Sensors and Actuators B 204 (2014) 250–272

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Nanoscale metal oxide-based heterojunctions for gas sensing:

A review
Derek R. Miller, Sheikh A. Akbar ∗ , Patricia A. Morris
Department of Materials Science and Engineering, The Ohio State University, Columbus, OH 43212, United States

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

Article history: Metal oxide-based resistive-type gas sensors are solid-state devices which are widely used in a number
Received 2 June 2014 of applications from health and safety to energy efficiency and emission control. Nanomaterials such
Received in revised form 17 July 2014 as nanowires, nanorods, and nanoparticles have dominated the research focus in this field due to their
Accepted 19 July 2014
large number of surface sites facilitating surface reactions. Previous studies have shown that incorporat-
Available online 29 July 2014
ing two or more metal oxides to form a heterojunction interface can have drastic effects on gas sensor
performance, especially the selectivity. Recently, these effects have been amplified by designing hetero-
Keywords:
junctions on the nano-scale. These designs have evolved from mixed commercial powders and bi-layer
Nanostructure
Heterojunction films to finely-tuned core–shell and hierarchical brush-like nanocomposites. This review details the var-
Gas sensor ious morphological classes currently available for nanostructured metal-oxide based heterojunctions
Metal oxide and then presents the dominant electronic and chemical mechanisms that influence the performance of
Semiconductor these materials as resistive-type gas sensors. Mechanisms explored include p–n and n–n potential bar-
Nanomaterial rier manipulation, n–p–n response type inversions, spill-over effects, synergistic catalytic behavior, and
microstructure enhancement. Tables are presented summarizing these works specifically for SnO2 , ZnO,
TiO2 , In2 O3 , Fe2 O3 , MoO3 , Co3 O4 , and CdO-based nanocomposites. Recent developments are highlighted
and likely future trends are explored.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2. Gas sensing mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
3. Heterostructure classes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.1. Mixed composite structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.2. Bi-layer and multi-layer films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3.3. Structures decorated with second-phase particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.4. Mixed 1D–1D structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.5. Core–shell structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
4. Mechanisms responsible for enhanced sensing performance in heterostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.1. Role of the interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.1.1. Effects of p–n nanojunctions on gas sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.1.2. Effects of n–n and p–p nanojunctions in gas sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4.1.3. Separation of unlike charge carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.1.4. n–p response type inversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.2. Synergistic and complimentary behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4.2.1. Complimentary decomposition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4.2.2. Catalyzed spill-over effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.3. Manipulation of microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264

∗ Corresponding author. Tel.: +1 614 292 6725.

E-mail address: akbar.1@osu.edu (S.A. Akbar).

http://dx.doi.org/10.1016/j.snb.2014.07.074
0925-4005/© 2014 Elsevier B.V. All rights reserved.
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272 251

5. Remaining challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

5.1. Long-term stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.2. Reproducibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.3. Characterizing the dispersion state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.4. Understanding the mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.5. Useful analogues to catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
5.6. Integration of nanostructured heterojunction materials into silicon microcircuit technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
6. Future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Biographies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271

1. Introduction such as decrease in activation energy [15], targeted catalytic activ-

ity [16] and synergistic surface reactions [17]; and geometrical
Solid-state resistive-type metal oxide gas sensors (MOGS) have effects such as grain refinement [18], surface area enhancement
been widely used in applications ranging from health and safety [19], and increased gas accessibility [20]. Understanding the mech-
(e.g., medical diagnostics, air quality monitoring, food processing, anisms that control the sensing behavior in these heterostructures
and detection of toxic, flammable and explosive gases), to energy will be essential for future advances in this field. A simple summary
efficiency and emission control in combustion processes. These diagram of these mechanisms is shown in Fig. 1. Detailed explana-
sensors are attractive because of their high sensitivity, low cost, tions and examples of these mechanisms can be found in Sections
simplicity, and compatibility with modern electronic devices. 4 and 5.
MOGS are typically designed to be small, portable, and to inte- No review focused specifically on nanostructured oxide hetero-
grate easily with the environment or structure in their application. junction materials for gas sensing has previously been published.
However, resistive-type MOGS generally have the disadvantage of Therefore, the authors present here an overview of the past devel-
poor selectivity between gases, where many gas species may cause opments to understand the current progress of the state-of-the-art
changes in the resistance, making it impossible for a single sen- in gas sensing using heterostructures. Several other excellent
sor to properly identify the gas. This problem can be solved, in reviews on gas sensor materials [21], nanostructures in gas sensing
part, by using a suite of coordinated sensors, known as an “elec- [2,22–25], p-type oxides in gas sensing [26], and gas sensing funda-
tronic nose,” to simultaneously analyze several (up to 36 or more) mentals [27–29] may further aid in background and understanding
sensor signals at once [1] using calibrated software to correctly of the content presented here. In the present review, we first
identify the gases present [2]. However, further enhancements present the many morphological classes of heterostructures inves-
in the selectivity of the materials are necessary to simplify the tigated in the literature, then present some of the mechanisms that
electronic nose design and eliminate false-positive or interfering lead to the resulting enhanced performance, concluding with future
signals. directions to explore. It is the hope of the authors that compil-
Many recent studies have shown that the selectivity and other ing and comparing the information and results from these studies
important sensing parameters of resistive-type MOGS can be will lead the reader to a more coherent understanding of influ-
improved through the use of composite metal oxides [3–7]. encing factors and help facilitate further advances in the sensor
The physical interface between two dissimilar materials is often field.
referred to as a heterojunction. The material incorporating these
two components is known as a heterostructure. By creating inti- 2. Gas sensing mechanism
mate electrical contact at the interface between two dissimilar
semiconducting materials, the Fermi levels across the interface The nature of the fundamental operating principles of gas
can equilibrate to the same energy, usually resulting in charge sensing are described briefly here. In resistive-type sensors, a metal
transfer and the formation of a charge depletion layer. This is oxide is deposited across two or more electrodes which measure
the basis for unique effects that can lead to increased sensor the change in the electrical resistance of the oxide in the presence of
performance, and will be discussed later. Additional anomalies the analyte gas. The resistance of the oxide may increase or decrease
can occur by having two dissimilar semiconducting materials in on exposure to the gas depending on the dominant charge car-
close proximity, with both interfaces exposed to the atmosphere. rier and type of gas interacting with the surface, as described in
A gas or liquid may react with one material most readily, and Table 1. Consider an n-type semiconductor such as SnO2 . Under
this reaction byproduct may then react with the second mate- normal (ambient) operating conditions, there is significant oxygen
rial in order to complete the reaction, referred to as a synergistic adsorption on the metal oxide surface. Oxygen molecules in air dis-
reaction. Nano-heterostructures are often used in gas sensors sociate and each oxygen atom accepts an electron from the material
because their small dimensions and high surface-to-volume ratios (if n-type) to complete the bond, decreasing the electron density in
amplify the above effects. Dopant oxides may also be used sim- the material and increasing the resistance of the oxide. The oxy-
ply to control the microstructure and morphology of the material gen only adsorbs onto the surface and thus the electrons are only
during processing. Though microstructure manipulation is often removed to a certain depth from the surface known as the Debye
the claim for improved performance, there are likely electronic length, (), typically on the order of 2–100 nm. The region within
and chemical effects also in play that were not thoroughly a Debye length of the surface is known as the depletion region
elucidated. because it is depleted of its normal charge carriers. The Debye
The improvements in sensing performance of these composites length may change as more or less oxygen is adsorbed on the sur-
has been attributed to many factors, including electronic effects face, which in turn causes a measurable change in the resistance.
such as: band bending due to Fermi level equilibration [8,9], charge It has been overwhelmingly shown that when crystallite dimen-
carrier separation [10], depletion layer manipulation [11–13] and sions are driven below about 20 nm, sensor response drastically
increased interfacial potential barrier energy [14]; chemical effects increases [29]. When the nanostructure dimensions allow all atoms
252 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

Surface-dependent Interface-dependent Structure-dependent

Resistance Microstructural
Catalyc Reacon manipulaon manipulaon

Enhancement Spill-over Solid-state

Surface
Interface
Conducon
Decrease
Increase
sensizaon via channel surface
mechanism effect transformaon
Synergisc
PE barrier grain size
carrier injecon narrowing area

n-n juncon p-n juncon

Optimal
Oxide Amorphous
heterostructure Noble metal Mixed Spherical 1D Core- Polycrystalline
decorated Brush oxide parcle
for mechanism decoraon
nanowires
nanocrystalline core-shell shell nanowires
coang

Fig. 1. Summary of most cited sensor performance enhancing mechanisms and the types of heterostructures that are most optimal for each mechanism type. Some types of
mechanisms and structures have been omitted for space.

to be within a Debye length of the surface, the entirety of the mate-
rial is depleted by the gas analyte, and the response is maximized.
If a reducing gas is introduced in this case, it reacts with the surface
adsorbed oxygen, pulling it from the surface, and simultaneously
donating an electron back into the semiconductor that causes a
decrease in the resistance. P-type materials would exhibit reverse
behavior as shown in Table 1.
The adsorption properties of the oxygen and reaction rates of
analyte gases are temperature-dependent, so most MOGS are also
equipped with a heater that allows operation at a pre-determined
optimal operating temperature. Sensor response is defined in sev-
eral different ways depending on the type of measurements taken,
but is most often defined as the ratio of resistance in air to resis-
tance in the presence of the gas, or Ra /Rg for an n-type material with
a reducing analyte, giving a value greater than 1. Alternatively, this
becomes Rg /Ra for an n-type material with an oxidizing analyte, also
giving a value greater than 1. These are reversed in p-type materials.
The parameter of sensitivity is defined as the degree to which the
response increases as the concentration of that analyte increases,
which can be found from the slope of a sensor’s calibration curve.
The response and recovery times (tres and trec ) of a gas sensor are
usually defined as the time it takes for the resistance to reach 90% of
its steady-state value after introduction or removal of the analyte
gas, respectively. Response, selectivity, sensitivity, operating tem-
perature, response time and recovery time are the most important
parameters for gas sensor performance. In most cases where the
heterostructure improved selectivity, the sensing response to the
targeted analyte was also enhanced. Reductions in response and
recovery times were also often reported, as were decreases in the
optimum operating temperature.
3. Heterostructure classes
Before presenting the sensing mechanisms using different het-
erostructures, it is necessary to introduce the various classes of
heterostructure combination types that have arisen. This will aid
understanding of how the structure and dispersion state of the con-
stituents can affect the solid–gas interaction. For simplicity, three
different structure–architecture types will be represented in this
review by the nomenclature in the following general examples:
• A hyphen between compounds (e.g. “SnO2 –ZnO”) represents a
simple mixture of the two constituents, being mostly randomly
distributed throughout the material.
• An “@” sign between compounds (e.g. “SnO2 @ZnO@CuO”) repre-
sents a base material with the following oxides added over it in
some way. For example, aligned SnO2 nanorods, sputtered with
a layer of ZnO, and then dipped in a CuO precursor solution.
• A forward slash between compounds (e.g. “SnO2 /ZnO”) repre-
sents a well-defined partition or interface between the two
oxides, as in a bi-layer, where the SnO2 is the top layer and the
ZnO is the bottom layer.
• “(SnO2 –In2 O3 )/In2 O3 ” would then represent a mixture of SnO2
and In2 O3 nanoparticles deposited onto an In2 O3 film to form a
bi-layer.
3.1. Mixed composite structures
In composite electronic materials, it is very important to prop-
erly characterize the dispersion state of each constituent in order
to understand how the interfaces or heterojunctions between the

Table 1
Sensing response behavior of n-type and p-type materials to reducing and oxidizing gases.

