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Optics Express

Optics Express

  • Editor: Andrew M. Weiner
  • Vol. 21, Iss. 7 — Apr. 8, 2013
  • pp: 8101–8115
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On the analogy between photoluminescence and carrier-type reversal in Bi- and Pb-doped glasses

Mark A. Hughes, Russell M. Gwilliam, Kevin Homewood, Behrad Gholipour, Daniel W. Hewak, Tae-Hoon Lee, Stephen R. Elliott, Takenobu Suzuki, Yasutake Ohishi, Tomas Kohoutek, and Richard J. Curry  »View Author Affiliations


Optics Express, Vol. 21, Issue 7, pp. 8101-8115 (2013)
http://dx.doi.org/10.1364/OE.21.008101


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Abstract

Reaction order in Bi-doped oxide glasses depends on the optical basicity of the glass host. Red and NIR photoluminescence (PL) bands result from Bi2+ and Bin clusters, respectively. Very similar centers are present in Bi- and Pb-doped oxide and chalcogenide glasses. Bi-implanted and Bi melt-doped chalcogenide glasses display new PL bands, indicating that new Bi centers are formed. Bi-related PL bands have been observed in glasses with very similar compositions to those in which carrier-type reversal has been observed, indicating that these phenomena are related to the same Bi centers, which we suggest are interstitial Bi2+ and Bi clusters.

© 2013 OSA

1. Introduction

Bismuth-doped glasses can give rise to photoluminescence (PL) at wavelengths ranging from 400 nm [1

1. G. W. Chi, D. C. Zhou, Z. G. Song, and J. B. Qiu, “Effect of optical basicity on broadband infrared fluorescence in bismuth-doped alkali metal germanate glasses,” Opt. Mater. 31(6), 945–948 (2009). [CrossRef]

] to 2500 nm [2

2. A. N. Romanov, Z. T. Fattakhova, A. A. Veber, O. V. Usovich, E. V. Haula, V. N. Korchak, V. B. Tsvetkov, L. A. Trusov, P. E. Kazin, and V. B. Sulimov, “On the origin of near-IR luminescence in Bi-doped materials (II). Subvalent monocation Bi⁺ and cluster Bi₅³⁺ luminescence in AlCl₃/ZnCl₂/BiCl₃ chloride glass,” Opt. Express 20(7), 7212–7220 (2012). [CrossRef] [PubMed]

], under variation of the pump wavelength and composition of the host glass. A wide variety of traditional glass hosts containing Bi have been investigated to date, mainly silicates [3

3. M. Peng, D. Chen, J. Qiu, X. Jiang, and C. Zhu, “Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence,” Opt. Mater. 29(5), 556–561 (2007). [CrossRef]

5

5. M. Peng, B. Wu, N. Da, C. Wang, D. Chen, C. Zhu, and J. Qiu, “Bismuth-activated luminescent materials for broadband optical amplifier in WDM system,” J. Non-Cryst. Solids 354(12-13), 1221–1225 (2008). [CrossRef]

] and germanates [6

6. J. Ren, J. Qiu, B. Wu, and D. Chen, “Ultrabroad infrared luminescence from Bi-doped alkaline earth metal germanate glasses,” J. Mater. Res. 22(06), 1574–1578 (2007). [CrossRef]

8

8. M. Peng, J. Qiu, D. Chen, X. Meng, and C. Zhu, “Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses,” Opt. Lett. 30(18), 2433–2435 (2005). [CrossRef] [PubMed]

], but also phosphates [9

9. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Near infrared broadband emission of bismuth-doped aluminophosphate glass,” Opt. Express 13(5), 1628–1634 (2005). [CrossRef] [PubMed]

], borates [10

10. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses,” Opt. Express 13(5), 1635–1642 (2005). [CrossRef] [PubMed]

], chalcogenides [11

11. G. P. Dong, X. D. Xiao, J. J. Ren, J. Ruan, X. F. Liu, J. R. Qiu, C. G. Lin, H. Z. Tao, and X. J. Zhao, “Broadband infrared luminescence from bismuth-doped GeS2-Ga2S3 chalcogenide glasses,” Chin. Phys. Lett. 25(5), 1891–1894 (2008). [CrossRef]

, 12

12. M. A. Hughes, T. Akada, T. Suzuki, Y. Ohishi, and D. W. Hewak, “Ultrabroad emission from a bismuth doped chalcogenide glass,” Opt. Express 17(22), 19345–19355 (2009). [CrossRef] [PubMed]

] and chlorides [2

2. A. N. Romanov, Z. T. Fattakhova, A. A. Veber, O. V. Usovich, E. V. Haula, V. N. Korchak, V. B. Tsvetkov, L. A. Trusov, P. E. Kazin, and V. B. Sulimov, “On the origin of near-IR luminescence in Bi-doped materials (II). Subvalent monocation Bi⁺ and cluster Bi₅³⁺ luminescence in AlCl₃/ZnCl₂/BiCl₃ chloride glass,” Opt. Express 20(7), 7212–7220 (2012). [CrossRef] [PubMed]

]. The origin of the infrared emission from Bi-doped glasses remains controversial, with convincing arguments being made for a variety of different emission centers, including Bi+ [10

10. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses,” Opt. Express 13(5), 1635–1642 (2005). [CrossRef] [PubMed]

], Bi5+ [13

13. Y. Fujimoto and M. Nakatsuka, “Infrared Luminescence from Bismuth-Doped Silica Glass,” Jpn. J. Appl. Phys. Part 2 Lett 40, L279–L281 (2001).

, 14

14. X. Wang and H. Xia, “Infrared superbroadband emission of Bi ion doped germanium-aluminum-sodium glass,” Opt. Commun. 268(1), 75–78 (2006). [CrossRef]

], Bi metal clusters [8

8. M. Peng, J. Qiu, D. Chen, X. Meng, and C. Zhu, “Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses,” Opt. Lett. 30(18), 2433–2435 (2005). [CrossRef] [PubMed]

], point defects [15

15. M. Y. Sharonov, A. B. Bykov, V. Petricevic, and R. R. Alfano, “Spectroscopic study of optical centers formed in Bi-, Pb-, Sb-, Sn-, Te-, and In-doped germanate glasses,” Opt. Lett. 33(18), 2131–2133 (2008). [CrossRef] [PubMed]

] and negatively charged Bi2 dimers [16

16. S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Luminescence Characteristics of Te- and Bi-Doped Glasses and Glass-Ceramics,” J. Ceram. Soc. Jpn. 115(1340), 259–263 (2007). [CrossRef]

, 17

17. V. O. Sokolov, V. G. Plotnichenko, and E. M. Dianov, “Origin of broadband near-infrared luminescence in bismuth-doped glasses,” Opt. Lett. 33(13), 1488–1490 (2008). [CrossRef] [PubMed]

]. However, there is a general consensus developing that more than one Bi center is responsible for the observed optical activity of the Bi dopant in glass. Pb doping has also been shown to have very similar absorption and photoluminescence behavior to that of Bi in glasses [15

