Materials Science Forum Submitted: 2020-11-08

ISSN: 1662-9752, Vol. 1022, pp 35-41 Accepted: 2020-11-19

© 2021 Trans Tech Publications Ltd, Switzerland Online: 2021-02-24

Color Identification Mark by Laser Processing of Silver Surface

Romanov Valeriy1a, Nguyen Tuan-Anh1b, Shchedrina Nadezhda1c,
Lutoshina Daria1d, Mikhailovskii Vladimir2e, Danilov Denis2f, Sergeev Maxim1g,
Odintsova Galina1h
1
ITMO University, Kronverksky Pr. 49, bldg. A, St. Petersburg, 197101, Russia
2
St. Petersburg State University, 13B Universitetskaya Emb., St Petersburg 199034, Russia
a
vvromanov@itmo.ru (corresponding author), bnta.itmo@gmail.com, cschedrina.nadezda@itmo.ru,
d
ld3282@itmo.ru, ev.mikhailovsky@spbu.ru, fd.danilov@spbu.ru, gmmsergeev@itmo.ru,
h
gvodintsova@itmo.ru

Keywords: silver, plasmon effects, nanoparticles, nanosecond laser pulses

Abstract. Coloring silver for decorative purposes and for applying identification marks is an
important task. In this paper, we consider a method for coloring silver surfaces using VIS plasmonic
response in laser-induced nanoparticles (NPs). An analysis was made of the resulted morphology
and chemical composition of nanoparticles obtained with nanosecond laser pulses. The dependence
of the size and distribution of silver NPs on the laser exposure parameters is determined. The
developed color palette was characterized using colorimetric coordinates.

Introduction
Silver has been known to humanity since ancient times. This metal is characterized by its relatively
low reactivity, not soluble in hydrochloric, and it dilutes sulfuric acids. Due to this, the applications
of silver are constantly increasing, ranging from electrical engineering to the manufacture of coins.
Silver is widely used in the jewelry industry. Often there is a necessity to change the appearance of
a silver product, for example, for jewelry coloring and decorating. However, the application of
identification marks is frequently required on the silver product surface for protection against
falsification. The appearance of such identification marks can be different, but adding color can
provide a higher level of protection.
Among the traditional methods for coloring silver products, the most frequent ones are oxidation
[1], the method of applying hot and cold enamels [2, 3], and galvanic coatings [4]. However, the
above methods have numerous disadvantages such as not enough resistance to external impacts,
inability to implement them without consumables, and low processing speed.
Laser methods for coloring and marking silver products are very promising due to high accuracy,
high processing speed, and implementation without additional consumables, such as, for example,
coloring materials.
The main methods of laser coloration are lithography [5-7], oxidation of the metal surface [8],
the creation of laser-induced periodic surface structures [9], and the plasmonic metal nanoparticles
(NPs) formation. However, the use of lithography is a complex multi-stage process, and therefore
not suitable for industrial applications. The corresponding disadvantages apply to the method of
oxidizing a metal surface, where coloration is carried out by transferring an oxidizing metal film to
the silver substrate surface for further laser heating and creating color on a surface due to
interference. The formation of laser-induced periodic surface structures allows achieving unusual
visual effects, however, the produced colors strongly depend on the angle of light incidence [10].
Therefore, it was decided to use the plasmon resonance effect due to the silver NPs formation,
which allows coloring precious metals without consumables. An example of such work was
presented using a femtosecond laser [11].
In this paper, we consider the possibility of using a nanosecond laser, which is more accessible
and more common in industry than a femtosecond laser, to create identification marks on the silver
surface of metals due to the plasmon resonance effect on the silver nanoparticles.

