• Proceedings of the Korea Association of Crystal Growth Conference
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• 1996.06a
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• pp.258-292
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• 1996

In the last year great interest appears to YBCO thin films preparation on different substrate materials. Preparation of epitaxial film is a very difficult problem. There are many requirements to substrate materials that must be fullfilled. Main problems are lattice mismatch (misfit) and similarity of structure. From paper [1] or follows that difference in interatomic distances and angles of substrate and film is mire important problem than similarity of structure. In this work we present interatomic distances and angle relations between substrate materials belonging to ABCO4 group (where A-Sr or Ca, B-rare earth element, C-Al or Ga) of different orientations and YBCO thin films. There are many materials used as substrates for HTsC thin films. ABCO4 group of compounds is characterized by small dielectric constants (it is necessary for microwave applications of HTsC films), absence of twins and small misfit [2]. There most interesting compounds CaNdAlO4, SrLaAlO4 and SrLaGaO4 were investigated. All these compounds are of pseudo-perovskite structure with space group 14/mmm. This structure is very similar to structure of YBCO. SLG substrate has the lowest misfit (0.3%) and dielectric constant. For preparation of then films of substrates of this group of compound plane of <100> orientation are mainly used. Good quality films of <001> orientations are obtained [3]. In this case not only a-a misfit play role, but c-3b misfit is very important too. Sometimes, for preparation of thin films substrates of <001> and <110> orientations were manufactured [3]. Different misfits for different YBCO faces have been analyzed. It has been found that the mismatching factor for (100) face is very similar to that for (001) face so there is possibility of preparation of thin films on both orientations. SrLaAlO4(SLA) and SrLaGaO4(SLG) crystals of general formula ABCO4 have been grown by the Czochralski method. The quality of SLA and SLG crystals strongly depends on axial gradient of temperature and growth and rotation rates. High quality crystals were obtained at axial gradient of temperature near crystal-melt interface lower than 50℃/cm, growth rate 1-3 mm/h and the rotation rate changing from 10-20pm[4]. Strong anisotropy in morphology of SLA and SLG single crystals grown by the Czochralski method is clearly visible. On the basics of our considerations for ABCO4 type of the tetragonal crystals there can appear {001}, {101}, and {110} faces for ionic type model [5]. Morphology of these crystals depend on ionic-covalent character of bonding and crystal growth parameters. Point defects are observed in crystals and they are reflected in color changes (colorless, yellow, green). Point defects are detected in directions perpendicular to oxide planes and are connected with instability of oxygen position in lattice. To investigate facets formations crystals were doped with Cr3+, Er3+, Pr3+, Ba2+. Chromium greater size ion which is substituted for Al3+ clearly induces faceting. There appear easy {110} faces and SLA crystals crack even then the amount of Cr is below 0.3at.% SLG single crystals are not so sensitive to the content of chromium ions. It was also found that if {110} face appears at the beginning of growth process the crystal changes its color on the plane {110} but it happens only on the shoulder part. The projection of {110} face has a great amount of oxygen positions which can be easy defected. Pure and doped SLA and SLG crystals measured by EPR in the<110> direction show more intensive lines than in other directions which allows to suggest that the amount of oxygen defects on the {110} plane is higher. In order to find the origin of colors and their relation with the crystal stability, a set of SLA and SLG crystals were investigated using optical spectroscopy. The colored samples exhibit an absorption band stretching from the UV absorption edge of the crystal, from about 240 nm to about 550 m. In the case of colorless sample, the absorption spectrum consists of a relatively weak band in the UV region. The spectral position and intensities of absorption bands of SLA are typical for imperfection similar to color centers which may be created in most of oxide crystals by UV and X-radiation. It is pointed out that crystal growth process of polycomponent oxide crystals by Czochralski method depends on the preparation of melt and its stoichiometry, orientation of seed, gradient of temperature at crystal-melt interface, parameters of growth (rotation and pulling rate) and control of red-ox atmosphere during seeding and growth (rotation and pulling rate) and control of red-ox atmosphere during seeding and growth. Growth parameters have an influence on the morphology of crystal-melt interface, type and concentration of defects.

