February 15, 2009 / Vol. 34, No.

4 / OPTICS LETTERS

437

Second-harmonic generation in IR-transparent -GeS2 crystallized glasses

Changgui Lin,1 Haizheng Tao,1,2 Xiaolin Zheng,1 Ruikun Pan,1 Haochun Zang,1 and Xiujian Zhao1,*
1

Key Laboratory of Silicate Materials Science and Engineering, Ministry of Education, Wuhan University of Technology, Wuhan, Hubei 430070, China 2 taohaizheng@hotmail.com *Corresponding author: opluse@whut.edu.cn

Received November 5, 2008; revised January 2, 2009; accepted January 6, 2009; posted January 12, 2009 (Doc. ID 103679); published February 9, 2009 IR-transparent -GeS2 crystallized glasses were fabricated by crystallization of the glass with a stoichiometric composition corresponding to target crystal and only -GeS2 crystallites were precipitated. A clear second-harmonic generation was observed in the crystallized glasses by the Maker fringe technique. The optical nonlinear susceptibility, 2 , of -GeS2 crystallized glasses was found to be 7.3 pm/ V, being comparable to that created by thermal/electric or other poling methods, which opens a new way to an optical converter operating in the mid-IR spectral region. 2009 Optical Society of America OCIS codes: 190.2620, 190.4720, 160.2750, 160.4760.

Much effort has recently been devoted to the development of materials that are suitable for the applications of parametric frequency converters and electrooptic modulators in IR spectral regions. The high expense of single-crystal production has prompted a search for glass and glass ceramics with second-order nonlinear (SON) optical properties [13]. Owing to the wide IR spectral range of transparency, chalcogenide glass and glass ceramics have been under intense research in recent years [4,5]. Theoretically, SON properties are forbidden in amorphous materials owing to their macroscopic inversion symmetry. Glass ceramics, fortunately, do break this symmetry when ceramic phases do not have a center of inversion, such as -GeS2 [5], CdGa2S4 [6], and AgGaGeS4 [7], and also preserve the usual advantage of fabrication versatility of glasses. In addition, a new method of phase matching, the so-called quasi-phasematching technique, will make chalcogenide glass ceramics a potential optical converter in the mid-IR region [8]. As far as we know, critical to most applications is the transparency of these materials; thus the major interest is to produce IR-transparent chalcogenide glass ceramics with SON optical properties. It is well known that the difference of refractive index between crystallites and a glass host must be small enough to obtain the transparent glass ceramics. Hence, transparent glass ceramics can be expected through the ceramization of glasses with a stoichiometric composition corresponding to target crystals. Nevertheless, it is difcult to obtain a glass with the stoichiometric composition corresponding to the double-frequency crystal, and only the target crystal is precipitated when crystallized. It is well known that GeS2 glass can be prepared using a conventional melt-quenching technique, and according to the report in [9], the -GeS2 crystalline phase would be formed only by the crystallization of the GeS2 glass below 497 C. In this Letter, -GeS2 is focused on because of its polar orthorhombic phase with a space group of Fdd2 (noncentrosymmetry) [9]. Owing to the same stoichimetric composition between the host glass GeS2 and the
0146-9592/09/040437-3/$15.00

target crystal -GeS2, both the SON properties and good IR-transparency can be achieved in the -GeS2 crystallized glass. A GeS2 glass was prepared through a conventional melt-quenching method using high purity Ge and S (all of 5 N) as raw materials [4,5]. Glass disks 10 mm 1 mm were obtained from the glass rods and polished to optical quality on both sides. To avoid surface oxidation during heat treatment, glass disks were transferred into silica ampoules, which were then sealed under a vacuum of about 102 Pa. Characteristic temperatures of the GeS2 glass, Tg = 498.8 C (glass transition temperature) and Tx = 551.9 C (onset of crystallization), were determined by differential scanning calorimetry at a heating rate of 10 C / min (Netzsch STA 449C). According to the phase diagram in the GeS binary system [9], it is notable that only the -GeS2 crystalline phase is precipitated when heat treated below 497 C Tt . Therefore, to control the speed of crystal growth, heat treatment of as-prepared glasses was undertaken at 460 C THT far below the Tg and Tt. Crystallization was conducted by heating the glass at 10 C / min to THT, holding at THT for various durations and then cooling slowly to room temperature. The intensity of the second-harmonic wave (SHW) of the crystallized glass was measured using the Maker fringe technique. The source was a Q-switched Nd:YAG laser operating at a 1064 nm fundamental wavelength with a pulse of 10 ns; -quartz with a thickness of 1.11 mm was used as a reference. X-ray diffraction (XRD) patterns of the crystallized glasses obtained by heat treatments (THT = 460 C, t = 48 120 h) are shown in Fig. 1 in which the bulk samples were used. Only the -GeS2 crystal phase is precipitated in the samples, except the appearance of the -S8 phase in the sample heat treated for a long duration of 120 h. The generation of -S8 is possibly ascribed to the transformation of SS bonds by a long heat treatment, and this was further conrmed by the corresponding Raman spectra (as shown in Fig.
2009 Optical Society of America