15. M. Y. Sharonov, A. B. Bykov, V. Petricevic, and R. R. Alfano, “Spectroscopic study of optical centers formed in Bi-, Pb-, Sb-, Sn-, Te-, and In-doped germanate glasses,” Opt. Lett. 33(18), 2131–2133 (2008). [CrossRef] [PubMed]

]. Broadband Bi-doped fiber lasers operating at wavelengths between 1150 and 1550 nm [18

18. I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett. 6(7), 487–504 (2009). [CrossRef]

], with powers up to 20 W [19

19. S. V. Firstov, A. V. Shubin, V. F. Khopin, M. A. Mel'kumov, I. A. Bufetov, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bismuth-doped germanosilicate fibre laser with 20-W output power at 1460 nm,” Quantum Electron. 41(7), 581–583 (2011). [CrossRef]

] and slope efficiencies of up to 30% [20

20. V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Efficient Bismuth-Doped Fiber Lasers,” IEEE J. Quantum Electron. 44(9), 834–840 (2008). [CrossRef]

], have been reported. A mode-locked Bi-doped fiber laser with 900 fs pulses has also been demonstrated [21

21. S. Kivisto, J. Puustinen, M. Guina, O. G. Okhotnikov, and E. M. Dianov, “Tunable modelocked bismuth-doped soliton fibre laser,” Electron. Lett. 44(25), 1456–1458 (2008). [CrossRef]

]. Bismuth-doped glasses are therefore, potentially, an extremely important class of material for use in broadband lasers and optical amplifiers. One of the main limitations of Bi-doped fiber lasers fabricated so far is the inability to obtain lasing with doping concentrations more than around 0.005 wt% [22

22. A. B. Rulkov, A. A. Ferin, S. V. Popov, J. R. Taylor, I. Razdobreev, L. Bigot, and G. Bouwmans, “Narrow-line, 1178nm CW bismuth-doped fiber laser with 6.4W output for direct frequency doubling,” Opt. Express 15(9), 5473–5476 (2007). [CrossRef] [PubMed]

]. This means that the fibers need to be on the order of 100 m in length, which causes problems of background loss and nonlinearities. Absorption tails located close to lasing wavelengths cause additional losses [23

23. S. Yoo, M. P. Kalita, J. Sahu, J. Nilsson, and D. Payne, “Bismuth-doped fiber laser at 1.16 mm,” in Lasers and Electro-Optics, Conference on Quantum Electronics and Laser Science. CLEO/QELS, 2008), 1–2.

]. The presence of Bi centers not involved in the lasing process could cause concentration quenching and absorption losses. Therefore, an understanding of the nature of the Bi centers, and the ability to control which Bi centers are present, is critical for the ability to increase doping concentration, reduce losses and bring the performance of Bi- doped fiber lasers in line with that of rare-earth-doped fiber lasers.

Chalcogenide glasses are a broad class of increasingly important technological materials used in phase-change memories, solar cells, sensors and non-linear optical devices. They almost invariably display p-type electronic conductivity, and are known to remain p-type when melted with common donor atoms. The ability to reverse the carrier type in these glasses would enable electronic devices to be integrated with other chalcogenide-glass-based devices and may enable the fabrication of LEDs and laser diodes that emit at novel wavelengths.

Conventionally, Bi and Pb dopants are introduced into the glass melts (‘melt-doping’). We define melt-doping as an equilibrium doping method because the dopants are able to react with the glass material, above the glass-transition temperature, Tg, for sufficient time for the dopants to achieve their lowest energy bonding configuration. We define non-equilibrium doping as the inclusion of a dopant into the glass matrix below Tg. Ion implantation is a precise, non-equilibrium doping technique which is essential to the fabrication of most modern integrated circuits (ICs). It is relevant to Bi-doped glasses because it may allow control over which Bi centers are present in the glass. It is also relevant for the development of high-performance electronic devices based on Bi-doped glasses because it is the most precise doping technique in use today, and it may be possible to reverse the carrier type of chalcogenide glasses by impurity doping under non-equilibrium conditions [30

30. H. Fritzsche and M. Kastner, “The effect of charged additives on the carrier concentrations in lone-pair semiconductors,” Philos. Mag. B 37(3), 285–292 (1978). [CrossRef]

], as has been shown for Cd, Al, Zn and Mg (non-equilibrium) diffusion-doped As2Se2Te1 glass [31

31. S. Okano, H. Yamakawa, M. Suzuki, and A. Hiraki, “Fabrication of Chalcogenide Amorphous Semiconductor Diodes Using Low Temperature Thermal Diffusion Techniques,” Jpn. J. Appl. Phys. 26(Part 1, No. 7), 1102–1106 (1987). [CrossRef]

33

33. S. Okano, M. Suzuki, and M. Suzuki, “Electrical contact properties of metal-chalcogenide amorphous-semiconductor systems,” Jpn. J. Appl. Phys. 20(9), 1635–1640 (1981). [CrossRef]

]. In this work, we report, for the first time, that the order of the reaction which generates optically active Bi centers varies significantly between different glass hosts. We also report, for the first time, PL from Bi- and Pb-implanted glasses, some of which have compositions very close to those in which carrier-type reversal has been reported, and suggest that these phenomena are produced by the same, or a similar, active center. If our hypothesis is correct, it may assist in hastening the elucidation of the origin of these phenomena.

2. Experimental

2.1 Sample preparation

A gallium lanthanum sulphur oxide (GLSO) sputtering target was prepared by mixing 70% gallium sulphide, 24% lanthanum sulphide and 6% lanthanum oxide in a dry-nitrogen purged glove box. The raw materials were melted for 24 hours in dry argon, in 2 inch diameter vitreous carbon crucibles, annealed at the glass-transition temperature and then sliced to form a 3mm thick sputter target. We sputtered 100 nm thick films of GLS onto 1µm thick thermally oxidized SiO2 on Si substrates. The RF sputtering power was 60W, with an Ar flow of 15 SCCM. Details of the fabrication of bulk Bi-doped GLSO [12

12. M. A. Hughes, T. Akada, T. Suzuki, Y. Ohishi, and D. W. Hewak, “Ultrabroad emission from a bismuth doped chalcogenide glass,” Opt. Express 17(22), 19345–19355 (2009). [CrossRef] [PubMed]

], SiAlLiO [34

34. T. Suzuki and Y. Ohishi, “Ultrabroadband near-infrared emission from Bi-doped Li2O-Al2O3-SiO2 glass,” Appl. Phys. Lett. 88(19), 191912 (2006). [CrossRef]

] and GeAlPbO [35

35. M. Hughes, T. Suzuki, and Y. Ohishi, “Advanced bismuth doped lead-germanate glass for broadband optical gain devices,” J. Opt. Soc. Am. B 25(8), 1380–1386 (2008). [CrossRef]

] can be found elsewhere. The Ge33S67 and Ga5Ge25S70 bulk samples were synthesized from high-purity elemental Ge (5N purity), Ga (7N purity) and S (5N purity) in evacuated (10−3 Pa) and sealed fused silica ampoules placed in a rocking furnace and heated to 975 °C for 24 hours. The melt was then air-quenched to room temperature. The obtained glass samples were annealed at Tg-10 °C for 2 hours, and then cut and polished into samples around 10x10x1mm in size.

