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New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.100-101
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    • 2012
  • The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

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Synthesis and Electrochemical Properties of (La0.6Sr0.4)(Co0.2Fe0.8)O3 cathode for SOFC on pH Control Using Modified Oxalate Method (Modified Oxalate Method 의해 합성한 SOFC용(La0.6Sr0.4)(Co0.2Fe0.8)O3 Cathode의 pH 변화에 따른 특성)

  • Lee, Mi-Jai;Choi, Byung-Hyun;Kim, Sei-Ki;Park, Sang-Sun;Lee, Kyung-Hee
    • Journal of the Korean Electrochemical Society
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    • v.10 no.4
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    • pp.288-294
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    • 2007
  • The LSCF cathode far Solid Oxide Fuel Cell was investigated to develop high performance unit cell at intermediate temperature by modified oxalate method with different electrolytes and different pH. The LSCF powders employed La, Sr, Co and Fe oxides, oxalic acid, ethanol and $NH_4OH$ solution were synthesized with pH controlled as 2, 6, 7, 8, 9 and 10 at $80^{\circ}C$ Single crystalline phase was obtained from pH $2{\sim}9$. on the other hand, $La_2O_3$ appeared from pH 10. Very fine powder with particle size of 50 nm was obtained at calcination temperature of $800^{\circ}C$ for 4 hours. LSCF cathode synthesized at pH 7 showed the highest electric conductivity in the temperature range of $600^{\circ}C$ to $900^{\circ}C$ its value was 950 S/cm at $900^{\circ}C$ Under same synthesis conditions, polarization resistance of each LSCF cathode was changed with different calcination temperatures. As-prepared powder presented 2.52, 1.54 and $2.58\;{\Omega}$ at $600^{\circ}C$ with ScSZ, 8Y-YSZ and GDC as its electrolyte respectively after calcination at $800^{\circ}C$ for 4 hours.

Environmental Geochemical Characteristics of the Acid Mine Drainage and Stream Sediments in the Abandoned Honam Coal Mine Area, Korea (호남탄전지역 폐탄광의 산성광산배수와 하상퇴적물의 환경지구화학적 특성)

  • Park, Young-Seog;Kim, Jong-Kyun;Kim, Jin;Jang, Woo-Seog;Lee, Ki-Hyung;Han, Min-Su
    • Economic and Environmental Geology
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    • v.35 no.3
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    • pp.241-255
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    • 2002
  • The purpose of this study is to investigate environmental geochemical characteristics for the acid mine drainage and stream sediments in the abandoned Honam coal mine area. For the chemical analysis, stream winter samples were collected at 54 sites and for the mineralogical and chemical analysis, stream sediments samples were collected at 34 sites. Physical and chemical characteristics of stream water were measured at the site and chemical compositions were analyzed by ICP-AES, ICP-MS and IC. Mineralogical characteristics of stream sediments samples were determined using XRD, SEM and EDS. In physical and chemical properties, stream water shows thats pH 2.85~8.12, Eh -62~215 mV, EC 0.205~146 ms/m, ER 0.234~255 {$\Omega}{\cdot}$m, DO 0.03~1068 mg/L and TDS 10.96~1420mg/L. In chemical compositions, we obtain that K 0.118~3.184 mg/L, Mg 2.1~114.48 mg/L, Ca 2.59~l25.02 mg/L, Al 0.01~44.72 mg/L, Fe 0.108~89.49 mg/L and Na 5.45~125.41 mg/L. Stream sediments are commonly composed of quartz, illite and goethite in the result of x-ray diffraction. After heat treatment at 98$0^{\circ}C$, the hematite peaks are distinctly shown. In consideration of heavy metals (include Fe) for steam sediments, Fe ranges 22575~34713 ppm, Zn 41.66~970.3 ppm, Cd 0.52~52.07 ppm, Cu 1.25~198.5 ppm and Pb 0.43~77.35 ppm.

