15 Vol. 15,No. 4 2003 4 HIGH POWER LASER AND PARTICL E BEAMS Apr.,2003 4 :100124322 (2003) 0420326205 Ξ ZrO 2 / SiO 2,,,,,, (, 200092) : ZrOCl 2 8H 2 O, 2 ZrO 2 SiO 2 K9 ZrO 2 / SiO 2, ZrO 2 / SiO 2,, 2 1064nm, 15ns Q, : 2 ; ; ; ; :O484. 4 :A [1 2 ],, [1, ] ICF,, 2 ZrO 2 / SiO 2 ZrOCl 2 8H 2 O, ZrO 2, ; ZrO 2 PVP [2 ], ZrO 2 22J / cm 2 ( 1064nm, 1ns) [3 ] SiO 2 [4 ], 2 ZrO 2 / SiO 2,,,, 1 1. 1 ( TEOS) TEOS, (N H 4 OH), ( Eth) 1 2 20, 30min, 80 C 3 6h, SiO 2 SiO 2 : ; ZrOCl 2 8H 2 O, c (Zr) = 0. 2 0. 3mol L - 1 ; ( ), p H 1 3 4 ;, 168 C, 3h,, nm ZrO 2 ZrO 2, ZrO 2 ZrO 2 ZrO 2 15 % ( PVP), ZrO 2 2PVP 1. 2 ( 60 %) (20 25 C), SiO 2 Ξ :2002212227 ; :2003202226 : (20133040,69978017) ;863 (2002A842052) ; (8152nm012,0159nm039) ; (02SL001) : (19782),,, E2mail :duoduo2yang @sohu. com
4 : ZrO 2 / SiO 2 327 ZrO 2 SiO 2 / ZrO 2 50mm K9, 2500 4000r/ min, 50 300nm,, 1kW 365nm, 4cm 1. 3 ( TP - 77, ), 632. 8nm He2Ne ; UV755B 2 ; TJ 270-30, 4cm - 1 ; (XL30FEG) ; ISO11254-2. 1 ( Nd : YA G, 1 064nm, 800mJ, 15ns, 1Hz) 2 2. 1 Fig 1. Changes of thickness(a) and refractive index (b) of ZrO 2 films with heating temperature and UV irradiation time 1 ZrO 2 (a) (b) ZrO 2 1, 4 000r/ min, 1h, 10,30 60min, nm,,, 400 C, 400 C 1h 400 C,,, ;, ZrO 2 400 C 2 ZrO 2 600 C 400 C 600 C, 400 C Fig. 2 SEM photomicrograph of ZrO 2 film after different heat treatment 2 SEM
328 15,, 60 400 C, 400 C 1,, [6 ZrO 2 ], ZrO 2, D 1, D 2, D 3, d 1, d 2, d 3, D 1 / d 1 = D 2 / d 2 = D 3 / d 3 =, 1 1 ZrO 2 Table 1 Changes of thickness of ZrO 2 f ilms with heating temperature and spin speed temperature/ 100 200 300 400 500 600 2 000 T min - 1 thickness/ nm 81. 61 77. 36 67. 63 42. 98 42. 74 41. 86 4 000 T min - 1 thickness/ nm 56. 55 53. 21 47. 23 29. 66 29. 50 29. 11 ratio 1. 443 1. 454 1. 432 1. 449 1. 449 1. 438, 1. 2 %,, 2. 2 [7 ] ZrO 2 PVP, ZrO 2 PVP SiO 2 PVP, [6, ] 3 100 C 1h 10min ZrO 2 2PVP 1 665cm - 1 ( - C = O),1 280 1 410cm - 1, ( - CH 2 ) Fig. 3 IR spectra of ZrO 2 2PVP films after heat treatment and UV irradiation 3 100 C 1h 10min ZrO 2 2PVP ( - CH 2 ), 1 070 1 150cm - 1 (C - O - C) 700 950cm - 1 N - H, ; N - H [8, PVP ] Fig. 4 Cross2sectional SEM micrograph of 52layer SiO 2 / ZrO 2 2PVP film after UV irradiation 4 5 SiO 2 / ZrO 2 2PVP 5 SiO 2 / ZrO 2 2PVP, 10min SEM, 4, 5 SiO 2 / ZrO 2 2PVP, 74. 9 % ; 85. 2 %, 440nm, 5
4 : ZrO 2 / SiO 2 329 2. 3 SiO 2 SiO 2, 2, ; 100nm ; ( 6) 7 ( 2 500r/ min), 3 438 cm - 1, O2H,, 1 087cm - 1 Fig. 5 UV2VIS spectra of 52layer SiO 2 / ZrO 2 2PVP films after heat treatment and UV irradiation Si2O,, 5 100 C 1h 10min 5 SiO 2 / ZrO 2 2PVP 2 2 SiO 2 Table 2 Thickness and refractive index of SiO 2 f ilms before and after solvent exchange spin speed/ (r min - 1 ) ( heating temperature :60 C, time :1h) d b d a n b n a n b n a 1 000 271. 95 1. 19 323. 87 2 000 351. 56 204. 39 1. 19 1. 20 416. 65 246. 09 3 000 271. 86 169. 74 1. 20 1. 21 326. 29 204. 58 4 000 221. 50 160. 79 1. 21 1. 19 268. 02 192. 35 Fig. 6 SEM micrographs of SiO 2 films 6 SiO 2 SiO 2 SiO 2 / ZrO 2 2PVP, 5 100 C 1h, SEM, 8,,, ; ZrO 2 2PVP,, SiO 2, 23J / cm 2 27J / cm 2 3,400 C ZrO 2 Fig. 7 IR spectra of SiO 2 films before and after solvent exchange 7 SiO 2
