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Sensors and Actuators B 192 (2014) 607–627

Sensors and Actuators B 192 (2014) 607–627 Contents lists available at ScienceDirect Sensors and Actuators B:

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

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

B: Chemical journal homepage: www.elsevier.com/locate/snb Review Highly sensitive and selective gas sensors using

Review

Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview

Hyo-Joong Kim, Jong-Heun Lee

Department of Materials Science and Engineering, Korea University, Seoul 136-713, Republic of Korea

Korea University, Seoul 136-713, Republic of Korea a r t i c l e i n

a r

t i c

l e

i n f o

Article history:

Received 24 August 2013 Received in revised form 30 October 2013 Accepted 5 November 2013 Available online 15 November 2013

Keywords:

Gas sensor p-Type oxide semiconductor p–n junction Selectivity Sensitivity

a b s t r a c t

High-performance gas sensors prepared using p-type oxide semiconductors such as NiO, CuO, Cr 2 O 3 , Co 3 O 4 , and Mn 3 O 4 were reviewed. The ionized adsorption of oxygen on p-type oxide semiconductors leads to the formation of hole-accumulation layers (HALs), and conduction occurs mainly along the near- surface HAL. Thus, the chemoresistive variations of undoped p-type oxide semiconductors are lower than those induced at the electron-depletion layers of n-type oxide semiconductors. However, highly sensitive and selective p-type oxide-semiconductor-based gas sensors can be designed either by controlling the carrier concentration through aliovalent doping or by promoting the sensing reaction of a specific gas through doping/loading the sensor material with oxide or noble metal catalysts. The junction between p- and n-type oxide semiconductors fabricated with different contact configurations can provide new strategies for designing gas sensors. p-Type oxide semiconductors with distinctive surface reactivity and oxygen adsorption are also advantageous for enhancing gas selectivity, decreasing the humidity dependence of sensor signals to negligible levels, and improving recovery speed. Accordingly, p-type oxide semiconductors are excellent materials not only for fabricating highly sensitive and selective gas sensors but also valuable additives that provide new functionality in gas sensors, which will enable the development of high-performance gas sensors.

© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction

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608

2. Gas sensing mechanisms of n-

and p-type oxide

semiconductors .

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608

2.1.

Origin of n- and p-type

semiconductivity

in

oxides

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608

2.2.

Formation of electronic core–shell configuration in

metal oxides

by oxygen adsorption

 

608

2.3.

Conduction and gas-sensing mechanisms of n- and

p-type oxide

semiconductors

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610

3. sensitive gas sensors using p-type oxide semiconductors

Highly

 

611

3.1.

Morphological design of nanostructures

611

3.2.

Electronic sensitization by controlling doping

614

3.3.

Chemical sensitization by loading catalyts

615

4. selective gas sensors using p-type oxide

Highly

616

5. High-performance

gas sensors using oxide p–n

junctions .

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618

5.1. longitudinal

Gas

sensors

using

oxide

p–n

junctions

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618

5.2. nanocomposites between p- and n-type oxide semiconductors

Gas

sensors

using

 

620

5.3.

Gas sensors using 1-dimensional n-type oxide semiconductors decorated with p-type oxide nanoclusters

 

621

6. High-performance gas sensors using p-type-oxide-semiconductor-loaded n-type oxide semiconductors

 

622

6.1. Enhancement of recovery speed by

loading NiO onto SnO 2 hollow spheres

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622

6.2. Humidity-independent gas sensors

.

Acknowledgment

References

Biographies

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7. Conclusions

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using NiO-loaded SnO 2 nanostructures . . . .

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622

623

623

623

627

Corresponding author at: Department of Materials Science and Engineering, Korea University, Anam-Dong, Sungbuk-Gu, Seoul 136-713, Republic of Korea. Tel.: +82 2 3290 3282; fax: +82 2 958 3584. E-mail address: jongheun@korea.ac.kr (J.-H. Lee).

0925-4005/$ – see front matter © 2013 Elsevier B.V. All rights reserved.

