Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding
Principal difference in origin of high-order optical non-linearities caused by metallic nanoparticles such as Cu, Ag, and Au embedded destructively in oxide- and chalcogenide-type glassy matrices has been analyzed from the viewpoint of semiempirical chemical bond approach. The numerical criterion ha...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2017
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| Cite this: | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding / O.I. Shpotyuk, M.M. Vakiv, M.V. Shpotyuk, S.A. Kozyukhin // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 26-33. — Бібліогр.: 53 назв. — англ. |
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| author | Shpotyuk, O.I. Vakiv, M.M. Shpotyuk, M.V. Kozyukhin, S.A. |
| author_facet | Shpotyuk, O.I. Vakiv, M.M. Shpotyuk, M.V. Kozyukhin, S.A. |
| citation_txt | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding / O.I. Shpotyuk, M.M. Vakiv, M.V. Shpotyuk, S.A. Kozyukhin // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 26-33. — Бібліогр.: 53 назв. — англ. |
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| description | Principal difference in origin of high-order optical non-linearities caused by metallic nanoparticles such as Cu, Ag, and Au embedded destructively in oxide- and chalcogenide-type glassy matrices has been analyzed from the viewpoint of semiempirical chemical bond approach. The numerical criterion has been introduced to describe this difference in terms of the mean molar bond energies character for chemical interaction between unfettered components of the destructed host glassy matrix and embedded guest atoms. It has been shown that “soft” covalent-bonded networks of chalcogenide glasses of As/Ge–S/Se systems differ essentially from glass-forming oxides like silica by the impossibility to accommodate agglomerates of metallic nanoparticles. In contrast, such nanostructured entities can be well stabilized in Cu-, Ag-, or Au- embedded oxide glasses in full accordance with numerous experimental evidences. Recent unsubstantiated speculations trying to ascribe this ability to fully-saturated covalent matrices of chalcogenide glasses like As₂S₃ are analyzed and criticized as misleading and inconclusive.
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
26
PACS 61.43.Fs, 61.80.Ed, 78.20.-e
Metallic nanoparticles (Cu, Ag, Au) in chalcogenide
and oxide glassy matrices: comparative assessment
in terms of chemical bonding
O.I. Shpotyuk1-3*, M.M. Vakiv1, M.V. Shpotyuk5, S.A. Kozyukhin4
1Institute of Materials of SRC “Carat”, 202 Stryjska str., 79031 Lviv, Ukraine
2O.G. Vlokh Institute of Physical Optics, 23, Dragomanov str., 79005 Lviv, Ukraine
3Jan Dlugosz University, 13/15 al. Armii Krajowej, Czestochowa, 42200, Poland
4N.S. Kurnakov Institute of General and Inorganic Chemistry,
31, Leninsky Pr., Moscow, 199991, Russia
5Lviv Polytechnic National University, 12, Bandera str., 79013 Lviv, Ukraine
* The corresponding author e-mail: olehshpotyuk@yahoo.com
Abstract. Principal difference in origin of high-order optical non-linearities caused by
metallic nanoparticles such as Cu, Ag and Au embedded destructively in oxide- and
chalcogenide-type glassy matrices has been analyzed from the viewpoint of semi-
empirical chemical bond approach. The numerical criterion has been introduced to
describe this difference in terms of mean molar bond energies character for chemical
interaction between unfettered components of destructed host glassy matrix and
embedded guest atoms. It has been shown that “soft” covalent-bonded networks of
chalcogenide glasses of As/Ge–S/Se systems differ essentially from glass-forming oxides
like silica by impossibility to accommodate agglomerates of metallic nanoparticles. In
contrast, such nanostructurized entities can be well stabilized in Cu-, Ag- or Au-
embedded oxide glasses in full accordance with numerous experimental evidences.
Recent unsubstantiated speculations trying to ascribe this ability to fully-saturated
covalent matrices of chalcogenide glasses like As2S3 are analyzed and criticized as the
misleading and inconclusive ones.
Keywords: chalcogenide glasses, glass-forming oxides, surface plasmon resonance,
nanoparticle, chemical bond.
