Non-Resonant Enhanced Raman

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NON-RESONANT ENHANCED RAMAN

SCATTERING OF LIGHT BY ZnO NANOCRYSTALS
NEAR SILVER AND GOLD...
Conference Paper · June 2013

DOI: 10.1142/9789814460187_0017
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ACS Nano
Non-resonant surface enhanced Raman scattering of ZnO

quantum dots
with Au and Ag nanoparticles
Journal: ACS Nano
Manuscript ID: nn-2013-00307a.R1
Manuscript Type: Article
Date Submitted by the Author: n/a
Complete List of Authors: Rumyantseva, Anna; Université de Technologie de Troyes,

Kostcheev, Sergei; Université de Technologie de Troyes,
Adam, Pierre-Michel; Université de Technologie de Troyes,
Gaponenko, Sergey; Stepanov Institute of Physics,
Vaschenko, Svetlana; Stepanov Institute of Physics,
Kulakovich, Olga; Stepanov Institute of Physics,
Ramanenka, Andrey; Belarusian State University, Physics
Guzatov, Dmitry; Yanka Kupala Grodno State University,
Korbutyak, Dmytro; V.Ye. Lashkaryov Institute of Semiconductor Physics,
Nat. Acad. Sci. of Ukraine,
Dzhagan, Volodymyr; V.Ye. Lashkaryov Institute of Semiconductor Physics,
Nat. Acad. Sci. of Ukraine,
Stroyuk, Alexander; Pysarzhevski Institute of Physical Chemistry,
Photochemistry Department
Shvalagin, Vitaliy; Pysarzhevski Institute of Physical Chemistry of Ukr. Nat.
Acad. Sci. of Ukraine, Photochemistry Department
ACS Paragon Plus Environment