http://dx.doi.org/10.1016/j.snb.2013.11.005

608

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

1. Introduction

Various oxide semiconductor based gas sensors have been used to detect harmful and toxic gases [1–9]. The most representative sensor materials are SnO 2 [10,11] and ZnO [12,13], which exhibit n-type oxide semiconductivity, and other n-type oxide semicon- ductors such as TiO 2 [14,15], WO 3 [16,17], In 2 O 3 [18,19], and Fe 2 O 3 [20,21] are being widely explored to find new functionalities of chemiresistivity. In contrast, the chemiresistors fabricated using p- type oxide semiconductors such as NiO, CuO, Co 3 O 4 , Cr 2 O 3 , and Mn 3 O 4 to date have received relatively little attention, and the related research to fabricate such chemiresistors is still in the early stages of development. According to the results of a search of web of knowledge on July 15, 2013 (the keywords used for the search were the chemical formula of the sensor material and “gas sen- sor*”; e.g., “SnO 2 ” and “gas sensor*” were used to search for SnO 2 gas sensors), the number of articles found on gas sensors using p-type oxide semiconductors (i.e., NiO, CuO, Co 3 O 4 , Cr 2 O 3 , and Mn 3 O 4 ) was only 9.41% of the 8504 articles available on the oxide- semiconductor-based gas sensors (the search results included the aforementioned p-type oxide semiconductor gas sensors and n- type oxide semiconductor gas sensors fabricated using SnO 2 , ZnO, TiO 2 , WO 3 , In 2 O 3 , and Fe 2 O 3 ) (Fig. 1). Table 1 summarizes the properties of the gas sensors fabricated using the various p-type oxide semiconductors such as NiO, CuO, Co 3 O 4 , Cr 2 O 3 , Mn 3 O 4 , and LaOCl–NiO, as surveyed in the literature [22–54]. The gas sensors were used to detect C 2 H 5 OH, HCHO, CO, NH 3 , (CH 3 ) 3 N (trimethy-

lamine), H 2 , H 2 S, C 6 H 4 (CH 3 ) 2 (xylene), and

whose concentrations were in the range 1–1000 ppm. The markedly different gas-sensing characteristics of n- and p- type oxide semiconductors should be understood in the context of the receptor functions, conduction paths, and gas-sensing mech- anisms of these two types of materials with different majority charge carriers: (1) the formation of an electron-depletion layer (EDL) in n-type oxide semiconductors or a hole-accumulation layer (HAL) in p-type oxide semiconductors by the adsorption of oxy- gen with negative charge; (2) conduction through the serial paths (i.e., the semiconducting particle cores and resistive interparticle contacts) in n-type oxide semiconductors or conduction through the parallel paths (i.e., the resistive particle cores and semicon- ducting near-surface regions) in p-type oxide semiconductors; and (3) chemoresistive variation at the interparticle contacts in n-type oxide semiconductors or at the near-surface regions in p-type oxide semiconductors. Compared to n-type oxide semiconductor gas sensors, p-type oxide semiconductor gas sensors exhibit not only shortcomings but also promising potentials for practical applications. Hübner et al. [55] suggested that the response of a p-type oxide semi- conductor gas sensor to a given gas was equal to the square root of that of an n-type oxide semiconductor gas sensor to the same gas when the morphological configurations of both sensor mate- rials were identical. This finding indicates that the responses of p-type oxide semiconductor sensors to gases should be enhanced in order to more accurately detect trace concentrations of various analyte gases. Nevertheless, the crucial importance of p-type oxide semiconductors as chemiresistive materials should not be under- estimated considering that most p-type oxide semiconductors such as NiO, CuO, Cr 2 O 3 , Co 3 O 4 , and Mn 3 O 4 have been extensively used as good catalysts [56–59] to promote selective oxidation of various volatile organic compounds (VOCs). From this perspective, p-type oxide semiconductors are promising material platforms for devel- oping the new functionalities of chemiresistors. Moreover, the p–n junction between oxide semiconductor materials can also be used to alter the gas-sensing characteristics of gas sensors by varying the electrical properties near heterointerfaces [60]. Further, the dis- tinctive oxygen adsorption of p-type oxide semiconductors may

C 6 H 5 (CH 3 ) (toluene)

be used to design high-performance gas sensors that show low humidity dependence and rapid recovery kinetics [61,62]. Accordingly, p-type oxide semiconductors can provide a vari- ety of new functionalities in oxide chemiresistors. However, to the best of our knowledge, there have been no comprehensive reviews previously published on gas sensors using p-type oxide semicon- ductors as sensing or additive materials. In this study, we review various high-performance gas sensors using p-type oxide semi- conductors. As shown in Fig. 2, our review places special focus on (1) the gas-sensing mechanism of p-type oxide semiconduc- tors, (2) new strategies to enhance the response of p-type oxide semiconductor sensors to gases through electronic and chemical sensitization, (3) highly selective gas sensors fabricated using p- type oxide semiconductors, (4) various gas sensors fabricated using oxide p–n junctions, and (5) designing reliable n-type oxide semi- conductor gas sensors by loading p-type oxide additives.

2. Gas sensing mechanisms of n- and p-type oxide

semiconductors

2.1. Origin of n- and p-type semiconductivity in oxides

The major charge carriers in Si-based semiconductors can be manipulated by proper doping of donor or acceptors [63]. In contrast, the major charge carriers in wide-bandgap oxide semicon- ductors are determined either by doping aliovalent cations [64] or by oxygen nonstoichiometry [65]. For example, undoped oxygen- deficient SnO 2 shows n-type semiconductivity since the formation of oxygen vacancies accompanies the generation of electrons [66]. The p-type semiconductivity of undoped NiO can be explained by the deficiency of metal ions in the material [67]. The concentration of charge carriers in materials used for the gas sensor applications may be changed or tuned to the proper range at the operation temperature in order to achieve high responses to gases and/or to control the resistance of the sensor material so that the sen- sor system may use simple measurement circuit. Since the oxygen nonstoichiometry cannot be varied at fixed sensing temperature and ambient atmosphere, the doping of higher and lower valency cations may be used to control the charge carrier concentration of gas sensing materials [68,69].

