Influence of 532 and 355 nm Nanosecond Laser Pulses on

Photodestruction of Silver Nanoparticles in Photo-thermo-refractive

Glasses

Alexander Ignatiev, Dmitry Ignatiev, Dmitry Klyukin, Nikolay Nikonorov, Rustam Nuryev and

Alexander Sidorov

ITMO University, Kronverksky 49, St. Petersburg, Russia

Keywords: Nanosecond Laser, Silver Nanoparticle, Glass, Photodestruction.

Abstract: In this research we investigate an influence of wavelength of nanosecond laser radiation on the process of

silver nanoparticles photodestruction in photo-thermo-refractive glass. Second and third harmonic of

nanosecond YAG:Nd laser have been applied to irradiate photo-thermo-refractive silicate glasses with silver

nanoparticles and different halogenides (F, Cl, Br) as dopants. Optical spectroscopy and X-ray diffraction

analysis have revealed a presence of core/shell nanoparticles Ag/AgBr and Ag/Na

0.8

0.2

Cl. Irradiation of

samples by third harmonic at 355 nm wavelength causes a red shift of surface plasmon resonance band (35

nm) whereas nanosecond laser radiation at 532 nm does not cause significant shift of the surface plasmon

resonance band. Such a difference is caused by mechanisms involved in the photodestruction process.

1 INTRODUCTION

Phototermorefractive (PTR) glasses are perspective

material for recording of highly efficient volume

phase holograms operating in red visible and near IR

spectral range (700-3000 nm) (Dubrovin et al., 2014;

Ignatiev et al., 2015). The PTR-glasses allow to

precipitate silver nanoparticles (SNPs) possessing

high absorption coefficient in visible spectral range

(λ

max

=414-490 nm) and nanosize crystalline phase of

NaF in local area of the glass host by photo-thermo-

induced crystallization (Nikonorov et al., 2010).

Unfortunately, this absorption band of SNPs restrict

to the using the holograms in short visible range.

There are several investigation devoted to the

photodestruction of silver nanoparticles in glass

matrix. An influence of femtosecond laser radiation

on SNPs in glass matrix after ion-exchange was

widely investigated (Podlipensky et al., 2004;

Stalmashonak et al., 2007). However, the

mechanisms of photodestruction of relatively big

nanoparticles larger than 20 nm differ from the small

ones and require particular attention. The influence

of laser irradiation with wavelength 532 nm was

well described for silver-containing silicate glass.

Nevertheless, it is still very important to use a laser

radiation with an appropriate wavelength to reduce

the possible damage to the hologram efficiency in

such glasses. In the present work we demonstrated a

possibility of reduction of the absorption band by

bleaching technology with the use of pulse (9 ns)

laser radiation with two wavelengths at 355 and 532

nm. The features of SNPs with different shells and

surrounding in glass matrix are considered using X-

ray diffraction analysis and optical spectroscopy.

2 EXPERIMENTAL

In our studies we have used PTR glass of sodium-

alumina-silicate system, Na

О – Al

– ZnO – SiO

– NaF –NaCl(Br), activated by CeO

(0.007 mol%),

(0.02 mol%), and Ag

O(0.007 mol%).

The glasses were synthesized in fused silica

crucibles at 1500 °С in the environment air. Stirring

with a Pt thimble was used to homogenize the liquid.

After melting, the glasses were cooled down to 500

°С , then annealed at glass transition temperature (T

= 494 °С for Ag-Br and Ag-Cl samples, 473 °С for

Ag-Br-F sample) for 1h, and cooled down to room

temperature with a rate of 0.15K/min. The samples

were prepared as the polished plates with the

thickness 1 mm.

Ignatiev, A., Ignatiev, D., Klyukin, D., Nikonorov, N., Nuryev, R. and Sidorov, A.

Inﬂuence of 532 and 355 nm Nanosecond Laser Pulses on Photodestruction of Silver Nanoparticles in Photo-thermo-refractive Glasses.

DOI: 10.5220/0005669702410245

In Proceedings of the 4th International Conference on Photonics, Optics and Laser Technology (PHOTOPTICS 2016), pages 243-247

ISBN: 978-989-758-174-8

243

Table 1: Glass compositions.

Components Ag-Br,

(mol.%)

Ag-Cl,

(mol.%)

Ag-Br-F,

(mol.%)

O 0.006 0.006 0.006

Br 1.5 0 1.5

Cl 0 1.5 0

F 2 2 6

Samples were irradiated by high pressure mercury

lamp. Then a thermal treatment of samples was

carried out in programmable muffle furnaces

(Neibotherm) at 520 °С at 90 min. The irradiation of

the samples were carried out by pulsed (9 ns)

YAG:Nd

laser TII LS-2131M (Lotis) with second

harmonic at 532 nm, pulse energy 70 mJ and third

harmonic at 355 nm, pulse energy 22 mJ at

frequency 10 Hz. The spectral measurements were

carried out by means of spectrophotometer Lambda

650 (Perkin-Elmer) in the range 200-800 nm with

the step of 1 nm. The X-ray diffraction spectra were

obtained on an Ultima IV diffractometer (Rigaku).

