Tin Dioxide

Related terms:

Dye-Sensitized Solar Cells, Gas Sensor, Nanowires, Metal Oxide, Tin Oxide, Titani-
um Dioxide, Conductivity, Oxide, Nanoparticles

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Trends in metal oxide thin films: Syn-

thesis and applications of tin oxide
Khalifa Aguir, ... Tomas Fiorido, in Tin Oxide Materials, 2020

Abstract
Tin dioxide is one of the most studied metal oxide thin film materials, thanks to
its remarkable optical and electronic properties. It has attracted high attention for
sensor and optoelectronic applications. Several techniques including spray, sol-gel
coating, pulsed laser deposition, and radio-frequency (RF) reactive magnetron sput-
tering have been used for obtaining SnO2 thin films. This chapter, discusses the
possibility of synthetizing thin films with a wide variety of structures and, conse-
quently, presenting different properties. SnO2 properties are strongly dependent on
the crystallographic nanostructuring and their modifications during annealing.

In the gas-sensing area, the nanostructured film is a key challenging and a promis-
ing path. The nanostructures of the well-established metal oxide semiconductor
(MOS) gas-sensing materials, such as SnO2, WO3, ZnO, and TiO2, have demon-
strated high and fast response with improved sensitivity at low gas concentration.
Among various MOS nanostructural materials, tin oxide (SnO2), a wide bandgap
n-type semiconductor, has been the most popular gas sensors.

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Fundamentals of Binary Metal Ox-
ide–Based Supercapacitors
Deepak P. Dubal, ... Do-Heyoung Kim, in Metal Oxides in Supercapacitors, 2017

4.2.5 Tin Oxide

Tin dioxide (SnO2) is an n-type wide-band-gap semiconductor material that has
received much attention for various applications, including in lithium batteries
[96,97], supercapacitors [98,99], gas sensors [100,101], and catalysis [102], because
of its tunable physicochemical properties. Mainly the effective functioning of SnO2
depends on the morphologies and structural features. Therefore, in the literature,
considerable efforts have been made to prepare nanostructured SnO2 with different
surface morphologies such as NRs [103,104], nanowires [105,106], and nanosheets
[107]. The higher electric conductivity and the nanostructured nature of SnO2 could
be beneficial for supercapacitor application, as it attributes to a large surface for
electrolyte cation hosting and contributes to higher SC. In comparison with other
metal oxides the capacitance value of SnO2 is smaller, which is in the range of
50–400 F g−1.

To store the electric charges, it follows Eqs. (4.10)–(4.12). A mechanism based on the
surface adsorption of electrolyte cations (C+) such as K+ on SnO2 and simultaneously,
the intercalation of H+ or alkali metal cations (C+) in the bulk of the electrode upon
reduction followed by deintercalation upon oxidation.

(4.10)

(4.11)

(4.12)

Many researchers have made efforts to manipulate the structures and morphologies
of SnO2 to improve their performances and widen applications for supercapacitors.
But the SC of bare SnO2 is not high enough for use in supercapacitor applications.
Therefore, to fulfill the application demand and to improve the capacitance value
of the SnO2-based electrode, different strategies have been adopted, including the
doping of some elements and preparation of hybrid or composite electrodes. Yan
et al. [108] synthesized SnO2/MnO2 composite for the application of supercapacitors
and reported the SC of 800 F g−1. Fig. 4.8A shows the CV curves of the SnO2/MnO2
composites at different scan rates in 1 M Na2SO4 electrolyte, whereas Fig. 4.8B
shows the CV curve of SnO2 grown on the SS substrate at a scan rate of 2 mV s−1.
The SnO2/RuO2 composite prepared by the Kuo and Wu [109] was reported to have
a maximum SC of 930 F g−1.

Figure 4.8. (A) Cyclic voltammetry (CV) curves of the SnO2/MnO2 composites at

different scan rates in 1 M Na2SO4 aqueous solution. (B) CV curve of SnO2 grown
on stainless steel (SS) substrate at a scan rate of 2 mV s−1.Reproduced from J. Yan,
E. Khoo, A. Sumboja, P.S. Lee, ACS Nano 4 (2010) 4247, with the permission from
American Chemical Society.

