Vol. 236 Nos.
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`I—2, December 15th, 1993
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`ISSN 0040 6090
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`Proceedings of the 20th lntemational Conference on Metallurgical Coatings ‘and Thin
`Films, San Diego, CA, USA, April 19-23, 1993
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`Guest Editors: G. E. McGuire, A. Illattlwws and H. A. Jelm
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`
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`-J’_€"«
`E L S E V I E R
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`SEQUOIA
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`Editor-in-chz'ef:
`J.E. Greene
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`Volume 236 (1993)
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`me 236 (I993)
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`Absrracting—Index1'ng Services
`This journal is cited by the following Abstracting and/or Indexing Services. Metal Abstracts, Chemical Abstracts,
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`International Standard Serial Number 0040-6090
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`© 1993—Elsevier Sequoia. All rights reserved
`09254005/93/$6.00
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`N soup FILMS
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`VOLUME 236, NUMBERS 1-2, DECEMBER 15. 1993
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`Contents
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`OPTICAL THIN FILMS
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`Optically active films and ion processing of optical materials
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`Properties of transparent conducting oxides deposited at room temperature .
`L. Davis (Fort Lauderdale, FL, USA)
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`Optical switching technology for glazings .
`C. M. Lampert (Berkeley, CA, USA)
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`Low temperature preparation of transparent conducting ZnO:Al thin films by chemical beam deposition . .
`H. Sato, T. Minami, S. Takata, T. Miyata and M. Ishii (lshikawa, Japan)
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`SnO2 transparent conductor films produced by filtered vacuum arc deposition .
`A. Ben-Shalom, L. Kaplan, R. L. Boxman, S. Goldsmith and M. Nathan (Tel-Aviv, Israel)
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`14
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`27
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`Transparent conducting p—type Ni0 thin films prepared by magnetron sputtering .
`H. Sato, T. Minami, S. Takata and T. Yamada (lshikawa, Japan)
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`Characterization of n-CdS/p-CuGa, In, _, Se, thin film heterojunctions .
`Y. Apama, P. S. Reddy, B. Srinivasulu Naidu and P. Jayarama Reddy (Tirupati, India)
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`32
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`CVD, PECVD and non-vacuum deposition techniques for optical coating
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`37
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`Low temperature preparation of SrTiO3 thin films .
`E. Dayalan and M. S. Tomar (Tulsa, OK, USA)
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`Thermal stability of pyrolytic tin oxide films on aluminium .
`A. Roos (Uppsala, Sweden), G. Chinyama (Lusaka, Zambia) and P. Hedenqvist (Uppsala, Sweden)
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`40
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`Optical properties and equilibrium temperatures of titanium-nitride- and graphite-coated Langmuir probes for space
`application .
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`M. Veszelei and E. Veszelei (Uppsala, Sweden)
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`Deposition and characterization of multicomponent oxide films and multilayers from aqueous solution .
`G. J. Exarhos and N. J. Hess (Richland, WA, USA)
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`46
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`5]
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`Silicon based, protective transparent multilayer coatings deposited at high rate on optical polymers by dual-mode MW/r.f.
`PECVD .
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`J. C. Rostaing, F. Coeuret (Jouycn—Josas, France), B. Drevillon, R. Etemadi, C. Godet, J. Hue, J. Y. Parey and
`V. A. Yakovlcv (Palaiseau, France)
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`Inhomogeneous dielectrics grown by plasma-enhanced chemical vapor deposition .
`S. Lim, J. H. Ryu, J. F. Wager (Corvallis, OR, USA) and L. M. Casas (Ft. Monmouth, NJ, USA)
`Characterization of magnetron-sputtered diamond-like thin films for optical coatings in IR .
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`G. A. Clarke and R. R. Parsons (Vancouver, B.C., Canada)
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`DIAMOND AND RELATED MATERIALS
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`Electronic and optical applications of diamond and related materials
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`Thermal reaction of Ta thin films with polycrystalline diamond .
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`J. S. Chen, E. Kolawa, M.-A. Nicolet and F. S. Pool (Pasadena, CA, USA)
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`Effect of oxygen on hydrogenated amorphous carbon films.
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`Y. Suefuji, Y. Nakamura. Y. Watanabe, S. Hirayama and K. Tamakr (Kanagawa, Japan)
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`Fabrication of amorphous diamond films .
