Accepted Manuscript

Title: Self-assembly of the stretchable AuNPs@MoS2 @GF

substrate for the SERS application

Authors: Tianming Li, Yuanyuan Xu, Feng Yang, Chao

Zhang, Chuanxi Yang, Zhencui Sun, Hao Zhang, Xiaobo
Yuan, Tingyin Ning, Cheng Yang

PII: S0169-4332(17)31960-8
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2017.06.305
Reference: APSUSC 36505

To appear in: APSUSC

Received date: 28-4-2017

Revised date: 27-6-2017
Accepted date: 29-6-2017

Please cite this article as: Tianming Li, Yuanyuan Xu, Feng Yang, Chao Zhang, Chuanxi
Yang, Zhencui Sun, Hao Zhang, Xiaobo Yuan, Tingyin Ning, Cheng Yang, Self-
assembly of the stretchable AuNPs@MoS2@GF substrate for the SERS application,
Applied Surface Sciencehttp://dx.doi.org/10.1016/j.apsusc.2017.06.305

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Self-assembly of the stretchable AuNPs@MoS2@GF substrate for the

SERS application

Tianming Li a,1, Yuanyuan Xua,b,1, Feng Yanga,b,1, Chao Zhang a, Chuanxi Yangc,
Zhencui Sund, Hao Zhanga, Xiaobo Yuana, Tingyin Ninga, and Cheng Yanga,b

a School of Physics and Electronics, Shandong Normal University, Jinan 250014, People’s Republic of China
b Institute of Materials and Clean Energy, Shandong Normal University, Jinan 250014, People’s Republic of China
c China Agricultural University, Beijing 100083, People’s Republic of China
d School of Science, Shandong Jiaotong University, Jinan 250023, People’s Republic of China

Large-area stretchable three-dimensional (3D) AuNPs@MoS2@GF as the SERS

substrates are proposed here, which were fabricated by using CVD and stamp-transfer
processes. 3D graphene foams (GF) are used to increase the sensitivity and
stretchability, benefiting from the high specific surface area, chemical absorption and
mechanical strength. Few-layered MoS2 films, which can be formed by thermal
decomposition of the ammonium tetrathiomolybdate ((NH4)2MoS4), are used to
absorb the molecules and form the high-density AuNPs with the reaction of
tetrachloroauric acid. The stretchability (ε) of such stretchable foams up to 100% can
be achieved. SERS spectra of CV molecules show that AuNPs@MoS2@GF can detect
as low as 10-10 M. Such stretchable substrates can be used as an ultrasensitive
biosensor to detect the molecules on surfaces of any shape.

Highlights:
 An ingenious AuNPs@MoS2@G Foam hybrids are fabricated by us in a gentle
and simple way.
 The AuNPs@MoS2@GF is proposed as stretchable, strong and sensitive
SERS-based three-dimensional sensor.
 The stretching up to 100% has almost no effect to the SERS performance of
AuNPs@MoS2@GF.
 Such stretchable substrate can directly be used as an ultrasensitive swab to
detect the molecules on surfaces of any shape.

Corresponding author at: School of Physics and Electronics, Shandong Normal University, Jinan
250014, People’s Republic of China.

