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Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 15, Iss. 5 — Mar. 5, 2007
  • pp: 2398–2408
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Study on the third and second-order nonlinear optical properties of GeS2-Ga2S3-AgCl chalcohalide glasses

Guoping Dong, Haizheng Tao, Xiudi Xiao, Changgui Lin, Yueqiu Gong, Xiujian Zhao, Saisai Chu, Shufeng Wang, and Qihuang Gong  »View Author Affiliations


Optics Express, Vol. 15, Issue 5, pp. 2398-2408 (2007)
http://dx.doi.org/10.1364/OE.15.002398


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Abstract

Third-order optical nonlinearities, χ(3) of GeS2-Ga2S3-AgCl chalcohalide glasses have been studied systematically utilizing the femtosecond time-resolved optical Kerr effect (OKE) technique at 820nm, showing that the value of χ(3) enhances with increasing atomic ratio of (S+Cl/2)/(Ge+Ga). From the compositional dependence of glass structure by Raman spectra, a strong dependence χ(3) upon glass structure has been found, i.e. compared with [ClxS3-xGe(Ga)-Ge(Ga)S3-xClx] ethane-like s.u. as the structural defectiveness, [Ge(Ga)S4-xClx] mixed tetrahedra make greater contribution to the enhancement of χ(3). The maximum χ(3) among the present glasses is as large as 5.26×10-13esu (A1 (80GeS2-10Ga2S3-10AgCl)), and the nonlinear refractive index (n2) of A1 glass is also up to 4.60×10-15 cm2/W. In addition, using Maker fringe technique, SHG was observed in the representative A1 glass poled by electron beam (25 kV, 25 nA, 15 min), and the second-order optical nonlinear susceptibility is estimated to be greater than 6.1 pm/V. There was no evident structural change detected in the as-prepared and after irradiated A1 glass by the Raman spectra, and maybe only electronic transition and distortion of electron cloud occurred in the glasses. The large third/second-order optical nonlinearities have made these GeS2-Ga2S3-AgCl chalcohalide glasses as promising materials applied in photoelectric fields.

© 2007 Optical Society of America

1. Introduction

2. Experimental

2.1. Glass synthesis and characterization

Optical transmission was recorded with a spectrophotometer (Shimadzu UV-1601) in the visible and near-IR region (Vis-NIR). To study the structure of these glasses, Raman spectroscopy was conducted by the micro Raman Spectrometer (Type: Renishaw inVia) using the back (180°) scattering configuration at room temperature. For the avoidance of local laser damage and crystallization, an Ar+ laser (λ=514nm) with a power less than 2 mW was used as an excitation source. The error was within the range of ± 1cm-1.

2.2 Third-order optical nonlinearity characterization

2.3. Second-order optical nonlinearity characterization

The polished glass plate with representative composition A1 (80GeS2-10Ga2S3-10AgCl) was placed into EPMA (JXA-8800R) (the pressure of sample chamber is lower than 7×10-3 Pa), and then irradiated by electron beam (voltage: 25kV; current: 25nA) for 15min. No distinct physical damage was observed on the glassy surface after irradiation.

3. Results and Discussion

Fig. 1. Linear absorption spectrum of the representative A1 (80GeS2-10Ga2S3-10AgCl) glass

3.1 Third-order optical nonlinearities (OKE) and their structural dependence (Raman spectroscopy)

Figure 2(a) shows the OKE signal of the standard reference (CS2). Its signal has an asymmetrical decay tail more than 1ps due to the molecular reorientation relaxation processes. The OKE signals of the representative GeS2-Ga2S3-AgCl glasses with the thickness of 1±0.02mm are illustrated in Fig. 2(b), and no decay tail can be observed. The solid lines are the Fit Gaussian curves which are symmetrical and the full width at half maximum is 160fs, indicating that the response time in the present glass is subpicosecond. Similarly, the third-order nonlinear optical responses of other compositions are also instantaneous and symmetrical.

