Abstract
The published data on the atomic layer deposition of thin platinum-group metal (Ru, Rh, Pd, Os, Ir, and Pt) films with the use of different reactant precursors and second reactants (O2, O3, H2, etc.) are generalized in the context of microelectronic technologies. A procedure for analyzing the data on the atomic layer deposition kinetics is discussed. The rate of atomic layer deposition of metallic ruthenium is not higher than 0.15 nm/cycle. An inverse dependence of the limiting atomic layer deposition growth rate on the precursor molecular mass is established. The rates of atomic layer deposition of thin films of all the remaining metals in the group range between 0.03–0.07 nm/cycle, which is lower than the values for a monolayer of these metals by several times. The methodology and ways of enhancing the reliability of the kinetic data on the atomic layer deposition are discussed, including the need for taking into account the sample surface types and effects of nucleation delays at the initial growth stages of the thin platinum-group metal film. The possible occurrence of chemical deposition reactions with intermediate products involved at the pulsed injection of the reactants is considered.
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REFERENCES
Xia, L.-Q. and Chang, M., Chemical vapor deposition, in Handbook of Semiconductor Manufacturing Technology, 2nd ed., Doering, R. and Nishi, Y., Boca Raton, FL: CRC, 2008, pp. 13-1–13-87.
Vasilyev, V.Yu., Thin Film Chemical Vapor Deposition in Integrated Circuit Technology: Equipment, Methodology and Thin Film Growth Experience, New York: Nova Science, 2014.
Ritala, M. and Leskelä, M., in Handbook of Thin Film Materials, Nalwa, H.S., Ed., San Diego: Academic, 2001, vol. 1, pp. 103–159.
George, S.M., Atomic layer deposition: an overview, Chem. Rev., 2010, vol. 110, no. 1, pp. 111–131.
Hamalainen, J., Ritala, M., and Leskelä, M., Atomic layer deposition of noble metals and their oxides, Chem. Mater., 2014, vol. 26, no. 1, pp. 786–801.
Vasil’ev, V.Yu., Ultra-thin metal films of the platinum group for application in nano- and micro-technologies, Nano-Mikrosist. Tekh., 2016, vol. 18, no. 7, pp. 454–464.
Vasilyev, V.Yu., Morozova, N.B., and Igumenov, I.K., Chemical vapour-phase deposition of ruthenium-containing thin films, Russ. Chem. Rev., 2014, vol. 83, no. 8, pp. 758–782.
Vasilyev, V.Yu., Morozova, N.B., Basova, N.D., Igumenov, I.K., and Hassan, A., Chemical vapour deposition of IR-based coatings: chemistry, processes and applications, RCS Adv., 2015, vol. 5, pp. 32034–32063.
Puurunen, R.L., Surface chemistry of atomic layer deposition: a case study for the trimethylaluminum/water process, J. Appl. Phys., 2005, vol. 97, p. 121 301.
Elam, J.W., Zinovev, A., Han, C.Y., Wang, H.H., Welp, U., Hryn, J.N., and Pellin, M.J., Atomic layer deposition of palladium films om Al2O3 surfaces, Thin Solid Films, 2006, vol. 515, nos. 1–2, pp. 1664–1673.
Kim, J.-Y., Kil, D.-S., Kim, J.-H., Kwon, S.-H., Ahn, J.-H., Roh, J.-S., and Park, S.-K., Ru films from bis(ethylcyclopentadienyl)ruthenium using ozone as a reactant by atomic layer deposition for capacitor electrodes, J. Electrochem. Soc., 2012, vol. 159, no. 6, pp. H560–H564.
Kukli, K., Aarik, J., Aidla, A., Uustare, T., Jogi, I., Lu, J., Tallarid, M., Kemell, M., Kiisler, A.-A., Ritala, M., and Leskelä, M., Structure and morphology of ru films grown by atomic layer deposition from 1-ethyl-1'-methyl-ruthenocene, J. Cryst. Growth, 2010, vol. 312, nos. 12–13, pp. 2025–2032.
Kukli, K., Ritala, M., Kemell, M., and Leskela, M., High temperature atomic layer deposition of ruthenium from N,N-dimethyl-1-ruthenocenylethylamine, J. Electrochem. Soc., 2010, vol. 157, no. 1, pp. D35–D40.
Methaapanon, R., Geyer, S.M., Lee, H.-B.-R., and Bent, S.F., The low temperature atomic layer deposition of ruthenium and the effect of oxygen exposure, J. Mater. Chem., 2012, vol. 22, pp. 25154–25160.
Wang, H., Gordon, R.G., Alvis, R., and Ulfig, R.M., Atomic layer deposition of ruthenium thin films from an amidinate precursor, Chem. Vap. Deposit., 2009, vol. 15, nos. 10–12, pp. 312–319.