Sensor response behavior n-type material p-type material Example gases

Reducing gases Resistance decreases Resistance increases H2 , H2 S, CO, NH4 , Ethanol, Acetone, CH4
Oxidizing gases Resistance increases Resistance decreases O2 , O3 , NOX , CO2 , SO2
Dominant charge carrier Electrons (e− ) Holes (h+ ) –
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
Fig. 2. Schematic showing the likely dispersion state of In2 O3 -based composites synthesized via the sol–gel process. Variants include core–shell (a, d and f) decorated with
second-phase particles (c and e), formation of mixed phases (d–f) and components in solid solution (b and f).
Reprinted with permission from Ref. [38].
constituents affect the behavior of the material as a sensor. The
largest influence on the dispersion state comes from the processing
routes, as well as the actual dopant used. It should be noted
that even though the percent composition may be the same as
another sample, the behavior can be quite different, as shown in
a direct comparison between TiO2 -doped SnO2 synthesized via
co-precipitation as well as mechanical mixing yielding similar ran-
domized dispersions. However results showed that the optimum
composition for H2 sensing was 10 mol% for co-precipitation and
20 mol% TiO2 for mechanical mixing [30]. The easiest way to obtain
metal oxide composites is by simple mechanical mixing of exist-
ing oxide powders. de Lacy Costello et al. have published a series
of studies [17,31,32] which showed that the addition of 25–50 wt%
ZnO powder to SnO2 powder increased sensitivity to organic com-
pounds, citing a synergistic mechanism in the decomposition of
these molecules. In other studies, the addition of TiO2 powders to
SnO2 has shown to increase sensitivity to H2 [8,30,33].
The majority of oxide composites and mixtures in recent
literature are random dispersions of the oxide constituents syn-
thesized via various solution-based processes such as the sol–gel
method [34–39], microemulsion [19], precipitation [9,30,40–42]
and hydrothermal techniques [43]. These techniques allow for
more precise control of crystallite size, surface area, and stoi-
chiometry of the resulting powders compared to using commercial
powders. This type of synthesis route requires detailed char-
acterization of the dispersion state in order to understand the
mechanisms at work. Many papers assume that a random dis-
persion of nanoparticles results, but others have found spherical
core–shell structures, solid solutions, or presence of new phases.
Korotcenkov et al. detailed their best estimate at the various dis-
persions resulting from doping In2 O3 with several other precursors
through the sol–gel method, as shown in Fig. 2 [38]. They concluded
that the various dopants’ effects on sensing performance are pri-
marily a result of the different grain structures formed. Without
proper characterization of these structures, it is difficult to guess the
degree of physical contact between each constituent, which then
Fig. 3. (a) SEM image of ZnSnO3 -SnO2 nanoflakes (reprinted with permission from Ref. [20]); (b) SEM image of ZnO–Eu2 O3 nanostrips (reprinted with permission from Ref.
[43]); (c) H2 –N2 gas-etched spinodally-decomposed SnO2 –TiO2 grains [46].
253
limits the insight that can be gained from the sensing results. Simi-
lar mixed nanocrystalline films can be synthesized via advanced
deposition techniques such as sputtering [44] and pulsed-laser
deposition (PLD) [45]. These allow an even higher degree of control
of stoichiometry, film thickness, morphology, and growth kinetics
by varying the gas atmosphere, power input, substrate temperature
and target material.
Several other unique morphologies of mixed oxide structures
have also been reported as shown in Fig. 3. Non-traditional
morphologies have been created through simple hydrothermal
synthesis, including ZnSnO3 @SnO2 nanoflakes [20] and ZnO–Eu2 O3
nanostrips [43] Additionally, our own work has demonstrated a
high-temperature gas etching process in a spinodally-decomposed
SnO2 –TiO2 pellet, which increased the surface area by creating
heavily faceted grains [46]. These structures are reported to exhibit
improved sensing performance [20,43,46].
3.2. Bi-layer and multi-layer films
Heterostructures with a large, defined interface such as bi-layers
and multi-layers allow for easier characterization of the electronic
properties of the interface due to its well-defined dimensions and
contact area. It also becomes much easier to study the thermal sta-
bility of the interface, including diffusion across the junction and
possible growth of new mixed phases [47]. However, these struc-
tures may be less desirable for some applications due to lower
surface area and low gas-accessibility to the heterojunction inter-
face. These well-defined 2D layers can be made through several
processing routes including, most commonly, the sol–gel method
[48–50] and sputtering [47,51], but also by more advanced tech-
niques such as electrochemical deposition with periodic potential
changes [52,53]. In horizontal 2D bi-layer structures, the analyte
gas must diffuse through the top material to reach the heterojunc-
tion. Dandeneau et al. minimized this problem by using pyrolysis
to enhance and optimize the porosity of the upper CuO film [50].
Cui et al. used the electrochemical deposition method to create
254 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
Fig. 4. (a and b) TEM images of Cr2 O3 -decorated ZnO NWs; (c) high-angle annual dark field (HAADF) scanning TEM (STEM) image and EDS elemental mapping of Zn, Co, and
O (reprinted with permission from Ref. [62]); (d) SEM PdO-decorated flower-like ZnO nanostructures; (e) TEM image of PdO-decorated flower-like ZnO nanostructures, with
inset showing magnification of circled area (reprinted with permission from Ref. [61]).
many periodic interfaces and added the Au electrodes in such a
way as to expose the junctions directly to the atmosphere [52]. An
additional level of complexity can be introduced by making the top
layer itself a mixture of two components. Ivanovskaya et al. showed
that a [␥-Fe2 O3 –In2 O3 (1:1)]/In2 O3 film outperformed a simpler
␥-Fe2 O3 /In2 O3 film in the detection of 100 ppm ethanol, though it
should be mentioned that the latter film had better CO sensitivity
than its tested counterparts [49].
3.3. Structures decorated with second-phase particles
Another very common class of heterostructure consists of a
host material decorated with nanoparticles of a second material.
Often used in catalysis, photocatalysis, and photovoltaics, these
secondary particles can act as catalysts or sensitizers and enhance
performance [54,55]. Usually, the second phase is not suitable for
comprising the host structure (due to instability, cost, synthesis
route, or conductivity), and must be applied in small, discrete
amounts to be most effective. The gas sensing community has
applied these principles with great success. A very simple method
of synthesis involves creating the base nanostructures through
a hydrothermal treatment, and then using a solution-based pro-
cess to coat the resulting powders with a metal–organic precursor
that then oxidizes with a proper heat treatment [12,56]. More
advanced processes include combined hydrothermal templating
and sputtering [57], as well as thermal evaporation of the secondary
species [5,58,59]. Woo et al. were able to grow ZnO nanowires
directly from deposited gold electrodes via the vapor–liquid–solid
(VLS) mechanism, and found that the additional decoration of
Cr2 O3 nanoislands by thermal evaporation enhanced response
toward trimethylamine (TMA) [5]. Fig. 4a–c provides micrographs
of the structure. Chowdhuri et al. demonstrated that in the case
of SnO2 @CuO systems, the deposition and synthesis processes
affected the performance, and also that an optimal size existed for
the CuO nanoclusters in H2 S sensing [59]. Another unique com-
posite, ZnO@ZnS hollow dumbbell-graphene nanocomposites, was
synthesized by a two-step polymer-assisted hydrothermal method
and sulfurization treatment, and demonstrated excellent alcohol
sensing performance as well as the ability to photocatalytically
break down methyl orange [10]. Kim et al. significantly showed
that loading NiO onto hierarchical SnO2 spheres decreased humid-
ity effects on sensing of CO due to the high affinity of NiO to
moisture, leaving the SnO2 mostly unaffected [60]. Lou et al. used
hydrothermal synthesis of PdO-decorated ZnO flower-like nano-
structures to create a sensor with enhanced response to ethanol
and toluene which could be selected by the operating temperature
(Fig. 4d and e) [61].
Noble metal nanoparticles such as Pt, Pd, Ag, and Au have also
been used as second-phase particles applied to host oxides with
great success [63–67]. The noble metal nanoparticles act as cat-
alysts by lowering the activation energy for the reaction, which
improves molecular dissociation and the reaction rate [22]. In most
cases, large increase in sensing response, decrease in response and
recovery times, and decrease in optimal operating temperature are
observed [68,69]. However, these noble metal nanoparticles gener-
ally increase synthesis cost and have known instability issues such
as catalytic poisoning (activity reduction) from certain vapors and
tendencies to coarsen and cluster at higher operating temperatures
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272 255

Fig. 5. Composite heterojunction electrospun nanofibers; (a) TEM image of NiO-ZnO composite fibers with NiO and ZnO both incorporated into a single fiber; (b) HRTEM
image of p–n NiO-ZnO heterojunction from fiber in red box in (a) (reprinted with permission from Ref. [75]); (c) SEM image of as-spun side-by-side p–n CuO–TiO2 composite
nanofibers; (d) TEM image of p–n CuO–TiO2 composite nanofibers, with arrows pointing to inset HRTEM images confirming crystalline lattice of CuO (top) and TiO2 (bottom)
(reprinted with permission from Ref. [78]). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)

[68]. Though very promising and deserving of further study, they
will not be a focus of this review.
3.4. Mixed 1D–1D structures
A very economical way of creating 1D composites is through
electrospinning. Electrospinning uses a high voltage to draw a thin
fiber of a polymer–metal–organic solution from a needle toward
the substrate. The deposited fibers then must typically be calcined
over 600 ◦ C in order to remove the organics and increase crys-
tallinity [70]. The different oxides can be deposited in sequence,
effectively forming a bi- or multi-layered film [71,72], ground
and mixed post-spinning to form a paste of mixed fibers, or two
or more precursors can be spun in the same solution, creating
true composite nanofibers [14,73–76]. A new method has also
been demonstrated where two separate fibers can simultaneously
be spun side-by-side, forming a long continuous heterojunction
[77,78]. Depending on the type of processing and synthesis meth-
ods, the actual heterojunction area in these composites may differ.
It is important to realize that electrospun fibers typically consist
of strings of oxide nanoparticles (Fig. 5a and b) and thus may not
transfer charge carriers as efficiently as single-crystalline nanorods
or nanowires due to the higher likelihood of recombination. How-
ever, this also means that there are more surface and defect sites
with which the analyte gas can interact, which may result in higher
sensitivity [70]. Electrospun fiber films are also advantageous due
to their open porosity, which allows for very good gas accessibility.
Two forms of electrospun composites maximizing the heterojunc-
tion area are shown in Fig. 5.
A special type of heterostructure consists of a 1D feature grown
radially from a host 1D structure. This results in a “brush-like”
nanostructure. This has been achieved both by multi-step thermal
evaporation [79–81] and by a two-step hydrothermal process [82].
Chen et al. showed that the growth direction and orientation of the
secondary SnO2 nanorods can have an interfacial orientation rela-
tionship with the ␣-Fe2 O3 core nanorods, as shown in Fig. 6e [82].
This presents unique opportunities to control the crystallographic
nature of the interface by using core nanorods of different crystal-
lographic growth directions. It has been shown that the family of
exposed planes in the nanostructure can affect the gas-solid inter-
action [83]. In some cases, the growth kinetics can be manipulated
to allow control of the aspect ratio and morphology of the secondary
features, as shown in Fig. 6a–d. A very open, porous structure allows
easy gas accessibility to a well-defined heterojunction interface.
Future work may allow the choice of crystallographic planes mak-
ing up the interface, which would allow further manipulation of
electronic properties.
3.5. Core–shell structures
Core–shell structures are among the most promising types of
heterostructures for the future of gas sensing as well as cataly-
sis. This morphology provides a way to maximize the interfacial
area between two or more materials while still minimizing the
amount of material acting as bulk. There are several ways to
create core–shell structures, and most are relatively simple. The
host material structure widely varies and can be synthesized
by many methods including hydrothermal, thermal evaporation,
256 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