`S. Falabella, D. B. Boercker and D. M. Sanders (Livermore, CA, USA)
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`82
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`Elsevier Sequoia
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`Page 5 of 13
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`Synthesis of diamond and related materials
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`Selective area deposition of diamond on 4 in Si wafers .
`W. Hanni, C. Miiller, M. Binggeli, H. E. Hintermann, P. Krebs and A. Grisel (Neuchatel, Switzerland)
`Plasma diagnostics of a d.c. arcjct chemical vapor deposition diamond reactor .
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`S. W. Reeve and W. A. Weimer (China Lake, CA, USA)
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`87
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`Diamond and related materials (Poster session)
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`Properties of mixed-phase BN films deposited by r.f. PACVD .
`D. C. Cameron, M. Z. Karim and M. S. J. Hashmi (Dublin, Ireland)
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`Thermal expansion of chemical vapor deposition grown diamond films .
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`S. B. Qadri, C. Kim, B. F. Skelton, T. Hahn and J. E. Butler (Washington, DC, USA)
`Diamond thin films synthesized by a multinozzle oxy-acetylene chemical vapour deposition method .
`W. Zhu, B. H. Tan and H. S. Tan (Singapore, Singapore)
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`Application of nickel plating for the synthesis of chemical vapour deposition of diamond on steels .
`H. C. Shih, W. T. Hsu, C. T. Hwang, C. P. Sung, L. K. Lin and C. K. Lee (Hsinchu, Taiwan)
`Nucleation of diamond particles by hot filament chemical vapour deposition .
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`Microwave diamond synthesis with high oxygen hydrocarbons—(carbon dioxide, oxygen) .
`C.-F. Chen, S.-H. Chen, T.-M. Hong (Hsinchu, Taiwan), H.-W. Ko and S. E. Sheu (Lungtan, Taiwan)
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`ADVANCES IN COATING AND THIN FILM CHARACTERIZATION
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`Microstructural characterization and imaging techniques
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`scanning electron microscope .
`S. D. Walck, J. S. Zabinski, M. S. Donley (Wright Patterson, OH, USA) and J. E. Bultman (Dayton, OH, USA)
`XRD characterization of multilayered systems .
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`P. Scardi, L. Lutterotti (Mesiano, Italy) and A. Tomasi (Povo, Italy)
`Temperature dependence of atomic mixing at the copper—silicon interface.
`A. M. Ektessabi (Kyoto, Japan)
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`Low energy electron microscopy studies of Ge and Ag growth on Si(lll).
`A. W. Denier van dcr Gon, R. M. Tromp and M. C. Reuter (Yorktown Heights, NY, USA)
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`Surface and thin film analysis techniques
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`146
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`Thermal modeling of a calorimetric technique for measuring the emittance of surfaces and coatings .
`D. A. Jaworske (Cleveland, OH, USA)
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`Further investigation of proton elastic scattering cross-section on carbon and silicon .
`T. Xie (McMinnville, OR, USA), J. Liu (Chicago, IL, USA) and H. J. Fischbeck (Norman, OK, USA)
`Energy calibration accomplished by proton resonance scattering simulation .
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`T. Xie (McMinnville, OR, USA), J. Liu (Chicago, IL, USA) and H. J. Fischbeck (Norman, OK, USA)
`Application of X-ray photoclectron spectroscopy valence bands in studying ceramic surfaces and interfaces .
`D. Majumdar and D. Chatterjee (Rochester, NY, USA)
`Auger electron spectroscopy studies of interfacial reactions in metal/semiconductor multilayers activated during dilferential
`scanning calorimetry measurements.
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`A Zalar (Ljubljana, Slovenia), S Hofmann, F Pimentel (Stuttgart, Germany) and P Panjan (Ljubljana, Slovenia)
`New trends in analytical tribology .
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`J. M. Martin and M. Belin (Ecully, France)
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`Optical properties and surface morphology studies of palladium contacts on mercuric iodide single crystals .
`M. A. George, M. Azoulay, A. Burger, Y. Biao, E. Silberman (Nashville, TN, USA) and D. Nason (Goleta, CA, USA)
`Non-destructive characterization techniques
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`169
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`180
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`Decorative hard coatings: advances in optical characterization techniques
`U. Beck, G. Reiners and K. Witt (Berlin, Germany)
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`Photothermal characterization of optical thin films .
