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Mid-IR (34m) fluorescence and ASE studies in Dy3+ doped tellurite and germanate glasses and a fs laser inscribed waveguide

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IOP PUBLISHING Laser Phys. Lett. 10 (2013) 085802 (6pp)

LASER PHYSICS LETTERS

doi:10.1088/1612-2011/10/8/085802

LETTER

Mid-IR (34 m) uorescence and ASE studies in Dy3+ doped tellurite and germanate glasses and a fs laser inscribed waveguide
B D O Richards1 , T Teddy-Fernandez2 , G Jose1 , D Binks3 and A Jha1
1

Institute for Materials Research, School of Process, Environmental and Materials Engineering, The University of Leeds, Leeds LS2 9JT, UK 2 Laser Processing Group, Instituto de Optica, CSIC, Serrano 121, E-28006-Madrid, Spain 3 Photon Science Institute and School of Physics and Astronomy, The University of Manchester, Manchester, M13 9PL, UK E-mail: b.d.o.richards@leeds.ac.uk

Received 12 October 2012, in nal form 21 March 2013 Accepted for publication 8 April 2013 Published 14 June 2013 Online at stacks.iop.org/LPL/10/085802 Abstract We present the uorescence spectroscopy of a range of Dy3+ doped tellurite (TeO2 ) and germanate (GeO2 ) glasses and compare with Dy3+ doped ZBLAN glass. When excited using an 808 nm laser diode, Dy3+ ions emit radiation at around 3 m from the 6 H13/2 6 H15/2 (3500 cm1 ) energy level transition, which has been exploited in Dy3+ doped uoride bre lasers. When Dy3+ is doped into TeO2 and GeO2 based glasses, the uorescence from the 6H 6 13/2 H15/2 transition is shown to be broader and red-shifted compared to that in ZBLAN glass. Mid-IR ASE from a fs laser inscribed Dy3+ doped tellurite glass waveguide is also presented. The results of Dy3+ mid-IR uorescence spectroscopy and the potential of oxide glasses as mid-IR sources are discussed. (Some gures may appear in colour only in the online journal)

1. Introduction
Mid-IR lasers and sources in the 34 m range are desirable for various applications, particularly those exploiting the 35 m atmospheric absorption window such as long-range free-space, spectroscopy, sensing and lidar. Silica bres are extremely robust and widely used in the near-IR, but silica glass high phonon energy of 1100 cm1 precludes their use at wavelengths longer than around 2.3 m due to the multiphonon absorption edge of the glass. The low phonon energy of around 550 cm1 of ZBLAN glass (so called because it contains uorides of Zr, Ba, La, Al and Na) has enabled it to be extensively exploited as a laser host material
1612-2011/13/085802+06$33.00 1

for sources in the mid-IR using various rare earth ions such as Ho3+ at 2.9 m [1] and 3.9 m [2], Er3+ at 2.8 m [3] and Dy3+ at 2.96 m [4]. However, the relative fragility and inferior glass stability of ZBLAN bres may limit their usefulness for certain important applications. Moreover, the output of Dy3+ doped ZBLAN bre lasers at 2.9 m coincides with strong water absorptions. Alternatives to uoride glass for use at mid-IR wavelengths include tellurite and germanate glasses. Tellurite and germanate glasses are based on the glass formers TeO2 and GeO2 and have phonon energies in the ranges 650800 cm1 and 900 cm1 , respectively [5, 6]. The infrared transmission range of tellurite glass is commonly quoted in the literature to be up to around
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Table 1. Glass compositions studied in this work. Sample ID DyTZN1 DyTZN3 DyZBLAN1 DyGPNG1 Composition 80 TeO2 10 ZnO10 Na2 O (mol%) + 1 wt% Dy2 O3 80 TeO2 10 ZnO10 Na2 O (mol%) + 3 wt% Dy2 O3 53 ZrF4 20 BaF2 3.5 LaF3 3.5 AlF3 20 NaF1 DyF3 (mol%) 56 GeO2 31 PbO9 Na2 O4 Ga2 O3 (mol%) + 1 wt% Dy2 O3