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1
2 Non-resonant surface enhanced Raman scattering of ZnO quantum dots
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with Au and Ag nanoparticles
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6 Anna Rumyantseva, Sergey Kostcheev, and Pierre-Michel Adam
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8 Université de Technologie de Troyes, 12 Rue Marie-Curie BP 2060, 10010 Troyes Cedex,
9 France
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11 Sergey Gaponenko, Svetlana Vaschenko, Olga Kulakovich
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13 B.I.Stepanov Insitute of Physics, National Academy of Sciences of Belarus, Minsk 220072
14 Belarus
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Andrey Ramanenka
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Belarussian State University, 4 Nezavisimosti Ave., Minsk 220030 Belarus
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21 Dmitry Guzatov
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23 Yanka Kupala State Grodno University, Grodno, 220023, Belarus
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25 Dmytro Korbutyak, Volodymyr Dzhagan
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27 V.Ye. Lashkaryov Institute of Semiconductor Physics, Nat. Acad. Sci. of Ukraine, Pr. Nauky 45,
28 03028 Kyiv, Ukraine
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30 Oleksandr Stroyuk, Vitaly Shvalagin
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32 L.V. Pysarzhevsky Institute of Physical Chemistry, Nat. Acad. Sci. of Ukraine, Pr. Nauky 31,
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34 03028 Kyiv, Ukraine
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52 Abstract
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54 Pronounced 104-fold enhancement of Raman scattering has been obtained for ZnO nanocrystals
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56 on substrates coated with 50 nm Ag nanoparticles under non-resonant excitation with a
57 commercial red-emitting laser. This makes feasible beyond 10-18 mole detection of ZnO
58 nanocrystals with a commercial setup using 0.1 mW continuous wave laser and can be
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1
2 purposefully used in analytical applications where conjugated nanocrystals serve as Raman
3 markers. For Au-coated surfaces the enhancement is much lower and the heating effect in the
4 course of Raman experiments are pronounced.
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11 Plasmonic enhancement of fluorescence and Raman scattering has been extensively studied for
12 molecular systems during last decades [1-3] and is considered as important driving phenomenon
13 in nanoscience towards ultrasensitive analysis in medicine, forensic, environmental, and cultural
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heritage research. It occurs owing to local incident field enhancement and local density of states
15
16 enhancement promoted by generation of localized plasmons and/or surface Plasmon-polaritons
17 at nanotextured metal-dielectric interfaces. For surface enhanced Raman scattering (SERS)
18 extreme enhancement factors more than 1010 are reported allowing for single molecules
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20
detection. For fluorescence, however, quenching occurs along with enhancement mechanism and
21 the overall fluorescence yield rises up typically by an order of magnitude provided an optimal
22 spacing of 5 to 10 nm from metal is maintained to prevent non-radiative relaxation of electron
23 excited states. For semiconductor nanocrystals (quantum dots) plasmonic enhancement of
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25 photoluminescence is well established for a decade [4-6]. However, plasmonic enhancement of
26 Raman scattering for quantum dots has not been extensively examined to date. Surprisingly
27 enough, since the pioneering paper in 1993 by Honma et al. [7] only a few reports have been
28
published on the matter. These authors reported approximately 102-fold enhancement of Raman
29
30 signal from CdS colloidal nanocrystals mixed with silver colloidal nanoparticles upon resonant
31 excitation of CdS nanocrystals by a blue-green Ar laser (467 nm wavelength). Milekhin et al [8]
32 observed 700-fold increase in Raman intensity for a Langmuir—Blodgett film containing CdS
33
34 nanocrystals covered with Ag clusters. The excitation wavelengths in the blue-green range
35 corresponded to resonant absorption of CdS dots overlapping with the extinction maximum of
36 silver clusters. Increase of Raman scattering for both resonant and non-resonant excitation was
37
observed for CdSe dots deposited on gold patterned surfaces though enhancement factors are not
38
