use of inexpensive source materials; (ii)
the low toxicity of the waste materials; and (iii) the long product life
produced by the prevention of solvent evaporation and dust incor-
poration (Feys et al., 2012). However, aqueous-based inks have
relatively slow drying rates, especially when they are deposited
on non-paper substrates, e.g., glass, ceramic, or steel.
Solvent-based inks are based on organic solvents (most com-
monly toluene, cyclohexanone, and acetylacetone), as well as a
single alcohol or mixtures of different alcohols, e.g., methanol,
ethanol, isopropanol, ethylene glycol, 2-methoxyethanol, and
alpha-terpineol. This kind of ink evaporates more rapidly than
Viscosity (cP) Surface tension (dynes/cm) Density (g/cm3 )
1–10 25–70 ∼1
5–30 35–70 ∼1
1–20 35–70 ∼1
aqueous-based inks and is thus suitable for the generation of sin-
gle or multilayer metal oxides on various substrates with a variety
of thicknesses for all kinds of applications. Although solvent-based
inks are widely used in the materials fabrication field, they emit
volatile organic compounds and are susceptible to print head clog-
ging because of the rapid evaporation at the nozzle.
The major challenge to the application of IJP to metal oxide
synthesis is therefore the formulation of stable, acceptable inks.
Metal species precursors
In general, three different metal oxide precursors can be iden-
tified for jettable ink formulations: metal salt solutions, colloidal
nanoparticles based on sol–gel chemistries, and colloidal suspen-
sions of metal oxide nanoparticles. The variable precursors in the
basic nature of the three systems are likely to lead to differences in
the mechanism of fabrication of the material.
Colloidal suspensions of metal oxide nanoparticles
The first method used for the preparation of jettable ink relies
on the formulation of stable colloidal suspensions of metal oxide
nanoparticles. In a jettable ink, the properties of the soluble metal
oxide nanoparticles are only influenced by the particle size and the
viscosity, meaning that the inks can be produced in large quanti-
ties and dispersed in high concentrations. The critical issues for
printability are particle size and the distribution of the suspen-
sions. The particle size must be controlled because small particles
tend to aggregate, which eventually leads to clogging of the micro-
channels of the print head. The particle size in the suspension
should be far smaller (e.g., 50-fold) than the nozzle diameter and
should have a narrow size distribution (Kuscer, Stavber, Trefalt, &
Kosec, 2012). A general method that is used to prevent aggregation
or agglomeration is the addition of surfactants or polymeric addi-
tives to the particle surface, which can subsequently be removed
by heat treatment (>300 ◦ C) or by the microwave flash method.
Another key element is the homogeneous dispersion of the metal
oxide nanoparticles in a liquid with a specific viscosity and sur-
face tension to ensure that the droplet departs from the nozzle
and to produce high quality droplet morphologies. Normally, small
amounts of appropriate non-ionic amphiphiles and glycerol can be
added to suspensions to modify the printable properties of the ink
solutions.
For successful inkjet printing of a suspension precursor in an
aqueous-based system, two conditions are required: (i) An inkjet
printer with a relatively large nozzle (50–140 ␮m) should be used
to print the micrometer-sized metal oxide particles, and (ii) the
ultrafine powders must be prepared by chemical or mechanical
methods, such as microwave synthesis (Arin et al., 2012; Lehnen,
Zopes, & Mathur, 2012), hydrothermal synthesis (Andio, Browning,
Morris, & Akbar, 2012; Cerna et al., 2013), sol–gel processing (Costa,
Pinheiro, Henriques, & Laia, 2012; Huang, Yang, Li, Cai, & Jiang,
2008), ultrasonication mixing (Fasaki et al., 2012), or ball milling
mixing (Dou, Wang, Guo, & Derby, 2011; Kuscer et al., 2012; Zhou,
Yang, & Yuan, 2008). In these methods, ethylene glycol is usually
used as a binder to control the viscosity; an acid such as HCl, poly-
acrylic acid, carboxylic acid, or acetic acid is added to maintain the
pH value and thus provide the surface charge of the metal oxide
 X. Liu et al. / Particuology 19 (2015) 1–13
Fig. 2. The formation mechanism of a metal oxide thin film (Lee et al., 2007).
nanoparticles; and a surfactant offers suitable wetting properties
and effective stabilization of the nanoparticles.
The majority of published works on the use of colloidal sus-
pensions of metal oxide nanoparticles have used an evaporating
solvent, mainly because this system leads to high-density pow-
der compacts (up to 30 wt% solid content) (Jeong, Lee, Kim, Kim,
& Na, 2010) and reduces dimensional changes during subsequent
sintering processes (Dou et al., 2011). Table 2 lists several ink
formulations based on colloidal suspensions for IJP and their
properties. For a solvent-based suspension ink system, the most
commonly used solvent is an alcohol, such as ethanol, methanol
or isopropanol. Addition of small amounts of a dispersive agent
and a surfactant to the solution can enhance the dispersion of the
