분무열분해법으로 CeO2:Er/Yb 형광체 제조 및 발광특성 최적화

정경열 ( Kyeong Youl Jung ),박재훈 ( Jea Hoon Park ),송신애 ( Shin Ae Song ) 한국공업화학회 2015 공업화학 Vol.26 No.3

Submicron-sized CeO2:Er3+/Yb3+ upconversion phosphor particles were synthesized by spray pyrolysis, and their luminescent properties were characterized by changing the concentration of Er3+ and Yb3+. CeO2:Er3+/Yb3+ showed an intense green and red emission due to the 4S3/2 or 2H11/2 → 4I15/2 and 4F9/2 → 4I15/2 transition of Er3+ ions, respectively. In terms of the emission intensity, the optimal concentrations of Er and Yb were 1.0 % and 2.0%, respectively, and the concentration quenching was found to occur via the dipole-dipole interaction. Upconversion mechanism was discussed by using the dependency of emission intensities on pumping powers and considering the dominant depletion processes of intermediate energy levels for the red and green emission with changing the Er3+ concentration. An energy transfer from Yb3+ to Er3+ in CeO2 host was mainly involved in ground-state absorption (GSA), and non-radiative relaxation from 4I11/2 to 4I13/2 of Er3+ was accelerated by the Yb3+ co-doping. As a result, the Yb3+ co-doping led to greatly enhance the upconversion intensity with increasing ratios of the red to green emission. Finally, it is revealed that the upconversion emission is achieved by two photon processes in which the linear decay dominates the depletion of intermediate energy levels for green and red emissions for CeO2:Er3+/Yb3+ phosphor.

분무열분해법으로 제조된 SrAl2O4:Ho3+ 녹색 형광체의 발광특성

정경열 ( Kyeong Youl Jung ),김우현 ( Woo Hyun Kim ) 한국화학공학회 2015 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.53 No.5

Ho3+가 도핑된 SrAl2O4 상향전환 형광체 분말을 분무열분해법으로 제조하고 활성제의 농도, 후 열처리 온도 변화에 따른 결정학적 구조와 발광 특성을 조사하였다. 또한 유기 첨가제 사용에 따른 형광체의 결정구조, 표면적 및 휘도 변화를 조사하였다. SrAl2O4:Ho3+는 Ho3+의 5F4/5S2→5I8 전이에 기인한 강한 녹색 발광을 보였다. 가장 높은 발광 강도를 보이는 Ho3+ 농도는 0.1%였고, 그 이상의 농도에서는 활성 이온간 쌍극자-쌍극자 상호 작용에 의에 농도소강이 일어나 발광 휘도는 급격히 감소하였다. 여기 광원의 전력 세기에 따른 발광 휘도 변화 관찰로부터 SrAl2O4:Ho3+의 녹색발광은 2광자가 관여된 바닥상태흡수-여기상태흡수 과정을 통해 효율적으로 일어남이 확인되었다. 합성된 분말의 주상은 단사정계이고 일부 육방정계 상이 존재하였다. 후 열처리 온도를 1000 °C에서 1350 °C로 증가시킴에 따라 SrAl2O4:Ho3+는 육방정계 상이 줄어 들면서 단상정계의 결정성이 향상되었다. 그러나 1350 °C에서도 일부 육방정계 상은존재하였다. 구연산(CA)과 에틸렌 글리콜(EG)을 첨가해준 분무 용액으로부터 제조한 경우, 육방정계 상이 없는 순수한 단사정계 상으로 향상된 결정성을 가지는 SrAl2O4:Ho3+가 제조되었다. 또한 유기 첨가제와 함께 N,NDimethylformamide(DMF)를 분무용액에 넣어 줌으로써 형광체의 표면적을 크게 감소시킬 수 있었다. 그 결과 CA/EG/DMF를 넣고 제조한 SrAl2O4:Ho3+ 형광체는 유기 첨가물 없이 제조한 형광체에 비해 발광 휘도가 약 168% 향상되었다. 이러 한 휘도 증대는 SrAl2O4:Ho3+ 형광체의 결정상이 순수해졌고, 결정성 증대와 표면 결함을 최소화시킨 결과라고 결론 지었다. Ho3+ doped SrAl2O4 upconversion phosphor powders were synthesized by spray pyrolysis, and the crystallographicproperties and luminescence characteristics were examined by varying activator concentrations and heattreatment temperatures. The effect of organic additives on the crystal structure and luminescent properties was also investigated. SrAl2O4:Ho3+ powders showed intensive green emission due to the 5F4/5S2 → 5I8 transition of Ho3+. The optimal Ho3+ concentration in order to achieve the highest luminescence was 0.1%. Over this concentration, emission intensities were largely diminished via a concentration quenching due to dipole-dipole interaction between activator ions.According to the dependence of emission intensity on the pumping power of a laser diode, it was clear that the upconversion of SrAl2O4:Ho3+ occurred via the ground state absorption-excited state absorption processes involving two near-IR photons. Synthesized powders were monoclinic as a major phase, having some hexagonal phase. The increase of heat-treatment temperatures from 1000 °C to 1350 °C led to crystallinity enhancement of monoclinic phase, reducing hexagonal phase. The hexagonal phase, however, did not disappear even at 1350 °C. When both citric acid (CA) and ethylene glycol (EG) were added to the spray solution, the resulting powders had pure monoclinic phase without forming hexagonal phase, and led to largely enhancement of crystallinity. Also, N,N-Dimethylformamide (DMF) addition to the spray solution containing both CA and EG made it possible to effectively reduce the surface area of SrAl2O4:Ho3+ powders. Consequently, the SrAl2O4:Ho3+ powders prepared by using the spray solution containing CA/EG/DMF mixture as the organic additives showed about 168% improved luminescence compared to the phosphor prepared without organic additives. It was concluded that both the increased crystallinity of high-purity monoclinic phase and the decrease of surface area were attributed to the large enhancement of upconversion luminescence.

