Applied Surface Science 364 (2016) 660–669

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Contribution of oligomer/carbon dots hybrid semiconductor

nanoribbon to surface-enhanced Raman scattering property
Guiyang Zhang a,1 , Lin Hu b,∗,1 , Kerong Zhu c,1 , Manqing Yan a,1 , Jian Liu a,1 ,
Jiaxiang Yang a,1 , Hong Bi a,∗,1
a
College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230601, China
b
High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei, 230031, China
c
Department of Physics, Anhui University, Hefei, 230601, China

a r t i c l e i n f o a b s t r a c t

Article history: The hybrid Ag-(PS-PSS)/C-dots nanobelts (NBs) have been prepared by decorating Ag nanoparticles (NPs)
Received 23 September 2015 on surface of the ultra-long, semiconducting (PS-PSS)/C-dots nanoribbons (NRs) via an electroless plating
Received in revised form 1 December 2015 method. The as-prepared Ag-(PS-PSS)/C-dots NB has been demonstrated to be an excellent substrate for
Accepted 28 December 2015
surface-enhanced Raman scattering (SERS) with a detection limit of 10−14 M and an enhancement factor of
Available online 30 December 2015
3.35 × 108 while using rhodamine 6G as probe molecules. Moreover, we have investigated the application
of Ag-(PS-PSS)/C-dots NBs as SERS substrate for detection of coumarins. Further, the Ag-(PS-PSS)/C-dots
Keywords:
NB could be used as a sacrificial template to form a novel kind of hollow porous Ag nanotubes (NTs) by
Semiconductor
Carbon dots
simply removing the inner NR in tetrahydrofuran. However, the obtained Ag NTs show a weaker SERS
Nanostructure effect compared to that of the Ag-(PS-PSS)/C-dots NBs, which indicates that the inner organic/C-dots NR
Surface-enhanced plays an essential role in SERS property of the Ag-(PS-PSS)/C-dots NBs. Here the organic (PS-PSS)/C-dots
Raman scattering (SERS) NR not only acts as a dielectric support for Ag NPs to reduce the surface plasmon damping at the Ag-NR
Rhodamine 6G interface due to the high electrical conductivity but also their large surface area are favorable for creating
more “hot-spots”. In addition, the embedded sp2 -hybridized C-dots in NR can adsorb more aromatic R6G
molecules via ␲–␲ interaction, which also drives R6G molecules approaching to the “hot-spots”, thus
enhancing the SERS signals. Based on our results, it is believed that the employment of semiconducting
organic (PS-PSS)/C-dots ribbon-like structures to fabricate sensitive SERS substrates is an interesting new
approach.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction field (EM) enhancement and chemical effect are responsible for
the SERS activity [4,5]. The former is associated with the local-
In recent years, there is renewed interest in both the funda- ized surface plasmon resonances (SPR) occurring at the surfaces of
mentals and applications of surface-enhanced Raman scattering rough metal substrates, which leads to more intense Raman scat-
(SERS) although it was discovered several decades ago [1]. SERS tering from molecules near or adsorbed onto the metal surface, and
offers a tremendous enhancement of the intensity of the vibra- the latter involves specific interactions between analyte molecules
tional signals over 10 orders of magnitude, which has opened a and the metal surface, including the direct charge transfer or indi-
new avenue for conventional Raman spectroscopy and made it rect electron-hole pair excitation processes [6,7]. A wide range of
a very useful tool for chemical and biomolecular detection [2,3]. strategies, particularly new concepts on design of SERS substrates
Typically, noble metals, particularly such as gold (Au) and silver have been developed by use of assembled or aligned nanowire
(Ag), have shown excellent SERS sensitivity and thus been called (NW) arrays [8,9], or high-quality 2D crystals decorated with Au
SERS-active materials. It is widely accepted that electromagnetic nanorods [10] for enhancement of the SERS property. New tech-
niques for nanofabrication, the design of substrates that maximize
the EM enhancement, and the discovery of single-molecule SERS
are driving the resurgence of SERS studies [1,11].
∗ Corresponding authors. Tel./fax: +86 65591485.
Among all of the SERS-active substrates, Ag shows a superior
E-mail addresses: hulingg@mail.ustc.edu.cn (L. Hu), bihong@ahu.edu.cn (H. Bi).
1
Electronic Supplementary Information (ESI) available: See DOI:
SERS performance and various Ag nanostructures with the uni-
10.1039/b000000x/. form and highly reproducible SERS-active properties have been

http://dx.doi.org/10.1016/j.apsusc.2015.12.214
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669 661