Manuscript received 23.11.16; revised version received 20.01.17; accepted for
publication 01.03.17; published online 05.04.17.
1. Introduction
In recent years, the glassy-like composites containing
embedded metallic nanoparticles (MNPs) occupy an
important niche in modern photonics as promising
plasmonic media possessing excellent nonlinear optical
properties (increased high-order non-linearities) [1-7].
Electro-magnetic excitations of conduction electrons in
nanostructurized metallic entities, exemplified by
agglomerates of externally-embedded silver Ag, gold Au
or copper Cu MNPs, result in localized surface plasmon
resonance (LSPR), the phenomenon serving as a basis
for biomedical sensing with controllable effects on NP
size, shape and chemical environment [8]. In this view,
chalcogenide glasses (ChG), e.g. melt-quenched vitreous
compounds of chalcogens (S, Se, Te, but not O) with
some elements from IV-V groups of the Periodic Table
(Ge, As, Sb, Bi, etc.) [9], which possess few orders
higher optical non-linearities as compared with glass-
forming oxides (GFO) such as fused silica SiO2 [1, 2,
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
27
10], attract high attention. Therefore, from a device
standpoint, the chemical-technological approaches
allowing further enhancing these non-linearities in
different glassy-like matrices seem very important.
Nowadays, different types of technologies have
been employed to enhance optical non-linearities in
MNPs-embedded glasses, which include thermal-
electrical and optical poling, controllable nucleation and
crystallization at nano- and microscales, quenching,
laser- and/or electron-driven precipitation of metal ions
combined with further heat treatment, as well as ion-
beam irradiation (ion implantation) [7, 11-15].
Noteworthy, in view of principally different chemistry,
not all of these methods are equally suitable for GFO
and ChG.
In general, the methods allowing formation of
MNPs in a bulk glass can be grouped in physical, when
these additives are directly introduced in a glassy matrix
or previously created MNPs are covered with glassy
layer [16-18]), and chemical, when MNPs are formed
due to in-situ chemical interaction of some precursors
with a glassy matrix [19]. Physical methods related with
direct embedding MNPs, such as ion beam implantation,
are known to be highly destructive to ensure metastable
agglomeration of guest MNPs in the host glassy matrix,
the degree of destruction being strongly dependent on
atomic compactness of the latter [7, 20]. In relatively
dense GFO containing great amount of silica SiO2 [6, 7,
15, 20] or network ChG composed by close packing of
structural polyhedrons interlinked via chalcogen chains
(such as As2S3, As2Se3, As/Ge–S/Se, Ge–As/Sb–S/Se)
[10, 21], the host glassy matrix should be significantly
destroyed to accommodate the embedded MNPs.
Therefore, the agglomeration occurs under tight
chemical interaction between these metallic atoms and
components of the destructed glass, the preferential
character of this interaction defining geometrical
appearance of MNPs (sizes and shapes) and, finally,
effect of optical non-linearities.
Thus, the principal difference between GFO and
ChG should be carefully examined to clarify expected
consequences resulting from embedded MNPs. In this
paper, we try to do this from the viewpoint of chemical
bond approach [22-24], one of the most productive semi-
empirical quantitative route providing valuable insight
on atomistic arrangement in solids, put forward by
Phillips in the earliest 1970s [25].
2. Chemical bonding disproportionality in a glass
Distribution of chemical bonds in a host glassy matrix is
known to be essentially disturbed under destructive
nanostructurization such as ion implantation owing to
nuclear collisions of implanted ions with target atoms,
destruction of bonds and further deionization
transforming metallic (M) ions in neutral atoms [20, 26].
Chemical interaction of embedded M atoms (M = Cu,
Ag, Au) with unfettered atoms in the glassy-like matrix
becomes possible under these conditions resulting in
new bond distribution.