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`In-situ characterization techniques
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`Kinetics of aluminium film oxidation measured by a modified quartz crystal microbalance
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`M. Martin and E. Fromm (Stuttgart, Germany)
`Investigation of the adhesion mechanisms of silicon alloy thin films on polymer substrates by IR ellipsometry
`B. Drévillon (Palaiseau, France), J. C. Rostaing (Les Loges en Josas France) and S. Vallon (Palaiseau France)
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`Mechanical properties and film adhesion
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`Elastic behaviour of TiN thin films. .
`M. Elena, M l30nell1 (Povo, Italy), C E Bottam, G Ghislotti (Milano, Italy), A Miotello (Povo, Italy), P Mutt:
`and P. M. OSS1 (Milano, Italy)
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`230
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`The nanoindentation response of systems with thin hard carbon coatings .
`S. V. Hainsworth, T. Bartlett and T. F. Page (Newcastle upon Tyne, UK)
`The temperature-variant hardness response of duplex TBCs .
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`P. C. Twigg and T. F. Page (Newcastle upon Tyne, UK)
`Finite element studies of tensile testing on thin film multilayers .
`D. Krus, Jr, and R. W. Hoffman (Cleveland, OH, USA)
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`An overview on metal/PET adhesion .
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`J. F. Silvain (Talence, France) and J. J. Ehrhardt (Villers-lés-Nancy, France)
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`Interface structure and adhesion of sputtered Ti layers on Si: the efi‘ect of heat treatment .
`I. Kondo, T. Yoneyama, K. Kondo, O. Takenaka (Kariya, Japan) and A. Kinbara (Tokyo, Japan)
`Cusp-like flaws along a rough surface .
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`J. Li, C.-H. Chiu, H. Gao (Stanford, CA, USA) and T.-W. Wu (San Jose, CA, USA)
`Measurement of Young’s moduli of TiC-coated film by the X-ray method .
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`H. Asada (Nagoya, Japan), Y. Kishi and Y. Hirose (Kanazawa, Japan)
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`Measurement of the adhesion of TiN and Al coatings by fracture mechanics tests .
`D. Miiller, Y. R. Cho and E. Fromm (Stuttgart, Germany)
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`253
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`TOPICAL CONFERENCE ON ADVANCED METALLIZATION
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`Advanced metallization: materials and processes
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`Advanced multilayer metallization schemes with copper as interconnection metal . .
`S. P. Murarka, R. J. Gutmann (Troy, NY, USA), A. E. Kaloyeros and W. A. Lanford (Albany, NY, USA)
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`Properties of titanium and aluminum thin films deposited by collimated sputtering .
`D. Liu, S. K. Dew, M. J. Brett (Edmonton, Alb., Canada), T. Janaoek, T. Smy (Ottawa, Ont., Canada) and
`W. Tsai (Palo Alto, CA, USA)
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`Selective plasma deposition .
`M. A. Ray, J. Duarte and G. E. McGuire (Research Triangle Park, NC, USA)
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`Advanced dielectrics and planarization: materials and processes
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`Stability and surface morphology of films obtained by a chemical vapor deposition process .
`H. J. Viljoen (Lincoln, NE, USA)
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`281
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`Characterization of phosphosilicate glass films obtained using plasma-enhanced chemical vapor deposition from tetra-
`ethylorthosilicate and trimethylphosphite .
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`C. L. Pillote, F. A. Shemansky (Mesa, AZ. USA). T- Scale and G- 13- Raupp (Tempe, AZ. USA)
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`287
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`Diflusion barriers
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`Kinetics and conformality of TiN films from TDEAT and ammonia . . .
`T. S. Cale, M. B. Chaara, G. B. Raupp (Tempe, AZ, USA) and I. J. Raaijmakers (San Jose, CA, USA)
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`m(l3r_p](ooll:wa4DX,e§oun2oJ,lslllgeid, 1. s. Chen, M.-A. Nicolet and R. Ruiz (Pasadena, CA, USA)
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`Study of sputtered molybdenum nitride as a diffusion barrier.