5 m. However, to the authors knowledge, uorescence has never previously been demonstrated at wavelengths longer than around 3 m in a rare earth doped oxide glass [7] although mid-IR supercontinua in tellurite photonic crystal bres have however previously been demonstrated to extend to almost 5 m [8]. Tellurite and germanate glasses are also more stable than uoride glass exemplied by their higher Tg and Tx Tg values [9, 10], making them more desirable for industrial laser applications. The emergence of extended transmission windows in hollow-core anti-resonant silica [11] and chalcogenide [12] bres, together with the possibility of a laser utilizing the 35 m window offers novel opportunities for long wavelength system development for sources and power delivery, thereby opening opportunities for security, chemical and environment sensing and medicine. In this letter we report the broad, mid-IR uorescence from Dy3+ doped tellurite and germanate glasses at around 3.4 m. An important consideration when fabricating oxide glasses for mid-IR operation is the presence of OH ion contamination in the glass which has a broad and intense absorption band at around 3 m. Therefore, in order to achieve efcient 3 m emission in these glasses it is important to minimize OH contamination and techniques for removal are also discussed in the letter.

2. Experimental details
The glass samples for spectroscopy and laser inscription were fabricated using the standard melt-quench technique, discussed elsewhere [13]. The precursor oxide and uoride chemicals had a purity of 99.99% and were batched and then melted in electric tube furnaces. The glass compositions studied during this work are listed in table 1. Tellurite and ZBLAN glasses were melted at 750 C in gold crucibles in an atmosphere of owing (2 l min1 ) O2 which had passed through a chiller and gas purication cartridge to remove moisture and other contaminants such as CO2 . Germanate glasses were melted at 1200 C in a platinum crucible also in a dry O2 atmosphere, as described for the tellurite glasses. Glass melts were cast into brass moulds which had been preheated and were then annealed close to the glass transition temperature for 3 h before being cooled to room temperature at a rate of 1 C min1 . The glasses were then polished to an optical nish ready for spectroscopic characterization. Absorption spectra of the glasses were measured using Perkin Elmer Lambda 19 UVvisNIR and Bruker Vertex 70 FTIR spectrometers. The Dy3+ uorescence spectra were measured using an Edinburgh Instruments FLS920 steady-state and time resolved uorescence spectrometer tted with a liquid
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nitrogen-cooled InSb photo-detector for mid-IR wavelengths, and an InGaAs photo-detector for near-IR wavelengths. Samples were excited using a 4.5 W, 808 nm laser diode source and germanium and silicon lters were placed between the sample and the emission monochromator for mid-IR and near-IR uorescence measurements, respectively. Cryogenic measurements were carried out using an Oxford Instruments cryostat. The bottom level transition of Dy3+ ions in glass is resonant with TeOH bond stretching absorption bands, therefore, for laser operation to be viable from this transition in oxide glass, it is vital that OH contamination be minimized. There are several techniques which can be used during glass fabrication to minimize OH ion content, including uorination and gas bubbling. The addition of up to 15 mol% of ZnF2 in tellurite glass has been demonstrated to virtually eliminate OH absorption in the mid-IR resulting in glasses with low loss whist maintaining glass stability [14]. Similarly, OH absorption has been demonstrated to be drastically reduced in germanate glass with the inclusion of PbF2 in the glass batch [10]. Fluorides in the glass batch react with bonded OH groups and atmospheric H2 O to HF gas which is ejected from the glass melt [10]. Bubbling glass melts with non-reactive and reactive gases such as dry O2 and Cl2 , respectively, helps to remove OH and free-water contamination. Non-reactive gases such as O2 remove OH by reaching an equilibrium between the OH in the glass and the H2 O in the gas bubble; therefore it is essential that steps are taken to ensure that the gas used to bubble the glass melt is as dry as possible. A reactive gas such as Cl2 is most effective as it reacts with OH and H2 O in the glass to form HCl gas [15]. Figure 1 shows the FTIR absorption spectra of a range of tellurite glasses which have been bubbled with O2 gas for varying durations. The peak absorption coefcient of the OH band at 3.37 m can be clearly seen to reduce during the rst 75 min of bubbling until an equilibrium is reached with the H2 O content of the gas. Further OH reduction could be achieved by combining uorination with reactive gas bubbling.

