Formation of luminescent centers in photo-thermo-refractive silicate glasses under the action of UV laser nanosecond pulses

A. I. Ignatiev; D. A. Klyukin; V. S. Leontieva; N. V. Nikonorov; T. A. Shakhverdov; A. I. Sidorov

doi:10.1364/OME.5.001635

Introduction

Since the last quarter of the 20th century photo-thermo-refractive (PTR) glasses have been attracting a lot of attention due to their unique optical properties [1]. PTR glass is a photosensitive glass that changes its refractive index after the exposure by the near UV radiation (300–350 nm) followed by a thermal treatment in the vicinity of 500 °C. PTR glass has been used for holographic recording of various types of volume diffractive optical elements [2], and finds a wide range of applications for laser technique and photonics. PTR glasses are the complicated systems with a lot of dopants such as cerium, antimony and silver that play a key role in the luminescence centers formation and changing of the glass refractive index [3]. Moreover, they are very suitable materials for the investigation of optical properties of silver molecular clusters (MCs) because the as-prepared glass is transparent at the near UV range and after the glass melting silver is presented in the glass in ionic state and charged MCs state. According to the explanation of U. Kreibig molecular cluster it is a form of matter that consists of a few amount of atoms or ions [4]. The notation charged MC means that such a molecular cluster consists of neutral atoms and charged ions. As long as silver ions possess high mobility in the silicate glass matrix it is possible to combine them into MCs of various sizes. As was shown before [3] such sub-nanosized objects possess quite different luminescent bands under UV radiation excitation. A lot of scientific groups investigated silver MCs behavior in noble gases [5,6], solutions [7], zeolites [8], polymers [9] and glasses [3,10,11]. For the glass matrix there are several approaches for the formation of silver MCs. Basically they consist in the reduction of silver ions and charged MCs followed by activation of the thermal diffusion of silver atoms and ions [3]. The most effective approaches for the starting of the clusterization process are the laser [10,12,13] or the electron beam [14,15] irradiation and the subsequent thermal treatment [11]. Laser glass modification is one of the most prevalent ways to the manipulation of silver ions, atoms and MCs due to the spreading of powerful laser systems with various wavelengths in last decades. Non-linear processes that are involved in the interaction between light and matter result in peculiar changes of glass matrix and MCs themselves, such as ion exchange in a focal point [16], waveguide recording [17], nanoparticles formation [18,19] etc. Simo and associates have considered a process of silver nanoparticles growth going by silver MCs [11]. They demonstrated that there is a threshold temperature below that nanoparticles can’t be raised in some glass matrix. The luminescent properties of silver MCs was also widely investigated in various glass matrixes [3,10,20]. The influence of UV nanosecond laser radiation on silver-doped zincphosphate glass was studied with a comparison of such an impact with femtosecond laser pulses [12]. The ability of the PTR glasses to change the luminescent or the absorption properties under the laser radiation action makes them promising as a media for optical information recording.

In our previous work [21] we have shown that the UV nanosecond laser pulses irradiation of the luminescent PTR glasses, which were preliminary irradiated to the absorption band of Ce³⁺ ions (λ = 305 nm) by the mercury lamp, results in the luminescence quenching. The subsequent irradiation of the samples by the UV mercury lamp, or the thermal treatment led to the recovery of the luminescence. The present work is the continuation of [3]. The aim of the present work is the study of effect of the UV nanosecond laser pulses irradiation on the similar glasses, which were not preliminary irradiated by the UV mercury lamp, and initially possess very weak luminescence. The effect of the thermal treatment below and above glass transition temperature after the laser irradiation is also investigated.

