Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg
The influence of magnesium impurities on the luminescent properties of ZnS:Cu,Mg obtained by self-propagating high-temperature synthesis (SHS) has been investigated. Special attention was paid to changes in photoluminescence spectra caused by relaxation processes in ZnS:Cu,Mg-SHS. It was shown that...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2017
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| Zitieren: | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg / Yu.Yu. Bacherikov, A.G. Zhuk, R.V. Kurichka, O.B. Okhrimenko, A.V. Gilchuk, O.V. Shcherbyna, M.V. Herkalyuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 2. — С. 191-194. — Бібліогр.: 25 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860271163635138560 |
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| author | Bacherikov, Yu.Yu. Zhuk, A.G. Kurichka, R.V. Okhrimenko, O.B. Gilchuk, A.V. Shcherbyna, O.V. Herkalyuk, M.V. |
| author_facet | Bacherikov, Yu.Yu. Zhuk, A.G. Kurichka, R.V. Okhrimenko, O.B. Gilchuk, A.V. Shcherbyna, O.V. Herkalyuk, M.V. |
| citation_txt | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg / Yu.Yu. Bacherikov, A.G. Zhuk, R.V. Kurichka, O.B. Okhrimenko, A.V. Gilchuk, O.V. Shcherbyna, M.V. Herkalyuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 2. — С. 191-194. — Бібліогр.: 25 назв. — англ. |
| collection | DSpace DC |
| container_title | Semiconductor Physics Quantum Electronics & Optoelectronics |
| description | The influence of magnesium impurities on the luminescent properties of ZnS:Cu,Mg obtained by self-propagating high-temperature synthesis (SHS) has been investigated. Special attention was paid to changes in photoluminescence spectra caused by relaxation processes in ZnS:Cu,Mg-SHS. It was shown that the introduction of magnesium into ZnS:Cu-SHS leads to a change in symmetry of the ZnS crystal lattice. It leads to relaxation, quenching the photoluminescence bands caused by the presence of copper impurities in ZnS.
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| first_indexed | 2026-03-21T11:33:50Z |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 2. P. 191-194.
doi: https://doi.org/10.15407/spqeo20.02.191
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
191
PACS 78.55.Et
Luminescent properties of fine-dispersed self-propagating
high-temperature synthesized ZnS:Cu,Mg
Yu.Yu. Bacherikov1, A.G. Zhuk1, R.V. Kurichka1, O.B. Okhrimenko1, A.V. Gilchuk2, O.V. Shcherbyna2,
M.V. Herkalyuk2
1V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine
41, prospect Nauky, 03028 Kyiv, Ukraine; e-mail: Yuyu@isp.kiev.ua
2National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnical Institute”
37, prospect Peremogy, 03056 Kyiv, Ukraine
Abstract. The influence of magnesium impurities on luminescent properties of
ZnS:Cu,Mg using obtained by self-propagating high-temperature synthesis (SHS) has
been investigated. Special attention was paid to changes of photoluminescence spectra
caused by relaxation processes in ZnS:Cu,Mg-SHS. It was shown that introduction of
magnesium into ZnS:Cu-SHS leads to a change in symmetry of ZnS crystal lattice. It
leads to relaxation quenching the photoluminescence bands caused by presence of copper
impurities in ZnS.
Keywords: self-propagating high-temperature synthesis, photoluminescence spectra,
luminescence excitation spectra, electron microscopy.
Manuscript received 12.01.17; revised version received 26.04.17; accepted for
publication 14.06.17; published online 18.07.17.
1. Introduction
The increasing flow of information stimulates studies of
materials that can be used as luminophores for basic
components of display devices [1-3]. At the same time,
luminescent characteristics of light-emitting materials
largely depend on the material structure [4, 5], ratio of
impurities acting as luminescence activators and co-
activators [6, 7], etc. Studies of the materials obtained
using unconventional methods, such as SHS, are of
particular interest. Using SHS can reduce the cost of
obtained luminophores, because this method is a low-
cost technology.
In almost all studies of luminophores, the main task
is to increase the intensity of radiation and possibility of
using the obtained material in electroluminescent
devices. In [8], it was shown improvement of
electroluminescent characteristics in thin-film devices
based on ZnS:Cu,Mn after doping MgF2 and MgS. Also,
increasing the intensity of photoluminescence (PL) after
introduction of MgS or MgCl2 in defined concentration
was noted [8].
At the same time, the resistance to degradation of
luminophores is a necessary condition for their
successful use. Most of luminophores looses their
efficiency, which may be related both to valence change
caused by oxidation, and to degradation of crystal lattice.
In the second case, atoms diffuse through material and
react with ambient matter. The results of degradation
were not only decreasing the quantum efficiency of
luminophore, but also changing the spectral
characteristics of its luminosity.