Fig. 6. (a–d) SEM images and schematics showing progression of tungsten oxide nucleation and growth on SnO2 nanowires via thermal evaporation. Scale bar 100 nm;
(reprinted with permission from Ref. [80]) (e) ␣-Fe2 O3 @SnO2 brush-like heterostructures grown via two-step hydrothermal with clear orientation relationship (reprinted
with permission from Ref. [82]); (f) ZnO nanorods grown from In2 O3 core nanowires showing both 2-fold and 6-fold orientation relationships. Scale bar 3 ␮m (reprinted with
permission from Ref. [81]); (g) Six-fold oriented ZnO nanowires growing on Ga2 O3 nanowire cores (reprinted with permission from Ref. [84]).

physical-vapor deposition (PVD), chemical-vapor deposition
(CVD), electrospinning, sol–gel methods, and others. Then, a thin
layer (typically <20 nm) is deposited onto most or all surfaces of
this structure via solution processes such as hydrothermal [4,66],
spin- or dip-coating [85,86], or advanced processes such as sputter-
ing (Fig. 7a) [87] and atomic-layer deposition (Fig. 7b) (ALD) [11].
Solution-based processes have limited control over the amount of
uptake of the shell material, which then limits control of the thick-
ness of the outer layer. Sputtering and ALD allow for any desired
shell thickness to be applied simply by controlling the deposition
time. For example, Choi et al. electrospun SnO2 nanofibers directly
onto a substrate and then used ALD to form a shell of ZnO, control-
lable to ∼0.45 nm per cycle (Fig. 7b) [11]. In most cases aside from
electrospun cores, the 1D core is a single crystal and the shell is
polycrystalline. This structure may also utilize the optimization of
the separate receptor and transducer functions using a high-surface
area polycrystalline coating for reception and a single-crystalline
“highway” anchored to the substrate for transduction. Alterna-
tively, oxide nanoparticles can be suspended in solution with a
secondary metal oxide precursor and subsequently dried and cal-
cined to form a spherical core–shell structure [88]. In other work,
sol–gel methods are used and after heat treatment one species
tends to segregate to the surface of the nanoparticles, effectively
forming a core–shell structure as well [36,89]. The main difference
between core–shell and a decorated second-phase structure is the
degree of coverage of the host material. Core–shell structures max-
imize the MI Ox –MII Ox interface, but may be disadvantageous if the
MI Ox –gas interface is needed for the reaction. If both MI Ox –gas

Fig. 7. (a) HRTEM image showing a ∼2 nm NiO polycrystalline coating on the large single-crystal core SnO2 nanowire (reprinted with permission from Ref. [87]); (b) TEM–EDX
concentration line profiles of Zn, O, and Sn measured across the electrospun core–shell SnO2 @ZnO nanofiber diameter (reprinted with permission from Ref. [11]).
Table 2
Heterostructure gas sensing performance of SnO2 -based nanomaterials.
Analyte gas Composition Synthesis route Morphology Meas. temp. Response Concentration tres trec Selective Against Ref.
Ethanol 50 vol% SnO2 –ZnO Combinatorial solution Mixed multilayer 300 ◦ C 4.69a 200 ppm 72 s NA acetone, CO, H2 , NO2 , C3 H8 [48]
deposition nanoparticles
Ethanol 50 wt% SnO2 –ZnO Electrospinning SnO2 –ZnO Composite 360 ◦ C 17a, * 2500 ppm 5s 1s NA [73]
nanofibers
Ethanol 5 wt% La2 O3 –SnO2 Powder solution coating La2 O3 -coated SnO2 300 ◦ C 740a, * 1000 ppm 20 min 20 min NA [90]
nanoparticles
Ethanol ZnSnO3 @SnO2 Hydrothermal ZnSnO3 nanorods@SnO2 270 ◦ C 27.8a 50 ppm 1s 1.8 s acetone, benzene, [20]
Nanoflakes chloroform, MeOH,
formaldehyde, CO
Ethanol 1.5 mol% Fe2 O3 –SnO2 Sol–gel method Mixed nanoparticles 250 ◦ C 24i 10 ppm NA NA NA [16]
H2 (3 wt% ZnO–SnO2 )@CuO Pressed-dipped CuO-coated (ZnO–SnO2 305 ◦ C 16a 200 ppm NA NA CO [6]
powder)
H2 SnO2 @2.6 mol% ZnO PECVD-spin coating ZnO-coated SnO2 350 ◦ C 18.4b 100 ppm NA NA CO, NH3 , CH4 [85]
nanorods
H2 (0.005 mol MoO3 )–SnO2 Sol–gel method Mixed 240 ◦ C 10f 1000 ppm 5s 10 s NA [91]
H2 1 wt% Co3 O4 –SnO2 Precipitation Mixed nanoparticles 250 ◦ C 9100a 1000 ppm NA NA CO [42]
H2 S Cu2 O/SnO2 Cyclic electrochemical Thin-film horizontal RT 45f 50 ppm NA NA toluene, LPG [52]
deposition multilayers

D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

H2 S CuO/SnO2 Sputtering-oxidation Single bi-layer 433◦ K 70J, * 16.6 ppm NA NA NA [47]
H2 S 6% CuO/SnO2 PLD Mixed nanocrystals 150 ◦ C 4300c 20 ppm 3s NA NA [45]
H2 S SnO2 @CuO Thermal SnO2 film@CuO clusters 150 ◦ C 8100a 20 ppm 12 s 366 s NA [59]
evaporation-oxidation
H2 S 1 mol% CeO2 –SnO2 Solution precipitation Mixed nanoparticles 300◦ K 3a 5 ppm 40 s 20 s LPG, EtOH, NOx , CO [37]
H2 S SnO2 @ZnO Thermal ZnO-coated SnO2 350 ◦ C 2.1a, * 500 ppm NA NA CO, CH4 [87]
evaporation-sputtering nanowires
H2 S (5 wt% ZnO–SnO2 )@3.68 wt% Ball mill + dipping CuO-coated ZnO–SnO2 150 ◦ C 60,443d 50 ppm 15 s 7 min NOx , LPG, CO2 , CH4 [86]
CuO powder
◦ d
H2 S 5 wt% ZnO–SnO2 Ball mill ZnO–SnO2 powder 250 C 250 50 ppm NA NA NA [86]
H2 S SnO2 Ball mill SnO2 powder 350 ◦ C 10d 50 ppm NA NA NA [86]
NO2 SnO2 @ZnO Electrospinning-ALD ZnO-coated SnO2 RT 0.4c 5 ppm ∼50 s* ∼450 s* NA [11]
nanofibers
NO2 40% ZnO–SnO2 Reverse microemulsion SnO2 with amorphous 250 ◦ C 34.5b 500 ppm NA NA NA [19]
ZnO coating
NO2 20% WO2 -SnO2 Sol precipitation Particles 200 ◦ C 186b 200 ppm NA NA NA [35]
NO2 (20% WO2 –SnO2 )@MgO Sol precipitation MgO Coated particles 150 ◦ C 418b 200 ppm NA NA NA [35]
NO2 (40 wt% In2 O3 –SnO2 )@10 wt% Co-precipitation Al2 O3 -Coated 200 ◦ C 632b 450 ppm NA NA CO [18]
Al2 O3 nanoparticles
NO2 40% In2 O3 –SnO2 Co-precipitation Particles 200 ◦ C 7.5b 1000 ppm NA NA NA [18]
CO 40% In2 O3 –SnO2 Co-precipitation Particles 250 ◦ C 16a 1000 ppm NA NA NA [18]
CO SnO2 @In2 O3 2-step Au-catalyzed-self- Brush-like SnO2 @In2 O3 300 ◦ C 1.9a 200 ppm 135 s 460 s NA [79]
catalytic
VLS
CO SnO2 @NiO Thermal NiO-coated SnO2 250 ◦ C 15.9a 500 ppm NA NA CH4 [87]
evaporation-sputtering nanowires
CO (0.002 mol MoO3 )–SnO2 Sol–gel method Mixed 140 ◦ C 30f 1000 ppm 5s 5s NA [91]
CO 50 wt% Co3 O4 -SnO2 Precipitation Mixed nanoparticles 100 ◦ C 175b 1000 ppm NA NA H2 [42]
CO (3 wt% ZnO–SnO2 )@CuO Pressed-dipped CuO-coated (ZnO–SnO2 235 ◦ C 15.4a 200 ppm NA NA H2 [6]
powder)
CH4 25 wt% In2 O3 –SnO2 Co-precipitation Coated nanoparticles 300 ◦ C 7.2a 850 ppm NA NA NA [9]
CH4 20 wt% TiO2 -(25 wt% Co-precipitation Coated nanoparticles 300 ◦ C 13.6a 850 ppm NA NA CO [9]
In2 O3 –SnO2 )
Ethyl-ene 0.3 wt% WO3 –SnO2 Solution precipitation Mixed nanoparticles 300 ◦ C 1.7a 6 ppm ∼10 min* ∼10 min* NA [41]
SO2 1 mol% NiO–SnO2 Pechini method NiO-coated SnO2 25 ◦ C 0.84d, * 18 ppm 4.5 min 15 min O2 , C3 H8 , NOx [89]
Cl2 W18 O49 –SnO2 Sequential thermal Brush-like SnO2 @W18 O49 RT 11.0l 6 ppm 4.6 min 17 min H2 S, CO, NOx , NH3 [80]
evaporation
Butanol 50 wt% ZnO–SnO2 Mechanical mixing Mixed particles 350 ◦ C 300g, * 5 ppm NA NA EtOH, propanol, hexanol, [17]
butanal, decane
◦ a, *
TMA 10 wt% ZnO–SnO2 Precipitation- Mixed SnO2 330 C 126 50 ppm 2s 5s NH3 , DMA, MA, EtOH, MeOH, [92]
hydrothermal nanoparticles/ZnO Acetone
nanorods
Note: a S = Ra /Rg ; b S = Rg /Ra ; c S = R/Rg ; d S = R/Ra ; e S = (R/Rg ) × 100; f S = (R/Ra ) × 100; g S = (I/Ia ) × 100; h S = Vg /Va ; i S = Gg /Ga ; j S = G/Ga ; k S = G/Gg ; l S = Ig /Ia .

