Abstract

Understanding and controlling laser-induced refractive index modifications in bulk chalcogenide glasses is important for a range of photonics applications targeting the mid-infrared spectral region. We focus here on material engineering aspects and pulse spatio-temporal design characteristics that are able to induce and maintain positive refractive index changes in laser-irradiated Sulfur-based chalcogenide glass, mandatory for 3D photonic design. Specifically we study the photoinscription process of a Ge-doped Sulfur-based chalcogenide glass, Ge15As15S70, irradiated by focused ultrafast near-infrared laser pulses where Ge doping plays a determinant role in generating high-contrast positive index changes. By means of aposteriori and real-time in situ observations we show that positive refractive index changes (type I) are the result of a restructuring of the glass matrix and a photo-induced contraction process initiated by two-photon electronic excitation leading to bond softening, molecular mobility, structural changes and rearrangements. Oppositely, negative refractive index changes (type II) could be associated with two different processes: photo-expansion at higher intensities and hydrodynamic evolution initiated by plasma generation and laser heating, with thermomechanical relaxation and stress unload. Alongside the role of Ge in setting various degrees of the matrix connectivity, the structural arrangement developed under different thermal history schemes for glass preparation is equally important as it defines to which extent further structural flexibility is possible. Thus we indicate the role of glass matrix metastability in generated high-contrast refractive index changes and we show that a higher degree of relaxation is an impediment for contrasted positive index changes, while these are developing in unrelaxed glasses, where several degrees of structural flexibility exist. Alongside dynamic time-resolved imaging experiments probing the development and relaxation of excitation, we also show, via static Raman analysis of the modified regions, that significant structural changes are induced by laser irradiation and we discuss the potential processes involved.

© 2016 Optical Society of America

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2014 (3)

M. K. Bhuyan, P. K. Velpula, J. P. Colombier, T. Olivier, N. Faure, and R. Stoian, “Single-shot high aspect ratio bulk nanostructuring of fused silica using chirp-controlled ultrafast laser Bessel beams,” Appl. Phys. Lett. 104(2), 021107 (2014).
[Crossref]

J. D. Musgraves, P. Wachtel, B. Gleason, and K. Richardson, “Raman spectroscopic analysis of the Ge-As-S chalcogenide glass-forming system,” J. Non-Cryst. Solids 386, 61–66 (2014).
[Crossref]

C. D’Amico, G. Cheng, C. Mauclair, J. Troles, L. Calvez, V. Nazabal, C. Caillaud, G. Martin, B. Arezki, E. LeCoarer, P. Kern, and R. Stoian, “Large-mode-area infrared guiding in ultrafast laser written waveguides in Sulfur-based chalcogenide glasses,” Opt. Express 22(11), 13091–13101 (2014).
[Crossref] [PubMed]

2013 (2)

2012 (4)

2011 (3)

2010 (2)

2009 (3)

2008 (2)

J. S. Sanghera, C. M. Florea, L. B. Shaw, P. Pureza, V. Q. Nguyen, M. Bashkansky, Z. Dutton, and I. D. Aggarwal, “Non-linear properties of chalcogenide glasses and fibers,” J. Non-Cryst. Solids 354(2-9), 462–467 (2008).
[Crossref]

J. S. Sanghera and I. D. Aggarwal, “Active and passive chalcogenide glass optical fibers for IR applications: a review,” J. Non-Cryst. Solids 256–257, 462–467 (2008).
[Crossref]

2007 (3)

2006 (3)

2004 (2)

B. Bureau, X. H. Zhang, F. Smektala, J.-L. Adam, J. Troles, H. li Ma, C. Boussard-Plèdel, J. Lucas, P. Lucas, D. Le Coq, M. R. Riley, and J. H. Simmons, “Recent advances in chalcogenide glasses,” J. Non-Cryst. Solids 345–346, 276–283 (2004).
[Crossref]

A. Zoubir, M. Richardson, C. Rivero, A. Schulte, C. Lopez, K. Richardson, N. Hô, and R. Vallée, “Direct femtosecond laser writing of waveguides in As2S3 thin films,” Opt. Lett. 29(7), 748–750 (2004).
[Crossref] [PubMed]

2003 (2)

A. Zakery and S. Elliott, “Optical properties and applications of chalcogenide glasses: a review,” J. Non-Cryst. Solids 330(1-3), 1–12 (2003).
[Crossref]

G. Chen, H. Jain, M. Vlcek, S. Khalid, J. Li, D. A. Drabold, and S. R. Elliott, “Observation of light polarizationdependent structural changes in chalcogenide glasses,” Appl. Phys. Lett. 82, 606–608 (2003).