nanoparticles in the mixed solvent, thus preventing the aggrega-
tion of the suspensions.
Because colloidal suspensions of metal oxide nanoparticles are
predisposed to cause the agglomeration of inks, which affects
droplet generation, the use of precursors of metal salt solutions
and colloidal nanoparticles based on sol–gel chemistries is recom-
mended.
Metal salt solutions
A metal salt precursor is a solution that contains solvated
molecules. This is the simplest, lowest-cost process for fabrication
of ink formulations. Chang et al. (Han, Lee, Herman, & Chang, 2009;
Lee, Chang, Herman, & Chang, 2007) used metal halide precur-
sors dissolved in acetonitrile to form printable inks. After printing,
the films were converted into metal oxides via a thermal reaction
between the metal halide film and water. The metal oxide film
fabrication mechanism is shown in Fig. 2.
Parkinson’s group (He & Parkinson, 2011; Seley, Ayers, &
Parkinson, 2013; Woodhouse & Parkinson, 2008; Woodhouse,
Herman, & Parkinson, 2005) used an appropriate metal nitrate salt,
e.g., Fe(NO3 )3 , Cu(NO3 )2 , CsNO3 , Nd(NO3 )3 , Co(NO3 )2 , or Al(NO3 )3 ,
with NH4 NO3 and HNO3 dissolved in water to produce ink for-
mulations for combinatorial IJP synthesis and for the discovery of
multi-component metal oxide catalysts with water photoelectroly-
sis activity (Soler-illia, Sanchez, Lebeau, & Patarin, 2002). Recently,
this group successfully mixed the platinum group (i.e., Pt, Pd,
Rh, Ir, and Ru) metal salts (H2 PtCl6 , Pd(NO3 )2 , RhCl3 , RuCl3 and
(NH4 )2 IrCl6 ) into structural metal salts (Mn(NO3 )2 , Al(NO3 )3 , SnCl2 ,
and NH4 NbO(C2 O4 )2 ) with water and glycols. After inkjet printing
and the subsequent thermal reaction, the films were converted into
the corresponding metal oxides and were used as oxygen evolution
electrocatalysts in acidic electrolytes (Fan et al., 2008).
Colloidal nanoparticles based on sol–gel chemistry
The printing “ink” can also use colloidal nanoparticles as
precursors based on sol–gel chemistries. The IJP synthesis pro-
cess of this kind of precursor ink is illustrated in Fig. 3. First,
5
Fig. 3. The IJP synthesis process based on sol–gel chemistry.
a homogeneous solution is prepared by the dissolution of metal
precursors (e.g., metal alkoxides) in an organic solvent or a
water-organic mixed solvent. Second, the homogeneous solution is
converted into a printable colloidal nanoparticle sol by treatment
with a suitable reagent (e.g., acid, base, or complexing ligands),
which is then the printing “ink”. Third, a suitable inkjet printer is
used to generate printed thin films that dry to form a gel layer.
Finally, the gel layer is thermally annealed into the oxides.
For this type of precursor ink solution, control of the growth
kinetics of the various metal alkoxides is of critical importance to
avoid agglomeration of the colloidal nanoparticles, which can lead
to clogging of the print head nozzles. The optimal diameters of col-
loidal nanoparticles can be stabilized in the 1–100 nm range in a
liquid solution by addition of complexing ligands such as acids.
Another issue with sol–gel ink solutions is the hydrolysis and
condensation of metal chlorides or alkoxides. The dissimilar con-
densation kinetics and chemistries of the precursors often lead to
undesirable macroscopic inorganic–organic phase separations that
affect the applications of the functional materials. Strategies used to
control the hydrolysis/condensation rates of the precursors for gen-
eration of suitable inkjet inks include the use of stabilizing ligands,
non-aqueous media, and controlled hydrolysis by limited addition
of water (Fan et al., 2008; Hench & West, 1990; Niederberger &
Pinna, 2009; Soler-illia et al., 2002).
As an example, titanium dioxide (TiO2 ) thin film generation
combines a sol–gel chemistry with the IJP technique. The Ti sources
come from metal alkoxides and organometallic compounds, which
have organic ligands attached to metal or metalloid atoms. Table 3
presents the parameters for the IJP synthesis process based on
the use of a colloidal nanoparticle ink and sol–gel chemistry. The
most commonly studied Ti sources are titanium isopropoxide (or
titanium tetraisopropoxide, TTIP) and tetrabutyl orthotitanate (or
tetra-n-butyl titanate, TNBT).
The sol–gel conversion of the Ti source involves two main reac-
tions using metal alkoxides: hydrolysis and condensation. During
hydrolysis, the alkoxide groups ( OR) of Ti4+ are replaced via a
nucleophilic attack on the oxygen atom of a water molecule to
release an alcohol (ROH), leading to the formation of a metal
hydroxide:
Ti(OR)4 + H2 O → HO Ti(OR)3 + ROH.
Depending on the amounts of water and the catalyst that are
present, the hydrolysis may be only partially completed. This type
of hydrolysis reaction leads to a sol ink, which is a dispersion of
colloidal particles in a liquid. The prepared sol formulations are fil-
tered through a specifically-sized membrane to filter out any large
particles and precipitations of particles.
Condensation reactions occur between two partially hydrolyzed
molecules to form Ti O Ti bonds and release a small molecule
6 X. Liu et al. / Particuology 19 (2015) 1–13