2.2. Formation of electronic core–shell configuration in metal

oxides by oxygen adsorption

At 100–500 C, oxygen molecules adsorb onto the surfaces of n-type oxide semiconductors such as SnO 2 and ZnO and ionize into species such as O 2 , O , and O 2 by taking electrons near the surfaces of the semiconductors [5,6]. In general, the ionosorption species of O 2 , O , and O 2 are known to be dominant at <150 C, between 150 and 400 C, and at >400 C, respectively [6]. This leads to the formation of an electronic core–shell configuration (Fig. 3a); that is, an n-type semiconducting region at the cores of particles and resistive EDL at the shells of the particles. The adsorption of oxygen anions in p-type oxide semiconductors forms the HAL near the sur- face of the material because of the electrostatic interaction between the oppositely charges species (Fig. 3b), which again establishes the electronic core–shell configuration; that is, the insulating region at the cores of particles and semiconducting HALs near the surface of the particles. The majority of charge carriers near the surfaces of oxide semi- conductors and the number of oxygen anions on the surfaces of oxide semiconductors are significantly different in p- and n-type oxide semiconductors. Iwamoto et al. [70] used temperature- programmed desorption (TPD) after oxygen had been adsorbed under defined conditions onto various materials to investigate the

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

609

Lee / Sensors and Actuators B 192 (2014) 607–627 609 Fig. 1. Studies on n- and

Fig. 1. Studies on n- and p-type oxide semiconductor gas sensors (internet search of Web of Knowledge on July 15, 2013).

amount of oxygen adsorbed in 16 metal oxides by measuring the total amount of oxygen desorbed below 560 C (V 560 ) (Fig. 4). Note that the V 560 values of p-type oxide semiconductors such as CuO, Co 3 O 4 , NiO, MnO 2 , and Cr 2 O 3 are markedly larger than those of n-type oxide semiconductors such as Fe 2 O 3 , SnO 2 , ZnO, and TiO 2 . Among n-type oxide semiconductors, the transition metal oxides, Fe 2 O 3 with multi-valency characteristics showed the highest V 560 value. This finding indicates that a large amount of oxygen is adsorbed in transition metal oxides whose oxidation states may vary. Although the V 560 values for a few of the oxides slightly devi- ated from the overall correlation, V 560 tended to decrease with increasing the heat of formation of oxides per gram of oxygen atoms

( H f ) (Fig. 4). The low stability (i.e., low H f ) of multivalent transition metal oxides can lead to increased oxygen adsorption in the materials. For example, the charge compensation through the oxidation of Ni 2+ to Ni 3+ reportedly promotes and facilitates the adsorption of oxygen onto NiO [71,72]. Thus, the large amount of oxygen adsorbed in p-type transition metal oxides can be under- stood in relation to the low stability of oxides associated with redox reactions promoted by variable oxidation states. The distinctive surface characteristics of p-type oxide semiconductors can show various reactivities to reducing gases and dissimilar interactions with humidity and thus can provide different gas-detection char- acteristics.

Table 1 Various p-type metal oxide semiconductor-based gas sensors surveyed in literature [22–54].

Sensor material

Target gas

Structures

Particle size (nm)

Gas concentration

Sensing temp. ( C)

Refs.

 

(ppm)

NiO

C 2 H 5 OH

Nanoflowers Nanotubes Nanowires Hemispheres Hollow spheres Porous thin films Thin films Hierarchical NSs a Nanowires Dendritic wires Nanowires

200–800

20–200

150–400

[22–26]

HCHO

1000–2000

5–100

240–350

[27–29]

CO

3500

20

180–260

[30]

NH 3

150–200

50

RT (room

[31,32]

   

temperature)

 

(CH 3 ) 3 N

230

500

350

[25]

CuO

C 2 H 5 OH

Nanoparticles Nanorods Hierarchical NSs Thin film Urchin-like NSs Porous thin film Nanowires Nanorods Nanosheets Hollow spheres Thin film Nanowires

100–10,000

50–1000

RT–240

[33–36]

H 2

3000

100–1000

200–300

[37,38]

H 2 S

100–15,000

0.1–100

RT–300

[39–43]

NH 3

100

10,000

RT

[44]

Co 3 O 4

C 2 H 5 OH

Nanocubes

20–6000

10–500

135–2000

[45–47]

 

Microspheres

 

HCHO C 6 H 4 (CH 3 ) 2

Nanocrystals

430–560

100–1000

200

[48]

Nanocubes

20

100–200

200

[46]

Cr 2 O 3

C 2 H 5 OH

Mesoporous NSs

20–621

250–1000

300–450

[49–51]

 

Thin film

 

H 2 S C 6 H 4 (CH 3 )

Thin film

621

1000

170

[51]

Microspheres

1200

200

300–450

[52]

Mn 3 O 4

C 2 H 5 OH

Nanowires

50

2.5–100

300–450

[53]

LaOCl–NiO

C 2 H 5 OH

Nanofibers

1000

100

400

[54]

a NSs: nanostructures.