2.2 Sample characterization

Photoluminescence (PL) spectra of bulk samples were obtained by exciting with a 808 nm laser diode, or 514 nm Ar- ion laser. The emission was dispersed by a Jasco CT-25C monochromator which used a 600 or 1200 lines/mm grating. The slit width was ~2.5 mm, which corresponded to a resolution of ~10 nm. The stray excitation light was blocked with appropriate long-pass filters. Detection was realized with a Hamamatsu H9170 NIR photomultiplier tube (PMT), Newport Si, or InGaS detectors, coupled with standard phase-sensitive detection. All spectral measurements were corrected for the wavelength-dependent response of the measurement system by calculating a correction spectrum (C(λ)), with C(λ) = Ical(λ)/Imeas(λ), where Imeas(λ) is the luminescence spectrum of an Ushio calibrated white-light source measured by the detection system and Ical(λ) is the luminescence spectrum of the calibrated white-light source supplied by the manufacturer. Due to their weak emission, PL spectra of implanted samples were taken on a Renishaw 2000 microRaman system incorporating a Si CCD detector array, with a detection range of 400 – 1100 nm, and 514 or 782 nm excitation laser lines. A 50x microscope objective was used to focus the excitation onto the implanted sample surface. Several spectra were taken at different positions on the sample and then averaged. It was found that the variation in PL intensity between different positions on the same sample was less than 5%. This technique can therefore be used to compare the relative PL intensity between different implants. We also measured the PL from unimplanted samples to account for any PL that could be coming from the unimplanted film or substrate. These spectra were then subtracted from the PL spectra of the implanted samples. The PL intensity of unimplanted samples was less than around 5% of that of the implanted samples in the thin-film samples, and less than 25% in the bulk samples. Spectra were corrected by measuring the broadband PL of a Bi-doped glass with a known spectral luminance. Ripples in some of the PL spectra measured on the Raman system are an artifact caused by the various filters. Differential thermal analysis (DTA) measurements were taken using a Rigaku Thermo Plus TG-DTA. Rutherford back-scattering (RBS) measurements were made on a 2MV Tandetron accelerator using 2 MeV He beams.

3. Results and discussion

3.1 Review of bulk oxides and chalcogenides

3.2 Reaction mechanism in bulk oxide glasses

Figure 3
Fig. 3 DTA scan of Bi-doped lead germanate glasses.
shows the DTA scans of Bi-doped germanate glasses containing 4 and 10 mol % PbO. The Bi content is low enough not to affect the measurement. The scans show that there is only one phase present in the glass containing 4% PbO; however, in the 10% PbO glass, there are clearly two crystallization temperatures (Tc) and two melting temperatures (Tm), and possibly two glass-transition temperatures (Tg), indicating a phase separation. This could be seen as being analogous to the phase separation observed in Bi-doped GeS glasses displaying carrier-type reversal when the Bi content is increased past 11 mol% [25

25. K. L. Bhatia, D. P. Gosain, G. Parthasarathy, and E. S. R. Gopal, “On the structural features of doped amorphous chalcogenide semiconductors,” J. Non-Cryst. Solids 86(1-2), 65–71 (1986). [CrossRef]

, 26

26. L. Tichý, H. Tichá, A. Třiska, and P. Nagels, “Is the n-type conductivity in some Bi-doped chalcogenide glasses controlled by percolation?” Solid State Commun. 53(4), 399–402 (1985). [CrossRef]

]. The addition of other modifiers to germanate glasses usually does not cause phase separation; for example, only one Tg and Tc were observed in 1Bi2O3:5Al2O3:20SrO:75GeO2 glass [57

57. J. Ren, Y. Qiao, C. Zhu, X. Jiang, and J. Qiu, “Optical amplification near 1300 nm in bismuth-doped strontium germanate glass,” J. Opt. Soc. Am. B 24(10), 2597–2600 (2007). [CrossRef]

]. Thermal analysis of high Bi-content oxide and chalcogenide glasses is a priority for making comparisons to the phase separation observed in Bi:GeS.

3.3 Ion-implanted chalcogenides

Figure 4
Fig. 4 TRIM simulation of Bi- and Pb-implanted GLSO, GeS and GaGeS glass at various doses and energies, and RBS profile of Pb implanted in GLSO thin film. Inset shows a close-up of the lower dose samples.
shows ‘transport of ions in matter’ (TRIM) computer simulations of the implanted-ion depth distribution of the various implants and target samples used in this study, along with an RBS measurement of the depth distribution of Pb in a GLSO thin film, implanted with a 3x1015 ions/cm2 dose and an energy of 350 keV. TRIM simulations give distributions in ion/cm3, which we converted to at.% using the measured density of the bulk glasses. The simulations show that the peak doping concentrations for a 1x1016 ions/cm2 dose is around 3-4 at.%, reducing approximately linearly with dose, even though the energy was varied. Comparing the RBS measurement to the appropriate simulation indicates that the area under the distributions (equivalent to dose) is larger in the simulation; this indicates that the density of the film is higher than the bulk density we used to convert to at.%. RBS analysis also indicated that the composition of the film was Ga26La12S45O17, whereas the sputtering target had a composition of Ga26La14S57O3, indicating preferential sputtering of O, and/or post-deposition atmospheric oxidation of the film. The measured depth profile has a significantly shorter range (40 nm) than the simulated profile (80 nm), indicating that the TRIM software overestimates the penetration of the ions due to higher densities or other unknown material effects, or significant sputtering of the film is occurring during implantation. However, sputter markers indicated no decrease in depth, greater than the measurement resolution of 5 nm, between implanted and unimplanted regions. This may be due to implantation-induced expansion of the film, since we would expect measurable sputtering at this dose. In summary, peak concentrations may be slightly lower, and ion ranges significantly lower, than found in the simulations.

Figure 5(a)
Fig. 5 (a) PL spectra of Bi- and Pb-implanted GLSO thin films at various doses. Excitation was at 782 nm. The inset shows a close-up of low PL intensities. (b) log-log plot showing the integrated PL intensity against Bi2O3 content in La2O3-Al2O3-SiO2 glass, after [58], and dose in Bi-implanted GLSO thin films.
shows the PL spectra of Bi- and Pb-implanted GLSO films at various doses, excited at 782 nm. The Bi implants all display a PL peak at 820 nm, with a shoulder at 920 nm at low doses. The Pb implant has a similar peak at 860 nm; this is analogous to the similarity between Bi- and Pb-doped germanates. The PL intensity dependence on dose is super-linear, so we plotted the log of the integrated PL intensity (I) against the log of the Bi implant dose in Fig. 5(b) and found that it has a power-law dependence on dose (d): Id1.4. If we assume that the PL efficiency does not decrease with dose (which it should not, because this would lead to a non-power-law dependence), then this power-law dependence can be seen as being analogous to the power-law dependence of Bi absorption on Bi content in oxide glasses, shown in Fig. 2, and hence provides evidence for the existence of Bi clusters in the implanted films. We also extracted the dependence of PL intensity on Bi2O3 content in La2O3-Al2O3-SiO2 glass, from Fig. 2 in ref [58

58. M. Qian, C. Yu, J. Cheng, K. Li, and L. Hu, “The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass,” J. Lumin. 132(10), 2634–2638 (2012). [CrossRef]

], plotted this on Fig. 5(b) also, and found a similar power-law dependence, again linking Bi-doped chalcogenides and oxides.

