Dense Ge nanocrystal layers embedded in oxide obtained by controlling the diffusion–crystallization process

Amorphous Ge/SiO2 multilayer structures deposited by magnetron sputtering have been annealed at different temperatures between 650 and 800 °C for obtaining Ge nanocrystals in oxide matrix. The properties of the annealed structures were investigated by transmission electron microscopy, Raman spectroscopy, and low temperature photoluminescence. The Ge crystallization is partially achieved at 650 °C and increases with annealing temperature. Insight of the Ge nanocrystal formation was acquired by comparing two annealing procedures, i.e., in a conventional tube furnace and by a rapid thermal annealing. By rapid thermal annealing in comparison to conventional furnace one, the Ge crystallization process is faster than Ge diffusion, resulting in the formation of more compact layers of Ge nanocrystals with 8–9.5-nm size as Raman spectroscopy reveals. These findings are important to improve the annealing efficiency in the nanocrystals formation for a precise control of their sizes and location in oxide matrix and for the possibility to create systems with interacting nanoparticles for charge or excitonic transfer. The infrared photoluminescence of Ge nanocrystals at low temperatures shows strong emission with two sharp peaks at about 1,000 meV.

[1]  S. Takeoka,et al.  Size-dependent near-infrared photoluminescence from Ge nanocrystals embedded in SiO2 matrices , 1998 .

[2]  M. Green,et al.  Rapid thermal annealing and crystallization mechanisms study of silicon nanocrystal in silicon carbide matrix , 2011, Nanoscale research letters.

[3]  Yoshihiko Kanemitsu,et al.  Visible photoluminescence of Ge microcrystals embedded in SiO2 glassy matrices , 1991 .

[4]  Residual stress in Si nanocrystals embedded in a SiO2 matrix , 2006 .

[5]  G. Iordache,et al.  Structural investigations of Ge nanoparticles embedded in an amorphous SiO2 matrix , 2011 .

[6]  Y. Yu,et al.  Origin of photoluminescence peaks in Ge–SiO2 thin films , 2002 .

[7]  K. Rottwitt,et al.  Formation and characterization of varied size germanium nanocrystals by electron microscopy, Raman spectroscopy, and photoluminescence , 2011 .

[8]  Guanqun Xie,et al.  Optical characteristics of Si/SiO2 multilayers prepared by magnetron sputtering , 2009 .

[9]  M. Gomes,et al.  Low-temperature fabrication of layered self-organized Ge clusters by RF-sputtering , 2011, Nanoscale research letters.

[10]  C. Yuan,et al.  Preparation and photoluminescence properties of Ge nanocrystals embedded in SiO2 matrices with Ge–GeOx core–shell structure , 2009 .

[11]  B. Korgel,et al.  Raman Spectroscopy of Oxide-Embedded and Ligand-Stabilized Silicon Nanocrystals. , 2012, The journal of physical chemistry letters.

[12]  M. Gomes,et al.  Raman study of stress effect on Ge nanocrystals embedded in Al2O3 , 2010 .

[13]  Maja Buljan,et al.  Ellipsometric study of thermally induced redistribution and crystallization of Ge in Ge:SiO2 mixture layers , 2011 .

[14]  A. Kolobov,et al.  Formation of Ge nanocrystals embedded in aSiO2matrix: Transmission electron microscopy, x-ray absorption, and optical studies , 2003 .

[15]  A. Pathak,et al.  Structural studies of Ge nanocrystals embedded in SiO2 matrix , 2007 .

[16]  T. Stoica,et al.  Ge dots embedded in SiO2 obtained by oxidation of Si/Ge/Si nanostructures , 2006 .

[17]  M. Krause,et al.  Reactive dc magnetron sputtering of (GeOx–SiO2) superlattices for Ge nanocrystal formation , 2010 .

[18]  Keiichi Yamamoto,et al.  Growth of Ge Microcrystals in SiO2 Thin Film Matrices: A Raman and Electron Microscopic Study , 1991 .

[19]  S. Manna,et al.  Microstructural, chemical bonding, stress development and charge storage characteristics of Ge nanocrystals embedded in hafnium oxide , 2011 .

[20]  Y. Kanemitsu,et al.  Near-infrared photoluminescence from Ge nanocrystals in SiO2 matrices , 2000 .

[21]  James S. Harris,et al.  MBE growth of tensile-strained Ge quantum wells and quantum dots , 2012 .

[22]  C. Yuan,et al.  Dielectric matrix imposed stress–strain effect on photoluminescence of Ge nanocrystals , 2009 .

[23]  M. Green,et al.  Size controlled synthesis of Ge nanocrystals in SiO2 at temperatures below 400 °C using magnetron sputtering , 2010 .

[24]  F. C. Loh,et al.  Densification of radio frequency sputtered silicon oxide films by rapid thermal annealing , 1998 .