E-mail address: chengyang@sdnu.edu.cn

1
These authors contributed equally
1. Introduction

2D nanomaterials (such as Graphene and MoS2) based surface-enhanced Raman

scattering (SERS) substrates have drawn a tremendous amount of attention recently,
resulting from the flexibility, chemical absorption and the reduction of the back action
noise [1-8]. To improve the performance of 2D nanomaterials towards high sensitive
SERS applications, recent studies have focused on the hybrid nanostructures that
combine with metal nanostructure [9-12]. In these hybrid nanostructures, besides the
nature chemical enhancement based SERS function, 2D nanomaterials, as atomically
flat substrates, have multiple roles, such as conducting shell, atomically thin support,
molecule absorber and stabilizer, photoluminescence quencher, and protective layer to
slow or inhibit the oxidation of metal nanostructure [13-15].
Compared with flat 2D materials based rigid substrates, the hybrid nanostructures
fabricated on the macroscopic 2D materials surface to form the 3D flexible hybrid
substrates have several great advantages: (1) the molecules are easily absorbed on the
surface of graphene due to the their ultra-high surface area [16,17]; (2) multiple
cascaded amplification mechanisms (localized surface plasmon mode and optical
standing waves [28,19] or optical refraction [28,20]) of the incident laser can be used;
(3) the distances of the metal nanoparticles are adjustable by such stretchable 3D
substrates[27,21,22]; (4) such flexible hybrids can be used to directly detect the
analyte molecules on arbitrary curvilinear structures [17,23]. C. Srichan proposed the
AgNPs@FG@Si substrate, formed by using DC magnetron sputtering AgNPs on the
foam graphene substrate [24], as a novel SERS substrate to detect MB. The
enhancement factor of AgNPs@FG@Si sensor is found to be four orders of
magnitude larger than that of AgNPs@Si substrate.
Self-assembly of the metal nanoparticles is demonstrated easier and more efficient
to cover all the surface of the 3D branches [25-27]. Researchers found that AuNPs can
be self-assembled on the surface of MoS2 in virtue of the nature reducing capacity of
MoS2 [28], which is a kind of typical layered 2D chalcogenide material with the
advantages of high light transmission, chemical stability, biomolecular affinity and
low-temperature synthesis [29,30]. Importantly, the charge transfer and dipole–dipole
coupling of MoS2 layers may cause large enhancement in the SERS signal [31,32]. So,
the self-assembly of the AuNPs@MoS2 on 3D G@Ni foam substrate is promising and
fabricated in our report. Such fabricated AuNPs@MoS2 on 3D G@Ni foam substrates
are not flexible and stretchable due to the existed Ni metal. While, real applications of
SERS have required flexible and mechanically robust SERS substrates [15,27,33-36],
which can attach tightly to the surface of the detected product to maintain a high
SERS signal.
Here, we proposed and obtained a stretchable 3D AuNPs@MoS2@GF hybrid
structures by the formation of the AuNPs@MoS2 onto the 3D G@Ni foam substrate、
etching of the metal Ni and stamp-processes. The stretchability of such stretchable
foams up to 100% can be achieved. SERS performances are consistent undergoing
different deformation, indicating that AuNPs@MoS2@GF can be used as
cut-and-paste SERS substrates to cover on the surface of arbitrary configuration for
highly sensitive in-situ detection.

2. Experimental methods

2.1 Formation of Graphene@NF.

(1) Nickel foam are used and putted into the quartz tube of the furnace. (2)
Double-pump system are used to decrease the pressure to the 10-3 Pa. H2 with the flow
of 50 sccm was then piped in the tube to remove the remaining nickel oxide when the
temperature reached 300 ℃ (3) When the temperature of the quartz tube increases to
the 1000 ℃, CH4 with the flow of 50 sccm was introduced into the tube for different
growth time.

2.2 Preparation of MoS2@Graphene@NF

(1) 0.05g ATTM mixed with 5ml DFM are sued to prepare (NH4)2MoS4 precursor.
(2) Graphene@NF are soaked it into the (NH4)2MoS4 precursor for 10 seconds and
spin-coated to enable the solution cover it evenly. (3) Annealing process with 500℃
for 90 minutes are used to form the MoS2@Graphene@NF.

2.3 In-situ growth of stretchable AuNPs@MoS2@Graphene@NF

(1) MoS2@Graphene@NF is immersed in an HAuCl4 solution (0.1mM) to produce

the AuNPs without any reduced agents (2) 1mol/L FeCl3 solution are sued to remove
the nickel scaffold. .