Fig. 1. Scheme of the fabrication process of Ag-(PS-PSS)/C-dots NBs and hollow porous Ag NTs for SERS.

obtained, such as Ag nanoparticles (NPs) array [12], Ag NWs [13], EF of 2.5 × 108 for detecting rhodamine 6G (R6G). [21] Nevertheless,
Ag nanorods array [14], hierarchical peony-like Ag microflowers the EFs of aforementioned Ag NPs or alternative nanostructures,
[15], Ag nanoplates [16] or hexagonal nanoplates embedded in Ag/polymer nanocomposites and Ag-graphene nanosheets are far
the alumina gel-like porous matrix [17], and “flower-like” Ag NPs away from the ideal theoretical EF value of 1014 –1015 [25].
[18]. More experiments have proven that the extremely high SERS To date, the main challenge is how to easily prepare SERS-active
enhancement factors (EFs) and single-molecule sensitivity come substrates with that can provide great detection sensitivity. In our
from the compact, non-fractal Ag particle cluster, dimer or larger previous work, a kind of ultra-long and semiconducting nanorib-
because the EM field in the gap region of them can be drastically bons (NRs) have been synthesized by C-dots induced self-assembly
amplified [3,19]. It is also demonstrated that the EFs of multiparticle of oligomers of styrene (St) and sodium 4-styrenesulfonate (NaSS)
aggregates for Ag would be several orders of magnitude higher than and thus named as (PS-PSS)/C-dots NRs [32]. Here we demonstrate
individual NPs due to the collective SPRs with interparticle plas- that the hybrid Ag-(PS-PSS)/C-dots nanobelts (NBs) can be pre-
mon coupling [19,20]. The enhancement can be further enlarged pared by decorating (PS-PSS)/C-dots NRs surface with Ag NPs via a
by constructing NPs very close to each other since the EM enhance- facile electroless plating method as illustrated in Fig. 1. As a con-
ment is highly sensitive to the shape of NPs and the interparticle trol, the hollow porous Ag nanotubes (NTs) were simply prepared
distance [21]. Notably, a few reports revealed that high SERS sensi- by soaking the hybrid NBs in tetrahydrofuran (THF). However, the
tivity came from honeycomb architecture of carbon quantum dots Ag NTs exhibit the weaker SERS signals compared to those of the
(C-dots) [22] and graphene-quantum-dots assembled nanotubes hybrid NBs, indicating the significant role of SERS-active substrates.
(GQD-NTs) [23] which was probably associated with the collective Although we were not the first to use of surface decorated fiber-like
properties of ensembles. In particular, silicon (Si) NWs coated with structures for SERS applications [33], the employment of semi-
Ag NPs have been found favorable for magnifying SERS signals since conducting organic (PS-PSS)/C-dots ribbon-like structures is an
the large surface area of the Si NWs is available to create more “hot interesting new approach. This new and important finding would
spots” [24,25]. Recently, it was demonstrated that the SERS signal be beneficial for the SERS community as well as for the material
intensity can be enhanced by increasing the aspect ratio of the Si scientists.
NWs when their height is less than 1 ␮m [26].
On the other hand, if an Ag NP placed near a dielectric substrate 2. Experimental section
where no plasmons exist, the charges induced are weak. This weak
interaction can be sufficient to break the symmetry of the dielectric 2.1. Materials
environment of the NP, lifting the degeneracy between its plasmon
modes [2]. Recently, the Ag/PVA nanofiber mat [3], electrospun St from Aldrich was passed through a basic alumina column,
nanofibrous polyacrylonitrile membranes decorated with Ag NPs then vacuum distilled from calcium hydride (CaH2 ) and stored at
[27], and electrospun TiO2 /Ag nanofelts [28] have been reported to −20 ◦ C prior to use. NaSS and potassium persulphate (KPS) pur-
be promising as SERS-active substrates for cost-effective and repro- chased from Sinopharm were used as received. R6G was purchased
ducible applications. Compared to Ag/polymer nanocomposites, from Aldrich. Silver nitrate (AgNO3 ), sodium hydroxide (NaOH) and
Ag-graphene composite nanosheets [29] may be more appropriate ammonium hydroxide (NH4 OH) were purchased from Sinopharm
SERS-active substrates because of a great SPR-assisted EM enhance- (Shanghai, China) and used without further purification.
ment apart from a possible charge transfer between the analyte
molecules and the graphene substrates, which result in a chemical 2.2. Preparation of (PS-PSS)/C-dots NRs
enhancement. Indeed, it has been observed that the intensities of
the Raman signals on monolayer graphene are much stronger than The preparation of (PS-PSS)/C-dots NRs is according to the pre-
that on a SiO2 /Si substrate [30]. However, when graphene is used vious report in our lab. [32] In a typical synthesis, 50 mg of KPS
as a substrate to support metals, the damping of plasmons on the and 6 mg of NaSS were dissolved in ethanol/water mixture of
graphene layer reduces the localized light intensity. A thin dielec- (16.5 ml/4.5 ml) in a 25-mL three-neck flask equipped with a reflux
tric layer, i.e. HfO2 between the graphene layer and Au NPs could condenser and a Teflon-coated magnetic stirring bar. This system
reduce the surface plasmon damping at the Au–graphene inter- was heated to 70 ◦ C under magnetic stirring. When the temperature
face, and thus the Raman intensity increases sharply by plasmonic reached 70 ◦ C, 0.2 mL of a St was added to the flask, and 2 min later,
resonance enhancement while maintaining efficient fluorescence 3.0 mL of the C-dots solution in ethanol (0.15 mg/mL) was added in
quenching [31]. Very recently, it was reported that the EM enhance- dropwise. The reaction system was kept heating at 70 ◦ C for another
ment could be readily tuned by the number of graphene layers 2 h before the product was collected. The product was obtained by
sandwiched between Au nanoparticles, which demonstrated a high precipitation in cold diethyl ether twice, centrifugation, and then
662 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669

