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Virtual Journal for Biomedical Optics

Virtual Journal for Biomedical Optics

| EXPLORING THE INTERFACE OF LIGHT AND BIOMEDICINE

  • Editors: Andrew Dunn and Anthony Durkin
  • Vol. 8, Iss. 7 — Aug. 1, 2013
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Simple and efficient defect-tailored fiber-based UV-VIS broadband white light generation

Chien-Chih Lai, Nai-Chia Cheng, Cheng-Kai Wang, Jeng-Wei Tjiu, Ming-Yi Lin, and Sheng-Yao Huang  »View Author Affiliations


Optics Express, Vol. 21, Issue 12, pp. 14606-14617 (2013)
http://dx.doi.org/10.1364/OE.21.014606


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Abstract

We propose and demonstrate a facile approach for ultraviolet-visible broadband generation from a sapphire crystal core–borosilicate glass cladding hybrid fiber using a laser-heated pedestal growth technique. Considerable formation of F– and F2–type color emitters is effectively facilitated by Ti4+ ions and Al3+ vacancies, retaining efficient luminescence and high crystallinity of the sapphire core. These color centers intensify the ultraviolet, blue, and green emissions at 370, 450, and 540 nm, whereas the 650-nm red emission is contributed by Cr3+ in the octahedral sites of the corundum structure. Over 1-mW white light with an optical-to-optical efficiency of up to nearly 5% and 1931 Commission International de l’Eclairage chromaticity coordinate of (0.287, 0.333) is achieved under 325-nm excitation.

© 2013 OSA

1. Introduction

In the last decade, studies have increasingly focused on in vivo optical coherence tomography (OCT) systems and their superior capability to replace conventional invasive biopsy in various applications such as dermatology, ophthalmology, and neurology as well as cardiac catheterization [1

1. D. Huang, E. A. Swanson, C. P. Lin, J. S. Schuman, W. G. Stinson, W. Chang, M. R. Hee, T. Flotte, K. Gregory, C. A. Puliafito, and J. G. Fujimoto, “Optical coherence tomography,” Science 254(5035), 1178–1181 (1991). [CrossRef] [PubMed]

5

5. N. C. Cheng, T. H. Hsieh, Y. T. Wang, C. C. Lai, C. K. Chang, M. Y. Lin, D. W. Huang, J. W. Tjiu, and S. L. Huang, “Cell death detection by quantitative three-dimensional single-cell tomography,” Biomed. Opt. Express 3(9), 2111–2120 (2012). [CrossRef] [PubMed]

]. In recent times, the rapid development of powerful OCT systems with high axial resolutions has been hampered by the lack of suitable broadband light emissions, keeping in mind the fact that the axial resolution is primarily defined by the 3-dB bandwidth and the square of the center wavelength of the light source. As a representative case, the typical axial resolution offered by commercially mature superluminescent diodes (wavelength: 800−900 nm) is 5–10 μm [68], which is unsuitable for three-dimensional cellular imaging. Development has also been hampered by the higher temperature sensitivity and lower reliability of these systems. Unfortunately, most visible (VIS) to near-infrared (NIR) broadband sources such as Ti3+:sapphire (Ti3+:α-Al2O3) mode-locked lasers and photonic-crystal-fiber-based supercontinuum are both expensive and extremely sophisticated [9

9. R. A. Leitgeb, W. Drexler, A. Unterhuber, B. Hermann, T. Bajraszewski, T. Le, A. Stingl, and A. F. Fercher, “Ultrahigh resolution Fourier domain optical coherence tomography,” Opt. Express 12(10), 2156–2165 (2004). [CrossRef] [PubMed]

, 10

10. Z. Zhi, J. Qin, L. An, and R. K. Wang, “Supercontinuum light source enables in vivo optical microangiography of capillary vessels within tissue beds,” Opt. Lett. 36(16), 3169–3171 (2011). [CrossRef] [PubMed]

], making their use for clinical diagnostics difficult. Moreover, in many biomedical applications such as fluorescence microscopy and flow cytometry, broad ultraviolet-visible (UV-VIS) emission is of importance because most fluorochromes have large absorbances [11

11. P. Blandin, S. Lévêque-Fort, S. Lécart, J. C. Cossec, M.-C. Potier, Z. Lenkei, F. Druon, and P. Georges, “Time-gated total internal reflection fluorescence microscopy with a supercontinuum excitation source,” Appl. Opt. 48(3), 553–559 (2009). [CrossRef] [PubMed]

, 12

12. W. G. Telford, F. V. Subach, and V. V. Verkhusha, “Supercontinuum white light lasers for flow cytometry,” Cytometry A 75A(5), 450–459 (2009). [CrossRef] [PubMed]

]. In particular, wavelengths below 450 nm are difficult to cover in the aforementioned supercontinuum generations owing to the large detuning from the excitation. Therefore, there is a strong need to develop functional light sources for biophotonics with emitting wavelengths lower than those of typical Ti3+:sapphire crystals and photonic crystal fibers, especially in the ultrabroadband UV-VIS region.

Transition-metal ions are widely employed in the fields of bioimaging and telecommunication [13

13. C. C. Lai, H. J. Tsai, K. Y. Huang, K. Y. Hsu, Z. W. Lin, K. D. Ji, W. J. Zhuo, and S. L. Huang, “Cr4+:YAG double-clad crystal fiber laser,” Opt. Lett. 33(24), 2919–2921 (2008). [CrossRef] [PubMed]

15

15. C. C. Lai, C. P. Ke, S. K. Liu, C. Y. Lo, D. Y. Jheng, S. C. Wang, S. R. Lin, P. S. Yeh, and S. L. Huang, “Intracavity and resonant Raman crystal fiber laser,” Appl. Phys. Lett. 100(26), 261101 (2012). [CrossRef]

] because their 3d electronic configurations are tightly coupled to the host vibrations both in the VIS and the NIR regions. Studies have mostly focused on multiple transition-metal ions for the improvement of new broadband luminescent materials; however, this approach may lead to a deterioration in the crystal quality, and consequently, to a short lifetime and weak luminescence that cannot satisfy practical requirements [16

16. P. Boutinaud, P. Putaj, R. Mahiou, E. Cavalli, A. Speghini, and M. Bettinelli, “Quenching of lanthanide emission by intervalence charge transfer in crystals containing closed shell transition metal ions,” Spectrosc. Lett. 40(2), 209–220 (2007). [CrossRef]

]. An alternative approach is to develop defect-driven broadband gain media by intentionally introducing emissive color centers such as anion/cation vacancies and interstitials into a matrix. Owing to the strong coupling between the ligand fields of the color centers and the lattice phonons, the resulting optical transition typically represents wide-range vibrational bands, as has been observed in semiconductors and metal-oxide insulators [17

17. P. D. Townsend, “Colour centres past, present and future,” Nature 258(5533), 293–296 (1975). [CrossRef]

, 18

18. B. Henderson, Defects in Crystalline Solids (Arnold, London, 1972).

]. Among these, thermodynamically stable sapphire in the corundum form with hexagonal close-packed (HCP) oxygen finds wide applications in the field of photonics and as an abrasive, catalyst, and insulator owing to its high mechanical strength, high electrical resistivity, and high optical transparency [19

19. J. W. Leem and J. S. Yu, “Wafer-scale highly-transparent and superhydrophilic sapphires for high-performance optics,” Opt. Express 20(24), 26160–26166 (2012). [CrossRef] [PubMed]