Table 2
A list of synthesized metal oxides based on colloidal suspension precursors.

Solvent Precursor Agent Particle size Inkjet printer Reference

Methanol + ␣-terpineol ZrO2 –8 mol% Y2 O3 Bis(2- ∼0.4 ␮m Piezoelectric Van Driessche et al. (2013), Tomov et al. (2010)
ethylhexyl)phthalate,
ethyl cellulose
Ethylene glycol (EG) + ethanol In2 O3 :Sn (ITO) Polyvinylpyrrolidone 5–8 nm Piezoelectric Kim, Choi, Hong, and Kwak (2013)
2-Isopropoxyethanol (ZnO)1−x (TiO2 )x ∼170 nm Piezoelectric Girgis, Fang, Hassan, Kathab, and Rao (2013)
EG + isopropanol, toluene ZnO Hexylamine 20 ± 5 nm Piezoelectric Vaseem, Lee, Shin, and Hahn (2012)
Dietylene glycol (DEG) TiO2 10 nm Piezoelectric Raimondo et al. (2012)
Ethanol/methanol ITO ∼15 nm Thermal Lai, Chen, and Chen (2011)
Ethanol ITO 25 nm Piezoelectric Jeong et al. (2010)

Table 3
A list of sol–gel chemistries for IJP synthesis of TiO2 thin films.

Solvent Precursor Agent Viscosity (mPa s) Surface tension Inkjet printer Thermal Reference
(mN/m) process
(◦ C)

Ethanol TTIP Polyvinyl 1.4 28 Electrohydrodynamic 450 Duraisamy,

pyrrolidone Muhammad, Kim,
Jo, and Choi (2012)
Water + ethanol TNBT Citric acid, NH4 OH 4.3 24.6 Electromagnetic 500–650 Arin et al. (2011)
Water + ethanol TNBT Triethanolamine, 5.2 25.3 Electromagnetic 500–650 Arin et al. (2011)
NH4OH
Xylene + water TTIP Triton X 102 4.86 – Piezoelectric 450 Morozova et al.
(2011)
Ethanol+ acetylacetone, water TTIP Polyethyleneglycol 1.38 – Piezoelectric 450 Cerna, Vesely, and
Dzik (2011)
Acetyl acetone TTIP – <20 – Piezoelectric 450 Dzik, Vesely, and
Chomoucka (2010)

