The growth of tungsten nitride carbide (WNxCy) films obtained by atomic layer deposition using triethylboron, tungsten hexafluoride, and ammonia precursors is determined by the density and type of reactive sites. The film properties change as a function of thickness. On silicon dioxide and silicon carbide, growth is initially nonlinear such that the transient regimes are characterized by island formation, as evidenced by a parabolic tungsten growth curve extending to film thicknesses of up to 5 nm. Such films have low densities of similar to 4-6 g cm(-3) corresponding to only similar to 30%-45% of the bulk density of similar to 13.1 g cm(-3) determined for a WN0.45C0.55 composition. X-ray reflectivity, thermal desorption, and elastic recoil detection spectroscopies reveal surface roughening and compositional and density differences close to the substrate surface. The offset from linear growth in the case of WNxCy films deposited on silicon dioxide is induced by the initial reaction of silanol and siloxane groups with triethylborane resulting in passivating ethylsilyl groups on the surface. A transient regime is not observed for WNxCy growth on hydrogen-terminated silicon with the initial growth being dominated by the reduction of tungsten hexafluoride to tungsten. On silicon nitride a short transient regime is observed relative to the carbide and oxide surfaces attributed to the enhanced binding of the triethylboron precursor. (c) 2006 American Institute of Physics.
Kim H., Atomic layer deposition of metal and nitride thin films: Current research efforts and applications for semiconductor device processing, 10.1116/1.1622676
M. Ritala and M. Leskelä, in Handbook of Thin Film Materials, edited by H. S. Nalva (Academic, New York, 2002), Vol. 1, p. 135.
Puurunen Riikka L., Analysis of hydroxyl group controlled atomic layer deposition of hafnium dioxide from hafnium tetrachloride and water, 10.1063/1.1689732
Puurunen Riikka L., Vandervorst Wilfried, Island growth as a growth mode in atomic layer deposition: A phenomenological model, 10.1063/1.1810193
Satta A., Vantomme A., Schuhmacher J., Whelan C. M., Sutcliffe V., Maex K., Initial growth mechanism of atomic layer deposited TiN, 10.1063/1.1760217
Hoyas A. Martin, Schuhmacher J., Shamiryan D., Waeterloos J., Besling W., Celis J. P., Maex K., Growth and characterization of atomic layer deposited WC0.7N0.3 on polymer films, 10.1063/1.1631070
Travaly Y., Schuhmacher J., Hoyas A. M., Van Hove M., Maex K., Abell T., Sutcliffe V., Jonas A. M., Interface characterization of nanoscale laminate structures on dense dielectric substrates by x-ray reflectivity, 10.1063/1.1874301
W.M. Li et al., Proceedings of the IEEE IITC, Burlingame, CA, June 3–5, 2002 (IEEE, New York, 2002), p. 191.
Pal S., Sanyal M. K., Hazra S., Kundu S., Schreiber F., Pflaum J., Barrena E., Dosch H., Morphology and transport properties of nanostructural gold on silicon, 10.1063/1.1635989
Parratt L. G., Surface Studies of Solids by Total Reflection of X-Rays, 10.1103/physrev.95.359
Pedersen J. S., Hamley I. W., Analysis of neutron and X-ray reflectivity data. II. Constrained least-squares methods, 10.1107/s0021889893006272
Hitchman Michael L., Jobson Andrew D., Kwakman Loek F.Tz., Some considerations of the thermodynamics and kinetics of the chemical vapour deposition of tungsten, 10.1016/0169-4332(89)90552-7
Green M. L., Ho M.-Y., Busch B., Wilk G. D., Sorsch T., Conard T., Brijs B., Vandervorst W., Räisänen P. I., Muller D., Bude M., Grazul J., Nucleation and growth of atomic layer deposited HfO2 gate dielectric layers on chemical oxide (Si–O–H) and thermal oxide (SiO2 or Si–O–N) underlayers, 10.1063/1.1522811
Puurunen Riikka L., Vandervorst Wilfried, Besling Wim F. A., Richard Olivier, Bender Hugo, Conard Thierry, Zhao Chao, Delabie Annelies, Caymax Matty, De Gendt Stefan, Heyns Marc, Viitanen Minna M., de Ridder Marco, Brongersma Hidde H., Tamminga Yde, Dao Thuy, de Win Toon, Verheijen Marcel, Kaiser Monja, Tuominen Marko, Island growth in the atomic layer deposition of zirconium oxide and aluminum oxide on hydrogen-terminated silicon: Growth mode modeling and transmission electron microscopy, 10.1063/1.1787624
Creighton J.R., The surface chemistry and kinetics of tungsten chemical vapor deposition and selectivity loss, 10.1016/0040-6090(94)90448-0
Satta A., Schuhmacher J., Whelan C. M., Vandervorst W., Brongersma S. H., Beyer G. P., Maex K., Vantomme A., Viitanen M. M., Brongersma H. H., Besling W. F. A., Growth mechanism and continuity of atomic layer deposited TiN films on thermal SiO2, 10.1063/1.1522485
Haukka S., Adsorption Controlled Preparation of Heterogeneous Catalysts (1998)
