本文研究是利用不同能量電漿處理製程，藉通入含N、C、O氣體與過渡元素Cr、Ti來製備硬質膜CrxNy、DLC及光觸媒薄膜TiO2，並藉由對表面微結構分析，探討製備參數對鍍膜表面性質之影響。
第一章主要研究是以小於100 eV電漿能量之磁控濺射物理蒸鍍方法，在不同N2流量控制下與過渡元素Cr反應，分別製備出Cr, Cr2N, and CrN等相結構，發現以Cr2N相結構因表面有高密度N-H 或O-H鍵結形成，成為 C-H含碳物質吸附之有利位置，因此具有最低總表面能及極性分量表面能特性，水滴接觸角可高達120°。更進一步以田口實驗計畫方法，發現IC 封裝用環氧樹脂材料成形時之黏模力高低，與表面粗度及鍍層表面能有極密切相關，研究結果成功於工業界生產線獲得驗證。
第二章主要研究是以5∼45 keV高電漿能量之浸沒式離子植入方法，將Ar, N2 及 C2H2等氣體離子，在10分鐘極短處理時間下對含氫DLC 鍍層作後繼表面處理，探討對DLC 鍍層微結構、介電常數及奈米機械性質之影響。結果發現只有C2H2氣體離子植入處理，能有效提高DLC 鍍層奈米硬度87 % 達25.3 GPa及降低介電常數達2.5，其主要原因乃由於sp3/sp2 鍵結比例提高，同時提出在植入影響區內其反應機制。
第三章主要研究是以小於100 eV電漿能量之磁控濺射物理蒸鍍方法，在不同N2/O2流量比例下與過渡元素Ti形成TiO2-xNx鍍層，藉由微結構、光譜分析及亞甲基藍色素分解速率，探討氮元素對光觸媒效率之影響。結果發現適當氮的摻雜會導致光學能隙的降低，及吸收光譜朝可見光區產生紅移現象。當TiO2-xNx鍍層具有高銳鈦礦(101)結晶相，及多孔表面型態下顯示具有最高光觸媒色素分解效率。

This thesis is to study the microstructure and its related surface properties of CrxNy、DLC and TiO2 films prepared by different plasma energy processes such as physical vapor deposition (PVD) and plasma immersion ion implantation (PIII) processes.
In the first chapter of this thesis, the different Cr-based coatings (Cr, Cr2N and CrN) were prepared by PVD process with lower plasma energy condition (less than 100 eV). The surface energy properties of these Cr-based coating were studied and the relationship between the surface properties and adhesion forces with respect to epoxy molding compound (EMC) were also investigated. It is found that the PVD-Cr2N coating has the largest contact angle of water and the lowest polar components and surface energy. The low surface energy is attributed to the high density of surface reactive sites and the formation of N-H bonds and O-H bonds on the film surface that act as the effective adsorption sites for carbon.
The second chapter focuses on the modification of the electrical and mechanical properties of DLC films with high plasma energy (5∼45 keV) , PIII post-treatment. It is found that using high ion energy and a short treating time can modify the sp3 content, the nano-hardness and the Young’s modulus of the DLC films. The formation mechanisms of sp3 C-C bonds in the implanted DLC film involve the reaction among compressive stress field, bonds breakage and recombination process induced by hydrogen and carbon ion.
The third chapter deals with the structure and photocatalytic properties of nitrogen-doped TiO2 film prepared by PVD process with lower plasma energy condition (less than 100 eV). The TiO2-xNx films are indirect transition type and optical band gap energy is various with increasing nitrogen flow rate. The TiO2-xNx film with high crystallinity and porous surface morphology shows the best degradation rate of methylene blue solution.

Contents
Preface…………………………………………………………………….I
Abstract…………………………………………………………………IV
Contents…………………………………………………………………VI
List of Table………………………………………………………… VIII
List of figure………………………………………………………… …IX

Chapter Ι
The influence of Cr-based coating on the adhesion force between epoxy molding compounds and IC encapsulation mold
1. Introduction……………………………………………………………1
2. Experimental details………………………………………………… 1
2.1 Substrate preparation and coatings
2.2 Contact angle and surface energy
2.3 Normal adhesion force measurement
2.4 Taguchi analysis
3. Results and discussion……………………………………………… 6
3.1 Film structure analysis
3.2 Surface energy and contact angle
3.3 Taguchi analysis
3.4 Performance evaluation
4. Conclusions………………………………………………………… 11
5. Tables…………………………………………………………………13
6. Figures……………………………………………………………… 19

Chapter ΙΙ
Electrical and mechanical properties of DLC coatings modified by plasma immersion ion implantation
1. Introduction………………………………………………………… 27
2. Experimental details…………………………………………………28
3. Results and discussion…………………………………………… 30
3.1 Film structure
3.2 Dielectric constant
3.3 Nano-indentation
4. Conclusions………………………………………………………… 36
5. Tables…………………………………………………………………37
6. Figures……………………………………………………………… 38

