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Chemistry

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Published: July 26th, 2016

DOI:

10.3791/54268

1McKetta Department of Chemical Engineering, The University of Texas at Austin

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2×1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

Perovskite materials are becoming increasingly attractive due to their highly symmetric cubic or pseudocubic structure and myriad of properties. These materials, with general formula ABO3, consist of A atoms coordinated with 12 oxygen atoms and B atoms coordinated with six oxygen atoms. Owing to their simple structure, yet wide range of potential elements, perovskite materials provide ideal candidates for heterostructure devices. Epitaxial oxide heterostructures boast ferromagnetic,1-3 anti/ferroelectric,4 multiferroic,5-8 superconductive,7-12 and m....

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1. Preparing Sr and Ti Precursors for ALD Experiments

  1. Load the clean, dry saturators and new precursors into the antechamber of a glove box. Follow the glove box's loading procedure to ensure proper purging of air and moisture. Transfer the materials into the main chamber.
    Note: This group uses in-house built saturators (see Figure 3) with components purchased commercially. Details of the saturator assembly can be found in the List of Specific Reagents and Equipmen.......

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Figures 5 and 6 show typical X-ray photoelectron spectra and RHEED images from a cleaned and deoxidized Ge substrate. A successfully-deoxidized Ge substrate is characterized by its "smiley face" 2×1 reconstructed RHEED pattern.26,39 In addition, Kikuchi lines are also observed in the RHEED images, which indicate the cleanliness and long range order of the sample.40 The sharpness and intensity of the diffraction pattern a.......

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The cleanliness of the Ge substrate is the key to success when growing the epitaxial perovskite using ALD. The amount of time a Ge substrate spends between degreasing and deoxidization, and the amount of time between deoxidization and STO deposition, should be kept at a minimum. Samples are still subject to contaminant exposure even under the UHV environment. Prolonged exposure may lead to redeposition of adventitious carbon or Ge reoxidation, resulting in poor film growth. This group has employed a widely-used degreasin.......

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This research was supported by the National Science Foundation (Awards CMMI-1437050 and DMR-1207342), the Office of Naval Research (Grant N00014-10-10489), and the Air Force Office of Scientific Research (Grant FA9550-14-1-0090).

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Name Company Catalog Number Comments
MBE DCA M600
Cryopump for MBE Brooks Automation, Inc. On-Board 8
Residual Gas Analyzer for MBE Extorr, Inc. XT200M
ALD Reaction Chamber Huntington Mechanical Laboratories N/A Custom manufactured, hot-wall, stainless steel, rectangular (~20 cm long, 460 cm3)
ALD Saturator Swagelok/Larson Electronic Glass See comments Custom-built from parts supplied by Swagelok and Larson Electronic Glass. The saturator is made out of 316 stainless steel and Pyrex. All parts are connected via butt welding. Swagelok catalog numbers:SS-4-VCR-7-8VCRF, SS-4-VCR-1, SS-8-VCR-1-03816, SS-8-VCR-3-8MTW, 316L-12TB7-6-8, SS-8-VCR-9, SS-4-VCR-3-4MTW, SS-T2-S-028-20  Larson Electronic Glass catalog number: SP-075-T
Manual Valves for Saturators Swagelok SS-DLVCR4-P and 6LVV-DPFR4-P. Both diaphragm-sealed valves are used interchangably by this group. The specific connectors (VCR male/female/etc.) to use will depend on the actual system design.
ALD Valves Swagelok 6LVV-ALD3TC333P-CV
ALD System Tubing Swagelok 316L tubing of various sizes. This group uses inner diameter of 1/4"
ALD power supply AMETEK Programmable Power, Inc. Sorensen DCS80-13E
ALD Temperature Controller Schneider Electric Eurotherm 818P4
ALD Valve Controller  National Instruments LabView Program developed within the group
XPS VG Scienta
RHEED Staib Instruments CB801420 18 keV at ~3° incident angle
RHEED Analysis System k-Space Associates kSA 400
Digital UV Ozone System Novascan PSD-UV 6
Ozone Elimination System Novascan PSD-UV OES-1000D
Strontium bis(triisopropylcyclopentadienyl) Air Liquide HyperSr Mildly reactive to air and water. Further information supplied by Air Liquide can be found at https://www.airliquide.de/inc/dokument.php/standard/1148/airliquide-hypersr-datasheet.pdf
Titanium tetraisopropoxide (TTIP) Sigma-Aldrich 87560 Flammable in liquid and vapor phase
Ge (001) wafer MTI Corporation GESBA100D05C1 4", single-side polished Sb-doped wafer with ρ ≈ 0.04 Ω-cm
Argon (UHP) Praxair N/A
Deionized Water N/A N/A 18.2 MΩ-cm