분무열분해법에 의해 제조된(Ca, Sr)₂MgSi₂O₇:Eu²⁺ 형광체의 발광 특성

이호민,정경열,정하균,이종흔,Lee, Ho Min,Jung, Kyeong Youl,Jung, Ha-Kyun,Lee, Jong Heun 한국화학공학회 2006 Korean Chemical Engineering Research(HWAHAK KONGHA Vol. No.

분무열분해법을 이용하여$(Ca,Sr)_{2-y}MgSi_2O_7:Eu^{2+}{_y}$ 형광체 분말을 제조하고 $Eu^{2+}$의 농도, 후열처리온도 변화 및 Ca/Sr 비에 따른 발광특성을 조사하였다. 또한, Ca/Sr의 비를 변화시켜 발광특성의 변화를 관찰하였다. $Ca_2MgSi_2O_7$나 $Sr_2MgSi_2O_7$ 분말 모두 $1,000^{\circ}C$ 이상의 온도에서 열처리를 했을 때 순수한 정방정계 상이 제조되었다. $Ca_2MgSi_2O_7:Eu^{2+}{_y}$ 녹색 형광체는 $Eu^{2+}(y)$의 농도가 5 mol%, 후열처리 온도가 $1,250^{\circ}C$ 일 때 가장 높은 발광 강도는 보였다. ${(Ca_{1-x},Sr_x)}_{1.95}MgSi_2O_7:{Eu^{2+}}_{0.05}$의 발광 파장은 Sr의 농도가 증가함에 따른 결정장 감소로 인해 524nm에서 456nm로 점진적으로 blue shift 되었다. $Sr_2MgSi_2O_7:Eu^{2+}$는 Sr 자리에 약 10 mol% Ca를 치환시킴으로써 청색 형광체의 발광 강도는 크게 향상되었다. 제조된 분말들은 치밀하지 못하고 다공성 구조를 가져 후열처리 전에는 구형을 유지하였으나 열처리($900{\sim}1,300^{\circ}C$) 후에는 구형의 형상을 잃고 입자들 간의 응집이 발생하였다. $(Ca,Sr)_{2-y}MgSi_2O_7:Eu^{2+}{_y}$ (CMS) phosphor particles were prepared by using a spray pyrolysis process. The luminescent property was optimized by changing the content of Eu and the post-treatment temperature. The luminescence characteristics were also monitored with changing the ratio of Ca to Sr. The pure tetragonal $Ca_2MgSi_2O_7$ or $Sr_2MgSi_2O_7$ particles were obtained when the post-treatment temperature was over $1,000^{\circ}C$. The highest emission intensity of CMS particles were achieved when the concentration (y) of Eu and the treatment temperature were 0.05 and $1,250^{\circ}C$,respectively. The emission wavelength $({\lambda}_{max})$ of ${(Ca_{1-x},Sr_x)}_{1.95}MgSi_2O_7:{Eu^{2+}}_{0.05}$ was gradually shifted from 524 nm to 456 nm with increasing the content of Sr due to the reduction of crystal field strength. The emission intensity and its width of $Sr_2MgSi_2O_7:Eu$ was greatly enhanced by substituting Ca of less than 10 mol% for Sr without any significant peak shift. The morphology of as-prepared particles was spherical, but changed to irregular-shaped one after the post treatment at the temperature range from 900 at $1,300^{\circ}C$.