Chapter ΙΙI
The structure and photocatalytic properties of nitrogen-doped TiO2 film prepared by sputtering deposition
1. Introduction………………………………………………………… 49
2. Experimental…………………………………………………………50
2.1 Film preparation and characterization
2.2 Optical and photocatalytic properties
3. Results and discussion………………………………………………52
3.1 Film structure analysis
3.2 Optical band gap
3.3 Photocatalytic activity
4. Conclusions………………………………………………………… 58
5. Tables…………………………………………………………………59
6. Figures……………………………………………………………… 62

References……………………………………………………………… 73

References

Agouram, S., Bodart, F., Terwagne, G.,〝Characterization of reactive unbalanced magnetron sputtered chromium oxynitride thin films with air,〞Surface and Coating Technology, 180-181(2004) 164-168.
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., Taga, Y., 〝Visible-light photocatalysis in nitrogen-doped titanium oxides, 〞Science, 293 (2001) 269-271.
Bouali, B., Ganachaud, F., Chapel, J.P., Pichot, C., Lanteri, P., 〝Acid-base approach to latex particles containing specific groups based on wettability measurements, 〞 J. Collid and Interface Science, 208(1998) 81-89.
Chang, S.J. and Hwang, S.J.,〝Design and fabrication of an IC encapsulation molding adhesion force tester,〞IEEE Trans. Electronics Packaging Manufacturing, Vol. 26 No 4 (2003) 281-285.
Cheah, L.K., Shi, X., Tay, B.K., Liu, E., 〝Modification of tetrahedral amorphous carbon film by concurrent Ar ion bombardment during deposition, 〞Surface and Coating Technology, 105 (1998) 91-96.
Chen, J.S., Lau, S.P., Sun, Z., Chen, G.Y., Li, Y.J., Tay, B.K., Chai, J.W.,” Metal-containing amorphous carbon films for hydrophobic application,” Thin Solid Films, 398-399 (2001) 110-115.
Chowdhury, S., Laugier, M.T., Rahman, I.Z., 〝Effect of target self-bias voltage on the mechanical properties of diamond-like carbon films deposited by RF magnetron sputtering, 〞Thin Solid Films, 468 (2004) 149-154.
Chu, P.K. and Chung, C., 〝Applications of plasma immersion ion implantation in microelectronics- a brief review, 〞Surface and Coating Technology, 136 (2001) 151-156.
Conard, J. R., 〝Sheath thickness and potential profiles of ion-matrix sheaths for cylindrical and spherical electrodes, 〞J. Applied Physics, 62 No.3 (1987) 777-779.
Ding, Z., Hu, X.J., Yue, P.L., Lu, G.Q., Greenfield, P.F., 〝Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition, 〞Catalysis Today, 68 (2001) 173-182.
Endo, K. and Tatsumi, T., 〝Fluorinated amorphous carbon thin films grown by plasma enhanced chemical vapor deposition for low dielectric constant interlayer dielectrics, 〞 J. Applied Physics, 78 (1995) 1370-1372.
Esteve, J., Romero, J., Gomez, M., and Lousa, A., 〝Cathodic chromium carbide coatings for molding die application, 〞Surface and Coating Technology, 188-189 (2004) 506-510.
Fallon, P.J., Veerasamy, V.S., Davis, C.A., Robertson, J., Amaratunga, G.A.J., Milne, W.I., Koskinen,〝Properties of filtered-ion-beam-deposited diamondlike carbon as a function of ion energy,〞Physical Review, B 48 (1993) 4777-4782.
Fang, J.H., Lu, X.M., Zhang, X.F., Fu, D.G., Lu, Z.H., 〝CdSe/TiO2 nanocrystalline solar cells,〞Supramolecular Science, Vol.5 No. 5-6 (1998) 709-711.
Ferrari, A.C., Robertson, J., 〝Interpretation of Raman spectra of disordered and amorphous carbon, 〞 Physical Review, B61 No.20 (2000) 14095-14107.
Ferrari, A.C., Rodil S.E., Robertson, J., Milne, W.I., 〝Is stress necessary to stabilize sp3 bonding in diamond-like carbon?,〞Diamond and Related Materials, 11 (2002) 994-999.
Ferrari, A.C.,〝Determination of binding in diamond-like carbon by Raman spectroscopy ,〞 Diamond and Related Materials, 11 (2002) 1053-1061.
Gerbig, Y.B., Phani, A.R., Haefke, H., 〝Influence of nanoscale topography on the hydrophobicity of fluoro-based polymer thin film, 〞 Applied Surface Science, 242 (2005) 251-255.