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`v. P. Anitha, A. Bhattacharya, N. G. Patil and s. Maior (Bombay, India)
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`Properties of chemical-vapor-deposited titanium nitride .
`J. B. Price, J. O. Borland and S. Selbrede (Sunnyvale, CA, USA)
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`Evaluation of amorphous (Mo, Ta, W)—Si—N dilfusion barriers for (Si)|Cu metallizations .
`J. S. Reid, E. Kolawa, R. P. Ruiz and M.-A. Nicolet (Pasadena, CA, USA)
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`Manufacturing aspects of low pressure chemical-vapor-deposited TiN barrier layers .
`E. 0. Travis and R. W. Fiordalice (Austin, TX, USA)
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`325
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`330
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`Characterization of low pressure chemically vapor-deposited tungsten nitride films .
`S. D. Marcus and R. F. Foster (Phoenix, AZ, USA)
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`334
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`Spatial composition variation in sputtered Ti—W films .
`B. R. Rogers (Mesa, AZ, USA) and T. S. Cale (Tempe, AZ, USA)
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`Topical conference on advanced metallization (Poster session)
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`Mass and surface conductivity gain on polymer surfaces metallized using vacuum arc deposition .
`R. L. Boxman and S. Goldsmith (Tel Aviv, Israel)
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`Properties of reactively sputter-deposited Ta—N thin films .
`X. Sun, E. Kolawa, J.-S. Chen, J. S. Reid and M.-A. Nicolet (Pasadena, CA, USA)
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`341
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`347
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`352
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`Three-dimensional simulation of an isolation trench refill process .
`H. Liao and T. S. Cale (Tempe, AZ, USA)
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`Author Index .
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`36]
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`Subject Index .
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`Page 8 of 13
`
`

`

`Thin Solid Films, 236 (1993) 347-351
`
`347
`
`Properties of reactively sputter-deposited Ta—N thin films
`
`Xin Sun, Elzbieta Kolawa, Jen—Sue Chen, Jason S. Reid and Marc-A. Nicolet
`Cali ornia Institute of Technology, Pasadena, CA 9ll25 (USA)
`
`Abstract
`
`We deposited Ta—N films by reactive r.f. sputtering from a Ta target with an N —Ar gas mixture Allo s over a
`composition range 0-60 at.%N have been synthesized. We report on their composition structure andyelectrical
`resistivity before and after vacuum annealing in the temperature range 500-800 °C. We found that the film rowth
`rate decreases with increasing ratio of the nitrogen flow rate to the total flow rate while the nitrogen contentgin the
`films first increases with the N2 partial flow rate and then saturates at about 60 at.%. B.c.c.-Ta Ta2N TaN and
`Ta,N6 appear in succession as the nitrogen content rises, with Ta,N being the only single-phase film obtained. The
`atomic density of the films generally increases with the nitrogen content
`in the film. Transmission electron
`micrographs show that the grain size decreases from about 25 to 4 nm as the nitrogen concentration increases from
`20 to 50 at.%. The 'l‘a2N phase can exist over a wide range of nitrogen concentration from about 25 to 45 at.%. For
`as-deposited films an amorphous phase exists along with polycrystalline Ta2N in the center portion of that range.
`This phase crystallizes after vacuum annealing at 600 °C for 65 min. A diagram of stable and metastable phases for
`Ta—N films based on X-ray diffraction and transmission electron microscopy results is constructed. The resistivity
`is below 0.3 mil cm for films with 0-50 at.% N and changes little upon vacuum annealing at 800 °C.
`
`
`1. Introduction
`
`Thin films of Ta and its various compounds have
`long been of practical and scientific interest [1]. In the
`recent past tantalum nitride has attracted attention for
`applications as a thin film resistor with a low tempera-
`ture coeflicient of resistivity [2, 3], as a stable Schottky
`contact to silicon [4] and as a thin film diffusion barrier
`between silicon and metal overlayers of Ni [5], Al [6-9]
`and most recently Cu [10, 11]. As diffusion barriers in
`metal—semieonductor contacts,
`refractory metal ni-
`trides have long been recognized as an attractive class
`of material because of their high stability and good
`conductivity [12]. As an impurity in polycrystalline
`transition metal films, nitrogen has also been shown to
`restrict diffusion and increase the barrier effectiveness
`of those films, presumably by decorating the extended
`defects that act as fast diffusion paths in polycrystalline
`metallic films [13]. In substantial atomic concentrations,
`nitrogen can also promote the formation of amorphous
`metallic alloys with most early transition metals. The
`resulting films tend to combine the advantages of the
`high inertness of the respective metal nitrides with the
`absence of fast diffusion paths as they exist in polycrys-
`talline films (for a review see ref. 14).