257
*
Denotes a value not explicitly stated in the study, but approximated from a graphical plot.
258 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
and MII Ox –gas interfaces are needed, the decorated second-phase
particles would be most advantageous. Huang et al. showed that
the thickness of the ZnO shell on SnO2 nanorods was a key factor
in sensing behavior [85]. Additionally, they report that a complete
ZnO shell showed an n–p–n response transition while a decoration
of ZnO nanoclusters showed only n-type behavior, which will be
discussed in Section 4.1.4.
Tables 2–4 provide a compilation of a large portion of recent
studies using nanostructured metal-oxide based heterojunctions
for gas sensing applications. Data are sorted first by base material,
second by gas analyte, and third by choice of secondary material.
Table 2 focuses on SnO2 , Table 3 on ZnO, and Table 4 compiles data
from TiO2 , In2 O3 , Fe2 O3 , MoO3 , Co3 O4 , and CdO-based nanomate-
rials, segregated by horizontal dashed lines. The direct comparison
of gas sensing measurements by different research groups is very
difficult due to various gas concentrations, response definition con-
ventions, sensor design, film thickness, operating temperature, etc.
The best that can be drawn is from the comparisons to the native
oxides prepared in the same fashion and reported in the same study.
These are included in Tables 2–4 where relevant. In studies that
tested a range of compositions, the specific compositions listed for
each study were the optimal composition found. Additionally, the
measurement temperature reported was usually the optimal oper-
ating temperature for that composition. “NA” is listed where no
specific data were available, and asterisks denote values approxi-
mated from graphical plots. The reader is encouraged to refer to the
original publication for additional details such as performance as
a function of composition, layer thickness, operating temperature,
etc.
4. Mechanisms responsible for enhanced sensing
performance in heterostructures
A survey of the literature reveals that a large number of het-
erostructured MOGS research studies are strictly empirical, with
a trial-and-error type approach in finding suitable materials or
composites for a given application. Conclusions in the literature
often state that the presence of the second constituent has a drastic
effect on sensing performance, but do not give detailed mechanis-
tic explanations. It is obviously expensive and time-consuming to
delve into this problem, and may seem unnecessary if the empir-
ical results are already suited to the application. However, more
detailed analysis of these heterojunction mechanisms may even-
tually lead to an understanding that allows for bottom-up design
of a material for a given sensing application, likely saving time
and money in the long term. For this reason, we highlight those
studies that have attempted to thoroughly explain their results,
in the hope that future studies may gain more understanding
from these efforts. At present, there is no one theory that can
govern all heterostructure–gas interactions because of the diver-
sity of structures and materials available. One must understand
the fundamentals in surface chemistry and reactions, energy band
structure, catalytic behavior, and microstructural development in
order to comprehend the scope of these mechanisms. Though many
classes of dissimilar materials can form electronic heterojunctions,
the focus of this section is on oxide–oxide interfaces and mix-
tures for gas sensing, as there is a wide range of mechanisms in
play and no comprehensive review of the subject has before been
published.
4.1. Role of the interface
The heterojunction interface is perhaps the most important con-
sideration when analyzing the behavior of a semiconducting metal
oxide composite. A very common interface used to modulate gas
sensing properties is a p–n junction. N-type gas sensors are much
more widely used than p-type gas sensors due to several consider-
ations such as stability in low oxygen environments and response
compatibility to measuring devices [28]. However, these materials
can be combined in different ways to utilize the effects of the p–n
junction and improve sensing performance [5,13,14,26,93,102]. For
reference, several materials with their respective dominant con-
duction types are presented in Table 5.
When the Fermi energy (EF ) of a semiconducting material is dif-
ferent than that of a second material with which it has an electrical
connection, the electrons at the higher energies will flow across
the interface to unoccupied lower-energy states until the Fermi
energies have equilibrated. This is equivalent to electron–hole
recombination in the vicinity of a p–n junction. This is often called
“Fermi level-mediated charge transfer.” A schematic of this is
shown in Fig. 8a. This leads to a zone depleted of charge carriers
at the interface called the depletion region. A potential energy (PE)
barrier develops at this interface due to the band bending which
is caused by the difference in original Fermi levels of the materi-
als. Electrons must overcome this PE barrier in order to cross this
interface, as seen in Fig. 8b.
4.1.1. Effects of p–n nanojunctions on gas sensing
Consider an n-type ZnO nanowire sensor decorated with p-type
Co3 O4 nanoislands (similar to Fig. 4a–c) [5]. The normal ambient
resistance of the nanowires in air (Ra ) will be even higher than
without the heterojunction due to the depletion region at the het-
erojunction interface extending into the ZnO nanowire, decreasing
the width of the charge conduction channel. A reduced cross-
sectional area available for charge conduction in the nanowire will
result in an increased resistance. Additionally, charge conduction
across the p–n interface will further contribute to the increase of
the resistance. When an oxidizing gas such as NO2 is introduced,
any additional increase in the resistance due to adsorption is now
minimized. However, when a reducing gas is introduced, a large
decrease in the resistance is possible due to the initial value of Ra
being exceedingly high, as response is typically measured as Ra /Rg
[5]. This by itself should only be true if the depletion depth (there-
fore resistance) caused by the Co3 O4 nanoislands is more sensitive
to the atmosphere than the ZnO nanowires alone. The authors also
attribute the enhanced response toward ethanol above 360 ◦ C to
its total conversion to CO2 and H2 O, which has been reported as
low as 380 ◦ C in the presence of a Co3 O4 catalyst [103]. These two
factors allowed the researchers to enhance selectivity to a reduc-
ing gas, e.g. , ethanol, by subsequently reducing the response to
the oxidizing gas NO2 , which often causes interference with the
measurements due to its presence from vehicle emissions during
roadway blood-alcohol (ethanol) BreathalyzerTM testing [5].
Similarly, Cr2 O3 was applied to ZnO nanowires and tested in the
presence of tri-methylamine (TMA) [62]. The study showed that
nanoislands drastically enhanced response, while a complete coat-
ing decreased the response compared to pristine ZnO nanowires
(Fig. 9). They concluded that the Cr2 O3 also narrowed the ZnO
conduction channel as explained above in both cases, increasing
the air resistance and creating a larger change when the reduc-
ing gas TMA was introduced. In this case, Cr2 O3 was also chosen
because it has shown catalytic effects toward methylamine decom-
position. It was also shown that the dominant conduction path
in the continous core–shell nanostructures was through the p-
type Cr2 O3 layer, and thus showed p-type behavior on exposure
to TMA [62]. A simultaneous study [104] by Mashock et al. on SnO2
nanoparticle-coated CuO nanowires correlates well with the above
result. This nanostructure is of opposite nature, utilizing a p-type
core (CuO) and an n-type coating (SnO2 ). Still, a depletion region
forms at the interface and impinges upon the conducting core. Since
p-type materials are dominated by surface conduction due to the
Table 3
Heterostructure gas sensing performance of ZnO-based nanomaterials.

Analyte gas Composition Synthesis route Morphology Meas. temp. Response Concentration tres trec Selective against Ref
◦ a
Ethanol ZnO@ZnS Polymer-assisted ZnS nanoparticle-coated 210 C 23 1000 ppm 15 s 15 s NA [10]
hydrothermal- ZnO hollow dumbbells
sulfurization
Ethanol ZnO@ZnS @Graphene Polymer-assisted Graphene-coated ZnS 210 ◦ C 38a 1000 ppm 15 s 15 s Acetone, [10]
hydrothermal- nanoparticle-coated ZnO formaldehyde,
sulfurization hollow dumbbells benzene, cylcohexane
Ethanol 2:1 mol ZnO:SnO2 Electrospinning Composite nanofibers 300 ◦ C 18a, * 100 ppm 5s 6s NH3 , C2 H2 , NOx , CH4 , [74]
H2 , CO

D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

Ethanol 25 wt% SnO2 –ZnO Mechanical mixing Mixed particles 350 ◦ C ∼82j, * 100 ppb NA NA NA [32]
Ethanol 6%CeO2 -Al2 O3 -ZnO LDH solution Particle 260 ◦ C 170a 1000 ppm 2s 10 s MeOH, toluene, [93]
formamide
Ethanol Al2 O3 -ZnO LDH solution Particle 260 ◦ C 9a 1000 ppm 14 s 87 s NA [93]
Ethanol ZnO Electrospun Nanofibers 300 ◦ C 7a 100 ppm NA NA NA [72]
Ethanol In2 O3 /ZnO Electrospun Nanofiber bi-layer 210 ◦ C 25a 100 ppm 2s 1s NA [72]
Ethanol ZnO/In2 O3 /ZnO Electrospun Nanofiber tri-layer 210 ◦ C 17a 100 ppm NA NA NA [72]
Ethanol ZnO Electrospun Nanofibers 300 ◦ C 9a 100 ppm 1s 5s NA [14]
Ethanol 4.5 wt% Cr2 O3 -ZnO Electrospun Nanofibers 300 ◦ C 24a 100 ppm 1s 5s CH4 , H2 , CO, NO, NO2 [14]
Ethanol ZnO@Co3 O4 VLS-thermal evaporation Co3 O4 nanoisland-coated 400 ◦ C 21.9a 100 ppm 100 s* 200 s* NO2 , CO, H2 , CH4 , C2 H6 , [5]
ZnO nanowires C3 H8 , i-C4 H10
Ethanol 2:8 mol CuO:ZnO Co-precipitation Mixed powder 115 ◦ C 96h, * 100 ppm 13 s 5s NA [94]
Acetone ZnO@TiO2 2-step CVD TiO2 -coated ZnO 400 ◦ C 22i 100 ppm 1 min 1 min CO, EtOH [3]
nanoplatelet film
H2 TiO2 /NiO DC Sputtering 100 nm TiO2 over 10 nm 200 ◦ C 70a 10,000 ppm NA NA NA [51]
NiO film
◦ g
H2 ZnO@SnO2 MBE/PLD SnO2 -coated ZnO 400 C 70 500 ppm NA NA NA [95]
nanowires
H2 S ZnO Traditional hydrothermal Nanorods 100 ◦ C 25a, * 100 ppm NA NA NH3 , MeOH, EtOH, [12]
butanol, acetone, ether
H2 S ZnO@3 wt% CuO Traditional ZnO porous nanorods@CuO 100 ◦ C 39a, * 100 ppm 120 s >150 s NH3 , MeOH, EtOH, [12]
hydrothermal/solution nanoparticles butanol, acetone, ether
synthesis
H2 S 2:8 mol CuO:ZnO Co-precipitation Mixed powder 115 ◦ C 20h, * 100 ppm 13 s 5s NA [94]
NO2 5% Eu2 O3 -ZnO Traditional hydrothermal Porous strips 300 ◦ C 16b 3 ppm 3 min 3 min CO [43]
NH3 2 mol% ␣-Fe2 O3 -ZnO Hydrothermal-solution Mixed nanoparticles RT 10,000l 0.4 ppm 20 s 20 s TMA, EtOH, MeOH [96]
mixing
NH3 ZnO@Cr2 O3 Powder film dip-coating Cr2 O3 -coated ZnO powder RT 13.7j 300 ppm 25 s 75 s LPG, CO2 , EtOH, H2 , Cl2 [97]
LPG ZnO@0.47 wt% Cr2 O3 Powder film dip-coating Cr2 O3 -coated ZnO powder 350 ◦ C 46j 100 ppm 18 s 42 s NH3 , CO2 , EtOH, H2 , [7]

Note: a S = Ra /Rg ; b S = Rg /Ra ; c S = R/Rg ; d S = R/Ra ; e S = (R/Rg ) × 100; f S = (R/Ra ) × 100; g S = (I/Ia ) × 100; h S = Vg /Va ; i S = Gg /Ga ; j S = G/Ga ; k S = G/Gg ; l S = Ig /Ia .
*
Denotes a value not explicitly stated in the study, but approximated from a graphical plot.

259
 260
Table 4
Heterostructure gas sensing performance of TiO2 , In2 O3 , Fe2 O3 , MoO3 , Co3 O4 , and CdO-based nanomaterials.

Analyte gas Composition Synthesis route Morphology Meas. temp. Response Concentration tres trec Selective against Ref.