]. The formation of corundum is of great interest in the field of cosmology owing to its occurrence in presolar stars [20

20. R. M. Stroud, L. R. Nittler, and C. M. Alexander, “Polymorphism in presolar Al2O3 grains from asymptotic giant branch stars,” Science 305(5689), 1455–1457 (2004). [CrossRef] [PubMed]

]. Several common approaches have been reported to intentionally introduce defect centers in sapphire crystals. The color centers in sapphire are mainly attributable to oxygen monovacancies (F+ and F centers) and oxygen divacancies (F2+ and F2 centers) caused by high-temperature thermochemical reactions in a reduced atmosphere [21

21. K. H. Lee and J. H. Crawford, “Additive coloration of sapphire,” Appl. Phys. Lett. 33(4), 273–275 (1978). [CrossRef]

23

23. M. Itou, A. Fujiwara, and T. Uchino, “Reversible photoinduced interconversion of color centers in α-Al2O3 prepared under vacuum,” J. Phys. Chem. C 113(49), 20949–20957 (2009). [CrossRef]

] or by high-energy bombardment with high-dose particles [24

24. B. Jeffries, G. P. Summers, and J. H. Crawford, “F–center fluorescence in neutron–bombarded sapphire,” J. Appl. Phys. 51(7), 3984–3986 (1980). [CrossRef]

26

26. K. J. Caulfield, R. Cooper, and J. F. Boas, “Luminescence from electron-irradiated sapphire,” Phys. Rev. B Condens. Matter 47(1), 55–61 (1993). [CrossRef] [PubMed]

]. However, unlike particle irradiation, normal thermochemical reduction cannot create sufficient amounts of F2–type centers, which leads to a limited emission bandwidth. Similarly, bombardment causes serious problems such as poor crystallinity and low-yield emission because heavy irradiation damages the microstructure and consequently causes concentration quenching of the luminescent centers [24

24. B. Jeffries, G. P. Summers, and J. H. Crawford, “F–center fluorescence in neutron–bombarded sapphire,” J. Appl. Phys. 51(7), 3984–3986 (1980). [CrossRef]

27

27. M. D. Rechtin, “A transmission electron microscopy study of the defect microstructure of Al2O3, subjected to ion bombardment,” Radiat. Eff. 42(3-4), 129–144 (1979). [CrossRef]

]. Thus far, no study has successfully produced a substantial amount of F– and F2–type-based broadband emission using a facile approach while maintaining high crystallinity, which is admittedly recognized as a challenge in the fields of optical and materials science.

Herein, we propose and demonstrate a facile approach for generating UV-VIS broadband emissions from a sapphire crystal core–borosilicate glass cladding hybrid fiber by the laser-heated pedestal growth (LHPG) technique. Efficient white light with milliwatt-level output and 1931 Commission International de l’Eclairage (CIE) chromaticity coordinate of (0.287, 0.333) has been obtained by the excitation of a 325-nm laser. The broad spectrum extends from 330 nm, which is over 50 nm further into the ultraviolet region than in previously reported results. The extra bandwidth is activated via oxygen and aluminum defect centers, which were facilitated by Ti and Cr ions. In addition, the broadband luminescences can be tuned from orange-red light to greenish light and finally to white light by simply altering the defect concentrations while preserving efficient emission and high crystallinity. A possible interpretation of defect center formation is also discussed. Compared to conventional thermochemical- and bombardment-based approaches, the proposed approach requires only a different growth temperature along with a different heating environment in the LHPG system, making it more attractive for practical fiber-based broadband generation.

2. Experimental

2.1. Device fabrications

Figure 1
Fig. 1 Schematic of growth of sapphire crystalline-core fiber.
shows details of the procedure by which borosilicate-glass-clad sapphire crystalline-core fibers are grown. First, a c-axis sapphire source rod with a 0.5 mm × 0.5 mm cross section was used as the starting material. The starting materials were prepared by the Czochralski method in strongly reducing conditions that favor Ti3+ over Ti4+ ions, with up to 98% Ti ions in the 3 + valence state [28

28. A. Sanchez, A. J. Strauss, R. L. Aggarwal, and R. E. Fahey, “Crystal growth, spectroscopy, and laser characteristics of Ti:Al2O3,” IEEE J. Quantum Electron. 24(6), 995–1002 (1988). [CrossRef]

, 29

29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

]. Through three diameter reduction steps by the LHPG technique, a 40-μm-diameter sapphire single-crystalline core was grown in an oxidizing atmosphere. To effectively facilitate the F– and F2–type centers and to tailor UV-VIS wideband generation, minor amounts of Ti and Cr ions (50–100 ppm) were incorporated into the 40-μm-diameter sapphire single-crystalline core. Then, this core was inserted into a borosilicate glass hollow tube with a 320-μm outer diameter and regrown using the same LHPG system to form the borosilicate-glass-clad sapphire crystalline-core fiber. Note that the glass cladding process in the second step was conducted in a ~10−3-Torr reducing environment. The schematic and end views of an as-grown 40-μm-diameter sapphire crystalline-core fiber are shown in the right-hand side of Fig. 1.

2.2. Nanostructural and spectroscopic characterizations

Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis were performed using an electron probe microanalyzer (JXA-8900R, JEOL). The nanostructure of the crystalline-core glass-clad interface and the corresponding selected-area electron diffraction (SAED) were investigated by a field-emission high-resolution transmission electron microscope (HR-TEM, Tecnai G2 F20, FEI) operating at 200 kV. The HR-TEM specimen was prepared using a dual-beam focused ion beam (FIB, SMI3050, Seiko) that can cut precisely at a specific location.

Photoluminescence (PL) and Raman experiments were carried out by using a 325-nm He-Cd laser (IK3802R-G, Kimmon Koha) and analyzed by a high-spectral-resolution spectrometer (LabRAM HR 800, JOBIN-YVON) with an 1800 mm−1 grating. A 40 × objective lens with a numerical aperture of 0.50 (LMU-40X-NUV, OFR) was employed to achieve a sub-micrometer spatial resolution. To generate amplified spontaneous emission from the sapphire crystalline-core fiber, an 18-mm-long fiber was wrapped in Sn-Pb alloy at 400 °C and clamped to an Al heat sink after cooling to room temperature. Figure 2
Fig. 2 Schematic of room-temperature white light measurement. FL, focusing lens.
shows the schematic of the room-temperature white light measurement. The 325-nm pump beam was first incident onto a variable attenuator, and it was coupled to the core of a sapphire crystalline-core fiber through a 40 × objective (LMU-40X-NUV, OFR). The white light output and the residual pump beam were collimated by an achromatic lens with 10-mm focal length and further filtered by a long-wavelength-pass filter (BLP01-325R-25, Semrock) before detection by a UV-enhanced Si photodetector (818-UV, Newport). The spectral sensibility of the employed photodetector is in the range of 200–1100 nm.