3 RESULTS AND DISCUSSIONS

After the mercury lamp irradiation and thermal

treatment, x-ray diffraction analysis of the samples

has been conducted. Fig.1a,b shows that Ag-Cl and

Ag-Br samples contain Na

0.8

0.2

Cl and AgBr

crystalline phase. It’s been suggested (Nikonorov et

al., 2010) that such a crystal can be formed at SNPs

as shell. The formation of NaF crystalline phase

occurs at relatively high concentration of F

ions (6

mol.%) and it happens only when glass composition

involves Cl or Br ions (Fig.1c). Therefore, it is

reasonable to suggest that depending on glass

composition SNPs have Na

0.8

0.2

Cl shell in Ag-Cl

sample, AgBr shell in Ag-Br sample and AgBr and

NaF shells in Ag-Br-F sample (inset on Fig.1a-c). A

significant decrease of glass refractive index after

UV irradiation and thermal treatment also proves the

formation of NaF surroundings (Ivanov et al., 2015).

Curves 1 and 2 at Fig.2 present optical density

spectra of investigated glasses before and after

mercury lamp irradiation and followed thermal

treatment. One can see that initially glasses were

colorless down to 350 nm. After the treatment an

absorption peak at 453 nm has appeared (Curve 1 at

Fig.1). This absorption is connected with surface

plasmon resonance (SPR) of SNPs in dielectric

matrix. Generally, SNPs are characterized by SPR

peak at 408-411 nm (Garcia, 2011), but in case of

Ag-Br and Ag-Br-F samples it is shifted to 453 nm

due to AgBr shell, which has larger value of

refractive index (Nikonorov et al., 2009). Maximum

of SPR peak for Ag-Cl samples is located at 419 nm.

Such a difference in SPR peak wavelength can be

Figure 1: (a) Ag-Cl sample X-ray diffraction data PTR

glasses containing 0.13 mol% Ag

O and 2.2 mol% NaCl

(b) Ag-Br sample X-ray diffraction data for PTR glasses

containing 0.06 mol% Ag2O and 1.5 mol% NaBr (c) Ag-

Br-F sample X-ray diffraction data for PTR glasses

containing 0.06 mol% Ag2O, 1.5 mol% NaBr and 6.0

mol% NaF.

PHOTOPTICS 2016 - 4th International Conference on Photonics, Optics and Laser Technology

244

related with the width of halide shell or refractive

index of the shell (Nikonorov et al., 2009), but this

question won’t be considered in this research.

Figure 2: (a) Ag-Br-F after 532. 1- as-prepared glass, 2 –

before laser irradiation, 3 – 150 pulses, 4 – 300 pulses, 5 –

450 pulses, 6 – 1800 pulses. (b) Ag-Br-F after 355. 1 - as-

prepared glass, 2 – before laser irradiation, 3 – 600 pulses,

4 - 1800 pulses, 5 – 3000 pulses, 6 – 6000 pulses.

Following laser irradiation was conducted using

two harmonics of nanosecond laser at 532 and 355

nm with energy density 0.5 and 0.2 J/cm

respectively. Fig.2 shows the result of the action of

nanosecond laser pulses at 532 nm on Ag-Br-F

sample. One can see that the intensity of SPR peak

decreases with the increase of laser radiation dose,

whereas the SPR band position does not change. An

influence of nanosecond laser pulses at 355 nm

wavelength is differs significantly. Curves 3-8 also

shows the decrease of SNP band intensity

accompanied with its red shift on 30-35 nm. Also

there is a slight increase in absorption at 270-325 nm

spectral range, which can be associated with the

formation of glass network defects and a formation

of silver molecular clusters Ag

(Klyukin et al.,

2014).

Figure 3: Influence of laser pulses with 532 nm (a) and

355 nm (b) wavelength on Ag-Br-F (1), Ag-Br (2) and

Ag-Cl (3) samples.