438

OPTICS LETTERS / Vol. 34, No. 4 / February 15, 2009

Fig. 1. (Color online) XRD patterns of the crystallized glasses obtained by heat treatments at THT = 460 C for (a) 48, (b) 72, (c) 96, (d) 120 h, and JCPDF cards of (e) no. 26693 ( -GeS2, orthorhombic system) and (f) no. 74-1465 ( -S8, orthorhombic system).

Fig. 3. (Color online) Mid-IR transmission spectra of asprepared and the sample heat treated at 460 C for 72 h. The inset is Vis-NIR transmission spectra of as-prepared and samples heat treated at 460 C for 48, 72, 96, and 120 h, respectively. The thickness of all samples is about 1 mm.

2). First, Raman spectra of the glass ceramics with a small amount of -GeS2 crystallites are approximately similar to the low-resolution spectrum of -GeS2 [10]. Second, the Raman intensity of 255 cm1 is decreasing with the elongation of heat-treated durations. This phenomenon shows that the contribution of the precipitated -GeS2 to the Raman spectra is to decrease the Raman scattering intensity of S3Ge-GeS3 ethanelike units located at about 255 cm1, which is originated from the local shortage of sulfur. When the precipitated -GeS2 crystallites largely increases, a new vibrational band located at 411 cm1 appears clearly in the samples heat treated for 96 and 120 h, respectively. It is a characteristic vibrational band of -GeS2 crystals as shown in Fig. 2(f). The other two emerged bands located at 218 and 470 cm1 in crystallized glasses after heat treatment of 120 h are ascribed to the stretching A1 mode of the

-S8 phase [11]. Finally, no appearance of new Raman peaks except for the characteristic ones of -GeS2 crystals for the samples heat treated at 460 C for 48 96 h further veried the only crystallization of the -GeS2 phase. Figure 3 shows the optical transmission spectra of the as-prepared and heat-treated samples. Despite the decreasing transmittance in the visible-near IR (Vis-NIR) region (the inset of Fig. 3), only a slight drop (0.7%) can be observed in IR windows of 4.5 5.5 m, which is ascribed to the similarity of refractive indices of glass host and target crystal based on the theory of scattering loss presented by Hendy [12]. In addition, the bigger drop of transmittance in the interested region of 3 12 m except 4.5 5.5 m is maybe due to the enhanced parasitic absorption loss of impurity originated from the contamination during ceramization that can be eliminated through the improvement of preparing process [13]. The scanning electron microscope (SEM) image for the cross section of transparent crystallized glass heat treated at THT = 460 C for 72 h is shown in Fig. 4. It is seen that the -GeS2 crystalline layer with a thickness of about 120 nm is formed at the surface. Figure 5 shows Maker fringe patterns of -GeS2 crystallized glasses fabricated at THT = 460 C for 48 120 h. The analysis of experimental fringe patterns was carried out on the basis of the Maker fringe

Fig. 2. Raman spectra of (a) as-prepared GeS2 glass; GeS2 glasses heat treated at 460 C for (b) 48, (c) 72, (d) 96, and (e) 120 h, and (f) -GeS2 ([10]).

Fig. 4. SEM image of the cross section of -GeS2 surface crystallized glass obtained at THT = 460 C for 72 h.

February 15, 2009 / Vol. 34, No. 4 / OPTICS LETTERS

439

Fig. 5. (Color online) Maker fringe patterns of the crystallized samples. The maximum of SH intensity of the reference Y-cut quartz is set to 1.