  1. Phan, M. -. H., Yu, S. -. C. Review of the magnetocaloric effect in manganite materials. J. Magn. Magn. Mater. 308 (2), 325-340 (2007).
  2. Serrate, D., Teresa, J. M. D., Ibarra, M. R. Double perovskites with ferromagnetism above room temperature. J. Phys. Condens. Matter. 19 (2), 023201 (2007).
  3. Cheng, J. -. G., Zhou, J. -. S., Goodenough, J. B., Jin, C. -. Q. Critical behavior of ferromagnetic perovskite ruthenates. Phys. Rev. B. 85 (18), 184430 (2012).
  4. Ahn, C. H. Ferroelectricity at the Nanoscale: Local Polarization in Oxide Thin Films and Heterostructures. Science. 303 (5657), 488-491 (2004).
  5. Catalan, G., Scott, J. F. Physics and Applications of Bismuth Ferrite. Adv. Mater. 21 (24), 2463-2485 (2009).
  6. Ramesh, R., Spaldin, N. A. Multiferroics: progress and prospects in thin films. Nat. Mater. 6 (1), 21-29 (2007).
  7. Vrejoiu, I., Alexe, M., Hesse, D., Gösele, U. Functional Perovskites - From Epitaxial Films to Nanostructured Arrays. Adv. Funct. Mater. 18 (24), 3892-3906 (2008).
  8. Jang, H. W., et al. Metallic and Insulating Oxide Interfaces Controlled by Electronic Correlations. Science. 331 (6019), 886-889 (2011).
  9. Hwang, H. Y., et al. Emergent phenomena at oxide interfaces. Nat. Mater. 11 (2), 103-113 (2012).
  10. Stemmer, S., Millis, A. J. Quantum confinement in oxide quantum wells. MRS Bull. 38 (12), 1032-1039 (2013).
  11. Stemmer, S., James Allen, S. Two-Dimensional Electron Gases at Complex Oxide Interfaces. Annu. Rev. Mater. Res. 44 (1), 151-171 (2014).
  12. Biscaras, J., et al. Two-dimensional superconductivity at a Mott insulator/band insulator interface LaTiO3/SrTiO3. Nat. Commun. 1, 89 (2010).
  13. Dagotto, E. Complexity in Strongly Correlated Electronic Systems. Science. 309 (5732), 257-262 (2005).
  14. Jin, K., et al. Novel Multifunctional Properties Induced by Interface Effects in Perovskite Oxide Heterostructures. Adv. Mater. 21 (45), 4636-4640 (2009).
  15. McKee, R. A., Walker, F. J., Chisholm, M. F. Crystalline oxides on silicon: the first five monolayers. Phys. Rev. Lett. 81 (14), 3014 (1998).
  16. Warusawithana, M. P., et al. A Ferroelectric Oxide Made Directly on Silicon. Science. 324 (5925), 367-370 (2009).
  17. Niu, G., Vilquin, B., Penuelas, J., Botella, C., Hollinger, G., Saint-Girons, G. Heteroepitaxy of SrTiO3 thin films on Si (001) using different growth strategies: Toward substratelike qualitya. J. Vac. Sci. Technol. B. 29 (4), 041207 (2011).
  18. Yu, Z., et al. Advances in heteroepitaxy of oxides on silicon. Thin Solid Films. 462-463, 51-56 (2004).
  19. Yu, Z., et al. Epitaxial oxide thin films on Si (001). J. Vac. Sci. Technol. B. 18 (4), 2139-2145 (2000).
  20. Demkov, A. A., Zhang, X. Theory of the Sr-induced reconstruction of the Si (001) surface. J. Appl. Phys. 103 (10), 103710 (2008).
  21. Zhang, X., et al. Atomic and electronic structure of the Si/SrTiO3 interface. Phys. Rev. B. 68 (12), 125323 (2003).
  22. Ashman, C. R., Först, C. J., Schwarz, K., Blöchl, P. E. First-principles calculations of strontium on Si(001). Phys. Rev. B. 69 (7), 075309 (2004).
  23. Kamata, Y. High-k/Ge MOSFETs for future nanoelectronics. Mater. Today. 11 (1-2), 30-38 (2008).
  24. Fischetti, M. V., Laux, S. E. Band structure, deformation potentials, and carrier mobility in strained Si, Ge, and SiGe alloys. J. Appl. Phys. 80 (4), 2234-2252 (1996).
  25. Liang, Y., Gan, S., Wei, Y., Gregory, R. Effect of Sr adsorption on stability of and epitaxial SrTiO3 growth on Si(001) surface. Phys. Status Solidi B. 243 (9), 2098-2104 (2006).