washing with a mixture of ethanol/water (4/1, v/v) three times as 3. Results and discussion
well as ethanol one time.
3.1. Morphology and Structure of the Ag-(PS-PSS)/C-dots NBs
2.3. Surface-Decoration of Ag NPs on (PS-PSS)/C-dots NBs
Fig. 2a and b shows SEM and TEM images of the (PS-PSS)/C-dots
Surface-decoration of Ag NPs was carried out via an electroless NRs, respectively. The structure and formation mechanism of the
plating method similar to the literature [27]. Firstly, 15 M NH4 OH (PS-PSS)/C-dots NR have been described in our previous report [32],
solution was added into 1 mL of 0.04 M AgNO3 solution dropwise which is built on electrostatic self-assembly of alternating C-dots
until the brown precipitate dissolved under the stirring, and then and PS-PSS oligomer blocks while the C-dots stacking along length
15 wt% NaOH solution was added into the system, resulting in the direction with intermediate polymer layers. The obtained NRs are
formation of brown precipitate; thereafter, additional 15 M NH4 OH very wide and thin with a width of 1-2 ␮m and an ultra-long length
solution was added in dropwise until the system became clear and (>100 ␮m). Upon reaction with the Tollen’s reagent, [Ag(NH3 )2 ]+
colorless again. Secondly, the Tollen’s reagent was prepared by mix- ions were reduced into Ag atoms as shown in Eq. (1) [27,34]:
ing the Ag-precursor with 1 mL 0.011 M dextrose aqueous solution
D-CHO + 2[Ag(NH3 )2 ]+ + 3OH− → 2Ag + D-COO- + 4NH3 + 2H2 O
for 10 s under stirring. Thirdly, (PS-PSS)/C-dots NBs were immersed
in the Tollen’s reagent for electroless plating of Ag with reaction (1)
time of 1, 3, 10 and 20 min, respectively. Finally, the resulting Ag-
(PS-PSS)/C-dots NB products were rinsed with a mixture of ethanol
The generated Ag atoms would grow into NPs on the surface
and water (4/1, v/v) for several times and then dried in air naturally.
of NR during the electroless plating process. Fig. 2c shows a typ-
ical SEM image of the as-prepared Ag-(PS-PSS)/C-dots NBs with
2.4. Preparation of Hollow Porous Ag NTs the reaction time of 3 min, in which the surface is rough and dec-
orated with a plenty of tiny Ag NPs. A magnified TEM image of
Firstly, the Tollen’s reagent was prepared by using 0.4 mol of an individual NB in Fig. 2d reveals that the Ag NPs in average
AgNO3 . Secondly, (PS-PSS)/C-dots NBs was then immersed in the size of 10–20 nm distribute homogeneously on the surface of the
Tollen’s reagent solution for electroless plating of Ag with reac- NB and the gaps between neighbored nanoparticles are 5.54, 8.61
tion time of 5 min. Thirdly, 2 mL of THF was added to the reaction and 9.86 nm, respectively. The corresponding selected-area elec-
solution dropwise, and then the solution was stirred at room tron diffraction (SAED) pattern of the NB is in concentric rings
temperature for 30 min. Finally, the hollow porous Ag NTs were (the inset of Fig. 2e), which indicates that the polycrystalline Ag
collected after repeatedly washing with deionized water and cen- NPs are randomly attached to the surface of NBs without particu-
trifuged at 5000 rpm for 1 min for several times. lar orientations. Moreover, Fig. 2f displays the XRD pattern of the
Ag-(PS-PSS)/C-dots-3 min NBs, confirming the face-centered cubic
2.5. Characterizations (fcc) structure of Ag NPs in the NB. There are four peaks at 2␪ = 38.2,
44.4, 64.6, and 77.4, assigning to (1 1 1), (2 0 0), (2 2 0), and (3 1 1)
The morphologies of Ag-(PS-PSS)/C-dots NB products were crystal planes of fcc-Ag, respectively. The mean grain size can be