610

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627 Fig. 2. High-performance gas sensors fabricated

Fig. 2. High-performance gas sensors fabricated using p-type metal oxide semiconductors.

2.3. Conduction and gas-sensing mechanisms of n- and p-type

oxide semiconductors

Although both n- and p-type oxide semiconductors establish electrical core–shell layers by adsorbing oxygen, they exhibit significantly different conduction behaviors. The sensor resistance of n-type oxide semiconductors is mainly determined by the resistive shell-to-shell contacts formed between the particles in oxide semiconductors (Fig. 5a). Thus, equivalent circuits of n-type semiconductor gas sensors can be explained as serial connections between semiconducting cores (R core ) and resistive interparticle contacts (R shell ) (Fig. 5b). When an n-type semiconductor gas sensor is exposed to a reducing gas (e.g., CO), ionized oxygen anions (i.e., O 2 , O , and O 2 ) are used to oxidize the reducing gas, and the remanent electrons are injected into semiconducting

core, which decreases the sensor resistance proportional to the concentration of reducing analyte gas. Accordingly, the high responses to trace concentrations of various reducing gases in n-type oxide semiconductors reported in the literature [73–77] are attributed to the significant variation in the chemiresistivity at the interparticle contacts. In stark contrast, the conduction in p-type oxide semicon- ductors can be explained by the competition between parallel paths across the wide, resistive core (R core ) and along the narrow, p-semiconducting shell (R shell ) regions. The detailed conduction model and energy band diagram of p-type oxide semiconductor gas sensors are well explained by Barsan et al. [78] (Fig. 6a). In Fig. 6a, the B region represents the semiconductor grain–grain contacts, while A and C regions show electrode (metal)–semiconductor contacts. Under this configuration, the electrons injected into the

Under this configuration, the electrons injected into the Fig. 3. Formation of electronic core–shell structures in

Fig. 3. Formation of electronic core–shell structures in (a) n-type and (b) p-type oxide semiconductors.

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

611

Lee / Sensors and Actuators B 192 (2014) 607–627 611 Fig. 4. Correlation between amount of

Fig. 4. Correlation between amount of desorbed oxygen (V 560 ) and heat of formation

of oxides per gram of oxygen atom ( H

).

f

Reproduced with permission from Ref. [70].

material through the oxidation reaction between the reducing gas and the oxygen anions on the surface of the oxide semiconductors decreases the concentration of holes in the shell layer, which in turn increases the sensor resistance (Fig. 6b and c). However, if one assumes that the oxide semiconductor particles are larger than twice the thickness of the HAL (t HAL ), the slight change in the concentration of holes in the shell layer due to electron–hole recombination will not lead to significant variation in the chemire- sistivity at the interparticle contacts, which is feasible considering that the conduction in p-type oxide semiconductors mainly occurs along semiconducting shells. Hübner et al. [55] reported that the gas response of p-type-oxide-semiconductor-based gas sen- sors (S p ) (i.e., the relative change in sensor conductance/resistance when a sensor is exposed to a gas) is equal to the square root of that of n-type oxide semiconductor-based gas sensors (S n ) whose mor- phologies are identical to the p-type-oxide-semiconductor-based gas sensors. The relation is given as follows:

S p = S n .

(1)

This insightful equation clearly shows that designing highly sensitive gas sensors using p-type oxide semiconductors is chal- lenging. The C 2 H 5 OH-detection characteristics of n- and p-type

oxide semiconductors were the most abundant in the literature. Accordingly, we plotted the responses (R a /R g for n-type oxide semiconductors, R g /R a for p-type oxide semiconductors, R a : resis- tance in air, R g : resistance in gas) of various n- and p-type oxide semiconductors for various concentrations of C 2 H 5 OH in Fig. 7 [22–25,27,30,33–36,45–48,79–100] to demonstrate that it is chal- lenging to design highly sensitive gas sensors with p-type oxide semiconductors. Even if we take into account some variation in gas responses due to the variation in the morphology of the oxide semiconductor particles and the temperatures at which the con- centrations of C 2 H 5 OH were measured, the graph clearly shows that the gas responses of n-type oxide semiconductors tend to be significantly higher than those of p-type oxide semiconductors, which is consistent with Eq. (1). The resistance of p-type oxide semiconductor is known to decrease upon exposure to oxidizing gases such as NO 2 and O 3 . This is explained by the increase of hole concentration in the shell layer due to the ionosorption of oxidizing gas. However, chemore- sistive variation of p-type oxide semiconductors to oxidizing gas seems to be also not high considering the gas sensing mechanism.