39 reported [9,10]. Raman scattering enhancement for quantum dots goes well far beyond basic
40 research since Raman labels have been proposed to substitute fluorescent labels in high-
41 sensitive biomolecule detection in medicine, e.g. identification of onco-sensitive markers in
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43
bioliquids [11]. Sharpness and specificity of Raman spectra versus fluorescence emission spectra
44 promise better recognition and enable multiplexing. Recent successful implementation of ZnS
45 quantum dot Raman labeling of proteins [12] should be noted. In the context of the growing
46 interest in various optical applications of ZnO [13,14], SERS for ZnO nanocrystals became the
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48 subject of active experimental studies. Shah et al. reported noticeable enhancement of Raman
49 scattering from ZnO core nanocrystals covered with a silver nanoshell [15]. The excitation
50 source applied was a 325 nm He-Cd laser to enable resonant ZnO excitation. Similar approach to
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52
ZnO/Au synthesis with the same type of excitation source yielded two- and three-fold increase in
53 Raman efficacy only [16,17]. Recently Milekhin et al. demonstrated 103-fold enhancement of
54 Raman scattering for surface optical phonon modes with ZnO nanocrystals in Langmuir—
55 Blodgett films covered with silver clusters by vacuum deposition [18]. However, since
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57 nanocrystals in films can hardly be applied to biomolecule labeling, these findings are to be
58 extended towards SERS implementation and analysis for colloidal ZnO nanocrystals.
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1
2 In this paper, we report on substantial enhancement of non-resonant scattering for
3 colloidal ZnO nanocrystals adsorbed on a metal films consisting of Ag and Au nanopartilces
4 obtained with the red (632 nm) laser source which is favorable in terms of minor intrinsic
5
6 photoluminescence excitation in biospectroscopy when quantum dots are considered as
7 promising Raman markers.
8
9
10 Results and discussion
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12 Nanocrystals and substrates. Since the ZnO nanocrystal size (4.5 nm) is comparable with the
13
Bohr exciton diameter, quantum size effect arises manifesting in a pronounced shift of
14
15
absorption onset towards higher photon energies, i.e. shorter wavelengths as compared to the
16 band gap energy of the bulk ZnO in accordance with the data reported in [19,20]. This is shown
17 in Fig. 1 in the optical density spectrum, D = - lg(I/I0) with I (I0) being transmitted (incident)
18 light intensity,
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40 Fig. 1. (Color online) Optical density spectrum of ZnO nanocrystals in ethanol solution in a 2
41 mm thick cell. The inset shows a portion of spectrum in narrow range.
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43 An example of typical electron microscope image along with the optical density spectrum
44
of a Ag-covered glass substrate is given in Fig. 2. Silver nanoparticles are mostly nearly
45
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spherical and have the average diameter approx. 50 nm while a few of them being rod-shaped.
47 The optical density spectrum features typical extinction maximum near 400 nm with a noticeable
48 optical density in the red edge corresponding to the laser wavelength (632 nm) used in Raman
49 measurements. This red extinction band results either from a small portion of bigger
50 nanoparticles or from nanoparticle aggregates. A shoulder near 400 nm can be tentatively
51 attributed to a quadrupolar mode.
52 The average diameter of Au nanoparticles was approx. 15 nm as can be seen in Fig. 3.
53 The optical density spectrum of Au-coated glass substrate shows wide extinction spectrum with
54
the maximum close to the laser wavelength applied (632 nm).
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39 Fig. 2. Electron microscope image and optical density spectrum
40 of a glass substrate with deposited silver nanoparticles
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23 Fig. 3. Electron microscope image and optical density spectrum
24 of a glass substrate with deposited gold nanoparticles.
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27 SERS with Ag substrates. At the quantities and concentration of ZnO nanocrystals used in the
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experiments, no detection of Raman lines is possible for references samples without silver or
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30 gold predeposited on glass substrates (Fig. 4, curves “ZnO on glass”).
31 In case of silver substrates, Raman signal is enhanced by at least 104 times as can be seen