observed by using field-emission scanning electron microscopy estimated from the half-width of the XRD peaks according to Scher-
(SEM) (S-4800, Hitachi Co., Japan) and transmission electron rer’ formula [35]. As a result, the calculated grain size of Ag NPs
microscopy (TEM) (JEM-2100, JEOL, Japan). The FT-IR spectra were is 17.8 nm, which is in agreement with the average particle size
recorded on a spectrometer (NEXUS-870, Nicolet Instrument Co., acquired from TEM analyses of Fig. 2d. It is found that the size and
USA) in the range of 400–4000 cm−1 . The UV–Vis spectra of sam- quantity of Ag NPs mainly depend on reaction time. The aggrega-
ples in aqueous solution were measured on a spectrophotometer tion size of Ag NPs can be tuned by controlling the reaction time of
(U-4100, Hitachi Co., Japan) in the range of 200–900 nm. Powder electroless plating. Fig. 3 shows TEM images and the corresponding
X-ray diffraction (XRD) analyses were carried out on a XD-3 diffrac- size distribution histograms of Ag NPs in four NB samples that have
tometer with Cu K␣ radiation. The electrical characteristics of the reacted for 1, 3, 10 and 20 min, respectively. Obviously, the mean
(PS-PSS)/C-dots NR and Ag-(PS-PSS)/C-dots NB were carried out size of Ag NPs increased from 5.9 nm to 14.1, 42.4 and 55. 8 nm as
with table-top cryogenic probe station (Lake Shore, Model TTPX) the reaction time prolongs.
using a Keithley 2400 sourcemeter.
3.2. SERS Sensitivity of the Ag-(PS-PSS)/C-dots NBs
2.6. SERS Measurements
The aggregation size of Ag NPs will play an important role
The sample preparation procedure for Raman investigation is in determining the SERS sensitivity of Ag-(PS-PSS)/C-dots NBs.
similar to that in literature [28], as illustrated in Fig. S1, ESI†. At Since the degree of NP aggregation is the key to the enhance-
first, predetermined amounts of R6G were dissolved in ethanol to ment, controlling the aggregation process could lead to optimal
make the R6G solutions with different concentrations. Second, the SERS detection [36]. Fig. 4a shows SERS sensitivities of 10−3 M
Ag-(PS-PSS)/C-dots NB samples were soaked in the R6G solution at R6G adsorbed on the surface of above four hybrid NB samples.
a certain concentration and then dried by a stream of N2 gas. One Notably, the strongest Raman signal was collected from the Ag-
droplet of the corresponding R6G solution was also dropped on to (PS-PSS)/C-dots-3 min sample that with a small but not the least
the glass substrate and used as a reference for the Raman character- mean size of Ag NPs. In addition, here the 785 nm excitation light
izations after drying. At last, SERS spectra were obtained by using was used because of the following four reasons: (1) can avoid
a Renishaw Raman inVia Reflex spectroscopy system with a 532- fluorescence background of organic dye molecules and photochem-
nm or 785-nm laser. Both laser powers on samples were 0.5 mW to ical degradation or transformation of adsorbed species [17]; (2)
avoid sample heating and photo-induced damages. The laser was longer wavelength excitation, i.e. 785 nm is less harmful to the
focused onto the sample surface using a 50 × long working distance biological samples; (3) also can avoid the interference of strong
objective. All of SERS spectra were collected at room temperature fluorescence of C-dots under 532 nm excitation; (4) above all, R6G
(ca. 20 ◦ C) in continuous mode with an acquisition time of 30 s and does not present Raman resonances at this wavelength. This is a
accumulated for 1 time. very important point even though it is still not fully clear to what
 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669 663