This is supported by the literature data [23,101–104] that pure NiO and CuO sensor showed relatively low responses (R a /R g = 1.0–7.5) to 10–100 ppm NO 2 .

3. Highly sensitive gas sensors using p-type oxide

semiconductors

It is essential to enhance the gas response of p-type oxide semi- conductors in order to use them in practical sensor applications. The gas response of p-type oxide semiconductor gas sensors can be enhanced by (1) tuning the morphology of the nanostructures in the oxide semiconductors, (2) doping with additives to elec- tronically sensitize the oxide semiconductor, or (3) loading noble metals or metal oxide catalysts to chemically sensitize the oxide semiconductors.

3.1. Morphological design of nanostructures

The sizes of nanostructures in n-type oxide semiconductors determine the degree of electron depletion [105–108], while the morphologies, assembled configuration, and agglomeration of nanostructures dominate the chemiresistivity of the interpar- ticle contacts and the gas accessibility [109–112]. Thus, small nanostructures whose configurations are readily accessible to gas molecules are advantageous to design highly sensitive n-type oxide

are advantageous to design highly sensitive n-type oxide Fig. 5. Gas-sensing mechanism and equivalent circuit of

Fig. 5. Gas-sensing mechanism and equivalent circuit of n-type oxide semiconductors.

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J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627 Fig. 6. (a) Sensing layer of

Fig. 6. (a) Sensing layer of p-type oxide semiconductor gas sensors: simplified depiction of the relevant sensing layer elements (low) (A, C: metal–semiconductor contact, B: semiconductor grain–grain contact), relevant energy band diagram (upper) suggested by Barsan et al. Reproduced with permission from [78]. (b, c) Simplified gas sensing mechanism and equivalent circuit of p-type oxide semiconductors.

semiconductor gas sensors. The gas responses of p-type oxide semiconductors also depend upon the size of the nanostructures because the chemiresistive variation of oxide semiconductors is the results of the interaction between an analyte gas and the surfaces of oxide semiconductors. The gas responses of n-type oxide semiconductors dramatically increase to a very high level with decreasing size of the metal oxide semiconductor particles to smaller than twice the thickness of the EDL (t EDL ) [105–107]. However, the dependence of the gas responses of p-type oxide semiconductors on particle size has not yet been well-established. The gas responses for large and small p-type metal oxide semiconductor particles can be semiquantitatively compared using the simplified cube model that Barsan et al. suggested (Fig. 8) [78]. The gas responses of

a large or small cube whose edges are 100 or 20 nm long were

calculated. In both large and small cubes, the t HAL value (X 0 in Fig. 8a) was assumed to be 5 nm. The cube whose edge length (D)

is 100 nm can be divided into 3 parts according to the conduction

path and resistivity: (1) two thin p-semiconducting slabs (whose

on the exterior (parts

1 and 4; resistance: R 1 and R 4 ); (2) thin semiconducting layers

surrounding the insulating cube (i.e., two slabs whose dimensions are 100 nm × 90 nm × 5 nm and two slabs whose dimensions are 90 nm × 90 nm × 5 nm) (part 2; resistance: R 2 ); and (3) one insulating cube (whose dimensions are 90 nm × 90 nm × 90 nm) at

dimensions are 100 nm × 100 nm × 5 nm)

the central region (part 3; resistance: R 3 ) (Fig. 8b). We assumed

repre-

sents the resistivity of the resistive core, shell·air represents the

core / shell·air = 10

and

shell·gas / shell·air = 4

(where core

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

613

Lee / Sensors and Actuators B 192 (2014) 607–627 613 Fig. 7. (a) Responses of n-

Fig. 7. (a) Responses of n- and p-type oxide semiconductor gas sensors to C 2 H 5 OH reported in literature [79–95 (N1–N17), 22–25 (P1–P4), 27 (P5), 30 (P6), 33–36 (P7–P10), 45–48 (P11–P14), and 96–98 (P15–P17)] and (b) enhanced response of Fe-doped NiO hierarchical nanostructure to C 2 H 5 OH gas. Response was enhanced by electronically sensitizing nanostructures with Fe doping [99,100].