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.477-483
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• 2008

$La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ oxide was synthesized by a citrate method and a typical dense membrane of perovskite oxide has been prepared using as-prepared powder by pressing and sintering at $1300^{\circ}C$. Precursor of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ prepared by citrate method was investigated by TGA and XRD. Metal-citrate complex in precursor was decomposed into perovskite oxide in the temperature range of $260{\sim}410^{\circ}C$ but XRD results showed $SrCO_3$ existed as impurity at less than $900^{\circ}C$. Electrical conductivity of membrane increased with increasing temperature but then decreased over $700^{\circ}C$ in air atmosphere ($Po_2=0.2atm$) and $600^{\circ}C$ in He atmosphere ($Po_2=0.01atm$) respectively due to oxygen loss from the crystal lattice. The oxygen permeation flux increased with increasing temperature and maximum oxygen permeation flux of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ membrane with 1.6 mm thickness was about $0.31cm^3/cm^2{\cdot}min$ at $950^{\circ}C$. The activation energy for oxygen permeation was 88.4 kJ/mol in the temperature range of $750{\sim}950^{\circ}C$. Perovskite structure of membrane was not changed after permeation test of 40 h and the membrane was stable without secondary phase change with 0.3 mol Sr addition.

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.553-558
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• 2003

The crystal structure of $[n-Bu_4N]_2[Mo_6O_{19}]$(TBAM) (n-Bu4N=tetrabutylammonium) has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group C2/c, with lattice parameters ${\alpha}$=16.314(5), b=17.288(5), c=17.776(4)${\AA}$ ${\beta}$=101.47(3), and Z=4. In $[Mo_6O{19}]^{2-}$ anion, Mo atoms occupy six vertices of octahedron and each Mo atom is coordinated by six oxygen atoms to adopt distorted octahedral coordination geometry. The average bond distance of Mo-Ot (terminal), Mo-Ob (bridged) and Mo-Oc (central) are 1.680 ${\AA}$, 1.931 ${\AA}$ and 2.325 ${\AA}$ respectively. In $[n-Bu_4N]^+$ cation, the N atom possesses a slightly distorted tetrahedral geometry. There are some potential extensive C-H ${\cdots}$ O hydrogen bonds in the lattice, by which connecte molecules and stabilize the crystal structure. Thermogravimetric analysis suggests that thermal decomposition of the title compound includes two transitions and it loses weight at 356.0 and 803.5 $^{\circ}$, respectively, and the residue presumable be $Mo_2O_2$. Accordingly, the title compound has high thermal stability.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.491-497
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• 1987

$ThO_2-Tm_2O_3$ (TDT) solid solutions containing 1,3,5,8,10, and 15 mol% $Tm_2O_3$ were synthesized from spectroscopically pure $ThO_2$ and $Tm_2O_3$ polycrystalline powders. The TDT solid solutions were indentified to the fluorite structure by the X-ray powder technique. The values of the lattice parameter were decreased with increasing amount of $Tm_2O_3$ incorporated. But, there was no linearity for the samples containing 8, 10, and 15 mol% $Tm_2O_3$. It was concluded that these samples became incomplete solid solutions. From the intensity analyses of X-ray diffraction patterns, the residual factor was found below 0.13 even for the 15 mol% TDT system. lt was confirmed from the DTA and TGA analyses that any phase transitions did not occur under the experimental condition executed. Comparing the pycnometric density with the lattice parameter obtained from XRD, it was suggested that the predominant defect model be an oxygen vacancy.