분무열분해법에 의해 제조된 구형의 녹색 LaPO₄:Tb 형광체의 발광특성

이교광,강윤찬,전일운,정경열,박희동,Lee, Kyo-Kwang,Kang, Yun-Chan,Zeon, Il-Woon,Jung, Kyeong-Youl,Park, Hee-Dong 한국재료학회 2002 한국재료학회지 Vol.12 No.9

Fine $LaPO_4$:Tb phosphor particles with spherical shape were prepared by spray pyrolysis. The influence of the precursor type of phosphorous such as ($NH_4$)$_2$$HPO_4$, $NH_4$$H_2$$PO_4$, ($NH_4$)$_3$$PO_4$ and $H_3$$PO_4$ on the morphology and brightness of particles was investigated. As-prepared particles by spray pyrolysis had spherical shape when ($NH_4$)$_2$ $HPO_4$ and $NH_4$$H_2$$PO_4$ were used as the precursor of phosphorous. The precursor type of phosphorous affected the photoluminescence intensity of $LaPO_4$:Tb phosphor particles, but not significant. With changing the content of activator(Tb) and excess of phosphorous, the optimal composition giving the highest photoluminescence intensity was found. The spherical morphology of prepared $LaPO_4$:Tb particles was completely maintained even after the posttreatment up to $1050^{\circ}C$. When the posttreatment temperature was over $1100^{\circ}C$, the particles did not have the spherical shape anymore. However, the highest photoluminescence intensity of prepared $LaPO_4$:Tb particles was obtained at $1050^{\circ}C$. The photoluminescence characteristics of prepared $_LaPO4$:Tb under the vacuum ultraviolet(VUV) illumination was comparable with that of the commercial $Zn_2$$V_4$:Mn and (La,Ce)PO$_4$:Tb phosphor particles. At the optimal condition, the decay time of prepared spherical $LaPO_4$:Tb phosphor particles was about 6.8ms.

분무열분해공정에 의한 메조기공 알루미나 제조에 있어 Al 전구체 영향

김주현,정경열,박균영,Kim, Joo-Hyun,Jung, Kyeong-Youl,Park, Kyun-Young 한국분말야금학회 2010 한국분말재료학회지 (KPMI) Vol.17 No.3

Mesoporous alumina particles were prepared by spray pyrolysis using cetyltrimethyl-ammonium bromide (CTAB) as a structure directing agent and the effect of Al precursor types on the texture properties was studied using $N_2$ adsorption isotherms, small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The surface area and the microstructure of alumina particles were significantly influenced by the Al precursor type. The largest BET surface area was obtained when Al chloride was used, whereas alumina particles prepared from Al acetate had the largest pore volume. According to small-angle X-ray scattering (SAXS) analysis, the alumina powders prepared using nitrate and acetate precursors had a clear single SAXS peak around $2{\theta}=1.0{\sim}1.5^{\circ}$, indicating that regular mesopores with sponge-like structure were produced. On the basis of TEM, SAXS, and $N_2$ isotherm results, the chloride precursor was most profitable to obtain the largest surface area ($265\;m^2/g$), whereas, the nitrate precursor is useful for the preparation of non-hollow mesoporous alumina with regular pore size, maintaining high surface area (${\sim}233\;m^2/g$).