Fig.3 shows the influence of laser radiation dose

on the shift of SPR peak of each sample. One can

see that the similar behavior is observed for all the

glasses. Namely, the position of SPR peak doesn’t

alter significantly after laser pulses at 532 nm

(Fig.3a). Only Ag-Cl sample demonstrates slight

blue shift after 2000 pulses, which can be associated

with the decrease of refractive index around

nanoparticles or size of SNPs. However, the position

of SPR peak of SNPs alters dramatically during the

laser irradiation by pulses at 355 nm wavelength

(Fig.3b). Each sample demonstrates 10-15 nm red

shift after the first 500 pulses and it continues with

smaller rate until the glass is fully transparent. Table

2 contains the maximum SPR peak shift for each

sample. Clearly that only after the laser irradiation at

355 nm significant SPR peak shift occurs. It should

be noted that laser irradiation of the samples was

conducting until the full bleaching. Therefore, it is

possible to compare the rate of photobleaching of

the samples for particular pulse energy. For Ag-Cl

sample it took approximately 6000 pulses to bleach

it fully by laser radiation at 532 nm, whereas for Ag-

Br and Ag-Br-F the number of pulses doesn’t exceed

2500 pulses. So Ag-Br and Ag-Br-F glass samples

have an advantage to compare with Ag-Cl glass as

long as they can be photobleached by the

nanosecond laser at 532 nm almost 2 times faster.

Inﬂuence of 532 and 355 nm Nanosecond Laser Pulses on Photodestruction of Silver Nanoparticles in Photo-thermo-refractive Glasses

245

This result can be explained by closer position of

SPR peak to the laser wavelength at 532 nm, so the

probability of laser absorption much higher in case

of Br-containing samples with SPR peak near 450

nm. Nevertheless, in case of laser irradiation at 355

nm there is no similar dependence, where the

photobleaching process of Ag-Br sample takes

10000 pulses, whereas Ag-Br-F and Ag-Cl samples

become colorless even after 6000 pulses. It is also

reasonable to suggest that the photobleaching by

laser pulses at 532 nm wavelength took less pulses

because of higher energy density (0.5 J/cm

) to

compare with laser pulses at 355 nm (0.2 J/cm

Table 2: SPR band shift.

Laser

wavelength,

Ag-Br, nm Ag-Cl, nm Ag-Br-F, nm

532 2 1 1

355 27 32 35

According to the theoretical research (Nikonorov et

al., 2009) the position of SPR peak depends on the

permittivity of the nanoparticle itself, its shell and

surrounding dielectric. It is assumed that SNP in the

investigated glasses are surrounded by high

refractive index shell (AgBr, Na

0.8

0.2

Cl), which

causes the initial SPR peak red-shifted position. The

following laser irradiation results in the

photodestruction of SNP, which can occur in

different ways (Hashimoto et al., 2012). It seems

that two main mechanisms of the photodestruction

take place: photothermal evaporation and Coulomb

explosion. Near-field ablation hardly involved in the

photodestruction of considered glasses as long as it

requires high intensity density, which can be

achieved rather by femtosecond laser pulses.

Therefore, it reasonable to explain the red shift of

SPR peak after laser irradiation at 355 nm by

photodestruction of SNP through the photothermal

evaporation of silver ions that come from the

nanoparticles core to the surroundings. That process

causes a local increase of refractive index of SNP

shell and following red-shift of SPR peak. This

process occurs gradually because the laser pulse

wavelength slightly overlap with SPR band.

Coulomb explosion mechanism is likely involved in

the photodestruction of SNPs by laser radiation at

532 nm. In this case SNPs are breaking at smaller

ones and as long as it occurs in condensed material

like glass with high value of viscosity the smaller

parts of SNPs can not overcome the glass matrix and

they stay near each other surrounded by shell with

the same refractive index. The reason of involving of

such mechanisms of photodestruction for particular

wavelengths is not quite understood yet.

4 CONCLUSIONS

In conclusion, we have demonstrated a possibility of

reduction of the absorption band by bleaching

technology with the use of pulse (9 ns) laser

radiation with two wavelengths at 355 and 532 nm.

X-ray diffraction analysis have revealed the

existence of AgBr, Na

0.8

0.2

Cl and NaF crystalline

phase in the investigated glasses after the mercury

lamp irradiation and following thermal treatment.

Such a crystalline phase is located around SNPs and

affects on the SPR band position. During the

irradiation the SNPs absorption band decreases

depending on the exposure dose. This process

accompanies with a red shift of SPR band (35 nm)

after the laser pulses at 355 nm, whereas there is no

significant shift of the absorption band after the laser

pulses at 532 nm. The photothermal evaporation is

responsible for the photodestruction of SNPs in case

of laser pulses at 355 nm, whereas the Coulomb

explosion can explain the results of the action by the

nanosecond laser pulses at 532 nm. The technology

allowed us to control the size of the silver

nanoparticeles in PTR glasses and record the phase

holograms in visible range.

ACKNOWLEDGEMENTS

This work was financially supported by Russian

Scientific Foundation (Agreement # 14-23-00136).

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