2.4 Stamp-transfer method

(1) prestretching elastomer, which was affixed to the edge of a plastic culture dish,
are covered quickly and horizontally onto the floating flexible AuNPs@MoS2@GF. (2)
elastomer, coated with AuNPs@MoS2@GF, are uplifted slowly with an oblique angle.
(3)remove the elastomer from the plastic culture dish to relax naturally.

2.5 SERS measurements

The Raman instrument used in this study was Horiba HR Evolution 800 with
excitation by a laser (532 nm). The laser beam was focused on a sample of about 1
μm in size. For each sample, the SERS spectra on display were the average value of
spectra of three different positions of the substrate. The SERS measurements were
performed from at least 8 random locations that were more than 3 mm apart with an
accumulation time of 10 s. If there is no special instruction, the mentioned Raman
spectra are expressed in terms of average spectra.

2.6 Stretching-relaxing experiment

Two ends of the stretchable AuNPs@MoS2@GF was immobilized on the fixed and
movable ends of the controller respectively (which is shown in Fig. 4a). Stretching
length and times were set up by adjusting the controller. When the stretching process
was ended and AuNPs@MoS2@GF is taken down from the motor motion controller,
Raman spectra were collected after it shrinked to the original length.

2. Results and Discussion

Fig. 1. Main fabrication processes of the stretchable AuNPs@MoS2@GF substrates.

Main processes of the stretchable AuNPs@MoS2@GF substrates are illustrated as

Fig. 1. CVD 、 etching and stamp-transfer processes are used here. The
stretching-relaxing of the stretchable AuNPs@MoS2@GF substrates and their Raman
measurement are also given here.
Fig. 2. (a) SEM images of Ni foam ((a) and the inset) under different magnification; (b) SEM

images of MoS2@G@Ni foam. The inset (b1) and (b2) are TEM images of MoS2 and Graphene

respectively; (c) SEM images of AuNPs@MoS2@G@Ni foam ((c) and the inset, inset (b3)) under

different magnification; (d) and (e) SEM images of the stretchable AuNPs@MoS2@GF under

different magnification, insets (e1) and (e2) are TEM images of the AuNPs; Energy spectrum

analysis images of Au@MoS2@GF (Au, Mo and C).

SEM and TEM were used for the morphology characterization of the different
substrates, as shown in Fig. 2. The morphologies of MoS2 and Graphene are
characterized by TEM images (shown in the inset (1), (2) of Fig. 2(b)), which
demonstrated the MoS2@G@Ni foam was prepared. There are not the obviously
differences of the foam-like network substrates without etching (Ni foam (Fig. 2(a)
and the inset, MoS2@G@Ni foam (b) and AuNPs@MoS2@G@Ni foam (inset of (b))
under lower magnification. It can be easily observed that denser AuNPs are formed on
the surface of the MoS2@G@Ni foam, shown in Fig. 2(c). After Ni scaffold was
carefully removed by immersing the substrate into the hot FeCl3 solution, a monolith
of a continuous and interconnected AuNPs@MoS2@GF 3D network, was obtained
and shown in the Fig. 2(d) and Fig. 2(e). Unlike the flat skeleton
AuNPs@MoS2@G@Ni foam without the nickel etching, stretchable
AuNPs@MoS2@GF appear collapse drastically, causing many wrinkles, imperfection
and edges without the support of nickel skeleton. The AgNPs density of the
stretchable AuNPs@MoS2@GF (shown in Fig. 2(e)) is larger than that of
AuNPs@MoS2@G@Ni foam (shown in the inset of Fig. 2(c)). The inset (1) and (2)
of Fig. 2(e) indicate the distribution of AuNPs is dense and even. The AuNPs
structures are presented in Fig. (d), presenting that the diameter of AuNPs is about 55
nm. This is caused by two reasons: (1) adjacent skeleton layers get close and even
stick together due to the nickel absence; (2) with the relax of the prestretched
elastomer substrates, the distance between the Au nanoparticles is further reduced to
gather more AuNPs. Energy spectrum analysis [37], a kind of technology that can
indicate the compositions of the specimens, are used to prove the existence of Au, Mo
and graphene.