resistivity of the p-semiconducting shell in air, and shell·gas rep- resents the resistivity of the p-semiconducting shell under the gas atmosphere), the gas response (R g /R a ) of the large cube (D: 100 nm) was calculated as 2.618. The gas response (R g /R a ) of the small cube (D: 20 nm) was similarly calculated as 3.801. When the large cube is markedly thicker than 2t HAL (or 2X 0 in Fig. 8a), the entire resistance of the sensor depends less upon the variation in the resistance of shell layer because the conduction along the resistive core region, whose cross-sectional area is very wide, will dominate. The gas response will accordingly remain low unless the chemiresistive variation at the shell region is very high. In contrast, when the length of the edge of the large cube is comparable to or slightly larger than 2t HAL , the chemiresistive variation at the shell layer con- tributes more to the change in the resistance of the sensor, which leads to the higher gas response. From this perspective, decreasing the size of metal oxide semiconductor particles also enhances the response of p-type oxide semiconductor gas sensors to various gases. Note that the gas-detection characteristics of p-type oxide semiconductor gas sensors and their dependence on particle size

can be tuned by varying t HAL /D, core / shell·air , core·gas / shell·air , and so on. It should be noted that a new formula for estimating gas response is necessary when the particle size is smaller than 2t HAL . The interparticle contact area is also a key parameter that can affect the gas response of p-type oxide semiconductors. We elec- trospun and subsequently heated Co 3 O 4 at 600 C to prepare a configuration of connected Co 3 O 4 nanofibers [113] whose crys- tallite sizes were 105.8 ± 42.7 nm. The Co 3 O 4 nanofibers were ultrasonically treated for 1 h to completely disconnect and break them apart into nanoparticles. The gas response of the ultrasoni- cally treated Co 3 O 4 nanoparticles to 100 ppm C 2 H 5 OH at 301 C was R g /R a = 2.71, significantly lower than that (R g /R a = 45.3) of the con- nected configuration of Co 3 O 4 nanofibers whose crystallite size was identical. Barsan et al. [78] suggested that the gas response of p-type oxide semiconductors whose grains were larger than the Debye length (L D ) could increase with increasing diameter of the neck between two particles when the grain size is constant. Therefore, the marked decrease in gas response of the ultrasonically treated Co 3 O 4 nanofibers was attributed to the decrease in the contact

nanofibers was attributed to the decrease in the contact Fig. 8. Simplified model of p-type metal

Fig. 8. Simplified model of p-type metal oxide grains, used for the calculation of the grain resistance: (a) the cubic grain model; (b) sketch of the electrical connection between the different grain parts; and (c) the corresponding DC equivalent circuit of the grain.

Reproduced with permission from [78].

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Table 2 Effect of morphology of particles (S special morphology /S another morphology ) on gas response of p-type metal oxide semiconductor-based gas sensors [23,26,27,37,41,48,114–116].

Sensor

Target gas

Morphology

Sensing temperature ( C)

Gas concentration

Response

Morphological

Refs.

material

(ppm)

(S

=R g /R a )

effect

NiO

C 2 H 5 OH

Hemispheres

300

100

S Hemisphers = 4.2

1.5

[23]

 

Thinfilm = 2.7

S

 

NiO

C 2 H 5 OH

Nanotubes

250

50

S Nanotubes = 4.2 S Nanofibers = 1.4 S Hollow spheres = 2.55 S Nanoparticles = 1.73 S Hierarchical = 5.8 S Nanorods = 3.4

3

[26]

NiO

C 4 H 9 OH

Hollow spheres

350

500

1.47

[27]

CuO

H 2

Hierarchical

NSs a

200

100

1.70

[37]

CuO

H 2 S

Hierarchical

NSs

190

1

S Hierarchical = 4.5 S Solid spheres = 3.2 S Mesocrystal = 3.15 S Nanoparticles = 1.55 S Nanorods = 6.5 S Nanoparticles = 2.2 S Nanosheets = 57.7 S Nanoparticles = 5.5 S Nanobers = 1.72 S Nanoparticles = 1.12

1.40

[41]

Co 3 O 4

HCHO

Mesocrystals

200

500

2.03

[48]

Co 3 O 4

CO

Nanorods

250

50

2.95

[114]

CO 3 O 4

C 2 H 5 OH

Nanosheets

400

100

10.5

[115]

Cr 2 O 3

C 2 H 5 OH

Nanofibers

400

1000

1.53

[116]

a NSs: nanostructures.

area between particles, indicating that the interparticle connection configuration is an important factor to consider when designing highly sensitive p-type oxide semiconductor gas sensors. The effect of morphology on the variation in the gas response of the p-type oxide semiconductors surveyed in the literature is summarized in Table 2 [23,26,27,37,41,48,114–116]. The variations in the morphology of the nanostructures include the differences in size, interparticle contact, and agglomeration. Thus, it remains difficult to elucidate in detail the effect of each variable on the gas-detection characteristics of oxide semiconductors. However, it is obvious that morphology is an important parameter for tuning the gas responses of oxide semiconductors. Although the response ratios of nanostructures with two different morphologies in the NiO, CuO, Co 3 O 4 , and Cr 2 O 3 oxide semiconductors surveyed in the literature are generally low (i.e., in the range 1.4–2.95) although one a report showed relatively high ratio (10.5) [115]. Note that the enhanced gas response achieved using well-defined or well- dispersed nanostructures in p-type oxide semiconductor sensors is lower than that achieved using the n-type oxide semiconductor sensors, which can be attributed to the inherently low gas response of p-type oxide semiconductor sensors because of their distinctive gas-sensing mechanism.