3. Results and discussion

3.1. Absorption coefcient Figure 2 compares the absorption coefcient spectra of 1 wt% Dy3+ doped TZN, GPNG and ZBLAN glasses. The glass samples exhibit Dy3+ absorption bands at 2800, 1690, 1280, 1100, 900 and 800 nm due to transitions from the 6 H15/2 ground state to the 6 H13/2 , 6 H11/2 , 6 H9/2 and 6 F11/2 , 6 H7/2

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Figure 1. The FTIR absorption coefcient spectra of TZN tellurite glasses with varying durations of O2 bubbling. The inset graph shows the variation of the peak OH absorption band at 3.37 m as a function of O2 gas bubbling duration.

Figure 3. Normalized mid-IR uorescence spectra of DyTZN1, DyGPNG1 and DyZBLAN1 glass samples when excited using an 808 nm laser diode source.

3.2. Fluorescence spectroscopy 3.2.1. Room temperature uorescence. Fluorescence from the 6 H13/2 6 H15/2 bottom level transition of Dy3+ was detected in the ZBLAN, TZN and GPNG samples when an 808 nm laser diode was used to excite the 6 F5/2 energy level. Figure 3 compares the uorescence spectra of the various Dy3+ doped glass samples and shows that in the oxide glasses the uorescence is red-shifted to a peak value of 3.33.4 m compared to 2.95 m in ZBLAN glass. The FWHM of the 6 H13/2 6 H15/2 uorescence peak is larger in TZN glass (500 nm) and germanate glass (380 nm) than in the ZBLAN glass host (223 nm), and also extends to up to 4 m at the long wavelength tail of the uorescence peak. Rare earth ions doped into tellurite glass generally exhibit broader emission linewidths than in uoride glass due to the presence of three different TeO4 structural units which result in different TeO bond lengths, and therefore different ion-host eld strengths [16]. Based on the absorption spectra of Dy3+ doped TZN and ZBLAN glass, the absorption cross-section has been calculated and used to determine the emission cross-section using the McCumber theory. Figure 4 compares the absorption and emission cross sections of Dy3+ doped into TZN and ZBLAN glasses and shows that in a tellurite glass host, the emission crosssection is much broader and shifted to longer wavelengths, similar to the measured spontaneous uorescence spectra shown in gure 3. The peak emission cross-section of the Dy3+ : 6 H13/2 6 H15/2 transition is also much larger in tellurite glass (2.3 1020 cm2 at 3.7 m) than in ZBLAN glass (4.6 1021 cm2 at 2.9 m) which is benecial for subsequent laser operation. The lifetime of the Dy3+ : 6 H13/2 energy level in tellurite and uoride glass hosts was measured by modulating the output of the 808 nm laser diode and recording the decay of the detector signal with the monochromator set to the peak uorescence wavelength (i.e. 2.95 m for uoride glass and 3.4 m for tellurite glass). Figure 5 compares the normalized uorescence decay of the Dy3+ : 6 H13/2 energy
3

Figure 2. The absorption coefcient spectra of DyTZN1 and DyZBLAN1. The absorption bands are attributed to absorption from the Dy3+ : 6 H15/2 ground state to the labelled excited state energy level.

and 6 F9/2 , 6 F7/2 and 6 F5/2 energy levels, respectively. The 800 nm absorption band of Dy3+ coincides with widely available, high power laser diode sources which can be used to pump Dy3+ doped devices, however, it is desirable to pump with longer wavelength sources in order to reduce the quantum defect. The 6 H13/2 absorption band in the GPNG samples appears more intense that the other samples, however, this absorption peak is also partly due to OH absorption in the sample which had not undergone optimized drying. Currently, diode laser sources operating at longer wavelengths which coincide with Dy3+ absorption bands are not widely available, but codoping with Yb3+ for example may enable the use of 980 nm laser diode pumping. In ZBLAN glass, there are several Dy3+ absorption bands in 290450 nm range, however, in TZN glass these are mostly obscured by the electronic absorption edge of the glass.

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Figure 4. Absorption and emission cross-section spectra of DyTZN1 and DyZBLAN1 glass samples. The absorption cross-section data is derived from the measured absorption coefcient spectra, and via the McCumber theory, used to calculate the emission cross-section data.