3. Results and discussion

3.1. Nanostructural analyses

Figures 3(a)
Fig. 3 (a) End face image of a sapphire crystal core–borosilicate glass cladding hybrid fiber. (b) Magnified SEM image of the 40-μm-diameter sapphire core. (c) Schematic of the sapphire structure viewed along the c axis. Large white, small blue, and small dashed circles represent O, Al atoms, and octahedral hollows between the closely packed O2- ions, respectively. (d),(e) EDX mappings of Al and Si, showing the closest hexagonal packing, as depicted in (c). (f) EDX spectrum of the sapphire core. (e),(f) HR-TEM images of the core-clad interface, showing high crystallinity as evidenced by the sharp SAED spots in the inset.
and 3(b) show the finely polished end face of a sapphire crystalline-core fiber. The hexagon-like shape of the sapphire core can be clearly discerned in Fig. 3(b), and this is in satisfactory agreement with the c-axis HCP sapphire crystal structures shown in Fig. 3(c) [30

30. E. R. Dobrovinskaya, L. A. Lytvynov, and V. Pishchik, Sapphire: Material, Manufacturing, Applications (Springer, New York, 2009), Chap. 2.

]. Figures 3(d) and 3(e) show the corresponding EDX mappings of the major compositions (Al and Si). Further, the EDX results also indicate that the 40-μm sapphire crystalline core is mounted quite well in the surrounding borosilicate glass cladding, reflecting effective optical wave confinement. Figure 3(f) shows the representative EDX spectrum of the sapphire crystal core, which exhibits the main Al and O peaks, whereas the Cu and Ga counts are from the supporting copper grid and the FIB ion gun, respectively. Figure 3(g) shows the low-magnification HR-TEM images taken along [112¯ 0] at the crystal-core glass-clad interface. The atomic structure image [Fig. 3 (h)] corresponding to the red box in Fig. 3(g) reveals a sharp atomic-scale interface with no evident defects, demonstrating that the sapphire core has a nearly perfect single-crystal structure. This can be confirmed by the sharp SAED spots [inset of Fig. 3(h)].

3.2. Defect-tailored broadband tuning

Figure 4(a)
Fig. 4 325-nm-excited (a) PL and (b) Raman spectra of the starting material (gray), 40-μm sapphire core (blue, refer to step 1 in Fig. 1), and 40-μm sapphire core with borosilicate glass cladding (red, refer to step 2 in Fig. 1).
shows the 325-nm-excited PL spectral evolution from the starting material to the as-grown sapphire crystalline-core fiber, as shown in Fig. 1. Several sharp peaks corresponding to the spontaneous Raman signals of the sapphire crystals are observed in the short wavelength region. A magnified view of this Raman region is shown in Fig. 4(b). According to group theory, only two A1g modes and five Eg modes are Raman active [31

31. W. Zhu and G. Pezzotti, “Phonon deformation potentials for the corundum structure of sapphire,” J. Raman. Spectrosc. 42(11), 2015–2025 (2011). [CrossRef]

]. All the observed modes are labeled in Fig. 4(b). The Raman spectra of these three samples reveal seven unambiguous characteristic c-axis sapphire peaks. Note that strongly enhancing the Raman signals of the as-grown glass-clad sapphire fiber [red lines in Fig. 4(a)] indicates the effectiveness of waveguide confinement with high crystallinity and low propagation loss of ~0.1 dB/cm. In the PL results shown in Fig. 4(a), i.e., spectrum of step 2 indicated by a red curve, three broad luminescent bands at 330–400, 400–600, and 600–650 nm are observed. These differ from those of the starting material [gray curve in Fig. 4(a)] and step 1 [blue curve in Fig. 4(a)], which show typical orange-red emissions with remarkably weak blue and UV bands because of insufficient oxygen monovacancies, as is discussed later. The corresponding chromaticity coordinates of these three samples are presented in the 1931 CIE diagram shown in Fig. 5
Fig. 5 Color evolutions during growth of sapphire crystalline-core fibers.
. The CIE diagram shows that the emission colors from the starting material to the as-grown glass-clad sapphire crystalline-core fiber vary from orange-red to greenish via step 1 and then to white light via step 2. Their CIE coordinates are (0.413, 0.402), (0.260, 0.424), and (0.287, 0.333), respectively. These results clearly demonstrate the noticeable variability and different physical mechanism of color center formation during LHPG processes.

3.3. Mechanisms for color center formation

Having demonstrated that we can tune the luminescent properties, we investigate the defect formation mechanism with respect to different fiber growth environments. Referring to step 1 in Fig. 1, the PL spectrum of the 40-μm sapphire crystalline core was found to comprise seven different bands based on Gaussian deconvolution analyses, as shown in Fig. 6
Fig. 6 Greenish broadband spectrum from 40-μm sapphire crystalline core showing a considerable amount of F22+ centers (577 nm) and aggregated VAl with Ti4+ ions (485 nm), respectively.
. These PL bands peaking at 375, 420, 458, 485, 531, 577, and 648 nm are consistent with the known F and F2 centers, Ti3+/Ti4+ ions and Ti4+-facilitated aluminum vacancies (Ti4+VA1), and Cr3+ ions with peaks at 380, 420, 460, 480, 510, 590, and 650 nm [23

23. M. Itou, A. Fujiwara, and T. Uchino, “Reversible photoinduced interconversion of color centers in α-Al2O3 prepared under vacuum,” J. Phys. Chem. C 113(49), 20949–20957 (2009). [CrossRef]

, 29

29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

, 32

32. B. Macalik, L. E. Bausá, J. García-Solé, F. Jaque, J. E. Muñoz Santiuste, and I. Vergara, “Blue emission in Ti-sapphire laser crystal,” Appl. Phys. B 55, 144–147 (1992).

34

34. A. I. Surdo and V. S. Kortov, “Exciton mechanism of energy transfer to F–centers in dosimetric corundum crystals,” Radiat. Meas. 38(4-6), 667–671 (2004). [CrossRef]

], as summarized in Table 1

Table 1. Comparison of Defect Center Emissions

table-icon
View This Table
. The aggregated VA1 with Ti4+ ions are due to the high binding energy of such Ti4+VA1 clusters [29

29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

]. As listed in Table 1, the F+ luminescent band shifts from 330 nm to 352 nm because a longer excitation is used, i.e., 260 nm versus 325 nm. This is typical of classical F–type-center luminescence in phonon-assisted alkali halides [35

35. D. B. Fitchen, R. H. Silsbee, T. A. Fulton, and E. L. Wolf, “Zero-phonon transitions of color centers in alkali halides,” Phys. Rev. Lett. 11(6), 275–277 (1963). [CrossRef]

, 36

36. P. Görlich, H. Karras, G. Kötitz, and R. Rauch, “Phonon-assisted colour centre fluorescence of additively coloured alkali earth fluoride crystals,” Phys. Status Solidi, B Basic Res. 25(1), K15–K18 (1968). [CrossRef]

] owing to the strong coupling nature of a trapped charge to the lattice with large Huang-Rhys factors and Stokes shifts [37

37. B. D. Evans and M. Stapelbroek, “Optical properties of the F+ center in crystalline Al2O3,” Phys. Rev. B 18(12), 7089–7098 (1978). [CrossRef]

].