Fig. 2. Time-resolved OKE signals of (a) a standard CS2 reference and (b) A1 (80GeS2-10Ga2S3-10AgCl) and B4 (64GeS2-16Ga2S3-20AgCl) glasses at a wavelength of 820nm

For the amorphous materials, the ultrafast third-order nonlinear optical response mainly originates from the distortion of electron cloud and/or the motion of nuclei [18

18. J. E. Aber, M. C. Newstein, and B. A. Garetz, “Femtosecond optical kerr effect measurement in silicate glasses,” J. Opt. Soc. Am. B 17, 120–127 (2000). [CrossRef]

]. If the optical nonlinearity only originates from the former, the nonlinear response of glasses is expected to be less than 10 fs. However, the decay of this response will have the relaxation times between 100fs and 10ps if the nonlinear optical response originates from the motion of nuclei. Considering the longer pulse duration (120fs) used in this study which is too long to excite high-frequency Raman vibrations in our experiment and the better symmetry of the obtained OKE signals (no distinct decay tail), it can be deduced that the ultrafast third-order nonlinear optical response of GeS2-Ga2S3-AgCl glasses is predominantly attributed to the ultrafast distortion of the electron cloud. In addition, for the present chalcohalide glasses, the S atoms are only two-fold coordinated and possess lone pair electrons which are normally non-bonding. These non-bonding electrons lie at the top of the valence band. Therefore these lone pair electrons are preferentially excited when stimulated by the light and subsequently produce some short-lived free electrons plasma together with the band filling effects [19

19. Q. M. Liu, X. J. Zhao, F. X. Gan, J. Mid, and S. X. Qian, “Femtosecond optical Kerr effect study of Ge10As40S30Se20 film,” Solid State Commun. 134, 513–517 (2005) [CrossRef]

]. It is just the forming of the short-lived electrons that makes GeS2-Ga2S3-AgCl glasses show an ultrafast response time within 200fs.

Besides the ultrafast third-order nonlinear optical response, the value of third-order optical nonlinear susceptibility, χ (3) is another important parameter when evaluating the applications of materials in the photoelectric field. Using the standard procedure of measurement by keeping the CS2 reference medium and samples under the same condition, the value of χ (3) can be calculated by the following Eq. [20]:

χS(3)=χR(3)(ISIR)12(nSnR)2
(1)

where the subscript S and R represent the samples and the CS2 reference, respectively, I is the OKE signal intensity and n is the linear refractive index. The linear refractive index, nR and χ (3) of the reference CS2 are taken to be 1.62 and 1×10-13 esu, respectively [21

21. K. Minoshima, M. Taiji, and T. Kobayashi, “Femtosecond time-resolved interferometry for the determination of complex nonlinear susceptibility,” Opt. Lett. 16, 1683–1685 (1991). [CrossRef] [PubMed]

]. Using the maximum values of the Fit Gaussian curves of OKE signals in CS2 reference and samples, the OKE signal intensity ratio of A1 (80GeS2-10Ga2S3-10AgCl) glass sample to CS2 reference, IS/IR is up to 9.09. Then χ (3) can be calculated to be as large as 5.26×10-13 esu according to the Eq. (1). With the conversion n2(cm2/W)≈0.04χ (3)(esu)/n2 which has been frequently employed by researchers[1

1. K. Tanaka, “Optical nonlinearity in photonic glasses,” J. Mater. Sci. Mater. Electron. 16, 633–643 (2005). [CrossRef]

], the nonlinear refractive index, n2, of A1 glass is estimated to be up to 4.60×10-15 cm2/W. The values of IS/IR, n2 and χ (3) of other samples are also listed in Table 1. For the (100-x)GeS2-xGa2S3 pseudo-binary glasses, the values of IS/IR decrease gradually when GeS2 is replaced by Ga2S3. On Series A (100-2x)GeS2-xGa2S3-xAgCl, where the ratio of Ga2S3 to AgCl is equal to 1, the values of IS/IR also decrease with the additions of Ga2S3 and AgCl. Lastly, for the glasses on Series B 0.8(100-x)GeS2-0.2(100-x)Ga2S3-xAgCl, where the ratio of GeS2 to Ga2S3 maintains as 4:1, the values of IS/IR increase tardily with the addition of AgCl.