32 from Fig. 4 (curve denoted as “ZnO on Ag”). Remarkably that owing to strong enhancement of
33 Raman scattering, silver coated samples showed high intensity with less than 0.1 mW laser
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power and just 2-5 s acquisition times. The estimated quantity of ZnO involved in the data
36 acquisition is approx. 0.1 fM. Taking into account the short acquisition times (5 s) and the low
37 laser power applied (0.08 mW) one can see that the detection limit readily goes down to below
38 0.001 femto-moles for typical commercial Raman microscopes (supposing higher available
39 power and/or longer acquisition times).
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1
2 Fig. 4. (Color online) Raman spectrum of ZnO nanocrystals on a silver coated glass substrate
3 (ZnO on Ag), and the reference spectra for ZnO nanocrystals on silver-free substrate (ZnO on
4 glass) and for silver substrate without ZnO (Ag only).
5
6 Raman spectrum contains a peak at 570 cm-1, well pronounced peak at 815 cm-1, and
7 additional less pronounced peak at approx. 676 cm-1. The dominating line at 570 cm-1 is assigned
8
to longitudinal optical (LO) phonons. Among ten types of optical phonon modes inherent to
9
10
wurtzite crystals [21,22] only two can be observed in the backscattering geometry employed in
11 our setup. These are E2-high- (437—444 cm-1) and A1-LO- (574—579 cm-1) modes [23]. The
12 former typically dominates in Raman spectra of ZnO powders whereas the latter is the most
13 pronounced mode in thin ZnO films. In our case a low-energy shift of the mode by a few cm-1
14 occurs.
15 There are a number of reasons that may cause the observed shift: (i) continuous down-
16 ward shift up to more than 10 cm-1 due presence of oxygen vacancies in ZnO lattice [24,25];
17 (ii) manifestation of interface modes at about 550 cm-1 [26] which are not resolved but result in
18
an apparent left-hand asymmetry of the band in Fig. 4 and shift of its maximum; (iii) heating of
19
20
nanocrystals by laser light [27] resulting in decrease in vibrational frequency because of crystal
21 lattice expansion. Due to flat phonon dispersion near Brilluoin zone center, the effect of phonon
22 confinement is negligible for 4.5 nm large ZnO NCs [28,29].
23 Contribution from possible heating in course of illumination during Raman signal
24 acquisition can be evaluated by varying light intensity applied in the experiments. However,
25 varying intensity within more than 3 orders of the magnitude did not result in any shift of the
26 570 cm-1 line (Fig. 5). Therefore low-energy shift of the A1-LO-mode in the Raman spectrum
27 cannot be related to heating and should be attributed to presence of oxygen vacancies in ZnO
28
lattice and/or to manifestation of surface modes. The latter interpretation is in agreement with the
29
30 recent observation of dominating plasmonic enhancement of surface modes in ZnO nanocrystals
31 [30].
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52 Fig. 5. (Color online) Raman spectra of ZnO nanocrystals on top of silver substrate
53 for various intensity of incident light. I0 corresponds to 200 kW/cm2 approx.
54
55 The pronounced band at 815 cm-1 can be treated as manifestation of surface enhanced
56 Raman scattering from oxygen complexes on silver surface. This assignment has been proposed
57 by several groups ([30,31] and Refs. therein). The band is assigned to the O-O stretching
58 vibration of molecularly adsorbed oxygen species. Notably, in our experiments the band does
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60
1
2 manifest itself only in presence of ZnO nanocrystals solution deposited on top of the Ag coated
3 substrates. On a ZnO free portion of Ag coated substrates no signature of this band can be
4 detected (Fig. 4, curve labeled “Ag only”). Therefore zinc oxide nanoparticles are supposed to
5 promote oxygen adsorption on silver surface.
6 Possible rationale can be as following. Being the n-type semiconductor, when exposed to
7 ambient air ZnO nanocrystals may adsorb oxygen from air. Oxygen molecules can serve as
8
acceptors to semiconductor and in case of excessive amount of “free” electrons in nanocrystals
9
10 can form traps for them. Thus a negatively charged surface layer develops. Molecules O2− can
11 leave the surface only if they lose an electron. Therefore, in our experiments the oxygen groups
12 localized at ZnO surface exhibit plasmonically enhanced Raman scattering.
13
14
SERS with Au substrates. Surface enhanced Raman scattering has been also readily observed
15
16
upon deposition of ZnO nanocrystals on Au coated glass substrates. The A1-LO-mode remains to
17 be pronounced and in many cases it is the only detectable line within the range of 200…2000
18 cm-1 (Fig. 6, curve denoted as “ZnO on Au”). In many cases pronounced wide bands near 1300
