Germanium antimony (Ge-Sb) thin films with tuneable compositions have been fabricated on SiO2/Si, borosilicate glass, and quartz glass substrates by chemical vapour deposition (CVD). Deposition takes place at atmospheric pressure using metal chloride precursors at reaction temperatures between 750 and 875°C. The compositions and structures of these thin films have been characterized by micro-Raman, scanning electron microscope (SEM) with energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD) techniques. A prototype Ge-Sb thin film phase-change memory device has been fabricated and reversible threshold and phase-change switching demonstrated electrically, with a threshold voltage of 2.2–2.5?V. These CVD-grown Ge-Sb films show promise for applications such as phase-change memory and optical, electronic, and plasmonic switching. 1. Introduction There is currently worldwide interest in the development of the next generation of computer memory, fuelling research in new materials which can be used to potentially store vast amounts of information. Phase-change random access memory (PCRAM) has attracted considerable interest as a candidate for the next generation of nonvolatile devices which will meet current and future needs of higher density, power consumption, and operation speed [1, 2]. Ternary Ge2Sb2Te5 (GST) compounds are widely regarded as the most commercially viable and practical phase-change family of materials for this application. These materials are currently being trialled commercially, and processes which deposit GST films by RF sputtering are being implemented into production lines [3]. Chemical vapour deposition techniques are expected to play a role in device fabrication and recently metal organic chemical vapour deposition (MOCVD) process has been applied to deposit GST materials in submicron cell pores [4]. In addition, the atomic layer deposition (ALD) process, which uses a mixture of metal organic and metal chloride precursors, has been reported for the fabrication of GST thin films. However, the contamination of O, H, C, and Cl atoms was reported as a consequence of the low deposition temperature [5]. There remains however many challenges [6] which include the need to control device-to-device variability and undesirable changes in the phase-change material that can be induced by the fabrication procedure. In addition the relatively long crystallization time of GST (~ hundreds nanoseconds) limits the ultimate operation speed of the PCRAM device [7]. A confined cell structure where the phase-change material is formed inside a
References
[1]
M. H. R. Lankhorst, B. W. S. M. M. Ketelaars, and R. A. M. Wolters, “Low-cost and nanoscale non-volatile memory concept for future silicon chips,” Nature Materials, vol. 4, no. 4, pp. 347–352, 2005.
[2]
C. W. Jeong, S. J. Ahn, Y. N. Hwang et al., “Highly reliable ring-type contact for high-density phase change memory,” Japanese Journal of Applied Physics, vol. 45, no. 4B, pp. 3233–3237, 2006.
[3]
A. Pirovano, A. L. Lacaita, A. Benvenuti, F. Pellizzer, and R. Bez, “Electronic switching in phase-change memories,” IEEE Transactions on Electron Devices, vol. 51, no. 3, pp. 452–459, 2004.
[4]
R.-Y. Kim, H.-G. Kim, and S.-G. Yoon, “Structural properties of Ge2Sb2Te5 thin films by metal organic chemical vapor deposition for phase change memory applications,” Applied Physics Letters, vol. 89, no. 10, Article ID 102107, 2006.
[5]
M. Ritala, V. Pore, T. Hatanp?? et al., “Atomic layer deposition of Ge2Sb2Te5 thin films,” Microelectronic Engineering, vol. 86, no. 7–9, pp. 1946–1949, 2009.
[6]
G. W. Burr, M. J. Breitwisch, M. Franceschini et al., “Phase change memory technology,” Journal of Vacuum Science and Technology B, vol. 28, no. 2, pp. 223–262, 2010.
[7]
R. A. Cobley and C. D. Wright, “Parameterized SPICE model for a phase-change RAM device,” IEEE Transactions on Electron Devices, vol. 53, no. 1, pp. 112–117, 2006.
[8]
Y. S. Park, K. J. Choi, N. Y. Lee et al., “Writing current reduction in phase change memory device with U-shaped heater (PCM-U),” Japanese Journal of Applied Physics, vol. 45, no. 20–23, pp. L516–L518, 2006.
[9]
C. N. Afonso, J. Solis, F. Catalina, and C. Kalpouzos, “Ultrafast reversible phase change in GeSb films for erasable optical storage,” Applied Physics Letters, vol. 60, no. 25, pp. 3123–3125, 1992.