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Electrical properties of tin oxide mate-

rials
Pedro H. Suman, in Tin Oxide Materials, 2020

3.1 Electrical properties of undoped and n- and p-doped SnO2

materials
Tin dioxide (SnO2), also known as stannic oxide, is the most abundant form of tin
oxide on earth extracted from the cassiterite mineral and has been widely used
in a range of technological applications including transparent conductors [1, 2],
chemical sensors [3, 4], high-efficiency solar cells [5], and catalysts [6, 7]. The
most chemical and thermal stable crystalline structure of SnO2 at ambient pressure
is the rutile-type structure with tetragonal unit cell (lattice constants a = b = 4.7382 Å
and c = 3.1871 Å) and space group P42/mnm [8], where the tin atoms are sixfold
coordinated to threefold coordinated oxygen atoms. However, the formation of
orthorhombic and cubic structures can also be favored in high-pressure conditions
[9, 10]. Due to the presence of intrinsic defects (oxygen vacancies (VO) and interstitial
tin (Sni)) in the tetragonal lattice acting as charge donor sites, SnO2 presents typical
n-type conductivity with wide direct bandgap transition of 3.6 eV located at the
 -point of the Brillouin zone and optical transparency in the visible spectrum [11,
12]. The deep understanding of these features in terms of the crystal and electronic
structures and nature and amount of defects are notably relevant to control the
electrical conductivity of SnO2 materials aiming practical applications.

As undoped SnO2 is a native n-type semiconductor, the electrical conduction model

used to describe its electrical properties is mainly associated with its intrinsic donor
defects. Interstitial tin donor level is fully ionized in the conduction band (CB) [13],
whereas shallow (singly ionized oxygen vacancy) and deep (doubly ionized oxygen
vacancy) donor levels associated to the oxygen vacancies are present in the bandgap
(0.03 and 0.15 eV below the bottom of the CB, respectively [14, 15]). It means
that the oxygen vacancies are expected to modulate the electron concentration (ne)
resulting from the ionization of these two donor levels, and the ionized electrons
are enabled to move through the solid lattice via temperature or other driving
force [16]. In this way, the small-polaron hopping mechanism is used to explain the
electron conduction as a function of the temperature in metal oxide semiconductors
(SMOx) with a high degree of defects [17, 18]. Considering this model for undoped
SnO2 where the electron conduction takes place in a nonadiabatic regime at high
temperature (T >  D/2, where D is the Debye temperature, which is 500 K for
SnO2 [19, 20]), the electron conductivity ( ), the electron concentrations (ne), and
the electron mobility (μe) in a nonstoichiometric system are related by the following
equations:

(3.1)

(3.2)

where e is the electron charge, μ0 indicates the pre-exponential factor, T is the

temperature, EH is the charge hopping energy, and k is the Boltzmann constant.
Both equations reveal that μe and, consequently, are temperature-dependent.

The influence of the oxygen vacancies on the electrical conductivity of SnO2 has been
demonstrated experimentally by measuring the conductivity of SnO2 at different
temperatures. The conductivity was found to vary inversely with the oxygen partial
pressure, i.e., the increasing of the oxygen content leads to lower conductivities [14,
21]. However, this behavior is not supported by some first-principles calculations,
which attributes the n-type conductivity of SnO2 to hydrogen acting as the unin-
tentional donor [22–24]. Porte et al. examined the influence of key growth variables
(e.g., growth temperature and oxygen pressure in the chamber) on the structural and
electronic properties of SnO2 films grown by pulsed-laser deposition (PLD) method
[25]. Fig. 3.1A shows the variation of the carrier concentration and the bandgap
energy as a function of the temperature deposition of the SnO2 thin films. As the
temperature increases, the n-type carrier concentration was reduced by three orders
of magnitude, indicating that the density of n-type donor defects in SnO2 is lower
at high temperatures. Fig. 3.1B displays the change of the optical bandgap (Eg) and
the Fermi energy (EF) in terms of the temperature. Above 400°C, constant values
of 3.6–3.7 eV and 4.5–4.6 eV were found to the bandgap and the Fermi energies,
respectively, whereas abrupt shifts in the bandgap energy (3.2–3.3 eV) and the Fermi
energy (4.7–4.8 eV) values were observed at 300°C due to the band tailing effects
present in amorphous films [26].