Fig. 3. (a) Raman spectra of the CVD graphene, MoS2, and MoS2@G hybrid structure; (b) SERS

spectra of 10-6M CV molecules collected on AuNPs@MoS2@G@NF and AuNPs@MoS2@GF;

Raman spectra of CV molecules on Au@MoS2@GF with different concentrations from 10-5 to

10-10 M. (d) Raman intensity of CV peaks at 910, 1176 and 1365 cm-1 as a function of the CV

molecular concentration with the high coefficient of determination (R2) of 0.972, 0.985 and 0.989,
respectively.

In order to prove the existence of the high-quality MoS2@G hybrid structure,

Raman spectra of the CVD graphene, MoS2, and MoS2@G hybrid structure on the Ni
foam are obtained in Fig. 3(a). It can be easily observed the existence of the peaks at
~377 and 408 cm−1 [38,39], which are attributed to E12g and A1g of the MoS2, and the
peaks at ~ 1580 and ~ 2698 cm-1 [40,41], which are the fingerprint of graphene.
Actually, Raman peaks of the MoS2 and graphene can also be observed after the
deposition of the AuNPs, which are shown in Fig. 3(b) and 3(c). While, it is must
mentioned that the Raman peak intensity of the MoS2 and graphene in the stretchable
AuNPs@MoS2@GF substrate is smaller that that in the AuNPs@MoS2@G@NF
substrate, due to the removal of the metal Ni.
Expect that of the MoS2 and graphene, the peak intensities of the CV molecules
(10-6 M, as the probe molecules to check the SERS performance) in the stretchable
AuNPs@MoS2@GF substrates also decrease a little, which is inevitable. But it is not
too much to affect the detection of the CV molecules (shown in Fig. 3(b)), resulting
from the dense AuNPs. It is important for our stretchable SERS sensors. Fig.3(c)
indicates SERS spectra of CV with varied concentration ranging from 10-5 to 10-10 M
to check the detection sensitivity of the CV molecules. The characteristic signals of
CV still can be detected as low as 10−10 M, which has potential for sensitive and fast
detection. Moreover, to show the capability of quantitative detection, the SERS
intensity of the vibration located at 910, 1176 and 1365 cm-1 [42,43] versus the
concentration (10-6 M -10-10 M) of CV molecules as well as the linear fit calibration
curves of these three characteristic peaks are plotted in Fig. 3(d). The coefficient of
determination (R2) of the linear fit calibration curve for the peaks of 613, 778 and
1365 cm-1 is reached to 0.971, 0.985 and 0.989, respectively. Anyway, the as-prepared
stretchable 3D AuNPs@MoS2@GF substrate possessed synergistic effects of the
intrinsic properties of the AuNPs and MoS2@GF, making it exhibit attractive SERS
application.
Fig. 4. (a) Photographs of the stretching process: before (a1) and after stretching of (a2) ε = 50%,

(a3) ε = 75%, (a4) ε = 100%; (b) SEM images of AuNPs@MoS2@GF: (b1) and (b2) show the

AuNPs@MoS2@GF without stretching under different magnification, (b3) and (b4) show the

AuNPs@MoS2@GF with 500 stretching-relaxation cycles; (c)The SERS spectra of 10-6M CV

molecules collected with the different stretching-relaxation cycles of the stretchable substrate with

the stretching of 100%; (d) The SERS spectra of 10-6M CV molecules collected with the different

stretching and relaxing.