For As-based ChG like stoichiometric glassy g-
As2(S/Se)3, the bond balance is governed by
thermochemical stability/disproportionality between
hetero-to-homonuclear bonding [9]:
2(As–S/Se) ↔ (As–As) + (S/Se–S/Se). (1)
The energetic balance of this reaction (1) is left-
shifted attaining 40 kJ/mol for g-As2S3, as it follows
from comparison of mean molar bond energies
calculated from standard atomization enthalpies of
relevant chemical compounds gathered in Table 1 (such
estimation is appreciated within an error-bar of
±10 kJ/mol). Under non-equilibrium conditions (like
rapid quenching from high temperatures exceeding the
boiling point of As2S3 [9, 27-30]), this reaction can
stretch towards right side, thus meaning a great amount
of “wrong” homonuclear bonds in the As–S alloy (not
typical for stoichiometry of As–S system) and other
structural defects, such as charged miscoordinated atoms
[9]. With transition to g-As2Se3, the energetic balance of
hetero-to-homo-nuclear bonding (1) is only slightly
reduced reaching 35 kJ/mol.
The similar consideration can be validated for Ge-
based ChG like glassy g-GeS/Se2, where hetero-to-
homonuclear bonding disproportionality can be
presented as:
2(Ge–S/Se) ↔ (Ge–Ge) + (S/Se–S/Se). (2)
The energetic balance of this reaction (2) is also
left-shifted with somewhat higher barrier of 65 kJ/mol
for g-GeS2 and nearly the same 40 kJ/mol for g-GeSe2.
The character of chemical bonding
disproportionality is not principally changed in GFO,
where heteronuclear bonds also prevail over the
homonuclear ones. However, energetic balance of
corresponding hetero-to-homonuclear bonding is
strongly enhanced as compared to ChG. Thus, the mean
molar energy of Si-O chemical bond in silica (i.e. g-
SiO2) is more than twice favorable than in ChG
environment being as high as 465 kJ/mol (see Table 1)
[9]. Therefore, the chemical bonding disproportionality
in this GFO defined as
2(Si–O) ↔ (Si–Si) + (O–O). (3)
shifts left towards heteronuclear Si–O bonds,
subsequently reaching 375 kJ/mol in a balance, that is
nearly one order higher as in typical ChG.
This remarkable difference allows wider band-gaps
in GFO, making them optically transparent and colorless
in the visible spectral range. So, it seems reasonable that
this energetically favorable structural arrangement can
be notably disturbed only by high-energy destructive
influences. That is why dielectric GFO like silica g-SiO2
are often distinguished as “hard” glasses, in an obvious
contrast to semiconductor ChG, which are typically
termed as “soft” glasses [31].
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
28
3. Generalized energetic χ-criterion for chemical
bonding in destructed glassy matrices
The behavior of small amounts of metallic additives in
different ChG environment have been remarkably
reviewed in the known monograph by Borisova et al.
[32] near a three decades ago. In full harmony with this
consideration, our preliminary analysis [33, 34] shows
that difference in the dissociation energies of chemical
bonds composing a host glassy matrix for embedded
guest M ions can be parameterized to serve as a
signature for preferential chemical bonding in destructed
host-quest matrix. Let’s generalize this approach to
compare the above chemical bonding consideration in
respect to reactions (1)-(3) attributed to typical GFO and
ChG affected by M ions implantation.
By signing cation-type and anion-type atoms in a
glassy target as K and X, respectively (so that K = Si,
As, Ge and X = O, S, Se, Te), the chemical
disproportionality in such a system under implanted
metallic atoms M (M = Cu, Ag, Au) can be presented by
analogy with above reactions (1)-(3) via similar hetero-
to-homonuclear bonding disproportionality
2(M–X) ↔ (M–M) + (X–X). (4)
The generalized disproportionality under condition of
all chemical interactions possible between existing entities
(destructed bonds of host glassy matrix and implanted guest
M ions) can be defined as sequent bond transformation
resulting with respect to reactions (1)-(4) in
2(K–X) + (M–M) ↔ (K–K) + (X–X) + (M–M) ↔
↔ (K–K) + 2(M–X). (5)
Thereby, new balance of chemical bonding in a
host glassy matrix possessing preferential heteronuclear
(K–X) environment with embedded destructively M
atoms is stabilized in an equilibrium between left and
right sides of the above reaction (5). If energetic barrier
ΔE of his reaction occurs to be positive (right-hand
shifted equilibrium), the implanted M atoms destroy
existing bond distribution in the host matrix by forming
heteronuclear (M–X) bonds at the cost of “wrong”
homonuclear (K–K) ones. Otherwise, the agglomeration
of MNPs occurs owing to prevalence of (M–M)
interaction and renovation of destructed (K–X) bonds.