The goal of this work was to study the influence
of magnesium impurities that were introduced into
ZnS as activator and co-activator in fine-dispersed
ZnS:Cu obtained using the SHS method, and time
evolution of luminescent characteristics of obtained
luminophores.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 2. P. 191-194.
doi: https://doi.org/10.15407/spqeo20.02.191
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
192
2. Materials and methods
Fine-dispersed undoped ZnS-SHS, Mg-doped ZnS:Mg
and doped with magnesium and copper ZnS:Cu,Mg were
obtained using SHS. Magnesium and copper doping was
carried out by adding Cu and Mg chlorides directly in
the process of synthesis. For synthesis, Zn and S were
taken in the stoichiometric ratio. Concentration of Cu
was close to 1.2 wt.%. For synthesis of ZnS:Mg, the
concentration of Mg was ~1.2 wt.%. For synthesis of
ZnS:Cu,Mg, the amount of MgCl2 in the charge was
~5 wt.%. Charge materials were analytical grade.
Photoluminescence spectra were registered at room
temperature by using the spectrometer SDL-2.
Investigation of particle sizes and morphology was
carried out using the method of scanning electron
microscopy with the device REM-106 I. Samples were
investigated using the accelerating voltage 20 keV in the
regime of backscattered electrons.
Measurements of elemental composition were per-
formed using energy-dispersive X-ray spectroscopy (EDS).
3. Experimental results and discussion
Electron microscopy study of ZnS:Cu,Mg-SHS showed
that the synthesized powders consist of two fractions.
One fraction consists of large particles with dimensions
up to several decades of micrometers. The second
fraction consists of particles of micron and submicron
sizes (Fig. 1a). The minimum Ferret diameter was
chosen as a characteristic particle size. The histogram of
particle sizes distribution is shown in Fig. 1b. The
function of distribution was approximated by lognormal
low and, according to this approximation, the average
particle size was 1.32±0.01 μm.
According to EDS measurements (Fig. 2),
elemental composition of fine-dispersed ZnS:Cu,Mg-
SHS is close to the stoichiometric one:
Zn48.8S49.0Cu0.7Mg1.5.
Fig. 3a represents PL spectra of ZnS-SHS,
ZnS:Mg-SHS and ZnS:Cu,Mg-SHS. As can be seen
from Fig. 3a, curves 1 and 2 in the spectra of undoped
ZnS-SHS and ZnS:Mg are almost identical by their
spectral composition. This means that luminescence of
both powders is self-activated and caused by identical
centers. Slight broadening the PL line in the area of long
waves can be associated with disturbance in lattice of
ZnS during the process of introducing the impurity with
very different ionic radius.
The PL spectrum of undoped ZnS-SHS is a broad
line in the area of 400 to 650 nm with λmax~ 505 nm.
This band is complicated and consists of several
individual components. Decomposition of the PL
spectrum of ZnS-SHS into components is presented in
Fig. 3b. The PL bands with λmax ~ 455-465 nm was
related to native defects and their complexes that may
include co-activator and oxygen [9, 10]. These
complexes are centers of self-activated (SA)
luminescence. According to [9, 10], SA-luminescence of
undoped ZnS consists of range of closely located and, in
general, overlapped bands of PL related with different
defects (Fig. 3b).
Investigation of spectral composition of
ZnS:Cu,Mg-SHS PL spectra, registered immediately
after synthesis, showed a significant difference in
comparison with the spectrum of undoped ZnS-SHS and
ZnS:Mg-SHS. As can be seen from Fig. 3a, curve 3,
spectrum of ZnS:Cu,Mg that was registered immediately
after synthesis is a broad asymmetric sub-band with
λmax~ 530 nm. This band is complicated and consists of
at least three individual components with λmax~450, ~500
and ~520 nm. It is well known that PL band of ZnS:Cu
in the blue-green region is complex, and usually is a
superposition of several sub-bands related to copper
dopant and native defects of ZnS. The nature of the
luminescent centers responsible for the blue and green
lines is ZnS was studied in sufficient detail in [11-18].
0 1 2 3 4 5 6 7 8
0
100
200
300
400
C
ou
nt
s
Size, μm
a b
Fig. 1. а) Electron microscopic image of ZnS:Cu,Mg-SHS powder. b) Size distribution of particles in ZnS:Cu,Mg-SHS.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 2. P. 191-194.
doi: https://doi.org/10.15407/spqeo20.02.191
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
193
0 1 2 3 4 5 6 7 8 9 10 11 12
0
10000
20000
30000
40000
50000
Mg
Zn
Zn
Cu
In
te
ns
ity
(A
.U
.)
Energy, keV
Zn
S
Fig. 2. EDS spectrum of fine-dispersed ZnS:Cu,Mg-SHS.
350 400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
In
te
ns
iv
e,
a
rb
.u
.
1
2
3
4
λ, nm.
a
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
In
te
ns
iv
e,
a
rb
.u
.
λ, nm.
b
Fig. 3. а) PL spectra of: ZnS-SHS (1), ZnS:Mg-SHS (2),
ZnS:Cu,Mg-SHS (3) immediately after synthesis, ZnS:Cu,Mg-
SHS 7 days after synthesis (4); b) decomposition of ZnS-SHS
spectrum into components.
Authors [11-17] showed that the center responsible
for the appearance of Cu green line was insulated copper
ion that replaced the zinc one in the lattice of ZnS. It was
determined that symmetry of this center is not less than
that of the regular lattice point in cubic or hexagonal
lattice of ZnS. At the same time, this center doesn’t in-
clude co-activator. The blue band was related with forma-
tion of donor-acceptor type associations Cui-CuZn [18].
