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1 Krean Chem. Eng. Res., Vl. 44, N. 4, August, 2006, pp 재현성있는메조포러스 박막의제조에대한연구 miçm m*çi**çqj***ç***çs*, ne, ** ne r 90 * e qk }} 300 *** l rl ne 39-1 ( p r, p }ˆ) Reprducible Synthesis f Peridic Mesprus Thin Film Jae Yung Hur, Hyung Ik Lee*, Yung-Kwn Park**, Oh-Shim J***, Gwi-Nam Bae*** and Ji Man Kim*, Department f Envirnmental Engineering, **Faculty f Envirnmental Engineering, University f Seul, 90, Chennng-dng, Dngdaemun-gu, Seul , Krea *Department f Chemistry, Sungkyunkwan University, 300, Chenchen-dng, Jangan-gu, Suwn , Krea ***Envirnment & Prcess Technlgy Divisin, Krea Institute f Science and Technlgy, 39-1, Hawlgk-dng, Sungbuk-gu, Seul , Krea (Received 4 July 2006; accepted 13 July 2006) k q p r s k p p band gap p p l p sd p l v p re pp, p d m p l sl m p k q p lv rp rrp rl m. p nk l r~ pp s~mp qsl p s rl p r ~ m d tp m p p p. ll 2 sp sp v p q p lp p e sp }q m. p p HCl r~p r~m P-123p p s k Žr tp p p dm m m l e p m p XRDm TEM p m. h Abstract There has been numerus reprts fr the synthesis f mesprus thin films due t nt nly the high surface area and regular messcale pres but als wide band gap and pht activity. Hwever, the synthesis has been restricted by the limited reprducibility mainly due t the extrardinarily fast hydrlysis and cndensatin rate f titania precursrs. In this reprt, mlar cmpsitin f reactin batch (HCl/Ti and Ti/P123) and exterir cnditin (humidity and temperature) during cating and anealing prcess. Thereafter, the mesprus thin films were characterized by XRD and TEM. Key wrds: Mesprus, Thin Film,, Sl-gel l p p r s p n p rp v s d e vp p p l[1], p s d e v pnl p k p s d rp l ep t v p[2]. vp p p v pp T whm crrespndence shuld be addressed. jimankim@skku.edu, qn }l p p p v p l ~q,,, q, lv r [2-12] p n ql k rn p qqp p l q p ep ppˆ p vp. p p, l lel sp v Žn ˆp p l l p p v p. 1995l Antnellim Yingp s~ phsphate qn r n l sp v mp [3], Sanchezm lvp CTABrp s~ l EISA 399

2 400 qmëp pëmëtmeëëv (evapratin-induced self-assembly) p p l Tim HClp l sp, Žp petri dishl k m, k ml l} l 2D hexagnal(p6 m) s v Žn ˆp mp[13], Yuem Ga s ~ P123 pn l Tim H 2 Op hydrlysism cndensatin pp sr CeCl 3 ~ l n lrkr p s d m[14]., Jimmy p s~ n v k, pž pn l 3 s (wrmhle-like framewrk)p p p v lr krp sp m[15]. p ˆp n pq r p l rqm kqp p plv l pn l pl r l l l, s d p p er pnl tn pq. prp s p v vp s~p q rp q s p l p s- p pn l p. l pl p p SiO 2 m p r v p sp v s l rp nl mp, sp v p l lnp k. r~ rp s~mp qnp e p k n p p pp l srp l, p sp p s(s,, s~p s, r s, ph, l} m )l l q p lv n p[2, 4]. sp p rp r~ nkl q sl pp l rp l p p p pp rr srp tn l, p srp }p p p q p sr qnr n n n l p p p lr pf ssp sr k., sp rr sr pf ˆp sp p q p p p. ll rp sp l pf r l sp v p rs prp q p p re q. p ph srp r~p p sr s~ n ky triblck cplymerp sr l sp v sp l l m., pnkp Ž rl dm np v p p s l m v p (aging) rl mm d l p p s rp ˆ m. 2. prpanl : 0.011~0.034 P123pl. nkp ml 10 e. llv Ž nkp v lˆm Žmp ve eˆ l Ž l d Ž l p eˆ, m 8 C, 25 C, 40 Cl 5p e. srp 1 C/minp dm 120 Cv m 120 Cl 1e veˆ, e dm e 350 Cv l, 350 Cl 3e ve s~ n P123 r. 3. s d p pl prp s d p m v sp r~ p s rp ssp p sp p r tn np. nl l m p m p pl p p r~p s, r n P123 pm ky qm r ~p p n HClp kl ph s d p l m l l l m. n sp k p v r~ n l s d rs m. lšp(ethxide), kp p(i-prpxide), Šp(n-butxide) r~p n mp, v r~p pp l lˆm, kp Žm, ˆmp eˆ p pp p. pp p lšp>kp p>špp p, s d p p kp p Ti r~ rr p pl l rr p k pl(fig. 1). sp rp kp s d p l m l e p m. n P123 s~ ky triblck cplymerp P123(PEO 20 PPO 70 PEO 20 ) n m. k Ti-k e p r~ n m, p rp p p e m. 4.3 gp Ti(IV) isprpxide (TTIP) 3.12 gp HCl(35 wtí)l l ml 5 t, 12 gp 1-prpanll 1~3 gp P123 n nk m. n ekp 1 TTIP : 1.6~2.2 HCl : 6~8 H 2 O : k Fig. 1. XRD patterns f mesprus different precursrs, after calcinatin at 350 C (1.0 Ti(OR) 4 : P123 : 2.0 HCl : 13 prpanl).

