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Abstract: An overview of recent researches of surface plasmon resonance (SPR) sensing technology
in Laboratory of Science and Technology of Micro-Nano Optics (LMNO), University of Science and
Technology of China, is presented. Some novel SPR sensors, such as sensors based on metallic
grating, metal-insulator-metal (MIM) nanoring and optical fiber, are designed or fabricated and
tested. The sensor based on localized surface plasmon resonance (LSPR) of metallic nanoparticles is
also be summarized. Because of the coupling of propagating surface plasmons and localized surface
plasmons, the localized electromagnetic field is extremely enhanced, which is applied to
surface-enhanced Raman scattering (SERS) and fluorenscence enhancement. Future prospects of
SPR and/or LSPR sensing developments and applications are also discussed.
Keywords: Surface plasmons resonance, localized surface plasmon resonance, sensor, electromagnetic-field
enhancement, high sensitivity
2. Current research activities on SPR grating-based SPR sensors depends on the resonant
and LSPR sensors at LMNO incident angle (Fig. 2). The sensitivity of the
negative diffraction order(m﹤ 0) is tens of times
Our research works are focused on new-style
higher than that of positive diffraction order (m﹥0)
SPR sensors, bimetallic sensor chip for
at large resonant angle, which is also much higher
Kretschmann configuration, optical fiber SPR
than that of conventional prism-based SPR sensor.
sensors and LSPR sensors on SERS and
For hydrogen detection, a thin Pd film is deposited
fluorescence enhancement.
on the metallic grating. When the Pd-coated gold
2.1 Novel-style SPR sensors grating is exposed to hydrogen with different
Two types of SPR sensors with different styles concentrations, the permittivity of Pd layer will
are designed: metallic grating SPR sensor [16] and change. Then the change in the resonant angle can
racetrack resonator SPR sensor [17]. Metallic be detected. The theoretical resolution of hydrogen
grating SPR sensor has a high sensitivity for gas concentration of the order of 0.001% is obtained
detection, and racetrack resonator SPR sensor has a according to our design.
broad linear detection range of analyte RI and high 800
m<0
extinction ratio.
Sensitivity (degree/RIU) 600
2.1.1 Metallic grating SPR sensor
400
We designed a highly sensitive grating-based
SPR sensor for the gas detection [16]. The sensor
200 m>0
has a high sensitivity at larger resonant incident
angle if negative diffraction order of metallic grating 0
0 10 20 30 40 50 60 70 80 90
is used to excite the surface plasmons, as shows in Resonant angle (degree)
Fig. 1. Fig. 2 Sensitivity of the resonant angle of grating-based SPR
x sensors versus the resonant angle of incidence ( λ=850 nm,
Detector
na=1.02) [16].
Light source
Air
Analyte
1.0 n
d Grating p
0.8
Fig. 1 Illustration of the SPR sensor based on metallic
3rd order n:1.32
diffraction grating [16]. +2nd order
Reflectivity
0.6 n:1.33
n:1.34
The resonant incident angle can be determined n:1.35
from the match condition of momentum at the 0.4 n:1.36
n:1.37
interface of the metallic grating and analyte:
0.2 +1st order
m na2 2
k0 k0 na sin res m (1) 4th order
m na2 0.0
0 20 40 60 80 100
where m is the permittivity of the metal, θres is the Angle of incidence, (degree)
resonant angle of incidence, na is the RI of analyte, Fig. 3 Reflectance spectra of rectangle-grating-based SPR
m is an integer representing the diffraction order, sensors with different analyte refractive indices [18].
and sign “+” and sign “-” correspond to m﹥0 and The sensitivity of the metallic-grating-based
m﹤0, respectively. SPR sensor can be improved by using double-dips
The sensitivity (dres/dn) of the resonant angle of method [18]. As shown in Fig. 3, when the RI of the
Yong CHEN et al.: Review of Surface Plasmon Resonance and Localized Surface Plasmon Resonance Sensor 39
Transmittance
1.52
grating SPR sensors. 0.4
1.54
1.56
2.1.2 SPR sensor based on racetrack resonator 1.58
1.60
0.2
SPR sensing technique can be performed with an
ultracompact racetrack resonator based on single
0.0
mode metal-insulator-metal (MIM) plasmonic gap 1.50 1.55 1.60 1.65 1.70
Wavelength (m)
waveguide (Fig. 4).