`To elucidate the influence of nitrogen on the diffusion
`barrier performance,
`it is essential to clarify how the
`deposition conditions and subsequent annealing treat-
`ment alter the structural and electrical properties of 3
`film. The objective of the present study is to establish
`
`0040~6090/93/$6.00
`
`Page 9 of 13
`
`these facts for reactively sputter-deposited tantalum
`nitride films with a particular concern for the existence
`of amorphous Ta—N. The study generally follows the
`approach of a similar investigation of the W-N system
`[15].
`
`2. Procedures
`
`Silicon wafers, either covered with thermally grown
`SiO2 or patterned with photoresist, and segments of
`carbon tape were used as substrates on a stationary
`platform. -Ta—N films were deposited on these sub-
`strates by reactive r.f. magnetron sputtering from a
`7.5 cm planar Ta cathode in an N,—Ar ambient. The
`substrate holder was placed about 7cm below the
`target and was neither cooled nor heated externally.
`The background pressure was 5 X l0'7 Torr or less
`prior to the film deposition. The flow rates of N, and
`Ar and the total gas pressure were adjusted by mass
`flow controllers. The total pressure was monitored with
`a capacitive manometer in a feedback loop. We varied
`the N2 partial flow rate, defined as the ratio of the
`nitrogen flow rate to the total flow rate of argon and
`nitrogen, from 0% to 25% to get 10 sets of films With
`different compositions. The total flow rate was in the
`range 55-80 cm3 min". The highest flow rate was used
`to maintain good control of the nitrogen flow when its
`fraction was small. The forward sputtering power and
`total gas pressure were kept at 300W and 10 mTorr
`
`© 1993 —- Elsevier Sequoia. All rights reserved
`
`

`

`348
`
`X. Sun et al. / Reactively sputter-deposited Ta —N thin films
`
`so
`
`39
`
`5 so
`.1’.
`
`é ‘o
`,5
`5 3°
`1;
`'3 2°
`§
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`o
`
`5
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`
`15
`
`2o
`
`25
`
`N2 partial flow rats (%J
`
`Fig. 2. Nitrogen concentration in Ta-N films vs. N, partial flow rate
`in the chamber. The symbols indicate that the films are typically of
`multiphase composition.
`
`cally of multiphase composition, as determined by X-
`ray diffraction. Similar trends in deposition rate and
`nitrogen concentration have been reported previously
`for d.c.-sputtered Ta-N films [6], but the functional
`dependences on the N2 flow rate of those results and
`ours cannot readily be compared because the nitrogen
`flow rate was varied under different experimental con-
`straints. X-ray analyses reveal that the film deposited
`in pure Ar is b.c.c.-Ta. For a nitrogen concentration
`between about 10 and 20 at.%, Ta2N is present
`in
`addition to the b.c.c.-Ta phase. The only crystalline
`phase present between about 20 and 50 at.% N is Ta,N,
`but an amorphous component also appears in the cen-
`ter portion of that range. At 50 at.% N, TaN is present,
`together with Ta,N5 as the nitrogen concentration ex-
`oeeds the 50 at.% value. The structure of tantalum
`
`nitrides can be described as close-packed arrangements
`of Ta atoms with N atoms inserted in interstitial sites.
`
`The space group of Ta,N is P63/mmc [16], with equal
`numbers of sites for Ta and N atoms, while the nitrogen
`atoms occupy half of the sites randomly [17]. However,
`deviations from this occupancy ratio can occur, which
`explains the finite range of existence of Ta2N. The
`range here exceeds that reported for thermal equi-
`librium conditions [18] and is presumably due to the
`non-equilibrium aspects of the sputter deposition tech-
`nique. The sequence of the phases observed here is
`consistent with the equilibrium phase diagram [18],
`where b.c.c.-Ta is known to have a low solubility for N,
`Ta2N exists over a range of about 10 at.% around its
`stoichiometric composition and TaN is a narrow phase.
