• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2255-2259
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• 2012

Aggregation of titania nanotubes (TNTs) fabricated by hydrothermal method were calcined in air and dry nitrogen; Changes in morphology and crystallinity of the nanotubes were studied by means of TEM, EDX, and XPS. EDX patterns and XPS spectra proved that there were a certain densities of oxygen vacancies in TNTs annealed in $N_2$. The photocatalysis experiments revealed TNTs/$N_2$ possesses significantly higher photocatalytic efficiency than TNTs annealed in dry air to degrade methylene blue. The correlation between oxygen vacancies and photocatalytic property may be attributed to: 1) oxygen vacancies might have affected results on water molecules adsorption and increase of the hydroxyl concentration; and 2) oxygen vacancies resulted in some changes in electronic structure of TNTs/$N_2$ aggregation and Fermi level extends into the conducting band.

• Journal of the Korean Ceramic Society
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• v.28 no.12
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• pp.989-995
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• 1991

By means of the secondary ion mass spectrometer, the tracer diffusion of oxygen in rutile single crystal was measured as function of temperature and oxygen partial pressure. The tracer diffusivity was determined from the depth profile of 18O. The Po2 dependence of D suggests that the dominant defects in TiO2-y are oxygen vacancies (V{{{{ { ‥} atop { o} }}) and interstitial titanium ions (Ti{{{{ {‥‥} atop {i} }}). The doubly ionized oxygen vacancies are prominent at low temperature and Po2. However, the tetravalent interstitial titanium ions predominate at teperature above 120$0^{\circ}C$.

• Transactions on Electrical and Electronic Materials
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• v.6 no.5
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• pp.214-220
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• 2005

The ferroelectric properties of the $Pt/PZT(Pb(Zr,Ti)O_3)/Pt$ capacitors are severely degraded when they are annealed in hydrogen-containing environment. Hydrogen atoms created by the catalytic reaction of Pt top electrode during annealing in hydrogen ambient penetrate into PZT films and generate oxygen vacancies by the reduction of the PZT films, which is likely to cause the degradation. The degree of hydrogen-induced degradation and the direction of voltage shift in P-E curves of the pre-poled PZT capacitors after annealing in hydrogen ambient is dependent on the polarity of the pre-poling voltage. This implies that oxygen vacancies causing hydrogen induced degradation are generated by hydrogen ions having a polarity. The degraded ferroelectricity of the PZT capacitors can be effectively recovered by the shift of oxygen vacancies toward the Pt top electrode interface during post-annealing in oxygen environment with applying negative unipolar stressing.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.318-318
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• 2011

Etching of an ultrathin aluminum oxide film on NiAl(110) substrate by methanol is studied by home-built scanning tunneling microscopy at room-temperature. We deposited liquid methanol on thin alumina film by using a high speed solenoid valve suitable for deposition of thermally unstable molecules. It is found that only the reflection domain boundary between two domains was preferentially etched by methanol. Since the reflection domain boundary has many oxygen vacancies and irregular structures, judging from the fact, we assume that oxygen vacancies cause the chemically reactive phenomena of methanol in reflection domain boundary on an alumina film. The reactivity of the reflection domain boundary is attributed to the oxygen vacancies due to irregular structures. Similar reactivity is found on the oxygen deficient alumina produced on top of the intact alumina.

• Transactions on Electrical and Electronic Materials
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• v.15 no.6
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• pp.315-319
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• 2014

In this paper, we investigate visible light stress instability in radio frequency (RF) sputtered a-IGZO thin film transistors (TFTs). The oxygen flow rate differs during deposition to control the concentration of oxygen vacancies, which is confirmed via RT PL. A negative shift is observed in the threshold voltage ($V_{TH}$) under illumination with/without the gate bias, and the amount of shift in $V_{TH}$ is proportional to the concentration of oxygen vacancies. This can be explained to be consistent with the ionization oxygen vacancy model where the instability in $V_{TH}$ under illumination is caused by the increase in the channel conductivity by electrons that are photo-generated from oxygen vacancies, and it is maintained after the illumination is removed due to the negative-U center properties.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2271-2275
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• 2013

We report on the photoelectrochemical properties of partially reduced mesoporous titania thin films. The fabrication is achieved by synthesizing mesoporous titania thin films through the self-assembly of a titania precursor and a block copolymer, followed by aging and calcination, and heat-treatment under a $H_2$ (1 torr) environment. Depending on the temperature used for the reaction with $H_2$, the degree of the reduction (generation of oxygen vacancies) of the titania is controlled. The oxygen vacancies induce visible light absorption, and decrease of resistance while the mesoporosity is practically unaltered. The photoelectrochemical activity data on these films, by measuring their photocurrent-potential behavior in 1 M NaOH electrolyte under AM 1.5G 100 mW $cm^{-2}$ illumination, show that the three effects of the oxygen vacancies contribute to the enhancement of the photoelectrochemical properties of the mesoporous titania thin films. The results show that these oxygen deficient $TiO_2$ mesoporous thin films hold great promise for a solar hydrogen generation. Suggestions for the materials design for improved photoelectrochemical properties are made.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.37 no.3
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• pp.231-240
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• 2024