The PL spectrum of ZnS:Cu,Mg-SHS undergoes
great changes in 7 days after synthesis (Fig. 3a, curve 4).
PL bands caused by copper dopant and presented in
Fig. 3a, curve 3, are almost absent in the spectrum
registered in 7 days after synthesis (Fig. 3a, curve 4).
Comparison of the PL spectrum of ZnS:Cu,Mg-SHS
registered a week after synthesis and the PL spectrum of
undoped ZnS-SHS showed that PL spectra in these cases
can be related to the centers of radiative recombination,
which have similar nature. At the same time, the PL
band with the maximum in the range of 500 nm, which
is related with self-activated PL in ZnS, is dominant in
the spectrum of pure ZnS-SHS, ZnS:Cu,Mg-SHS and
ZnS:Mg-SHS (Fig. 3a).
These data indicate that centers of radiative
recombination which includes copper are destroyed
during the relaxation processes in material. Probably, it
is caused by increasing in the degree of ZnS lattice
deformation in processes of magnesium introduction,
because the ionic radius of Mg is much less than that of
Zn and Cu. According to [19], Mg ions can partially fill
tetrahedral interstitial sites or replace Zn in ZnS lattice.
The volume of the unit cell, in which Mg is inserted,
decreases due to shorter ion radius of Mg.
Consequently, mechanical stress and deformation of
ZnS lattice occur. Furthermore, introduction of
magnesium can change the phase ratio in ZnS [19]. It is
well known [11, 20] that introduction of copper usually
stabilizes the cubic phase, but introduction of
magnesium stabilizes the hexagonal phase, according
to [21]. Therefore, since both copper centers include
CuZn, it is quite possible that simultaneous decrease of
green and blue bands is caused by copper shifting from
the main position into the interstitial site due to
deformation or to the change of lattice symmetry.
Perhaps, this process will be accompanied by dropping
out of Cu as separate fraction.
It should be mentioned that SHS – is physical-
chemical process that proceeds in extreme conditions at
high temperature and with a high rate of heating the
substance in a wave of combustion [22, 23]. These
factors lead to formation of several phases of material
(with different crystal structure, character of bonds,
symmetry, etc.) during the process of synthesis in wide
temperature and pressure ranges. All this contributes to
the appearance of unstable structural states in material.
Therefore, at the beginning of introduction of
MgCl2 into the charge, magnesium compounds lead to
mass transfer between particles of ZnS, i.e. act as a flux
[21, 24, 25]. According to [4, 11], it may contribute to
introduction of an activator (copper or some other
dopants) into lattice of luminophore. In the further
relaxation processes (especially if synthesis conditions
facilitate the formation of unstable structural states or
phases), presence of magnesium promotes deformation
processes, which leads to changes in symmetry of ZnS
crystal lattice. It becomes a reason for quenching the PL
bands, which is caused by presence of copper impurities.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 2. P. 191-194.
doi: https://doi.org/10.15407/spqeo20.02.191
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
194
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|
| id | nasplib_isofts_kiev_ua-123456789-214934 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2026-03-21T11:33:50Z |
| publishDate | 2017 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| record_format | dspace |
| spelling | Bacherikov, Yu.Yu. Zhuk, A.G. Kurichka, R.V. Okhrimenko, O.B. Gilchuk, A.V. Shcherbyna, O.V. Herkalyuk, M.V. 2026-03-04T12:53:25Z 2017 Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg / Yu.Yu. Bacherikov, A.G. Zhuk, R.V. Kurichka, O.B. Okhrimenko, A.V. Gilchuk, O.V. Shcherbyna, M.V. Herkalyuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 2. — С. 191-194. — Бібліогр.: 25 назв. — англ. 1560-8034 PACS: 78.55.Et https://nasplib.isofts.kiev.ua/handle/123456789/214934 https://doi.org/10.15407/spqeo20.02.191 The influence of magnesium impurities on the luminescent properties of ZnS:Cu,Mg obtained by self-propagating high-temperature synthesis (SHS) has been investigated. Special attention was paid to changes in photoluminescence spectra caused by relaxation processes in ZnS:Cu,Mg-SHS. It was shown that the introduction of magnesium into ZnS:Cu-SHS leads to a change in symmetry of the ZnS crystal lattice. It leads to relaxation, quenching the photoluminescence bands caused by the presence of copper impurities in ZnS. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg Article published earlier |
| spellingShingle | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg Bacherikov, Yu.Yu. Zhuk, A.G. Kurichka, R.V. Okhrimenko, O.B. Gilchuk, A.V. Shcherbyna, O.V. Herkalyuk, M.V. |
| title | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg |
| title_full | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg |
| title_fullStr | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg |
| title_full_unstemmed | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg |
| title_short | Luminescent properties of fine-dispersed self-propagating high-temperature synthesized ZnS:Cu,Mg |
| title_sort | luminescent properties of fine-dispersed self-propagating high-temperature synthesized zns:cu,mg |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/214934 |
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