Figure 6. Near-IR uorescence spectra of Dy3+ doped tellurite glass (DyTZN3) as a function of temperature.

Figure 7. Mid-IR uorescence spectra of Dy3+ doped tellurite glass (DyTZN3) as a function of temperature. Figure 5. Fluorescence decay and rise curve of DyTZN3 sample when excited using a modulated 808 nm laser diode source. The inset shows the uorescence decay curve of the DyZBLAN1 glass using the same excitation source.

further detailed investigation which is beyond the scope of this letter and will be addressed in subsequent publications. 3.2.2. Cryogenic uorescence. Fluorescence measurements were carried out on the DyTZN3 sample using an 808 nm laser diode excitation source at cryogenic temperatures to better understand the energy transfer mechanisms involved. Figures 6 and 7 show the uorescence results of the 1.7 m Dy3+ : 6 H11/2 6 H15/2 , and 3.3 m Dy3+ : 6 H13/2 6H 15/2 transitions, respectively. The uorescence intensity from both the Dy3+ : 6 H11/2 6 H15/2 , and 6 H13/2 6 H15/2 transitions reduces with decreasing temperature, suggesting that at low temperatures, the population at the 6 H11/2 and 6H 13/2 energy levels is diminished and emission is occurring through a more temperature sensitive route, the structural origin of which is unclear at present and appears to be determining the mid-IR phosphor-like behaviour observed in the room temperature data. Figure 6 also shows that the intensity of the 1.3 m uorescence band does not signicantly change with temperature. Exciting Dy3+ ions at 808 nm requires several non-radiative, phonon assisted decay processes in order to populate the 6 H9/2 and 6 F11/2 , 6 H11/2
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level in tellurite and uorides glasses showing a lifetime of 650 s in uoride glass compared to around 5.9 s in tellurite glass. It is worth noting that the exact same experimental set-up and detector was used for the lifetime measurements of both the tellurite and ZBLAN samples. The slow rise- and fall-times at 3.4 m in tellurite glass suggest that relaxation to the 6 H13/2 level is the rate-limiting step, therefore codoping with suitable dopants may potentially be advantageous for enhancing the population build-up rate of the upper laser level through cross-relaxation processes. Another route to enhance the population of the 6 H13/2 level may be to use a longer wavelength pump source and a sensitizer ion to excite the 6 H13/2 upper laser level directly. The decay mechanism of Dy3+ ions in tellurite glass appears to be a room temperature, mid-IR, phosphor-like phenomenon resulting in very long upper level lifetimes. This requires

Laser Phys. Lett. 10 (2013) 085802

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Figure 8. The energy level diagram of Dy3+ . Solid and dashed lines represent radiative and non-radiative transitions, respectively.

and 6 H13/2 energy levels, as exemplied in the energy level diagram in gure 8. Reduced phonon coupling at low temperatures reduces the population at the 6 H9/2 and 6F 6 6H 11/2 , H11/2 and 13/2 levels, and likely results in increased radiative decay from the 6 F5/2 pump level. The fact that the 1.3 m uorescence intensity does not reduce at low temperatures is likely due to the fact that decay to the 6 H9/2 and 6 F11/2 levels occurs via a sequence of single-phonon steps, whilst decay to lower energy levels requires larger energy, multiphonon steps, the likelihood of which decreases more quickly with decreasing temperature. Under 808 nm pumping, very little visible uorescence from ESA or upconversion was detected in TZN glass. As can be seen in gure 2, the upper level of Dy3+ (4 F9/2 ) from which visible transitions occur, is resonant with the electronic band edge of TZN glass reducing the probability of radiative transitions from this level.

Figure 9. (a) The DIC image of the waveguide (fs laser beam normal to the paper). (b) The DIC image of the transverse section of the waveguide (arrow shows the guiding region). (c) The 1600 nm output mode from the waveguide.

