Journal of Materials Science

, Volume 50, Issue 9, pp 3477–3484 | Cite as

Germanosilicate glass–ceramics for non-linear optics

  • Mafalda Ventura
  • Gonçalo Monteiro
  • Rui M. Almeida
  • R. Schwarz
  • Luís F. Santos
Original Paper


Glass samples in the GeO2·SiO2·Nb2O5·K2O system, with different K2O/Nb2O5 ratios, were prepared, and glass–ceramics were obtained by controlled crystallization. Characterization included density measurements (Archimedes’ method), differential thermal analysis, X-ray diffraction (XRD), and Raman and UV–Visible spectroscopies. Crystal volume fractions were estimated from density measurements, while XRD was used to estimate the crystal size, by the Scherrer formula. XRD and Raman data showed that a K2O/Nb2O5 ratio of 1 promoted the formation of the crystalline phase K3.8Nb5Ge3O20.4 and transparent glass–ceramics could be obtained with a crystalline fraction of 79 % and an average crystal size of 19 nm, while a K2O/Nb2O5 ratio of 2 promoted the formation of KNbO3 crystalline phase, and a translucent glass–ceramic was obtained with a crystalline fraction of 27 % and a crystal size of 14 nm. The Maker fringe method was used to compare the second-harmonic generation efficiency of the glass–ceramics with a Y-cut quartz reference.


  1. 1.
    Golubev NV, Sigaev VN, Stefanovich SYu, Honma T, Komatsu T (2008) Nanosized structural transformation and nonlinear optical properties of lithium niobium germanate glasses. J Non-Cryst Solids 354:1909–1914CrossRefGoogle Scholar
  2. 2.
    Narita K, Benino Y, Fujiwara T, Komatsu T, Hanada T, Hirotsu Y (2004) Prominent nanocrystallization of 25K2O·25Nb2O5·50GeO2 Glass. J Am Ceram Soc 87:113–118CrossRefGoogle Scholar
  3. 3.
    Tanaka H, Yamamoto M, Takahashi Y, Benino Y, Fujiwara T, Komatsu T (2003) Crystalline phases and second harmonic intensities in potassium niobium silicate crystallized glasses. Opt Mater 22:71–79CrossRefGoogle Scholar
  4. 4.
    Pernice P, Aronne A, Sigaev V, Kupriyanova M (2000) Crystallization of the K2O·Nb2O5·2SiO2 glass: evidences for existence of bulk nanocrystyalline structure. J Non-Cryst Solids 275:216–224CrossRefGoogle Scholar
  5. 5.
    Pernice P, Aronne A, Sigaev VN, Sarkisov PD, Molev VI, Stefanovich SYu (1999) Crystallization behavior of potassium niobium silicate glasses. J Am Ceram Soc 82:3447CrossRefGoogle Scholar
  6. 6.
    Benino Y, Takahashi Y, Fujiwara T, Komatsu T (2004) Second order optical non-linearity of transparent glass-ceramic materials induced by alternating field. J Non-Cryst Solids 345&346:422–427CrossRefGoogle Scholar
  7. 7.
    Enomoto I, Benino Y, Fujiwara T, Komatsu T (2006) Synthesis of nanocrystals in KNb(Ge, Si)O5 glasses and chemical etching of nanocrystallized glass fibers. J Sol State Chem 179:1821–1829CrossRefGoogle Scholar
  8. 8.
    Santos R, Santos LF, Almeida RM, Deubener J, Wondraczek L (2010) Crystallization of niobium germanosilicate glasses. J Sol State Chem 183:128–135CrossRefGoogle Scholar
  9. 9.
    Sigaev VN, Stefanovich SYu, Champagnon B, Gregora I, Pernice P, Aronne A, LeParc R, Sarkisov PD, Dewhurst C (2002) Amorphous nanostructuring in potassium niobium silicate glasses by SANS and SHG: a new mechanism for second-order optical non-linearity of glasses. J Non-Cryst Solids 306:238–248CrossRefGoogle Scholar
  10. 10.
    Narita K, Takahashi Y, Benino Y, Fujiwara T, Komatsu T (2004) Unique crystallization and formation of nonlinear optical (Na, K)NbO3 phases in (Na, K)NbGeO5 glasses. Opt Mater 25:393–400CrossRefGoogle Scholar
  11. 11.
    Aronne A, Sigaev VN, Champagnon B, Fanelli E, Califano V, Usmanova LZ, Pernice P (2005) The origin of nanostructuring in potassium niobiosilicate glasses by Raman and FTIR spectroscopy. J Non-Cryst Solids 351:3610–3618CrossRefGoogle Scholar
  12. 12.
    Cullity BD (1967) “Elements of X-Ray Diffraction”, 3rd ed edn. Addison-Wesley Publishing Company Inc, BostonGoogle Scholar
  13. 13.
    Baier-Saip JA, Ramos-Moor E, Cabrera AL (2005) Raman study of phase transitions in KNbO3. Sol St Commun 135:367–372CrossRefGoogle Scholar
  14. 14.
    Santos LF, Wondraczek L, Deubener J, Almeida RM (2007) Vibrational spectroscopy study of niobium germanosilicate glasses. J Non-Cryst Solids 353:1875–1881CrossRefGoogle Scholar
  15. 15.
    Maker PD, Terhune RW, Nisenoff M, Savage CM (1962) Effects of dispersion and focusing on the production of optical harmonics. Phys Rev 8:21Google Scholar
  16. 16.
    Petrovic MS, Suchocki A, Powell RC, Cantwell G (1991) Transmission second harmonic generation in CdTe at 1.064 µm. Appl Phys A 53:535CrossRefGoogle Scholar
  17. 17.
    Rodriguez FJ, Wang FX, Kauranen M (2008) Calibration of the second-order nonlinear optical susceptibility of surface and bulk of glass. Opt Expr 16:8704CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Mafalda Ventura
    • 1
  • Gonçalo Monteiro
    • 1
  • Rui M. Almeida
    • 1
    • 2
  • R. Schwarz
    • 1
    • 3
  • Luís F. Santos
    • 1
    • 2
  1. 1.ICEMS, Instituto Superior TécnicoUniversidade de LisboaLisbonPortugal
  2. 2.Centro de Química Estrutural/Departamento de Engenharia Química, Instituto Superior TécnicoUniversidade de LisboaLisbonPortugal
  3. 3.CEFEMA/Departamento de Física, Instituto Superior TécnicoUniversidade de LisboaLisbonPortugal

Personalised recommendations