분무열분해 공정을 이용하여 스트론튬 알루미네이트 녹색 형광체의 합성 및 발광 특성 개선

김미나 ( Mi Na Kim ),정경열 ( Kyeong Youl Jung ) 한국화학공학회 2011 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.49 No.5

SrAl2O4:Eu green phosphor was prepared by spray pyrolysis and its luminescence properties were controlled by replacing the Al sites with boron and using organic modifier or drying control chemical additive. It was clear that the substitution of B into the Al sites was helpful to obtain pure monoclinic SrAl2O4 phase and greatly enhance the emission intensity. In terms of the emission intensity, the optimal content of boron was about 1 at% with respect to the aluminum element. The luminescence intensity of Sr0.9Al.98B0.02O4:Eu0.1 phosphor could be improved by the use of 0.2 M organic additives in the spray solution. Futhermore, using 0.5 M dimethylformamide(DMF) as a drying control chemical with organic additives made it possible to improve about 172% the emission intensity of Sr0.9Al1.98B0.02O4:Eu0.1 phosphor. According to XRD analysis, the organic additive and DMF used enhanced the crystallinity without any change in the crystal phase. When used only the organic additive without DMF, the surface area of the prepared Sr0.9Al1.98B0.02O4:Eu0.1 phosphor became enlarged. The use of DMF with the organic additive resulted in significant reduction in the surface area. It was concluded that the increase of the crystallinity as well as the reduction of surface area mainly contribute to the improvement in the luminescence intensity of Sr0.9Al1.98B0.02O4:Eu0.1 phosphor prepared using DMF and organic additives.

식물세포배양으로부터 Paclitaxel 정제를 위한 메조다공성 실리카의 기공크기 영향

오현정(Oh, Hyeon-Jeong),정경열(Kyeong Youl Jung),김진현(Jin-Hyun Kim) 한국생물공학회 2013 KSBB Journal Vol.28 No.3

분무열분해 공정에 의해 물리적 특성이 다른 네 종류의 메조다공성 실리카를 제조하여 식물세포배양 유래 항암물질 paclitaxel 정제에 사용하였다. 실리카 흡착제의 물리적 특성에서 표면적과 기공부피 보다는 기공크기 (기공지름)이 흡착제 처리 효과에 많은 영향을 미침을 알 수 있었다. 특히 적절한 기공지름 (~9.07 nm)에서 가장 높은 순도 (~46.1%)와 수율 (~82.3%)의 paclitaxel을 얻을 수 있었다. 이러한 불순물 (타르 및 왁스 성분 포함) 제거 효과는 흡착제 처리 후 흡착제를 메탄올로 세척한 시료의 HPLC 분석 결과와 흡착제에 붙은 유기물의 TGA 정량 분석 결과로도 확인할 수 있었다. Four types of mesoporous spherical silica adsorbents with different physical properties were prepared by spray pyrolysis and were used for the purification of the anticancer agent paclitaxel from plant cell cultures. Pore size had a greater effect on the removal of plant-derived impurities during the pre-purification of paclitaxel compared with surface area and pore volume. An appropriate pore diameter (~9.07 nm) was required to achieve the highest purity (~46.1%) and yield (~82.3%) of paclitaxel. These results were confirmed by HPLC analysis of the absorbent after treatment and Thermogravimetric analysis of the organic substances bonded to the adsorbent.

분무열분해법으로 YAG:Ce 제조시 용액 조건이 발광특성에 미치는 영향

이유미,강태원,정경열,Lee, You-Mi,Kang, Tae-Won,Jung, Kyeong-Youl 한국분말야금학회 2012 한국분말재료학회지 (KPMI) Vol.19 No.3

YAG:Ce yellow phosphor particles were synthesized by spray pyrolysis with changing the solution properties and their luminous properties, crystal structure, and morphological changes were studied by using PL measurement, XRD, and SEM analysis. It was clear that the solution properties significantly affected the crystal phase, crystallite size, the PL intensity, and the morphology of YAG:Ce particles. At low calcination temperature, the addition of urea only to the spray solution was helpful to form a pure YAG phase without any impurity phases, as the result, the highest luminescence intensity was achieved at the calcination temperature of $900^{\circ}C$. When the calcination temperatures were larger than $1300^{\circ}C$, however, the YAG particles prepared without any additive showed the highest luminescent intensity. Regardless of the solution conditions, the emission intensity of YAG:Ce particles prepared by spray pyrolysis showed a linear relation with the crystallite size. In terms of the morphology of YAG:Ce particles, the addition of both DCCA and $NH_4OH$ to the spray solution was effective to prepare a spherical and dense structured YAG particles.

