Photosensitive Organic-Inorganic Hybrid Materials for Room Temperature Gas Sensor Applications
Abstract
:1. Introduction
2. Results and Discussion
2.1. Characteristics of Nanocrystalline Semiconductor Oxides
2.2. Characteristics of Ru(II) Heterocyclic Complex
2.3. Characteristics of Hybrid Samples
2.4. Gas Sensor Properties
- (i)
- Pure tin dioxide did not exhibit photosensitivity (Figure 9c), and the effective photoresponse SPh = 1 for all NO2 concentrations under illumination with blue, green and red light (Figure 10a). Nevertheless, the observed change in the resistance as a function of the NO2 concentration makes it possible to calculate the magnitude of the sensor signal by Equation (7). The maximum sensor signal of blank SnO2 was measured under green light illumination (Figure 10b).This effect can be due to the participation of oxygen vacancies of tin dioxide in the adsorption of NO2. As shown by the authors of [65], the acceptor levels related to the oxygen vacancies in SnO2 lie at 1.4 eV (bridging vacancies) and 0.9 eV (in-plane vacancies) above the valence band, which correspond to the energy of an electron transition from an acceptor level of Ea = 2.2 eV (563 nm) and Ea = 2.3 eV (538 nm), respectively. The absence of the photosensitivity (SPh = 1), together with the measurable sensor signal (S > 1), can be due to the fact that, for the finely dispersed tin dioxide, the main process of interaction with NO2 is the reaction (5). Since the electron affinity of NO2 is larger than the one for O2, the position of energy levels of electrons localized on NO2 molecules chemisorbed on a SnO2 surface is deeper than that for chemisorbed oxygen. Thus, electron transfer in accordance with the reaction (5) will lead to a decrease in the Fermi level of the semiconductor. Since the band structure of nanocrystalline SnO2 with a particle size of 3–4 nm corresponds to the situation of flat zones [66], the decrease in the Fermi level indicates the decrease in the electrical conductivity, providing the sensor signal in the presence of NO2.
- (ii)
- With a blue illumination, pure In2O3 exhibited a noticeable photosensitivity (Figure 9a). The value of the effective photoresponse at a fixed concentration of NO2 decreased with the increasing wavelength of the activating light (wavelengths of 470, 535 and 630 nm were used) (Figure 10a). A similar trend was observed for the concentration dependence of sensor signal. The maximum values of sensor signal in the whole range of NO2 concentrations were obtained under blue light (Figure 10b). This tendency is in accordance with the fact that for nanocrystalline In2O3, the photoconductivity is nonzero at photon energies more than 2.25 eV (λ < 550 nm), which can be explained by the generation of electrons from localized levels located in the bandgap [64].
- (iii)
- The sensitization of semiconducting oxides with the Ru-TT organic complex leads to the increase in both the effective photoresponse SPh of the materials and their sensor signal S towards NO2 (Figure 9b,d). For the SnO2 R-TT hybrid material, the effective photoresponse and sensor signal values decreased upon transition from blue to green and then to red light illumination (Figure 10). The observed tendency agrees with the absorption spectrum and the spectral dependence of the photoconductivity of this hybrid material. In the case of the In2O3 Ru-TT hybrid, the maximum values of the photoresponse and the sensor signal at high concentrations of NO2 were obtained under red light. It appears to be an artifact. The values of the dark resistance Rdark observed under these measurement conditions exceeded 109 Ohm, which is the upper limit of the measuring system. The measurement of such resistances occurred with a large error and a high noise level.
3. Materials and Methods
3.1. Materials Synthesis
3.1.1. Synthesis of Ru(II) Complex
3.1.2. Synthesis of Nanocrystalline SnO2 and In2O3 and Hybrid Materials
3.2. Materials Characterization
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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E1/2(red), V | E1/2(ox), V | EHOMO, eV | ELUMO, eV |
---|---|---|---|
−1.27/−1.21 | 1.23 | −6.15 | −3.46 |
−1.48/−1.41 | 1.42 | ||
−1.96/−1.84 | 1.52 |
Sample | dXRD a, nm | dTEM b, nm | Ssurf c, m2/g | SPh e in Pure Air (λ = 470 nm) | |
---|---|---|---|---|---|
SnO2 | 4 ± 1 | 4 ± 1 | 110 ± 5 | - | 1.00 |
SnO2 Ru-TT | 1.4 ± 0.1 | 2.72 | |||
In2O3 | 7 ± 1 | 7 ± 2 | 60 ± 5 | - | 1.30 |
In2O3 Ru-TT | 2.1 ± 0.2 | 3.15 |
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Rumyantseva, M.; Nasriddinov, A.; Vladimirova, S.; Tokarev, S.; Fedorova, O.; Krylov, I.; Drozdov, K.; Baranchikov, A.; Gaskov, A. Photosensitive Organic-Inorganic Hybrid Materials for Room Temperature Gas Sensor Applications. Nanomaterials 2018, 8, 671. https://doi.org/10.3390/nano8090671
Rumyantseva M, Nasriddinov A, Vladimirova S, Tokarev S, Fedorova O, Krylov I, Drozdov K, Baranchikov A, Gaskov A. Photosensitive Organic-Inorganic Hybrid Materials for Room Temperature Gas Sensor Applications. Nanomaterials. 2018; 8(9):671. https://doi.org/10.3390/nano8090671
Chicago/Turabian StyleRumyantseva, Marina, Abulkosim Nasriddinov, Svetlana Vladimirova, Sergey Tokarev, Olga Fedorova, Ivan Krylov, Konstantin Drozdov, Alexander Baranchikov, and Alexander Gaskov. 2018. "Photosensitive Organic-Inorganic Hybrid Materials for Room Temperature Gas Sensor Applications" Nanomaterials 8, no. 9: 671. https://doi.org/10.3390/nano8090671