Fig. 3.1. (A) Carrier concentration measured by AC Hall effect measurements and
(B) optical bandgap estimated from Tauc plot of UV-Vis spectra and Fermi levels as
a function of the temperature deposition of SnO2 thin films.Reproduced with per-
mission from Porte Y, Maller R, Faber H, AlShareef HN, Anthopoulos TD, McLachlan
MA. Exploring and controlling intrinsic defect formation in SnO2 thin films. J Mater
Chem C 2016;4:758–65. Published by The Royal Society of Chemistry.

The impact of the oxygen pressure during the deposition (PD) on the carrier concen-
tration and the bandgap was also studied. A three-orders of magnitude reduction in
the carrier concentration was obtained by increasing PD (Fig. 3.2A), which is related
to the decrease of VO and Sni or the presence of Oi or VSn to balance the n-type
defects. At oxygen-rich atmosphere, the low formation energy of Oi or VSn defects
favors its presence, while in this same condition, the high formation energy of VO
and Sni prevents their creation, once SnO2 films approach its stoichiometry due to
the greater oxygen incorporation in the lattice [27]. No considerable variation in the
bandgap energy (3.6–3.7 eV) was observed as a function of the oxygen pressure.
However, it was found an abrupt change in the EF above 150 mTorr (Fig. 3.2B).
Overall, the authors demonstrated the ability to accurately control the mobility and
concentration of the charge carrier by controlling the experimental parameters for
the fabrication of the films.
Fig. 3.2. (A) Carrier concentration measured by AC Hall effect measurements and
(B) optical bandgap estimated from Tauc plot of UV-Vis spectra and Fermi levels
as a function of the background oxygen pressure for the deposition of SnO2 thin
films. Bandgap values obtained from Batzill et al. [28].Reproduced with permission
from Porte Y, Maller R, Faber H, AlShareef HN, Anthopoulos TD, McLachlan MA.
Exploring and controlling intrinsic defect formation in SnO2 thin films. J Mater
Chem C 2016;4:758–65. Published by The Royal Society of Chemistry.

The doping process is an extensively used approach for tuning the electrical proper-
ties of SnO2 materials by introducing electron degeneracy. However, for efficient
doping, the ionic radius of the dopant has to be close to or smaller than the host
Sn4+ ion. P-type conductivity in SnO2 is commonly achieved by adding group III-A
elements with lower valence than Sn4+, including Al [29], In [30], and Ga [31, 32]
acting as acceptor dopants. These elements are incorporated in the Sn sites and
produce shallow acceptor, decreasing the intrinsic n-type conductivity by increasing
the hole concentration [22]. Li [33] and Mg [34, 35] are other impurities also used
for this purpose. The incorporation of group-VA impurities (N, P, As, and Sb) would
be another strategy to reach p-type doping in SnO2. These elements have one less
valence electron than O and one more valence electron than Sn and, therefore, they
are supposed to exhibit amphoteric behavior in SnO2 [36]. It means that they work as
acceptors for O site substitution (p-type doping), but also as donors when incorpo-
rated on the Sn site (n-type doping). However, first-principles electronic-structure
calculations demonstrated that the group-V impurities preferentially incorporate on
tin sites (except for N), and thus n-type doping is more likely to occur [36].

Taking advantage of these properties, several physical and chemical methods have
been used to produce different SnO2 structures that include 3D architectures
[37–39], thin films, [40, 41], and nanomaterials (nanowires, nanotubes, nanobelts,
and nanoparticles) [42–45]. However, the preparation and characterization of low-di-
mensional inorganic nanomaterials have received considerable attention over the
years due to the outstanding electrical properties and remarkable potential for many
applications. Esro et al. examined the impact of the Sb doping on the electronic
properties of highly transparent SnO2 films composed of nanocrystals and prepared
by the van der Pauw technique [46]. Both the electron concentration (ne) and the
electron mobility (μe) increased following an increase in the Sb content from 0% to
2%, reaching maximum values of 6.4 × 1020 cm−3 and ~ 32 cm2 V−1 s−1, respectively
for 2% of Sb loading (Figs. 3.3C and D). Inversely, the resistivity and sheet resistivity
Rs reached minimum values of 7.35 × 10−4 Ω cm and 32 Ω sq.−1, respectively in the
corresponding Sb loading (Fig. 3.3A and B). These parameters exhibited an opposite
behavior above 2% of Sb doping.