Experimental

PTR silicate glasses based on the Na₂O–ZnO–Al₂O₃–SiO₂–NaF–NaCl system and doped with Ag₂O (0.12 mol. %), the photosensitizer CeO₂ and the reducer Sb₂O₃ were synthesized in ITMO University (St. Petersburg, Russia). These glasses were similar to the used in [20]. The second group of the samples was not doped with CeO₂ and Sb₂O₃. These glasses possess the PTR properties, but a mechanism of refractive index changing is different and consists in the formation of defect centers by femtosecond laser irradiation [22]. The glass transition temperature of the samples was measured by the differential scanning calorimeter STA 449 F1 Jupiter (NETZSCH-Gerätebau GmbH) and was equal 495 °C. It must be noted, that during the glass synthesis part of Ce ions change the valence from IV to III and as well as Sb ions – from III to V [23]. The samples to be investigated were prepared in a form of a plane-parallel polished plates 1.0 mm thick. The as-prepared glasses were transparent, colorless and had a weak luminescence in a visible spectral range. For the irradiation of the samples we used the third harmonic (λ = 355 nm) of YAG:Nd laser LS-2131M (Lotis TII) with the maximum energy of 30 mJ, pulse duration of 5 ns and repetition rate 1 Hz. The focus of laser beam was located at the distance of 3 cm from the backward surface of the sample with the beam diameter of 1.0 mm on the forward surface. The dose of the irradiation was varied by the change of the number of laser pulses. UV mercury lamp wasn’t used in current experiment but has been used in previous one concerning with luminescence quenching [21]. For the thermal treatment of the samples at 350 °C and 500 °C the muffle furnace (Nabertherm) was used. The optical density spectra of the samples were recorded in the 300–800 nm spectral region using Lambda 650 (Perkin–Elmer) spectrophotometer. The luminescence and excitation spectra were measured by the MPF-44A (Perkin–Elmer) spectrofluorimeter. The luminescence spectra were corrected taking into account the spectral sensitivity of the spectrofluorimeter photodetector. For the excitation spectra, no correction was conducted. The spectral measurements were performed at room temperature The photos of the irradiated zones luminescence were obtained by the luminescence microscope MSFU-K (LOMO) with the excitation at λ = 400 nm.

Results

The as-prepared PTR glasses have the very weak luminescence in a visible spectral region. Figure 1 shows the luminescence spectrum of the as-prepared PTR glass for the excitation wavelength 320 nm. It can be seen that for this excitation wavelength the two luminescence bands are present with the maxima at 380 nm and 540 nm. The contribution to the shorter wavelength band makes mainly Ce³⁺ ions [24].The contribution to the longer wavelength band makes Ag₂⁺ MCs [25] and Ag₃²⁺ MCs [26].

Fig. 1 Luminescence spectrum of the PTR glass before UV nanosecond laser irradiation. Excitation wavelength is 320 nm.

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Figure 2 shows the difference of the luminescence of the PTR and silver-containing glass samples after the UV nanosecond laser action with and without preliminary irradiation by the UV mercury lamp into the absorption band of Ce³⁺ ions. It can be seen that in the first case (Fig. 2(a)) the luminescence bleaching takes place. The luminescence around photobleached areas are caused by UV mercury lamp irradiation [27]. In the second case (Fig. 2(b)) the laser action results in the intense luminescence appearance in the irradiated zones. The same result was obtained for the glass, which did not contain Ce and Sb ions (Fig. 2(c)). The following results are described for the PTR glasses which were not irradiated by the UV mercury lamp.

Fig. 2 Luminescence of the silver-containing glasses after the UV nanosecond laser irradiation with (a) and without (b,c) preliminary irradiation by the UV mercury lamp. (a,b): PTR glasses, (c): the glass sample without Ce and Sb ions. Excitation wavelength is 365 nm.

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After the UV nanosecond laser irradiation the weak yellow color in the irradiated zones of the samples appear. Figure 3 shows the optical density spectra of the PTR glass samples after UV nanosecond laser irradiation with the different doses. The absorption band at λ = 305-310 nm is related to the Ce³⁺ ions. It can be seen that the laser irradiation led to the increase of the absorption in the spectral range 300-550 nm. This effect is caused by the transformation of the silver ions and charged silver MCs to the neutral state [3,28,29]. The contribution to the absorption rise at λ = 300-350 nm makes the increase of the concentration of structural defects of a glass network [29,30].