3 q p sd p rsl l 401 Fig. 2. XRD patterns f mesprus different amunt f P123, after calcinatin at 350 C (1 TTIP: x P123 : 2.0 HCl : 7.5 H 2 O : 13.2 prpanl). pmp v kp nkl k pmp qnl p r~m qs p, p q r kpm rl rp v p (k 7~10 nm)p }. v, r sp sp vp l p srp rp l p ˆ ls p p l lvl p p[16, 17]. Fig. 2 r, P123p l s d p p r r p X- r(xrd) lt. r~ l P123p kp , , , p p XRD Ž p P123p kp p, p p l r sp ppp k p p P123 n sl r pp l rl rp r s eˆ ll, p P123, p nl p ss l pp r l p r l s mr p r. P123=0.0171p s d p TEM 2D-hexagnal s ppp pl, p 2D-hexagnal sp p nl. p rp np pnkp ph p, p r~p p pp k rm r~p qnl m p ~ s s l tn n r rp. Fig. 3p r~ HClp eˆ s d p XRD lt. m p p n Fig. 3. XRD patterns f mesprus different amunt f HCl, after calcinatin at 350 C (1.0 TTIP: P123 : x HCl : 3.7x H 2 O : 13 prpanl). r~p l r~ 2 p p HClp n l p p pp lr mp l r sp s d p p p k pl. p sp r l sp s d lp p lv p ˆ rs Ž r l} rlp d m p sl r s s d p vp p ep e p l k l, p dm m m l l l. Fig. 4l re m p, Žrl d p t ˆ s d l m j. t(d 45Í)l d Žp l p l nm l v, lˆm Žm eˆ l p lp np ep sp tp p } p l q r sp sp XRD p ltl. v l d Ž rl dl p p p pp }rp k t pp, lˆmp Žm eˆ tl p d Ž nl p pp lr pnl Ž nk l np vv sr pl n q r sp s d p lp p. p p pnkp nm p Žmp eˆ l Ž mp nl q r sp p lp pl. Krean Chem. Eng. Res., Vl. 44, N. 4, August, 2006

402 qmëp pëmëtmeëëv Fig. 4. XRD patterns f mesprus thin films, prepared under different spin cating cnditin, after calcinatin at 350 C (1.0 TTIP: 0.0085 P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl).

TEM images f mesprus thin films prepared under different spin cating envirnments (1.0 TTIP : 0.0085 P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl). tlm Žm l Ž p v e Œrq (HRTEM)p n l p s s m(fig. 5).

s d p rs rl Ž r k Ž eˆ r n tn p r p, m ssl m p p k pl. Fig. 6p XRD l pp m p p p p m, 8 Cl l} e sp s vp k pl. 4. s d v tl p s d l pn p ppl p q r p l rkp plm.

4 402 qmëp pëmëtmeëëv Fig. 4. XRD patterns f mesprus thin films, prepared under different spin cating cnditin, after calcinatin at 350 C (1.0 TTIP: P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl). Fig. 6. XRD patterns f mesprus thin films, prepared under different aging temperature, after calcinatin at 350 C (1.0 TTIP: P123 : 2.0 HCl : 7.5 H 2 O : 13 Prpanl). Fig. 5. TEM images f mesprus thin films prepared under different spin cating envirnments (1.0 TTIP : P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl). tlm Žm l Ž p v e Œrq (HRTEM)p n l p s s m(fig. 5). XRD m m p t(d 45Í)l Ž l lp e v s l p, Žm l Ž ep n 2D hexagnal s q r sp k l., Žm l rs ep n TEM lp q (5.7 nm) XRD (5.5 nm) p p p k p. s d p rs rl Ž r k Ž eˆ r n tn p r p, m ssl m p p k pl. Fig. 6p XRD l pp m p p p p m, 8 Cl l} e sp s vp k pl. 4. s d v tl p s d l pn p ppl p q r p l rkp plm. ll s d p q p p re q s k Ž r Ž p r~p p p pl t n d np v s d p l m p s rp l pf q p l s d p rs pl. l lp vp k ld. y 1. Kresge, C. T., Lenwicz, M. E., Rth, W. J., Vartuli, J. C. and Beck, J. S., Ordered Mesprus Mlecular Sieves Synthesized by a Liquid-crystal Template Mechanism, Nature, 359, (1992).