Fig. 3.3. (A) Sheet resistivity, (B) resistivity, (C) carrier concentration, and (D) elec-
tron mobility of Sb-doped SnO2 as a function of the Sb loading.Reproduced with
permission from Esro M, Georgakopoulos S, Lu H, Vourlias G, Krier A, Milne WI,
et al. Solution processed SnO2:Sb transparent conductive oxide as an alternative to
indium tin oxide for applications in organic light emitting diodes. J Mater Chem C
2016;4:3563–70. Published by The Royal Society of Chemistry.

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Tin oxide nanomaterials: Active centers
and gas sensor properties
Alexander Gaskov, ... Artem Marikutsa, in Tin Oxide Materials, 2020

Abstract
Nanocrystalline tin dioxide SnO2 is of considerable interest for the creation of
solar cells, solid-state chemical sensors, and oxidation catalysts. High adsorption
properties and reactivity of nanocrystalline SnO2 are due to high concentration
of surface adsorption centers, especially the coordinately unsaturated tin cations
Sn4c, Sn5c, chemisorbed oxygen, and oxygen vacancies VO. In the recent years,
many works have been devoted to the development of various approaches to the
synthesis of nanocrystalline SnO2 and to the investigation of its reactivity. The main
direction of research of nanocrystalline SnO2 is aimed at increasing the selectivity
of adsorption and promoting chemical reactions on the surface. The selectivity of
the chemical properties of nanocrystalline SnO2 can be achieved by tuning the
type and concentration of surface active centers by bulk doping immobilization of
modifiers: nanoparticles based on noble metals or transition elements oxides. The
data on the effect of catalytic modifiers on the composition, microstructure, type and
concentration of active sites, and reactivity of nanocrystalline SnO2 are systematized
in this section.

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Varistor technology based on SnO2

Mateus Gallucci Masteghin, ... Paulo Roberto Bueno, in Tin Oxide Materials, 2020

11.5 Future remarks

A brief history of the tin dioxide-based varistors was described from the material
science viewpoint. The content was based on the technological importance and inno-
vative aspect where academical improvements and understanding have taken place
on the microstructures and atomic scale defects. Associated parameters dictating
electrical properties are better controlled and manipulated in a predictable way using
the step-wise methodical addition of the cations to the SnO2 recipe. In terms of
industrial applications, SnO2 has already achieved some niches of the marketplace.
The valid application of the ZnO-based varistors can be matched by a technically
possible cheapest innovation. SnO2 still needs more miles to go for achieving all
aspects of the parameters necessary for the power system requirements. When
the authentic innovation comes in this industrial sector the current contributors
in the marketplace will raise their cost to survive. Nevertheless, competition keeps
improving performance, quality, and protective characteristics.

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Tin oxide materials

Marcelo Ornaghi Orlandi, in Tin Oxide Materials, 2020

1.3 Hexagonal compact to tetragonal structure of tin dioxide

When we consider the crystalline structure of tin dioxide, it is interesting that its
formation is based on a hexagonal compact structure of oxygen ions. The hexagonal
compact structure is formed by an initial layer of oxygen atoms (red atoms in Fig. 1.4,
labeled A1). The second oxygen layer (labeled B1) rest in the middle of the oxygens’
from the first layer (upward or downward triangles; in Fig. 1.4 it was chosen upward
triangles). For better visualization, the atoms from the B1 layer are circumscribed by
dashed lines. Then, the third layer of oxygen must superpose the first layer of atoms
(labeled as A2), thus creating a repeating structure in the space (ABABAB…).

Fig. 1.4. Hexagonal lattice of anions is the base for the rutile structure of SnO2, in
which “a” and “c” directions are shown. The other “a” direction is perpendicular to
the plane of the paper.