Among these centers, F22+, F2, and Ti4+VA1 were found to mostly contribute to greenish emissions. However, the luminescent band at ~530 nm has also been assigned to donor centers such as interstitial aluminum ions (AlAl×) [38

38. M. G. Springils and J. A. Valbis, “Visible luminescence of colour centres in sapphire,” Phys. Status Solidi, B Basic Res. 123(1), 335–343 (1984). [CrossRef]

]. At this point, a 40-μm sapphire single-crystalline core was grown in an oxidizing atmosphere, implying that the formation of Ti4+ ions is preferred, and this viewpoint persisted for long [28

28. A. Sanchez, A. J. Strauss, R. L. Aggarwal, and R. E. Fahey, “Crystal growth, spectroscopy, and laser characteristics of Ti:Al2O3,” IEEE J. Quantum Electron. 24(6), 995–1002 (1988). [CrossRef]

, 29

29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

]. This enables one to obtain a rather large Ti4+ emission band at 420 nm. The blue emission of Ti4+ is a characteristic charge-transfer transition, as observed in many wide-band-gap materials, following the scenario [29

29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

, 39

39. W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. I. Charge-exchange energies and titanium-bound excitons,” Phys. Rev. B Condens. Matter 51(9), 5682–5692 (1995). [CrossRef] [PubMed]

, 40

40. W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. II. Charge-transfer transition states, carrier trapping, and detrapping,” Phys. Rev. B Condens. Matter 51(9), 5693–5698 (1995). [CrossRef] [PubMed]

]
Ti4++hν325nmTi3++h+(Ti4+)*Ti4++hν420nm,
(1)
where this model suggests that a hole (h+) is photoionized by 325-nm UV excitation. (Ti4+)* and ν represent the excited Ti4+ ion and the frequency of the light, respectively.

Another salient feature is that the introduction of Ti4+ causes the formation of aluminum vacancies for charge compensation. In other words, electroneutrality requires that a vacancy be formed for every three Ti4+ ions under oxidation, which is expressed as
12O2+2TiAl×OO×+23VAl'''+2TiAl,
(2)
where TiAl×, OO×, and TiAl represent Ti3+, interstitial oxygen, and Ti4+ in the Kröger-Vink notation, respectively [41

41. F. A. Kröger, The Chemistry of Imperfect Crystals (North Holland Publishing Company, Amsterdam, 1974).

]. Indeed, as compared to the starting material in Fig. 4, we found that the growth of the 40-μm sapphire crystalline core by heating under the present oxidation condition produces nearly 7 times enhancement at 485 nm, indicating the domination of Ti4+-facilitated VAl at this stage. On the other hand, oxidation can cause increasing interstitial oxygen (OO×) by consuming oxygen vacancies (VO), resulting in no observable amount of F–type centers, as shown in Fig. 5. This can be expressed as follows:
12O2+VO+2TiAl×OO×+2TiAl.
(3)
Equations (2) and (3) suggest that Schottky-type disorders exist in the as-grown 40-μm sapphire crystalline core.

It is also noteworthy that the aggregated VAl vacant centers with Ti4+ ions are negatively charged, and therefore, the incorporation of these centers must be concomitant with the introduction of positively charged F2–type centers. This leads to a compatible concentration of F22+ centers along with a lesser amount of F2+ centers, as denoted by orange curves in Fig. 6. In this case, heat treatments were carried out in air to enhance oxygen divacancy concentrations, as conducted in Mg-doped sapphire single crystals [22

22. R. Ramírez, M. Tardío, R. González, Y. Chen, and M. R. Kokta, “Photochromism of vacancy-related defects in thermochemically reduced α-Al2O3:Mg single crystals,” Appl. Phys. Lett. 86(8), 081914 (2005). [CrossRef]

, 33

33. R. Ramírez, M. Tardío, R. González, J. E. Muñoz Santiuste, and M. R. Kokta, “Optical properties of vacancies in thermochemically reduced Mg-doped sapphire single crystals,” J. Appl. Phys. 101(12), 123520 (2007). [CrossRef]

].

To clarify the effect of the growth environment on the broadband luminescence, we examine the vacuum-assisted heating process, referring to step 2 in Fig. 1. The glass cladding sapphire core was conducted under vacuum at ~10−3 Torr, indicating that the reduction of the sapphire core increases the concentration of Ti3+ beyond that of Ti4+. We thus see a much smaller extent of Ti4+ than that of Ti3+, i.e., 406 nm versus 446 nm in Fig. 7
Fig. 7 UV-VIS broadband white light generation from 40-μm sapphire crystalline core fiber with borosilicate glass cladding. The luminescent spectrum is fitted by Gaussian profiles, showing a thermal-induced interconversion between F+ and F22+ centers.
. The considerable amount of aggregated VAl with Ti4+ ions centered at 471 nm can be ascribed to the isochronal introduction of negatively charged defects VAl, because the F– and F2–type centers and Ti4+ ions are positively charged centers, attaining local charge neutrality.

In Fig. 7, for this sample in the wavelength of <400 nm, it is noteworthy that the PL intensities of F and F+ are nearly two times higher than those of the starting material and 40-μm sapphire core without glass cladding, as shown in Fig. 4(a). Furthermore, in this sample, the F22+ center shows a quietly low PL intensity. Previously, Ramírez et al. postulated the following reaction to account for the observed reversible thermal-induced interconversion between F+ and F22+ centers [33

33. R. Ramírez, M. Tardío, R. González, J. E. Muñoz Santiuste, and M. R. Kokta, “Optical properties of vacancies in thermochemically reduced Mg-doped sapphire single crystals,” J. Appl. Phys. 101(12), 123520 (2007). [CrossRef]

]:
2F+F22++ϕ.
(4)
where ϕ is the binding energy of the F22+ centers. For thermal treatment above 673 K, analogous to the case in step 1 (Fig. 1), F+ centers aggregate more satisfactorily and energetically and form F22+ centers. Taking into consideration the fact that when a starting material is heated using a CO2 laser in the LHPG system, bulk sapphire melts at a temperature above the melting temperature of sapphire at 2,054 °C. The resulting as-grown 40-μm sapphire crystalline core contains substantial amounts of F22+ centers, exhibiting a strong emission at 577 nm, as shown in Fig. 6. Furthermore, this high-temperature heat treatment often results in large aluminum vacancy, aluminum interstitial, and oxygen interstitial concentration ratios owing to their high formation energy, as evidenced by the strong greenish light at 450–600 nm in Fig. 6. On the other hand, at temperatures below 673 K, i.e., step 2 in Fig. 1, the F+ center mobility is too low to be a cluster, yielding relatively low luminescence at ~590 nm. In fact, for step 2, the glass cladding in the LHPG process was made near the transition temperature of borosilicate glass at 525 °C, producing a pliable state, and attached to the sapphire crystalline core.

Under 325-nm laser excitation, maximum white light output power over 1 mW was achieved when the incident pump power was 24.3 mW, as shown in Fig. 8
Fig. 8 White light output power as a function of incident pump power, showing a maximum output power up to milliwatt order.
. It is noteworthy that the milliwatt-level white generation with corresponding optical-to-optical efficiency of nearly 5% is the highest among existing active waveguide schemes [42

42. D. Manzani, Y. Ledemi, I. Skripachev, Y. Messaddeq, S. J. L. Ribeiro, R. E. P. de Oliveira, and C. J. S. de Matos, “Yb3+, Tm3+ and Ho3+ triply-doped tellurite core-cladding optical fiber for white light generation,” Opt. Mater. Express 1(8), 1515–1526 (2011). [CrossRef]

44

44. X. Liu, B. Chen, E. Y. B. Pun, and H. Lin, “White upconversion luminescence in Tm3+/Ho3+/Yb3+ triply doped K+–Na+ ion-exchanged aluminum germinate glass channel waveguide,” Opt. Mater. 35(3), 590–595 (2013). [CrossRef]

]. This high conversion efficiency is attributable to the large emission cross sections of the color emitters [45

45. T. T. Basiev, P. G. Zverev, and S. B. Mirov, Color Center Lasers, Handbook of Laser Technology and Applications (Institute of Physics Publishing, Bristol, 2003).