2002 (2)

R. Stoian, M. Boyle, A. Thoss, A. Rosenfeld, G. Korn, I. V. Hertel, and E. E. B. Campbell, “Laser ablation of dielectrics with temporally shaped femtosecond pulses,” Appl. Phys. Lett. 80(3), 353 (2002).
[Crossref]

A. M. Ljungstrom and T. M. Monro, “Light-Induced Self-Writing Effects in Bulk Chalcogenide Glass,” J. Lightwave Technol. 20(1), 78–85 (2002).
[Crossref]

2001 (4)

O. M. Efimov, L. B. Glebov, K. A. Richardson, E. Van Stryland, T. Cardinal, S. H. Park, M. Couzi, and J. L. Bruneel, “Waveguide writing in chalcogenide glasses by a train of femtosecond laser pulses,” Opt. Mater. 17(3), 379–386 (2001).
[Crossref]

O. M. Efimov, L. B. Glebov, K. A. Richardson, E. Van Stryland, T. Cardinal, S. H. Park, M. Couzi, and J. L. Bruneel, “Waveguide writing in chalcogenide glasses by a train of femtosecond laser pulses,” Opt. Mater. 17(3), 379–386 (2001).
[Crossref]

K. S. Bindra, H. T. Bookey, A. K. Kar, B. S. Wherrett, X. Liu, and A. Jha, “Nonlinear optical properties of chalcogenide glasses: Observation of multiphoton absorption,” Appl. Phys. Lett. 9(13), 1939–1941 (2001).
[Crossref]

G. Boudebs, F. Sanchez, J. Troles, and F. Smektala, “Nonlinear optical properties of chalcogenide glasses: comparison between MachZehnder interferometry and Z-scan techniques,” Opt. Commun. 199(5-6), 425–433 (2001).
[Crossref]

2000 (1)

H. Jain, S. Krishnaswami, A. C. Miller, P. Krecmer, S. R. Elliott, and M. Vicek, “In situ high-resolution X-ray photoelectron spectroscopy of light-induced changes in As-Se glasses,” J. Non-Crys. Solids 274, 115–123 (2000).

1999 (3)

T. Cardinal, K. A. Richardson, H. Shim, A. Schulte, R. Beatty, K. Le Foulgoc, C. Meneghini, J. F. Viens, and A. Villeneuve, “Non-linear optical properties of chalcogenide glasses in the system As-S-Se,” J. Non-Cryst. Solids 256–257, 353–360 (1999).
[Crossref]

J. Lucas, “Infrared glasses,” Cur. Op. Sol. St. Mat. Sci. 4, 181–187 (1999).

B. G. Aitken and C. W. Ponader, “Physical properties and Raman spectroscopy of GeAs sulphide glasses,” J. Non-Cryst. Solids 257, 143–148 (1999).
[Crossref]

1998 (2)

1997 (1)

H. Kanbara, S. Fujiwara, K. Tanaka, H. Nasu, and K. Hirao, “Third-order nonlinear optical properties of chalcogenide glasses,” Appl. Phys. Lett. 70(8), 925–927 (1997).
[Crossref]

1996 (1)

H. Fritzche, “Photo-induced fluidity of chalcogenide glasses,” Solid State Commun. 99(3), 153–155 (1996).
[Crossref]

1995 (1)

H. Hisakumi and K. Tanaka, “Optical microfabrication of chalcogenide glasses,” Science 270(5238), 974–975 (1995).
[Crossref]

1994 (1)

H. Hisakumi and K. Tanaka, “Giant photoexpansion in As2S3 glass,” Appl. Phys. Lett. 65(23), 2925 (1994).
[Crossref]

1991 (1)

V. M. Lyubin and V. K. Tikhomirov, “Novel photo-induced effects in chalcogenide glasses,” J. Non-Cryst. Solids 135(1), 37–48 (1991).
[Crossref]

1989 (1)

K. Tanaka, “Structural phase transitions in chalcogenide glasses,” Phys. Rev. B Condens. Matter 39(2), 1270–1279 (1989).
[Crossref] [PubMed]

