Journal of the Ceramic Society of Japan

Paper112 [11] 599603 (2004)^óOGLV}vðp¢½yqh|VUÉæéVJÌ`¬·ÀNOEcüEÁ¡çqEi¡LFÞ_Þì§YÆZp¤C2430435 _Þì§CV¼sº¡ò 7051Þ(L)R^~l[VERg[ET[rXC2291134 _Þì§Í´sºãò 5293

Formation of Silica Coatings from Perhydropolysilazane Using
Vacuum Ultraviolet Excimer Lamp
Yasuhiro NAGANUMA, Satomi TANAKA, Chihiro KATO and Toyohiko SHINDOÞKanagawa Industrial Technology Research Institute, 7051, Shimo­imaizumi, Ebina­shi, KanagawaÞContamination Control Services, 5293, Shimokuzawa, Sagamihara­shi, Kanagawa 22911342430435

Silica coatings have been prepared by the spin­coating technique with the 172 nm vacuum ultraviolet (VUV) ir­
radiation using a Xe2Þexcimer lamp. Perhydropolysilazane was used as a precursor. The chemical states, compo­
sition and optical transmittance of VUV­irradiated films were investigated by Fourier transform infrared, X­rayphotoelectron, UV­visible absorption spectroscopies. The results showed that VUV irradiation was effective toremove hydrogen and nitrogen from the coating film and to incorporate oxygen to the film, so that the filmtransforms into silica. The effects of VUV treatment on the film were found to be dependent on oxygen concen­
tration in surrounding gas. It was suggested that the effect of oxidation reaction due to active oxygen species
and/or ozone is larger than that of the cleavage of a chemical bonding by photon energy.
[Received June 4, 2004; Accepted September 22, 2004]
Key­words : Perhydropolysilazane, Silica, Thin film, Spin­coating, Vacuum ultraviolet light, Excimer lamp

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vªÀp»³êÄ«½5)DVUV õÍC1 õq ½èÌGlM[ªCÙÆñÇÌ¨¿É¨¯é´qÌGlM[æèà599600^óOGLV}vðp¢½yqh|VUÉæéVJÌ`¬Fig. 1. Schematic diagram of the VUV irradiation apparatus.

B. À±R[eBOntÆµÄCPHPS ÌLVntiNAgWpCNN110jðóßµÄgpµ½DZxª 5÷ÌntðVREGn(100)ãÉC1500 rpm Å 2 min XsR[gµ½D»Ìã40
CÅ10 min £³¹CR[eBOð¾½D±ÌÉ Xe2ÞGLV}viNH[NVXeY»CQEX230SX, 100 W/m2 jðp¢ÄCg·172 nm Ì VUV õð1 h ÆËµ½DÆËðÆµÄC¿ÆvÌ£i Dj
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C é¢Í500CÌM·xiTHjÅ40 min ÁMµ½àì»µ½DÌÔOzûXyNgðt[GÏ·ÔOªõiFTIRjõxviÃ»ì»CFTIR8200PCjÉæè§ß@ðp¢Ä4000©ç400 cm|1 ÌgÍÍÅªèµ½D\ÊyÑàÌg¬ÉÂ¢ÄCX üõdqªõiXPSjªÍuiAob
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êé1060 cm|1 tßÌzûs[N­xª­­ÈèC500
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ÆËðsÁ½êà¯lÌÏ»ª©çê½Dµ©µCÆËðÉæèXyNgÌ`óÍÙÈèCÆË£Åär·éÆC2mm ÌÆ«æèà20 mm ÌûªCÆËÉæé SiN zûs[NÌ¸­ªå«­CVJÖÌ]»ªiñÅ¢½DXÉCD20mm ÌÆ«ÍCCO2÷ é¢Í20÷Æµ½Æ«Ì¼ûÆàÉC300
CÅMðµ½Æ«æèàVJÖÌ]»ªiÞ±ÆªFig. 2. FTIR spectra of spin­coated films dried, heat­treated andVUV­irradiated. TH is heat treatment temperature. CO and D are oxy­
gen concentration and distance between the lamp window and thesample, respectively.