Thus, we can enter the generalized energetic χ-
criterion describing agglomeration of MNPs embedded
destructively into the host glassy matrix as
χ = 2[M–X] + [K–K] – 2[K–X] – [M–M] =
= 2([M–X] – [K–X]) + ([K–K] – [M–M]), (6)
where notes in square brackets define the mean molar
energy of corresponding covalent chemical bonds. The
negative values of χ-criterion correspond to
agglomeration of MNPs in host glass, while the positive
ones are signatures of preferential interaction between M
atoms and unfettered atoms of destructed glass (K and
X) resulting in a mixed metal-glass matrix.
The mean molar energies of heteronuclear (M-X)
bonds for M atoms (M = Cu, Ag, Au) in GFO and ChG
environment calculated as bond dissociation energies in
diatomic molecules [35] are given in the comparative
diagram in Fig. 1. Under a comparison with Table 1, it is
evident these bond energies are essentially reduced as
those character for Si–O bonds in g-SiO2, while they are
comparable and even slightly greater than dissociation
energies of heteronuclear bonds in ChG. It means that
under ion implantation the destructed Si–O bonds in g-
SiO2 will be renewed, facilitating agglomeration of
“pure” MNPs in a host bulk (provided implantation dose
is sufficient to ensure rather high MNPs excess above
the solubility limit [7, 20, 26]). It is worth to note that, in
respect to the calculated χ-criterion, agglomeration of
Au MNPs in oxide environment has an obvious
preference (χ = –480 kJ/mol) over other metallic
additives.
Hence, the χ-criterion for chemical bonding (6) is
strongly negative for GFO like silica glass g-SiO2
(Fig. 1). However, this is not a case of ChG, where χ-
criterion is nearly one-order smaller as in GFO. This is
clearly revealed for Cu atoms embedded destructively in
environment of As–S, As–Se, Ge–S or Ge–Se chemical
bonds. For Ag and Au atoms in sulphide As–S or Ge–S
bond environment, the χ-criterion becomes negative, but
still does not exceeding a few tens of kJ/mol. Thus, it
means that in all these cases the clustering of MNPs is
principally impossible.
1
Si‐O
2
As‐S
3
As‐Se
4
Ge‐S
5
Ge‐Se
χ
‐c
ri
te
ri
on
, k
J/
m
ol
85
‐100
‐200
‐300
100
‐325
30 50 45
a: M = Cu
0
‐430
100 30
‐100
‐200
‐400
‐45 ‐5 ‐30
b: M = Ag
0
‐300
100 50
‐100
‐200
‐400
‐35
15
‐20
c: M = Au
0
‐300
‐480
Fig. 1. Comparative diagram of χ-criterion (kJ/mol) values for
Cu (a), Ag (b) and Au (c) atoms embedded in Si–O (1), As–
S (2), As–Se (3), Ge–S (4) and Ge–Se (5) chemical bond
environment.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
29
Table 1. Mean molar bond energies E for main glass-forming cations in oxide and chalcogenide environment [9].
Bond Е, kJ/mol Bond Е, kJ/mol Bond Е, kJ/mol Bond Е, kJ/mol
As–As 200 Ge–Ge 185 Si–Si 225 O–O 330*
As–O 335 Ge–O 355 Si–O 465 S–S 280
As–S 260 Ge–S 265 Si–S 310* Se–Se 225
As–Se 230 Ge–Se 225 Si–Se 270* Te–Te 195
As–Te 205 Ge–Te 200 Si–Te 230
Note: * - corrected under bond dissociation energies for diatomic molecules taken from [35].