3.2. Electronic sensitization by controlling doping

The chemiresistive variation in oxide semiconductor gas sensors emanates from the change in the charge carrier con- duction in oxide semiconductors upon reaction with analyte gas. Thus, the concentration of charge carriers and the con- figuration of the electrical core–shell are key parameters for tuning the gas responses of oxide semiconductors. Enhancement of gas response by tuning the concentration of charge carriers is referred to as “electronic sensitization” [117]. To date, there have been many reports on the use of acceptor doping [118,119] to decrease the concentrations of electrons throughout entire semiconductors or to decrease the concentrations of electrons adjacent to second phases [120] in order to make n-type oxide semiconductors more sensitive to reducing gases. Designing highly sensitive p-type oxide semiconductor gas sensors by tuning the concentration of holes has scarcely been reported. Nevertheless, electronically sensitizing p-type oxide semiconductors is an impor- tant method of developing practical p-type oxide semiconductor gas sensor applications, especially considering that achieving high gas response in p-type oxide semiconductors is challenging even

when very small nanostructures are used, because of the distinctive gas-sensing mechanism of p-type oxide semiconductors. The present authors [99] have previously reported that dop- ing p-type NiO with Fe can significantly enhance the gas response of p-type NiO. We prepared hollow NiO spheres (shell thickness:

12 nm; diameter: 300 nm) doped with 0.3 at% Fe by coating thin layers of Fe precursors onto Ni template spheres, partially oxidizing the outer Ni spheres into NiO, dissolving the metallic Ni core in dilute HCl, and heating the hollow spheres at 600 C (Fig. 9a–c). To study the effect of Fe doping on the gas-detection characteristics of NiO we also prepared for comparison undoped NiO hollow spheres by similar processes of coating Ni precursors, heating the spheres, and subsequently removing the Ni core tem- plates. Doping the sensor with Fe increased the response (R g /R a ) of the sensor to 100 ppm C 2 H 5 OH at 350 C from 5.5 to 172.5 (Fig. 9d and e). Motivated by the Fe-doping-induced 31.4-fold increase in the gas response of the sensor, we then used electrospinning to prepare pure NiO nanofibers and NiO nanofibers doped with Fe concen- trations in the range 0.18–13.2 at% in order to investigate how Fe doping enhanced the gas response of NiO [100]. The gas responses (R g /R a ) of the sensors to 100 ppm C 2 H 5 OH increased to 115.6 times with increasing concentration of Fe dopant to 3.04 at% (Fig. 10). The change in the particle size due to Fe doping could be excluded from the main reason for the sensitization from the dramatically different gas responses of pure NiO fibers and 1.02 at% Fe-doped NiO nanofibers in spite of similar particle sizes and BET sur- face area. Note that electrons are generated to compensate for substituting Fe 3+ ions into Ni 2+ sites, which can decrease the con- centration of holes in NiO through the recombination reaction as follows:

Fe 2 O 3 2NiO

−→ 2Fe Ni

+ 2O X O +

1

2

O 2 (g) + 2e .

(2)

This incorporation reaction clearly explains the increase in sen- sor resistance with increasing concentration of Fe dopant. The gas response of the sensor also showed a similar increase with increasing concentration of Fe dopant (Fig. 10). This finding strongly suggests that the gas response of the sensor is correlated with the concentration of charge carriers in the material. That is, the Fe-doped NiO (which contained a lower concentration of holes in the HAL) was more sensitive to the same number of electrons injected into the sensor from the reaction with analyte gas than the undoped NiO (which contained a higher concentration of holes in

H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

615

Lee / Sensors and Actuators B 192 (2014) 607–627 615 Fig. 9. (a, b) TEM images

Fig. 9. (a, b) TEM images and (c) element-mapping image of 0.3 at% Fe-doped NiO hollow spheres and (d, e) C 2 H 5 OH-detection characteristics of pure and 0.3 at% Fe-doped NiO hollow spheres measured at 350 C, according to Ref. [99].

the HAL). The gas responses of the 3.04 at% Fe-doped NiO nanofibers and the 0.3 at% Fe-doped hollow NiO spheres to 100 ppm C 2 H 5 OH were (R g /R a = 245.0) [100] and (R g /R a = 172.5) [99], respectively, and are two of the highest gas responses ever reported for p-type oxide semiconductors (Fig. 7b). Moreover, the 3.04 at% Fe-doped NiO nanofibers showed a substantial response of R g /R a = 3.35 even to 0.05 ppm C 2 H 5 OH. This result demonstrates that p-type oxide semiconductors can be also used to develop practical sensor applications for detecting the ppb-level concentration of analyte gases. The present authors [104] reported the doping of 2.2 at% of Cr to CuO nanostructures by solvothermal reaction significantly increases the responses to 100 ppm NO 2 from R a /R g = 7.5 to R a /R g = 134.2 and the R a value from 0.92 M to 20.40 M at 250 C. The marked increase in the gas response can be explained by the increase in sensor resistance due to doping the CuO with trivalent Cr, indicating that the electronic sensitization is also a valid and effective approach to detect oxidizing gas as well as reducing gases in a highly sensitive manner.