Such stretchable hybrid substrate exhibited excellent malleability and SERS

properties. Fig. 4(a) shows the excellent malleability of the stretchable substrate with
the stretching of 50%, 75% and 100%, which are immobilized on a motorized moving
controller. Percentage means the proportion of the increased length of the stretched
AuNPs@MoS2@GF compared with that of the original AuNPs@MoS2@GF. Owing
to the strong adhesive strength of gummy acrylic acid substrates, the adhesion
between the foams and the substrate is very strong, foam-like structure would follow
the deformation of the stretched acrylic acid substrate. When the elastomer film is
uniaxially or biaxially stretched and relaxed over multiple cycles (more than 1000
cycles in our experiment), the AuNPs@MoS2@GFs still maintain their integrity and
perfect SERS performance, which can be attributed to its flexibility and high fracture
toughness. To demonstrate the wide suitability of SERS substrates under different
states such as tension and bending, we further study the SERS performance of such
AuNPs@MoS2@GF in the state of stretching through applying different stretching
force to it. Fig. 4(c) shows the SERS performance of AuNPs@MoS2@GF substrates
under stretch by adhereing the stretched substrates to the quartz plate to solve the CV
molecules and then relax to detect the Raman signals.
To further prove that AuNPs@MoS2@GF substrates have the ideal stability of
SERS performance, the AuNPs@MoS2@GF with the stretching of 100% was used for
SERS measurement after stretching and relaxation for different cycles. As is depicted
in Fig. 4(b), the morphologies, density and distribution of AuNPs is same for the
AuNPs@MoS2@GF before and after stretching-relaxation 500 cycles.
Electromagnetic enhancement is mainly depended on size, shape and density of
AuNPs, so the AuNPs@MoS2@GFs are still their completeness and SERS
performance with hundreds of stretching-relaxation cycles. The Raman spectra of
AuNPs@MoS2@GF with stretching-relaxation for 0, 30, 100, 500 cycles is provided
in Fig. 4(d), the value of AuNPs@MoS2@GF with different cycles is almost same,
which is consist with the SEM images. So, it is obviously that SERS performances of
foam substrates are consistent undergoing different deformation, indicating that
AuNPs@MoS2@GF can be used as cut-and-paste SERS substrates to cover on the
surface of arbitrary configuration for highly sensitive in-situ detection.
Fig. 5. SEM images of AuNPs@MoS2@GF with the deposition time of 9 min(a) and 15 min(b);
SERS spectra (c) of 10-6 M CV molecules collected on AuNPs@MoS2@GF with different AuNPs

results from the different deposition time; Raman intensity of CV peaks (d) at 910, 1176 and 1365

cm-1

As we all known, electromagnetic coupling results from the metal nanoparticles is

the main mechanism to form localized surface plasmon to the SERS application
[44-47]. Size, shape and density of the metal nanoparticles, which can be optimized
by adjusting the deposition condition (such as deposition time), affect the
electromagnetic coupling and the SERS spectra then [48-51]. By changing the time of
substrate immersed in HAuCl4 solution, several foams were obtained, soaked time of
foam is 1min, 5min, 9min, 11min, 13min and 15min respectively. It is clear that
with the increasing of the growth time, the size and density of AuNPs grown on the
foam surface is raise greatly. SEM images of the AuNPs@MoS2@GF substrates with
the 11-min deposition have been shown in Fig. 2(e) and 2(c). Compared to the foam
deposited within 11 min, that deposited within 9 min (shown in Fig. 5(a)) shows the
smaller size and density. While when growth time is more than 11min (such as 15min,
shown in Fig. 5(b)), AuNPs is so many and the growth of the AuNPs causes a kind of
aggregation like film, which will decreases the number of "hot spots". The effects on
the SERS spectra of the AuNPs deposited within different time in HAuCl4 solution
are studied and shown in Fig. 5(c) and 5(d). To select the best SERS substrate, the
standard probe (CV) is employed to study the SERS performance. The Raman
intensity of CV molecule of the Au@MoS2@GF within 11min deposition is highest.
Au nanoparticles aggregation of Au@MoS2@GF has close to each other and a little
aggregation, which can generate more "hot spots" than other substrates. The more
"hot spots" there are, the stronger the SERS signal [52,53]. So the SERS intensity is
consistent with the observation from SEM images.