Fig. 2. (a) SEM and (b) TEM images of the (PS-PSS)/C-dots NRs. (c) SEM image of the Ag-(PS-PSS)/C-dots-3 min NBs. (d) A magnified TEM image of an individual Ag-(PS-PSS)/C-
dots-3 min NB (the inset shows the gaps between neighbored nanoparticles are 5.54, 8.61 and 9.86 nm, respectively). (e) TEM image of an individual Ag-(PS-PSS)/C-dots-3 min
NB (the inset shows the corresponding SAED pattern). (f) XRD pattern of the Ag–(PS-PSS)/C-dots-3 min NBs.

extent the Raman resonance of a molecule is quenched by the signal due to interference of their fluorescence emission. So the
surface plasmons. Anyway, in many published articles that claim (PS-PSS)/C-dots NRs do not show obvious Raman signal, either.
to have achieved an extraordinary SERS enhancement using R6G However, the Raman spectrum of Ag-(PS-PSS)/C-dots exhibits two
as a probe molecule, the illumination wavelength used is resonant prominent bands at 1333 cm−1 and 1593 cm−1 , which is similar
and, thus, the enhancement is not solely due to surface effects but to those of the C-dots under the 325 nm excitation, attributed to
also to Raman resonance effects (maybe quenched to some extent D and G bands of graphitic carbon atoms, respectively [32,37]. The
but not completely suppress), i.e., it is not SERS but SERRS (Sur- intensity of D-band and G-band of Ag-(PS-PSS)/C-dots composite is
face Enhanced Resonant Raman Scattering). In the present case, obviously higher than that of pure C-dots, which is due to the sur-
only pre-resonance effects could contribute to the Raman signal. face enhancement Raman scattering effect of AgNPs [38,39]. This
As shown in Fig. 4b, We have collected 785 nm-excited Raman sig- result also indicates that there is photo-induced electron transfer
nals of 10−2 M R6G dropping on to the glass substrate and used as from C-dots to Ag NPs, and thus fluorescence quenching happens
a reference for the Raman characterizations after drying, 10−2 M to the (PS-PSS)/C-dots NRs after surface-decoration of Ag NPs, as
R6G dropping on the Ag-(PS-PSS)/C-dots-3 min NBs and 10−2 M shown in Fig. S3 (A, B), ESI†.
R6G dropping on the isolated Ag NPs obtained by dissolving the
Ag-(PS-PSS)/C-dots-3 min NBs in THF. In contrast, the Raman peak 3.2.1. SERS EF of Ag-(PS-PSS)/C-dots NBs and detection limit of
of 10−2 M R6G dropping onto the glass substrate was comparatively R6G
weak. R6G was chosen as the model molecule since it is one of
Furthermore, 532 nm-excited Raman spectra of C-dots, (PS- the most commonly used model molecules in SERS due to its
PSS)/C-dots NRs, and Ag-(PS-PSS)/C-dots NBs are also presented large Raman scattering cross section and well-established Raman
in Fig. S2, ESI†. As expected, the C-dots do not show any Raman spectral information. [40] In the present case, as shown in Fig. S1
664 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669

Fig. 3. (a, b, c, d) TEM images of the Ag-(PS-PSS)/C-dots-1 min, Ag-(PS-PSS)/C-dots-3 min, Ag-(PS-PSS)/C-dots-10 min and Ag-(PS-PSS)/C-dots-20 min NBs, respectively. (e, f,
g, h) Size distribution histograms of the Ag NPs in the corresponding NBs of a, b, c and d, respectively.