4. Non-stoichiometry effects
in M-embedded ChG matrices
Noteworthy, the ChG (contrary to GFO) can be
subjected to stretched variation in their chemistry
allowing non-stoichiometric chalcogen and cation-rich
glass-forming alloys [9]. But this specificity does not
change essentially the above energetic consideration
[36]. Indeed, with account of non-stoichiometry, the
generalized disproportionality reaction (5) can be
considered separately for intermetallic (M–M) bonding
in heteronuclear (K–X) and homonuclear (K–K) and (X–
X) environments, the corresponding reactions being as
follows:
2(K–X) + (M–M) ↔ 2(M–X) + (K–K), (7)
2(X–X) + (M–M) ↔ 2(M–X) + (X–X), (8)
2(K–K) + (M–M) ↔ 2(M–K) + (K–K). (9)
The energetic preference of resulting bond balance
in a glass can be estimated by accepting weighting
coefficients η of different bonds possible under a given
structural model:
ηK-X·[2(K–X) + (M–M)] + ηX-X·[2(X–X) + (M–M)] + ηK-
K·[2(K–K) + (M–M)] ↔
↔ ηK-X·[2(M–X) + (K–K)] + ηX-X·[2(M–X) + (X–X)] +
ηK-K·[2(M–K) + (K–K)]. (10)
where left side reflects energetic balance of
agglomerated MNP within renewed host matrix, and
right side corresponds to M atoms interacting with
unfettered atoms of destructed glass.
In real non-stoichiometric ChG media, chemical
interaction between embedded M and cation-type K
atoms can be ignored in view of smaller bond energies
[9], thus resulting in importance of only two first
components in both left and right sides of the above
reaction (10) to calculate the energetic χ-criterion in
non-stoichiometric ChG matrices:
χnst = ηK–X·[2(M–X) + (K–K)] + ηX–X·[2(M–X) + (X–X)] –
– ηK–X·[2(K–X) + (M–M)] – ηX–X·[2(X–X) + (M–M)] =
= ηK–X·[2(M–X) – 2(K–X) + (K–K) – (M–M)] + ηX–
X·[2(M–X) – (X–X) – (M–M)]. (11)
Table 2. Mean molar bond energies E (kJ/mol) of metallic
atoms (M = Cu, Ag, Au) in GFO and ChG environment
[35].
Bond Е,
kJ/mol Bond Е,
kJ/mol Bond Е,
kJ/mol
Cu–Cu 200 Ag–Ag 165 Au–Au 225
Cu–O 290 Ag–O 220 Au–O 225
Cu–S 275 Ag–S 220 Au–S 255
Cu–Se 255 Ag–Se 210 Au–Se 250
Accepting the values of molar bond energies
summarized in Tables 1 and 2 for ChG within the
chemically ordered covalent network model (COCNM)
[9], it can be easily shown that over-stoichiometric
chalcogen atoms only enhances χ-criterion, facilitating
incorporation of M atoms into the glass matrix, while
over-stoichiometric As or Ge has no essential effect on
chemical bonds.
So, destructed bonds in host ChG matrix do not
recover after destruction, being replaced by more
energetically favorable (M–X) bonds. This process
results in extraction of metal chalcogenide phase instead
of “pure” MNPs. Excess K atoms appearing under this
destruction migrate towards surface for further
interaction with environment. Undoubtedly, just this
impurity interaction is responsible for As2O3 extraction
at the surface of g-As2S3 under prolonged γ-irradiation in
ambient conditions [36, 37]. Similar changes occur also
in Ge-based ChG affected by cw laser illumination [38].
5. Experimental evidences on MNPs formation
in glassy substances
The above consideration with energetic χ-criterion for
MNPs clustering in a glass (6) concerns destructed host
glassy matrices, when chemical interaction between
some unfettered atoms of glassy target and embedded M
atoms cannot be neglected. As it occurs in GFO (or other
alternative media with high negative χ-criterions like
those given in diagram in Fig. 1 for M=Cu, Ag, Au in
Si-O bonding environment), ion implantation or other
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
30
destructive technology results in agglomeration of
MNPs, this process being defined by destruction
efficiency of host matrix (like dose and energy of
implanted ions). Typical variants of practical realization
of these nanostructurization technologies can be well
exemplified by research of Stepanov with co-authors [7,
20, 26] showing enhancement of optical non-linearities
in oxide dielectric media due to ion-synthesized MNPs.