Looking at the space between the A1 and B1 layers, all upward triangles in the A1 lay-
er will be tetrahedral interstitial sites (4 oxygen coordination) and all the downward
triangles will be octahedral interstitial sites (6 oxygen coordination). Since compact
structures present one octahedral site per lattice atom, half of these octahedral
interstices must be filled with tin cations to obtain the SnO2 stoichiometry. However,
the cations (with smaller effective size) will have a larger distance between each other
if they fill half of the downward triangle positions between the A1 and B1 layers (gray
spheres in Fig. 1.4). A shift in tin atoms is observed for the tin resting between the
B1 and A2 layers (green spheres in Fig. 1.4), and in Fig. 1.5, these tin ions will be
in the center of rutile structure. The next tin layer, sitting between the A2 and B2
layers, will superpose the first tin layer (gray atoms), thus forming a perfect crystal.
To obtain the reported tetragonal crystalline structure of SnO2, one must use the tin
ions as a reference, and the a = b ≠ c lattice parameters are shown in Fig. 1.4. It is
important to note that the “c” direction of the rutile structure has rows of vacant tin
sites, and this characteristic can influence the mass transport during the sintering
process and, in turn, the properties presented by rutile SnO2. It is worth mentioning
that if we replace the tin atoms with the titanium ones, we will produce the rutile
structure of TiO2.

Fig. 1.5. Representative of tetragonal rutile structure, in which tin atoms are at the
corners of the tetrahedron. In this figure, gray spheres represent tin atoms and red
spheres represent oxygen atoms.

The more traditional view of the rutile unit cell of tin dioxide is shown in Fig. 1.5. It
is composed of two tin atoms and four oxygen atoms. Based on Pauling’s rules, the
octahedral sites of a crystal will not be stable if the radius ratio between cation and
anion (rc/ra) is lower than 0.414, and the ionic radii for tin and oxygen are 0.69 and
1.38 Å, respectively. Since the radius of tin is half of that of oxygen, rc/ra = 0.5, the
octahedral interstices are stable for tin atoms in the SnO2 structure.

The phase diagram available for the Sn-O system [16] and exhibited in Fig. 1.6 shows
that Sn3O4 and SnO2 phases are stable at room temperature. Today, it is well accepted
that SnO is also stable at room temperature, and other Snn + 1O2n phases may also
exist. It is important to note that these mixed valence tin oxides are predicted to
stabilize in layered materials [17], which can be an advantage in fields in which
oriented crystals are important, such as those involving photodetectors and solar
cells.
Fig. 1.6. Phase diagram of the Sn-O system [16].With permission of Z. Metallkunde,
40, 1949, 374 (H. Spandau and E.J. Kohlmeyer) © Carl Hanser Verlag GmbH &
Co.KG, Muenchen.

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Health and environment perspective of

tin nanocompounds: A safety approach
Jose M. Granjeiro, ... Ana R. Ribeiro, in Tin Oxide Materials, 2020

6.1 Introduction
According to the European Chemicals Agency (ECHA), tin dioxide (CAS no.
18282-10-5—Molecular formula: SnO2) is manufactured and/or imported in the
European Economic Area in 1000–10,000 tons per year [1], representing a small
fraction of the world’s tin production that reached 422,900 tons in 2016. It is
produced by more than 22 countries with the most massive production belonging
to China, Indonesia, Peru, Bolivia, Brazil, and Australia [2, 3]. This substance is
used in a number of products: adhesives and sealants, metallic alloys, coating
products, fillers, putties, plasters, modeling clay, metal surface treatment products,
nonmetal-surface treatment products, inks and toners, pH regulators and water
treatment products, laboratory chemicals, paper chemicals and dyes, polishes and
waxes, polymers, semiconductors, textile treatment products and dyes, washing and
cleaning products, welding and soldering products and cosmetics, and personal care
products, according to ECHA [1].
Tin dioxide is not classified by the Globally Harmonized System (GHS), despite
some conclusive data have been obtained those are not sufficient for classif-
ication considering physical, health, or environmental hazard [1]. A summary of
toxicological (Table 6.1) and ecotoxicological information (Table 6.2) from ECHA
is displayed. It should be highlighted that tin dioxide does not fulfill any of the
screening criteria for persistence, bioaccumulation, or toxicity and, hence, due to
low potential for aquatic/sediment bioaccumulation of the substance is neither
measurable nor expected [1].