of ESI†, R6G molecules were adsorbed onto surface of the samples than the previously reported limit of 10−12 M of R6G on pure Ag
by soaking the Ag-(PS-PSS)/C-dots NB samples in the R6G/ethanol NPs [41] or high-density Ag NP film [42].
solution at a certain concentration. Fig. 5a shows the Raman spectra To estimate the SERS enhancement, we calculated the Raman
of (PS-PSS)/C-dots NR, Ag-(PS-PSS)/C-dots-3 min NB and 10−5 M EF per molecule as the ratio of the intensity in presence or absence
R6G adsorbed on Ag-(PS-PSS)/C-dots-3 min NB, respectively. Table of the active substrate [17]. EF for the 1507 cm−1 SERS band was
S1 in ESI† gives the 785 nm Raman band assignments of R6G. As estimated using the Eq. (2) [43,44]:
expected, prominent SERS signal with good signal-to-noise ratio    
is observed for the R6G adsorbed on Ag-(PS-PSS)/C-dots-3 min EF = Isers /Iref × Nref /Nsers (2)
NB, whereas R6G on the (PS-PSS)/C-dots NR only shows typical Where Isers is the intensity of the specific Raman band from the
benzene ring-related Raman peaks. Further, the 785 nm-excited analyte adsorbed on a SERS-active substrate, and Nsers is the num-
Raman signals of R6G adsorbed on Ag-(PS-PSS)/C-dots-3 min NB ber of molecules contributing to Isers . Similarly, Iref is the intensity
in solutions of different concentrations were collected, as shown of the same Raman band from the bulk analyte, normalized with
in Fig. 5b. The lowest concentration of R6G to be detected, namely, the laser power and acquisition time, and Nref is the number of
the detection limit of R6G reaches 10−14 M, which is even lower molecules that yield Iref . See also in detailed calculation of EFs, ESI†.
Although Etchegoin and coworkers have been nicely addressed
 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669 665

Fig. 4. (a)785 nm excited Raman spectra of 10−3 M R6G adsorbed on Ag-(PS-PSS)/C-dots-1 min, Ag-(PS-PSS)/C-dots-3 min, Ag-(PS-PSS)/C-dots-10 min and Ag-(PS-PSS)/C-
dots-20 min NBs, respectively. (b) 785 nm excited Raman spectra of 10−2 M R6G in ethanol solution, 10−2 M R6G adsorbed on the Ag-(PS-PSS)/C-dots-3 min NBs and 10−2 M
R6G adsorbed on the isolated Ag NPs in the same size.

the calculation of EF and quantification of the SERS enhancement region with greatly amplified electric fields, or so-called “hot spots”
several years ago [44], it is a never-ending story of EF correct [21,48]. The “hot spots” exist between adjacent nanoparticles and
calculation to allow for an accurate quantification of the SERS mag- near the sharp corners and asperities of the metal nanostructure
nitude [43,45]. Herein, the calculated EF for the 1507 cm−1 SERS [13,48]. In the present case, the ultra-long hybrid NR has a very large
band of the Ag-(PS-PSS)/C-dots-3 min NB is about 3.35 × 108 that surface area available for deposition of a plenty of Ag NPs. These Ag
is greater than the previously reported substrates such as Ag NP NPs would aggregate into clusters, dimers or the larger assemblies
arrays,12 Ag/polyacrylonitrile nanocomposites [27], Au-deposited in a size of 10–20 nm, in which the distance between adjacent Ag
C-dots honeycomb [22], (GQD-NTs)/Au [23], and Au@C-dots com- NPs decreases to an appropriate gap for the formation of more “hot
posite NPs [38]. It is worthwhile pointing out that in our calculation spots”. In fact, tunneling effects between particles can reduce the
the R6G molecules are assumed to be fully adsorbed as a monolayer local EM enhancement if the gaps between nanoparticles are below
on the surface of Ag-(PS-PSS)/C-dots NBs. This hypothesis repre- 1 nm [11,49]. In the meanwhile, such rough surface of Ag-(PS-
sents a theoretical maximum number of R6G molecules adsorbed PSS)/C-dots NB is more favorable for SPR-assisted EM enhancement
on the surface, which is an overestimate of the actual EF value [25]. when excited by those used in cited references [23,50–52]. More
recent reports have confirmed that SERS signals mainly come from
3.2.2. The SERS enhancement mechanism of Ag-(PS-PSS)/C-dots the “hot spots” which are formed at the gap region between two Ag
NBs NPs or the sharp surface of nanostructures [53–57]. Further, Fig. S4
As is well-known, many factors simultaneously contribute to in ESI† shows the UV–Vis absorption spectra of the (PS-PSS)/C-dots
the Raman enhancement effect. The fact has been proven countless NRs and Ag-(PS-PSS)/C-dots NBs in ethanol. Apart from the absorp-
times during the past years that the SERS magnitude depends on tion band at 250–280 nm of (PS-PSS)/C-dots NR, a broad tailband
the size, size distribution, surface state, surrounding environment, of reagent solution among the 250–700 nm also appears in the Ag-
shape, and nature of metal NPs [17,25,46]. However, it has been (PS-PSS)/C-dots-3 min NBs (blue arrows representing area), having
widely accepted that EM enhancement is the largest factor for the surface plasmon resonance (SPR) bands at a desired wavelength
SERS effect [47]. As for the metal hybrid substrates, the Raman sen- [56,58,59].
sitivity can be enhanced by 108 or more. Most of enhanced SERS Besides EM enhancement from the more generated “hot spots”,
sensitivity has benefited greatly from SPR-assisted EM enhance- the chemical interaction between Ag NPs and (PS-PSS)/C-dots NR
ment, where Raman scattering of molecules is enhanced by many also contributes to the enhanced Raman signals. As previously
orders of magnitude when the molecules are within the localized reported, [32] FT-IR spectrum of the (PS-PSS)/C-dots NR exhibit-