of water (oxolation) or an alcohol (alkoxolation), as shown in the
following:
(OR)3 Ti OH + HO Ti(OR)3 → (OR)3 Ti O Ti(OR)3 + H2 O,
(OR)3 Ti OR + HO Ti(OR)3 → (OR)3 Ti O Ti(OR)3 + ROH.
In the condensation reaction, the molecular precursor can build
increasingly large titanium-containing molecules to form a highly
cross-linked solid, resulting in a gel, which is an interconnected and
porous inorganic network that encloses a continuous liquid phase.
A thermal process is used to change the structure and prop-
erties of the printed film after gelation, e.g., reprecipitation of
the monomers or oligomers, or phase transformations. For TiO2
materials, in general, the calcination conditions require process
temperatures in the 450–650 ◦ C range.
Representative research into the generation of multi-
component metal oxides based on colloidal nanoparticle
precursors and the IJP technique can be found in the work of
Liu et al. (2012). They developed a simple, general, and inexpen-
sive formulation for the fabrication of more than 25 different
colloidal inks for IJP synthesis. The ink system is composed of an
amphoteric non-aqueous solvent, the metal species, and block
copolymers. The amphoteric solvents, e.g., alcohols or acetic
acid, are used to ensure the appropriate viscosity, density and
surface tension for all metal species. Block copolymers (e.g., F127,
P123, Brij 76) that can be co-assembled with metal ions and
nanoparticles are used as binders and structure-directing agents
to fabricate mesostructured metal oxides (2–50 nm). Fig. 4 outlines
the fabrication process for multi-component metal oxides using
IJP-assisted cooperative-assembly synthesis.
Applications for IJP synthesis of metal oxides
IJP-synthesized metal oxides have been used in a wide range
of applications, ranging from different functional devices (e.g.,
solar cells, transistors, and sensors) to catalysts (e.g., photo- and
electro-catalysts). Some of these applications are reviewed in this
section.
Catalysts
In earlier research, IJP has often been used as a promising and
useful tool for generation of a thin film with catalytic activity based
on metal oxide suspensions. One example of IJP synthesis of a pho-
tocatalytic thin film is the deposition of photocatalytically-active
transparent titanium oxide from a colloidal suspension. TiO2 is one
of the most studied photocatalysts for application to the degrada-
tion of organic pollutants (Kondo et al., 2005; Yu, Zhang, & Yu, 2002;
Zhang, Xu, Feng, Li, & Li, 2008). TiO2 suspensions can easily be pre-
pared from fine powders that can be purchased from a commercial
company or synthesized in a lab. Recently, Arin et al. (2012, 2013)
prepared TiO2 nanoparticle suspensions by microwave-assisted
hydrothermal synthesis for inkjet fabrication of homogeneous TiO2
coatings on glass substrates. The system used a piezoelectric inkjet
printer with a 23 ␮m-diameter orifice. After heat treatment, the
thin film has the photocatalytic activity required for decomposition
of a methylene blue solution under ultraviolet (UV) illumination.
Cerna et al. (2013) and Zori (2011) also synthesized stabilized
TiO2 colloidal dispersions, by hydrothermal synthesis and by a
micro-emulsion process, respectively, for the IJP synthesis of TiO2
photocatalysts. The IJP technique has also been considered to be
desirable for use in the combinatorial catalysis field since the 1998
discovery of electrocatalysts (Reddington et al., 1998). Because
the current theoretical knowledge is insufficient to predict the
complex catalytic system requirements, thousands or perhaps hun-
dreds of thousands of mixed catalyst compositions may need to be
produced and tested for efficiency until an effective material is dis-
covered. Use of the IJP synthesis approach means that a continuous
high-throughput process can be used to create samples of various
compositions in each experiment under the same experimen-
tal conditions. The operation is simple, low-cost and automatic.
 X. Liu et al. / Particuology 19 (2015) 1–13 7

Fig. 4. Multicomponent metal oxide synthesis scheme using an IJP-assisted cooperative-assembly method. A stable colloidal nanoparticle “ink” system consists of non-
aqueous solvents, structure-directing agents (SDAs), acids, and suitable metal precursors. An evaporation-induced cooperative-assembly process is used to generate the
desired mesoporous structures of the printed libraries (Liu et al., 2012).

