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Silicon nanocrystals embedded in oxide films grown by magnetron sputtering

1 V. Lashkaryov ISP of NASU, 45 Pr. Nauky, 03028 Kyiv, Ukraine
2 Racah Institute of Physics, Hebrew University, 91904 Jerusalem, Israel
3 CEMES/CNRS, University of Toulouse, 29 rue J. Marvig 31055 Toulouse Cedex 4, France

Special Issues: Nanomaterials for energy and environmental applications

This paper presents a comparison of the results that we obtained and reported over the last few years on the structural, optical and light emitting properties of Si-SiO2 and Si-Al2O3 films that were fabricated using a specific configuration of RF magnetron sputtering. In these films the Si volume fraction, x, varies along the film (which is typically 14 cm long) from a value of ~0.1 at one end to ~0.9 at the other end. For the films with x > 0.3, the formation of amorphous Si clusters was observed in as-deposited Si-SiO2 and Si-Al2O3 films. Si nanocrystals (Si-ncs) were generated by high-temperature annealing of the films in nitrogen atmosphere. We found that two processes can contribute to the Si-ncs formation: (i) the crystallization of the existing amorphous Si inclusions in the as-deposited films, and (ii) the thermally stimulated phase separation. Process (i) can be responsible for the independence of Si-ncs mean sizes on x in annealed films with x > 0.5. At the same time, difference in the structural and the light emitting properties of the two types of films was observed. For the samples of the same x, the Si-ncs embedded in the Al2O3 host were found to be larger than the Si-ncs in the SiO2 host. This phenomenon can be explained by the lower temperature required for phase separation in Si-Al2O3 or by the lower temperature of the crystallization of Si-ncs in alumina. The latter suggestion is supported by Raman scattering and electron paramagnetic resonance spectra. In contrast with the Si-SiO2, the Si-ncs embedded in Si-Al2O3 films were found to be under tensile stress. This effect was explained by the strains at the interfaces between the film and silica substrate as well as between the Si inclusions and the Al2O3 host. It was also shown that exciton recombination in Si-ncs is the dominant radiative channel in Si-SiO2 films, while the emission from the oxide defects dominates in Si-Al2O3 films. This can be due to the high number of non-radiative defects at Si-ncs/Al2O3 interface, which is confirmed by our electron paramagnetic resonance data and is consistent with our above suggestion of mechanical stresses in the Si-Al2O3 films.
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Keywords Si nanocrystals; SiO2; Al2O3; luminescence; defects

Citation: Larysa Khomenkova, Mykola Baran, Jedrzej Jedrzejewski, Caroline Bonafos, Vincent Paillard, Yevgen Venger, Isaac Balberg, Nadiia Korsunska. Silicon nanocrystals embedded in oxide films grown by magnetron sputtering. AIMS Materials Science, 2016, 3(2): 538-561. doi: 10.3934/matersci.2016.2.538