Figure 6
Fig. 6 PL spectra of Pb-implanted GLSO thin film, compared to various Pb- and Bi-doped germanate and GLSO bulk glasses, excited at around 800 nm. Spectra for Ge28O56F12A14Pb0.3 and Ge28O56F11A14Bi0.6 are after [15]
shows the PL spectra of 3x1015 ions/cm2 Pb-implanted GLSO thin film (0.7 at.% peak Pb concentration), compared to bulk Bi- and Pb-doped germanates and GLSO, excited at 782 or 808 nm. The Pb-implanted GLSO has a very similar PL spectrum to Pb-doped germanate glass (Ge29O66Al3Pb2), which again indicates the existence of similar Pb centers in Pb-doped chalcogenide and oxide glasses. The narrow PL peak at 860 nm is rather uncharacteristic of Bi- and Pb-doped glasses excited at around 800 nm; indeed, when the Ge29O66Al3Pb2 glass is doped with 0.3 at% Bi, the PL intensity increases by around 100 fold and switches to the characteristic broad PL at ~1200 nm. A different Pb-doped germanate glass (Ge28O56F12A14Pb0.3) displays the characteristic broad PL at ~1200 nm, rather than the narrow 860 nm PL; this could be due to the addition of F, or the lower doping concentration. The composition of the bulk Bi-doped GLSO (Ga28La12S42O18Bi0.4), is very similar to the composition of the 1x1015 ions/cm2 Bi-implanted GLSO film (Ga26La12S45O17Bi0.5). However, the PL spectra are rather different: bulk Bi:GLSO also has broad PL at ~1200 nm, whereas the 1x1015 ions/cm2 Bi-implanted GLSO film exhibits a narrow PL peak at 820 nm, which is associated with Ge29O66Al3Pb2 bulk glass. This result is significant because it indicates that ion implantation is able to generate new and different Bi centers, which are not present in a sample whose dopants are introduced during melting.

Figure 7
Fig. 7 PL spectra of Bi- and Pb-implanted GLSO films at various doses, and bulk Bi-doped GLSO and LAS glass, excited at 514 nm. The PL intensities of the implanted films are plotted relative to each other, the bulk samples are not. The upper inset shows a close-up of the lower intensity spectra. The lower inset shows a log-log plot showing the integrated PL intensity against Bi dose.
shows the PL spectra of Bi- and Pb-implanted GLSO thin films at various doses, along with bulk Bi-doped GLSO and Li2O-Al2O3-SiO2 (LAS) glass, excited at 514 nm. Bulk Bi:GLSO exhibits a PL peak at 950 nm. However, the 1x1014 ions/cm2 Bi-implanted GLSO has a characteristic red PL band, peaking at 700 nm, which is commonly observed in Bi-doped oxide glasses under green excitation [40

40. B. I. Denker, B. I. Galagan, V. V. Osiko, I. L. Shulman, S. E. Sverchkov, and E. M. Dianov, “Factors affecting the formation of near infrared-emitting optical centers in Bi-doped glasses,”Appl. Phys. B. 98(2-3), 455–458 (2010). [CrossRef]

]. The spectrum of the Bi:LAS glass in Fig. 7 also has a 700 nm PL band, which is very similar to that of the 1x1014 ions/cm2 Bi-implanted GLSO. Comparing the 1x1015 ions/cm2 Bi implant to bulk Bi:GLSO (which have very similar compositions) indicates that the 1x1015 ions/cm2 Bi implant has the 700 nm PL band associated with oxide glasses, and the 950 nm PL band observed in bulk Bi:GLSO, in equal intensities. If we extend our model of oxide glasses, in which red and NIR PL result from Bi2+ and Bin clusters, respectively, to Bi:GLSO, then implanted Bi is more likely to be incorporated as Bi2+ than melt-doped Bi. The 700 nm PL band remains approximately constant for 1x1014 and 1x1015 ions/cm2 Bi implants, which is similar to the effect discussed earlier for Bi:SiMgAlO [40

40. B. I. Denker, B. I. Galagan, V. V. Osiko, I. L. Shulman, S. E. Sverchkov, and E. M. Dianov, “Factors affecting the formation of near infrared-emitting optical centers in Bi-doped glasses,”Appl. Phys. B. 98(2-3), 455–458 (2010). [CrossRef]

]. For the 1x1016 ions/cm2 Bi implant, the 700 nm PL band becomes much stronger and broader. We were unable to detect any NIR PL from the implanted samples using the standard measurement system that we used for our bulk samples.

During ion implantation, accelerated ions are decelerated by collisions with the nuclei, and electronic clouds, of atoms in the target. After a series of collisions, the implanted ion comes to rest. These collisions result in the displacement of individual atoms, which causes damage to the atomic structure of the target. In silicon IC manufacture, this damage is usually relieved by subsequent annealing above the crystallization temperature. This annealing activates the dopant by allowing them to move from an interstitial site to a lattice site. Similarly to ion-implanted Si, we expect that ions implanted into chalcogenide glasses will initially enter interstitial sites. XPS and NEXAFS measurements of N2-implanted and nitrogen-codeposited Ge2Sb2Te5 amorphous chalcogenide films indicated that implanted N tended to accumulate in interstitial sites compared to codeposited N2 [59

59. Y. Kim, J. H. Baeck, M.-H. Cho, E. J. Jeong, and D.-H. Ko, “Effects of N2+ ion implantation on phase transition in Ge2Sb2Te5 films,” J. Appl. Phys. 100(8), 083502 (2006). [CrossRef]

]. This indicates that Bi2+ associated with Bi-implanted GLSO may be interstitial. 3x1015 ions/cm2 Pb-implanted GLSO has a single 700 nm PL band; however, since we do not have an equivalent bulk Pb:GLSO glass with which to compare, it is difficult to say if this PL band is caused by implantation or not. However, we would expect bulk Pb:GLSO to have a similar PL spectrum to Bi:GLSO, based on the similarities between the two dopants that we have reported so far. We assign this band to Pb+, which is isoelectronic with Bi2+.