Fig. 5. (a) 785 nm excited Raman spectra of (PS-PSS)/C-dots NR, Ag-(PS-PSS)/C-dots-3 min NB and 10−5 M R6G adsorbed on Ag-(PS-PSS)/C-dots-3 min, respectively. (b)
785 nm excited Raman spectra of R6G adsorbed on Ag-(PS-PSS)/C-dots-3 min NB soaked in R6G/ethanol solutions with different concentrations (the inset is a magnified
Raman spectrum of 10−14 M).
666 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669

Fig. 6. (a) UV–Vis spectra of a 10−5 M R6G solution and the supernatant of the R6G solution after it adsorbed by 0.3 mg/mL Ag-(PS-PSS)/C-dots-3 min NBs and Ag NPs-R6G,
respectively. (b) UV–Vis spectra of a 10−5 M R6G solution, and the supernatant of the R6G solution after it adsorbed by 0.3 mg/mL Ag-(PS-PSS)/C-dots-1 min, Ag-(PS-PSS)/C-
dots-3 min, Ag-(PS-PSS)/C-dots-10 min, and Ag-(PS-PSS)/C-dots-20 min NBs, respectively.

ing a strong SO3 − absorption feature at 1081 cm−1 owing to the tively. Some NTs were broken during the preparation as shown in
PSS segments in the NR. However, the IR absorption of SO3 − group Fig. 7C, E and F, since the process was a fast self-sacrificial dissolved
shifted remarkably to 1108 cm−1 after the surface-decoration of process of the NRs. Nevertheless, it is noticed that the hollow porous
Ag NPs on NR as shown in Fig. S5 of ESI†, possibly because the Ag NTs in Fig. 7 have very large intermediate space, the possible rea-
negatively charged SO3 − groups on the surface of NRs acted as son is that such a wide, thin and soft organic (PS-PSS)/C dots ribbon
active sites for adsorption of Ag+ cations during the electroless plat- would roll into hollow fiber-like structure during the process of
ing process. Moreover, the aforementioned fluorescence quenching chemical deposition of Ag NPs on its surface, therefore, the hollow
in the Ag-(PS-PSS)/C-dots NBs indicates that there is photo-induced porous Ag NTs look like prepared by removing fibers but not thin
electron transfer from C-dots to Ag NPs, in the meanwhile, the sp2 - belts.
hybridized C-dots in NR can adsorb more aromatic R6G molecules Moreover, as shown in Fig. 8a, the Raman signals of R6G on
via ␲–␲ interaction. This chemical interaction between R6G and hollow porous Ag NTs were also collected and compared with
the C-dots can drive R6G molecules approaching to the “hot-spots”, that on the Ag-(PS-PSS)/C-dots-20 min NBs, since these two sys-
thus enhancing the probability of a correct placement of the R6G tems have nearly equivalent mean size of Ag NPs of about 55 nm
molecules on the active SERS sites. Fig. 6 shows much more R6G and 65 nm, respectively. However, Ag-(PS-PSS)/C-dots-20 min NBs
molecules are adsorbed onto the surface of the Ag-(PS-PSS)/C-dots have obviously larger inter-particle distances between Ag NPs than
NBs than those onto the isolated Ag NPs in the same size (these that in hollow porous Ag NTs. Apparently, the hollow porous Ag
isolated Ag NPs were obtained by dissolving the hybrid Ag-(PS- NTs present weaker Raman signal enhancement than that of the
PSS)/C-dots NBs in THF for long time enough). Similarly, Au@C-dots Ag-(PS-PSS)/C-dots-20 min NBs. Fig. 8b shows the concentration-
hybrid NPs exhibited SERS performance superior to that of pure Au dependent SERS spectra of R6G molecules adsorbed on hollow
NPs, which was mainly caused by Au@C-dots absorbing more aro- porous Ag NTs in ethanol solutions. In this case, the detection limit
matic dye molecules via ␲–␲ stacking and electrostatic interaction. of R6G is 10−10 M that is greatly lower than that the semicon-
[38] Although there are many manifestations of chemical interac- ducting organic (PS-PSS)/C-dots substrate. The main reason is that
tion at interfaces, our understanding of these phenomena is limited. higher coalescence of the Ag NPs in the case of the NTs result-