Table 6.1. Tin dioxide toxicological information according to the European Chemi-
cals Agency (ECHA)

Hazard via Effects

Systemic effects (DNEL) Local effects
Acute/short T.E. Long T.E. Acute/short T.E. Long T.E.
Workers Inhalation 2 mg/m3 2 mg/m3 No hazard No hazard
route identified identified
Dermal route 5.7 mg/kg bw/day 5.7 mg/kg bw/day No hazard identi- No hazard identi-
fied fied
General Popu- Inhalation 6 mg/m3 6 mg/m3 No hazard No hazard
lation route identified identified
Dermal route 2 mg/kg bw/day 2 mg/kg bw/day No hazard identi- No hazard identi-
fied fied
Oral route 2 mg/kg bw/day 2 mg/kg bw/day N.A. N.A.

T.E.: Term Exposure; DNEL: Derived No Effect Level; N.A.: Not Available; Bw: Body
weight. For DNEL, local effects, the substance was not as an irritant to eye and skin,
so the DNEL is unnecessary to be generated for local effects.

Source: European Chemicals Agency, http://echa.europa.eu/, accessed: February

2019

Table 6.2. Tin dioxide ecotoxicological information according to the European

Chemicals Agency

Hazard for Effects

Aquatic Organism Freshwater PNEC: 0.1 mg/L
Marine water PNEC: 0.01 mg/L
Sewage Treatment Plant (STP) PNEC: 100 mg/L
Air No hazard identified
Terrestrial organism (soil) N.A.: testing technically not
feasible
Predators No potential for bioaccumula-
tion

PNEC: predicted no-effect concentration; N.A.: not available. PNECs for sediment
(freshwater or marine) and soil cannot be derived and are technically not feasible.
Source: European Chemicals Agency, http://echa.europa.eu/, accessed: February
2019.

Tin compounds, like fluoride or chloride salts, are present in many commercialized
products such as biocides, dentifrices, soft drinks, packaged food, among others.
In the form of SnF2 has been mainly used as a highly active antimicrobial agent
[4], and SnCl2 as reducing agent in the production of Technetium-99 m-labeled
radio-pharmaceuticals [5].

Many different industries synthesize, characterize, and use a large number of tin
engineered nanomaterials due to their unique physical-chemical properties. Despite
the no hazard classification according to GHS, tin dioxide nanoparticles toxicity is
still in debate, and some controversies remain. The measurement of tin toxicity
is a challenging issue due to their effect on test systems, protocol variability, and
incomplete report, promoting room for some irreproducibility.

In order to produce an overview of the primary use of tin dioxide materials/nano-

materials, highlighting the potential effect on health and environmental safe-
ty, the search key was used (“Tin Compounds/adverse effects”[Mesh] OR “Tin
Compounds/pharmacokinetics”[Mesh] OR “Tin Compounds/toxicity”[Mesh]) and
allowed the retrieve of 199 scientific articles recorded until February 2019 on the
Pubmed (https://www.ncbi.nlm.nih.gov/pubmed). Those articles were uploaded in
the VOSviewer (Version 1.6.10, http://www.vosviewer.com) [6] to produce maps
based on the keywords used in the 199 articles (Fig. 6.1). Tin compounds, humans,
animals, and tin fluoride were the most used among 101 recovered keywords (Fig.
6.1A). The early studies are related to tin fluoride, fluoride, dental plaque, and
dental enamel (blue circles) in opposition to most recent papers on tin compounds,
nanoparticles, occupational exposure, in vitro (cell survival, cell line) and in vivo
(tissue distribution, lung) studies (Fig. 6.1B). Studies in humans are related to
Dentistry, occupational diseases, and radiopharmaceuticals (Fig. 6.1C), while tin
compounds correlate with in vitro studies (mutagenesis and reactive oxygen species)
and occupational exposure (Fig. 6.1D).
Fig. 6.1. VOSvewer maps. (A) Density visualization: humans, tin compounds, and tin
fluorides are the most cited keywords; (B) Overlay visualization: colors range from
blue (oldest publication date) to green to yellow (newest publication date); Detail of
B highlighting the keywords connected with human (C) and tin compounds (D).