observed in transparent LaBGeO5 crystallized glass [15]. Also indicated in Fig. 5 are the SON optical susceptibilities for -GeS2 crystallized glasses. These data shown in Fig. 5 were analyzed using Eqs. (1) and (2), where the following values were used: n = 2.0675 and n2 = 2.1635. The largest SON susceptibility 2 was estimated to be 7.3 pm/ V in the sample heat treated at 460 C for 96 h. In conclusion, we fabricated the IR-transparent crystallized glasses from the glasses with a stoichiometric composition of a target crystal -GeS2 by means of the careful ceramization at THT = 460 C for various durations, and only the -GeS2 crystal phase is precipitated in the samples heat treated at 460 C for 48 to 96 h. The obtained glass ceramics still have a good transparency at the interested mid-IR spectral region. The largest 2 of -GeS2 crystallized glasses was found to be 7.3 pm/ V, comparable to that created by thermal/electric or other poling methods, indicating a high potential for the application of IR optical control devices. This work was partially funded by Natural Science Foundation of China (NSFC) (60808024), the National Science Foundation (NSF) of Hubei Province, and the Program for Changjiang Scholars and Innovative Research Team (PCSIRT, No. IRT0547), Ministry of Education, China. We thank L. H. Xue and H. S Yun at the Center for Materials Research and Analysis of Wuhan University of Technology for their help during Raman measurements. References
1. H. Guo, H. Tao, S. Gu, X. Zheng, Y. Zhai, S. Chu, X. Zhao, S. Wang, and Q. Gong, Solid State Chem. 180, 240 (2007). 2. Y. Takahashi, Y. Benino, T. Fujiwara, and T. Komatsu, Appl. Phys. Lett. 81, 223 (2002). 3. Y. Takahashi, K. Kitamura, Y. Benino, T. Fujiwara, and T. Komatsu, Appl. Phys. Lett. 86, 091110 (2005). 4. I. V. Kityk, M. Guignard, V. Nazabal, X. Zhang, J. Troles, F. Smektala, B. Sahraoui, and G. Boudebs, Physica B 391, 222 (2007). 5. M. Guignard, V. Nazabal, X. Zhang, F. Smektala, A. Morac, S. Pechev, H. Zeghlache, A. Kudlinski, G. Martinelli, and Y. Quiquempois, Opt. Mater. 30, 338 (2007). 6. H. Tao, C. Lin, S. Gu, C. Jing, and X. Zhao, Appl. Phys. Lett. 91, 011904 (2007). 7. C. Lin, H. Tao, R. Pan, X. Zheng, G. Dong, H. Zang, and X. Zhao, Chem. Phys. Lett. 460, 125 (2008). 8. M. Baudrier-Raybaut, R. Hadar, Ph. Kupecek, Ph. Lemasson, and E. Rosencher, Nature 432, 374 (2004). 9. A. Hruby, Czech J. Phys. B 23, 1263 (1973). 10. Z. Cernoek, E. Cernokov, and L. Bene, J. Mol. Struct. 435, 193 (1997). 11. G. Lucovsky, F. L. Galeener, R. C. Keezer, R. H. Geils, and H. A. Six, Phys. Rev. B 10, 5134 (1974). 12. S. Hendy, Appl. Phys. Lett. 81, 1171 (2002). 13. L. Calvez, H. Ma, J. Lucas, and X. Zhang, Adv. Mater. 19, 129 (2007). 14. J. Jerphagnon and S. K. Kurtz, Phys. Rev. B 1, 1739 (1970). 15. Y. Takahashi, Y. Benino, T. Fujiwara, and T. Komatsu, J. Appl. Phys. 89, 5282 (2001).

theory [14,15]. The Maker fringe pattern is generally given by P2 = where 2 L = n cos n2 cos
2 2 Cdefft 4T2

sin2
2 n2 n2 2

L 2 Lc , 2

is the angular dependent coherence where Lc length, L is the thickness of the nonlinear medium, and and 2 are the reection angles of the incident light and SHW, respectively. According to Eq. (2), it is seen that the patterns of the Maker fringe are decided by the thickness of nonlinear material. As indicated in Fig. 4, the -GeS2 surface crystallized glasses are composed of two optical nonlinear -GeS2 crystalline layers separated by an optical linear glass layer. The different angles of maximum second-harmonic (SH) intensity in Fig. 5(a) are properly attributed to the increasing thickness of the -GeS2 crystalline layer. The broad fringe patterns for the samples heat treated for 48 and 72 h would be due to the lack of coherency of the SHW generated from the surface -GeS2 crystalline layer whose thickness is much lower than the coherent . In addition, length Lc 2.77 m Lc = / 4 n2 -n the lobe proles in Fig. 5(b) should be due to the increase of volume fraction of internal crystals that was identied by the results of SEM measurement (not shown here), similar to the bulk-crystallized glasses [7]. On one hand, the SHW generated from -GeS2 crystalline layers is scattered by the internal small crystals; on the other hand, the SHW is also generated from these nonoriented internal crystals simultaneously. The decrease of the SHW signal when the absolute incident angle of the laser beam increases is mostly due to the Fresnel losses at the interfaces at high angles. The same results were also