H2 20 wt% SnO2 –TiO2 Co-precipitation Mixed nanoparticles 400 ◦ C 9.9c, * 20 ppm 12–14 s 4.5–5 min NA [30]
H2 10 wt% SnO2 –TiO2 Mechanical mixing Mixed nanoparticles 400 ◦ C 10.5c, * 20 ppm 12–14 s 4.5–5 min NA [30]
Ethanol 20 wt% SnO2 –TiO2 Colloidal mixing Mixed nanoparticles 553◦ K 51a, * 200 ppm 10–15 s 14–20 s NA [98]
Acetone 20 wt% SnO2 –TiO2 Colloidal mixing Mixed nanoparticles 633◦ K 55a, * 200 ppm 10–15 s 14–20 s NA [98]
O2 90% CeO2 –TiO2 Sol–gel method Mixed 420 ◦ C 9.5b 103 ppm 50 s 80 s NA [36]
Ethanol In2 O3 @ZnO 2-step VLS Core–shell In2 O3 350 ◦ C 265i 400 ppm NA NA NA [99]

D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

nanowires@ZnO
O3 (␥-Fe2 O3 –In2 O3 (9:1))/In2 O3 Sol–gel method Mixed 135 ◦ C 8670k 100 ppb NA NA NO2 [100]
nanoparticles/nanoparticles
NO2 (␣-Fe2 O3 –In2 O3 (9:1))/In2 O3 Sol–gel method Mixed 135 ◦ C 440k 5 ppm 20 s >900 s O3 [100]
nanoparticles/nanoparticles
Ethanol ␥-Fe2 O3 /In2 O3 Sol–gel method ␥-Fe2 O3 /In2 O3 bi-layer 300 ◦ C 68j, * 100 ppm 50–60 s 50–60 s NA [49]
Ethanol ␣-Fe2 O3 @SnO2 2-Step Hydrothermal Brush-like ␣-Fe2 O3 @SnO2 350 ◦ C 4.6a 10 ppm NA NA H2 , CH4 , C4 H10 [82]
Ethanol ␣-Fe2 O3 @SnO2 @4.8 wt% Au 2-Step Au-functionalized SnO2 -coated 320 ◦ C 3.11a 100 ppm 5s 5s MeOH, H2 S [66]
hydrothermal-solution ␣-Fe2 O3 nanospindles
reduction
Ethanol ␣-Fe2 O3 @SnO2 2-Step hydrothermal SnO2 -coated ␣-Fe2 O3 320 ◦ C 2.8a, * 100 ppm 9s 9s NA [66]
nanospindles
Ethanol ␣-Fe2 O3 @ZnO Hydrothermal-solution Core–shell ␣-Fe2 O3 220 ◦ C 22.1a 500 ppm 20 s 20 s H2 , CH4 [88]
mixing nanowires@ZnO
◦
Ethanol ␣-Fe2 O3 @ZnO 2-Step Hydrothermal Core–shell ␣-Fe2 O3 280 C 17.8 a
100 ppm ∼1 min ∼1 min MeOH, CO [4]
nanospindles@ZnO
Ethanol ␣-MoO3 @SnO2 Hydrothermal-solution SnO2 nanoparticle-coated 300 ◦ C 67.76a 500 ppm <1 min* <30 s* NA [56]
␣-MoO3 nanobelts
Ethanol 1.4 wt% TiO2 -MoO3 RF sputtering Mixed nanocrystals 400 ◦ C 250j 100 ppm NA NA NA [44]
CO 20 wt% WO3 -MoO3 RF sputtering Mixed nanocrystals 200 ◦ C 390j 15 ppm 2 min 2 min NA [44]
Ethanol MoO3 -WO3 Sol–gel method Mixed nanoparticles 300 ◦ C 10NA 100 ppm NA NA CO [39]
O3 MoO3 –TiO2 Sol–gel method Mixed nanoparticles 300 ◦ C 1.7NA 100 ppb 20 s 2 min NA [39]
Ethanol Co3 O4 Solution Strings of nanoparticles 170 ◦ C 6.2b 100 ppm NA NA NA [13]
Ethanol ZnO–Co3 O4 Solution ZnO-coated Co3 O4 170 ◦ C 46b 100 ppm NA NA NA [13]
nanoparticles
Ethanol CeO2 –CdO–Al2 O3 LDH solution Mixed nanoparticle 190 ◦ C 890a 1000 ppm 32 s 297 s NH3 , alkane mix, [101]
organics
Ethanol CdO-Al2 O3 LDH SOLUTION Mixed nanoparticle 250 ◦ C 6.4a 1000 ppm NA NA NA [101]

Note: S = Ra /Rg ; S = Rg /Ra ; S = R/Rg ; S = R/Ra ; S = (R/Rg ) × 100; S = (R/Ra ) × 100; S = (I/Ia ) × 100; S = Vg /Va ; S = Gg /Ga ; S = G/Ga ; k S = G/Gg ; l S = Ig /Ia .
a b c d e f g h i j

*
Denotes a value not explicitly stated in the study, but approximated from a graphical plot.
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272 261

Table 5
Response type behavior of several metal oxides, semiconductors, and polymers (adapted from Ref. [28]).

Material Type of conductivity

n p n, p

Metal oxides SnO2 , ZnO, TiO2 , In2 O3 , MoO3 , MgO, Al2 O3 , NiO, CeO2 , Mn2 O3 , Co3 O4 , La2 O3 , Y2 O3 , PdO, Fe2 O3 , HgO2
Ga2 O3 , Nb2 O5 , ZrO2 , CaO, V2 O5 , Ta2 O5 , WO3 Ag2 O, Bi2 O3 , Sb2 O3 , TeO2 , CuO, Cr2 O3
Semiconductors SiC, GaN, diamond Si, InP, GaAs
Polymers Polypyrrole, polythiophene, polyaniline Trans-polyacetylene, polyphenylene

accumulation layer formed on oxygen adsorption, the effect is likely
amplified. The researchers showed a large increase in resistance
after deposition of a discrete SnO2 nanoparticle coating, as would
be expected by the model we have presented. By doubling the
deposition time on a different sensor, they were able to create a
continuous nanoparticle coating forming a true core–shell struc-
ture. The longer deposition time caused an even higher resistance,
but also had a smaller increase in response to NH3 compared to
the nanowires with shorter deposition time. The authors cited two
contributing mechanisms to explain this: (1) NH3 reduces the CuO
nanowire surface by donating an electron, which increases its resis-
tance and (2) NH3 reduces the SnO2 nanoparticles by removing
adsorbed oxygen, which donates an electron and increases the car-
rier concentration in the nanoparticle coating, creating a stronger
p–n junction. The stronger junction pushes further into the CuO
nanowire core and increases the resistance, complimenting the
effects of the first mechanism. When a continuous shell is created
by the longer deposition, the SnO2 coating becomes the primary
conductive path, and the CuO core does not participate in the reac-
tion. They propose that a discrete particle coating allows both
mechanisms to take place, and therefore gives the best sensing
performance. This result is very similar to that explained above
by Woo et al., and shown in Fig. 9. As Mashock et al. go on to
caution, this model only takes into account conduction along the
axial direction of the nanowires, which is dominated by the avail-
able cross-sectional area for conduction, i.e. not affected by the
depletion region. It does not take into account the changes in the
potential energy barrier present at the interface between particles
as it varies with the degree of oxygen adsorption. Jain et al. attribute
the increase in LPG sensitivity of their SnO2 @NiO core–shell spher-
ical nanoparticles to the increased potential energy barrier height
from the formation of the p–n junction [105]. Unlike 1D structures,
spherical core–shell nanoparticles force electrons to overcome sev-
eral interfacial energy barriers in series and the performance is then
even more dependent on the heterojunction. These two mecha-
nisms are described further in Section 5.4.
4.1.2. Effects of n–n and p–p nanojunctions in gas sensing
Band bending can also occur in n–n and p–p heterojunctions
[80,98]. Zeng et al. propose that the electron migration from TiO2 to
the SnO2 seen in Fig. 8(c and d) can help facilitate additional oxygen
adsorption at the SnO2 surface due to the larger electron density
[98]. Kusior et al. also proposes this mechanism in the same sys-
tem [8]. The interface at a p–n junction has far fewer free electrons