Table 1. Linear and third-order nonlinear optical properties of GeS2-Ga2S3-AgCl glasses

table-icon
View This Table

For samples on Series B 0.8(100-x)GeS2-0.2(100-x)Ga2S3-xAgCl, where the ratio of GeS2 to Ga2S3 maintains as 4:1. Two distinct changes can be observed in the Raman spectra (see Fig. 4) with the the addition of AgCl. Firstly, the peaks at 340cm-1 and 255cm-1 shift slightly toward the lower frequency respectively due to the formation of [Ge(Ga)S4-xClx] mixed tetrahedra and [ClxS3-xGe(Ga)-Ge(Ga)S3-xClx] mixed ethane-like s.u.. It can be interpreted by the theory of molecular vibration [23

23. H. Z. Tao, X. J. Zhao, C. B. Jing, H. Yang, and S. Mao, “Raman scattering studies of the GeS2-Ga2S3-CsCl glassy system,” Solid State Commun. 133, 327–332 (2005). [CrossRef]

]. The vibrating frequency bears a relationship as follows:

vfμ
(2)

Fig. 3. Raman spectra of pseudo-binary (100-x)GeS2-xGa2S3 (x=0, 10, 20, 30) glasses
Fig. 4. Raman spectra of the pseudo-ternary glasses on Series B

Based on the structural evolution of the GeS2-Ga2S3-AgCl glasses, to further investigate the compositional and structural dependence of χ (3), the values of (S+Cl/2)/(Ge+Ga) which can reflect the structural integrity of glasses are listed in the last column in table 1. To our surprise, for all the samples on three Series, the value of χ (3) almost increases linearly with the value of (S+Cl/2)/(Ge+Ga). Take samples on Series B as an example, the values of (S+Cl/2)/(Ge+Ga) and IS/IR are collected with the content of AgCl in Fig. 5, which clearly shows that the values of (S+Cl/2)/(Ge+Ga) and χ (3) increase monotonously with the addition of AgCl, and the same phenomenon is observed on the other two Series as well. For more clearly, the value of IS/IR vs. (S+Cl/2)/(Ge+Ga) for all the samples on three Series are illustrated in Fig. 6, which indicates the strong dependence of the values of IS/IR upon (S+Cl/2)/(Ge+Ga).

This strong dependence can be interpreted as follows. Firstly, in the case of (100-x)GeS2-xGa2S3 pseudo-binary glasses, the values of (S+Cl/2)/(Ge+Ga) and IS/IR decrease when GeS2 is replaced by Ga2S3. Simultaneously, the peak at about 255cm-1 in Raman spectra (see Fig. 3) ascribed to the vibration of [S3Ge(Ga)-Ge(Ga)S3] ethane-like s.u. increases gradually due to the shortage of sulfur, which forces [Ge(Ga)S4] tetrahedra convert into [S3Ge(Ga)-Ge(Ga)S3] ethane-like s.u.. Secondly, the shortage of sulfur does not mitigate on Series A with the addition of Ga2S3 and AgCl in the same ratio, which is due to the decrease of (S+Cl/2)/(Ge+Ga). And at the same time, the magnitude of [Ge(Ga)S4-xClx] mixed tetrahedra decreases gradually. Subsequently, the values of IS/IR on Series A decrease with the addition of AgCl. However, for samples on Series B, the values of IS/IR increase tardily when GeS2 and Ga2S3 are replaced by AgCl. On this Series, the values of (S+Cl/2)/(Ge+Ga) increase with the addition of AgCl, which will result in the conversion from [ClxS3-xGe(Ga)-Ge(Ga)S3-xClx] mixed ethane-like s.u. to [Ge(Ga)S4-xClx] mixed tetrahedra and lead to the decrease of the peak at about 255cm-1 in Raman spectra (see Fig. 4).