19 and 1600 cm-1 were also detected These bands were found to present in the reference samples
20 without ZnO nanocrystals deposited. These bands are assigned to the underneath polyelectrolyte
21 layer which shows (possibly plasmonically enhanced) Raman scattering owing to finite
22 transmission of colloidal Au film. The observed peaks coincide with so-called В- and G-bands of
23 amorphous carbon [32] which in turn may develop in course of undesirable pyrolisis of
24
polyelectrolyte during laser light illumination. This looks plausible provided the light intensity in
25
26
experiments with Au substrates was typically at least 10 times higher than in case of silver
27 substrates.
28 Enhancement factors are roughly estimated to be at least 100 times. More accurate
29
30
estimate is hard to be done since the Raman line from ZnO deposited on an Au-free substrate is
31 not detectable for the amount of ZnO nanocrystals used (Fig. 6, ZnO on a substrate without Au).
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55 Fig. 6. Raman spectra of ZnO nanocrystals on a Au covered
56 substrate along with reference signals from ZnO nanocrystals on Au free
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substrate and from Au coated substrate without ZnO nanocrystals
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1
2
3
4 The dominating A1-LO-line in case of ZnO nanocrystals exhibits low-energy shift to approx.
5 553 cm-1 vs 570 cm-1 as has been detected in case of Ag-coated substrates. Measurements for
6
various intensities of incident light have shown unambiguously that this additional shift results
7
8 from laser induced heating of ZnO nanocrystals. Since photon wavelength corresponds to the
9 transparency spectral range of ZnO (see Fig. 1), nanocrystals cannot be heated by the laser light
10 directly. Therefore it is the presence of light absorbing Au substrate which causes heating of
11
12
nanocrystals. Note that enhanced heating of Au nanoparticles by laser radiation is well known
13 and has gained wide interest in the context of cancer laser therapy by hyperthermia
14 (photothermal cancer therapy) [33]. Monotonic long-wave shift of A1-LO-line with rising light
15 intensity is apparent in Fig. 7 (curves 2-5 and the inset). In these measurements, the acquisition
16
17 time has been modified inversely proportional to light intensity to keep the total amount of
18 absorbed energy constant. The sample area has not been subjected to any illumination between
19 Raman signal acquisition runs. The intensity was changed non-monotonically to exclude
20
possible heat acquisition or other memory-like effects. The results presented in Fig. 7 were
21
22 reproducible for many spots on the same sample.
23
24
25
26
27 ZnO nanocrystals
28 35000 560
on Au substrate
-1
29 555
cm
30
30000 556
31 550
32 0.0 0.5 1.0
33 Power (a.u.)
Intensity (counts)
25000 560
34
35 50% 4 s
36 20000 5 553
37 25% 8 s
38 4
562 100% 2 s
39 15000
40 2
41 10% 20 s
42 10000 3
43 10% 20 s
44 1
45 5000
46 300 400 500 600 700 800 900 1000
47 -1
Raman shift (cm )
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50 Fig. 7. Raman spectra of ZnO nanocrystals on a Au-coated glass substrate for various light
51 intensity indicated in per cent. 100% power corresponds corresponds to 200 kW/cm2 approx.
52 Numbering of curves from 1 to 5 corresponds to the order of experimental runs. Spectra
53 aligned vertically for clarity. The inset shows peak position versus laser power.
54
55 Similar results indicating heating-induced shift of Raman lines for ZnO nanocrystals upon
56
57 laser illumination without metal substrates but under resonant, strongly absorbed by ZnO
58 nanocrystals UV-light have been reported earlier [27]. Based on those results, the estimated
59 temperature to cause the observed shift exceeds 700oC.
60
1
2 An unexpected effect of “memory” or pre-annealing has been observed systematically for
3 ZnO nanocrystals adsorbed on Au-coated substrates. The enhanced Raman signal can only be
4 detected after at least a few second exposure to the laser light (632 nm wavelength, 8 mW
5
6 continuous power, 1.5 µm spot diameter). This is demonstrated by comparison of curve 1 with
7 curve 3 in Fig. 7. Both spectra are recorded with the same laser intensity and acquisition (i.e.
8 illumination) time but curve 3 was recorded after curve 2, i.e. after 2 s exposure of the same spot
9
to the full laser power. We suppose that heating in course of the above pre-illumination at full
10
11 power results in removal of the residual solvent and acetate-ion groups promoting closer
12 proximity of ZnO nanocrystals to Au nanoparticles which is necessary for efficient Raman
13 scattering enhancement. The effect is not observed in case of silver since there is no detectable
14