Titanium dioxide (TiO₂) holds significant scientific and technological relevance as a key photocatalyst and resistive random-access memory, demonstrating unique physicochemical properties and serving as an n-type semiconductor. Understanding the density and arrangement of oxygen vacancies (VOs) is crucial for tailoring TiO₂'s properties to diverse technological needs, driving increased interest in exploring oxygen vacancy complexes and superstructures. In this mini review, we summarize the recent understandings of the fundamental properties of oxygen vacancies in bulk rutile (R-TiO₂) and anatase (A-TiO₂) based on DFT and beyond method. We specifically focus on the excess electrons and their spatial arrangement of disordered single VO in bulk R and A-TiO₂, aligned with the experimental findings. We also highlight the theoretical works on investigating the geometries and stabilities of ordered VOs complexes in bulk TiO₂. This comprehensive review provides insights into the fundamental properties of excess electrons in reduced TiO₂, offering valuable perspectives for future research and technological advancements in TiO₂-based devices.

• Journal of Ceramic Processing Research
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• v.20 no.1
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• pp.18-23
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• 2019

Chemical looping combustion (CLC) is a promising carbon capture and storage (CCS) technology whose efficiency and cost primarily relies on the oxygen carrier materials used. In this paper, gadolinium-doped ceria (GDC, Ce0.9Gd0.1O1.95) was added as a promoter to improve the oxygen transfer rate of MgMnO3-δ oxygen carrier materials. Increasing GDC content significantly increased the oxygen transfer rate of MgMnO3-δ-GDC composites for the reduction reaction due to an increase in the surface adsorption of CH4 via oxygen vacancies formed on the surface of the GDC. On the other hand, the oxygen transfer rate for the oxidation reaction decreased linearly with increasing GDC content due to the oxygen storage ability of GDC. Adsorbed oxygen molecules preferentially insert themselves into oxygen vacancies of the GDC lattice rather than reacting with (Mg,Mn)O to form MgMnO3-δ during the oxidation reaction.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.297.2-297.2
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• 2013

Scavenging electricity from wasteful energy resources is currently an important issue and piezoelectric nanogenerators (NGs) based on zinc oxide (ZnO) are promising energy harvesters that can be adapted to various portable, wearable, self-powered electronic devices. Although ZnO has several advantages for NGs, the piezoelectric semiconductor material ZnO generate an intrinsic piezoelectric potential of a few volts as a result of its mechanical deformation. As grown, ZnO is usually n-type, a property that was historically ascribed to native defects. Oxygen vacancies (Vo) that work as donors exist in ZnO thin film and usually screen some parts of the piezoelectric potential. Consequently, the ZnO NGs' piezoelectric power cannot reach to its theoretical value, and thus decreasing the effect from Vo is essential. In the present study, c-axis oriented insulator-like sputtered ZnO thin films were grown in various temperatures to fabricate an optimized nanogenerator (NGs). The purity and crystalinity of ZnO were investigated with photoluminescence (PL). Moreover, by introducing a p-type polymer usually used in organic solar cell, it was discussed how piezoelectric passivation effect works in ZnO thin films having different types of defects. Prepared ZnO thin films have both Zn vacancies (accepter like) and oxygen vacancies (donor like). It generates output voltage 20 time lager than n-type dominant semiconducting ZnO thin film without p-type polymer conjugating. The enhancement is due to the internal accepter like point defects, zinc vacancies (VZn). When the more VZn concentration increases, the more chances to prevent piezoelectric potential screening effects are occurred, consequently, the output voltage is enhanced. Moreover, by passivating remained effective oxygen vacancies by p-type polymers, we demonstrated further power enhancement.

• Transactions on Electrical and Electronic Materials
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• v.17 no.2
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• pp.113-117
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• 2016

Temperature dependent reverse-bias current-voltage (I-V) characteristics in Cu Schottky contacts to oxygen plasma treated n-InP were investigated. For untreated sample, current transport mechanisms at low and high temperatures were explained by thermionic emission (TE) and TE combined with barrier lowering, respectively. For plasma treated sample, experimental I-V data were explained by TE or TE combined with barrier lowering models at low and high temperatures. However, the current transport was explained by a thermionic field emission (TFE) model at intermediate temperatures. From X-ray photoemission spectroscopy (XPS) measurements, phosphorus vacancies (VP) were suggested to be generated after oxygen plasma treatment. V_P possibly involves defects contributing to the current transport at intermediate temperatures. Therefore, minimizing the generation of these defects after oxygen plasma treatment is required to reduce the reverse-bias leakage current.