  • 1. Canham LT (1990) Silicon quantum wire array fabrication by electrochemical and chemical dissolution of wafers. Appl Phys Lett 57: 1046–1048.    
  • 2. Lehman V, Gosele U (1991) Porous silicon formation: A quantum wire effect. Appl Phys Lett 58: 856–858.    
  • 3. Shimizu-Iwayama T, Nakao S, Saitoh K (1994) Visible photoluminescence in Si+‐implanted thermal oxide films on crystalline Si. Appl Phys Lett 65: 1814–1816.    
  • 4. Chen XY, Lu YF, Tang LJ, et al. (2005) Annealing and oxidation of silicon oxide films prepared by plasma-enhanced chemical vapor deposition. J Appl Phys 97: 014913.    
  • 5. Khomenkova L, Korsunska N, Yukhimchuk V, et al. (2003) Nature of visible luminescence and its excitation in Si-SiOx systems. J Lumin 102/103: 705–711.    
  • 6. Baran N, Bulakh B, Venger Ye, et al. (2009) The structure of Si–SiO2 layers with high excess Si content prepared by magnetron sputtering. Thin Solid Films 517: 5468–5473.    
  • 7. Khomenkova L, Korsunska N, Baran M, et al. (2009) Structural and light emission properties of silicon-based nanostructures with high excess silicon content. Physica E 41: 1015–1018.    
  • 8. Qin GG, Liu XS, Ma SY, et al. (1997) Photoluminescence mechanism for blue-light-emitting porous silicon. Phys Rev B 55:12876–12879.    
  • 9. Khomenkova L, Korsunska N, Torchynska T, et al. (2002) Defect-related luminescence of Si/SiO2 layers. J Phys Condens Matter 14:13217–13221.    
  • 10. Sa’ar A (2009) Photoluminescence from silicon nanostructures: The mutual role of quantum confinement and surface chemistry. J Nanophotonix 3: 032501 (56 pages).
  • 11. Balberg I (2011) Electrical transport mechanisms in three dimensional ensembles of silicon quantum dots. J Appl Phys 110: 061301 (26 pages).
  • 12. Koshida N (2009) Device Applications of Silicon Nanocrystals and Nanostructures, Springer, 344 p.
  • 13. Jamal Deen M, Basu P K (2012) Silicon Photonics: Fundamentals and Devices, Wiley, 192 p.
  • 14. Khomenkova L, Portier X, Cardin J, et al. (2010) Thermal stability of high-k Si-rich HfO2 layers grown by RF magnetron sputtering. Nanotechnology 21: 285707 (10 pages).    
  • 15. Steimle RF, Muralidhar R, Rao R, et al. (2007) Silicon nanocrystal non-volatile memory for embedded memory scaling. Microelectronics Reliability 47:585–592.    
  • 16. Baron T, Fernandes A, Damlencourt JF, et al. (2003) Growth of Si nanocrystals on alumina and integration in memory devices. Appl Phys Lett 82: 4151–4153.
  • 17. Pillonnet-Minardi A, Marty O, Bovier C, et.al. (2001) Optical and structural analysis of Eu3+-doped alumina planar waveguides elaborated by the sol–gel process, Optical Materials 16: 9–13.
  • 18. Kenyon AJ (2002) Recent developments in rare-earth doped materials for optoelectronics. Progress in Quantum Electronics 26: 225–284
  • 19. Mikhaylov AN, Belov AI, Kostyuk AB, et al. (2012) Peculiarities of the formation and properties of light-emitting structures based on ion-synthesized silicon nanocrystals in SiO2 and Al2O3 matrices. Physics of the Solid State (St.Petersburg, Russia) 54: 368–382.    
  • 20. Yerci S, Serincan U, Dogan I, et al. (2006) Formation of silicon nanocrystals in sapphire by ion implantation and the origin of visible photoluminescence. J Appl Phys 100: 074301 (5 pages).    
  • 21. Núñez-Sánchez S, Serna R, García López J, et al. (2009) Tuning the Er3+ sensitization by Si nanoparticles in nanostructured as-grown Al2O3 films. J Appl Phys 105: 013118 (5 pages).    
  • 22. Bi L, Feng JY (2006) Nanocrystal and interface defects related photoluminescence in silicon-rich Al2O3 films. J Lumin 121:95–101.    
  • 23. Korsunska N, Khomenkova L, Kolomys O, et al. (2013) Si-rich Al2O3 films grown by RF magnetron sputtering: structural and photoluminescence properties versus annealing treatment. Nanoscale Res Lett 8: 273.    
  • 24. Korsunska N, Stara T, Strelchuk V, et al. (2013) The influence of annealing on structural and photoluminescence properties of silicon-rich Al2O3 films prepared by co-sputtering. Physica E 51: 115–119.    
  • 25. Khomenkova L, Kolomys O, Baran M, et al. (2014) Structure and light emission of Si-rich Al2O3 and Si-rich SiO2 nanocomposites. Microelectr Eng. 125: 62–67.
  • 26. Khomenkova L, Kolomys O, Baran M, et al. (2014) Comparative investigation of structural and optical properties of Si-rich oxide films fabricated by magnetron sputtering. Adv Mat Res 854: 117–124.
  • 27. HORIBA: Spectroscopic Ellipsometry, DeltaPsi2 Software Platform. http://www.horiba.com/scientific/products/ellipsometers/software/
  • 28. Hanak JJ (1970) The "Multiple-Sample Concept" in Materials Research: Synthesis, Compositional Analysis and Testing of Entire Multicomponent Systems. J Mater Sci 5: 964–971.    
  • 29. Abeles B, Sheng P, Coutts MD, et al. (1975) Structural and electrical properties of granular metal films. Adv Phys 24: 407–461.    
  • 30. Farooq M, Lee ZH (2002) Optimization of the sputtering process for depositing composite thin films. J Korean Phys Soc 40: 511–516.
  • 31. Khomenkova L, Korsunska N, Sheinkman M, et al. (2007) Chemical composition and light emission properties of Si-rich-SiOx layers prepared by magnetron sputtering. Semicond Phys Quantum Electron Optoelectron 10: 21–25.