S. Haukka (private communication).
Li W. M. (2005)
Chabal Y.J., Weldon M.K., Gurevich A.B., Christman S.B., Infrared Absorption Studies of Wet Chemical Oxides: Thermal Evolution of Impurities, 10.4028/www.scientific.net/ssp.65-66.253
Önneby C., Pantano C. G., Silicon oxycarbide formation on SiC surfaces and at the SiC/SiO2 interface, 10.1116/1.580951
Schuhmacher J., Materials for Information Technology
Besling W.F.A., Young E., Conard T., Zhao C., Carter R., Vandervorst W., Caymax M., De Gendt S., Heyns M., Maes J., Tuominen M., Haukka Suvi, Characterisation of ALCVD Al2O3–ZrO2 nanolaminates, link between electrical and structural properties, 10.1016/s0022-3093(02)00969-9
Gusev E.P., Cabral C., Copel M., D’Emic C., Gribelyuk M., Ultrathin HfO2 films grown on silicon by atomic layer deposition for advanced gate dielectrics applications, 10.1016/s0167-9317(03)00291-0
Zhang Jiasen, Yoshikado Shin, Aruga Tadashi, Shift multiplexing for holographic storage system using fiber bundle referencing, 10.1063/1.1535266
Copel M., Gribelyuk M., Gusev E., Structure and stability of ultrathin zirconium oxide layers on Si(001), 10.1063/1.125779
Puurunen Riikka L., Delabie Annelies, Van Elshocht Sven, Caymax Matty, Green Martin L., Brijs Bert, Richard Olivier, Bender Hugo, Conard Thierry, Hoflijk Ilse, Vandervorst Wilfried, Hellin David, Vanhaeren Danielle, Zhao Chao, De Gendt Stefan, Heyns Marc, Hafnium oxide films by atomic layer deposition for high-κ gate dielectric applications: Analysis of the density of nanometer-thin films, 10.1063/1.1866219
Park Ki‐Chul, Kim Ki‐Bum, Raaijmakers Ivo J. M. M., Ngan Ken, The effect of density and microstructure on the performance of TiN barrier films in Cu metallization, 10.1063/1.363620
Kundu S, Hazra S, Banerjee S, Sanyal M K, Mandal S K, Chaudhuri S, Pal A K, Morphology of thin silver film grown by dc sputtering on Si(001), 10.1088/0022-3727/31/23/001
Kizuka Tokushi, Nakagami Yuko, Ohata Tohru, Kanazawa Ikuzo, Ichinose Hideki, Murakami Hideoki, Ishida Yoichi, Structure and thermal stability of nanocrystalline silver studied by transmission electron microscopy and positron annihilation spectroscopy, 10.1080/01418619408242229
Klaus J.W., George S.M., Atomic layer deposition of SiO2 at room temperature using NH3-catalyzed sequential surface reactions, 10.1016/s0039-6028(99)01119-x
Becker Jill S., Gordon Roy G., Diffusion barrier properties of tungsten nitride films grown by atomic layer deposition from bis(tert-butylimido)bis(dimethylamido)tungsten and ammonia, 10.1063/1.1565699
Travaly Y., 723 (2003)
Bibliographic reference
Hoyas, AM ; Travaly, Y. ; Schuhmacher, J ; Sajavaara, T. ; Whelan, CM ; et. al. The impact of the density and type of reactive sites on the characteristics of the atomic layer deposited WNxCy films. In: Journal of Applied Physics, Vol. 99, no. 6 (2006)