Li, H., Farmer, D.B., Gordon, R.G., Lin, Y., and Vlassak, J., Vapor deposition of ruthenium from an amidinate precursor, J. Electrochem. Soc., 2007, vol. 154, no. 12, pp. D642–D647.
Min, Y.-S., Bae, E.J., Jeong, K.S., Cho, Y.J., Lee, J.-H., Choi, W.B., and Park, G.-S., Ruthenium oxide nanotube arrays fabricated by atomic layer deposition using a carbon nanotube template, Adv. Mater., 2003, vol. 15, no. 12, pp. 1019–1022.
Aaltonen, T., Ritala, M., Arstila, K., Keinonen, J., and Leskela, M., Atomic layer deposition of ruthenium thin films from Ru(thd)3 and oxygen, Chem. Vap. Deposit., 2004, vol. 10, no. 4, pp. 215–219.
Aaltonen, T., Ritala, M., Tung, Y.-L., Chi, Y., Arstila, K., Meinander, K., and Leskela, M., Atomic layer deposition of noble metals: exploration of the low limit of the deposition temperature, J. Mater. Res., 2004, vol. 19, no. 11, pp. 3353–3358.
Park, S.K., Kanjolia, R., Anthis, J., Odedra, R., Boag, N., Wielunski, L., and Chabal, Y., Atomic layer deposition of Ru/RuO2 thin films studied by in-situ infrared spectroscopy, J. Chem. Mater., 2010, vol. 22, no. 17, pp. 4867–4878.
Schaekers, M., Capon, B., Detavernier, C., and Blasco, N., The deposition of Ru and RuO2 films for dram electrode, ECS Trans., 2010, vol. 33, no. 2, pp. 135–144.
Gregorczyk, K., Henn-Lecordier, L., Gatineau, J., Dussarrat, C., and Rubloff, G., Atomic layer deposition of ruthenium using the novel precursor bis(2,6,6-trimethyl-cyclohexadienyl)ruthenium, Chem. Mater., 2011, vol. 23, no. 10, pp. 2650–2656.
Kim, S.-H., Low temperature atomic layer deposition of Ru thin films with enhanced nucleation using various Ru(0) metallorganic precursors and molecular O2, ECS Trans., 2011, vol. 41, no. 2, pp. 19–23.
Kukli, K., Kemell, M., Puukilainen, E., Aarik, J., Aidla, A., Sajavaara, T., Laitinen, M., Tallarida, M., Sundqvist, J., Ritala, M., and Leskela, M., Atomic layer deposition of ruthenium films from (ethylcyclopentadienyl)(pyrrolyl)ruthenium and oxygen, J. Electrochem. Soc., 2011, vol. 158, no. 3, pp. D158–D165.
Kukli, K., Aarik, J., Aidla, A., Jogi, I., Arroval, T., Lu, J., Sajavaara, T., Laitinen, M., Kiisler, A.-A., Ritala, M., Leskelä, M., Peck, J., Natwora, J., Geary, J., Spohn, R., Meiere, S., and Thompson, D.M., Atomic layer deposition of Ru films from bis(2,5-dimethylpyrrolyl)ruthenium and oxygen, Thin Solid Films, 2012, vol. 520, no. 7, pp. 2756–2763.
Vasilyev, V.Yu., Mogilnikov, K.P., and Song, Y.W., Surface selective growth of ruthenium films under low temperature CVD conditions, Electrochem. Solid State Lett., 2008, vol. 11, no. 12, pp. D89–D93.
Lee, S.-J., Kim, S.-H., Saito, M., Suzuki, K., Nabeya, S., Lee, J., Kim, S., Yeom, S., and Lee, D.-J., Plasma-free atomic layer deposition of Ru thin films using H2 molecules as a nonoxidizing reactant, J. Vac. Sci. Technol., A, 2016, vol. 34, no. 3, p. 031 509.
Yung, J.-H., Lee, S.-J., Lee, H.-J., Lee, M.-Y., Cheon, T., Bae, S.I., Saito, M., Suzuki, K., Nabeya, S., Lee, J., Kim, S., Yeom, S., Seo, J.H., and Kim, S.-H., Atomic layer deposition of Ru thin films using a new beta-diketonate Ru precursor and NH3 plasma as a reactant, J. Nanosci. Nanotechnol., 2015, vol. 15, no. 11, pp. 8472–8477.
Park, K.J. and Parsons, G.N., Selective area atomic layer deposition of rhodium and effective work function characterization in capacitor structures, Appl. Phys. Lett., 2006, vol. 89, no. 4, p. 043 111.
Hämäläinen, J., Puukilainen, E., Sajavaara, T., Ritala, M., and Leskelä, M., Low temperature atomic layer deposition of noble metals using ozone and molecular hydrogen as reactants, Thin Solid Films, 2013, vol. 531, pp. 243–250.