Figure 9
Fig. 9 PL from Bi-implanted bulk GeS and GaGeS glass, excited at 514 nm
shows the PL spectra, excited at 514 nm, of 1x1016 ions/cm2 Bi-implanted bulk Ge33S67 and Ga5Ge25S70 glass. The Bi-implanted regions should have compositions of Ge33S67Bi3.4 and Ga5Ge25S70Bi3.8. These compositions are even closer to those in which CTR has been observed - see Fig. 8(b). Both glasses display characteristic red Bi PL, indicating the presence of interstitial Bi2+, peaking at 670 in Ge33S67 and at 700 nm in Ga5Ge25S70, along with an unknown peak at 885 nm. The observation of both red and NIR PL bands in glasses with compositions close to those in which CTR has been reported indicated that both interstitial Bi2+ and Bi clusters are involved in CTR.

4. Conclusions

Acknowledgments

We would like to thank Prof. Guoping Dong and Dr. Mikhail Sharonov for supplying data from their publications. This work was supported by the UK EPSRC grants EP/I018414/1, EP/I019065/1 and EP/I018050/1.

References and links

1.

G. W. Chi, D. C. Zhou, Z. G. Song, and J. B. Qiu, “Effect of optical basicity on broadband infrared fluorescence in bismuth-doped alkali metal germanate glasses,” Opt. Mater. 31(6), 945–948 (2009). [CrossRef]

2.

A. N. Romanov, Z. T. Fattakhova, A. A. Veber, O. V. Usovich, E. V. Haula, V. N. Korchak, V. B. Tsvetkov, L. A. Trusov, P. E. Kazin, and V. B. Sulimov, “On the origin of near-IR luminescence in Bi-doped materials (II). Subvalent monocation Bi⁺ and cluster Bi₅³⁺ luminescence in AlCl₃/ZnCl₂/BiCl₃ chloride glass,” Opt. Express 20(7), 7212–7220 (2012). [CrossRef] [PubMed]

3.

M. Peng, D. Chen, J. Qiu, X. Jiang, and C. Zhu, “Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence,” Opt. Mater. 29(5), 556–561 (2007). [CrossRef]

4.

Y. Arai, T. Suzuki, Y. Ohishi, S. Morimoto, and S. Khonthon, “Ultrabroadband near-infrared emission from a colorless bismuth-doped glass,” Appl. Phys. Lett. 90(26), 261110 (2007). [CrossRef]

5.

M. Peng, B. Wu, N. Da, C. Wang, D. Chen, C. Zhu, and J. Qiu, “Bismuth-activated luminescent materials for broadband optical amplifier in WDM system,” J. Non-Cryst. Solids 354(12-13), 1221–1225 (2008). [CrossRef]

6.

J. Ren, J. Qiu, B. Wu, and D. Chen, “Ultrabroad infrared luminescence from Bi-doped alkaline earth metal germanate glasses,” J. Mater. Res. 22(06), 1574–1578 (2007). [CrossRef]

7.

M. Peng, J. Qiu, D. Chen, X. Meng, I. Yang, X. Jiang, and C. Zhu, “Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification,” Opt. Lett. 29(17), 1998–2000 (2004). [CrossRef] [PubMed]

8.

M. Peng, J. Qiu, D. Chen, X. Meng, and C. Zhu, “Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses,” Opt. Lett. 30(18), 2433–2435 (2005). [CrossRef] [PubMed]

9.

X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Near infrared broadband emission of bismuth-doped aluminophosphate glass,” Opt. Express 13(5), 1628–1634 (2005). [CrossRef] [PubMed]

10.

X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses,” Opt. Express 13(5), 1635–1642 (2005). [CrossRef] [PubMed]

11.

G. P. Dong, X. D. Xiao, J. J. Ren, J. Ruan, X. F. Liu, J. R. Qiu, C. G. Lin, H. Z. Tao, and X. J. Zhao, “Broadband infrared luminescence from bismuth-doped GeS2-Ga2S3 chalcogenide glasses,” Chin. Phys. Lett. 25(5), 1891–1894 (2008). [CrossRef]

12.

M. A. Hughes, T. Akada, T. Suzuki, Y. Ohishi, and D. W. Hewak, “Ultrabroad emission from a bismuth doped chalcogenide glass,” Opt. Express 17(22), 19345–19355 (2009). [CrossRef] [PubMed]

13.

Y. Fujimoto and M. Nakatsuka, “Infrared Luminescence from Bismuth-Doped Silica Glass,” Jpn. J. Appl. Phys. Part 2 Lett 40, L279–L281 (2001).

14.

X. Wang and H. Xia, “Infrared superbroadband emission of Bi ion doped germanium-aluminum-sodium glass,” Opt. Commun. 268(1), 75–78 (2006). [CrossRef]

15.

M. Y. Sharonov, A. B. Bykov, V. Petricevic, and R. R. Alfano, “Spectroscopic study of optical centers formed in Bi-, Pb-, Sb-, Sn-, Te-, and In-doped germanate glasses,” Opt. Lett. 33(18), 2131–2133 (2008). [CrossRef] [PubMed]

16.

S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Luminescence Characteristics of Te- and Bi-Doped Glasses and Glass-Ceramics,” J. Ceram. Soc. Jpn. 115(1340), 259–263 (2007). [CrossRef]

17.

V. O. Sokolov, V. G. Plotnichenko, and E. M. Dianov, “Origin of broadband near-infrared luminescence in bismuth-doped glasses,” Opt. Lett. 33(13), 1488–1490 (2008). [CrossRef] [PubMed]

18.

I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett. 6(7), 487–504 (2009). [CrossRef]

19.

S. V. Firstov, A. V. Shubin, V. F. Khopin, M. A. Mel'kumov, I. A. Bufetov, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bismuth-doped germanosilicate fibre laser with 20-W output power at 1460 nm,” Quantum Electron. 41(7), 581–583 (2011). [CrossRef]

20.

V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Efficient Bismuth-Doped Fiber Lasers,” IEEE J. Quantum Electron. 44(9), 834–840 (2008). [CrossRef]

21.

S. Kivisto, J. Puustinen, M. Guina, O. G. Okhotnikov, and E. M. Dianov, “Tunable modelocked bismuth-doped soliton fibre laser,” Electron. Lett. 44(25), 1456–1458 (2008). [CrossRef]

22.

A. B. Rulkov, A. A. Ferin, S. V. Popov, J. R. Taylor, I. Razdobreev, L. Bigot, and G. Bouwmans, “Narrow-line, 1178nm CW bismuth-doped fiber laser with 6.4W output for direct frequency doubling,” Opt. Express 15(9), 5473–5476 (2007). [CrossRef] [PubMed]

23.

S. Yoo, M. P. Kalita, J. Sahu, J. Nilsson, and D. Payne, “Bismuth-doped fiber laser at 1.16 mm,” in Lasers and Electro-Optics, Conference on Quantum Electronics and Laser Science. CLEO/QELS, 2008), 1–2.

24.

J. C. Phillips, “Constraint theory and carrier-type reversal in Bi-Ge chalcogenide alloy glasses,” Phys. Rev. B Condens. Matter 36(8), 4265–4270 (1987). [CrossRef] [PubMed]

25.