Fig. 8. Schematics explaining band bending at heterojunction interfaces with no adsorbed surface species. (a) p–n junction about to form between p-type Co3 O4 and n-type
ZnO. The available lower-energy valence band states (holes) stimulate electron transfer across the interface and the equilibration of Fermi energies (EF ). (b) Depletion layer
formed on both sides of p–n junction due to recombination, creating a potential barrier for electron flow. (c) n–n junction about to form between n-type SnO2 and n-type
TiO2 . The available lower-energy conduction band states stimulate electron transfer to n-SnO2 . (d) Depletion layer formed at n-TiO2 surface due to loss of electrons, and
accumulation layer formed at SnO2 surface due to added electrons, which enhances oxygen adsorption. A potential barrier was also formed at the interface. ECB : conduction
band edge energy, EVB : valence band edge energy, Egap : band gap energy, EF : Fermi energy ((c and d) adapted from Ref. [98]).
262 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
Fig. 9. TMA response (a) and resistance (b) to unmodified ZnO nanofibers, Cr2 O3 -decorated ZnO nanofibers, and ZnO–Cr2 O3 core–shell nanocables (NCs). The addition of
the p-type nanoislands caused a nearly two order of magnitude increase in air resistance and subsequently enhanced response to reducing gas TMA. The dominant charge
conduction in the core–shell nanocables was through the p-type Cr2 O3 layer, thus showing opposite response.
Reprinted with permission from Ref. [62].
due to electron–hole recombination, increasing resistance, while
the interface at an n-n junction simply transfers electrons into the
lower-energy conduction band, forming an “accumulation layer”
in the SnO2 rather than a depletion layer. The accumulation layer
can be depleted by subsequent oxygen adsorption on the surface
of the SnO2 , further increasing the potential energy barrier at the
interface, and enhancing the response.
These studies show that it is important to modulate potential
energy barrier height at the heterojunction interface under ambi-
ent oxygen adsorption conditions. This is the key for facilitating
the largest resistance decrease in n-type materials on introduction
of reducing gases. However, for the detection of oxidizing gases it
has been shown to be more beneficial to artificially generate a low
ambient resistance to allow for the largest resistance increase. Sen
et al. did this using a brush-like structure with W18 O49 nanowires
grown on SnO2 core nanowires (Fig. 6a–d) [80]. They propose that
the n-type W18 O49 donated electrons to the SnO2 core, decreasing
the base resistance in air [80]. The potential barrier generated at
the interface likely also increased, but this was not as much of a
factor for two reasons: the W18 O49 was not very reactive to the
gas and the SnO2 core was still directly exposed to the gas and
thus not dependent upon charge conduction across the hetero-
junction interface. The SnO2 cores were the main conduction path
through the material and so the injection of electrons from the
W18 O49 resulted in a lower air resistance. This is another result
that shows the importance of the architecture used to combine
the two types of materials, engineered to either conduct across the
interface or along the crystalline nanowires. However, one must be
careful in interpreting these results based solely on resistance mea-
surements. The addition of a second constituent will undoubtedly
change the resistance just by a rule-of-mixtures such that adding
a more conductive material will increase the conductivity. Other
variables that confound these explanations include film thickness,
nanostructure number density and distribution. If presenting one
of these mechanisms as an explanation, it is important to average
the measurements of several “identical” samples to remove vari-
ation in film depositions. A more precise measurement to remove
these confounding effects using single nanowires is also presented
in Section 5.4.
4.1.3. Separation of unlike charge carriers
An additional mechanism that can be used to enhance sensing
performance based on an interface is through charge carrier sepa-
ration. The electric field that is created across the depletion region,
much like in a p–n junction solar cell, acts to pull electrons in one
direction and holes in the opposite direction. Charge “directing”
can also exist in n–n junctions through balancing of Fermi ener-
gies, such as in ZnO–TiO2 [3]. Charge carrier separation minimizes
electron–hole recombination and thus increases charge carrier
density allowing for a more sensitive material. Zakrzewska and
Radecka uniquely showed that charge carrier separation can be uti-
lized for enhancing H2 sensor lifetime and performance by using
TiO2 added to SnO2 to photocatalytically break down organic con-
taminants that would otherwise degrade the sensor [106]. Here,
the working principles of photocatalysis are directly applied to the
sensor material giving it a dual functionality when illuminated with
UV light. This improved the long-term performance and stability of
the sensor.
4.1.4. n–p response type inversion
It is important to realize that the addition of a p-type material
will counteract the resistance change of the n-type material for a
given gas if the structure allows it to be an independent sensing
material in the composite. Sometimes the p-type constituent will
become the dominant sensing material over a certain range of con-
ditions. A few groups have reported the phenomenon of n–p or
n–p–n response inversion behavior [51,85]. Kosc et al. reported a
bi-layer TiO2 /NiO sputtered film that showed p-type conductivity
naturally until a critical concentration of reducing H2 was reached
[51]. The added electrons from broken oxygen bonds eventually
fully compensated the holes in the NiO layer and then the sensor
exhibited n-type behavior. This transition concentration was also
temperature-dependent. Huang et al. reported a n–p–n response
inversion in SnO2 @ZnO core–shell nanorods [85]. Fig. 10 shows the
mechanism that successfully selected H2 in the presence of other
reducing gases. They reported that a mixed Zn–O–Sn phase formed
at the heterojunction interface with intrinsic p-type behavior due
to acceptor-type doping of Zn2+ on Sn4+ sites. Hall measurements
confirmed that both the ZnO shell layer and SnO2 nanorods were
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
Fig. 10. Schematic showing the mechanism for H2 selectivity. (a) SnO2 nanorods
with continuous ZnO shell that is impermeable to gas analytes other than H2 , and
showed n–p–n transition on exposure to H2 . The key to the transition was the mixed
Sn–O–Zn p-type phase at the interface coupled with the continuous ZnO shell. (b)
Identical SnO2 nanorods except for an incomplete coating of ZnO nanoclusters. This
allowed larger gas molecules to interact directly with both n-type surfaces, and only
n-type behavior was observed.
Reprinted with permission from Ref. [85].
n-type. The ZnO shell (ca. 3 nm) was well within the Debye length
and so the depletion region extended into the n-type nanorods.
Upon exposure to low H2 concentration (<20 ppm) normal n-
type behavior was observed. Higher concentrations (20–1000 ppm)
reduced the depletion region thickness so that it only extended into
the p-type mixed Zn–O–Sn region, where electron injection would
increase the resistance, and a p-type behavior was exhibited. H2
concentrations above 1000 ppm then likely fully compensated the
p-type behavior by donation of electrons and creation of shallow
donor states by incorporating hydrogen, and n-type behavior was
again observed. The other reducing gases such as CO, NH3 , and CH4
were not able to diffuse through the ZnO layer due to their larger
molecular size and so only n-type behavior was observed for these
analytes. They comparatively studied ZnO nanoclusters not com-
pletely covering the SnO2 surface nor forming a mixed Zn–O–Sn
layer, which showed only n-type behavior and was not selective
against the larger reducing molecules [85].
4.2. Synergistic and complimentary behavior
Another important mechanism that should be considered in
composite materials is non-interface dependent complimentary
behavior, often referred to as synergistic behavior. In general, this
is when two different constituents in a material are each in con-
tact with the gas phase and each serve a different purpose that is
complimentary of the other. This has been reported in the litera-
ture most often as either decomposition of intermediate reaction
products or as a spill-over effect.
4.2.1. Complimentary decomposition
Many studies have shown that the successful detection of
alcohol can be enhanced by further decomposition of an inter-
mediate oxidation reaction product generated by the host oxide
[16,17,31,90]. It has been shown that alcohols generally undergo
263
Fig. 11. Conversion percentage from ethanol to various products as a function of
Fe2 O3 fraction (x = 0, pure SnO2 ) at (a) 250 ◦ C and (b) 300 ◦ C.
Reprinted with permission from Ref. [16].
either a dehydration or dehydrogenation reaction when catalyzed
by a metal oxide [16]. An acidic oxide surface favors dehydration
while a basic surface favors dehydrogenation. By testing a series
of metal cation dopants, Jinkawa et al. reported that the primary
ethanol reaction product shifted acetaldehyde (dehydrogenation)
to C2 H4 (dehydration) with increasing electronegativity of the
metal cation dopant [90]. Furthermore, the dehydration product
C2 H4 does not increase the electron concentration in the oxide
upon reaction, therefore having little or no effect on the sensing
signal [107]. The complete conversion of ethanol to CO2 and H2 O
is also more easily accomplished when dehydrogenation occurs.
This knowledge allowed Rumyantseva et al. to add basic Fe2 O3 to
SnO2 and reduce the proportion of surface acid sites, preferentially
selecting the dehydrogenation reaction [16]. The conversion per-
centage of these ethanol reaction products can be seen as a function
of Fe2 O3 concentration in Fig. 11. Furthermore, this concept can
be confirmed by referencing Tables 2–4 and noticing that an oxide
with a more electronegative (acidic) cation (SnO2 ) performs best for
ethanol sensing when an oxide with a less electronegative (basic)
cation (ZnO; Fe2 O3 ) is added. The large number of ethanol sensing
studies on ZnO and Fe2 O3 is also evidence of this.
Recent work in nanocomposites has also shown that having both
acidic and basic reaction centers with different redox properties
in a material can more completely break down an organic vapor
than one material alone [49,100]. de Lacy Costello et al. carefully
measured the reaction products of 1-butanol catalyzed by a heated
264 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

SnO2 , ZnO or ZnO–SnO2 composite [31]. They found that SnO2 was
most effective at oxidizing butanol to butanal and ZnO was mostly
ineffective at the decomposition of butanol but readily completed
the decomposition of butanal. Thus the SnO2 –ZnO system worked
synergistically to completely break down butanol, and showed the
best sensing behavior. This and the previous work show the anal-
ogy between resistive gas sensing and catalysis. It is important for
sensor researchers to check the catalysis literature, which often
present detailed analysis of reaction pathways that also happen
at the sensor surface. A host of new catalysis and photocatalysis
literature is now also focusing on nanostructured heterojunction
materials and the possibilities they present for selecting reaction
pathways and decomposition products [108,109].