Therefore, the IJP technique has also been considered for the study
and optimization of mixed metal oxide catalysts.
Parkinson et al. (Woodhouse and Parkinson, 2008; Woodhouse
et al., 2005) prepared metal species precursors (metal chlorides
and metal nitrates) with water and glycols or ethanol to form
suitable inks for IJP fabrication of multi-element libraries on con-
ductive glass substrates. By varying the gradient pattern of each
element, a variety of stoichiometric compositions and combina-
tions of metal oxides can be produced using a commercial thermal
ink jet printer (Fig. 5). Recently, this group extended their com-
positions from organometallic precursors (Ti(OC2 H5 )4 , Si(OC2 H5 )4 ,
and Al(C3 H5 O2 )3 ) to the platinum group metal species (H2 PtCl6 ,
Pd(NO3 )2 and RhCl3 ), which were used as structural stabilization
components for electrocatalysts (He and Parkinson, 2011; Seley
et al., 2013).
Katz et al. (2009) used QuadTone Raster Image Processor soft-
ware (QTR) to accurately and quantitatively control the relative
proportions of the printed metal solutions and the deposition
of the solution volumes. This capability obviated the need to
perform overprinting to increase the thin film thickness. Com-
pared with Parkinson’s earlier research, their system can produce
approximately 200 potential photoelectrodes at one time (with a
composition step size of 10%) (Fig. 6). They mixed the metal ion
solutions and printed them in 200 wells on glass coated with tin
oxide using an inkjet printer, and then heated the solutions on the
glass to form the mixed metal oxides.
Liu et al. (2012) recently developed an IJP-assisted cooperative
assembly system that is capable of high-throughput generation
of catalyst libraries (multi-component metal oxides) at a rate of
1,000,000 formulations per hour, with up to eight component
compositions of almost any Earth-abundant element. The system
consists of a modified inkjet printer and specially self-developed
software, and can deposit precise quantities of specially formu-
lated metal and non-metal solutions (rather than ink, the system
was developed based on sol–gel chemistry) on all kinds of sub-
strates. This system can generate binary, ternary, quaternary, up to
octonary mixtures with unprecedented speed and accuracy. As an
example, the octonary metal oxides that were developed via the IJP
technique are shown in Fig. 7.
This system has also been used to set up and produce millions
of candidate materials for solar-fuel generation at the Joint Cen-
ter for Artificial Photosynthesis (JCAP) at the California Institute of
Technology (http://solarfuelshub.org/research/high-throughput-
experimentation.html). The (photo-)electrocatalytic activities for
the oxygen evolution reaction and the hydrogen evolution reac-
tion of the IJP-synthesized (Ni Fe Co)Ox (Xiang et al., 2014) and
(Fe Co Ni Ti)Ox quaternary oxide libraries were also explored
(Gregoire, Xiang, Liu, Marcin, & Jin, 2013; Gregoire et al., 2013)
(Fig. 8). (Fe Co Ni Ti)Ox library 5456 samples were deposited
on fluorine-doped tin oxide (FTO)-coated glass plates (Fig. 8(a)).
The printed area of each composition sample was 1 mm2 . By
combination of IJP synthesis with high-efficiency electrochemical
measurement techniques, new materials for the solar fuel field can
be identified rapidly.
The most important features for fabrication of an optimum cat-
alyst are the compositions and structures of the materials used
(Katz et al., 2009; Liu et al., 2013). The composition determines
the supporter and the active sites of the catalyst. Large surface
areas, variable pore sizes, and designable pore networking can
be used to support active sites, along with reactant/product res-
idence time control. Liu et al. (2012) have found a simple direct
IJP method to control and continuously adjust the mesostructures

Fig. 5. (a) Template showing the gradient pattern used to print metal nitrate precursors for the Al–Co–Cs–Fe system (the Fe and Cu triangles are the internal standards for
n- and p-type photoactivity, respectively). (b) Laser screening at 532 nm with no applied bias in a 0.1 M NaOH solution. Qualitatively, it can be seen that the highest activity
is primarily associated with Co and with small amounts of Fe and Al (Seley et al., 2013).
8 X. Liu et al. / Particuology 19 (2015) 1–13

Fig. 6. Images of mixed-metal oxide spots printed on a fluorine-doped tin oxide (FTO)-coated glass substrate using an inkjet printer, which produced quantitatively prede-
termined mixtures of aqueous metal solutions that were then baked at 500 ◦ C to form the metal oxides. (a) and (b) show printed slides on a continuous FTO-coated glass
substrate, as used for the photocurrent measurement setup. Panels (a) and (b) show images of the same slide but with a different background in each case for improved
contrast in each image (Katz, Gingrich, Santori, & Lewis, 2009).