], and it is contributed to by the phonon-driven odd-parity vibrations. The emission cross sections of F– and F2–type color emitters in sapphire are one to two orders of magnitude higher than those in typical Ti3+:sapphire and Cr4+:YAG broadband gain media, namely, ~10−21–10−22 m2 versus ~10−23 m2 [28

28. A. Sanchez, A. J. Strauss, R. L. Aggarwal, and R. E. Fahey, “Crystal growth, spectroscopy, and laser characteristics of Ti:Al2O3,” IEEE J. Quantum Electron. 24(6), 995–1002 (1988). [CrossRef]

, 46

46. P. F. Moulton, “Spectroscopic and laser characteristics of Ti:Al2O3,” J. Opt. Soc. Am. B 3(1), 125–133 (1986). [CrossRef]

49

49. C. C. Lai, P. Yeh, S. C. Wang, D. Y. Jheng, C. N. Tsai, and S. L. Huang, “Strain-dependent fluorescence spectroscopy of nanocrystals and nanoclusters in Cr:YAG crystalline-core fibers and its impact on lasing behaviors,” J. Phys. Chem. C 116(49), 26052–26059 (2012). [CrossRef]

]. In addition, from the calculated numerical aperture of 0.89 and solid angle of 2.89 in a 40-μm-diameter sapphire core–borosilicate cladding hybrid fiber, one can evaluate a luminous flux of ~0.8 lm based on the milliwatt-order white light generation, giving a luminance of ~108 cd/m2. This result is comparable to those obtained using III-V and III-nitride light-emitting diodes [50

50. R. D. Dupuis and M. R. Krames, “History, development, and applications of high-brightness visible light-emitting diodes,” J. Lightwave Technol. 26(9), 1154–1171 (2008). [CrossRef]

, 51

51. H. X. Jiang and J. Y. Lin, “Nitride micro-LEDs and beyond – a decade progress review,” Opt. Express 21(S3), A475–A484 (2013). [CrossRef]

].

4. Conclusion

In conclusion, a white light exhibiting a CIE chromaticity coordinate of (0.287, 0.333) and 1.16-mW output power is successfully obtained using a sapphire crystal core–borosilicate glass cladding hybrid fiber with intentionally introduced defects and dopants as color emitters by the LHPG technique. We experimentally demonstrated that a reversible thermal-induced interconversion between F+ and F22+ centers occurs simply by heating in different environments. The thus prepared glass-clad sapphire crystalline-core fiber consists of not only dopant-facilitated aluminum vacancies but also oxygen monovacancies and divacancies, which remains challenging in sapphire crystals. Our proposed facile approach can possibly enable control of broadband color tuning while attaining high crystallinity. Efficient white-light generation is suitable for the previously mentioned biomedical applications for long-range and fiber-type endoscope-compatible milliwatt-level light sources.

Acknowledgments

The authors are grateful to Prof. S. L. Huang for the insightful discussion. The authors also thank Mrs. L. C. Wang and Mr. H. D. Chiang for conducting the HR-TEM and EDX experiments at the facilities at National Sun Yat-Sen University, Kaohsiung, Taiwan. C. C. Lai acknowledges the strong funding support from the National Science Council of Taiwan via the grant NSC 101-2112-M-259-MY3 as well as the start-up funding from the National Dong Hwa University.

References and links

1.

D. Huang, E. A. Swanson, C. P. Lin, J. S. Schuman, W. G. Stinson, W. Chang, M. R. Hee, T. Flotte, K. Gregory, C. A. Puliafito, and J. G. Fujimoto, “Optical coherence tomography,” Science 254(5035), 1178–1181 (1991). [CrossRef] [PubMed]

2.

W. Drexler, U. Morgner, R. K. Ghanta, F. X. Kärtner, J. S. Schuman, and J. G. Fujimoto, “Ultrahigh-resolution ophthalmic optical coherence tomography,” Nat. Med. 7(4), 502–507 (2001). [CrossRef] [PubMed]

3.

J. G. Fujimoto, “Optical coherence tomography for ultrahigh resolution in vivo imaging,” Nat. Biotechnol. 21(11), 1361–1367 (2003). [CrossRef] [PubMed]

4.

E. M. Frohman, J. G. Fujimoto, T. C. Frohman, P. A. Calabresi, G. Cutter, and L. J. Balcer, “Optical coherence tomography: a window into the mechanisms of multiple sclerosis,” Nat. Clin. Pract. Neurol. 4(12), 664–675 (2008). [CrossRef] [PubMed]

5.

N. C. Cheng, T. H. Hsieh, Y. T. Wang, C. C. Lai, C. K. Chang, M. Y. Lin, D. W. Huang, J. W. Tjiu, and S. L. Huang, “Cell death detection by quantitative three-dimensional single-cell tomography,” Biomed. Opt. Express 3(9), 2111–2120 (2012). [CrossRef] [PubMed]

6.

C. Zeiss, http://meditec.zeiss.com

7.

Optovue, http://www.optovue.com

8.

Thorlabs, http://www.thorlabs.com

9.

R. A. Leitgeb, W. Drexler, A. Unterhuber, B. Hermann, T. Bajraszewski, T. Le, A. Stingl, and A. F. Fercher, “Ultrahigh resolution Fourier domain optical coherence tomography,” Opt. Express 12(10), 2156–2165 (2004). [CrossRef] [PubMed]

10.

Z. Zhi, J. Qin, L. An, and R. K. Wang, “Supercontinuum light source enables in vivo optical microangiography of capillary vessels within tissue beds,” Opt. Lett. 36(16), 3169–3171 (2011). [CrossRef] [PubMed]

11.

P. Blandin, S. Lévêque-Fort, S. Lécart, J. C. Cossec, M.-C. Potier, Z. Lenkei, F. Druon, and P. Georges, “Time-gated total internal reflection fluorescence microscopy with a supercontinuum excitation source,” Appl. Opt. 48(3), 553–559 (2009). [CrossRef] [PubMed]

12.

W. G. Telford, F. V. Subach, and V. V. Verkhusha, “Supercontinuum white light lasers for flow cytometry,” Cytometry A 75A(5), 450–459 (2009). [CrossRef] [PubMed]

13.

C. C. Lai, H. J. Tsai, K. Y. Huang, K. Y. Hsu, Z. W. Lin, K. D. Ji, W. J. Zhuo, and S. L. Huang, “Cr4+:YAG double-clad crystal fiber laser,” Opt. Lett. 33(24), 2919–2921 (2008). [CrossRef] [PubMed]

14.

C. C. Lai, S. C. Wang, Y. S. Lin, T. H. Chen, and S. L. Huang, “Near-field spectroscopy of broadband emissions from γ-Al2O3 nanocrystals in Cr-doped double-clad fibers,” J. Phys. Chem. C 115(41), 20289–20294 (2011). [CrossRef]

15.

C. C. Lai, C. P. Ke, S. K. Liu, C. Y. Lo, D. Y. Jheng, S. C. Wang, S. R. Lin, P. S. Yeh, and S. L. Huang, “Intracavity and resonant Raman crystal fiber laser,” Appl. Phys. Lett. 100(26), 261101 (2012). [CrossRef]

16.