Judging from the discussion mentioned above, it can be deduced that [Ge(Ga)S4] and [Ge(Ga)S4-xClx] mixed tetrahedra with high hyperpolarizability make greater contribution to the enhancement of χ (3) compared with the structural defectiveness of the present glasses such as [S3Ge(Ga)-Ge(Ga)S3] and [ClxS3-xGe(Ga)-Ge(Ga)S3-xClx] mixed ethane-like s.u. In addition, as the terminator of the glassy network, the addition of chlorine atoms originated from AgCl will induce the degradation of integrity of glassy network and more structural defectiveness may be formed, which will partially counteract the mitigation of the shortage of sulfur. These considerations can better interpret the sharp decrease of the values of IS/IR from A2 to A3 and the slow enhancement of the values from B1 to B6. To sum up, an integrated and homogeneous glassy network with less structural defectiveness is more beneficial to the enhancement of χ (3).

Fig. 5. The ratio of IS/IR and (S+Cl/2)/(Ge+Ga) collected as a function of the content of AgCl for the pseudo-ternary glasses on Series B
Fig. 6. Optical Kerr signal ratio of IS/IR collected as a function of the values of (S+Cl/2)/(Ge+Ga) for the glasses on three Series

3.2 Second-order optical nonlinearity (Maker fringe technique)

R.A. Myers, et al, [24

24. R. A. Myers, N. Mukherjee, and S. R. J. Brueck, “Large second-order nonlinearity in poled fused silica,” 16, 1732–1734 (1991).

] have provided that an effective second-order optical nonlinearity, χ (2) associated intimately with χ (3) via the Eq.: χ (2)=χ (3)Edc, which indicates that A1 glass possessing the largest χ (3) in this system may exhibit large second-order optical nonlinearity. In addition, high transmission at the operated fundamental wavelength (1064nm) and SH wavelength (532nm) (see Fig. 1) of this sample together with its better glass-forming ability [17

17. G. P. Dong, H. Z. Tao, X. D. Xiao, C. G. Lin, and X. J. Zhao, “Study on the formation, thermal, optical and physical properties of GeS2-Ga2S3-AgCl novel chalcohalide glasses,” J. Phys. Chem. Solids (Submit).

] also enable A1 glass as the optimal composition of this glassy system for the study on second-order optical nonlinearity.

Fig. 7. Maker fringe pattern of the A1 (80GeS2-10Ga2S3-10AgCl) glass poled by the electron beam

As one of the important techniques to study the structure of glasses, Raman scattering measurement was conducted in this experiment. Figure 8 shows the Raman spectra of the as-prepared and after irradiated A1 (80GeS2-10Ga2S3-10AgCl) glass. No any obvious change is observed in the spectra, which indicates that no distinct structural change can be detected. Maybe it is only electronic transition and distortion of electron cloud that occurred within the irradiated A1 glass. It can be further deduced that no damage appeared about the structure of the glass.

Fig. 8. Raman spectra of the as-prepared 80GeS2-10Ga2S3-10AgCl glass and the irradiated one

Furthermore, more detailed studies on the optimization of experimental conditions and compositions are necessary to make them perform high optical nonlinear susceptibility and meet the need of all-optical devices.

4. Conclusion

Third/second-order optical nonlinearities of GeS2-Ga2S3-AgCl chalcohalide glasses have been studied by OKE and Maker fringe technique, respectively. The maximum χ (3) within the present pseudo-ternary chalcogenide glasses, which is as large as 5.26×10-13esu, was obtained in the glass with the composition 80GeS2-10Ga2S3-10AgCl. Furthermore, through irradiating by electron beam upon this glass, a large second-order optical nonlinear susceptibility which is estimated to be greater than 6.1 pm/V was also obtained. The dependence of χ(3) upon structure of these glasses revealed by the experimental results indicates that an integrated and homogeneous glass network with less structural defectiveness such as [ClxS3-xGe(Ga)-Ge(Ga)S3-xClx] mixed ethane-like s.u. and larger number of [Ge(Ga)S4-xClx] mixed tetrahedra with high hyperpolarizability is more beneficial to the enhancement of χ (3). These GeS2-Ga2S3-AgCl chalcohalide glasses with large third/second-order optical nonlinearities are expected to be used as one of the most promising candidates in photoelectric fields.

Acknowledgment

This work was partially funded by the National Natural Science Foundation of China (No. 50125205, 10647142).

References and links

1.

K. Tanaka, “Optical nonlinearity in photonic glasses,” J. Mater. Sci. Mater. Electron. 16, 633–643 (2005). [CrossRef]

2.