[57] Further works are required to develop a comprehensive under- ing in a lower density of “hot-spots”; that is to say, removal of
standing for this chemical interaction SERS. the inner (PS-PSS)/C-dots NR substrate makes the Ag NPs towards
Furthermore, the embedding dielectric medium can also play a more aggregation. This result confirms the semiconducting organic
vital role. It is known that when metal NPs are embedded in a high (PS-PSS)/C-dots substrate plays an important role in SERS property
dielectric medium, alteration of SPR with significant enhancement of the Ag-(PS-PSS)/C-dots NBs. As above-mentioned, when metal
of intensity is possible, which can contribute towards high Raman NPs are embedded in a high dielectric medium, alteration of SPR
enhancement. [17,60–63] In the present case, the dielectric matrix with significant enhancement of intensity is possible, which can
of Ag NPs is the semiconducting (PS-PSS)/C-dots NR that is com- contribute towards high Raman enhancement. Here the (PS-PSS)/C-
posed of alternating C-dots and organic PS-PSS oligomer blocks. dots NR not only acts as a dielectric support for Ag NPs to reduce
[32] Moreover, the dielectric PS-PSS oligomer blocks within the the surface plasmon damping at the Ag-NR interface and create
NR could reduce the surface plasmon damping at the Ag NP-NR more “hot-spots”, but also can adsorb more R6G molecules via ␲–␲
interface. In addition, Fig. S6 of ESI† indicates that the electric con- interaction between the embedded sp2 -hybridized C-dots in NR
ductivity of the (PS-PSS)/C-dots NR was estimated to be 3.368 S/m and aromatic rings of R6G. This chemical interaction between R6G
while that of the Ag-(PS-PSS)/C-dots NB increases 2 order of mag- and the C-dots also drives R6G molecules approaching to the “hot-
nitude to 3.368 × 102 S/m. The nonlinear I–V curves of NR reveals spots”, thus enhancing the probability of a correct placement of
the semiconducting behavior of the (PS-PSS)/C-dots NRs while the the R6G molecules on the active SERS sites. Despite the tremen-
linear I–V curves and much higher conductivity of NB demonstrate dous efforts and major advances that have been achieved in SERS
that the Ag-(PS-PSS)/C-dots NBs are conductive after surface dec- research, the exact mechanisms of SERS are still a matter of debate.
oration of Ag NPs. As a control, the Ag-(PS-PSS)/C-dots-20 min NBs [64]
were immersed in THF for enough time so that the inner (PS-PSS)/C- The above-mentioned large enhancement suggests that the Ag-
dots NRs was removed and then a novel kind of hollow porous (PS-PSS)/C-dots NBs can indeed serve as robust substrates for
Ag NTs could be obtained. Fig. 7A and B shows SEM images of SERS. Furthermore, we have investigated the application of Ag-
the hollow porous Ag NTs at low and high magnifications, respec- (PS-PSS)/C-dots NBs as SERS substrate for detection of coumarins
 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669 667

Fig. 7. (A,B) SEM images of the hollow porous Ag NTs at low and high magnifications, respectively. (C) A broken Ag NT. (D) Size distribution histogram of Ag NP aggregates
in the hollow porous Ag NTs. (E,F) SEM images of hollow porous Ag NTs obtained after the Ag-(PS-PSS)/C-dots NBs dissolved in THF, shown at different magnifications.

Fig. 8. 785 nm-excited Raman spectra of (a) Ag-(PS-PSS)/C-dots, 10−4 M R6G adsorbed on Ag-(PS-PSS)/C-dots-20 min NBs, and 10−4 M R6G adsorbed on hollow porous Ag
NTs, respectively; (b) different concentrations of R6G molecules adsorbed on hollow porous Ag NTs in ethanol solutions.
668 G. Zhang et al. / Applied Surface Science 364 (2016) 660–669

Yang liangbao (Institute of Intelligent Machines, Chinese Academy

of Sciences, Hefei, China) for his helpful discussion.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.apsusc.2015.12.
214.

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