K. L. Bhatia, D. P. Gosain, G. Parthasarathy, and E. S. R. Gopal, “On the structural features of doped amorphous chalcogenide semiconductors,” J. Non-Cryst. Solids 86(1-2), 65–71 (1986). [CrossRef]

26.

L. Tichý, H. Tichá, A. Třiska, and P. Nagels, “Is the n-type conductivity in some Bi-doped chalcogenide glasses controlled by percolation?” Solid State Commun. 53(4), 399–402 (1985). [CrossRef]

27.

V. K. Bhatnagar and K. L. Bhatia, “Frequency dependent electrical transport in bismuth-modified amorphous germanium sulfide semiconductors,” J. Non-Cryst. Solids 119(2), 214–231 (1990). [CrossRef]

28.

S. R. Elliott and A. T. Steel, “Mechanism for Doping in Bi Chalcogenide Glasses,” Phys. Rev. Lett. 57(11), 1316–1319 (1986). [CrossRef] [PubMed]

29.

P. Kounavis, E. Mytilineou, and M. Roilos, “p-n junctions from sputtered Ge25Se75 - xBix films,” J. Appl. Phys. 66(2), 708–710 (1989). [CrossRef]

30.

H. Fritzsche and M. Kastner, “The effect of charged additives on the carrier concentrations in lone-pair semiconductors,” Philos. Mag. B 37(3), 285–292 (1978). [CrossRef]

31.

S. Okano, H. Yamakawa, M. Suzuki, and A. Hiraki, “Fabrication of Chalcogenide Amorphous Semiconductor Diodes Using Low Temperature Thermal Diffusion Techniques,” Jpn. J. Appl. Phys. 26(Part 1, No. 7), 1102–1106 (1987). [CrossRef]

32.

S. Okano, M. Suzuki, T. Imura, and A. Hiraki, “Chalcogenide amorphous-semiconductor diodes,” Jpn. J. Appl. Phys. Part 2 Lett 24, L445–L448 (1985).

33.

S. Okano, M. Suzuki, and M. Suzuki, “Electrical contact properties of metal-chalcogenide amorphous-semiconductor systems,” Jpn. J. Appl. Phys. 20(9), 1635–1640 (1981). [CrossRef]

34.

T. Suzuki and Y. Ohishi, “Ultrabroadband near-infrared emission from Bi-doped Li2O-Al2O3-SiO2 glass,” Appl. Phys. Lett. 88(19), 191912 (2006). [CrossRef]

35.

M. Hughes, T. Suzuki, and Y. Ohishi, “Advanced bismuth doped lead-germanate glass for broadband optical gain devices,” J. Opt. Soc. Am. B 25(8), 1380–1386 (2008). [CrossRef]

36.

S. Parke and R. S. Webb, “The optical properties of thallium, lead and bismuth in oxide glasses,” J. Phys. Chem. Solids 34(1), 85–95 (1973). [CrossRef]

37.

B. Denker, B. Galagan, V. Osiko, I. Shulman, S. Sverchkov, and E. Dianov, “The IR emitting centers in Bi-doped Mg-Al-Si oxide glasses,” Laser Phys. 19(5), 1105–1111 (2009). [CrossRef]

38.

M. A. Hughes, T. Suzuki, and Y. Ohishi, “Compositional dependence of the optical properties of bismuth doped lead-aluminum-germanate glass,” Opt. Mater. 32(9), 1028–1034 (2010). [CrossRef]

39.

M. Hughes, T. Suzuki, and Y. Ohishi, “Towards a high-performance optical gain medium based on bismuth and aluminum co-doped germanate glass,” J. Non-Cryst. Solids 356(6-8), 407–418 (2010). [CrossRef]

40.

B. I. Denker, B. I. Galagan, V. V. Osiko, I. L. Shulman, S. E. Sverchkov, and E. M. Dianov, “Factors affecting the formation of near infrared-emitting optical centers in Bi-doped glasses,”Appl. Phys. B. 98(2-3), 455–458 (2010). [CrossRef]

41.

X. Jiang and A. Jha, “An investigation on the dependence of photoluminescence in Bi2O3-doped GeO2 glasses on controlled atmospheres during melting,” Opt. Mater. 33(1), 14–18 (2010). [CrossRef]

42.

Y. Zhou, N. Gai, and J. Wang, “Comparative investigation on spectroscopic properties of Er3+ between Ce3+-doped and B2O3-added bismuth glasses,” J. Phys. Chem. Solids 70(2), 261–265 (2009). [CrossRef]

43.

H. Masai, Y. Takahashi, and T. Fujiwara, “Addition effect of SnO in optical property of Bi2O3-containing aluminoborate glass,” J. Appl. Phys. 105(8), 4 (2009). [CrossRef]

44.

A. Winterstein, S. Manning, H. Ebendorff-Heidepriem, and L. Wondraczek, “Luminescence from bismuth-germanate glasses and its manipulation through oxidants,” Opt. Mater. Express 2(10), 1320–1328 (2012). [CrossRef]

45.

A. Lebouteiller and P. Courtine, “Improvement of a bulk optical basicity table for oxidic systems,” J. Solid State Chem. 137(1), 94–103 (1998). [CrossRef]

46.

V. Dimitrov and S. Sakka, “Electronic oxide polarizability and optical basicity of simple oxides. I,” J. Appl. Phys. 79(3), 1736–1740 (1996). [CrossRef]

47.

M. A. Hughes, T. Suzuki, and Y. Ohishi, “Spectroscopy of bismuth doped lead-aluminum-germanate glass and yttrium-aluminum-silicate glass,” J. Non-Cryst. Solids 356(44-49), 2302–2309 (2010). [CrossRef]

48.

J. Ren, J. Qiu, D. Chen, C. Wang, X. Jiang, and C. Zhu, “Infrared luminescence properties of bismuth-doped barium silicate glasses,” J. Mater. Res. 22(07), 1954–1958 (2007). [CrossRef]

49.

W. Xu, M. Peng, Z. Ma, G. Dong, and J. Qiu, “A new study on bismuth doped oxide glasses,” Opt. Express 20(14), 15692–15702 (2012). [CrossRef] [PubMed]

50.

H. Bach, F. K. G. Baucke, and D. Krause, Electrochemistry of Glasses and Glass Melts, Including Glass Electrodes (Springer, 2000).

51.

M. A. Hamstra, H. F. Folkerts, and G. Blasse, “Materials chemistry communications. Red bismuth emission in alkaline-earth-metal sulfates,” J. Mater. Chem. 4(8), 1349 (1994). [CrossRef]

52.

M. Peng, C. Wang, D. Chen, J. Qiu, X. Jiang, and C. Zhu, “Investigations on bismuth and aluminum co-doped germanium oxide glasses for ultra-broadband optical amplification,” J. Non-Cryst. Solids 351(30-32), 2388–2393 (2005). [CrossRef]

53.