1987 (1)

S. Sugai, “Stochastic random network model in Ge and Si chalcogenide glasses,” Phys. Rev. B Condens. Matter 35(3), 1345–1361 (1987).
[Crossref] [PubMed]

1982 (1)

J. A. Savage, “Optical properties of chalcogenide glasses,” J. Non-Cryst. Solids 47(1), 101–115 (1982).
[Crossref]

1980 (1)

P. J. S. Ewen and A. E. Owen, “Resonance Raman scattering in As-S glasses,” J. Non-Cryst. Solids 35, 1191–1196 (1980).
[Crossref]

1975 (1)

G. Lucovsky, R. J. Nemanich, S. A. Solin, and R. C. Keezer, “Coordination dependent vibrational properties of amorphous semiconductors alloys,” Solid State Commun. 17(12), 1567–1572 (1975).
[Crossref]

1974 (2)

G. Lucovsky, F. L. Galeener, R. C. Keezer, R. H. Geils, and H. A. Six, “Structural interpretation of the infrared and Raman spectra of glasses in the alloy system Ge1-xSx,” Phys. Rev. B 10(12), 5134–5146 (1974).
[Crossref]

J. P. De Neufville, S. C. Moss, and S. R. Ovshinsky, “Photostructural transformations in amorphous As2Se3 and As2S3 films,” J. Non-Cryst. Solids 13(2), 191–223 (1974).
[Crossref]

1972 (1)

G. Lucovsky, “Optic Modes in Amorphous As2S3 and As2Se3,” Phys. Rev. B 6(4), 1480–1489 (1972).
[Crossref]

1970 (2)

R. Shuker and R. W. Gammon, “Raman-Scattering Selection-Rule Breaking and the Density of States in Amorphous Materials,” Phys. Rev. Lett. 25(4), 222–225 (1970).
[Crossref]

L. Boesch, A. Napolitano, and P. B. Macedo, “Spectrum of Volume Relaxation Times in B2O3,” J. Am. Ceram. Soc. 53(3), 148–153 (1970).
[Crossref]

1967 (1)

P. Macedo and A. Napolitano, “Effects of a distribution of volume relaxation times in the annealing of BSC glass,” J. Res. Natl. Bur. Stand. 71(3), 231–238 (1967).
[Crossref]

Adam, J.-L.

B. Bureau, X. H. Zhang, F. Smektala, J.-L. Adam, J. Troles, H. li Ma, C. Boussard-Plèdel, J. Lucas, P. Lucas, D. Le Coq, M. R. Riley, and J. H. Simmons, “Recent advances in chalcogenide glasses,” J. Non-Cryst. Solids 345–346, 276–283 (2004).
[Crossref]

Aggarwal, I. D.

J. S. Sanghera, C. M. Florea, L. B. Shaw, P. Pureza, V. Q. Nguyen, M. Bashkansky, Z. Dutton, and I. D. Aggarwal, “Non-linear properties of chalcogenide glasses and fibers,” J. Non-Cryst. Solids 354(2-9), 462–467 (2008).
[Crossref]

J. S. Sanghera and I. D. Aggarwal, “Active and passive chalcogenide glass optical fibers for IR applications: a review,” J. Non-Cryst. Solids 256–257, 462–467 (2008).
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H. Jain, S. Krishnaswami, A. C. Miller, P. Krecmer, S. R. Elliott, and M. Vicek, “In situ high-resolution X-ray photoelectron spectroscopy of light-induced changes in As-Se glasses,” J. Non-Crys. Solids 274, 115–123 (2000).

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L. Labadie, G. Martin, N. C. Anheier, B. Arezki, H. A. Qiao, B. Bernacki, and P. Kern, “First fringes with an integrated-optics beam combiner at 10μm. A new step towards instrument miniaturization for mid-infrared interferometry,” Astron. Astrophys. 531, A48 (2011).
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O. M. Efimov, L. B. Glebov, K. A. Richardson, E. Van Stryland, T. Cardinal, S. H. Park, M. Couzi, and J. L. Bruneel, “Waveguide writing in chalcogenide glasses by a train of femtosecond laser pulses,” Opt. Mater. 17(3), 379–386 (2001).
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O. M. Efimov, L. B. Glebov, K. A. Richardson, E. Van Stryland, T. Cardinal, S. H. Park, M. Couzi, and J. L. Bruneel, “Waveguide writing in chalcogenide glasses by a train of femtosecond laser pulses,” Opt. Mater. 17(3), 379–386 (2001).
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Riley, M. R.