Fig. 3 Optical density spectra of the PTR glass before and after UV nanosecond laser irradiation. 1 – before irradiation, 2 – 5 laser pulses, 3 – 10, 4 – 20.

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The luminescence spectra of the irradiated zones of the PTR glass are shown at Fig. 4(a). It can be seen that the luminescence band consists at least of three bands. The short wavelength band with the maximum at 380 nm is related to the Ce³⁺ ions, Ag⁰, and Ag₃ MCs [24,28,31]. The luminescence at the 450-500 nm spectral region is caused by the Ag⁰, Ag₂ and Ag₄ MCs [28,32]. The luminescence band at 580-660 nm is related to the Ag₃ MCs [28]. It was shown previously that Ce³⁺ ions increasing of its concentration increase a luminescence intensity of silver MCs [31]. Figure 4(b) shows the difference between the luminescence excitation spectra of PTR glass after the UV mercury lamp irradiation and after the UV nanosecond laser irradiation. It can be seen that the excitation spectra differ depending on the irradiation source. This indicates that the wavelength, the duration and the radiation intensity effect on the concentration of silver neutral MCs of different types. At the same time absorption spectra almost do not depend on the irradiation source [27].

Fig. 4 (a): Luminescence spectra of the irradiated zones of the PTR glass before the thermal treatment. Excitation wavelengths: 1 – 320 nm, 2 – 340, 3 – 360. (b): A comparison of the normalized excitation spectra after the UV mercury lamp irradiation (1) and after the UV nanosecond laser irradiation (2). Luminescence wavelength is 540 nm. Laser irradiation dose is 20 pulses.

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Figures 5(a) and 5(b) show the luminescence and excitation spectra of PTR glass samples after the thermal treatment at temperature less than the glass transition temperature. It can be seen that the luminescence spectrum in the visible range changes considerably with respect to Fig. 4(a): the half-width of the luminescence band became narrow and its maximum shifts to 460 nm. The luminescence intensity increases, and its color changes from the orange to green (Fig. 5(c) and 5(d)). The reason of this can be the increase of the concentration of Ag₄ MCs which have the luminescence band at 458 nm [32] and decrease of the concentration of Ag3 MCs which have the luminescence band at 616 nm [33,34] by the following process:

A g_{3} + A g^{0} \to A g_{4} .

The excitation spectra after the thermal treatment changes insignificantly (Fig. 5(b)).

Fig. 5 Luminescence (a) and excitation (b) spectra of the PTR glass after the irradiation by the 20 laser pulses and the thermal treatment at 350 °C during 1 h. (a): Excitation wavelengths: 1 – 285 nm, 2 – 360 nm. (b): Luminescence wavelengths: 1 – 380 nm, 2 – 460 nm. (c, d): Luminescence of the irradiated zones before (c) and after (d) the thermal treatment correspondingly. Excitation wavelength is 400 nm.

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The thermal treatment at the temperature above the glass transition temperature led to the non-reversible quenching of the luminescence in the centers of the irradiated zones (Fig. 6, Fig. 7). But at the perimeters of the irradiated zones the luminescence intensity increases. The optical density spectra (Fig. 8), measured in the centers of the irradiated zones show the appearance of the wide absorption band in the 380-550 spectral range typical to the plasmon resonance of silver nanoparticles [28]. The color of the centers of the irradiated zones changes from weak yellow to brown (see inset in Fig. 8). The described changes indicate that during the thermal treatment the neutral silver MCs transform to the silver nanoparticles by the trapping of Ag atoms. The decrease of silver MCs concentration and the increase of the absorption result in the luminescence quenching. It can be seen from Fig. 8 that the appeared absorption band is the superposition of the at least two absorption bands. This can be caused by the two reasons [35]: (i) the presence in a glass of non-spherical silver nanoparticles, and (ii) the electromagnetic interaction between nanoparticles located close to each other. Similar situation was considered for PTR glass with silver nanoparticles after UV light with wavelength λ = 325 nm and heat treatment [36].