  26. McDaniel, M. D., et al. A Chemical Route to Monolithic Integration of Crystalline Oxides on Semiconductors. Adv. Mater. Interfaces. 1 (8), (2014).
  27. Leskelä, M., Ritala, M. Atomic layer deposition (ALD): from precursors to thin film structures. Thin Solid Films. 409 (1), 138-146 (2002).
  28. George, S. M. Atomic Layer Deposition: An Overview. Chem. Rev. 110 (1), 111-131 (2010).
  29. McDaniel, M. D., Posadas, A., Wang, T., Demkov, A. A., Ekerdt, J. G. Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition. Thin Solid Films. 520 (21), 6525-6530 (2012).
  30. McDaniel, M. D., et al. Growth of epitaxial oxides on silicon using atomic layer deposition: Crystallization and annealing of TiO2 on SrTiO3-buffered Si(001). J. Vac. Sci. Technol. B. 30 (4), 04E11 (2012).
  31. McDaniel, M. D., et al. Epitaxial strontium titanate films grown by atomic layer deposition on SrTiO3-buffered Si(001) substrates. J. Vac. Sci. Technol. A. 31 (1), 01A136 (2013).
  32. Ngo, T. Q., et al. Epitaxial growth of LaAlO3 on SrTiO3-buffered Si (001) substrates by atomic layer deposition. J. Cryst. Growth. 363, 150-157 (2013).
  33. Ngo, T. Q., et al. Epitaxial c-axis oriented BaTiO3 thin films on SrTiO3-buffered Si(001) by atomic layer deposition. Appl. Phys. Lett. 104 (8), 082910 (2014).
  34. McDaniel, M. D., et al. Incorporation of La in epitaxial SrTiO3 thin films grown by atomic layer deposition on SrTiO3-buffered Si (001) substrates. J. Appl. Phys. 115 (22), 224108 (2014).
  35. McDaniel, M. D., et al. Atomic layer deposition of crystalline SrHfO3 directly on Ge (001) for high-k dielectric applications. J. Appl. Phys. 117 (5), 054101 (2015).
  36. Jahangir-Moghadam, M., et al. Band-Gap Engineering at a Semiconductor-Crystalline Oxide Interface. Adv. Mater. Interfaces. 2 (4), (2015).
  37. Posadas, A., et al. Epitaxial integration of ferromagnetic correlated oxide LaCoO3 with Si (100). Appl. Phys. Lett. 98 (5), 053104 (2011).
  38. Ponath, P., Posadas, A. B., Hatch, R. C., Demkov, A. A. Preparation of a clean Ge(001) surface using oxygen plasma cleaning. J. Vac. Sci. Technol. B. 31 (3), 031201 (2013).
  39. Braun, W. . Applied RHEED: Reflection High-Energy Electron Diffraction During Crystal Growth. , (1999).
  40. Moulder, J. F., Stickle, W. F., Sobol, P. E., Bomben, K. E. . Handbook of X-ray Photoelectron Spectroscopy. , (1992).
  41. Vehkamäki, M., Hatanpää, T., Hänninen, T., Ritala, M., Leskelä, M. Growth of SrTiO3 and BaTiO3 thin films by atomic layer deposition. Electrochem. Solid-State Lett. 2 (10), 504-506 (1999).
  42. Vehkamäki, M., et al. Atomic Layer Deposition of SrTiO3 Thin Films from a Novel Strontium Precursor-Strontium-bis(tri-isopropyl cyclopentadienyl). Chem. Vap. Depos. 7 (2), 75-80 (2001).
  43. Ritala, M., Leskelä, M., Niinisto, L., Haussalo, P. Titanium isopropoxide as a precursor in atomic layer epitaxy of titanium dioxide thin films. Chem. Mater. 5 (8), 1174-1181 (1993).
  44. Aarik, J., Aidla, A., Uustare, T., Ritala, M., Leskelä, M. Titanium isopropoxide as a precursor for atomic layer deposition: characterization of titanium dioxide growth process. Appl. Surf. Sci. 161 (3-4), 385-395 (2000).
  45. Premkumar, P. A., Delabie, A., Rodriguez, L. N. J., Moussa, A., Adelmann, C. Roughness evolution during the atomic layer deposition of metal oxides. J. Vac. Sci. Technol. A. 31 (6), 061501 (2013).

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