Highly Sensitive ZnO(Ga, In) for Sub-ppm Level NO2 Detection: Effect of Indium Content

Vorobyeva, N. A.; Rumyantseva, M. N.; Филатова, Д. Г.; Спиридонов, Ф. М.; Зайцев, В. Б.; Zaytseva, Anna; Gaskov, Alexander

doi:10.3390/chemosensors5020018

Cited by 14 publications

(13 citation statements)

References 33 publications

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“…We henceforth refer to the upper six Zn-O layers (corresponding to the upper three bilayers) as the six surface-like layers [37]. Regarding doping, our experimental evidence indicates that a 4-5 at.% In concentration [i.e., [In]/([In]+[Zn])] is sufficient for it to overcome its solubility in ZnO and to segregate to the surface [38]. Here we substitute two Zn atoms with In in our supercell slab model, which represents an In concentration of 4.17 at.%.…”

Section: Methodsmentioning

confidence: 99%

First-principles study of CO and OH adsorption on in-doped ZnO surfaces

Saniz

Sarmadian

Partoens

et al. 2019

Journal of Physics and Chemistry of Solids

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We present a first-principles computational study of CO and OH adsorption on non-polar ZnO (1010) surfaces doped with indium. The calculations were performed using a model ZnO slab. The position of the In dopants was varied from deep bulk-like layers to the surface layers. It was established that the preferential location of the In atoms is at the surface by examining the dependence of the defect formation energy as well as the surface energy on In location. The adsorption sites on the surface of ZnO and the energy of adsorption of CO molecules and OH-species were determined in connection to In doping. It was found that OH has higher bonding energy to the surface than CO. The presence of In atoms at the surface of ZnO is favorable for CO adsorption, resulting in an elongation of the C-O bond and in charge transfer to the surface. The effect of CO and OH adsorption on the electronic and conduction properties of surfaces was assessed. We conclude that In-doped ZnO surfaces should present a higher electronic response upon adsorption of CO.

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Section: Methodsmentioning

confidence: 99%

First-principles study of CO and OH adsorption on in-doped ZnO surfaces

Saniz

Sarmadian

Partoens

et al. 2019

Journal of Physics and Chemistry of Solids

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“…They have many advantages: high sensitivity, small size, fast response, and low cost in mass production. n-Type metal oxides are widely used as sensitive materials [1], for example, SnO 2 [2,3], ZnO [4,5,6], In 2 O 3 [7,8], WO 3 [9], TiO 2 [10] and so on. One of the main disadvantages of these materials is their high sensitivity to humidity, which makes it difficult to use them in real outdoor conditions.…”

Section: Introductionmentioning

confidence: 99%

Co3O4 as p-Type Material for CO Sensing in Humid Air

Vladimirova

Krivetskiy

Rumyantseva

et al. 2017

Sensors

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Nanocrystalline cobalt oxide Co3O4 has been prepared by precipitation and subsequent thermal decomposition of a carbonate precursor, and has been characterized in detail using XRD, transmission electron microscopy, and FTIR spectroscopy. The sensory characteristics of the material towards carbon monoxide in the concentration range 6.7–20 ppm have been examined in both dry and humid air. A sensor signal is achieved in dry air at sufficiently low temperatures T = 80–120 °C, but the increase in relative humidity results in the disappearance of sensor signal in this temperature range. At temperatures above 200 °C the inversion of the sensor signal in dry air was observed. In the temperature interval 180–200 °C the sensor signal toward CO is nearly the same at 0, 20 and 60% r.h. The obtained results are discussed in relation with the specific features of the adsorption of CO, oxygen, and water molecules on the surface of Co3O4. The independence of the sensor signal from the air humidity combined with a sufficiently short response time at a moderate operating temperature makes Co3O4 a very promising material for CO detection in conditions of variable humidity.

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“…Nanocrystalline zinc oxide modified by different amounts of In 2 O 3 was synthesized via an aqueous coprecipitation route (Vorobyeva et al, 2013(Vorobyeva et al, , 2017. The concentrations of In were 1, 3, 5, and 7 at %.…”

Section: Methodsmentioning

confidence: 99%

“…Doping by M(III) cations (Al, Ga, In) soluble in bulk Zno is commonly used to improve electronic conduction in nanocrystalline zinc oxide (Pearton et al, 2005;Ellmer, 2010;Kołodziejczak-Radzimska and Jesionowski, 2014). It has also been observed that dopants influence the sensitivity of zinc oxide to various target gases (Han et al, 2009;Kim et al, 2009;Phan and Chung, 2013;Hou and Jayatissa, 2014;Hjiri et al, 2015;Nulhakim et al, 2017;Vorobyeva et al, 2017). Understanding the effect of dopants on gas sensing requires a description of the chemical processes in gas-solid interactions, i.e., target molecule adsorption and redox reaction of the adsorbate with the surface.…”

Section: Introductionmentioning

confidence: 99%

“…Understanding the effect of dopants on gas sensing requires a description of the chemical processes in gas-solid interactions, i.e., target molecule adsorption and redox reaction of the adsorbate with the surface. Such descriptions are usually lacking in literature, since most studies are focused on the electronic properties of doped zinc oxide (Han et al, 2009;Hou and Jayatissa, 2014;Vorobyeva et al, 2017). Among the chemical aspects to be taken into account, there is information on active sites on the surface of the sensing material, adsorption sites for particular gas molecules and reactivity of the surface in redox interaction with the target gas.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Zinc Oxide Modification by Indium Oxide on Microstructure, Adsorbed Surface Species, and Sensitivity to CO

et al. 2019

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Additives in semiconductor metal oxides are commonly used to improve sensing behavior of gas sensors. Due to complicated effects of additives on the materials microstructure, adsorption sites and reactivity to target gases the sensing mechanism with modified metal oxides is a matter of thorough research. Herein, we establish the promoting effect of nanocrystalline zinc oxide modification by 1-7 at.% of indium on the sensitivity to CO gas due to improved nanostructure dispersion and concentration of active sites. The sensing materials were synthesized via an aqueous coprecipitation route. Materials composition, particle size and BET area were evaluated using X-ray diffraction, nitrogen adsorption isotherms, high-resolution electron microscopy techniques and EDX-mapping. Surface species of chemisorbed oxygen, OH-groups, and acid sites were characterized by probe molecule techniques and infrared spectroscopy. It was found that particle size of zinc oxide decreased and the BET area increased with the amount of indium oxide. The additive was observed as amorphous indium oxide segregated on agglomerated ZnO nanocrystals. The measured concentration of surface species was higher on In 2 O 3-modified zinc oxide. With the increase of indium oxide content, the sensor response of ZnO/In 2 O 3 to CO was improved. Using in situ infrared spectroscopy, it was shown that oxidation of CO molecules was enhanced on the modified zinc oxide surface. The effect of modifier was attributed to promotion of surface OH-groups and enhancement of CO oxidation on the segregated indium ions, as suggested by DFT in previous work.

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Highly Sensitive ZnO(Ga, In) for Sub-ppm Level NO2 Detection: Effect of Indium Content

Cited by 14 publications

References 33 publications

First-principles study of CO and OH adsorption on in-doped ZnO surfaces

First-principles study of CO and OH adsorption on in-doped ZnO surfaces

Co3O4 as p-Type Material for CO Sensing in Humid Air

Effect of Zinc Oxide Modification by Indium Oxide on Microstructure, Adsorbed Surface Species, and Sensitivity to CO

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