Grill, A., 〝Amorphous carbon based materials as the interconnect dielectric in ULSI chips, 〞Diamond and Related Materials, 10 (2001) 234-239.
Inoue, N., Yuasa, H., Okoshi, M., 〝TiO2 thin films prepared by PLD for photocatalytic application, 〞 Applied Surface Science, 197-198 (2002) 393-397.
Irmer, G., Dorner-Reisel, A., 〝Micro-raman studies on DLC coatings, 〞Advanced Engineering Materials, Vol.7 No.8 (2005) 694-705.
JCPDS, Powder Diffraction File 06-0694,35-0803, 11-0065
JCPDS, Powder Diffraction File, 84-1285 for anatase TiO2 phase, 78-1510 for rutile TiO2 phase.
Joshi, G.P., Saxena, N.S., Mangal, R., Mishra, A., Sharma, T.P., 〝Band gap determination of Ni-Zn ferrites, 〞Bull. Material Science., 26(2003) 387-389.
Kim, Je-Deok, Sugimura, H., Takai, O., 〝Water-repellency of a-C:H films deposited by rf plasma-enhanced CVD,〞Vacuum, 66 (2002) 379-383.
Lifshitz, Y., Kasi, S.R., and Rabalais, J.W.,〝Subplantation model for film growth from hyperthermal species: application to diamond,〞Physical Review Letters, 62 (1989) 1290-1293.
Logothetidis, S., Charitidis, C., Patsalas, P., 〝Engineering properties of fully sp3- to sp2-bonded carbon films and their modifications after post-growth ion irradiation, 〞Diamond and Related Materials, 11 (2002) 1095-1099.
Lugscheider, E. and Bobzin, K., 〝The influence on surface free energy of PVD-coatings, 〞 Surface and Coating Technology, 142-144 (2001) 755-760.
Lugscheider, E., Bobzin, K., Moller, M., 〝The effect of PVD layer constitution on surface free energy, 〞 Thin Solid Films, 355-356 (1999) 367-373.
Mardare, D., Tasca, M., Delibas, M., Rusu, G.I., 〝On the structural properties and optical tramsmittance of TiO2 r.f. sputtered thin films,〞Applied Surface Science,156 (2000) 200-206.
Meng, L.J. and dos Santos, M.P., 〝Investigations of titanium oxide films deposited by d.c. reactive magnetron sputtering in different sputtering pressures,〞Thin Solid Films, 226 (1993) 22-29.
Mohamed, S.H., Kappertz, O., Niemeier, T., Drese, R., Wakkad, M.M., Wuttig, M., 〝Effect of heat treatment on structure, optical and mechanical properties of sputtered TiOxNy films, 〞Thin Solid Films, 468 (2004) 48-56.
Nakajima, A., Hayashi, N., Taniguchi, Y., Kameshima, Y., Okada, K., 〝Effect of vacuum ultraviolet light illumination on the crystallization of sol-gel-derived titanium dioxide precursor films, 〞Surface and Coating Technology, 192 (2005) 112-116.
Owens, D.K. and Wendl, R.C.,〝Estimation of the surface free energy of polymers,〞 J. Applied Polymer Science, 13 (1969) 1741-1747.
Park, B., Jung, D.H., Lee, G., Lee, J.J., Joo, J.H., 〝Synthesis of films by ICP-assisted DC magnetron sputtering, 〞Surface and Coating Technology, 174-175 (2003) 643-647.
Park, C.K., Chang, S.M.,Uhm, H.S., Seo, S.H., Park, J.S.,〝XPS and XRR studies on microstructures and interfaces of DLC films deposited by FCVA method,〞 Thin Solid Films, 420-421 (2002) 235-240.
Qin, S., Zhou, Y.Z., Chan, C., Chu, P.K., 〝Fabrication of low electric constant materials for ULSI multilevel interconnection by plasma ion implantation, 〞IEEE Electronic Device Letter, 19 (11) (1998) 420-422.
Robertson, J., 〝Diamond-like amorphous carbon, 〞Materials Science and Engineering, R37 (2002) 129-281.
Schwan, J., Ulrich, S., Bathori, V., Erhardt, H., Silva, S.R.P., 〝Raman spectroscopy on amorphous carbon films, 〞J. Applied Physics, 80 (1996) 440-447.
Shannon, R. D., 〝Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, 〞Acta Crystallographica, A32 (1976), 751-767.
Stappen, M.V., Vandierendonck, K., Mol, C., Beeckman, E., Clercq, E.D.,〝Practice vs. laboratory tests for plastic injection molding,〞Surface and Coating Technology, 142-144 (2001) 143-145.
Suda, Y., Kawasaki, H., Ueda, T., Ohshima, T., 〝Preparation of high quality nitrogen doped thin film as a photocatalyst using a pulse laser deposition method, 〞Thin Solid Films, 453-454 (2004) 162-166.