This chapter focuses on the tin, particularly in the nano-form, due to its substantial
interest in commercial use, where all the concerns surrounding their (eco)toxicolog-
ical impacts in human health will be revised.

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Nanomaterials in Air Pollution Trace

Detection
João Flávio da Silveira Petruci, ... Arnaldo Alves Cardoso, in Nanomaterials Applica-
tions for Environmental Matrices, 2019

14.2.2 Conductometric Detection

Conceptually, conductometric detection is the simplest of the electroanalytical tech-
niques but it is inherently nonspecific. The concentration of the charge is obtained
through the measurement of the solution resistance (Hanrahan et al., 2004; Rassaei
et al., 2011).

14.2.2.1 Metal Oxide Semiconductor

Metal oxide semiconductor (MOS) sensors employ a metal oxide, such as tin dioxide,
that changes its electrical properties (usually the resistance) when exposed to the
target gas, this change can be measured and reflects the concentration of the
gas (Real-world application of new sensing technologies for air quality monitoring,
2013); a typical MOS sensor can be seen in Fig. 14.1. Such sensors are small in size
and weight, are cheaper (~$10) in comparison to EC sensors, present quick response
times, low detection limits, and lower power requirements (~100 mW). However,
they have a nonlinear response curve; and suffer from sensitivity to changes in envi-
ronmental conditions and interfering gases (Real-world application of new sensing
technologies for air quality monitoring, 2013; Fine et al., 2010; Granqvist et al.,
2007).

Figure 14.1. A schematic for metal oxide semiconductor sensors.

Spinelle et al. (2016) presented an evaluation of commercially available metal oxide

sensors for the monitoring of O3 in ambient air and they found a limit in the
detection of such sensors near to 2 ppb (Spinelle et al., 2016). For O3 measurements,
MOS sensors have been shown to be better than EC sensors, presenting a good
agreement with reference measurements and they do not suffer from a significant
cross-sensitivity to NO2. An example of a commercially available MOS sensor is the
AirBase CanarIT; the sensor enhances commercial MOS gas sensors that operate in
a plug and play mode to sample every 20 seconds. Benefits of the nanotechnology
used in this device include reduced costs, power requirements, and size. Addition-
ally, inter-sensor repeatability, long-term stability, and stability to temperature and
humidity fluctuations are enhanced (Williams et al., 2015).
> Read full chapter

Electrospinning
A. Macagnano, F. De Cesare, in Electrospun Materials for Tissue Engineering and
Biomedical Applications, 2017

17.3.2 Acetone sensors

Kim et al. at KAIST developed a highly sensitive exhaled-breath sensors, using tin
dioxide (SnO2) fibers assembled from thin, wrinkled SnO2 NTs [51]. These metal
oxide nanofiber-based chemoresistive gas sensors were expected to be usable in
portable real-time breath tests (Fig. 17.11). Such sensors were designed such as to
diagnose diabetes or lung cancer quickly and effectively by simply breathing into
a small nanofiber-based breathing sensor, mounted on a phone or other similar
device.

Fig. 17.11. Components of exhaled-breath sensor, showing optical microscope im-

age (right, top) of exhaled-breath sensing layer coated on sensor substrate [56].Cour-
tesy of Prof. Il-Doo Kim, Department of Materials Science and Engineering, KAIST.

Varying the flow rate of an electrospinning solution feed and then applying a
heat treatment provided the specific arrangement of these SnO2 fibers, called “mi-
crophase separations.” Such processing resulted in nanofibers with shape like an
open cylinder. Inside the cylinder, thin-film SnO2 NTs were layered and then rolled
up. A number of elongated pores ranging from 10 to 500 nm (nanometers) in length
along the fiber direction were generated on purpose on the surface of the SnO2
fibers, to allow exhaled gas molecules easily permeating the fibers. The inner and
outer walls of the SnO2 tubes were evenly coated with catalytic platinum (Pt) NPs.
According to the authors, highly porous SnO2 fibers showed fivefold higher acetone
responses than that of the dense SnO2 nanofibers.