330 15 Fig. 8 SEM photomicrograph of multilayer films 8 SiO 2 SEM,400 C ZrO 2, PVP, ; SiO 2 / ZrO 2 2PVP, SiO 2 1. 20,, SiO 2 / ZrO 2 SiO 2 / ZrO 2 : [ 1 ],,,. [ A ]. 2002 [ C].,2002. 401-404. ( Shen J, Wang J, Wu G M, et al. Techniques and applications of Sol2Gel derived coatings. Proc of the Nanotechnology Conference in Shanghai. Shanghai, 2002. 401 404) [ 2 ] Floch H G, Belleville P F. Sol2Gel optical thin films for an advanced megajoule2class Nd :glass laser ICF2driver[ A]. SPIE[ C]. 1997. 2633 : 432 445. [ 3 ] Zhang Q Y, Shen J, Wang J, et al. Sol2Gel derived ZrO 2 2SiO 2 highly reflective coatings[j ]. International Journal of Inorganic Materials, 2000, (2) :319 323. [ 4 ] Thomas I M. High laser damage thresholds porous silica antireflective coating[j ]. A ppl Opt,1986 (25) :1481. [ 5 ] Sermon P A, Vong M S W, Bazin N, et al. Recent developments in silica Sol2Gel antireflective (AR) coating[ A]. SPIE[ C]. 1997. 2633 :464. [ 6 ] Belleville P, Bonnin C, Priotton J J. Room2temperature mirror preparation using Sol2Gel chemistry and laminar - flow coating technique[j ]. Jour2 nal of Sol2Gel Science and Technology, 2000, (19) :223 226. [ 7 ] Mclnnes H A, Andrew J E, Bazin N J, et al. Alternative coating materials and treatments for the manufacture of Ultra2Violet Sol2Gel mirrors[ A]. SPIE[ C]. 2000,3902 :215 223. [8 ], P H. 100 [ M ]. :,1984. 75 89. ( ZhongxiXianger,Soloman P H. Infrared absorption spec2 troscopy[ M ]. Beijing :Science Press,1984. 75 89) Preparation of ZrO 2 / SiO 2 multilayer f ilms via chemical methods YAN G Fan,SHEN J un,wu Guang2ming, SUN Qi, FU Tian, ZHAN G Zhi2hua,WAN G J ue ( Pohl Institute of Solid S tate Physics, Tongji U niversity, S hanghai 200092, China) Abstract : In this paper, colloid2based multilayer coatings consisting of alternating layers of high2and low2refractive index compo2 nents were deposited on K9 glass and silicon wafer substrates by Sol2Gel spin2coating method. SiO 2 was used as the low2refractive index component and ZrO 2 as the high2refractive index material. The colloidal suspension of ZrO 2 was prepared by hydrothermal hydrolysis of ZrOCl 2. The solvent in colloidal suspension of SiO 2 was replaced by methoxyethanol through distillation. A high2pressure mercury lamp was used to do the irradiation treatment. SEM, IR and UV2V IS spectrophotometer were used to characterize the structure and optical properties of the films. Ellipssometry was used to study the thickness and refractive index of the films. The films were irradiated by a Q2 switched Nd : YA G high power laser whose wavelength was 1064nm and its pulse width was 15ns. The results show that solvent2ex2 change and UV2irradiation are effective methods to avoid the cracking in the multilayer films and the infiltrating between the layers and improve laser damage threshold of Sol2Gel films. Key words : Sol2Gel process ; Hydrothermal hydrolysis ; UV2irradiation ; Laser damage threshold ; Organic binder