G. Boudebs, S. Cherukulappurath, H. Leblond, J. Troles, F. Smektala, and F. Sanchez, “Experimental and theoretical study of higher-order nonlinearities in chalcogenide glasses,” Opt. Commun. 219, 427–433 (2003). [CrossRef]

3.

F. Smektala, J. Troles, V. Couderc, A. Barthelemy, G. Boudebs, F. Sanchez, H. Zeghlache, G. Martinelli, Y. Quiquempois, and S. Bailleux, “Third and second order nonlinear optical properties of Ge-Se-S-As chalcogenide glasses,” Proc SPIE 4628, 30–38 (2002). [CrossRef]

4.

X. F. Wang, S. X. Gu, J. G. Yu, C. L. Liu, X. J. Zhao, and H. Z. Tao, “Formation and properties of chalcogenide glasses in the GeS2-Ga2S3-CdS system,” Mater. Chem. Phys. 83, 284–288 (2004). [CrossRef]

5.

K. Ogusu, J. Yamasaki, S. Maeda, M. Kitao, and M. Minakata, “Linear and nonlinear optical properties of Ag-As-Se chalcogenide glasses for all-optical switching,” Opt. Lett. 29, 265–267 (2004). [CrossRef] [PubMed]

6.

R. C. Miller, “Optical second harmonic generation in piezoelec-tric crystals,” Appl. Phys. Lett. 5, 17–19 (1964). [CrossRef]

7.

H. Z. Tao, G. P. Dong, Y. B. Zhai, H. T. Guo, X. J. Zhao, Z. W. Wang, S. S. Chu, S. F. Wang, and Q. H. Gong, “Femtosecond third-order optical nonlinearity of the GeS2-Ga2S3-CdI2 new chalcohalide glasses,” Solid State Commun. 138, 485–488 (2006). [CrossRef]

8.

X. F. Wang, Z. W. Wang, J. G. Yu, C. L. Liu, X. J. Zhao, and Q. H. Gong, “Large and ultrafast third-order optical nonlinearity of GeS2-Ga2S3-CdS chalcogenide glass,” Chem. Phys. Lett. 399, 230–233 (2004). [CrossRef]

9.

A. Narazaki, K. Tanaka, and K. Hirao, “Surface structure and second-order nonlinear optical properties of thermally poled WO3-TeO2 glasses doped with Na+,” J. Opt. Soc. Am. B 19, 54–62 (2002). [CrossRef]

10.

P. G. Kazansky, A. Kamal, and P. S. J. Russell, “Erasure of thermally poled second-order nonlinearity in fused silica by electron implantation,” Opt. Lett. 18, 1141–1143 (1993). [CrossRef] [PubMed]

11.

T. Fujiwara, M. Talahashi, and A. J. Ikushima, “Second-harmonic generation in germanosilicate glass poled with ArF laser irradiation,” Appl. Phys. Lett. 71, 1032–1034 (1997). [CrossRef]

12.

M. X. Qiu, F. Pi, and G. Orriols, “The role of lead component in second-harmnonic generation in lead silica by electron-beam irradiation,” Appl. Phys. Lett. 73, 3040–3042 (1998). [CrossRef]

13.

I. V. Kityk, “IR-induced second harmonic generation in Sb2Te3-BaF2-PbCl2 glasses,” J. Phys. Chem. B 107, 10083–10087 (2003). [CrossRef]

14.

H.Z. Tao, S. Mao, G.P. Dong, H.Y. Xiao, and X.J. Zhao, “Raman scattering studies of the Ge-In sulfide glasses,” Solid State Commun. 137, 408–412 (2006). [CrossRef]

15.

G. P. Dong, H. Z. Tao, S. S. Chu, S. F. Wang, X. J. Zhao, Q. H. Gong, X. D. Xiao, and C. G. Lin, “Study on the structure dependent ultrafast third-order optical nonlinearity of GeS2-In2S3 chalcogenide glasses,” Opt. Commun. 270, 373–378 (2007). [CrossRef]

16.