P. Boutinaud, P. Putaj, R. Mahiou, E. Cavalli, A. Speghini, and M. Bettinelli, “Quenching of lanthanide emission by intervalence charge transfer in crystals containing closed shell transition metal ions,” Spectrosc. Lett. 40(2), 209–220 (2007). [CrossRef]

17.

P. D. Townsend, “Colour centres past, present and future,” Nature 258(5533), 293–296 (1975). [CrossRef]

18.

B. Henderson, Defects in Crystalline Solids (Arnold, London, 1972).

19.

J. W. Leem and J. S. Yu, “Wafer-scale highly-transparent and superhydrophilic sapphires for high-performance optics,” Opt. Express 20(24), 26160–26166 (2012). [CrossRef] [PubMed]

20.

R. M. Stroud, L. R. Nittler, and C. M. Alexander, “Polymorphism in presolar Al2O3 grains from asymptotic giant branch stars,” Science 305(5689), 1455–1457 (2004). [CrossRef] [PubMed]

21.

K. H. Lee and J. H. Crawford, “Additive coloration of sapphire,” Appl. Phys. Lett. 33(4), 273–275 (1978). [CrossRef]

22.

R. Ramírez, M. Tardío, R. González, Y. Chen, and M. R. Kokta, “Photochromism of vacancy-related defects in thermochemically reduced α-Al2O3:Mg single crystals,” Appl. Phys. Lett. 86(8), 081914 (2005). [CrossRef]

23.

M. Itou, A. Fujiwara, and T. Uchino, “Reversible photoinduced interconversion of color centers in α-Al2O3 prepared under vacuum,” J. Phys. Chem. C 113(49), 20949–20957 (2009). [CrossRef]

24.

B. Jeffries, G. P. Summers, and J. H. Crawford, “F–center fluorescence in neutron–bombarded sapphire,” J. Appl. Phys. 51(7), 3984–3986 (1980). [CrossRef]

25.

B. D. Evans, “A review of the optical properties of anion lattice vacancies, and electrical conduction in α-Al2O3: their relation to radiation-induced electrical degradation,” J. Nucl. Mater. 219, 202–223 (1995). [CrossRef]

26.

K. J. Caulfield, R. Cooper, and J. F. Boas, “Luminescence from electron-irradiated sapphire,” Phys. Rev. B Condens. Matter 47(1), 55–61 (1993). [CrossRef] [PubMed]

27.

M. D. Rechtin, “A transmission electron microscopy study of the defect microstructure of Al2O3, subjected to ion bombardment,” Radiat. Eff. 42(3-4), 129–144 (1979). [CrossRef]

28.

A. Sanchez, A. J. Strauss, R. L. Aggarwal, and R. E. Fahey, “Crystal growth, spectroscopy, and laser characteristics of Ti:Al2O3,” IEEE J. Quantum Electron. 24(6), 995–1002 (1988). [CrossRef]

29.

M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys. 75(2), 1111–1117 (1994). [CrossRef]

30.

E. R. Dobrovinskaya, L. A. Lytvynov, and V. Pishchik, Sapphire: Material, Manufacturing, Applications (Springer, New York, 2009), Chap. 2.

31.

W. Zhu and G. Pezzotti, “Phonon deformation potentials for the corundum structure of sapphire,” J. Raman. Spectrosc. 42(11), 2015–2025 (2011). [CrossRef]

32.

B. Macalik, L. E. Bausá, J. García-Solé, F. Jaque, J. E. Muñoz Santiuste, and I. Vergara, “Blue emission in Ti-sapphire laser crystal,” Appl. Phys. B 55, 144–147 (1992).

33.

R. Ramírez, M. Tardío, R. González, J. E. Muñoz Santiuste, and M. R. Kokta, “Optical properties of vacancies in thermochemically reduced Mg-doped sapphire single crystals,” J. Appl. Phys. 101(12), 123520 (2007). [CrossRef]

34.

A. I. Surdo and V. S. Kortov, “Exciton mechanism of energy transfer to F–centers in dosimetric corundum crystals,” Radiat. Meas. 38(4-6), 667–671 (2004). [CrossRef]

35.

D. B. Fitchen, R. H. Silsbee, T. A. Fulton, and E. L. Wolf, “Zero-phonon transitions of color centers in alkali halides,” Phys. Rev. Lett. 11(6), 275–277 (1963). [CrossRef]

36.

P. Görlich, H. Karras, G. Kötitz, and R. Rauch, “Phonon-assisted colour centre fluorescence of additively coloured alkali earth fluoride crystals,” Phys. Status Solidi, B Basic Res. 25(1), K15–K18 (1968). [CrossRef]

37.

B. D. Evans and M. Stapelbroek, “Optical properties of the F+ center in crystalline Al2O3,” Phys. Rev. B 18(12), 7089–7098 (1978). [CrossRef]

38.

M. G. Springils and J. A. Valbis, “Visible luminescence of colour centres in sapphire,” Phys. Status Solidi, B Basic Res. 123(1), 335–343 (1984). [CrossRef]

39.

W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. I. Charge-exchange energies and titanium-bound excitons,” Phys. Rev. B Condens. Matter 51(9), 5682–5692 (1995). [CrossRef] [PubMed]

40.

W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. II. Charge-transfer transition states, carrier trapping, and detrapping,” Phys. Rev. B Condens. Matter 51(9), 5693–5698 (1995). [CrossRef] [PubMed]

41.

F. A. Kröger, The Chemistry of Imperfect Crystals (North Holland Publishing Company, Amsterdam, 1974).

42.

D. Manzani, Y. Ledemi, I. Skripachev, Y. Messaddeq, S. J. L. Ribeiro, R. E. P. de Oliveira, and C. J. S. de Matos, “Yb3+, Tm3+ and Ho3+ triply-doped tellurite core-cladding optical fiber for white light generation,” Opt. Mater. Express 1(8), 1515–1526 (2011). [CrossRef]

43.

N. G. Boetti, J. Lousteau, D. Negro, E. Mura, G. Scarpignato, S. Abrate, and D. Milanese, “Multiple visible emissions by means of up-conversion process in a microstructured tellurite glass optical fiber,” Opt. Express 20(5), 5409–5418 (2012). [CrossRef] [PubMed]

44.

X. Liu, B. Chen, E. Y. B. Pun, and H. Lin, “White upconversion luminescence in Tm3+/Ho3+/Yb3+ triply doped K+–Na+ ion-exchanged aluminum germinate glass channel waveguide,” Opt. Mater. 35(3), 590–595 (2013). [CrossRef]

45.

T. T. Basiev, P. G. Zverev, and S. B. Mirov, Color Center Lasers, Handbook of Laser Technology and Applications (Institute of Physics Publishing, Bristol, 2003).

46.

P. F. Moulton, “Spectroscopic and laser characteristics of Ti:Al2O3,” J. Opt. Soc. Am. B 3(1), 125–133 (1986). [CrossRef]

47.

C. G. Durfee, T. Storz, J. Garlick, S. Hill, J. A. Squier, M. Kirchner, G. Taft, K. Shea, H. Kapteyn, M. Murnane, and S. Backus, “Direct diode-pumped Kerr-lens mode-locked Ti:sapphire laser,” Opt. Express 20(13), 13677–13683 (2012). [CrossRef] [PubMed]

48.