Effect of In Situ YAG on Microstructure and Properties of the Pressureless-Sintered $SiC-ZrB_2$ Electroconductive Ceramic Composites (상압소결(常壓燒結)한 $SiC-ZrB_2$ 전도성(電導性) 복합체(複合體)의 미세구조(微細構造)와 특성(特性)에 미치는 In Situ YAG의 영향(影響))

  • Shin, Yong-Deok;Ju, Jin-Young
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.55 no.11
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    • pp.505-513
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    • 2006
  • The present study investigated the influence of the content of $Al_2O_3+Y_2O_3$ sintering additives on the microstructure, mechanical and electrical properties of the pressureless-sintered $SiC-ZrB_2$ electroconductive ceramic composites. Phase analysis of composites by XRD revealed mostly of ${\alpha}-SiC(4H),\;ZrB_2,\;{\beta}-SiC(15R)$ and In Situ $YAG(Al_5Y_3O_{12})$. The relative density and the flexural strength showed the highest value of 86.8[%] and 203[Mpa] for $SiC-ZrB_2$ composite with an addition of 8[wt%] $Al_2O_3+Y_2O_3$ as a sintering aid at room temperature respectively. Owing to crack deflection and crack bridging of fracture toughness mechanism, the fracture toughness showed 3.7 and $3.6[MPa{\cdot}m^{1/2}]\;for\;SiC-ZrB_2$ composites with an addition of 8 and 12[wt%] $Al_2O_3+Y_2O_3$ as a sintering aid at room temperature respectively. Abnormal grain growth takes place during phase transformation from ${\beta}-SiC\;into\;{\alpha}-SiC$ was correlated with In Situ YAG phase by reaction between $Al_2O_3\;and\;Y_2O_3$ additives during sintering. The electrical resistivity showed the lowest value of $6.5{\times}10^{-3}[({\Omega}{\cdot}cm]$ for the $SiC-ZrB_2$ composite with an addition of 8[wt%] $Al_2O_3+Y_2O_3$ as a sintering aid at room temperature. The electrical resistivity of the $SiC-ZrB_2$ composites was all positive temperature coefficient(PTCR) in the temperature ranges from $25[^{\circ}C]\;to\;700[^{\circ}C]$. The resistance temperature coefficient showed the highest value of $3.53{\times}10^{-3}/[^{\circ}C]\;for\;SiC-ZrB_2$ composite with an addition of 8[wt%] $Al_2O_3+Y_2O_3$ as a sintering aid in the temperature ranges from $25[^{\circ}C]\;to\;700[^{\circ}C]$. In this paper, it is convinced that ${\beta}-SiC$ based electroconductive ceramic composites for heaters or ignitors can be manufactured by pressureless sintering.

Effect of In Situ YAG on Properties of the Pressureless-Sintered SiC-$ZrB_2$ Electroconductive Ceramic Composites (상압소결(常壓燒結)한 SiC-$ZrB_2$ 전도성(電導性) 복합체(複合體)의 특성(特性)에 미치는 In Situ YAG의 영향(影響))

  • Shin, Yong-Deok;Ju, Jin-Young;Ko, Tae-Hun;Lee, Jung-Hoon
    • The Transactions of The Korean Institute of Electrical Engineers
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    • v.57 no.11
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    • pp.2015-2022
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    • 2008
  • The effect of content of $Al_2O_3+Y_2O_3$ sintering additives on the densification behavior, mechanical and electrical properties of the pressureless-sintered $SiC-ZrB_2$ electroconductive ceramic composites was investigated. The $SiC-ZrB_2$ electroconductive ceramic composites were pressurless-sintered for 2 hours at 1,700[$^{\circ}C$] temperatures with an addition of $Al_2O_3+Y_2O_3$(6 : 4 mixture of $Al_2O_3$ and $Y_2O_3$) as a sintering aid in the range of $8\;{\sim}\;20$[wt%]. Phase analysis of $SiC-ZrB_2$ composites by XRD revealed mostly of $\alpha$-SiC(6H), $ZrB_2$ and In Situ YAG($Al_5Y_3O_{12}$). The relative density, flexural strength, Young's modulus and vicker's hardness showed the highest value of 89.02[%], 81.58[MPa], 31.44[GPa] and 1.34[GPa] for $SiC-ZrB_2$ composites added with 16[wt%] $Al_2O_3+Y_2O_3$ additives at room temperature respectively. Abnormal grain growth takes place during phase transformation from $\beta$-SiC into $\alpha$-SiC was correlated with In Situ YAG phase by reaction between $Al_2O_3$ and $Y_2O_3$ additive during sintering. The electrical resistivity showed the lowest value of $3.l4{\times}10^{-2}{\Omega}{\cdot}cm$ for $SiC-ZrB_2$ composite added with 16[wt%] $Al_2O_3+Y_2O_3$ additives at 700[$^{\circ}C$]. The electrical resistivity of the $SiC-TiB_2$ and $SiC-ZrB_2$ composite was all negative temperature coefficient resistance (NTCR) in the temperature ranges from room temperature to 700[$^{\circ}C$]. Compositional design and optimization of processing parameters are key factors for controlling and improving the properties of SiC-based electroconductive ceramic composites.