However, this is not a case of nanostructurization
under non-disturbed (or partially disturbed) bond
balance in a host glassy matrix, which possibly occurs
under positive values of χ-criterion presented in Fig. 1
for M atoms in ChG-type bonding. The latter can be
illustrated by ChG deposition on MNPs initially formed
at a surface of dielectric substrate, when upper glassy
film play the role of a covering layer ensuring necessary
difference in the refractive index n with MNPs [16-18].
Because of lack of essential disturbances in chemical
interaction within MNPs themselves and neighboring
medium, Kokenyesi with co-authors [16-18] observe, in
fact, the islands of embedded MNPs in homogeneous
ChG environment.
Chemical interactions are also partially suppressed
under condition of photostimulated diffusion of M atoms
(mainly Ag and Cu) into ChG films [39-41], the famous
research launched by Kostishin with co-authors [39]
nearly a half century ago. Light illumination causes local
misbalance of negative-positive electrical charge in the
film due to excitation of chalcogen lone-pair electrons,
resulting in transfer of electrically neutral M atom into
positively-charged M+ ions [40]. These M+ ions diffuse
along sites of chalcogen atoms, thus leaving principal
glass-forming structural units without essential changes,
as it was convincingly proved by Stronski with co-
authors [41] for Ag-photodoped As2S3 films. The M
additives stretch in a host amorphous matrix, being
involved preferentially in coordinative bonding with
chalcogen atoms along their diffusion paths, whereas
normal covalent bonding occurs only near structural
defects [41]. Doubtless, if point getters for guest M+ ions
were stabilized in host ChG film, it could be possible to
create photoexposure-guided agglomerates of MNPs.
Other example concerns the case, when chemical
host-quest interaction can be ignored due to looser
(inhomogeneous) structures of some glassy-like targets.
Such research can be well exemplified by experiments
on Ag-ions implantation in chalcohalide matrices
performed by Liu et al. [42, 43]. It was found that in
56GeS2-24Ga2S3-20KBr glass Ag ions embedded under
implantation with varied doses from 1016 to
2⋅1017 ions/cm2 can be agglomerated presumably in
inner spaces of lower densities, which allow appearance
of relatively large MNPs agglomerates reaching in sizes
even a few hundred nanometers. The enhanced third-
order optical non-linearities in these nanostructurized
chalcohalide glasses were shown to correlate strongly
with ion implantation doses and geometrical sizes of
agglomerated Ag MNPs [42, 43]. Recently [44], it was
shown that similar results could be achieved under Ag
ions implantation in melt-quenched 72GeS2-18Ga2S3-
10CdS glass, the typical sizes of Ag MNPs being ranged
from ∼90 nm (at 1016 ions/cm2 dose) to 300 nm (at
2⋅1017 ions/cm2 dose). This glassy target does not belong
to typical structurally-homogeneous ChG like g-
As2(S/Se)3 possessing glass-forming network with fully
saturated and uniform covalent bonding (for more
details, see [9, 45] and literature therein). Appearance of
large agglomerates of Ag MNPs in this case follows
from principal difference in chemical interaction
between embedded Ag ions and structurally-specific
glass components.
In an obvious contrast to the above argumentation,
we should also consider here the example on MNPs
clustering in ChG media in a denial sense as a result of
misleading speculations of some authors [46-48] trying
to ascribe unique clustering ability to M atoms
embedded destructively in all glassy substances (both
GFO and ChG) despite their chemical nature. Thus,
Kavetskyy with co-authors [46] claimed recently a
principal possibility to form agglomerates of ion-
implanted Cu MNPs in g-As2S3 and g-Ge15.8As21S63.2
like it occurred in silica glass g-SiO2 [15]. They asserted
that Cu MNPs could be gathered in spherical entities of
only 5 to 10 nm in radius, giving essential changes in
optical linear absorption at ∼580…590 nm and response
in nonlinear optical properties observed in Z-scan
measurements. However, even preliminary and very
unscrupulous insight gives an uncontroversial prove on
speculative character of such “conclusions”.