C. C. Lai, C. P. Ke, S. K. Liu, D. Y. Jheng, D. J. Wang, M. Y. Chen, Y. S. Li, P. S. Yeh, and S. L. Huang, “Efficient and low-threshold Cr4+:YAG double-clad crystal fiber laser,” Opt. Lett. 36(6), 784–786 (2011). [CrossRef] [PubMed]

49.

C. C. Lai, P. Yeh, S. C. Wang, D. Y. Jheng, C. N. Tsai, and S. L. Huang, “Strain-dependent fluorescence spectroscopy of nanocrystals and nanoclusters in Cr:YAG crystalline-core fibers and its impact on lasing behaviors,” J. Phys. Chem. C 116(49), 26052–26059 (2012). [CrossRef]

50.

R. D. Dupuis and M. R. Krames, “History, development, and applications of high-brightness visible light-emitting diodes,” J. Lightwave Technol. 26(9), 1154–1171 (2008). [CrossRef]

51.

H. X. Jiang and J. Y. Lin, “Nitride micro-LEDs and beyond – a decade progress review,” Opt. Express 21(S3), A475–A484 (2013). [CrossRef]

OCIS Codes
(060.2280) Fiber optics and optical communications : Fiber design and fabrication
(160.2220) Materials : Defect-center materials
(300.6280) Spectroscopy : Spectroscopy, fluorescence and luminescence

ToC Category:
Fiber Optics and Optical Communications

History
Original Manuscript: March 26, 2013
Revised Manuscript: June 5, 2013
Manuscript Accepted: June 6, 2013
Published: June 12, 2013

Virtual Issues
Vol. 8, Iss. 7 Virtual Journal for Biomedical Optics

Citation
Chien-Chih Lai, Nai-Chia Cheng, Cheng-Kai Wang, Jeng-Wei Tjiu, Ming-Yi Lin, and Sheng-Yao Huang, "Simple and efficient defect-tailored fiber-based UV-VIS broadband white light generation," Opt. Express 21, 14606-14617 (2013)
http://www.opticsinfobase.org/vjbo/abstract.cfm?URI=oe-21-12-14606