Effect of n-6/n-3 fatty acid ratio on lipid metabolism in obesity model rats (n-6/n-3 지방산 비율이 비만 랫드의 지질대사에 미치는 영향)

  • Shin, Jong-Suh;Um, Kyung-Hwan;Park, Byung-Sung
    • Journal of the Korean Applied Science and Technology
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    • v.35 no.3
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    • pp.654-666
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    • 2018
  • This study was determined the effects of dietary omega-6 and 3 fatty acid ratios (n-6/n-3, 0, 4:1, 15:1, 30:1) on lipid metabolism in obese model animal rats. Blood triacylglycerol, total cholesterol, LDL-C, glucose, ALT, AST, insulin, and leptin concentrations in n-6/n-3 group were decreased by 22.21, 20.60, 52.96, 15.71, 11.97, 9.13, 37.57, 45.98%, respectively, while HDL-C and phospholipid concentrations were increased by 28.38, 80.39% respectively, compared with control group, as especially in 4:1 group showed the greatest effect. SREPB-$1{\alpha}$ and SREPB-2 mRNA in liver tissues were down-regulated in n-6/n-3 group, but LPL-mRNA of PPARs in adipose tissue was up-regulated compared with control group. The adipocyte size in liver tissues was decreased in the order of n-6/n-3 ratio of 30:1, control, 15:1 groups, and the adipocyte size in adipose tissues was decreased in the order of n-6/n-3 ratio of control, 30:1, 15:1, 4:1 groups.

Cometabolism of $\omega$-Phenylalkanoic Acids with Butyric Acid for Efficient Production of Aromatic Polyesters in Pseudomonas putida BM01

  • Song, Jae-Jun;Choi, Mun-Hwan;Yoon, Sung-Chul;Huh, Nam-Eung
    • Journal of Microbiology and Biotechnology
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    • v.11 no.3
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    • pp.435-442
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    • 2001
  • Poly(3-hydroxy-5-phenylvalerate) [P(3HPV)] was efficiently accumulated from 5-phenylvalerate (5PV) in Pseudomonas putida BM01 in a mineral salts medium containing butyric acid (BA) as the cosubstrate. A nove aromatic copolyester, poly(5 mol% 3-hydroxy-4-phenylbutyrate-co- 95 mol% 3-hydroxy-6-phenylhexanoate) [P(3HPB-co-3HPC)] was also synthesized from 6-phenylhexanoate (6PC) plus Ba. The two aromatic polymers, P(3HPV) and P(3HPB-co-3HPC), were found to be amorphous and showed different glass-transition temperatures at $15^{\circ}C$ and $10^{\circ}C$, respectively. When the bacterium was grown ina medium containing 20 mM 5PV as the sole carbon source for 140 h, 0.4 g/l of dry cells was obtained in a flask cultivation and 20 wt% of P(3HPV) homopolymer was accumulated in the cells. However, when it was grown with a mixture of 2 mM 5PV and 50 mM BA for 40 h, the yield of dry biomass was increased up to 2.5 g/l and the content of P(3HPV) in the dry cells was optimally 56 wt%. This efficient production of P(3HPV) homopolymer from the mixed substrate was feasible because BA only supported cell growth and did not induce any aliphatic PHA accumulation. The metabolites released into the PHA synthesis medium were analyzed using GC or GC/MS. Two $\beta$-oxidation derivatives, 3-phenylpropionic acid and trans-cinnamic acid, were found in the 5V-grown cell medium and these comprised 55-88 mol% of the 5PV consumed. In the 6PC-grown medium containing Ba, seven ${\beta}$-oxidation and related intermediates were found, which included phenylacetic acid, 4-phenylbutyric acid, cis-4-phenyl-2-butenoic acid, trans-4-phenyl-3-butenoic acid, trans-4-phenyl-2-butenoic acid, 3-hydroxy-4-phenylbutyric acid, and 3-hydroxy-6-phenylhexanoic acid. Accordingly, based on the metabolite analysis, PHA synthesis pathways from the two aromatic carbon sources are suggested.