These results clearly show that electronic sensitization is a pow- erful tool that can be used to design highly sensitive p-type oxide semiconductor gas sensors. Most p-type oxide semiconductors such as Co 3 O 4 , NiO, Cr 2 O 3 , Mn 3 O 4 , and CuO are oxides of d-block transition metals and thus exhibit variable oxidation states. Accord- ingly, aliovalent doping should be carefully designed taking into account the coexistence of multivalent ions, the change in the radii of the host ions with the change in the valence of the ions, and the solubility limit of dopant in the oxide semiconductor matrix.

3.3. Chemical sensitization by loading catalyts

The gas response of p-type oxide semiconductors also increases by loading noble metals. The relevant results in the literature are summarized in Table 3 [24,30,121–124]. Wang et al. previously reported that decorating PdO onto ring-like NiO nanostructures enhanced the response (R g /R a ) of the sensor to 20 ppm CO from 8.2 to 27.5 [30]. They [122] also reported that the response of hierarchical hollow NiO nanostructures to CH 3 COCH 3 can be

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H.-J. Kim, J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627

J.-H. Lee / Sensors and Actuators B 192 (2014) 607–627 Fig. 10. Gas response (( R

Fig. 10. Gas response ((R g R a )/R a ) and sensor resistance in air (R a ) for pure and Fe-doped NiO nanofibers measured at (a-1, a-2) 350 C, (b-1, b-2) 375 C, (c-1, c-2) 400 C, (d-1, d-2) 425 C, (e-1, e-2) 450 C, and (g-1, g-2) 500 C.

Reproduced with permission from Ref. [100].

Table 3 Effect of noble metal catalyst loading on gas-sensing characteristics of p-type MOSs surveyed in literature [24,30,121–124].

Sensor materials

Target gas

Morphology

Sensing temperature ( C)

Gas concentration

Response

S Catalyst-loaded /S Pure

Refs.

 

(ppm)

(S

=R g /R a )

 
 

180

S

PdO-NiO

= 27.5

PdONiO

CO

Hierarchical NSs a

260

20

S NiO = 8.2

3.35

[24]

Pt–NiO–Pt

C 2 H 5 OH

Nanofibers

400

100

S Pt-NiO-Pt = 11.7

6.92

[30]

 

S NiO = 1.69

 

Au–NiO

H 2

Thin films

200

300

S Au-NiO = 1.3

1.22

[121]

 

S NiO = 1.06

 

Au–NiO

CH 3 COCH 3

Microspheres

240

50

S Au-NiO = 10.1 S NiO = 1.5

6.70

[122]

Pt–NiO

C 2 H 5 OH

Nanotubes

200

100

S Pt-NiO = 20.8 S NiO = 2.06

10.1

[123]

Au/Pt–CuO

HCHO

Nanoribbons

200

500

S Pt-CuO = 7.9 S Au-CuO = 6.2

Pt: 1.75

[124]

 

Au: 1.38

S CuO = 4.5

a NSs: nanostructures.

enhanced to 6.7 times by loading the nanostructures with Au nanoparticles. One of the present authors [24] previously demon- strated that loading Pt nanoparticles onto both the inner and outer walls of thin NiO tubes can enhance the response (R g /R a ) to 100 ppm C 2 H 5 OH from 1.69 to 11.7. It is noteworthy that in all three studies, the selectivity of the oxide semiconductor sensors to CO, CH 3 COCH 3 , and C 2 H 5 OH was also enhanced [24,30,122], indicating the chemical sensitization of noble metals or noble metal oxides. However, only a limited number of studies have reported the effects of noble metal catalysts on the gas-detection characteristics of p-type oxide semiconductors. Therefore, more investigations are needed in order to elucidate the effects.

4. Highly selective gas sensors using p-type oxide

semiconductors

A range of reducing gases can similarly react with oxygen anions on the surface of oxide semiconductors, which often hinders dis- tinguishing among various gases. The gas selectivities of various n- and p-type oxide semiconductor sensors have been reported during the last 5 years [22–25,30,35,36,45,48,81–85,125–131]. The

ratio between the response to a target gas and the highest response to an interfering gas (S target /