15 heating for silver-coated substrates owing to both different size and thermal properties of silver
16 nanoparticles versus gold ones (thermal capacity of gold is twice lower than for silver) as well as
17 to lower laser intensities applied in measurements with Ag-coated substrates. The high Raman
18 signals with lower laser intensities in case of Ag-coated substrates became possible owing to
19
20 stronger Raman scattering enhancement.
21
22 Theory. Raman scattering enhancement factor, FRS for an elementary probe dipole located at
23
point r in the vicinity of a metal nanobody upon irradiation with light of intensity I 0 and
24
25 frequency ω can be calculated in terms of the three contributing factors, namely (i) incident field
26 enhancement factor
27
28
29 GI (ω , r ) = I (ω , r ) / I 0 (ω ) , (1)
30
31 (ii) local photon density of states enhancement factor with respect to vacuum DOS D0 (ω ′)
32
33
34 GLDOS (ω ′, r ) = D (ω ′, r ) / D0 (ω ′) , (2)
35
36 and (iii) Gersten—Nitzan factor G (ω , r ) which accounts for the contribution of field reflected
37
38 from a nanobody to polarizability of a probe dipole at small distances (see Refs [1,3,34,35,36]
39 for detail). Therefore, the overall enhancement factor can be written as
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41 FRS (ω , ω ′, r ) = GI (ω , r ) GLDOS (ω ′, r ) G (ω , r ) . (3)
42
43
44 Notably, every contributing term depends on orientation of a probe dipole with respect to
45 nanobody and incident field polarization as well as on nanobody’s size and shape. To provide a
46 reasonable simplification of this originally rather complicated problem we restrict ourselves to a
47
48
single spherical silver nanoparticle and a nanocrystal whose dipole moment orientation is normal
49 to the silver nanoparticle surface. Silver was taken for modeling since superior enhancement up
50 to or even more than 104-fold looks rather challenging provided the laser wavelength is well far
51 from the main extinction maximum. It is reasonable to consider feasibility of these high
52
53 enhancement values within the framework of the current SERS theory [35,36]. In calculations,
54 the ZnO nanocrystal polarizability is taken to be 20 nm3 in accordance with [37].
55
56 Calculations were made for an Ag spherical particle, incident field polarization, a
57 quantum dot position and its dipole moment orientation as shown in the insert in Fig. 8. This
58
59 displacement offers higher possible enhancement factor. Noteworthy, the theory deals with fixed
60
1
2 optimal displacement/orientation of incident light polarization, dipole moment of a quantum dot
3 and an axis connecting semiconductor and silver nanoparticles centers. It cannot precisely
4 reproduce the experimental situation with random orientations and spacing as well as probable
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6 two-particle, three-particle and higher metal clusters formation.
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31 Fig. 8. Calculated Raman scattering enhancement factor for a nanocrystal located near a
32 spherical silver nanoparticle for nanoparticle diameter ranging from 30 to 60 nm.
33
34 From Fig. 8 one can see that in the model calculations the enhancement factors about 104 can
35 be reasonably understood with enhancement factor exhibiting steady growth with nanoparticle
36
37 size. The latter is important for development of long-wave extinction since it is the noticeable
38 extinction value at the laser wavelength which is the primary prerequisite for observation of
39 every plasmonic enhancement phenomenon in secondary emission, i.e. both in spontaneous
40 emission and in scattering of light. In real experiments, size, orientation and shape distributions
41
42 as well as random distances of nanocrystals from metal nanoparticles can result in lower
43 enhancement factor whereas probable formation of binary, ternary and higher silver nanoparticle
44 cluster can lead to higher enhancement factors.
45
46 In conclusion, the pronounced enhancement of non-resonant Raman scattering for ZnO
47
48 nanocrystals adsorbed on surfaces formed by silver and gold colloidal nanoparticles was
49 observed and examined. The effect was found for the ZnO longitudinal optical phonon line (560-
50 570 cm-1) with a red laser (632 nm), the photon energy of a laser being well below the ZnO
51
absorption onset (350 nm). The enhancement for silver substrates measures up to 104 times as
52
53 estimated for an overall harvested light from 1.5 µm spots. The estimated ZnO detection limit is
54 about 10-18 mole. The enhancement for gold substrates is about 102 times. In the case of silver
55 substrates a pronounced additional line has been detected (815 cm-1) which is assigned to oxygen
56
57
groups adsorbed at ZnO surface from air. The results obtained are valuable for application of