Fig. 5 Transmitted spectra with different analyte refractive
indices [17].
w Metal
2.2 Traditional SPR sensors
R
Et2
Ei2 The traditional SPR sensor contains two
g
w E i1 Et1
t different parts: Krestchmann prism coupler and
Lc
optical fiber coupler. Firstly, we investigated the
Fig. 4 Schematic of an MIM plasmonic racetrack resonator
temperature effect on the SPR sensor of
coupled to a straight waveguide [17].
Krestchmann configuration [20]; then, a bimetallic
The sensor is a compact and integratable one
SPR sensor chip is designed and tested in
which consists an MIM racetrack resonator and a
Biacore3000 for biomolecular detection [21]; after
straight MIM waveguide as an evanescent wave
that, wavelength-modulated and intensity-modulated
coupler. A broad-banded light propagates along the
optical fiber SPR sensors are studied, respectively
straight MIM waveguide, and the light satisfying the
[22, 23].
match condition will be coupled into the surface
plasmon mode of the MIM racetrack resonator. The 2.2.1 Temperature effect on the SPR sensor of
Krestchmann configuration
transmitted spectrum detected at the other end of the
straight MIM waveguide gives a harp dip at the For actual applications of SPR sensor, ambient
resonant wavelength, and the resonant wavelength temperature will affect the measuring result [24]. As
will red-shift as the RI of ambient material (the the most popular configuration, the effects of the
insulator in a racetrack resonator) increases (Fig. 5). temperature on an SPR sensor of Kretschmann
The theoretical sensitivity ( / ns ) of the configuration are investigated theoretically and
racetrack resonator SPR sensor in this design is experimentally.
about 1030 nm/RIU. To achieve high coupling Because of the change in properties of dielectric,
efficiency, the sensor should have a narrow resonant metal, and analyte layers, the resonant dips are
dip with a full width at half maximum (FWHM) of 9 shifted and broadened at high temperature (Fig. 6),
nm and a high extinction ratio of 34.5 dB. The which can be understood from the thermo-optic
“figure of merit” (FOM) [19] is defined as follows: effect in the dielectric and analyte, together with a
/ ns decrease of the plasmon frequency and an increase
FOM = . (2)
FWHM of the collision frequency in the metal layer when
The FOM of the racetrack resonator SPR sensors the temperature increases.
40 Photonic Sensors
70 000
film is deposited on the BK7 optical glass substrates,
60 000 then, a 10-nm Au film is deposited on the 40-nm Ag
Nomalized intensity (RU)
50 000 278K film, which has the best FOM based on theoretical
283K
40 000 288K
analysis.
293K
298K
Figure 8 presents the atomic force microscope
30 000
303K (AFM) images and resonant dips of the gold film
20 000 308K
313K and the gold/silver bimetallic film, respectively. The
10 000 surface roughness values of the single Au film and
0 10 20
Pixel
Au/Ag bimetallic film (10-nm Au with 40-nm Ag)
Fig. 6 Experimental SPR curves between normalized
are 0.810 nm and 2.635 nm, respectively. The
intensity and detective pixels at different temperatures [20].
roughness values of the Au film and bimetallic film
A theoretical model is constructed by are of the same order and are smooth enough for the
considering the temperature dependence of the SPR sensing experiments. The FWHM of the
properties of the metal, dielectric, and analyte layers. bimetallic layer is about 2/3 times narrower than that
The numerical result is shown in Fig. 7, which is of the single gold layer.
well consistent with the experimental result.
70 000
Change in response of SPR sensor (RU)
threat to consumers’ health [28]. Fig. 9 Sensorgram from testing the bimetallic chip sensing
For the bimetallic sensor chip, a 40-nm silver progress for 6 times [21].
