• Journal of the Korean Vacuum Society
• /
• v.15 no.5
• /
• pp.527-533
• /
• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• Journal of the Korean Society of Food Science and Nutrition
• /
• v.31 no.4
• /
• pp.609-614
• /
• 2002

The characteristics of thermoluminescence (TL) and electron spin resonance (ESR) and organoleptic qualities of gamma-irradiated raisin and dried banana were investigated during storage at 4$^{\circ}C$ for 6 months. The minerals separated from non-irradiated raisins showed TL glow curve (TL$_1$) with very low intensity around 200~30$0^{\circ}C$, while the irradiated samples at 1 kGy or more showed glow curves with higher intensity around 18$0^{\circ}C$, with linear increase by irradiation dose ($R^2$=0.9684), which made it possible to identify irradiated samples during 6 months. Moreover, TL ratios (TL$_1$/TL$_2$) through the reirradiation step at 1 kGy enhanced confidence in the identification of irradiated raisins. The ESR signals of multicomponent lines resulted from crystalline sugar radicals were shown in irradiated banana, identifying irradiated samples. The ESR signal intensity was dependent on irradiation doses ($R^2$=0.8977) and the signals were stable enough to be detected by 6th month after storage. Considering tile marketability of irradiated dried fruits during 6 months at low temperature TL and ESR analyses were shown suitable for the identification of irradiated raisins and dried banana, respectively.

• Journal of the Korean Chemical Society
• /
• v.28 no.6
• /
• pp.384-392
• /
• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Korean Journal of Food Science and Technology
• /
• v.44 no.6
• /
• pp.673-679
• /
• 2012

Ten commercially available red pepper powders were investigated using photostimulated-luminescence (PSL), thermoluminescence (TL) and electron spin resonance (ESR) analyses to confirm their irradiation status. The application of PSL, TL, and ESR analyses was also confirmed by in-house irradiation. In PSL-based screening, all samples gave negative photon counts (<700 PCs). The PSL calibration dose (1 kGy) showed a low sensitivity of 4 samples, while the others provided reliable screening results. TL glow curves demonstrated maximum peaks after $250^{\circ}C$ for the 6 samples; however 4 samples gave complex TL glow curves with maximum peaks in the range of $185-260^{\circ}C$ (radiation-specific), which could be the effect of an irradiated component in low concentration as the TL ratios of all samples were <0.1. Radiation-specific ESR features were absent in the all commercial samples. Variable irradiation detection properties were found; where the TL analysis showed the possible presence of an irradiated component in 4 samples requiring further monitoring and investigation.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.4
• /
• pp.439-444
• /
• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.90.1-90.1
• /
• 2010

Due to the rapidly diminishing energy sources and higher energy production cost, the interest in dye-sensitized solar cells (DSSCs) has been increasing dramatically in recent years. A typical DSSC is constructed of wide band gap semiconductor electrode such as $TiO_2$ or ZnO that are anchored by light-harvesting sensitizer dyes and surrounded by a liquid electrolyte with a iodide ion/triiodide ion redox couple. DSSCs based on one-dimensional nano-structures, such as ZnO nanorods, have been recently attracting increasing attention due to their excellent electrical conductivity, high optical transmittance, diverse and abundant configurations, direct band gap, absence of toxicity, large exiton binding energy, etc. However, solar-to-electrical conversion performances of DSSCs composed of ZnO n-type photo electrode compared with that of $TiO_2$ are not satisfactory. An important reason for the low photovoltaic performance is the dissolution of $Zn^{2+}$ by the adsorption of acidic dye followed by the formation of agglomerates with dye molecules which could block the I-diffusion pathway into the dye molecule on the ZnO surface. In this paper, we prepared the DSSC with the ZnO electrode using the chemical bath deposition (CBD) method under low temperature condition (< $100^{\circ}C$). It was demonstrated that the ZnO seed layers played an important role on the formation of the ZnO nanostructures using CBD. To achieve truly low-temperature growth of the ZnO nanostructures on the substrates, a two-step method was developed and optimized in the present work. Firstly, ZnO seed layer was prepared on the FTO substrate through the spin-coating method. Secondly, the deposited ZnO seed substrate was immersed into an aqueous solution of 0.25M zinc nitrate hexahydrate and 0.25M hexamethylenetetramine at $90^{\circ}C$ for hydrothermal reaction several times.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2016.02a
• /
• pp.416-416
• /
• 2016

Organic-inorganic metal halide perovskite solar cells have received attention because it has a number of advantages with excellent light harvesting, high carrier mobility, and facile solution processability and also recorded recently power conversion efficiency (PCEs) of over 20%. The major issue on perovskite solar cells have been reached the limit of small area laboratory scale devices produced using fabrication techniques such as spin coating and physical vapor deposition which are incompatible with low-cost and large area fabrication of perovskite solar cells using printing and coating techniques. To solution these problems, we have investigated the feasibility of achieving fully printable perovskite solar cells by the blade-coating technique. The blade-coating fabrication has been widely used to fabricate organic solar cells (OSCs) and is proven to be a simple, environment-friendly, and low-cost method for the solution-processed photovoltaic. Moreover, the film morphology control in the blade-coating method is much easier than the spray coating and roll-to-roll printing; high-quality photoactive layers with controllable thickness can be performed by using a precisely polished blade with low surface roughness and coating gap control between blade and coating substrate[1]. In order to fabricate perovskite devices with good efficiency, one of the main factors in printed electronic processing is the fabrication of thin films with controlled morphology, high surface coverage and minimum pinholes for high performance, printed thin film perovskite solar cells. Charge dissociation efficiency, charge transport and diffusion length of charge species are dependent on the crystallinity of the film [2]. We fabricated the printed perovskite solar cells with large area and flexible by the bar-coating. The morphology of printed film could be closely related with the condition of the bar-coating technique such as coating speed, concentration and amount of solution, drying condition, and suitable film thickness was also studied by using the optical analysis with SEM. Electrical performance of printed devices is gives hysteresis and efficiency distribution.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2009.11a
• /
• pp.36.2-36.2
• /
• 2009