5 q p sd p rsl l Sler-Illia, G. J. A. A., Sanchez, C., Lebeau, B. and Patarin, Chemical Strategies t Design Textured Materials: frm Micrprus and Mesprus Oxides t Nannetwrks and Hierarchical Structures, J. Chem. Rev., 102, (2002). 3. Antnelli, D. M. and Ying, J. Y., Angew. Chem. Int. Ed. Engl., 34, (1995). 4. Yang, P., Zha, D., Marglese, D. I., Chmelka, B. F. and Stucky, G. D., Generalized Syntheses f Large-pre Mesprus Metal Oxides with Semicrystalline Framewrks, Nature, 396, (1998). 5. On, D. T., A Simple Rute fr the Synthesis f Messtructured Lamellar and Hexagnal Phsphrus-Free Titania ( ), Langmuir, 15, (1999). 6. Dai, Q., Zhang, Z., He, N., Li, P. and Yuan, C., Preparatin and Characterizatin f Messtructured Titanium Dixide and its Applicatin as a Phtcatalyst fr the Wastewater Treatment, Mater. Sci. Eng. C, 8-9, (1999). 7. Wang, Y., Tang, X., Yin, L., Huang, W., Hachen, Y. R. and Gedanken, A., Snchemical Synthesis f Mesprus Titanium Oxide with Wrmhle-like Framewrk Structure, Adv. Mater., 12, (2000). 8. Qi, Z. M., Hnma, I. and Zhu, H. S., Fabricatin f Ordered Mesprus Thin Film fr Optical Waveguiding and Interfermetric Chemical Sensing, J. Phys. Chem. B, 110, (2006). 9. Fujii, H., Ohtaki, M. and Eguchi, K., Synthesis and Phtcatalytic Activity f Lamellar Titanium Oxide Frmed by Surfactant Bilayer Templating, J. Am. Chem. Sc., 120, (1998). 10. Wijnhven, J. E. G. J. and Vs, W. L., Preparatin f Phtnic Crystals Made f Air Spheres in Titania, Science, 281, (1998). 11. Imhf, A. and Pine, D. J., Ordered Macrprus Materials by Emulsin Templating, Nature, 389, (1997). 12. Jr., Stne, V. F. and Davis, R. J., Synthesis, Characterizaitn, and Phtcatalytic Activity f Titania and Nibia Mesprus Mlecular Sieves, Chem Mater., 10, (1998). 13. Sler-Illia, G. J. de A. A., Luis, A. and Sanchez, C., Synthesis and Characterizatin f Messtructured Titania-Based Materials thrugh Evapratin-Induced Self-Assembly, Chem. Mater., 14, (2002). 14. Yue, Y. and Ga, Z., Synthesis f Mesprus with a Crystalline Framewrk, Chem. Cmmun., (2000). 15. Jimmy, C. Y., New J. Chem., 26, (2002). 16. Kim, J. M., Sakamt, Y., Hwang, Y. K., Kwn, Y.-U., Terasaki, O., Park, S.-E. and Stucky, G. D., Structural Design f Mesprus Silica by Micelle-Packing Cntrl using Blends f Amphiphilic Blck Cplymers, J. Phys. Chem. B, 106, (2002). 17. Lee, H. I., Pak, C., Yi, S. H., Shn, J. K., Kim, S. S., S, B. G., Chang, H., Yie, J. E., Kwn, Y. U. and Kim, J. M., Systematic Phase Cntrl f Peridic Mesprus Organsilicas using Gemini Surfactants, J. Mater. Chem., 15, (2005). Krean Chem. Eng. Res., Vl. 44, N. 4, August, 2006

43(5)-11.fm

43(5)-11.fm Krean Chem. Eng. Res., Vl. 43, N. 5, Octber, 2005, pp. 616-620 기상공정에의한구형형상의헥사알루미네이트계형광체제조 Ç Ç içq Ç ly 143-701 ne v k 1 (2005 5 2p r, 2005 9 7p }ˆ) Preparatin f Hexaaluminate Phsphr Particles with Spherical