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References

  1. D. Huang, E. A. Swanson, C. P. Lin, J. S. Schuman, W. G. Stinson, W. Chang, M. R. Hee, T. Flotte, K. Gregory, C. A. Puliafito, and J. G. Fujimoto, “Optical coherence tomography,” Science254(5035), 1178–1181 (1991). [CrossRef] [PubMed]
  2. W. Drexler, U. Morgner, R. K. Ghanta, F. X. Kärtner, J. S. Schuman, and J. G. Fujimoto, “Ultrahigh-resolution ophthalmic optical coherence tomography,” Nat. Med.7(4), 502–507 (2001). [CrossRef] [PubMed]
  3. J. G. Fujimoto, “Optical coherence tomography for ultrahigh resolution in vivo imaging,” Nat. Biotechnol.21(11), 1361–1367 (2003). [CrossRef] [PubMed]
  4. E. M. Frohman, J. G. Fujimoto, T. C. Frohman, P. A. Calabresi, G. Cutter, and L. J. Balcer, “Optical coherence tomography: a window into the mechanisms of multiple sclerosis,” Nat. Clin. Pract. Neurol.4(12), 664–675 (2008). [CrossRef] [PubMed]
  5. N. C. Cheng, T. H. Hsieh, Y. T. Wang, C. C. Lai, C. K. Chang, M. Y. Lin, D. W. Huang, J. W. Tjiu, and S. L. Huang, “Cell death detection by quantitative three-dimensional single-cell tomography,” Biomed. Opt. Express3(9), 2111–2120 (2012). [CrossRef] [PubMed]
  6. C. Zeiss, http://meditec.zeiss.com
  7. Optovue, http://www.optovue.com
  8. Thorlabs, http://www.thorlabs.com
  9. R. A. Leitgeb, W. Drexler, A. Unterhuber, B. Hermann, T. Bajraszewski, T. Le, A. Stingl, and A. F. Fercher, “Ultrahigh resolution Fourier domain optical coherence tomography,” Opt. Express12(10), 2156–2165 (2004). [CrossRef] [PubMed]
  10. Z. Zhi, J. Qin, L. An, and R. K. Wang, “Supercontinuum light source enables in vivo optical microangiography of capillary vessels within tissue beds,” Opt. Lett.36(16), 3169–3171 (2011). [CrossRef] [PubMed]
  11. P. Blandin, S. Lévêque-Fort, S. Lécart, J. C. Cossec, M.-C. Potier, Z. Lenkei, F. Druon, and P. Georges, “Time-gated total internal reflection fluorescence microscopy with a supercontinuum excitation source,” Appl. Opt.48(3), 553–559 (2009). [CrossRef] [PubMed]
  12. W. G. Telford, F. V. Subach, and V. V. Verkhusha, “Supercontinuum white light lasers for flow cytometry,” Cytometry A75A(5), 450–459 (2009). [CrossRef] [PubMed]
  13. C. C. Lai, H. J. Tsai, K. Y. Huang, K. Y. Hsu, Z. W. Lin, K. D. Ji, W. J. Zhuo, and S. L. Huang, “Cr4+:YAG double-clad crystal fiber laser,” Opt. Lett.33(24), 2919–2921 (2008). [CrossRef] [PubMed]
  14. C. C. Lai, S. C. Wang, Y. S. Lin, T. H. Chen, and S. L. Huang, “Near-field spectroscopy of broadband emissions from γ-Al2O3 nanocrystals in Cr-doped double-clad fibers,” J. Phys. Chem. C115(41), 20289–20294 (2011). [CrossRef]
  15. C. C. Lai, C. P. Ke, S. K. Liu, C. Y. Lo, D. Y. Jheng, S. C. Wang, S. R. Lin, P. S. Yeh, and S. L. Huang, “Intracavity and resonant Raman crystal fiber laser,” Appl. Phys. Lett.100(26), 261101 (2012). [CrossRef]
  16. P. Boutinaud, P. Putaj, R. Mahiou, E. Cavalli, A. Speghini, and M. Bettinelli, “Quenching of lanthanide emission by intervalence charge transfer in crystals containing closed shell transition metal ions,” Spectrosc. Lett.40(2), 209–220 (2007). [CrossRef]
  17. P. D. Townsend, “Colour centres past, present and future,” Nature258(5533), 293–296 (1975). [CrossRef]
  18. B. Henderson, Defects in Crystalline Solids (Arnold, London, 1972).
  19. J. W. Leem and J. S. Yu, “Wafer-scale highly-transparent and superhydrophilic sapphires for high-performance optics,” Opt. Express20(24), 26160–26166 (2012). [CrossRef] [PubMed]
  20. R. M. Stroud, L. R. Nittler, and C. M. Alexander, “Polymorphism in presolar Al2O3 grains from asymptotic giant branch stars,” Science305(5689), 1455–1457 (2004). [CrossRef] [PubMed]
  21. K. H. Lee and J. H. Crawford, “Additive coloration of sapphire,” Appl. Phys. Lett.33(4), 273–275 (1978). [CrossRef]
  22. R. Ramírez, M. Tardío, R. González, Y. Chen, and M. R. Kokta, “Photochromism of vacancy-related defects in thermochemically reduced α-Al2O3:Mg single crystals,” Appl. Phys. Lett.86(8), 081914 (2005). [CrossRef]
  23. M. Itou, A. Fujiwara, and T. Uchino, “Reversible photoinduced interconversion of color centers in α-Al2O3 prepared under vacuum,” J. Phys. Chem. C113(49), 20949–20957 (2009). [CrossRef]
  24. B. Jeffries, G. P. Summers, and J. H. Crawford, “F–center fluorescence in neutron–bombarded sapphire,” J. Appl. Phys.51(7), 3984–3986 (1980). [CrossRef]
  25. B. D. Evans, “A review of the optical properties of anion lattice vacancies, and electrical conduction in α-Al2O3: their relation to radiation-induced electrical degradation,” J. Nucl. Mater.219, 202–223 (1995). [CrossRef]
  26. K. J. Caulfield, R. Cooper, and J. F. Boas, “Luminescence from electron-irradiated sapphire,” Phys. Rev. B Condens. Matter47(1), 55–61 (1993). [CrossRef] [PubMed]
  27. M. D. Rechtin, “A transmission electron microscopy study of the defect microstructure of Al2O3, subjected to ion bombardment,” Radiat. Eff.42(3-4), 129–144 (1979). [CrossRef]
  28. A. Sanchez, A. J. Strauss, R. L. Aggarwal, and R. E. Fahey, “Crystal growth, spectroscopy, and laser characteristics of Ti:Al2O3,” IEEE J. Quantum Electron.24(6), 995–1002 (1988). [CrossRef]
  29. M. Yamaga, T. Yosida, S. Hara, N. Kodama, and B. Henderson, “Optical and electron spin resonance spectroscopy of Ti3+ and Ti4+ in Al2O3,” J. Appl. Phys.75(2), 1111–1117 (1994). [CrossRef]
  30. E. R. Dobrovinskaya, L. A. Lytvynov, and V. Pishchik, Sapphire: Material, Manufacturing, Applications (Springer, New York, 2009), Chap. 2.
  31. W. Zhu and G. Pezzotti, “Phonon deformation potentials for the corundum structure of sapphire,” J. Raman. Spectrosc.42(11), 2015–2025 (2011). [CrossRef]
  32. B. Macalik, L. E. Bausá, J. García-Solé, F. Jaque, J. E. Muñoz Santiuste, and I. Vergara, “Blue emission in Ti-sapphire laser crystal,” Appl. Phys. B55, 144–147 (1992).
  33. R. Ramírez, M. Tardío, R. González, J. E. Muñoz Santiuste, and M. R. Kokta, “Optical properties of vacancies in thermochemically reduced Mg-doped sapphire single crystals,” J. Appl. Phys.101(12), 123520 (2007). [CrossRef]
  34. A. I. Surdo and V. S. Kortov, “Exciton mechanism of energy transfer to F–centers in dosimetric corundum crystals,” Radiat. Meas.38(4-6), 667–671 (2004). [CrossRef]
  35. D. B. Fitchen, R. H. Silsbee, T. A. Fulton, and E. L. Wolf, “Zero-phonon transitions of color centers in alkali halides,” Phys. Rev. Lett.11(6), 275–277 (1963). [CrossRef]
  36. P. Görlich, H. Karras, G. Kötitz, and R. Rauch, “Phonon-assisted colour centre fluorescence of additively coloured alkali earth fluoride crystals,” Phys. Status Solidi, B Basic Res.25(1), K15–K18 (1968). [CrossRef]
  37. B. D. Evans and M. Stapelbroek, “Optical properties of the F+ center in crystalline Al2O3,” Phys. Rev. B18(12), 7089–7098 (1978). [CrossRef]
  38. M. G. Springils and J. A. Valbis, “Visible luminescence of colour centres in sapphire,” Phys. Status Solidi, B Basic Res.123(1), 335–343 (1984). [CrossRef]
  39. W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. I. Charge-exchange energies and titanium-bound excitons,” Phys. Rev. B Condens. Matter51(9), 5682–5692 (1995). [CrossRef] [PubMed]
  40. W. C. Wong, D. S. McClure, S. A. Basun, and M. R. Kokta, “Charge-exchange processes in titanium-doped sapphire crystals. II. Charge-transfer transition states, carrier trapping, and detrapping,” Phys. Rev. B Condens. Matter51(9), 5693–5698 (1995). [CrossRef] [PubMed]
  41. F. A. Kröger, The Chemistry of Imperfect Crystals (North Holland Publishing Company, Amsterdam, 1974).
  42. D. Manzani, Y. Ledemi, I. Skripachev, Y. Messaddeq, S. J. L. Ribeiro, R. E. P. de Oliveira, and C. J. S. de Matos, “Yb3+, Tm3+ and Ho3+ triply-doped tellurite core-cladding optical fiber for white light generation,” Opt. Mater. Express1(8), 1515–1526 (2011). [CrossRef]
  43. N. G. Boetti, J. Lousteau, D. Negro, E. Mura, G. Scarpignato, S. Abrate, and D. Milanese, “Multiple visible emissions by means of up-conversion process in a microstructured tellurite glass optical fiber,” Opt. Express20(5), 5409–5418 (2012). [CrossRef] [PubMed]
  44. X. Liu, B. Chen, E. Y. B. Pun, and H. Lin, “White upconversion luminescence in Tm3+/Ho3+/Yb3+ triply doped K+–Na+ ion-exchanged aluminum germinate glass channel waveguide,” Opt. Mater.35(3), 590–595 (2013). [CrossRef]
  45. T. T. Basiev, P. G. Zverev, and S. B. Mirov, Color Center Lasers, Handbook of Laser Technology and Applications (Institute of Physics Publishing, Bristol, 2003).
  46. P. F. Moulton, “Spectroscopic and laser characteristics of Ti:Al2O3,” J. Opt. Soc. Am. B3(1), 125–133 (1986). [CrossRef]
  47. C. G. Durfee, T. Storz, J. Garlick, S. Hill, J. A. Squier, M. Kirchner, G. Taft, K. Shea, H. Kapteyn, M. Murnane, and S. Backus, “Direct diode-pumped Kerr-lens mode-locked Ti:sapphire laser,” Opt. Express20(13), 13677–13683 (2012). [CrossRef] [PubMed]
  48. C. C. Lai, C. P. Ke, S. K. Liu, D. Y. Jheng, D. J. Wang, M. Y. Chen, Y. S. Li, P. S. Yeh, and S. L. Huang, “Efficient and low-threshold Cr4+:YAG double-clad crystal fiber laser,” Opt. Lett.36(6), 784–786 (2011). [CrossRef] [PubMed]
  49. C. C. Lai, P. Yeh, S. C. Wang, D. Y. Jheng, C. N. Tsai, and S. L. Huang, “Strain-dependent fluorescence spectroscopy of nanocrystals and nanoclusters in Cr:YAG crystalline-core fibers and its impact on lasing behaviors,” J. Phys. Chem. C116(49), 26052–26059 (2012). [CrossRef]
  50. R. D. Dupuis and M. R. Krames, “History, development, and applications of high-brightness visible light-emitting diodes,” J. Lightwave Technol.26(9), 1154–1171 (2008). [CrossRef]
  51. H. X. Jiang and J. Y. Lin, “Nitride micro-LEDs and beyond – a decade progress review,” Opt. Express21(S3), A475–A484 (2013). [CrossRef]

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