500 550 600 650 700 750
0
10
20
30
40
50
60
70
O
pt
ic
al
tr
an
sm
is
si
on
T
, %
Wavelength λ, nm
2 3 6 4 5 1
Fig. 2. Comparison of optical transmission spectra of As–S
ChG (all the samples are ~1.0 mm in thickness): g-As2S3
before γ-irradiation (1) as compared with that of Fig. 14.1 from
Ref. [48], g-As2S3 before (2) and after Cu+ ion implantation
with 1.5⋅1017 cm–2 dose (3) as compared with that of Fig. 14.7
from Ref. [48]; g-As2S3 prepared, respectively, by quenching
from high-temperature 900 °С (4) or low-temperature 500 °С
state (5) as compared with that of Ref. [30]; S-rich g-As22S78
affected by phase separation caused by long-tern aging (6) as
compared with that of Ref. [52]. The spectral positions of
optical transmission edges were reproduced without measuring
points directly from indicated sources.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 26-33.
doi: https://doi.org/10.15407/spqeo20.01.026
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
31
First, the characteristic band of LSPR for Cu MNPs
in g-As2S3 with the refraction index n ≅ 2.5 was
attributed to ∼580…590 nm domain, which is the
characteristic frequency of LSPR in oxide environment
with much smaller n (below 2.0) [7]. In concomitance
with oxide matrices (such as SiO2, Al2O3, ZnO, etc.) [7,
15, 26], this LSPR band positioned in accordance to
known formula for spherical MNPs [49] should be
expected in ChG with refraction indices n > 2.4 only at
longer wavelengths (more than 620…630 nm), but not at
the shorter ones (∼580…590 nm).
Second, the results of Z-scan patterning (which was
presented as a main evidence for enhanced optical
nonlinearities in [46-48]) were given only for Cu-
implanted ChG affected by laser irradiation at various
intensities, but not compared with parent non-implanted
specimen. So, it was impossible at all to conclude (even
intuitively) on probable origin of this “effect”. As an
example of rational and unbiased consideration on this
issue, we refer to known works of Almeida et al.
[50, 51] on open aperture Z-scan signatures of nonlinear
optical absorption caused by Au MNPs in heavy-metal
oxide glasses of GB type (i.e. GeO2–Bi2O3). All these
evidences were always grounded on reliable comparison
between non-affected (parent) GB glasses and these
glasses affected by embedded Au MNPs (GB-Au). Such
experimental purity including obligatory comparison
with reference specimen (non-affected or parent) was
also a necessary condition for conclusion on third-order
optical non-linearity from ion-implanted Ag MNPs in
the cited Liu’s research [42-44].
Third, it seems doubtful (if any) to adopt
unambiguously that optical transmission spectrum in [46-
48] can be really ascribed to stoichiometric g-As2S3 of
∼1 mm in thickness. For more convincing argumentation
on this issue, different optical transmission spectra for As-
S ChG taken additionally from [30, 52] are compared as
depicted in Fig. 2. As a top of full misunderstanding, it
should be emphasized huge difference of more than
50 nm (!) in the wavelength position of optical
transmission edge for the same g-As2S3 measured before
ion implantation and gamma-irradiation in Ref. [48].
Comparison with ChG prepared in different quenching
regimes [30] testifies that latter is rather appropriate for g-
As2S3, but not spectra depicting short-wave optical
transmittance (500…550 nm) in Ref. [46-48]. Within
careful inspection of As–S system [52], it seems that only
non-stoichiometric S-rich ChG transmit incident light near
∼500 nm, but at obviously higher transparency (as
compared with that of the Fresnel formula [53], the 69%
in optical transmission corresponds to refractive index
n ≅ 2.5). So, their allegation on ion implantation in g-
As2S3 [46-48] is roughly falsified and simply speculative.