Yong CHEN et al.: Review of Surface Plasmon Resonance and Localized Surface Plasmon Resonance Sensor 41
The limit of the detection of the SMX for the at the longer wavelength.
bimetallic film is 1.8 ng/μl, which is lower than that 1.0 Alalyte RI
of the single gold film (3.2 ng/μl) [29] by comparing 1.3419
Normalized transmittance
0.9
1.3505
to traditional single gold films. 1.3635
0.8 1.3730
2.2.3 Optical fiber SPR sensors
0.7
MO Spectrometer
650
Sensing cell Collecting fib er
Light source
600
Co mp uter 550
Fig. 10 Experimental setup of the optical fiber SPR sensor [22].
500
As shown in Fig. 11, the transmittance spectra 1.32 1.33 1.34 1.35 1.36 1.37 1.38 1.39 1.40 1.41
Refractive index
shift to a longer wavelength when the analyte RI Fig. 12 Resonance wavelength vs the analyte RI (the dots are
increases. When the analyte RI is tuned from 1.3419 experimental results, and the lines are simulation results): the
to 1.3730, the resonance wavelength varies from dashed line is the simulation curve for the sensor with the MgF2
552.7 nm to 631.2 nm. The resonance peaks broaden film and the solid line is the simulation curve for the sensor
at the high RI because of the higher absorption loss without the MgF2 film [22].
42 Photonic Sensors
For a similar structure but without the MgF2 film, localized surface plasmon resonance is very
the intensity-modulated optical fiber SPR sensor is sensitive to the ambient refractive index. For the
studied with the radially polarized beam. Because of experiment, gold nanorods are easily be fabricated by
the rotational symmetry of the fiber, a radially the seeded growth method [38], and its aspect ratio can
polarized beam can improve the excite efficiency. also be tuned to have the proper resonant wavelength
The result is shown in Fig. 13. The sensitivity of the (Fig. 14).
structure with the radially polarized beam is 3 times Figure 14 illustrates the extinction spectra of two
higher than that of using linearly polarized beam. kinds of gold nanorods with different aspect ratios
1.00 of 2.5:1 and 4.2:1. The longitudinal LSPR peak
0.98
shifts to the longer wavelength as the refractive
index increases, and the shift amplitude depends on
0.96
the aspect ratio. The longer the aspect ratio is, the
I/I0
0.94
larger the shift will be. Thus we plot the longitudinal
0.92 LSPR peak versus refractive index in Fig. 15 that
0.90 shows nanorods with 4 different aspect ratios. It
1.340 1.345 1.350 1.355 1.360 1.365 reveals an almost linear relationship between
Refractive index (RIU)
longitudinal LSPR peak and refractive index ranging
Fig. 13 Normalized transmitted light intensity vs refractive
from 1.33 to 1.47 in our experiment. As the aspect
index (triangles: the results of the bare multi-mode fiber; circles:
ratio varies from 2.5 to 4.2, the sensitivity increases
the results of the silver coated multi-mode fiber with the linearly
from 216 nm/RIU to 352 nm/RIU.
polarized beam; squares: the results of the silver coated
multi-mode fiber with the radially polarized beam [23]. 1.0
0.6 1.3715
Due to the localized surface plasmon resonance, 1.3950
0.4 1.4155
the local electromagnetic field around the metallic 1.4380
0.2
nanoparitcles will be enhanced dramatically, and the
0.0
resonant wavelength is sensitive to the variation of 500 600 700 800 900 1000
Wavelength (nm)
the local dielectric environment. Our researches in
(a)
this area include LSPR for the RI measurement,
Refractive index
LSPs in the optical fiber for SERS enhancement 1.0 1.3355
1.3586
[32–34], coupling between LSPs/LSPs and 1.3905
0.8 1.4111
LSPs/SPs for SERS enhancement and fluorescence 1.4209
Extinct ion
0.6 1.4400
enhancement [35–37].