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Effect of Annealing Temperature on Microstructure and Properties of the Pressureless-Sintered $SiC-ZrB_2$ Electroconductive Ceramic Composites (상압소결(常壓燒結)한 $SiC-ZrB_2$ 전도성(電導性) 복합체(複合體)의 미세구조(微細構造)와 특성(特性)에 미치는 Annealing 온도(溫度)의 영향(影響))

  • Shin, Yong-Deok;Ju, Jin-Young
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.55 no.9
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    • pp.434-441
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    • 2006
  • The effect of pressureless-sintered temperature on the densification behavior, mechanical and electrical properties of the $SiC-ZrB_2$ electroconductive ceramic composites was investigated. The $SiC-ZrB_2$ electroconductive ceramic composites were pressureless-sintered for 2 hours at temperatures in the range of $1,750{\sim}1,900[^{\circ}C]$, with an addition of 12[wt%] of $Al_2O_3+Y_2O_3$(6:4 mixture of $Al_2O_3\;and\;Y_2O_3$) as a sintering aid. The relative density and mechanical properties are increased markedly at temperatures in the range of $1,850{\sim}1,900[{^\circ}C]$. The relative density, flexural strength, vicker's hardness and fracture toughness showed the highest value of 81.1[%], 230[MPa], 9.88[GPa] and $6.05[MPa\;m^{1/2}]$ for $SiC-ZrB_2$ composites of $1,900[{^\circ}C]$ sintering temperature at room temperature respectively. The electrical resistivity was measured by the Pauw method in the temperature ranges from $25[{^\circ}C]\;to\;700[{^\circ}C]$, The electrical resistivity showed the value of $1.36{\times}10^{-4},\;3.83{\times}10^{-4},\;3.51{\times}10^{-4}\;and\; 3.2{\times}10^{-4}[{\Omega}{\cdot}cm]$ for SZ1750, SZ1800, SZ1850 and SZ1900 respectively at room temperature. The electrical resistivity of the composites was all PTCR(Positive Temperature Coefficient Resistivity). The resistance temperature coefficient showed the value of $4.194{\times}10^{-3},\;3,740{\times}10^{-3},\;2,993{\times}10^{-3},\;3,472{\times}10^{-3}/[^{\circ}C}$ for SZ1750, SZ1800, SZ1850 and SZ1900 respectively in the temperature ranges from $25[{\circ}C]\;to\;700[{\circ}C]$, It is assumed that because polycrystallines such as recrystallized $SiC-ZrB_2$ electroconductive ceramic composites, contain of porosity and In Situ $YAG(Al_5Y_3O_{12})$ crystal grain boundaries, their electrical conduction mechanism are complicated. In addition, because the condition of such grain boundaries due to $Al_2O_3+Y_2O_3$ additives widely varies with sintering temperature, electrical resistivity of the $SiC-ZrB_2$ electroconductive ceramic composites with sintering temperature also varies with sintering condition. It is convinced that ${\beta}-SiC$ based electroconductive ceramic composites for heaters or ignitors can be manufactured by pressureless sintering.