Low dielectric materials have been great attention in the semiconductor industry to develop high performance interlayer dielectrics with low k for Cu interconnect technology. In our study, the dielectric properties of SiOC /SiO2 thin film derived from polyphenylcarbosilane were investigated as a potential interlayer dielectrics for Cu interconnect technology. Polyphenylcarbosilane was synthesized from thermal rearrangement of polymethylphenylsilane around $350^{\circ}C{\sim}430^{\circ}C$. Characterization of synthesized polyphenylcarbosilane was performed with 29Si, 13C, 1H NMR, FT-IR, TG, XRD, GPC and GC analysis. From FT-IR data, the band at 1035 cm-1 is very strong and assigned to CH2 bending vibration in Si-CH2-Si group, indicating the formation of the polyphenylcarbosilane. Number average of molecular weight (Mn) of the polyphenylcarbosilane synthesized at $400^{\circ}C$ for 6hwas 2, 500 and is easily soluble in organic solvent. SiOC/SiO2 thin film was fabricated on ton-type silicon wafer by spin coating using 30wt % polyphenylcarbosilane incyclohexane. Curing of the film was performed in the air up to $400^{\circ}C$ for 2h. The thickness of the film is ranged from $1{\mu}m$ to $1.7{\mu}m$. The dielectric constant was determined from the capacitance data obtained from metal/polyphenylcarbosilane/conductive Si MIM capacitors and show a dielectric constant as low as 2.5 without added porosity. The SiOC /SiO2 thin film derived from polyphenylcarbosilane shows promising application as an interlayer dielectrics for Cu interconnect technology.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.2
• /
• pp.281-285
• /
• 2002

The photophysical properties and the singlet oxygen generation efficiencies of meso-tetraphenyl-trithiasapphyrin $(S_3TPS)$ and meso-tetmkis(p-methoxy phenyl)-trithiasapphy rin ((p-MeO)-$S_3TPS$) have been investigated, utilizing steady-state and time-resolved spectroscopic methods to elucidate the possibility of their use as photosensitizers for photodynamic therapy (PDT). The observed photophysical properties were compared with those of other porphyrin-like photosensitizers in geometrical and electronic structural aspects, such as extended ${\pi}$ conjugation, structural distortion, and internal heavy atoms. The steady-state electronic absorption and fluorescence spectra were both red-shifted due to the extended ${\pi}$-conjugation. The fluorescence quantum yields were measured as very small. Even though intersystem crossing rates were expected to increase due to the increment of spin orbital coupling, the triplet quantum yields were measured as less than 0.15. Such characteristics can be ascribed to the more enhanced internal conversion rates compared with the intersystem crossing rates. Furthermore, the triplet state lifetimes were shortened to -1.0 ${\mu}s$ as expected. Therefore, the singlet oxygen quantum yields were estimated to be near zero due to the fast triplet state decay rates and the inefficient energy transfer to the oxygen molecule as well as the low triplet quantum yields. The low efficiencies of energy transfer to the oxygen molecule can be attributed to the lower oxidation potential and/or the energetically low lying triplet state. Such photophysical factors should be carefully evaluated as potential photosensitizers that have extended ${\pi}$-conjugation and heavy core atoms synthesized for red-shifted absorption and high triplet state quantum yields.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 2016.11a
• /
• pp.181-181
• /
• 2016

Hydrogenated microcrystalline silicon (${\mu}c-Si:H$) films have attracted much attention as materials of the bottom-cells in Si thin film tandem photovoltaics due to their low bandgap and excellent stability against light soaking. However, in PECVD, the source gas $SiH_4$ must be highly diluted by $H_2$, which eventually results in low deposition rate. Moreover, it is known that high-rate ${\mu}c-Si:H$ growth is usually accompanied by a large number of dangling-bond (DB) defects in the resulting films, which act as recombination centers for photoexcited carriers, leading to a deterioration in the device performance. During film deposition, Si nanoparticles generated in $SiH_4$ discharges can be incorporated into films, and such incorporation may have effects on film properties depending on the size, structure, and volume fraction of nanoparticles incorporated into films. Here we report experimental results on the effects of nonoparticles incorporation at the different substrate temperature studied using a multi-hollow discharge plasma CVD method in which such incorporation can be significantly suppressed in upstream region by setting the gas flow velocity high enough to drive nanoparticles toward the downstream region. All experiments were performed with the multi-hollow discharge plasma CVD reactor at RT, 100, and $250^{\circ}C$, respectively. The gas flow rate ratio of $SiH_4$ to $H_2$ was 0.997. The total gas pressure P was kept at 2 Torr. The discharge frequency and power were 60 MHz, 180 W, respectively. Crystallinity Xc of resulting films was evaluated using Raman spectra. The defect densities of the films were measured with electron spin resonance (ESR). The defect density of fims deposited in the downstream region (with nonoparticles) is higher defect density than that in the upstream region (without nanoparticles) at low substrate temperature of RT and $100^{\circ}C$. This result indicates that nanoparticle incorporation can change considerably their film properties depending on the substrate temperature.