`Various nitrogen-rich compounds
`(Ta5N,,, Ta.,N5,
`Ta3N,) are also reported [16, 18], of which only Ta,N5
`fits the observed X-ray lines well.
`The atomic density of the as-deposited films vs. the
`nitrogen concentration in the films is plotted in Fig. 3.
`The Ta film sputter deposited in pure Ar has a density
`
`respectively for all depositions. Sputter deposition was
`performed in a static mode for 5min. The carbon
`substrates were used to determine the nitrogen concen-
`tration in the films by 2 MeV “He” backscattering
`spectrometry. Photoresist-patterned films on Si sub-
`strates were obtained by lifting off in acetone and were
`subsequently used for measuring the film thickness with
`a Dektak profilometer. The atomic density of a film was
`calculated from its thickness and from the width of the
`
`Ta signal in the backscattering spectrum of the film.
`Films on oxidized Si substrates were annealed in a
`vacuum furnace at a pressure of about 5 x 10"’ Torr
`and temperatures ranging from 500 to 800 °C. All
`annealings lasted 65 min. All as-deposited and annealed
`films on oxidized Si were analyzed by backscattering
`spectrometry, four-point probe sheet resistance mea-
`surement, Co Kct X-ray diffraction using a stationary
`position-sensitive detector and by Cu Kot X-rays using
`a Read camera. We also made special depositions on
`copper grids covered with holey carbon. Plan-view mi-
`crostructures of these films were characterized by trans-
`mission electron microscopy (TEM) in a Philips EM430
`microscope operating at 300 keV.
`
`3. Results and discussion
`
`3.1. As-deposited films
`Figure 1 shows the growth rate of films for various
`N, partial flow rates in the chamber. The growth rate
`decreases rapidly as the amount of nitrogen increases.
`For films reactively sputtered in a gas mixture with 5%
`N2, the growth rate is only 70% of that in pure Ar. At
`the same time the nitrogen concentration in the films
`increases steeply at first and then tends to saturate at
`about 60 at.%, as shown in Fig. 2. The symbols in this
`and subsequent figures indicate that the films are typi-
`
`56
`
`it I)O
`
`o
`
`5
`
`10
`
`15
`
`2o
`
`25
`
`N2 partial flow rate (96)
`
`I. Film growth rate of reactively sputtered Ta-N films vs.
`Fig.
`nitrogen partial flow rate.
`r
`
`Page 10 of 13
`
`to rnTorr I 800W
`asdepoalled
`
`so
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`45
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`5 so
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`Page 10 of 13
`
`

`

`X- 5"" 5' “L I Rwctively -‘Putter-cieposited Ta—N mm films
`
`349
`
`
`
`
`
`Atomicdensity(1022cm‘3)
`
`10
`
`10 mTorr ISOOW
`as deposited
`
`{D
`
`0
`
`so
`40
`so
`20
`I0
`N concentration in film (atom °/0)
`
`so
`
`70
`
`Fig. 3. Atomic density of reactively sputtered Ta—N films with
`various nitrogen concentrations. Note that the Y axis starts from
`about 4.5 instead of zero. For reference, bulk densities are indicated
`with arrows on the Y axis.
`
`that of bulk Ta
`as
`same
`the
`almost
`is
`that
`(5.52 x 1022 cm‘3). The atomic density of the films
`generally increases as the amount of nitrogen increases.
`This change in density of the films corresponds to the
`successive appearance of Ta2N, TaN and Ta5N6 in the
`films as the nitrogen concentration increases.
`In the
`figure, the atomic densities of the films with high nitro-
`gen concentration are typically larger than those of
`their corresponding bulk compounds. Although this is
`unusual, these films contain some phases that are far
`from their exact stoichiometric composition, which
`might at least partly explain the results. The remaining
`discrepancy, if any, may be attributed to experimental
`uncertainties, which are due to the lateral non-unifor-
`mity of the film thickness and to the high background
`encountered in the backscattering signal of nitrogen.
`To classify the microstructure of the as-deposited
`films, special depositions (labelled A—E on the bottom
`abscissa of Fig. 5) were made on copper grids covered
`with holey-carbon. Correspondingly labelled bright-
`field micrographs are shown in Fig. 4. The grains