  • 32. Charvet S, Madelon R, Gourbilleau F, et al. (1999) Spectroscopic ellipsometry analyses of sputtered Si/SiO2 nanostructures. J Appl Phys 85: 4032 (8 pages).
  • 33. Buiu O, Davey W, Lu Y, et al. (2008) Ellipsometric analysis of mixed metal oxides thin films. Thin Solid Films 517: 453–455.
  • 34. Forouhi AR, Bloomer I (1986) Optical dispersion relations for amorphous semiconductors and amorphous dielectrics. Phys Rev B 34: 7018–7026.    
  • 35. Jelisson GE Jr, Modine FA (1996) Parameterization of the optical functions of amorphous materials in the interband region. Appl Phys Lett 69: 371–373.    
  • 36. Serenyi M, Lohner T, Petrik P, et al. (2007) Comparative analysis of amorphous silicon and silicon nitride multilayer by spectroscopic ellipsometry and transmission electron microscopy. Thin Solid Films 515: 3559–3562.    
  • 37. Houska J, Blazek J, Rezek J, et al. (2012) Overview of optical properties of Al2O3 films prepared by various techniques. Thin Solid Films 520: 5405–5408.    
  • 38. Bruggeman DAG (1935) Berechnung verschiedener physikalischer Konstanten von heterogenen Substanzen. I. Dielektrizitätskonstanten und Leitfähigkeiten der Mischkörper aus isotropen Substanzen. Annalen der Physik 416: 665–679.
  • 39. Khomenkova L, Labbé C, Portier X, et al. (2013) Undoped and Nd3+ doped Si‐based single layers and superlattices for photonic applications. Phys Stat Sol (a) 210: 1532–1543.    
  • 40. Campbell IH, Fauchet PM (1986) The effects of microcrystal size and shape on the one phonon Raman spectra of crystalline semiconductors. Solid State Commun 58: 739–741.
  • 41. Morales M, Leconte Y, Rizk R, et al. (2005) Structural and microstructural characterization of nanocrystalline silicon thin films obtained by radio-frequency magnetron sputtering. J Appl Phys 97: 034307.    
  • 42. Schamm S, Bonafos C, Coffin H, et al. (2008) Imaging Si nanoparticles embedded in SiO2 layers by (S)TEM-EELS. Ultramicroscopy 108: 346–357.    
  • 43. Skuja LN, Silin AR (1979) Optical properties and energetic structure of non-bridging oxygen centers in vitreous SiO2. Phys Stat Sol A 56: K11–K13.    
  • 44. Munekuni S, Yamanaka T, Shimogaichi Y, et al. (1990) Various types of nonbridging oxygen hole center in high‐purity silica glass. J Appl Phys 68: 1212–1217.    
  • 45. Bratus’ VYa, Yukhinchuk VA, Berezhinsky LI, et al. (2001) Structural transformations and silicon nanocrystallite formation in SiOx films. Semiconductors 35: 821–826.    
  • 46. Prokes SM, Carlos WE (1995) Oxygen defect center red room temperature hotoluminescence from freshly etched and oxidized porous silicon. J Appl Phys 78: 2671–2674.    
  • 47. Torchyska TV, Korsunska NE, Khomekova LYu, et al. (2000) Suboxide-related centre as the source of the intense red luminescence of porous Si. Microelectron Eng 51–52: 485–493.
  • 48. Song HZ, Bao XM (1997) Visible photoluminescence from silicon-ion-implanted SiO2 films and its multiple mechanisms. Phys Rev B 55: 6988–6993.    
  • 49. Dubin VM, Chazalviel J-N, Ozaman F (1993) In situ photoluminescence and photomodulated infrared study of porous silicon during etching and in ambient. J Lumin 57: 61–65.    
  • 50. Yin S, Xie E, Zhang C, et al. (2008) Photoluminescence character of Xe ion irradiated sapphire. Nucl Instr Methods B 12–13:2998–3001.
  • 51. Kokonou M, Nassiopoulou AG, Travlos A (2003) Structural and photoluminescence properties of thin alumina films on silicon, fabricated by electrochemistry. Mater Sci Eng B 101: 65–70.    
  • 52. Dogan I, Yildiz I, Turan R (2009) PL and XPS depth profiling of Si/Al2O3 co-sputtered films and evidence of the formation of silicon nanocrystals. Physica E 41: 976–981.    
  • 53. Varshni YP (1967) Temperature dependence of the energy gap in semiconductors. Physica 34: 149–154.    
  • 54. O’Donnell KP, Chen X (1991) Temperature dependence of semiconductor band gaps. Appl Phys Lett 58: 2925–2927.
  • 55. Peng X-H, Alizadeh A, Bhate N, et al. (2007) First-principles investigation of strain effects on the energy gaps in silicon nanoclusters. J Phys Condens Matter 19: 266212 (9 pages).    
  • 56. Menendez J, Cardona M (1984) Temperature dependence of the first-order Raman scattering by phonos in Si, Ge, and a-Sn: Anharmonic effects. Phys Rev B 29: 2051–2059.    
  • 57. Lautenschlager P, Garriga M, Vina L, et al. (1987) Temperature dependence of the dielectric function and interband critical points in silicon. Phys Rev B 36: 4821–4830.    
  • 58. Steasman A, Afanas’ev VV (1997) Point defect generation in SiO2 by interaction with SiO at elevated temperatures. Microelectr Eng 36: 201–204.    
  • 59. Jones BJ, Barklie RC (2005) Elecron paramagnetic resonance evolution of defects at the (100)Si/Al2O3 interface. J Phys D Appl Phys 38: 1178–1181.    
  • 60. Nast O, Wenham SR (2000) Elucidation of the layer exchange mechanism in the formation of polycrystalline silicon by aluminum-induced crystallization. J Appl Phys 88: 124–132.    


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