of the multi-component metal oxides over a wide range to enable
better exploration of the possible catalytic features that might be
present and that can be transitioned to through bulk synthesis
procedures. TEM analyses (Fig. 9) show that the structures of the
printed Cux Ti1.0 Ow (0 < x < 1.0) samples were consistent with those
obtained by conventional bench-top synthesis processes, with con-
figurations ranging from ordered (left), to wormlike (middle), to
disordered mesostructures (right).
Sensors
IJP is a promising process for the preparation of gas sensing
material films because (i) it enables device fabrication at low cost;
(ii) it allows accurate and reproducible deposition of small amounts
of material; and (iii) a number of films with different compositions
can easily be integrated on a single substrate.
Many n-type semiconducting metal oxides (e.g., WO3 , SnO2 , and
ZnO) have been widely used as gas sensors because these materials
offer rapid responses, high sensitivity and good chemical stability.
The interactions between these metal oxides and environmentally
and industrially relevant gases, including CO, CH4 , H2 , ethanol, and
H2 S, can cause a reversible change in the electrical conductivity
such that the volatile gases are absorbed.
Kukkola et al. (2012) prepared nanometer-scale metal-
decorated WO3 nanoparticles (Ag WO3 , Pt WO3 , Pd WO3 ), and
the as-prepared nanoparticle powders were then suspended in
deionized water to obtain dispersions for inkjet deposition gas
sensors. These surface-modified WO3 nanoparticles can efficiently
discriminate various gaseous analytes (e.g., H2 , NO, H2 S, and CO)
from sub-ppm concentrations up to nearly 0.1% concentration lev-
els in air.
Even when the same metal oxide is used, different synthesis
methods and structures combined with the IJP technique for gas
sensor fabrication can produce different response sensitivities for
volatile gases (Chang et al., 2010; Conedera et al., 2010). Andio et al.
(2012) confirmed the effects of the particle size and the structure of
a metal oxide film on the response and the transient effects of the
sensor. They formed three types of SnO2 structure (microstructured
nanoparticles, nano-structured microspheres and micro-sized par-
ticles, as shown in Fig. 10), and dispersed these structures in
water/glycerol solutions for IJP-based gas sensor fabrication. The
carbon monoxide (CO) gas response times for the microstructured

Fig. 7. TEM image of IJP-synthesized Mg0.1 Ni0.1 Mn0.06 Cr0.1 Cu0.07 Fe0.1 Co0.1 Ti1.0 Ow (calcined at 350 ◦ C) at a resolution of 360 × 360 dpi, and the element mappings of a single
Mg0.1 Ni0.1 Mn0.06 Cr0.1 Cu0.07 Fe0.1 Co0.1 Ti1.0 Ow particle (Liu et al., 2012).
 X. Liu et al. / Particuology 19 (2015) 1–13 9

Fig. 8. (a) An inkjet-printed metal oxide composition library plate on glass, (b)–(d) mappings of the oxygen evolution reaction catalytic current at an overpotential of 0.5 V
in 0.1 M NaOH (Gregoire, Xiang, Liu, et al., 2013).

Fig. 9. TEM images of Cux Ti1.0 Ow (0 < x < 1.0, 360 × 360 dpi print resolution, calcined at 350 ◦ C) samples with different x values (left, 0.005; middle, 0.05; right, 0.2) (Liu et al.,
2012).

nanoparticles and microspheres were faster than that of the micro-
sized material (Fig. 11). This shows that the particle size, the surface
area, and the microstructure of the oxide film are all important
factors for the overall performance of the sensor.
The composition of the metal oxide is also very important for
the gas response and selectivity of gas sensors. This is a critical
issue for the deposition of films with variable compositions or for
integration of several different gas sensing films on a single sensor
chip to form an electronic nose. Shen (2012) used SnO2 precur-
sor inks based on the sol–gel technique to form SnO2 gas-sensing
films doped with various elements (including Au, Ag, Pd, Co, Ni,
Cu, Sb, and Zr). This work shows that a number of films with
different compositions can be easily integrated on a single sub-
strate. The structural, electronic and sensing properties of these
films were studied. Metal salt solutions were dissolved or dis-
persed in anhydrous ethanol and were then used as precursor
inks for IJP (Fig. 12). Fig. 13 shows the H2 responses of a pure
SnO2 film and eight SnO2 -based films mixed with 1 mol% of sev-
eral different additive materials. The use of IJP for fast synthesis of
multi-element films with variable compositions can accelerate the

Fig. 10. SEM micrographs showing the microstructures of SnO2 films for (a) microstructured nanoparticles, (b) micron-sized particles, and (c) microspheres (Andio et al.,
2012).
10 X. Liu et al. / Particuology 19 (2015) 1–13