Fig. 6 Photos of the irradiated zones luminescence in the PTR glasses after the thermal treatment at 500 °C during 1 h for the 5 laser pulses (a), 10 pulses (b), and 20 pulses (c). Excitation wavelength is 400 nm.

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Fig. 7 The distribution of the luminescence intensity in the cross-sections of the irradiated zones, shown at Fig. 6. 1 – Fig. 6 (a), 2 – (b), 3 - (c).

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Fig. 8 Optical density spectra of the irradiated zones in the PTR glass after the thermal treatment at 500 °C during 1 h for the 5 laser pulses (1), 10 pulses (2), and 20 pulses (3). Inset – the photo of the sample after the thermal treatment.

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The similar results were obtained for the samples which did not contain Ce and Sb ions and were not previously irradiated by UV mercury lamp. This indicates that the contribution of these ions to the effects described above is negligible.

Discussion

The presented results and their comparison with the results, described in [21], show that the pre-history of the glass influences on the final effects considerably. The preliminary irradiation of glass by continuous UV radiation into the absorption band of Ce³⁺ ions led to the intense luminescence appearance, and the subsequent action of UV nanosecond laser pulses results in the luminescence quenching [20] (first case). In the glass, not irradiated by the UV mercury lamp, the action of UV nanosecond laser results in the luminescence appearance (second case). Let us compare the main processes in the both cases.

During the preliminary UV irradiation of PTR glass in the first case the photoionization of Ce³⁺ ions takes place, and Ce³⁺ ions transform to the Ce⁴⁺ state:

C e^{3 +} + h ν \to C e^{4 +} + e .

The produced free electrons can be trapped by Ag⁺ ions, charged silver MCs, Sb⁵⁺ ions and defects of a glass network:

A g^{+} + e \to A g^{0}

A g_{n} {_{}}^{+} + e \to A g_{n}

S b^{5 +} + e \to {[S b^{5 +}]}^{-}

The transformation of the charged silver MCs to the neutral state after the UV irradiation led to the appearance of the intense luminescence in visible spectral region [3] and of the broad absorption band in 340-470 nm spectral range, similar to the band, shown at Fig. 3 (curves 2-4). The irradiation of such glass by UV nanosecond laser pulses led to the luminescence quenching [21] throw the photoionization of neutral silver MCs:

A g_{n}^{0} + h ν \to A g_{n}^{+}

As long as neutral silver MCs possess the luminescence in the visible spectral range when they become charged the luminescence intensity goes down. This effect is caused by one-photon ionization of neutral molecular clusters, because their absorption band correlates with laser radiation wavelength (λ = 355 nm). Free electrons can be trapped by the Ce⁴⁺ ions:

C e^{4 +} + e \to C e^{3 +} .

That’s why in the first case the luminescence can be recovered only after the UV irradiation into the absorption band of Ce³⁺ (process (1)), or by the thermal treatment:

{[S b^{5 +}]}^{-} \to S b^{5 +} + e

In the second case the silver MCs initially are in the charged state, and there is no pronounced absorption bands at λ = 355 nm (curve 1 at Fig. 3). So the photoionization of silver MCs and point defects of glass network during UV nanosecond laser irradiation, at least for the first laser pulse, can be caused by the following processes: (i) by the nonlinear two-photon absorption, and (ii) by the two-step absorption. The probability of the first effect is high because of the high intensity of laser radiation in the irradiated zone (I > 80 MW/cm²). The two-step absorption consists of two absorption acts: the absorption of one photon with the creation of the metastable excited state, and the absorption of the other photon in the excited state, resulting in photoionization:

\begin{array}{l} X + h ν \to X *, \\ X * + h ν \to X^{+} + e . \end{array}

Here X is silver MC, or the defect of a glass network. It must be mentioned that the laser irradiation can result in the destruction of some silver MCs and some defects and in the creation of the new defects. This is the reason of the absorption increase in the spectral range 300-340 nm after laser irradiation (curves 2-4 at Fig. 3).