Fig. 6. SERS spectra (a) of 10-6 M CV molecules collected on AuNPs@MoS2@GF with different
AuNPs results from the different deposition times; Raman intensity of CV peaks (b) at 910, 1176

and 1365 cm-1; SEM images of AuNPs@MoS2@GF with the deposition times of 3 (a) and 7 (b).

In order to further increase the electromagnetic coupling and then the SERS spectra
intensity, many times of the deposition (11 min one time) are carried out in our
experiment. While, only a little increase of the Raman intensity (shown in Fig. 6(a)
and 6(b)) is obtained for the 3 and 5 times deposition. The Raman intensity is even
decreased when the deposition times is 7. SEM images (3 times shown in Fig. 6c and
7 times shown in Fig. 6(d) are used to discuss the effects. Density of AuNPs increases
slightly by the oxidation-reduction reaction between MoS2 and HAuCl4. So the
Raman intensity is increased for the 3 and 5 growth times. While, after AuNPs grow
seven times, the distribution of AuNPs is so dense and some AuNPs are decorated on
other AuNPs, shown in Fig. 6(d), that the number of "hot spots" is decreased, which
affects the Raman intensity. In our experiment, SERS intensity of the
AuNPs@MoS2@GF grown for 5 times is strongest. However, considering the
complex processes and few increasing, one time is used in our experiment.

Fig. 7. (a) Raman spectra of MB molecules collected by AuNPs@MoS2@Graphene

foam from the fish surface with different concentrations from 10-5 to 10-8 M. (b)
Raman intensity of MB peaks at 771 and 1402 cm-1 as a function of the MB molecular
concentration respectively.

To further investigate practical application of the AuNPs@MoS2@GF as

stretchable SERS substrates, a kind of food additive was examined. Methylene blue
(MB), an aromatic heterocyclic compound, is illegally added into water body to
increase the fish livability in the process of breeding by some vendors. The tiddlers
were pretreated with DI water three times. After drying, the tiddlers were immersed in
the new-prepared MB solution with different concentrations from 10-5 M to 10-8 M for
half an hour. Removing the tiddlers from the solution and placing the tiddlers into a
vacuum drying oven to evaporate any moisture. AuNPs@MoS2@GF are covered the
tiddlers to directly absorb MB solution from fish surface on 10 minutes. SERS
measurements are obtained from the AuNPs@MoS2@GF surface. The collected
SERS spectra of MB were demonstrated in Fig. 7(a). Many vibrational peaks located
in about 448, 771 and 1402 cm-1 are observed, which belong to MB according to the
normal Raman spectrum of MB powder [54]. The lowest detected concentration of
MB can as low as 10-8 M. This fact indicates that the AuNPs@MoS2@GF substrates
own excellent adsorption abilities and SERS properties. To prove the capability of
AuNPs@MoS2@Graphene foam products in the quantitative detection of MB, the
linear fit calibration curve is illustrated in Fig. 7(b). The intensities of the SERS
spectra of MB at 771cm-1 and 1402cm-1 are proportional to the logarithm of the
concentrations of the MB with a good linear relationship ( R2=0.949, 0.948
respectively) ranging from 10 -5 to 10-8 M.

3. Conclusions

Stretchable 3D AuNPs@MoS2@GF hybrid structures are obtained by the formation

of the AuNPs@MoS2 onto the 3D G@Ni foam substrate, etching of the metal Ni and
stamp-transfer processes. The optimized growth processes are studied to carry out the
SERS application. Such stretchable SERS substrates have the well stretchability and
Raman performance. SERS spectra show that CV molecules as low as 10-10 M can be
detected by such AuNPs@MoS2@GF substrate. SERS performances are also
consistent undergoing different deformation, indicating that AuNPs@MoS2@GF can
be used as cut-and-paste SERS substrates to cover on the surface of
arbitrary configuration for highly sensitive in-situ detection.

Acknowledgments

The authors are grateful for financial support from the National Natural Science
Foundation of China (11474187, 11274204 and 61205174), and Shandong Provincial
Natural Science Foundation, China (ZR2016AM19)

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