Senkevich, J.J., Tang, F., Rogers, D., Drotar, J.T., Jezewski, C., Lanford, W.A., Wang, G.-C., and Lu, T.-M., Sustrate-independent palladium atomic layer deposition, Chem. Vap. Deposit., 2003, vol. 9, no. 5, pp. 258–264.
Ten Eyck, G.A., Pimanpang, S., Bakhru, H., Lu, T.-M., and Wang, G.-C., Atomic layer deposition of Pd on an oxidized metal substrate, Chem. Vap. Deposit., 2006, vol. 12, pp. 290–294.
Weber, M.J., Mackus, A.J.M., Verheijen, M.A., van der Marel, C., and Kessels, W.M.M., Supported core/ shell bimetallic nanoparticles synthesis by atomic layer deposition, Chem. Mater., 2012, vol. 24, pp. 2973–2977.
Weber, M.J., Mackus, A.J.M., Verheijen, M.A., Longo, V., Bol, A.A., and Kessels, W.M.M., Atomic layer deposition of high-purity palladium films from Pd(hfac)2 and H2 and O2 plasmas, J. Phys. Chem. C, 2014, vol. 118, pp. 8702–8711.
Feng, H., Elam, J.W., Libera, J.A., Setthapun, W., and Stair, P.C., Palladium catalysts synthesized by atomic layer deposition for methanol decomposition, Chem. Mater., 2010, vol. 22, pp. 3133–3142.
Aaltonen, T., Ritala, M., Tung, Y.-L., Chi, Y., Arstila, K., Meinander, K., and Leskela, M., Atomic layer deposition of noble metals: exploration of the low limit of the deposition temperature, J. Mater. Res., 2004, vol. 19, no. 11, pp. 3353–3358.
Hämäläinen, J., Sajavaara, T., Puukilainen, E., Ritala, M., and Leskelä, M., Atomic layer deposition of osmium, Chem. Mater., 2012, vol. 24, pp. 55–60.
Hämäläinen, J., Puukilainen, E., Kemell, M., Costelle, L., Ritala, M., and Leskelä, M., Atomic layer deposition of iridium thin films by consecutive oxidation and reduction steps, Chem. Mater., 2009, vol. 21, pp. 4868–4872.
Choi, B.H., Lee, J.H., Lee, H.K., and Kim, J.H., Effect of interface layer on growth behavior of atomic-layer-deposited Ir thin film as novel Cu diffusion barrier, Appl. Surf. Sci., 2011, vol. 257, no. 22, pp. 9654–9660.
Lim, Y.H., Yoo, H., Choi, B.H., Lee, J.H., Lee, H.-N., and Lee, H.K., Atomic-layer-deposited Ir thin film as a novel diffusion barrier layer in Cu interconnection, Phys. Status Solidi C, 2011, vol. 8, no. 3, pp. 891–894.
Hämäläinen, J., Hatanpää, T., Puukilainen, E., Costelle, L., Pilvi, T., Ritala, M., and Leskelä, M., (MeCp)Ir(CHD) and molecular oxygen as precursors in atomic layer deposition of iridium, J. Mater. Chem., 2010, vol. 20, no. 36, pp. 7669–7675.
Hämäläinen, J., Hatanpaaa, T., Puukilainen, E., Sajavaara, T., Ritala, M., and Leskelä, M., Iridium metal and iridium oxide thin films grown by atomic layer deposition at low temperatures, J. Mater. Chem., 2011, vol. 21, no. 41, pp. 16488–16483.
Hämäläinen, J., Munnik, F., Ritala, M., and Leskelä, M., Atomic layer deposition of platinum oxide and metallic platinum thin films from Pt(acac)2 and ozone, Chem. Mater., 2008, vol. 20, no. 21, pp. 6840–6846.
Mackus, A.J.M., Leick, N., Baker, L., and Kes-sels, W.M.M., Catalytic combustion and dehydrogenation reactions during atomic layer deposition of platinum, Chem. Mater., 2012, vol. 24, no. 10, pp. 1752–1761.
Vasilyev, V.Yu., Ruthenium thin film growth kinetics under thermally-activated pulsed chemical vapor deposition conditions, in Advances in Chemistry Research, Taylor, J.C., Ed., New York: Nova Science, 2017, vol. 39, pp. 109–140.
Vasilyev, V.Yu., Low-temperature thermally-activated pulsed chemical vapor deposition of ruthenium thin films using carbonyl-diene precursor, in Ruthenium: Properties, Production and Applications, Watson, D.B., Ed., New York: Nova Science, 2011, pp. 2–85.
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Vasilyev, V.Y. Estimating the Interrelation between the Rate of Atomic Layer Deposition of Thin Platinum-Group Metal Films and the Molecular Mass of Reactant Precursors. Russ Microelectron 48, 208–219 (2019). https://doi.org/10.1134/S1063739719040103
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DOI: https://doi.org/10.1134/S1063739719040103