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36 Mining Industry: Innovations and Prospects for the Development of Materials
Science II

Materials and Methods

As a material for the research, round silver plates (0.925: 92.5% silver, 7.5% copper) were selected
with a diameter of 9 mm and a thickness of 0.9 mm, since it is the most common type of silver for
various applications. The silver surface was preliminarily polished to Ra = 0.076 μm, and further
cleaned in an ultrasonic bath in a solution of distilled water at a temperature of 28 ° C for 30
minutes.
The synthesis of silver nanoparticles was conducted from the vapor-gas phase as a result of silver
target laser ablation under the influence of nanosecond laser pulses. The surface treatment of silver
was carried out in the air using a Yb-fiber laser with a wavelength of 1064 nm. The laser beam
scanning over the surface was performed using two galvanic rotary mirrors. The beam was focused
using an F-theta lens with focal length of 216.1 mm into a spot with a diameter of d0 = 50 μm. The
schematics of the installation is shown in Figure 1.

Figure 1. A – Schematics of a laser installation: 1 – a fiber laser source, 2 – an optical radiation

transportation device, 3 – a silver plate with nanoparticles, 4 – a workboard, 5 – a controller, 6 –
galvanic rotary mirrors, 7 – F-theta lens, 8 – control personal computer. B – Schematic
representation of plasmonic properties of laser-induced silver nanoparticles

The laser-irradiated silver surface was characterized using optical (Carl Zeiss Axio Imager A1M
microscope) and scanning electron (scanning electron microscope (SEM) Zeiss Merlin)
microscopy, as well as energy dispersive X-ray microanalysis (an attachment to SEM Oxford
Instruments INCAx-act). SEM photographs were processed using ImageJ software to determine the
NPs size distribution. The silver surface was etched using a focused ion beam (with scanning
electron microscope Zeiss ORION).
The composition and size of the silver NPs were determined by transmission electron
microscopy (TEM) in a Libra 200 FE analytical transmission electron microscope with an X-Max
energy dispersive X-ray detector. For TEM, the samples were placed in a 2 ml centrifuge tube with
distilled water, which was installed into an ultrasonic bath at a temperature of 28 °C for 5 minutes.
A drop of the solution obtained during the preparation was placed from a test tube on a carbon mesh
using a dispenser.
A SF-56 spectrophotometer was used to measure the reflection spectra and to determine the
colorimetric coordinates under illumination with a D65 source of the silver surface after laser
irradiation.

Results
As a result of laser ablation at a constant pulse duration (τ) of 14 ns and a pulse repetition rate (f) of
75 kHz, in the range of scanning speeds (V) from 200 mm/s to 400 mm/s (with increments of 50
mm/s) and average laser irradiation power (P) from 7.2 W to 8.0 W (with increments of 0.2 W) the
 Materials Science Forum Vol.1022 37

silver surface was painted in different colors (Figure 2A). Some elements of the palette were
numbered for convenience results analysis.
Figures 2B and 2C show microphotographs and SEM images of samples S11, S51, and S55.

Figure 2. A – Palette obtained on the laser-irradiated silver surface under the following laser
treatment parameters: τ = 14 ns, f = 75 kHz, V = 200–400 mm/s with increments of 50 mm/s (along
the x axis) and P = 7.2-8.0 W with increments of 0.2 W (along the y axis). The surface of samples
S11, S51, and S55 after laser processing: B – micro images, C – SEM images

Histograms of the size distribution of silver nanoparticles were obtained based on SEM images
(Figure 3). The average nanoparticle diameter (dav) equals 15±6 nm for sample S11, 24±5 nm for
S51, 43±10 nm S55. The concentration of nanoparticles (N) is 4252 pc/μm2 for S11, 1560 pc/μm2 for
S51, and 969 pc/μm2 for S55.
It is seen that the size and width of the distribution of NPs increase, and the concentration of NPs
decreases with a reduction of the scanning speed and a growth in the average laser radiation power
(and, consequently, with a growth in the heating temperature of the silver surface).