• Korean Journal of Materials Research
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• v.9 no.3
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• pp.234-239
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• 1999

A Abstract Yttria-stabilized zirconia(YSZ) thin films were synthesized by plasma enhanced chemical vapor deposition process. $Zr[TMHD]_4$ $Y[TMHD]_3$ precursors and oxygen were used with the deposition temperature of $425^{\circ}C$ and rf power ranging 0-100 watt. Effects of the deposition parameters were studied by X-ray diffraction and thickness anal­ysis. YSZ thin films have cubic crystal structure with (200) orientation. From the results of EDX analysis, the converte ed content of TEX>$Y_2O_3$ was determined to be 0-36%, and the film thickness was increased with bubbling temperature which is considered to be due to increasing TEX>$Y_2O_3$ flux. The depth profiles of Zr, Y and 0 appeared relatively $\infty$nstant through film thickness. Columnar grains of $1000~2000\AA$ grew vertical to the substrate surface for the case of Ar carri­er gas. In case of He carrier gas, the grain size was observed to be about $1000~2000\AA$. X-ray diffraction data showed the increase of lattice constant with TEX>$Y_2O_3$ content. It was that the presence of the cracks formed during film deposition, partially released the stress generated by the increase of lattice constant.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.36 no.3
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• pp.249-254
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• 2023

La_0.7-xCe_xSr_0.3MnO₃ specimens were fabricated by a solid state reaction method and structural and electrical properties with variation of Ce⁴⁺ contents were measured. All specimens exhibited a polycrystalline rhombohedral crystal structure, and the (110) peaks were shifted to low angle side with increasing the amount of Ce⁴⁺ contents. As Ce⁴⁺ ions with different ion radii and charges are substituted with La³⁺ ions, electrical properties are thought to be affected by changes in the double exchange interaction between Mn³⁺-Mn⁴⁺ ions due to distortion of the unit lattice, a decrease in oxygen vacancy concentration, and an increase in lattice defects. Resistivity gradually decrease as the amount of Ce⁴⁺ added increased, and negative temperature coefficient of resistance (NTCR) properties were shown in all specimens. In the La_0.5Ce_0.2Sr_0.3MnO₃ specimens, electrical resistivity, TCR and B-value were 31.8 Ω-cm, 0.55%/℃ and 605 K, respectively.

• Journal of the Microelectronics and Packaging Society
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• v.30 no.3
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• pp.94-101
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• 2023

Zinc oxide(ZnO) is a semiconductor material with a bandgap of 3.37 eV and an exciton binding energy of 60 meV for various applications. Recently ZnO has been proven to enhance its electrical properties for utilization as an alternative for transparent conducting oxide (TCO) materials. In this study, cation(Al, Ga)-anion(F) single and double doped ZnO thin films were grown by atomic layer deposition (ALD) to enhance the electrical properties. The structural and optical properties of doped ZnO thin films were analyzed, and doping effects were confirmed to electrical characteristics. In single doped ZnO, it was observed that the carrier concentration was increased after doping, acting as a donor to ZnO. Among the single doping elements, F doped ZnO(FZO) showed the highest mobility and conductivity due to the passivation effect of oxygen vacancies. In the case of double doping, higher electrical characteristics were observed compared to single doping. Among the samples, Al-F doped ZnO(AFZO) exhibited the lowest resistance value. This results can be attributed to an increase in delocalized electron states and a decrease in lattice distortion resulting from the differences in ionic radius. The partial density of states(PDOS) was also analyzed and observed to be consistent with the experimental results.

• Korean Journal of Materials Research
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• v.4 no.8
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• pp.934-944
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• 1994

Effects of residual chloride on thermal decomposition behaviour of a-stannic acid and physical properties of $SnO_{2}$ powder were observed. The powder was fabricated by hydroxide method; $\alpha$-stannic acid was precipitated by mixing acqueous solutions of $SnCl_{4}$ and $NH_{4}$OH . The precipitate was washed with $NH_{4}NO_{3}$ solution while washing was controlled to be of three grades to modify its residual chloride content. The precipitate was dried at $1100^{\circ}C$ ~ 24h and calcined in air at $500^{\circ}C$ ~ $1100^{\circ}C$ for one hour. Thermal decomposition behaviour of $\alpha$-stannic acid was examined by a DT-TGA and a FTIR. Chemical composition and physical properties of $SnO_{2}$ powder were observed by an AES, a BET and a TEM, respectively. With a reduction in chloride content, the relative crystallite size of $SnO_{2}$ powder slightly increased by a low-temperature-calcining. However, at a high calcining temperature(T), the reverse relation occured. It was suggested that chloride ion replaces part of lattice oxygen site of a-stannic acid. Also, chloride ion on the site was suggested to retard de-hydration as well as crystalization at a low T while to promote crystal growth of $SnO_{2}$ by forming oxygen vacancy at a high T.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.327-327
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• 2009