Y. Ohishi, “Novel photonics materials for broadband lightwave processing,” in Optical Components and Materials IV, Proceedings of the Society of Photo-Optical Instrumentation Engineers (SPIE) 2007, 646908. [CrossRef]

54.

S. Sumimiya, T. Nanba, Y. Miura, and S. Sakida, “Optical Properties of Bi2O3-La2O3-Al2O3-B2O3 Glasses,” in Advances in Glass and Optical Materials II (John Wiley & Sons, Inc., 2006), pp. 127–133.

55.

B. Denker, B. Galagan, V. Osiko, I. Shulman, S. Sverchkov, and E. Dianov, “Absorption and emission properties of Bi-doped Mg-Al-Si oxide glass system,” Appl. Phys. B. 95(4), 801–805 (2009). [CrossRef]

56.

M. A. Hughes, T. Suzuki, and Y. Ohishi, “Compositional optimization of bismuth-doped yttria-alumina-silica glass,” Opt. Mater. 32(2), 368–373 (2009). [CrossRef]

57.

J. Ren, Y. Qiao, C. Zhu, X. Jiang, and J. Qiu, “Optical amplification near 1300 nm in bismuth-doped strontium germanate glass,” J. Opt. Soc. Am. B 24(10), 2597–2600 (2007). [CrossRef]

58.

M. Qian, C. Yu, J. Cheng, K. Li, and L. Hu, “The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass,” J. Lumin. 132(10), 2634–2638 (2012). [CrossRef]

59.

Y. Kim, J. H. Baeck, M.-H. Cho, E. J. Jeong, and D.-H. Ko, “Effects of N2+ ion implantation on phase transition in Ge2Sb2Te5 films,” J. Appl. Phys. 100(8), 083502 (2006). [CrossRef]

60.

N. Tohge, T. Minami, Y. Yamamoto, and M. Tanaka, “Electrical and optical properties of n-type semiconducting chalcogenide glasses in the system Ge-Bi-Se,” J. Appl. Phys. 51(2), 1048–1053 (1980). [CrossRef]

61.

J. Málek, J. Klikorka, L. Beneš, L. Tichý, and A. Tříska, “Electrical and optical properties of Ge20Sb15−xBixBi65 glasses,” J. Mater. Sci. 21(2), 488–492 (1986). [CrossRef]

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.6000) Materials : Semiconductor materials

ToC Category:
Materials

History
Original Manuscript: February 8, 2013
Revised Manuscript: March 2, 2013
Manuscript Accepted: March 10, 2013
Published: March 27, 2013

Citation
Mark A. Hughes, Russell M. Gwilliam, Kevin Homewood, Behrad Gholipour, Daniel W. Hewak, Tae-Hoon Lee, Stephen R. Elliott, Takenobu Suzuki, Yasutake Ohishi, Tomas Kohoutek, and Richard J. Curry, "On the analogy between photoluminescence and carrier-type reversal in Bi- and Pb-doped glasses," Opt. Express 21, 8101-8115 (2013)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-21-7-8101