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G. Boudebs, F. Sanchez, J. Troles, and F. Smektala, “Nonlinear optical properties of chalcogenide glasses: comparison between MachZehnder interferometry and Z-scan techniques,” Opt. Commun. 199(5-6), 425–433 (2001).
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Shaw, L. B.

J. S. Sanghera, C. M. Florea, L. B. Shaw, P. Pureza, V. Q. Nguyen, M. Bashkansky, Z. Dutton, and I. D. Aggarwal, “Non-linear properties of chalcogenide glasses and fibers,” J. Non-Cryst. Solids 354(2-9), 462–467 (2008).
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T. Cardinal, K. A. Richardson, H. Shim, A. Schulte, R. Beatty, K. Le Foulgoc, C. Meneghini, J. F. Viens, and A. Villeneuve, “Non-linear optical properties of chalcogenide glasses in the system As-S-Se,” J. Non-Cryst. Solids 256–257, 353–360 (1999).
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Smektala, F.

B. Bureau, X. H. Zhang, F. Smektala, J.-L. Adam, J. Troles, H. li Ma, C. Boussard-Plèdel, J. Lucas, P. Lucas, D. Le Coq, M. R. Riley, and J. H. Simmons, “Recent advances in chalcogenide glasses,” J. Non-Cryst. Solids 345–346, 276–283 (2004).
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G. Boudebs, F. Sanchez, J. Troles, and F. Smektala, “Nonlinear optical properties of chalcogenide glasses: comparison between MachZehnder interferometry and Z-scan techniques,” Opt. Commun. 199(5-6), 425–433 (2001).
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M. K. Bhuyan, P. K. Velpula, J. P. Colombier, T. Olivier, N. Faure, and R. Stoian, “Single-shot high aspect ratio bulk nanostructuring of fused silica using chirp-controlled ultrafast laser Bessel beams,” Appl. Phys. Lett. 104(2), 021107 (2014).
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V. M. Lyubin and V. K. Tikhomirov, “Novel photo-induced effects in chalcogenide glasses,” J. Non-Cryst. Solids 135(1), 37–48 (1991).
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Troles, J.

C. D’Amico, G. Cheng, C. Mauclair, J. Troles, L. Calvez, V. Nazabal, C. Caillaud, G. Martin, B. Arezki, E. LeCoarer, P. Kern, and R. Stoian, “Large-mode-area infrared guiding in ultrafast laser written waveguides in Sulfur-based chalcogenide glasses,” Opt. Express 22(11), 13091–13101 (2014).
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B. Bureau, X. H. Zhang, F. Smektala, J.-L. Adam, J. Troles, H. li Ma, C. Boussard-Plèdel, J. Lucas, P. Lucas, D. Le Coq, M. R. Riley, and J. H. Simmons, “Recent advances in chalcogenide glasses,” J. Non-Cryst. Solids 345–346, 276–283 (2004).
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G. Boudebs, F. Sanchez, J. Troles, and F. Smektala, “Nonlinear optical properties of chalcogenide glasses: comparison between MachZehnder interferometry and Z-scan techniques,” Opt. Commun. 199(5-6), 425–433 (2001).
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N. Jovanovic, P. G. Tuthill, B. Norris, S. Gross, P. Stewart, N. Charles, S. Lacour, M. Ams, J. S. Lawrence, A. Lehmann, C. Niel, J. G. Robertson, G. D. Marshall, M. Ireland, A. Fuerbach, and M. J. Withford, “Starlight demonstration of the Dragonfly instrument: an integrated photonic pupil-remapping interferometer for highcontrast imaging,” Mon. Not. R. Astron. Soc. 427(1), 806–815 (2012).
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Van Stryland, E.

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O. M. Efimov, L. B. Glebov, K. A. Richardson, E. Van Stryland, T. Cardinal, S. H. Park, M. Couzi, and J. L. Bruneel, “Waveguide writing in chalcogenide glasses by a train of femtosecond laser pulses,” Opt. Mater. 17(3), 379–386 (2001).
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M. K. Bhuyan, P. K. Velpula, J. P. Colombier, T. Olivier, N. Faure, and R. Stoian, “Single-shot high aspect ratio bulk nanostructuring of fused silica using chirp-controlled ultrafast laser Bessel beams,” Appl. Phys. Lett. 104(2), 021107 (2014).
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Vicek, M.