Effects of In Situ YAG on Properties of the Pressurless Annealed Sic-$TiB_2$ Electroconductive Ceramic Composites (무가압 어닐드한 Sic-$TiB_2$ 전도성 복합체의 특성에 미치는 In Situ YAG의 영향)

  • Shin, Yong-Deok;Ju, Jin-Young;Ko, Tae-Hun
    • The Transactions of The Korean Institute of Electrical Engineers
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    • v.57 no.5
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    • pp.808-815
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    • 2008
  • The composites were fabricated 61[vol.%] ${\beta}$-SiC and 39[vol.%] $TiB_2$ powders with the liquid forming additives of 8, 12, 16[wt%] $Al_2O_3+Y_2O_3$ as a sintering aid by pressureless annealing at 1650[$^{\circ}C$] for 4 hours. The present study investigated the influence of the content of $Al_2O_3+Y_2O_3$ sintering additives on the microstructure, mechanical and electrical properties of the pressureless annealed SiC-$TiB_2$ electroconductive ceramic composites. Reactions between SiC and transition metal $TiB_2$ were not observed in the microstructure and the phase analysis of the pressureless annealed SiC-$TiB_2$ electroconductive ceramic composites. Phase analysis of SiC-$TiB_2$ composites by XRD revealed mostly of ${\alpha}$-SiC(6H), ${\beta}$-SiC(3C), $TiB_2$, and In Situ YAG($Al_2Y_3O_{12}$). The relative density of SiC-$TiB_2$ composites was lowered due to gaseous products of the result of reaction between SiC and $Al_2O_3+Y_2O_3$. There is another reason which pressureless annealed temperature 1650[$^{\circ}C$] is lower $300{\sim}450[^{\circ}C]$ than applied pressure sintering temperature $1950{\sim}2100[^{\circ}C]$. The relative density, the flexural strength, the Young's modulus and the Vicker's hardness showed the highest value of 82.29[%], 189.5[Mpa], 54.60[Gpa] and 2.84[Gpa] for SiC-$TiB_2$ composites added with 16[wt%] $Al_2O_3+Y_2O_3$ additives at room temperature. Abnormal grain growth takes place during phase transformation from ${\beta}$-SiC into ${\alpha}$-SiC was correlated with In Situ YAG phase by reaction between $Al_2O_3$ and $Y_2O_3$ additive during sintering. The electrical resistivity showed the lowest value of 0.0117[${\Omega}{\cdot}cm$] for 16[wt%] $Al_2O_3+Y_2O_3$ additives at 25[$^{\circ}C$]. The electrical resistivity was all negative temperature coefficient resistance (NTCR) in the temperature ranges from $25^{\circ}C$ to 700[$^{\circ}C$]. The resistance temperature coefficient of composite showed the lowest value of $-2.3{\times}10^{-3}[^{\circ}C]^{-1}$ for 16[wt%] additives in the temperature ranges from 25[$^{\circ}C$] to 100[$^{\circ}C$].

Synthesis, crystal structure, and thermal property of piperazine-templated copper(II) sulfate, {H2NCH2CH2NH2CH2CH2}{Cu(H2O)6}(SO4)2

  • Kim, Chong-Hyeak;Park, Chan-Jo;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.18 no.5
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    • pp.381-385
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    • 2005
  • The title compound, $\{H_2NCH_2CH_2NH_2CH_2CH_2\}\{Cu(H_2O)_6\}(SO_4)_2$, I, has been synthesized under solvo/hydrothermal conditions and their crystal structure analyzed by X-ray single crystallography. Compound I crystallizes in the monoclinic system, $P2_1/n$ space group with a = 6.852(1), b = 10.160(2), $c=11.893(1){\AA}$, ${\beta}=92.928(8)^{\circ}$, $V=826.9(2){\AA}^3$, Z = 2, $D_x=1.815g/cm^3$, $R_1=0.031$ and ${\omega}R_2=0.084$. The crystal structure of the piperazine templated Cu(II)-sulfate demonstrate zero-dimensional compound constituted by doubly protonated piperazine cations, hexahydrated copper cations and sulfate anions. The central Cu atom has a elongated octahedral coordination geometry. The crystal structure is stabilized by three-dimensional networks of the intermolecular $O_{water}-H{\cdots}O_{sulfate}$ and $N_{pip}-H{\cdots}O_{sulfate}$ hydrogen bonds between the water molecules and sulfate anions and protonated piperazine cations. Based on the results of thermal analysis, the thermal decomposition reaction of compound I was analyzed to have three distinctive stages.