ª©Á½D±êÍCi3)`(5)®É¦µ½ O(1Djâ O3 Éæé_»ÉæèCÉ O ªæèÜêVJª`¬³ê½àÌÆl¦çêéDMyÑõÆËµ½Ì\Êg¬ÉÂ¢Ä]¿·é½ß
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CÅMµ½ÆCD2 mm ÅõÆËµ½©çÍ N ªÙÆñÇÏª³êÈ©Á½D±êæèCÖÌÆËª\ÊÉ¶Ý·é N ð·é±ÆªmF³ê½DÆËãÌÉ¨¯é Si2p XyNg
ÍC¢¸êÌÆËðÌêàCs[Nª103.7 eV tßÉÊuµCVJÉ¨¯és[NÊu13)Ææ­êvµ½DàÌg¬ÉÂ¢Ä²×é½ßÉCXPS Éæé[³ûüªÍðsÁ½D}SÉC»ê¼êMyÑõÆËãÌÉ¨¯éfvXvt@Cð¦·D»ÌÊC300CÌMÅÍCàÉà N ªc¶µÄ¢éªC500
CÅÌMãÉÍCN ªÏª³ê¸CÏêÈVJª`¬³êé±Æªª©Á½DÈ¨CúùmÌ SiO2 Ì[³ûüªÍÉæèàÆ
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Journal of the Ceramic Society of Japan

112 [11] 2004

601

Fig. 3. O1s, N1s and Si2p XPS spectra from spin­coated films heat­treated and VUV­irradiated. TH is heat treatment temperature. CO and D are
oxygen concentration and distance between the lamp window and the sample, respectively.

Fig. 4. XPS depth profiles of spin­coated films heat­treated and VUV­irradiated. TH is heat treatment temperature. CO and D are oxygen con­centration and distance between the lamp window and the sample, respectively.

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CO D~|e~100 10(6)±±ÅCI Í§ßõ­xCI0 ÍüËõ­xCe Íg·172 nm ÌVUV õÉ¨¯é O2 ÌzûWÅ èCe15 cm|1 Æµ½6) Di6)®æèàÆß½CÆËµÍCª CO2÷ é¢Í20÷ÌÆ«ÌÆË£ÉÎ·é VUV õÌ§ß¦ð}UÉ¦·D±êæèCD2 mm Å CO20÷ÌêÆCD20 mm Å CO2÷ÌêÌ¿\ÊÉB·éõÌ­xÍ¯¶Å èCO(1 DjâO3 Ì¶¬Êà¯¶Å éÆl¦çêéDµ©µC} 2 â} 4É¨¢ÄÏª³ê½æ¤ÉCD20 mm ÌÆ«Ìûª 2 mm æèàÉ N ªc¶¹¸CVJÖÌ]»ªiñÅ¢½D±Ìæ¤È¿Ìá¢ª¶¶½vöÆµÄÍC} 1 É¦·ÆËuÉ¨¢ÄCvÆ¿ÆÌ£ªZ¢ D2 mm ÅÍC¿ãûÉ¶¬µ½ O(1Djâ O3 ÍCÎ¬ÉæÁÄ¬³êÄµÜ¤Dµ©µCD20 mm ÅÍvÆ¿ÆÌÔÌÉ¨¢ÄCÀøIÈ¬¬ªx­Èé½ßÉØ¯Ôª·­ÈèCÖÌ O ÌæèÝCyÑ N ÆÌu·ª£i³ê½àÌÆ
ª³êéDFig. 5. Optical transmittance spectra of spin­coated films heat­treat­ed and VUV­irradiated. TH is heat treatment temperature. CO and D
are oxygen concentration and distance between the lamp window andthe sample, respectively.

Fig. 6. Calculated values of transmittance of vacuum ultravioletlight as a function of distance with oxygen concentration (CO) of 2÷and 20÷ by Eq. (6).

FTIR ªèÌÊ©çCD20 mm ÌðÌÆ«CCO2÷,20÷ÌoûÌðÅVJÖÌ]»ªÏª³ê½Dµ©µCCO
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