H. Jain, S. Krishnaswami, A. C. Miller, P. Krecmer, S. R. Elliott, and M. Vicek, “In situ high-resolution X-ray photoelectron spectroscopy of light-induced changes in As-Se glasses,” J. Non-Crys. Solids 274, 115–123 (2000).

Viens, J. F.

T. Cardinal, K. A. Richardson, H. Shim, A. Schulte, R. Beatty, K. Le Foulgoc, C. Meneghini, J. F. Viens, and A. Villeneuve, “Non-linear optical properties of chalcogenide glasses in the system As-S-Se,” J. Non-Cryst. Solids 256–257, 353–360 (1999).
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Villeneuve, A.

T. Cardinal, K. A. Richardson, H. Shim, A. Schulte, R. Beatty, K. Le Foulgoc, C. Meneghini, J. F. Viens, and A. Villeneuve, “Non-linear optical properties of chalcogenide glasses in the system As-S-Se,” J. Non-Cryst. Solids 256–257, 353–360 (1999).
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G. Chen, H. Jain, M. Vlcek, S. Khalid, J. Li, D. A. Drabold, and S. R. Elliott, “Observation of light polarizationdependent structural changes in chalcogenide glasses,” Appl. Phys. Lett. 82, 606–608 (2003).

Wachtel, P.

J. D. Musgraves, P. Wachtel, B. Gleason, and K. Richardson, “Raman spectroscopic analysis of the Ge-As-S chalcogenide glass-forming system,” J. Non-Cryst. Solids 386, 61–66 (2014).
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Wang, R.

Wherrett, B. S.

K. S. Bindra, H. T. Bookey, A. K. Kar, B. S. Wherrett, X. Liu, and A. Jha, “Nonlinear optical properties of chalcogenide glasses: Observation of multiphoton absorption,” Appl. Phys. Lett. 9(13), 1939–1941 (2001).
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Withford, M.

Withford, M. J.

N. Jovanovic, P. G. Tuthill, B. Norris, S. Gross, P. Stewart, N. Charles, S. Lacour, M. Ams, J. S. Lawrence, A. Lehmann, C. Niel, J. G. Robertson, G. D. Marshall, M. Ireland, A. Fuerbach, and M. J. Withford, “Starlight demonstration of the Dragonfly instrument: an integrated photonic pupil-remapping interferometer for highcontrast imaging,” Mon. Not. R. Astron. Soc. 427(1), 806–815 (2012).
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Yang, W.

M. A. Hughes, W. Yang, and D. W. Hewak, “Spectral broadening in femtosecond laser written waveguides in chalcogenide glass,” J. Opt. Soc. Am. B 26(7), 1370–1378 (2009).
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M. Hughes, W. Yang, and D. Hewak, “Fabrication and characterization of femtosecond laser written waveguides in chalcogenide glass,” Appl. Phys. Lett. 90(13), 131113 (2007).
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Zamfirescu, M.

Zhang, X. H.

B. Bureau, X. H. Zhang, F. Smektala, J.-L. Adam, J. Troles, H. li Ma, C. Boussard-Plèdel, J. Lucas, P. Lucas, D. Le Coq, M. R. Riley, and J. H. Simmons, “Recent advances in chalcogenide glasses,” J. Non-Cryst. Solids 345–346, 276–283 (2004).
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Zoubir, A.

Appl. Phys. Lett. (7)

H. Kanbara, S. Fujiwara, K. Tanaka, H. Nasu, and K. Hirao, “Third-order nonlinear optical properties of chalcogenide glasses,” Appl. Phys. Lett. 70(8), 925–927 (1997).
[Crossref]

K. S. Bindra, H. T. Bookey, A. K. Kar, B. S. Wherrett, X. Liu, and A. Jha, “Nonlinear optical properties of chalcogenide glasses: Observation of multiphoton absorption,” Appl. Phys. Lett. 9(13), 1939–1941 (2001).
[Crossref]

G. Chen, H. Jain, M. Vlcek, S. Khalid, J. Li, D. A. Drabold, and S. R. Elliott, “Observation of light polarizationdependent structural changes in chalcogenide glasses,” Appl. Phys. Lett. 82, 606–608 (2003).