58 quantum dot bioconjugates in ultrasensitive detection of biomolecules with quantum dots being
59 Raman markers.
60
1
2 Methods
3
4 ZnO nanocrystals synthesis. Colloidal ZnO nanocrystals in ethanol have been synthesized by
5 hydrolysis of zinc acetate (reagent grade) with sodium hydroxide (pure) at 0 °C as has been
6 described recently in detail [19]. After the synthesis colloidal ZnO solution was kept at 55-60 °C
7 for 2 h to promote ZnO particles crystallization. The molar zinc oxide concentration in solution
8 was 0.01 M corresponding to about 10-5 M in terms of nanocrystal concentration. The average
9
size of ZnO nanocrystals was approx. 4.5 nm according to measurements by dynamic light
10
11
scattering and estimations based on the well-documented dependences between the absorption
12 onset position and the size of nanocrystals.
13 Ag and Au substrates. To make SERS-active substrates, glass substrates of 1×2 cm2 in size
14 were cleaned by means of ultrasonic treatment in isopropanol and then kept in a mixture of
15 H2O−H2O2−NH3 (1:1:1) at 70°C for 15 min. After washing in water, substrates were covered
16
17 with a polycation layer (PDADMAC, 1 g/L in 0.5 M NaCl) during 20 min to develop a positive
18 charge on a glass surface. Silver and gold nanoparticles were synthesized by citrate reduction
19 technique of AgNO3 [38] and HAuCl4 [5], respectively, so metal particles were negatively
20
charged. Silver nanoparticles were nearly spherical and have the average diameter approx. 50 nm
21
22 with only a few of them being rod-shaped. The average diameter of Au nanoparticles was
23 approx. 15 nm. Metal nanoparticles were deposited on PDADMAC-modified substrates by
24 dipping of half of a substrate surface in Ag (Au) sol for 24 h. The metal-free remaining portion
25
26
of the substrate served as a reference sample.
27 Samples characterization. The optical extinction of substrates, films and solutions have been
28 characterized by optical density spectra, D = - lg(I/I0) with I (I0) being transmitted (incident)
29
30
light intensity, using a Cary-500 spectrophotometer (Varian, USA). Electron microscopy has
31 been performed using a Zeiss Geminy instrument.
32 Raman spectroscopy measurements. A 1 µl portion of 0.01 M solution of ZnO nanocrystals
33 were dropped on every substrate and dried during at least 1 hr. The portion of solution spread
34
over a few mm2 on a substrate surface. The reference samples have been prepared in a similar
35
36 way using a portion of glass substrate covered with a polyelectrolyte layer but with neither silver
37 nor gold deposited on top. To ensure stability of analyte and to check possible side effects,
38 experiments were taken from multiple spots on a surface and have been repeated several times
39 during the period of 2 weeks. Raman spectroscopy studies have been made using a Jobin-Yvon
40 Labram Raman microscope with a He-Ne laser source (emission wavelength is 632.8 nm), with
41 the full laser power 8.8 mW and a number of attenuating filters used to adjust light power to
42 lower values. The measurements were performed in reflection confocal geometry with a 50x-
43 objective for sample illumination and the scattered light harvesting. The light spot size at the
44
sample surface has been 1.5 µm approx. The typical acquisition times were in the range from 2
45
46 to 50 s. All measurements were done with averaging over at least 5 spectral sets. Remarkably,
47 the data reported in the paper were well reproducible in every case.
48
49
50 Acknowledgements. Financial support of NanoMat (www.nanomat.eu) by the “Ministère de
51 l’enseignement supérieur et de la recherche,” the “Conseil régional Champagne-Ardenne,” the
52
“Fonds Européen de Développement Régional (FEDER) fund,” and the “Conseil général de
53
54 l’Aube” is acknowledged. The has been also supported by the Republican Basic Research
55 Foundation of Belarus (Bealrus--Ukraine joint project), Fund for Fundamental Research of
56 Ukraine (project no. F40.2/068, F41, 1/017, F40.3/040), Alexander von Humboldt Foundation
57
58
(V. Dzhagan). Additionally acknowledged is UTT visiting professor grant (S. Gaponenko) as
59
60
1
2 well as Belarus National Schiolarship Programme of the World Federation of Scientists
3 (A. Ramanenka).
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NON-RESONANT ENHANCED RAMAN

Conference Paper · June 2013

Pierre-Michel Adam Olga Kulakovich

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Andrei A Ramanenka Volodymyr Dzhagan

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Non-resonant surface enhanced Raman scattering of ZnO

Journal: ACS Nano

Manuscript ID: nn-2013-00307a.R1

Manuscript Type: Article

Date Submitted by the Author: n/a

Complete List of Authors: Rumyantseva, Anna; Université de Technologie de Troyes,

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