4.2.2. Catalyzed spill-over effect

The other type of complimentary behavior often mentioned in
literature is the spill-over effect. Generally, a gas molecule reacts in
a specific way with one of the composite constituents and the reac-
tion creates a secondary product that remains adsorbed onto the
surface of the other constituent and then directly affects the sensing
performance. This process is most commonly described in the use of
a CuO composite material in H2 S detection [45,59,110,111]. Specif-
ically, the H2 S reacts with CuO nanoparticles and transforms them
into CuS. The left-over hydrogen then “spills over” onto the sur-
face of the host material and acts as a reducing agent, decreasing
the resistance [111]. In this way, the CuO helps to sensitize the
host oxide to the H2 S analyte. An additional effect of this reaction
allows further performance enhancement via complete removal of
the depletion layer [45,59,110,111]. CuO forms a p–n junction with
ZnO, increasing the resistance in air, Ra . CuS is a moderate con-
ductor and thus when conversion is complete, an ohmic junction is
formed which eliminates the depletion region and allows easy con-
duction across the interface and along the nanowires (Fig. 12) [112].
Chowdhuri et al. supported this hypothesis by finding an opti-
mal thickness of the CuO cluster on a SnO2 surface for maximum
sensing response [59]. With CuO clusters thicker than 8 nm com-
plete conversion to CuS does not occur, but below 8 nm the clusters Fig. 12. (a) A significant improvement in sensor performance (higher response,
lower operating temperature) is observed when the p-type CuO nanoparticles are
do not maximize the hydrogen spill-over effect and response drops
added to the n-type SnO2 nanowires. (b) Sensing mechanism of CuO sensitization
sharply. These systems therefore make use of multiple mechanisms to H2 S gas is explained. In air, a depletion region forms at the p–n junction, reducing
simultaneously to maximize the performance. the charge conduction channel. With H2 S present, CuO is transformed to CuS and
The spill-over effect has also been described for noble metal the depletion region is removed.
nanoparticles such as Pd catalyzing the dissociation of O2 subse- Reprinted with permission from Ref. [112].
quently spilling out the O- adsorbed ions onto the metal oxide
surface [27,34]. The main advantage of using added catalysts is
to lower the activation energy needed for reaction, which reduces can react, also enhancing response. A dopant oxide or metal pre-
response and recovery time and lowers operating temperature [28]. cursor can exist in many dispersion states as shown previously
Another slight variation of this could be called the “reverse spill- in Fig. 2 [38]. Korotcenkov et al. stress that there is no univer-
over” effect, where a molecule which preferentially adsorbed onto sal law describing effects of doping on gas sensor properties, and
one oxide readily reacts with another molecule adsorbed onto the that each dopant will behave differently depending on the concen-
other oxide and the heterojunction of the two constituents facili- tration, dispersion state, and application [68]. A series of papers
tates the desorption [87,113]. by one group has shown that In2 O3 [18], ZnO [19], TiO2 [9], and
WO3 [35] can be used to effectively limit grain growth of the SnO2
4.3. Manipulation of microstructure host nanoparticles during high-temperature crystallization follow-
ing solution-based synthesis processes. They found that there was
Many studies have indicated microstructural effects as a fac- an optimal calcination temperature at which maximum crystal-
tor in sensor performance enhancement using composites. These lization of SnO2 is achieved while the dopant oxides still exists
generally are not dependent on the heterojunction interface but as amorphous coatings on the SnO2 nanoparticles, suppressing
are worth mentioning as complicating factors in interpreting data. grain growth. Lower calcination temperatures allowed higher sur-
Many dopants introduce electronic effects and simultaneously face area, but the crystallinity was insufficient for good sensor
affect the microstructure and growth kinetics [105]. Purely geo- stability [35]. Other studies also reported dopant-controlled grain
metric considerations involve grain size reduction and surface area refinement during sintering in processing techniques such as sput-
enhancement. Although grain size reduction generally leads to tering [44], colloidal solution [98] and simple powder mixing [114].
higher surface area, the mechanisms should be distinguished. A Surface-cupricated (CuO-coated) mixed ZnO–SnO2 powders also
smaller grain size allows the entire nanoparticle to exist within showed grain refinement and enhanced response [6,86]. One must
the depletion zone, enhancing sensor response. An increased sur- take care that this growth-retarding coating does not completely
face area provides more active sites with which an analyte gas shield the gas from the active base sensor material. A recent study
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
showed that Cr2 O3 -doped ZnO sensor response to LPG reached a
maximum at 0.47 wt% and decreased at higher concentrations due
to increased masking of the ZnO surface active sites [7].
5. Remaining challenges
The recent works reported here have begun to uncover new and
innovative ways that nanostructured metal-oxide based hetero-
junction materials can enhance gas sensor performance. However,
these complex configurations and designs present new challenges
that must be overcome. Typical drawbacks and challenges in metal-
oxide gas sensors are highlighted in previously-mentioned reviews
[2,21,28], so here we will focus on those most relevant to nanostruc-
tured heterojunction materials.
5.1. Long-term stability
It is well-known that metal oxides are largely chemically sta-
ble relative to organic and hybrid sensor materials [28]. However,
problems with signal drift during sensor operation are widespread
in MOGS. As researchers move toward smaller nanoparticles and
attempt to utilize sharp interfaces, thermal and long-term tempo-
ral stability of sensor response will become even more challenging.
It is generally accepted that nanoparticles of smaller dimensions
are more likely to coarsen over time at high operating tempera-
tures than their larger, more stable counterparts. When one starts
to consider several metal oxide species segregated in regions less
than 50 atoms wide operating at 350 ◦ C for months at a time,
it is easy to see the challenge. Any small amount of diffusion
across these interfaces can form intermetallic or mixed oxide
compounds which would severely affect the electronic properties
of the potential barrier. Several studies have in fact shown evi-
dence of mixed phases forming at the heterojunction interface
[47,85,115]. The formation of these mixed phases, if undesired,
can be mitigated by using low-temperature synthesis techniques
and lowering the operating temperature, in order to limit diffusion
and/or reactions [21]. Fortunately, many of these heterojunction
architectures have also lowered optimum operating tempera-
tures. Higher stability can also be achieved by using 1D features
such as nanorods and nanowires which generally have a higher
degree of crystallinity and larger planar facets than spherical
nanoparticles [2,22].
5.2. Reproducibility
Reproducibility in performance from one sensor to another
under identical processing conditions is not often reported but is
essential when considering scaling up to large-scale production of
commercial devices. This becomes exceedingly difficult when deal-
ing with more than one constituent. Fabrication methods must be
able to effectively control the thickness and diameter of each layer
or crystalline particle to within a few nanometers. As stated above,
the Debye length of these materials is generally of the same order
of magnitude as the feature radius or thickness. Therefore, if the
shell of a core–shell material is occasionally made a few nanometers
larger than the Debye length, the sensor response may be signifi-
cantly degraded due to the appearance of a bulk region. The highest
degree of control during fabrication is given by plasma deposition
processes such as sputtering, PLD and ALD. However, much cheaper
and higher-throughput methods such as spin- or dip-coating may
be good enough for the application depending on the sensitivity
toward the Debye length. New ways of carefully controlling the
particle size and coating thickness in high-throughput processes
will be essential in the development of commercial nanostructured
heterojunction sensors.
265
5.3. Characterizing the dispersion state
As mentioned above, the dispersion state of the constituents in
the nanocomposite must be carefully characterized to investigate
the electronic mechanisms that determine the sensor performance.
The dispersion state should also be characterized in terms of repro-
ducibility between “identical” sensors. Any inhomogeneity in a
“random” mixed powder or sol–gel material may change the degree
of heterojunction contact area and affect the average potential
barrier height between grains. Techniques such as elemental dot-
mapping and line scans using HRTEM-EDS are very effective for
these purposes, as shown previously in Figs. 4c and 7b above and
here in Fig. 13. X-ray photoelectron spectroscopy (XPS) has also
been used in many studies to estimate the degree of electronic
interaction between different constituents, which manifests itself
as shifts in the electron binding energy [4,35]. The dispersion state
is also relevant in systems of decorated second-phase particles
which may coarsen and grow on the surface of the core nano-
structure. Heterojunctions with epitaxial relationships such as in
brush-like morphologies should also be studied to determine the
crystallographic relationships of the interface as this can affect
the potential barrier height and degree of electron scattering. The
area fraction of the core material surface exposed to the atmo-
sphere versus that which makes up the heterojunction interface
should also be quantified. This can be important when considering
mechanisms such as potential barrier height that are dependent on
the solid–solid interface, compared to synergistic mechanisms that
need both oxide–gas interfaces readily available.
5.4. Understanding the mechanism
Throughout the relevant literature there are dozens of different
explanations for improvements in gas sensing performance with
the addition of a second constituent. The variations in materials
synthesis, processing methods, testing methods, and characteriza-
tion make it nearly impossible to draw fundamentally supported
conclusions using comparisons between works from more than one
institution. The beginnings of a real fundamental understanding of
these materials must start with the simplest possible experiments,
minimizing or elimating complicating or confounding factors. To
this end, the authors propose a new focus on single-nanowire elec-
trical and sensing measurements.
There are two main competing mechanisms that must be
considered when designing heterostructures via resistance manip-
ulation. The first is the change in the potential energy barrier
encountered by an electron crossing a heterojunction interface.
Many papers propose that using p–n oxide combinations make this
energy barrier more sensitive to the given analyte gas, thus making
the sensor more responsive [7,97,105]. The measured resistance is
related to the interfacial potential energy barrier (V) by [56]:
 qV 
R = R0 exp (1)
kT
where R is the resistance of the material, R0 is the initial resistance, q
is the charge of an electron, V is the potential energy barrier height,
k is Boltzmann’s constant, and T is the temperature of the sensing
material.
The second mechanism is the narrowing of the charge conduc-
tion channel along the length of a nanowire via the n–p depletion
region impinging on the core. Many other papers propose that this
is the main mechanism for the improved performance, as the oxide
nanoparticle coating makes the resulting depletion region bound-
ary more sensitive than that of the depletion region created directly
on the core by the adsorption and desorption of oxygen [14,62,104].
Here, the measured resistance would depend mainly on the diam-
eter of the non-depleted core of the nanowires, which we may call
266 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
Fig. 13. HRTEM–EDS elemental mapping of (a–d) 0.02 CuO–ZnO and (e–h) 0.04 CuO–ZnO hollow spheres.
Reprinted with permission from Ref. [110].
the conduction channel diameter. Not including changes in resis-
tivity due to charge carrier concentration, this can be approximated
by the equation for resistance in a wire:
L
R=
Dcond
where R is the resistance of the sensor,  is the resistivity of the
material, L is the length of the nanowire, and Dcond is the diameter
of the non-depleted charge conduction channel along the core of
the nanowire.
This raises the question: “Which mechanism is most useful
for a gas sensor?” Consider the possibility of aligning a mat of
oxide nanowires either parallel or perpendicular to the current flow
direction. These architectures each allow the conduction channel
mechanism and interface potential energy barrier mechanism to
dominate, respectively. A thick ZnO nanowire mat aligned roughly
parallel to the current has been shown to have much lower resis-
tance than the same mat measured perpendicular to the alignment,
as should be expected [116]. Unfortunately, no gas sensor measure-
ments were performed. A more precise experiment was carried
out by Khan et al. [117], which found that the “. . .potential bar-
rier modulation of multiple nanowires was more efficient than the
modulation of the surface depletion of the single ZnO nanowire
in gas sensing [to H2 ].” No similar studies involving heterostruc-
tures have yet been performed, to the authors’ knowledge. Fig. 14
illustrates these two different mechanisms as they occur in pris-
tine SnO2 nanowires and CuO nanoparticle-coated SnO2 nanowires.
The potential energy barrier modification occurs at the interfaces
and is shown by the band diagrams in air and in a reducing atmo-
sphere. The charge conduction channel constriction occurs along
the length of the nanowires and is shown at the bottom of Fig. 14
where the depletion region is represented by the lighter color faded
regions.
Kar et al. [118] recently used ultrafast pump probe spectroscopy
and XPS valence band photoemission spectroscopy to show that
the potential energy barrier at the surface of a SnO2 nanowire in
air was approximately 0.65 eV due to oxygen adsorption. They fur-
ther determined that the depletion region accounted for a major
fraction of the cross-sectional area of a 200 nm diameter nanowire.
The potential energy barrier at the interface will then be decreased
in the presence of a reducing gas that removes adsorbed oxygen.
Alternatively, one can see that the potential energy barrier change at
the interface of a p–n junction such as CuO–SnO2 should be smaller
than 0.65 eV using very simplified calculations. The natural built-in
voltage at a perfect SnO2 –CuO interface is approximately 1.3 eV
for electrons moving from SnO2 into CuO. This built-in voltage
increases the resistance in the material and cannot be decreased
except by a forward bias voltage, which is not easily applied to
(2) a mixture of these phases. In air, as shown, oxygen adsorption
at the CuO surface will increase the hole concentration due to
removal of electrons for bonding, forming an accumulation layer
where the CuO becomes more heavily p-type. This should be the
only cause of an overall larger potential energy barrier at this
interface since a 0.65 eV increase in the SnO2 is only half of the
built-in voltage already established. The increased barrier in air
on CuO (Vair in Fig. 14) may be more or less than 0.65 eV as no
equivalent studies to Kar et al. have been found for other types of
nanowires in oxygen atmospheres, so these numbers are only sim-
ple estimates. If CuO’s surface states cause 0.65 eV of upward band
bending, it must first overcome approximately 0.3 eV of down-
ward bending from the depletion region, leaving resulting potential
energy barrier only capable of 0.35 eV of modulation. If adsorption
of oxygen is much larger than SnO2 , the resulting energy barrier
capable of modulation may be significantly larger than that of a
SnO2 –SnO2 interface. Iwamoto et al. found that p-type metal oxides
had higher oxygen desorption than n-type oxides as measured by
temperature-programmed desorption (TPD) [119]. However, this is
only measuring desorption and does not necessarily find the total
amount of adsorbed surface oxygen. Although this should make p-
type sensors more responsive, the surface-dominated conduction
paths in p-type oxides are a hindrance and generally limit the per-
formance [26]. More work is needed in this area to develop a more
robust model for interactions between these materials and analyte
gases.
As discussed above, Na et al. [5] propose that the large built-in
voltage developed at the p–n interface generates a higher resis-
tance in air and leads to a larger response for reducing gases by
the response convention Ra /Rg but also citing a possible catalytic
mechanism introduced by the p-type constituent. Several others
including Mashock et al. [104] cite the mechanism of using the
nanoparticle coating to enhance the constriction of the charge con-
ducting channel in the nanowire core. Also shown in Fig. 14, p-type
nanoparticles on an n-type core compliment the changes in the
depletion region of the core induced by oxygen adsorption. Oxy-
gen creates an accumulation region in the p-type nanoparticles
which makes it more heavily p-type and makes a stronger deple-
tion effect at the interface, driving the depletion region further into
the core nanowire in conjunction with oxygen adsorbed on the
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272 267

Fig. 14. Mechanisms responsible for the resistance changes in nanowire-based gas sensors. The left side shows pristine n-type SnO2 nanowires with the interfacial mechanisms
depicted at top and the conduction channel mechanism depicted at bottom. The right side similarly shows these mechanisms in n-type SnO2 nanowires coated with discrete
p-type CuO nanoparticles. ECB is the conduction band minimum, EF is the Fermi level, EVB is the valence band maximum, Vbi is the built-in voltage caused by band misalignment,
Vair is the increase in the potential energy barrier on oxygen exposure, Vred is the potential barrier in reducing atmosphere, LD is the Debye length, or depth of the depletion
region from the surface, and Dcond is the diameter of the non-depleted region available for charge conduction through the core. (Band gaps and Fermi level positions drawn
approximately to scale.)