M. Hughes, W. Yang, and D. Hewak, “Fabrication and characterization of femtosecond laser written waveguides in chalcogenide glass,” Appl. Phys. Lett. 90(13), 131113 (2007).
[Crossref]

R. Stoian, M. Boyle, A. Thoss, A. Rosenfeld, G. Korn, I. V. Hertel, and E. E. B. Campbell, “Laser ablation of dielectrics with temporally shaped femtosecond pulses,” Appl. Phys. Lett. 80(3), 353 (2002).
[Crossref]

M. K. Bhuyan, P. K. Velpula, J. P. Colombier, T. Olivier, N. Faure, and R. Stoian, “Single-shot high aspect ratio bulk nanostructuring of fused silica using chirp-controlled ultrafast laser Bessel beams,” Appl. Phys. Lett. 104(2), 021107 (2014).
[Crossref]

H. Hisakumi and K. Tanaka, “Giant photoexpansion in As2S3 glass,” Appl. Phys. Lett. 65(23), 2925 (1994).
[Crossref]

Astron. Astrophys. (1)

L. Labadie, G. Martin, N. C. Anheier, B. Arezki, H. A. Qiao, B. Bernacki, and P. Kern, “First fringes with an integrated-optics beam combiner at 10μm. A new step towards instrument miniaturization for mid-infrared interferometry,” Astron. Astrophys. 531, A48 (2011).
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Figures (7)

Fig. 1
Fig. 1 Comparison of the refractive index change results (PCM) of the waveguide laser photoinscription process in reference As2S3 (a) and Ge15As15S70 (b) glasses by 2 mW (@100 kHz) and 160 fs laser pulses. The translation speeds of the samples are indicated on the left. A larger processing window for positive index changes is observed in the case of Ge15As15S70. (c) Variation of the guided mode intensity (left axis) and waveguide index contrast (right axis) as a function of the translation speed of a reference Ge15As15S70 sample, for energy of 4 mW (@100 kHz).
Fig. 2
Fig. 2 Schematic of the thermal history of annealed chalcogenide glasses and its influence on the enthalpy of the microscopic glass structure.
Fig. 3
Fig. 3 Comparison of the index change results (PCM) of the waveguide photoinscription process with two different scan speeds in the reference (a, b) and longtime re-annealed Ge15As15S70 (c, d) samples by 2 mW (@100 kHz) and 160 fs laser pulses. For comparison, parts (e) and (f) show the photoinscription traces in a reference As2S3 sample. Figures (g) and (h) show the variation of the transverse relative refractive index profile (in grey levels) of the traces corresponding to the couple of figures (a, c) and (b, d) respectively. The decrease in the gray level correspond to index increase. Note the higher contrast obtained in the reference Ge15As15S70.
Fig. 4
Fig. 4 (a) Type II change produced in single-shot regime by a 1 µJ, 4 ps Bessel laser pulse focused into Ge15As15S70. (b) Type I changes produced in multi-shots regime by low energy 100 nJ, 80 fs Bessel laser pulses focused into Ge15As15S70. Type I changes can be produced only in multishots regime.
Fig. 5
Fig. 5 Integrated deposited energy density calculated using an NLSE code in the case of the interaction between a 100 nJ – 80 fs Bessel beam (a), and a 1 µJ – 4 ps Bessel beam (b).
Fig. 6
Fig. 6 (a) Time-resolved optical transmission microscopy imaging of the relaxation of the carrier plasma produced by a single-shot 1 µJ, 4ps Bessel laser pulse focused into Ge15As15S70. (b) Time-resolved imaging of plasma electron density with spatio-temporal excitation profiles. (c) Time-resolved phase contrast microscopy imaging; a pressure wave is clearly visible around 6ns. The time frame is the same for the figures (a), (b) and (c). (d) Averaged plasma electron density dynamics as function of the delay time between pump and probe. (e) Type II change produced in single-shot regime by a 1 µJ, 4 ps Bessel laser pulse focused into Ge15As15S70.
Fig. 7
Fig. 7 Raman shift of non-irradiated (red line) and irradiated (black line) Ge15As15S70 samples.

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