4. Dy3+ doped tellurite waveguide characterization

Using the fs laser inscription process described elsewhere [17], channel waveguides were inscribed using a femtosecond laser operating at 800 nm, 1 kHz repetition rate and 100 fs pulse width. Laser inscription was carried out with a 0.65 NA aspheric lens objective with various powers ranging from 300 nJ to 5 mJ and speeds from 0.01 to 6 mm s1 . Figure 9(a) shows the differential interference contrast (DIC) microscope image of the waveguide written with 500 nJ pulse energy and 0.025 mm s1 translation speed. Figure 9(b) shows the waveguide cross-section, indicating a strong negative index region at the centre with a positive index region on its top left (marked by arrow). A 1600 nm laser mode was propagated through the channels (gure 9(c)) to ensure guidance. The refractive index change was calculated to be around 6 103 .
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Figure 10. The normalized ASE spectrum of a Dy3+ doped tellurite waveguide compared to the spontaneous uorescence spectra of Dy3+ doped tellurite and ZBLAN bulk glass samples.

A bre pigtailed 808 nm laser diode source was butt-coupled to obtain the amplied spontaneous emission (ASE) from the waveguide, and the resulting spectrum is displayed in gure 10 and compared with the spontaneous uorescence from bulk Dy3+ doped tellurite and ZBLAN glass samples. The mid-IR ASE spectrum of the Dy3+ tellurite waveguide largely matches the line shape of the spontaneous uorescence from bulk Dy3+ tellurite glass, except with slightly enhanced intensity around 3 and 3.9 m suggesting potential enhancements in the bandwidth of this transition in waveguiding structures which is important for future waveguide and bre laser applications.

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5. Conclusions
In conclusion, Dy3+ doped heavy-metal oxide tellurite and germanate glasses and waveguides exhibit broader and red-shifted uorescence from the 6 H13/2 6 H15/2 transition compared to the current standard mid-IR laser glass ZBLAN. Dy3+ doped ZBLAN bre lasers have previously been demonstrated to operate at 2.95 m which coincides with the strong absorption of water, making them inappropriate for atmospheric applications such as sensing and lidar. A laser based on Dy3+ doped tellurite waveguide or bre could potentially operate at longer wavelengths up to around 3.3 m or beyond which is within the atmospheric transmission window. Tellurite and germanate glasses are also more robust and stable than ZBLAN glass making them more desirable in industrial applications.

References
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[6] Jha A et al 2012 Rare-earth ion doped TeO2 and GeO2 glasses as laser materials Prog. Mater. Sci. 57 142691 [7] Gomes L, Milanese D, Lousteau J, Boetti N and Jackson S D 2011 Energy level decay processes in Ho3+ -doped tellurite glass relevant to the 3 m transition J. Appl. Phys. 109 103110 [8] Domachuk P et al 2008 Over 4000 nm bandwidth of mid-IR supercontinuum generation in sub-centimeter segments of highly nonlinear tellurite PCFs Opt. Express 16 71618 [9] Richards B, Tsang Y, Binks D, Lousteau J and Jha A 2008 2 m Tm3+ /Yb3+ -doped tellurite bre laser J. Mater. Sci.-Mater. Electron. 20 S31720 [10] Jiang X, Lousteau J, Shen S and Jha A 2009 Fluorogermanate glass with reduced content of OH-groups for infrared ber optics J. Non-Cryst. Solids 355 20159 [11] Yu F, Wadsworth W J and Knight J C 2012 Low loss silica hollow core bers for 34 m spectral region Opt. Express 20 111538 [12] Kosolapov A F et al 2011 Demonstration of CO2 -laser power delivery through chalcogenide-glass ber with negative-curvature hollow core Opt. Express 19 257238 [13] Jha A et al 2012 Review on structural, thermal, optical and spectroscopic properties of tellurium oxide based glasses for bre optic and waveguide applications Int. Mater. Rev. 57 35782 [14] ODonnell M D, Miller C A, Furniss D, Tikhomirov V K and Seddon A B 2003 Fluorotellurite glasses with improved mid-infrared transmission J. Non-Cryst. Solids 331 4857 [15] Campbell J H et al 2000 Continuous melting of phosphate laser glasses J. Non-Cryst. Solids 263 34257 [16] Jha A, Shen S and Naftaly M 2000 Structural origin of spectral broadening of 1.5 m emission in Er3+ -doped tellurite glasses Phys. Rev. B 62 621527 [17] Fernandez T T et al 2010 Femtosecond laser written optical waveguide amplier in phospho-tellurite glass Opt. Express 18 2028997