The probability of non-resonant photoionization of Ce³⁺ ions by the mentioned processes is very low. So Ce ions during the laser pulses keep in the three-valence state, and, in contradiction to Ce⁴⁺ ions, cannot trap electrons. After the laser pulse the free electrons can be trapped by the Ag and Sb ions and by the charged silver MCs (processes (2-4)). As the free electrons are not trapped in this case by the Ce ions (process (5)), the concentration of free electrons is higher, than in the first case. This results in the increase of the luminescence intensity in the irradiated zone. The negligible role of Ce ions in the second case is confirmed by the experiments with the glasses without Ce.

The thermal treatment of the irradiated glass at temperature below T_g led to the loose of the trapped electron by the [Sb⁵⁺] ^̶ complex (process (6)) in PTR glasses and by the charged defects in the glasses without Sb ions. The additional free electrons are trapped by the mentioned silver ions and charged MCs and coarse the further increase of the luminescence intensity. The thermal treatment of the irradiated glass at temperature above T_g led to the growth of the silver nanoparticles with silver MCs being the centers of growth. When the silver nanoparticles appear in a glass the concentration of the luminescent MCs decreases, the absorption of glass increase because of the plasmon absorption band appearance, and the luminescence intensity in the center of the irradiated zone is bleached (Fig. 5, Fig. 6). In the contradiction to the central part of the irradiated zone no nanoparticles are formed and the luminescence intensity increases at its perimeter. The reason of this is the low intensity of laser radiation on the laser beam perimeter. This results in the low concentration of the free electrons after the laser pulse, and low efficiency of MCs transformation from the charged to neutral state. During the thermal treatment the loose of electrons by the [Sb⁵⁺] ^̶ complex or charged defects led to the increase of the neutral MCs, but the thermal treatment duration is not enough for the silver nanoparticles formation.

The preliminary treatment of the PTR glasses makes possible to form in them the positive or the negative images by the UV nanosecond laser irradiation through the mask or by the laser beam scanning. Figure 9 shows the luminescent PTR glass plates irradiated through the mask by the UV nanosecond laser radiation with and without the preliminary irradiation by the UV mercury lamp.

Fig. 9 The luminescent PTR glass plates irradiated through the mask by the UV nanosecond laser radiation with (a) and without (b) the preliminary irradiation by the UV mercury lamp.

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It should be mentioned also that optical information can be also recorded in the PTR glasses by the local absorption change under the action of UV nanosecond laser and the subsequent thermal treatment (see inset in Fig. 8).

Conclusions

It is shown experimentally that the result of the UV nanosecond laser irradiation of the PTR glasses depends on the pre-history of glass. If the PTR glass was preliminary irradiated by the UV radiation into the absorption band of Ce ions the UV nanosecond laser irradiation results in the silver MCs luminescence quenching. If the PTR glass was not preliminary irradiated by the UV radiation into the absorption band of Ce ions the UV nanosecond laser irradiation results in the neutral silver MCs luminescence appearance. The subsequent thermal treatment above the glass transition temperature results in the silver nanoparticles growth in the irradiated zones. The described effects can be used for the optical information recording by the local change of glass luminescence or absorption.

Acknowledgments

This work was financially supported by Ministry of Education and Science during the scientific-research work in the frame of the project part of state task in the scientific work area for the task # 11.1227.2014/K

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Formation of luminescent centers in photo-thermo-refractive silicate glasses under the action of UV laser nanosecond pulses

Abstract

Introduction

Experimental

Results

Discussion

Conclusions

Acknowledgments

References and links

Cited By

Figures (9)

Equations (9)

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