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References

  1. G. W. Chi, D. C. Zhou, Z. G. Song, and J. B. Qiu, “Effect of optical basicity on broadband infrared fluorescence in bismuth-doped alkali metal germanate glasses,” Opt. Mater.31(6), 945–948 (2009). [CrossRef]
  2. A. N. Romanov, Z. T. Fattakhova, A. A. Veber, O. V. Usovich, E. V. Haula, V. N. Korchak, V. B. Tsvetkov, L. A. Trusov, P. E. Kazin, and V. B. Sulimov, “On the origin of near-IR luminescence in Bi-doped materials (II). Subvalent monocation Bi⁺ and cluster Bi₅³⁺ luminescence in AlCl₃/ZnCl₂/BiCl₃ chloride glass,” Opt. Express20(7), 7212–7220 (2012). [CrossRef] [PubMed]
  3. M. Peng, D. Chen, J. Qiu, X. Jiang, and C. Zhu, “Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence,” Opt. Mater.29(5), 556–561 (2007). [CrossRef]
  4. Y. Arai, T. Suzuki, Y. Ohishi, S. Morimoto, and S. Khonthon, “Ultrabroadband near-infrared emission from a colorless bismuth-doped glass,” Appl. Phys. Lett.90(26), 261110 (2007). [CrossRef]
  5. M. Peng, B. Wu, N. Da, C. Wang, D. Chen, C. Zhu, and J. Qiu, “Bismuth-activated luminescent materials for broadband optical amplifier in WDM system,” J. Non-Cryst. Solids354(12-13), 1221–1225 (2008). [CrossRef]
  6. J. Ren, J. Qiu, B. Wu, and D. Chen, “Ultrabroad infrared luminescence from Bi-doped alkaline earth metal germanate glasses,” J. Mater. Res.22(06), 1574–1578 (2007). [CrossRef]
  7. M. Peng, J. Qiu, D. Chen, X. Meng, I. Yang, X. Jiang, and C. Zhu, “Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification,” Opt. Lett.29(17), 1998–2000 (2004). [CrossRef] [PubMed]
  8. M. Peng, J. Qiu, D. Chen, X. Meng, and C. Zhu, “Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses,” Opt. Lett.30(18), 2433–2435 (2005). [CrossRef] [PubMed]
  9. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Near infrared broadband emission of bismuth-doped aluminophosphate glass,” Opt. Express13(5), 1628–1634 (2005). [CrossRef] [PubMed]
  10. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses,” Opt. Express13(5), 1635–1642 (2005). [CrossRef] [PubMed]
  11. G. P. Dong, X. D. Xiao, J. J. Ren, J. Ruan, X. F. Liu, J. R. Qiu, C. G. Lin, H. Z. Tao, and X. J. Zhao, “Broadband infrared luminescence from bismuth-doped GeS2-Ga2S3 chalcogenide glasses,” Chin. Phys. Lett.25(5), 1891–1894 (2008). [CrossRef]
  12. M. A. Hughes, T. Akada, T. Suzuki, Y. Ohishi, and D. W. Hewak, “Ultrabroad emission from a bismuth doped chalcogenide glass,” Opt. Express17(22), 19345–19355 (2009). [CrossRef] [PubMed]
  13. Y. Fujimoto and M. Nakatsuka, “Infrared Luminescence from Bismuth-Doped Silica Glass,” Jpn. J. Appl. Phys. Part 2 Lett40, L279–L281 (2001).
  14. X. Wang and H. Xia, “Infrared superbroadband emission of Bi ion doped germanium-aluminum-sodium glass,” Opt. Commun.268(1), 75–78 (2006). [CrossRef]
  15. M. Y. Sharonov, A. B. Bykov, V. Petricevic, and R. R. Alfano, “Spectroscopic study of optical centers formed in Bi-, Pb-, Sb-, Sn-, Te-, and In-doped germanate glasses,” Opt. Lett.33(18), 2131–2133 (2008). [CrossRef] [PubMed]
  16. S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Luminescence Characteristics of Te- and Bi-Doped Glasses and Glass-Ceramics,” J. Ceram. Soc. Jpn.115(1340), 259–263 (2007). [CrossRef]
  17. V. O. Sokolov, V. G. Plotnichenko, and E. M. Dianov, “Origin of broadband near-infrared luminescence in bismuth-doped glasses,” Opt. Lett.33(13), 1488–1490 (2008). [CrossRef] [PubMed]
  18. I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett.6(7), 487–504 (2009). [CrossRef]
  19. S. V. Firstov, A. V. Shubin, V. F. Khopin, M. A. Mel'kumov, I. A. Bufetov, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bismuth-doped germanosilicate fibre laser with 20-W output power at 1460 nm,” Quantum Electron.41(7), 581–583 (2011). [CrossRef]
  20. V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Efficient Bismuth-Doped Fiber Lasers,” IEEE J. Quantum Electron.44(9), 834–840 (2008). [CrossRef]
  21. S. Kivisto, J. Puustinen, M. Guina, O. G. Okhotnikov, and E. M. Dianov, “Tunable modelocked bismuth-doped soliton fibre laser,” Electron. Lett.44(25), 1456–1458 (2008). [CrossRef]
  22. A. B. Rulkov, A. A. Ferin, S. V. Popov, J. R. Taylor, I. Razdobreev, L. Bigot, and G. Bouwmans, “Narrow-line, 1178nm CW bismuth-doped fiber laser with 6.4W output for direct frequency doubling,” Opt. Express15(9), 5473–5476 (2007). [CrossRef] [PubMed]
  23. S. Yoo, M. P. Kalita, J. Sahu, J. Nilsson, and D. Payne, “Bismuth-doped fiber laser at 1.16 mm,” in Lasers and Electro-Optics, Conference on Quantum Electronics and Laser Science. CLEO/QELS, 2008), 1–2.
  24. J. C. Phillips, “Constraint theory and carrier-type reversal in Bi-Ge chalcogenide alloy glasses,” Phys. Rev. B Condens. Matter36(8), 4265–4270 (1987). [CrossRef] [PubMed]
  25. K. L. Bhatia, D. P. Gosain, G. Parthasarathy, and E. S. R. Gopal, “On the structural features of doped amorphous chalcogenide semiconductors,” J. Non-Cryst. Solids86(1-2), 65–71 (1986). [CrossRef]
  26. L. Tichý, H. Tichá, A. Třiska, and P. Nagels, “Is the n-type conductivity in some Bi-doped chalcogenide glasses controlled by percolation?” Solid State Commun.53(4), 399–402 (1985). [CrossRef]
  27. V. K. Bhatnagar and K. L. Bhatia, “Frequency dependent electrical transport in bismuth-modified amorphous germanium sulfide semiconductors,” J. Non-Cryst. Solids119(2), 214–231 (1990). [CrossRef]
  28. S. R. Elliott and A. T. Steel, “Mechanism for Doping in Bi Chalcogenide Glasses,” Phys. Rev. Lett.57(11), 1316–1319 (1986). [CrossRef] [PubMed]
  29. P. Kounavis, E. Mytilineou, and M. Roilos, “p-n junctions from sputtered Ge25Se75 - xBix films,” J. Appl. Phys.66(2), 708–710 (1989). [CrossRef]
  30. H. Fritzsche and M. Kastner, “The effect of charged additives on the carrier concentrations in lone-pair semiconductors,” Philos. Mag. B37(3), 285–292 (1978). [CrossRef]
  31. S. Okano, H. Yamakawa, M. Suzuki, and A. Hiraki, “Fabrication of Chalcogenide Amorphous Semiconductor Diodes Using Low Temperature Thermal Diffusion Techniques,” Jpn. J. Appl. Phys.26(Part 1, No. 7), 1102–1106 (1987). [CrossRef]
  32. S. Okano, M. Suzuki, T. Imura, and A. Hiraki, “Chalcogenide amorphous-semiconductor diodes,” Jpn. J. Appl. Phys. Part 2 Lett24, L445–L448 (1985).
  33. S. Okano, M. Suzuki, and M. Suzuki, “Electrical contact properties of metal-chalcogenide amorphous-semiconductor systems,” Jpn. J. Appl. Phys.20(9), 1635–1640 (1981). [CrossRef]
  34. T. Suzuki and Y. Ohishi, “Ultrabroadband near-infrared emission from Bi-doped Li2O-Al2O3-SiO2 glass,” Appl. Phys. Lett.88(19), 191912 (2006). [CrossRef]
  35. M. Hughes, T. Suzuki, and Y. Ohishi, “Advanced bismuth doped lead-germanate glass for broadband optical gain devices,” J. Opt. Soc. Am. B25(8), 1380–1386 (2008). [CrossRef]
  36. S. Parke and R. S. Webb, “The optical properties of thallium, lead and bismuth in oxide glasses,” J. Phys. Chem. Solids34(1), 85–95 (1973). [CrossRef]
  37. B. Denker, B. Galagan, V. Osiko, I. Shulman, S. Sverchkov, and E. Dianov, “The IR emitting centers in Bi-doped Mg-Al-Si oxide glasses,” Laser Phys.19(5), 1105–1111 (2009). [CrossRef]
  38. M. A. Hughes, T. Suzuki, and Y. Ohishi, “Compositional dependence of the optical properties of bismuth doped lead-aluminum-germanate glass,” Opt. Mater.32(9), 1028–1034 (2010). [CrossRef]
  39. M. Hughes, T. Suzuki, and Y. Ohishi, “Towards a high-performance optical gain medium based on bismuth and aluminum co-doped germanate glass,” J. Non-Cryst. Solids356(6-8), 407–418 (2010). [CrossRef]
  40. B. I. Denker, B. I. Galagan, V. V. Osiko, I. L. Shulman, S. E. Sverchkov, and E. M. Dianov, “Factors affecting the formation of near infrared-emitting optical centers in Bi-doped glasses,”Appl. Phys. B.98(2-3), 455–458 (2010). [CrossRef]
  41. X. Jiang and A. Jha, “An investigation on the dependence of photoluminescence in Bi2O3-doped GeO2 glasses on controlled atmospheres during melting,” Opt. Mater.33(1), 14–18 (2010). [CrossRef]
  42. Y. Zhou, N. Gai, and J. Wang, “Comparative investigation on spectroscopic properties of Er3+ between Ce3+-doped and B2O3-added bismuth glasses,” J. Phys. Chem. Solids70(2), 261–265 (2009). [CrossRef]
  43. H. Masai, Y. Takahashi, and T. Fujiwara, “Addition effect of SnO in optical property of Bi2O3-containing aluminoborate glass,” J. Appl. Phys.105(8), 4 (2009). [CrossRef]
  44. A. Winterstein, S. Manning, H. Ebendorff-Heidepriem, and L. Wondraczek, “Luminescence from bismuth-germanate glasses and its manipulation through oxidants,” Opt. Mater. Express2(10), 1320–1328 (2012). [CrossRef]
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