Fig. 11. (a) Plot of material response as a function of temperature for SnO2 films on micro-hotplate devices when exposed to 35 ppm CO, and (b) plot of response vs. CO
concentration at a fixed temperature for the SnO2 films (Andio et al., 2012).

accurate determination of the optimal materials required for gas
sensors.
Other applications
The IJP technique can also be used to fabricate electronic devices,
such as thin film transistors (Kim et al., 2010; Lee et al., 2009; Tomov
et al., 2010), field-effect transistors (Dasgupta et al., 2012; Kolpin
et al., 2013; Wu et al., 2011), solar cells (Jeong et al., 2010; Kim
et al., 2013; Shimada et al., 2012; Sukeshini et al., 2009; Tomov
et al., 2010; Van Driessche et al., 2013), superconductive materi-
als (Feys et al., 2012; Juda et al., 2012; Van Driessche et al., 2012;
Vandaele et al., 2012), electroceramic devices (Kuscer et al., 2013),
luminescent materials (Chen et al., 2011), and memristor devices
(Duraisamy et al., 2012).
Metal oxide semiconductors, such as In Ga Zn oxide (IGZO),
ZnO, In Zn oxide (IZO), Zn Sn oxide (ZTO), and In Sn Zn oxide
(ITZO), are good potential alternative channel layer materials
for thin film transistors. In general, metal salt or organometal-
lic compounds are dispersed or dissolved in a solvent such as
2-methoxyethanol or ethylene glycol to formulate printable inks.
A typical ink solution used for the fabrication of the supercon-
ductive material YBa2 Cu3 O6.9 includes desiccated YBa2 Cu3 O6.9
powder, trifluoroacetic acid (TFAH), anhydrous acetone, methanol,

Fig. 12. Illustration of the preparation processes used for the inks and the metal oxide gas sensor thin films (Dasgupta et al., 2012).
 X. Liu et al. / Particuology 19 (2015) 1–13
Fig. 13. The response to H2 at 350 ◦ C of SnO2 -based thin films that were printed 4
times (Dasgupta et al., 2012).
and trifluoroacetic anhydride (TFAA). TFAH and acetone are used
as solvents; the methanol is used to dilute the gel and adjust the
concentration of the final solution to produce the ideal metal ion
concentration; and TFAA can remove any water from the solution.
Feys et al. (2012) developed fluorine-free water-based precursor
solutions, which were prepared by dissolution of stable, cost-
effective and easily available inorganic salts in an aqueous solution
of coordinating ligands to produce homogeneous materials.
Outlook
IJP is considered to be an innovative technique for the synthesis
and development of functional metal oxides. However, there are
two obstacles to more widespread application of this technique to
the fabrication of functional metal oxides. How to overcome these
obstacles is the current challenge to material scientists.
1. There are only a few industrial inkjet printers that have been
designed to print metal oxides. In addition, challenges such as
the fabrication of uniform and homogeneous multi-component
structures, coffee staining, and maintaining stability during
post-processing must be addressed through improvements in
our understanding of nano-ink fluid behavior. These challenges
limit the available opportunities to use this technique, especially
for newer researchers in this field. Therefore, greater efforts
must be focused on the development of a simple, low cost,
energy-efficient, and environmentally-friendly method for ink
formulation to produce the variable compositions and structures
required for the different applications. The interactions of the
droplets and the drop drying processes are clearly important
for determination of the quality, accuracy and properties of the
functional metal oxides. However, little systematic work with
regard to this aspect exists in the literature to date.
2. Current IJP techniques are mostly used to fabricate thin-film
metal oxides. The fabrication of three-dimensional (3D) objects
is a major challenge. Because the current ink formulations for
metal oxides are based on sol–gel chemistry, the increased
amounts of ink solids that would be required for 3D printing
would be difficult to achieve with the current formulations. The
development of a fast drying process for 3D printing may enable
greater complexity in the sol–gel ink system. However, these
11
difficulties will not hinder the exploration of the application of
these materials to the fabrication of large 3D device arrays.
Acknowledgements
The authors would like to thank the National Natural Science
Foundation of China (grant Nos. 21222307, 21271153, 51222202,
J1210042 and 21003106), the Fok Ying Tung Education Founda-
tion (grant No. 131015), the Zhejiang Provincial Natural Science
Foundation of China (grant No. R12B030002), and the Funda-
mental Research Funds for the Central Universities (grant No.
2012QNA3014) for their financial support.
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