[10]
J. Solis and C. N. Afonso, “Ultrashort-laser-pulse-driven rewritable phase-change optical recording in Sb-based films,” Applied Physics A, vol. 76, no. 3, pp. 331–338, 2003.
[11]
L. Van Pieterson, M. Van Schijndel, J. C. N. Rijpers, and M. Kaiser, “Te-free, Sb-based phase-change materials for high-speed rewritable optical recording,” Applied Physics Letters, vol. 83, no. 7, pp. 1373–1375, 2003.
[12]
L. Van Pieterson, M. H. R. Lankhorst, M. Van Schijndel, A. E. T. Kuiper, and J. H. J. Roosen, “Phase-change recording materials with a growth-dominated crystallization mechanism: a materials overview,” Journal of Applied Physics, vol. 97, no. 8, Article ID 083520, 7 pages, 2005.
[13]
L. Van Pieterson, E. W. Hesselink, J. C. N. Rijpers, M. Kaiser, M. A. Verheijen, and R. Elfrink, “Archival-overwrite performance of GeSnSb-based phase-change discs,” Journal of Applied Physics, vol. 99, no. 6, Article ID 066111, 2006.
[14]
T. J. Park, D. H. Kim, S. J. Park et al., “Phase transition characteristics and nonvolatile memory device performance of ZnxSb100-x alloys,” Japanese Journal of Applied Physics, vol. 46, no. 20-24, pp. L543–L545, 2007.
[15]
Y. C. Chen, C. T. Rettner, S. Raoux et al., “Ultra-thin phase-change bridge memory device using GeSb,” in Proceedings of the International Electron Devices Meeting (IEDM '06), San Francisco, Calif, USA, December 2006.
[16]
C. Cabral Jr., L. Krusin-Elbaum, J. Bruley et al., “Direct evidence for abrupt postcrystallization germanium precipitation in thin phase-change films of Sb-15 at. % Ge,” Applied Physics Letters, vol. 93, no. 7, Article ID 071906, 3 pages, 2008.
[17]
J.-H. Kim, K. Lee, S.-J. Chae et al., “Change in the resistivity of Ge-doped Sb phase change thin films grown by chemical vapor deposition according to their microstructures,” Applied Physics Letters, vol. 94, no. 22, Article ID 222115, 2009.
[18]
C. C. Huang and D. W. Hewak, “High-purity germanium-sulphide glass for optoelectronic applications synthesised by chemical vapour deposition,” Electronics Letters, vol. 40, no. 14, pp. 863–865, 2004.
[19]
C. C. Huang, D. W. Hewak, and J. V. Badding, “Deposition and characterization of germanium sulphide glass planar waveguides,” Optics Express, vol. 12, no. 11, pp. 2501–2506, 2004.
[20]
C. C. Huang, K. Knight, and D. W. Hewak, “Antimony germanium sulphide amorphous thin films fabricated by chemical vapour deposition,” Optical Materials, vol. 29, no. 11, pp. 1344–1347, 2007.
[21]
ASM international Alloy Phase Diagram and Handbook Committees, Alloy Phase Diagrams, vol. 3 of ASM Handbook, ASM International, 1992.
[22]
P. Kuisma-Kursula, “Scanning electron microscopy-energy dispersive spectrometry and proton induced x-ray emission analyses of medieval glass from Koroinen (Finland),” Archaeometry, vol. 41, no. 1, pp. 71–79, 1999.
[23]
A. Kobayashi, K. E. Newman, and J. D. Dow, “Densities of phonon states for (GaSb)1?x(Ge2)x,” Physical Review B, vol. 32, no. 8, pp. 5312–5327, 1985.
[24]
A. Roy, M. Komatsu, K. Matsuishi, and S. Onari, “Raman spectroscopic studies on Sb nanoparticles in SiO2 matrix prepared by rf-cosputtering technique,” Journal of Physics and Chemistry of Solids, vol. 58, no. 5, pp. 741–747, 1997.
[25]
Y. Jung, C. Y. Yang, S. H. Lee, and R. Agarwal, “Phase-Change ge-sb nanowires: synthesis, memory switching, and phase-instability,” Nano Letters, vol. 9, no. 5, pp. 2103–2108, 2009.
[26]
Z. L. Sámson, K. F. MacDonald, F. De Angelis et al., “Metamaterial electro-optic switch of nanoscale thickness,” Applied Physics Letters, vol. 96, no. 14, Article ID 143105, 2010.