Syarif, D.G., Miyashita, A., Yamaki, T., Sumita, T., Choi, Y., Itoh, H., 〝Preparation of anatase and rutile thin films by controlling oxygen partial pressure, 〞Applied surface science, 193(2002) 287-292.
Takeda, S., Fukawa, M., Hayashi, Y., Matsumoto, K., 〝Surface OH group governing adsorption properties of metal oxide films, 〞 Thin Solid Films, 339 (1999) 220-224.
Takeda, S., Fukawa, M., 〝Surface OH groups governing surface chemical properties of SiO2 thin films deposited by RF magnetron sputtering, 〞 Thin Solid Films, 444 (2003) 153-157.
Tamor, M.A., Vassell, W.C.,〝Raman fingerprinting of amorphous carbon films,〞J. Applied Physics, Vol.76, No.6 (1994) 3823-3830.
Tauc, J., 〝Absorption edge and internal electric fields in amorphous semiconductors, 〞Material Research Bull., 5(1970) 721-729.
Terashima, K., Minegshi, T., Iwaki, M., Kawashima, K., 〝Surface modification of electrodeposited chromium films by ion implantation, 〞Materials Science and Engineering, 90(1987) 229-236.
Wang, X.Y., Liu, Z., Klein, D., Coddet, C., 〝Microstructure and electrical properties of plasma sprayed porous TiO2 coatings containing anatase, 〞Thin Solid Films, 451-452 (2004) 37-42.
Wang, D.Y., Weng, K.W., Chang, C.L. and Ho, W.Y.,〝Synthesis of Cr3C2 coatings for tribological applications,〞Surface and Coating Technology, 120-121 (1999) 622-628.
Wen, F., Huang, N., Sun, H., Leng, Y.X., 〝Synthesis of nitrogen incorporated carbon films by plasma immersion ion implantation and deposition, 〞Surface and Coating Technology, 186 (2004) 118-124.
Weng, K.W., Chang, C.L., Wang, D.Y., 〝Effect of ion energy on degradation of diamond-like carbon films exposed to high-energy bombardment from an ion implanter,〞Diamond and Related Materials, 11 (2002) 1447-1453.
Wu, S., J. Polymer Science, Part C 34 (1971) 19.
Wunderlich, W., Oekermann, T., Miao, L., Hue, N.T., Tanemura, S., Tanemura, M., 〝Electric properties of nano-porous TiO2- and ZnO2-thin films-comparison of simulations and experiments, 〞J. of Ceramic Processing Research, vol.5, no 4 (2004) 343-354.
Xia, L., Sun, M., Liao, J., 〝The effect of negative bias pulse on the bonding configurations and properties of DLC films prepared by PBII with acetylene, 〞Diamond and Related Materials, 14 (2005) 42-47.
Yamagishi, M., Kuriki, S., Song, P.K., Shigesato, Y.,” Thin film TiO2 photocatalyst deposited by reactive magnetron sputtering”, Thin Solid Films, 442 (2003) 227-231.
Yi, J. W., Lee, Y.H., Farouk, B., 〝Low dielectric fluorinated amorphous carbon thin films grown from C6F6 and Ar plasma, 〞Thin Solid Films, 374 (2000) 103-108.
Yi, J. W., Lee, Y.H., Farouk, B., 〝Low dielectric fluorinated amorphous carbon thin films grown from C6F6 and Ar plasma, 〞Thin Solid Films, 374 (2000) 103-108.
Young, T., 〝An essay on the cohesion of fluid, 〞Philosophical Transactions of the Royal Society of London, 95(1805) 65-87.
Zakrzewska, K., Radecka, M., Kruk, A., Osuch, W., 〝Noble metal/titanium dioxide nanocermets for photoelectrochemical applications, 〞 Thin Solid Films, 157 (2003) 349-356.
Zeman, P., Takabayashi, S., 〝Nano-scaled photocatalytic TiO2 thin films prepared by magnetron sputtering, 〞Thin Solid Films, 433 (2003) 57-62.
Zhang, W., Li, Y., Zhu, S., Wang, F., 〝Influence of argon flow rate on TiO2 photocatalyst film deposited by dc reactive magnetron sputtering, 〞 Surface and Coating Technology, 182 (2004) 192-198.
Zhang, W.H. and Hhsieh, J. H., 〝Tribological behavior of TiN and CrN coatings sliding against an epoxy molding compound, 〞 Surface and Coating Technology, 130 (2001) 240-247.
Zheng, S.K., Wang, T.M., Wang, C., Xiang, G., 〝Photocatalytic activity study of TiO2 thin films with and without Fe ion implantation, 〞Nuclear Instrument and Methods in Physics Research B, 187 (2002) 479-484.