exposed regions of the n-type core. Heterostructures using n-type
coated n-type nanowires can also be considered in a similar man-
ner. Both of these mechanisms should be considered in any study
utilizing a randomly-oriented mixture of coated nanowires. Addi-
tionally, these resistance-based mechanisms will not always agree
with experimental results and other factors such as increased sur-
face area, increased defect sites, and catalytic activity toward the
analyte gas should be considered.
A single-nanowire measurement would be much the same as the
parallel nanowires except that it would completely eliminate any
oxide–oxide interfaces from the measurement. The only interface
that would contribute to the careful resistance measurement is that
of the metallic contacts, which can be independently measured and
subtracted from the total measurement [120]. Additionally, a mea-
surement could also be done where the current must move axially
through each nanowire but must overcome one or more countable
interfacial junctions in its path. This would allow one to find the
added effect of each interface on the sensor performance compared
to the single nanowire. This experiment should then be expanded
to nanowires coated with p-type or n-type nanoparticles in both
discrete and continuous fashion. A single-nanowire measurement
would quantify the resistance change induced by the depletion
region at the p–n interface impinging upon the nanowire core with-
out the current ever actually traversing that interface. The effects of
additional interfaces can be quantified by measuring across two or
more nanowires. These measurements should then be performed
in various atmospheres varying the concentration of oxidizing and
reducing gases to probe changes in depletion layer depth of the
various heterostructures. These experiments should begin to form
a mechanistic model for the role of different heterojunction inter-
faces and structures in gas sensing applications.
To the authors’ knowledge, no study has actually shown that
point contact between single p- and n-type oxide nanoparticles
or nanowires behaves like p–n junctions, in the way that they are
present in gas sensing films. In a closely related study, Park et al.
found that multiple ZnO–CuO nanowire interfaces measured in par-
allel across two electrodes showed asymmetric I–V character while
the ZnO–ZnO and CuO–CuO nanowire interfaces had symmetric
I–V character. This shows that at least some of the expected diode-
like behavior in retained in these low-quality or low-contact area
junctions between nanowires. It is very possible that the bulk semi-
conductor heterojunction band models do not accurately describe
the behavior of the oxide interfaces in a mixed nanocrystalline pow-
der film. The authors are currently undertaking much of the work
described above, but would like to stress that a large effort across
many institutions will be needed in order for these experiments to
develop a comprehensive model that will enable bottom-up design
of heterojunction-based sensors.
268 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
5.5. Useful analogues to catalysis
It is important to realize that the proposed experiments above
are not likely to explain other cited effects such as synergistic
mechanisms or targeted catalytic behavior. Using new materials
as gas sensors will also make it difficult to study the mechanisms
at work, as the electronic properties and surface reactions of these
materials are far less-studied. However, much photocatalysis and
catalysis work related to the reaction mechanisms of gases and
liquids at metal oxide surfaces will be helpful for understanding
the behavior of these sensors. An important point that warrants
inclusion here is the analogues between resistive gas sensing and
photocatalytic/catalytic materials. Many unique nanostructured
heterojunction materials have been developed specifically for pho-
tocatalytic and catalytic applications using constituents that are
typically found in gas sensors such as SnO2 , ZnO, and TiO2 [109].
Chalcogenides and halides specifically have been used as addi-
tives in catalysis and photocatalysis extensively with great success
[54,121–124]. Incorporating these materials into nanostructured
heterojunction gas sensors has also been shown to improve gas-
sensing performance [125,126]. Many of these heterojunctions
are used for separation of photogenerated charge carriers in dye-
sensitized solar cells or photocatalysis to increase charge carrier
lifetime and current extraction [127,128]. Others separate these
electrons/holes and funnel them into a material with a lower/higher
conduction/valence band energy where they can more readily per-
form the desired reduction/oxidation of the gas or liquid compound
[129]. Synthesis of catalytic materials generally follows the same
goals of high surface area, small crystallite size, high porosity, long-
term stability, rate of reaction, and ease of synthesis that is directly
applicable to gas sensing materials. Therefore, there is much to be
gained in sensor research by following relevant literature in pho-
tocatalytic and catalytic materials, and vice versa.
To facilitate this discussion, several excellent reviews using
oxides for photocatalysis and catalysis are listed here: recent
advances in heterogeneous photocatalysis [130], hierarchical
oxide-based composite nanostructures [109], charge separation
and transport in nanostructures [131], fundamentals of catalysis
in ceramics [132,133], and synthesis methods for nanoparticles in
catalysis including microemulsion [134] and self-assembly [135].
Examples of studies applicable to gas sensing include SnO2 -based
[136,137], ZnO-based [138–141], and TiO2 -based [128,142–144]
heterojunction materials. The catalysis literature usually presents
very good analysis of measured reaction products and reaction
pathways, which can further aid understanding of gas sensing
mechanisms in analogous oxide systems.
5.6. Integration of nanostructured heterojunction materials into
silicon microcircuit technology
One of the less-considered challenges for the future of
nanostructured heterojunction materials is integration with
advanced silicon-based microelectronic devices [70]. Complex
nano-heterostructures often have precise multi-step synthesis pro-
cesses that can limit compatibility with architectures desired in
multi-purpose microelectronic devices. For example, a device may
serve several diagnostic purposes besides gas sensing, and the
sensor platform will need to be integrated into a small section
of the circuitry. In these applications, it is impractical to use a
1 cm × 1 cm alumina platform with a several-␮m thick particulate
film that must be continually heated to 350 ◦ C. It is also increas-
ingly desirable to use silicon substrates so both the sensing and
signal processing can occur on a single patterned substrate. Micro-
electromechanical systems (MEMS) microhotplate platforms have
been developed by the National Institute of Standards and Tech-
nology (NIST) that have an array of up to 36 or more heated
sensor electrodes in a single device [145]. As the deposition region
is approximately 100 ␮m × 100 ␮m, only certain synthesis tech-
niques that allow precise deposition can be integrated with such
a device. For this reason, any heterojunction nanocomposite in
powder form will not be easily integrated through screen-printing
of thick films. Oxide nanoparticles can, however, be precisely
deposited as thin films by methods just as ink-jet printing, but any
agglomerates larger than about 5 ␮m may not pass easily through
the print head. CVD, PLD, and sputtering are all compatible with
proper masking of the neighboring substrates.
6. Future outlook
Recent work has greatly expanded our understanding of the role
of nanostructured heterojunctions as gas sensing materials. Going
forward, new materials and heterostructure designs will require
further study of mechanisms and influencing factors on gas sensing
performance. Future directions in nanostructured heterojunction
gas sensors should have a dual focus on (1) new materials and new
heterojunction interfaces, and (2) the mechanisms that govern the
sensing performance.
The present review focuses mostly on combinations of binary
compounds, but heterojunction interfaces are by no means limited
to these. Rare-earth perovskites [(RE)CoO3 , RE = La, Nd, Eu, Sm, Gd,
etc.] have shown promise as stable p-type sensing materials with
high activity toward the oxidation of CO and reduction of NO [28].
Nanostructured spinel ferrites have also shown good gas sensing
performance in the cases of Ce-doped CuFe2 O4 detecting LPG
[146], ZnFe2 O4 detecting formaldehyde [147], and NiFe2 O4 detec-
ting chlorine [148]. Qi et al. recently showed that p-La0.7 Sr0.3 FeO3
nanoparticle-coated SnO2 nanofibers had a much higher sensing
response to ethanol than either material on its own [149]. Further
research should also not be limited to just oxides.
Organic and hybrid organic/inorganic sensors have also shown
great promise as gas sensors [150–152]. These generally can have
better selectivity than metal oxides but often worse thermal and
temporal stability of sensing performance [28]. The selectivity can
be enhanced by introducing a “lock-and-key” sensing mechanism,
with little or no chance of false positive readings [153]. This is done
by attaching functional group to the polymer or carbon nanotube
surface with which only a single type of gas analyte will react and
cause a measurable change. The drawbacks of these organic materi-
als may be in part mitigated by using a metal oxide host structure to
create an organic/inorganic hybrid. This has been shown for exam-
ple in the case of an n–p TiO2 @polyaniline core–shell structure that
had higher sensitivity than the native polyaniline nanofibers, with
detection capabilities to ammonia as low as 25 ppb [154].
The architectures in which these materials are combined can
be just as important as the choice of materials themselves. This
was shown above, for example, by Huang et al. [85]. Core–shell
structures are very promising due to the maximization of interfacial
heterojunction area, which makes the electronic interactions of the
interface most dominant. The large surge in recent 1D nanostruc-
ture research [2,22,155,156] has developed an excellent platform
for future researchers to create 1D core–shell structures simply
by applying deposition processes such as spin-coating, sputtering
and ALD to existing methods. These processes could even allow
for multiple dissimilar shell layers of controlled thickness that
may give enhanced sensing responses. Several unique morpholo-
gies known as hierarchical structures have also been synthesized
through self-assembly and vapor phase growth processes [24].
Hierarchical structures are essentially anything made from sepa-
rate “building blocks” of their own defined shape in a sequential
manner. Self-assembly of 0D, 1D, and 2D building blocks can give
unique shapes and morphologies while resisting agglomeration
and densification that would result if the building blocks were
 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272
just deposited and dried [24]. Vapor phase growth of hierarchi-
cal materials is most often used to grow 1D–1D type brush-like
structures, and lends itself more easily to heterojunction formation
[81]. These morphologies can include hierarchical nano-brushes, -
urchins, -flowers, -combs, and -dendrites [24]. Hollow nanospheres
(Fig. 13) and nanoflowers have also recently shown much promise
due to their high porosity, gas-permeable walls, and wall thick-
nesses of less than two Debye lengths [26,110,136,157,158]. New
synthesis routes still need to be developed in order to self-assemble
these types of structures using building blocks of different oxides.
The mechanisms involved in vapor phase growth are also not well
understood in some oxides, and warrant further investigation.
As new processing and fabrication techniques become available
and allow for design of complex structures, it becomes exceed-
ingly essential to understand the fundamental sensing mechanisms
at work in order to properly choose the morphology and het-
erojunction architecture for a given sensing application. There
are now simply too many possibilities to use a purely empiri-
cal problem-solving approach. The authors stress a new focus on
single-nanowire heterostructure measurements to reduce variabil-
ity and confounding factors in mechanistically explaining observed
sensing behavior. Many of these mechanisms in nanostructured
heterojunctions are simultaneously being investigated by the catal-
ysis community, and interdisciplinary work should be encouraged
to this end. Several ways of enhancing the response, sensitivity and
selectivity in nanostructured metal-oxide based heterojunction
materials were elucidated above. Those most prominent include
engineering of the potential energy barrier at the interface by
using a second constituent, introduction of selective p–n and n–p–n
response inversions, selective synergistic surface reactions and
grain refinement. This is by no means an exhaustive list, but serves
to report those most cited as well as a few unique explanations that
hold promise for future development. These are likely just a fraction
of the possibilities and it is the hope of the authors that this review
will stimulate the reader to additional discoveries in the future.
Acknowledgements
Throughout the writing of this manuscript, the first author was
supported by a NASA Space Technology Research Fellowship. The
authors would also like to acknowledge helpful discussions with Dr.
Roberto Myers and Dr. Suliman Dregia of The Ohio State University.
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Biographies
Derek R. Miller is a Ph.D. candidate at The Ohio State University. He began his
graduate career in 2011 on an NSF GRFP Fellowship and in 2013 was awarded a NASA
NSTRF Fellowship. His research focuses on growing and synthesizing new oxide
nanostructures for applications in gas sensing, photovoltaics, and biocompatible
surfaces. His recent focus on fabrication of oxide nano-heterostructures to enhance
272 D.R. Miller et al. / Sensors and Actuators B 204 (2014) 250–272

performance in these applications has generated important questions that led to the
primary content of this review. Derek was also the 2013 Chair of the ACerS’ PCSA, a
national ceramics-focused student organization.
Sheikh A. Akbar is a Professor in Materials Science and Engineering at The Ohio
State University. He received his Ph.D. in 1985 from Purdue University. He teaches
courses on Sensor Materials, Electronic Ceramics, and Thermodynamics. He is the
Founding Director of the NSF Center for Industrial Sensors and Measurements (CISM)
and his main research interests include thin film sensors, metal oxide sensors, and
nano-textured biomedical coatings.
Patricia A. Morris is an Associate Professor in Materials Science and Engineering
at The Ohio State University. She received her B.S. from The Ohio State University
in 1980 and Ph.D. in 1986 from MIT. Dr. Morris was a Technical Leader working on
chemical sensors at Dupont from 1999 to 2005. Her current research interests focus
on oxide nanoparticles deposited on miniaturized sensors using ink-jet printing.