Figure 3. Silver NPs size distribution for samples S11 (dav = 15±6 nm; N = 4252 pc/μm2),
S51 (dav = 24±5 nm; N=1560 pc/μm2) and S55 (dav = 43±10 nm; N = 969 pc/μm2)

The analysis of the percentage of the elements on the silver surface before and after laser
irradiation (Figure 4) showed that the copper content increases compared to the untreated surface.
This appears to be a result of copper's greater affinity for oxygen than silver's and practically does
not change for samples S11, S51, and S55. With the increase in the average laser irradiation power
and the decrease in the scanning speed, the percentage of oxygen in the system rises, while the
percentage of silver declines. Apparently, this occurs due to the silver oxide film growth with a rise
in the heating temperature of the metal surface in the air.
38 Mining Industry: Innovations and Prospects for the Development of Materials
Science II

Figure 4. Percentage of O, Cu, Ag before (Ag) and after (S11, S51 and S55) laser treatment calculated
from SEM EDX data

To determine the thickness of the modified silver layer, areas were etched with a depth of
2–3 μm, a length of 4–6 μm, and a width of 1–3 μm using a focused ion beam.
The structures of the modified layer after laser irradiation are shown in the SEM images (Figure
5). It can be seen that the layer is porous and its thickness is about 2 μm. SEM images show that
around the NPs there is a region that differs in contrast, the size (h) of which is 21.7±4.0 nm for S11,
52.3 ± 8.8 nm for S51, and 80.5 ± 17.8 nm for S55. This is 1.8% of the total diameter of
1.20 ± 0.05 μm for the particle represented on sample S11, and 7.3% of the total diameter of
1.10 ± 0.11 μm for S55, and which, apparently, is silver oxide.

Figure 5. SEM images of a modified layer of a silver surface after etching samples S11, S51, and S55
with a focused ion beam

Further, the composition and size of laser-induced NPs for sample S51 were determined using
transmission electron microscopy (TEM). According to the TEM (in multibeam conditions) analysis
results (Figure 6), dav of the S51 nanoparticles is 8.8±2.2 nm. Almost no large nanoparticles were
found in the TEM images because the solution with NPs was processed in an ultrasonic bath. This
leads to the decomposition of NPs agglomerates located on the silver surface.
 Materials Science Forum Vol.1022 39

Figure 6. Silver NPs after laser processing of sample S51. A – TEM image in multibeam conditions;
B – the distribution diagram

High-resolution TEM analysis of individual nanoparticles showed that the NPs are composed of
silver in the crystalline phase (Figure 7). Interplanar spacing was also compared with various silver
and copper oxides, and no other matches were obtained. Energy-dispersive X-ray analysis of the
obtained nanoparticles also showed the absence of oxygen.

Figure 7. The silver NP after laser processing of sample S51. A – TEM image in multibeam
conditions; B – microdiffraction from the NPs in a selected area (diameter 80 nm)

The experimental and reference data for the silver lattice parameters are presented in Table 1.

Table 1. Calculation results of diffraction patterns of the silver cubic lattice (comparison of
experimental and theoretical data)
hkl 111 200 220 311 222 400
Experimental value 2,35 2,03 1,43 1,26 1,19 0,98

Theoretical value Ag 2,36 2,04 1,44 1,23 1,18 1,02

[12,13]

Then, reflection spectra were measured and the colorimetric coordinates of the silver surface
after laser irradiation were determined. Figure 8A shows that the plasmon resonance peak shifts to
the IR region with an increase in the average laser radiation power and a decrease in the scanning
speed. Also in Figure 8B, the colorimetric coordinates in the XYZ system are marked at the color
locus.
40 Mining Industry: Innovations and Prospects for the Development of Materials
Science II

Figure 8. Silver surface after laser processing. A – reflection spectra; B – colorimetric

coordinates in the XYZ - CIE 1931 system when illuminated with a D65 source

Conclusions
In this work, silver nanoparticles with sizes up to 100 nm were synthesized on the silver surface
from the vapor-gas phase formed as a result of laser ablation of a silver target under the action of
short laser pulses of nanosecond duration in air. The thickness of the modified layer is about 2 μm;
in addition to silver and copper, oxygen is also present in the layer.
With an increase in the average laser power and a decrease in the scanning speed the size and
distribution width of silver nanoparticles increase, the concentration decreases, and the plasmon
resonance peak shifts to the IR region. The developed palette can be successfully used for applying
colored identification marks on silver products.

Acknowledgments
The study is funded by a grant Russian Science Foundation (project № 19-79-10208).
SEM studies were done on the base of the Interdisciplinary Resource Center for Nanotechnology,
Research Park, St. Petersburg State University.

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