The following metal Pt doping of these tubes [57] showed a great potential for future
exhaled-breath-sensor applications, detecting promptly and accurately acetone or
toluene even at very low concentration—less than 100 parts per billion (ppb). The
exhaled acetone level of diabetes patients exceeds 1.8 parts per million (ppm), which
is two- to sixfold higher than that (0.3–0.9 ppm) of healthy people. Therefore, a highly
sensitive detection that responds to acetone below 1 ppm, in the presence of other
exhaled gases (and also under the humid environment of human breath), sounds as
an accurate performance to diagnose diabetes.

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Surface and interface electronic proper-

ties of tin oxide
Celso M. Aldao, in Tin Oxide Materials, 2020

5.1 Introduction
Metal oxides constitute an important class of materials, which exhibit diverse prop-
erties with a variety of applications [1]. Tin dioxide, in particular, is a wide band-gap
semiconductor with high electrical conductivity and optical transparency. It is of
interest in optoelectronic applications and also it is used in chemical applications as
support of metallic catalysts and for its own catalytic properties. In addition, tin oxide
plays a central role in the fabrication of solid-state gas sensors. Many oxides present
sensitivity to oxidizing and reducing gases but SnO2 is the most regularly used
material in this application [2]. As other oxides, tin oxide has been nanostructured
and grown as nanowires presenting high gas sensitivity [3].

In principle, as a catalyst and solid-state gas sensing material, the surface seems to
be of relevance while the bulk properties are responsible for making tin oxide a good
conductor. However, the presence of interfaces cannot be disregarded in dealing
with this transparent conduction oxide. On the other hand, we show that the bulk
properties must be considered in determining the materials properties in catalysis
and sensing applications. It is important to note that all this involves complex
mechanisms that continue being topics of ongoing research and controversy [4, 5].

Tin oxide combines low resistance with optical transparency in the visible range.
These properties make tin oxide and other metal oxides useful in applications related
to solar cells and a variety of optoelectronic devices [6, 7]. As many oxides, SnO2
 presents a high conductivity due to intrinsic defects, specifically oxygen vacancies.
Indeed, in its stoichiometric form tin dioxide is a good insulator but nonstoichiom-
etry, oxygen deficiency, increases its conductivity. Despite spread values, the donor
characters of regular native defects have been experimentally confirmed. Kilic and
Zunger [8] showed that the formation energy of oxygen vacancies and tin interstitials
in SnO2 is very low. Then, these defects form readily and defect levels can be easily
ionized.

Many oxides are used as a support material for dispersed metal catalysts but tin oxide
also exhibits good activity by itself. Transfer of electrons between reacting molecules
and solid oxide catalysts can be a complex phenomenon that requires energy levels
of the reacting molecule at a region of high density of states of the solid. Molecules
can be oxidized by the Mars-van Krevelen mechanism, by consuming lattice oxygen
that is reoxidized by the gas-phase oxygen. Thus, the catalyst must be characterized
by facile change of the oxidation state of its cations, property of many metal oxides,
including tin dioxide [9].

Solid-state gas sensors transduce a chemical quantity, such as a gas concentration,

into an electric signal. Metal-oxide semiconductors are the most common inorganic
materials used in chemical sensing of gases and vapors. They play a major role in
industrial applications such as automotive, aerospace, and food, as well as medical
and indoor detection of toxic gases produced by incomplete combustion of heating
systems. In particular, polycrystalline SnO2 is an attractive material due to its high
sensing response to reducing gases, long-term stability, robustness, and low cost.
The exact details of the mechanisms that cause a gas response are still controversial,
but it is widely accepted that trapping of electrons at adsorbed molecules and
band bending induced by these charged molecules are responsible for a change in
conductivity [10–16].

As seen, interfaces play the key role in the most important applications of tin oxide.
Thus, the understanding of the surface and interface phenomena becomes crucial
and then Schottky-like barriers formed at surfaces and at grain boundaries that
determine their properties. We show that the formation and properties of these
potential barriers are much more subtle than regularly assumed. In this chapter, we
focus on their formation, characteristics, and consequences.

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