It was also strange why implantation in [46-48]
arranged at higher doses (1017 ion/cm2) did not change
optical transmission of implanted ChG giving point-to-
point coincidence with data for initial non-implanted ChG
in the whole spectral range excepting the 580…590 nm
part (see Fig. 2). So, it seems that the authors of [46-48]
deal with inhomogeneous ChG (probably, one of S-
enriched compositions close to g-As2S8, provided ChG of
As–S system was really used), which have been
destructed just preliminary, i.e. before implantation
(maybe due to poor mechanical treatment or invalid
quenching route applied to stabilize ChG), and thus their
claim on full identity between ion implantation in GFO
and ChG is entirely misleading and inconclusive.
6. Conclusions
In summary, we would like to underline the principal
difference in the origin of high-order optical non-
linearities related with metallic nanoparticles embedded
destructively in oxide- and chalcogenide glassy matrices.
The chemical bonding approach is adequately applied to
describe this difference in terms of the mean molar bond
energies typical for interaction between unfettered atoms
of host glassy network and embedded guest atoms (Cu,
Ag, Au). Corresponding energetic barriers of bond
disproportionality for metallic atoms defined as χ-
criterion occur to be principally different in oxide and
chalcogenide environment. These findings are in full
agreement with numerous experiments exploring
destructive and non-destructive mechanisms of
embedding the metallic nanoparticles, but contradict
principally to misleading speculations with unproved
schemes for nanostructurization in ion-implanted
chalcogenide glass networks.
Acknowledgement
The authors acknowledge support from Science and
Technology Center in Ukraine under Pr. No 6174.
Discussions on surface plasmon resonance in noble-
metal media with N. Dmitruk and I. Blonskyy, as well as
helpful comments on optical nonlinearities in glasses
from V. Kadan are kindly acknowledged.
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| id | nasplib_isofts_kiev_ua-123456789-214916 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2026-03-21T19:36:00Z |
| publishDate | 2017 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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| spelling | Shpotyuk, O.I. Vakiv, M.M. Shpotyuk, M.V. Kozyukhin, S.A. 2026-03-03T11:10:15Z 2017 Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding / O.I. Shpotyuk, M.M. Vakiv, M.V. Shpotyuk, S.A. Kozyukhin // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 26-33. — Бібліогр.: 53 назв. — англ. 1560-8034 PACS: 61.43.Fs, 61.80.Ed, 78.20.-e https://nasplib.isofts.kiev.ua/handle/123456789/214916 https://doi.org/10.15407/spqeo20.01.026 Principal difference in origin of high-order optical non-linearities caused by metallic nanoparticles such as Cu, Ag, and Au embedded destructively in oxide- and chalcogenide-type glassy matrices has been analyzed from the viewpoint of semiempirical chemical bond approach. The numerical criterion has been introduced to describe this difference in terms of the mean molar bond energies character for chemical interaction between unfettered components of the destructed host glassy matrix and embedded guest atoms. It has been shown that “soft” covalent-bonded networks of chalcogenide glasses of As/Ge–S/Se systems differ essentially from glass-forming oxides like silica by the impossibility to accommodate agglomerates of metallic nanoparticles. In contrast, such nanostructured entities can be well stabilized in Cu-, Ag-, or Au- embedded oxide glasses in full accordance with numerous experimental evidences. Recent unsubstantiated speculations trying to ascribe this ability to fully-saturated covalent matrices of chalcogenide glasses like As₂S₃ are analyzed and criticized as misleading and inconclusive. The authors acknowledge support from the Science and Technology Center in Ukraine under Pr. No 6174. Discussions on surface plasmon resonance in noblemetal media with N. Dmitruk and I. Blonskyy, as well as helpful comments on optical nonlinearities in glasses from V. Kadan, are kindly acknowledged. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding Article published earlier |
| spellingShingle | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding Shpotyuk, O.I. Vakiv, M.M. Shpotyuk, M.V. Kozyukhin, S.A. |
| title | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| title_full | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| title_fullStr | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| title_full_unstemmed | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| title_short | Metallic nanoparticles (Cu, Ag, Au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| title_sort | metallic nanoparticles (cu, ag, au) in chalcogenide and oxide glassy matrices: comparative assessment in terms of chemical bonding |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/214916 |
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