G.P. Dong, H.Z. Tao, X.D. Xiao, C.G. Lin, X.J. Zhao, and S. Mao, “Mechanism of electron beam poled SHG in 0.95GeS2∙0.05In2S3 chalcogenide glasses,” J. Phys. Chem. Solids (doi:10.1016/j.jpcs.2006.10.002).

17.

G. P. Dong, H. Z. Tao, X. D. Xiao, C. G. Lin, and X. J. Zhao, “Study on the formation, thermal, optical and physical properties of GeS2-Ga2S3-AgCl novel chalcohalide glasses,” J. Phys. Chem. Solids (Submit).

18.

J. E. Aber, M. C. Newstein, and B. A. Garetz, “Femtosecond optical kerr effect measurement in silicate glasses,” J. Opt. Soc. Am. B 17, 120–127 (2000). [CrossRef]

19.

Q. M. Liu, X. J. Zhao, F. X. Gan, J. Mid, and S. X. Qian, “Femtosecond optical Kerr effect study of Ge10As40S30Se20 film,” Solid State Commun. 134, 513–517 (2005) [CrossRef]

20.

M. K. Casstevens, M. Samoc, J. Pfleger, and P. N. Prasad, “Dynamics of third-order nonlinear optical processes in Langmuir-Blodgett and evaporated films of phthalocyanines,” J. Chem. Phys. 92, 2019–2024 (1990). [CrossRef]

21.

K. Minoshima, M. Taiji, and T. Kobayashi, “Femtosecond time-resolved interferometry for the determination of complex nonlinear susceptibility,” Opt. Lett. 16, 1683–1685 (1991). [CrossRef] [PubMed]

22.

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

23.

H. Z. Tao, X. J. Zhao, C. B. Jing, H. Yang, and S. Mao, “Raman scattering studies of the GeS2-Ga2S3-CsCl glassy system,” Solid State Commun. 133, 327–332 (2005). [CrossRef]

24.

R. A. Myers, N. Mukherjee, and S. R. J. Brueck, “Large second-order nonlinearity in poled fused silica,” 16, 1732–1734 (1991).

25.

T. E. Everhart and P. H. Hoff, “Determination of kilovolt electron energy dissipation vs penetration distance in solid materials,” J. Appl. Phys. 42, 5837–5846 (1971). [CrossRef]

26.

M. Guignard, V. Nazabal, J. Troles, F. Smektala, H. Zeghlache, Y. Quiquempois, A. Kudlinski, and G. Martinelli, “Second-harmonic generation of thermally poled chalcogenide glass,” Opt. Express. 13, 789–795 (2005). [CrossRef] [PubMed]

OCIS Codes
(160.4330) Materials : Nonlinear optical materials
(170.5660) Medical optics and biotechnology : Raman spectroscopy
(320.7110) Ultrafast optics : Ultrafast nonlinear optics

ToC Category:
Materials

History
Original Manuscript: December 15, 2006
Revised Manuscript: January 25, 2007
Manuscript Accepted: January 29, 2007
Published: March 5, 2007

Citation
Guoping Dong, Haizheng Tao, Xiudi Xiao, Changgui Lin, Yueqiu Gong, Xiujian Zhao, Saisai Chu, Shufeng Wang, and Qihuang Gong, "Study on the third and second-order nonlinear optical properties of GeS2-Ga2S3-AgCl chalcohalide glasses," Opt. Express 15, 2398-2408 (2007)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-15-5-2398