ZnO with a large band gap (~3.37 eV) and exciton binding energy (~60 meV), is suitable for optoelectronic applications such as ultraviolet (UV) light emitting diodes (LEDs) and detectors. However, the ZnO-based p-n homojunction is not readily available because it is difficult to fabricate reproducible p-type ZnO with high hall concentration and mobility. In order to solve this problem, there have been numerous attempts to develop p-n heterojunction LEDs with ZnO as the n-type layer. The n-ZnO/p-GaN heterostructure is a good candidate for ZnO-based heterojunction LEDs because of their similar physical properties and the reproducible availability of p-type GaN. Especially, the reduced lattice mismatch (~1.8 %) and similar crystal structure result in the advantage of acquiring high performance LED devices. In particular, a number of ZnO films show UV band-edge emission with visible deep-level emission, which is originated from point defects such as oxygen vacancy, oxygen interstitial, zinc interstitial[1]. Thus, defect-related peak positions can be controlled by variation of growth or annealing conditions. In this work, the undoped ZnO film was grown on the p-GaN:Mg film using RF magnetron sputtering method. The undoped ZnO/p-GaN:Mg heterojunctions were annealed in a horizontal tube furnace. The annealing process was performed at $800^{\circ}C$ during 30 to 90 min in air ambient to observe the variation of the defect states in the ZnO film. Photoluminescence measurements were performed in order to confirm the deep-level position of the ZnO film. As a result, the deep-level emission showed orange-red color in the as-deposited film, while the defect-related peak positions of annealed films were shifted to greenish side as increasing annealing time. Furthermore, the electrical resistivity of the ZnO film was decreased after annealing process. The I-V characteristic of the LEDs showed nonlinear and rectifying behavior. The room-temperature electroluminescence (EL) was observed under forward bias. The EL showed a weak white and strong yellowish emission colors (~575 nm) in the undoped ZnO/p-GaN:Mg heterojunctions before and after annealing process, respectively.

• Applied Chemistry for Engineering
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• v.30 no.6
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• pp.757-761
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• 2019

The catalytic yields of POM to hydrogen over M(1)-Ni(5)/AlCeO₃ (M = La, Ce, Y) were investigated using a fixed bed flow reactor under atmosphere. The crystal phase behavior of reduced La(1)-Ni(5)/AlCeO₃ catalysts before and after the reaction were studied via XRD analysis. FESEM and EDS analyses were further performed to show the uniformed distribution of La, Ni, and Ce metal particles on the catalyst surface. XPS results showed O^2-, O₂^2- species and metal ions such as Ce³⁺, Ce⁴⁺, La³⁺ and Ni²⁺ etc. were on the catalyst surface. When 1 wt% of La was added to Ni(5)/AlCeO₃ catalyst, Ni2p_3/2 and Ce3d_5/2 increased 52.7 and 6.3%, respectively. The yield of hydrogen on the La(1)-Ni(5)/AlCeO₃ catalyst was 89.1%, which was much better than that of M(1)-Ni(5)/AlCeO₃ (M = Ce, Y). As Ce⁴⁺ ions of CeO₂ produced by the reaction of AlCeO₃ with oxygen were substitute to La³⁺, it made oxygen vacancies in the lattice and further improved the hydrogen yield by increasing the dispersion of Ni atoms with strong metal-support interaction (SMSI) effect.