[25]  G. Nilsson,et al.  Phonon Dispersion Relations in Ge at 80 °K , 1971 .

[26]  Kaiming Zhang,et al.  COMPARISON OF MODELS FOR RAMAN SPECTRA OF SI NANOCRYSTALS , 1997 .

[27]  Rasit Turan,et al.  Characterization of Ge nanocrystals embedded in SiO2 by Raman spectroscopy , 2004 .

[28]  P. Liao,et al.  Matrix and quantum confinement effects on optical and thermal properties of Ge quantum dots , 2012 .

[29]  Sasaki,et al.  Resonant Raman study of phonon states in gas-evaporated Ge small particles. , 1993, Physical review. B, Condensed matter.

[30]  A. Dana,et al.  TEM studies of Ge nanocrystal formation in PECVD grown SiO2:Ge/SiO2 multilayers , 2006 .

[31]  Christophe Delerue,et al.  Quantum confinement in germanium nanocrystals , 2000 .

[32]  W. K. Choi,et al.  Influence of reductant and germanium concentration on the growth and stress development of germanium nanocrystals in silicon oxide matrix , 2006 .

[33]  Stacked Ge nanocrystals with ultrathin SiO₂ separation layers. , 2011, Nanotechnology.

[34]  Magdalena Lidia Ciurea,et al.  Annealing temperature effect on structure and electrical properties of films formed of Ge nanoparticles in SiO2 , 2013 .

[35]  T. Finstad,et al.  Growth of Ge nanoparticles on SiO2/Si interfaces during annealing of plasma enhanced chemical vapor deposited thin films , 2007 .

[36]  L. Ley,et al.  The one phonon Raman spectrum in microcrystalline silicon , 1981 .

[37]  S. Manna,et al.  Optical and electrical properties of undoped and doped Ge nanocrystals , 2012, Nanoscale Research Letters.

[38]  N. Frateschi,et al.  The effect of Ge implantation dose on the optical properties of Ge nanocrystals in SiO2 , 2006, Nanotechnology.

[39]  E. Haller,et al.  Photoluminescence of bulk germanium , 2012 .

[40]  Y. Chabal,et al.  Modified phonon confinement model for Raman spectroscopy of nanostructured materials , 2010 .

[41]  H. Fukuda,et al.  Characterization of Ge nanocrystal embedded in SiO2 films , 2001 .

[42]  The charge trapping and memory effect in SiO2 thin films containing Ge nanocrystals , 2010 .

[43]  V. Holý,et al.  The influence of deposition temperature on the correlation of Ge quantum dot positions in amorphous silica matrix , 2009, Nanotechnology.

[44]  M. Green,et al.  Characterisation of size-controlled and red luminescent Ge nanocrystals in multilayered superlattice structure , 2010 .

[45]  W. K. Choi,et al.  Phonon confinement in Ge nanocrystals in silicon oxide matrix , 2011 .

[46]  M. Green,et al.  Electrical properties of conductive Ge nanocrystal thin films fabricated by low temperature in situ growth , 2011, Nanotechnology.

[47]  R. Turan,et al.  Evolution of SiO2/Ge/HfO2(Ge) multilayer structure during high temperature annealing , 2010 .

[48]  J. Sangrador,et al.  Crystallization of Amorphous Si0.6Ge0.4 Nanoparticles Embedded in SiO2: Crystallinity Versus Compositional Stability , 2010 .

[49]  M. Ciurea,et al.  Structure and electrical transport in films of Ge nanoparticles embedded in SiO2 matrix , 2012, Journal of Nanoparticle Research.

[50]  M. Green,et al.  Fabrication of multilayered Ge nanocrystals by magnetron sputtering and annealing , 2008, Nanotechnology.

[51]  S. Cloutier,et al.  Direct-bandgap luminescence at room-temperature from highly-strained Germanium nanocrystals. , 2010, Optics express.

[52]  I. Boyd,et al.  Enhanced luminescence from encapsulated silicon nanocrystals in SiO2 with rapid thermal anneal , 2006 .

[53]  Rapid thermal annealing of size-controlled Si nanocrystals: Dependence of interface defect density on thermal budget , 2011 .

[54]  Ge-Si-O phase separation and Ge nanocrystal growth in Ge:SiO(x)/SiO(2) multilayers--a new dc magnetron approach. , 2011, Nanotechnology.

[55]  Xiaowei Wang,et al.  Near-infrared photoluminescence in germanium oxide enclosed germanium nano- and micro-crystals , 2007, Nanotechnology.

[56]  B. Schmidt,et al.  Stress measurements of germanium nanocrystals embedded in silicon oxide , 2003 .

[57]  S. Chua,et al.  Raman and photoluminescence properties of Ge nanocrystals in silicon oxide matrix , 2004 .