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References

  1. K. Tanaka, "Optical nonlinearity in photonic glasses," J. Mater. Sci. Mater. Electron. 16, 633-643 (2005). [CrossRef]
  2. G. Boudebs, S. Cherukulappurath, H. Leblond, J. Troles, F. Smektala, and F. Sanchez, "Experimental and theoretical study of higher-order nonlinearities in chalcogenide glasses," Opt. Commun. 219, 427-433 (2003). [CrossRef]
  3. F. Smektala, J. Troles, V. Couderc, A. Barthelemy, G. Boudebs, F. Sanchez, H. Zeghlache, G. Martinelli, Y. Quiquempois, and S. Bailleux, "Third and second order nonlinear optical properties of Ge-Se-S-As chalcogenide glasses," Proc SPIE 4628, 30-38 (2002). [CrossRef]
  4. X. F. Wang, S. X. Gu, J. G. Yu, C. L. Liu, X. J. Zhao, and H. Z. Tao, "Formation and properties of chalcogenide glasses in the GeS2-Ga2S3-CdS system," Mater. Chem. Phys. 83, 284-288 (2004). [CrossRef]
  5. K. Ogusu, J. Yamasaki, S. Maeda, M. Kitao, and M. Minakata, "Linear and nonlinear optical properties of Ag-As-Se chalcogenide glasses for all-optical switching," Opt. Lett. 29, 265-267 (2004). [CrossRef] [PubMed]
  6. R. C. Miller, "Optical second harmonic generation in piezoelec-tric crystals," Appl. Phys. Lett. 5, 17-19 (1964). [CrossRef]
  7. H. Z. Tao, G. P. Dong, Y. B. Zhai, H. T. Guo, X. J. Zhao, Z. W. Wang, S. S. Chu, S. F. Wang, and Q. H. Gong, "Femtosecond third-order optical nonlinearity of the GeS2-Ga2S3-CdI2 new chalcohalide glasses," Solid State Commun. 138, 485-488 (2006). [CrossRef]
  8. X. F. Wang, Z. W. Wang, J. G. Yu, C. L. Liu, X. J. Zhao, and Q. H. Gong, "Large and ultrafast third-order optical nonlinearity of GeS2-Ga2S3-CdS chalcogenide glass," Chem. Phys. Lett. 399, 230-233 (2004). [CrossRef]
  9. A. Narazaki, K. Tanaka, and K. Hirao, "Surface structure and second-order nonlinear optical properties of thermally poled WO3-TeO2 glasses doped with Na+," J. Opt. Soc. Am. B 19, 54-62 (2002). [CrossRef]
  10. P. G. Kazansky, A. Kamal, P. S. J. Russell, "Erasure of thermally poled second-order nonlinearity in fused silica by electron implantation," Opt. Lett. 18, 1141-1143 (1993). [CrossRef] [PubMed]
  11. T. Fujiwara, M. Talahashi, and A. J. Ikushima, "Second-harmonic generation in germanosilicate glass poled with ArF laser irradiation," Appl. Phys. Lett. 71, 1032-1034 (1997). [CrossRef]
  12. M. X. Qiu, F. Pi, and G. Orriols, "The role of lead component in second-harmnonic generation in lead silica by electron-beam irradiation," Appl. Phys. Lett. 73, 3040-3042 (1998). [CrossRef]
  13. I. V. Kityk, "IR-induced second harmonic generation in Sb2Te3-BaF2-PbCl2 glasses," J. Phys. Chem. B 107, 10083-10087 (2003). [CrossRef]
  14. H.Z. Tao, S. Mao, G.P. Dong, H.Y. Xiao and X.J. Zhao, "Raman scattering studies of the Ge-In sulfide glasses," Solid State Commun. 137, 408-412 (2006). [CrossRef]
  15. G. P. Dong, H. Z. Tao, S. S. Chu, S. F. Wang, X. J. Zhao, Q. H. Gong, X. D. Xiao, and C. G. Lin, "Study on the structure dependent ultrafast third-order optical nonlinearity of GeS2-In2S3 chalcogenide glasses," Opt. Commun. 270, 373-378 (2007). [CrossRef]
  16. G.P. Dong, H.Z. Tao, X.D. Xiao, C.G. Lin, X.J. Zhao, S. Mao, "Mechanism of electron beam poled SHG in 0.95GeS2·0.05In2S3 chalcogenide glasses," J. Phys. Chem. Solids (doi:10.1016/j.jpcs.2006.10.002).
  17. G. P. Dong, H. Z. Tao, X. D. Xiao, C. G. Lin, and X. J. Zhao, "Study on the formation, thermal, optical and physical properties of GeS2-Ga2S3-AgCl novel chalcohalide glasses," J. Phys. Chem. Solids (Submit).
  18. J. E. Aber, M. C. Newstein, and B. A. Garetz, "Femtosecond optical kerr effect measurement in silicate glasses," J. Opt. Soc. Am. B 17, 120-127 (2000). [CrossRef]
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