팔라듐 함침 무기막에 의한 혼합가스로부터 수소분리

정경열,윤건영,박승빈,양승만 ( Kyeong Youl Jung,Keon Yeong Yoon,Seong Bin Park ) 한국화학공학회 1996 화학공학의이론과응용 Vol.2 No.1

Preparation and Luminescence Optimization of CeO₂:Er/Yb Phosphor Prepared by Spray Pyrolysis

정경열,박재훈,송신애,Jung, Kyeong Youl,Park, Jea Hoon,Song, Shin Ae The Korean Society of Industrial and Engineering C 2015 공업화학 Vol.26 No.3

분무열분해법을 이용하여 서브 미크론 크기의 $CeO_2:Er^{3+}/Yb^{3+}$ 상향 변환 형광체 입자를 합성하고 $Er^{3+}$ 및 $Yb^{3+}$ 농도 변화에 따른 발광특성을 조사하였다. 합성한 $CeO_2:Er^{3+}/Yb^{3+}$는 $Er^{3+}$ 활성이온의 $^4S_{3/2}/^2H_{11/2}{\rightarrow}^4I_{15/2}$ 및 $^4F_{9/2}{\rightarrow}^4I_{15/2}$ 전이에 기인한 강한 녹색 및 적색 발광을 보였다. 가장 높은 발광을 보이는 활성제 농도는 Er = 1.0% 그리고 Yb = 2.0%이며, 농도소광 현상은 쌍극자-쌍극자 상호작용을 통해 일어남이 확인되었다. 레이저 다이오드 여기 광 세기에 대한 발광강도 의존성을 활성이온 농도에 따라 조사하였고, 발광 중간 에너지 레벨의 주 소멸과정을 고려하여 발광 메커니즘을 조사하였다. $Yb^{3+}$에서 $Er^{3+}$으로 에너지 전달은 바닥 상태 흡수(ground state absorption, GSA)에 기여하고, $Yb^{3+}$ 도핑은 $^4I_{11/2}{\rightarrow}^4I_{13/2}$ 전이를 가속화시켜 적색/녹색 발광세기 비를 상승시킨다. 최종적으로 분무열분해법으로 제조된 $CeO_2:Er^{3+}/Yb^{3+}$ 형광체의 발광은 선형 감쇠가 중간 에너지 레벨의 고갈을 지배하는 2 광자 프로세스에 의해 일어남을 확인하였다. Submicron-sized $CeO_2:Er^{3+}/Yb^{3+}$ upconversion phosphor particles were synthesized by spray pyrolysis, and their luminescent properties were characterized by changing the concentration of $Er^{3+}$ and $Yb^{3+}$. $CeO_2:Er^{3+}/Yb^{3+}$ showed an intense green and red emission due to the $^4S_{3/2}$ or $^2H_{11/2}{\rightarrow}^4I_{15/2}$ and $^4F_{9/2}{\rightarrow}^4I_{15/2}$ transition of $Er^{3+}$ ions, respectively. In terms of the emission intensity, the optimal concentrations of Er and Yb were 1.0 % and 2.0%, respectively, and the concentration quenching was found to occur via the dipole-dipole interaction. Upconversion mechanism was discussed by using the dependency of emission intensities on pumping powers and considering the dominant depletion processes of intermediate energy levels for the red and green emission with changing the $Er^{3+}$ concentration. An energy transfer from $Yb^{3+}$ to $Er^{3+}$ in $CeO_2$ host was mainly involved in ground-state absorption (GSA), and non-radiative relaxation from $^4I_{11/2}$ to $^4I_{13/2}$ of $Er^{3+}$ was accelerated by the $Yb^{3+}$ co-doping. As a result, the $Yb^{3+}$ co-doping led to greatly enhance the upconversion intensity with increasing ratios of the red to green emission. Finally, it is revealed that the upconversion emission is achieved by two photon processes in which the linear decay dominates the depletion of intermediate energy levels for green and red emissions for $CeO_2:Er^{3+}/Yb^{3+}$ phosphor.