0.4
2.3.1 LSPR for RI measurement 0.2
3000
720 0.2
2000
1.34 1.36 1.38 1.40 1.42 1.44 Curve B
Refractive index 1000
2.3.2 Optical fiber SERS sensors Fig. 16 Experimental schematic diagram for focusing light
on the tip–Curve A: R6G molecules SERS signal obtained from
Two different types of optical fiber are used in
the metal-coated taper tip; Curve B: signal from the same
our experiment: polymer optical fiber (POF) and
concentration R6G solution absorbed on glass slide without gold
photonic crystal fiber (PCF). Compared with the
nanorods, both with excitation power 0.3 mW, scan time 3 s
silica fiber, POF shows a more flexible, effective
[32].
and robust performance and better biocompatibility
Additionally, a broad spectral PCF SERS sensor
in the sensing [39–41] while PCF can provide very
is developed by using the solid core holey PCF with
large internal surface area because of air-hole arrays the silver nanoparticle cluster. A PCF SERS sensor
for SERS action. A POF SERS sensor and a PCF is fabricated by injecting the mixture of the
SERS sensor are developed in our experiment as 4-mercaptobenzoic acid (4-MBA) aqueous solution
follows: with the silver colloid solution into the air holes of
To fabricate the POF SERS sensor, we used the the PCF.
etching method [42] to prepare the POF tip with a The experiment setup is shown in Fig. 17. A
diameter of 2 μm–3 μm. Then several drops of gold continuous-wave Ar-ion laser (514.5 nm) and a
nanorods colloids were placed directly on the POF diode laser (785 nm) are used as the excitation
tip and dried naturally. After that, the POF SERS source to verify the broad spectral characteristics of
probe was dipped into rhodamine 6G (R6G) solution the SERS probe.
(10–9 M) to detect the R6G SERS signal.
For the common “optrod” configuration [43], Probe
directly with an inverted microscope objective, Fig. 17 Schematic diagram of the experimental setup [33].
which is also used for collecting the signal. The As shown in Fig. 18, by using the visible light of
spectra are achieved, as shown in Fig. 16. As a 514.5 nm and near-infrared light of 785 nm, the PCF
comparison, the same concentration analyte on the SERS sensor has a good performance by obtaining
glass slide without gold nanorods is also measured. an excellent and consistent SERS spectrum.
The SERS signal is enhanced 9-order magnitude Furthermore, the liquid holes’ cladding results in a
which can be attributed to the local field of gold decrease of the numerical aperture and V parameter,
44 Photonic Sensors
which can be explained as that some high-order layer. Afterward Ag cubes are chemically
guide modes in air holes’ cladding leak into the synthesized by reducing AgNO3 with ethylene
aqueous holes’ cladding. Besides the low efficient glycol [47–48] and dripped onto the R6G/PMMA
way of the evanescent field, leakage modes can layer. After drying at the room temperature for 24
create important action in the solid core PCF SERS hours, a coupled cube-hole array system is
probe. fabricated.
100 nm
+
20 000 514.5 nm Ar
Ag nanocubes
R6G/PMMA spacer Raman signal
Intensity (a.u.)
16 000 Curve A
Ag nanohole array 30 nm
12 000 25 nm
AAO substrate
40 m
Curve B
8000
1000 1200 1400 1600 1800 Fig. 19 Sketch of the coupled cube-hole array system [35].
Raman shift (cm– 1)
(a) Figure 20 presents the sketches of five types of
750 structures and corresponding Raman spectra.
Structure (d) is the coupled cube-hole array system
with significant Raman signals. The enhancement
Intensity (a.u.)
500
two sides which raise the local field intensity in the whole coupling region.
1363
1650
Structure (a)
1510
16 000 Structure (b)
1575
Structure (c)
14 000 Structure (d)
Structure (e)
(c) (d) 12 000
1311
Intensity (a.u.)
612
1183
10 000
774
1129
8000
6000 (d)
4000 (e)
(e) Ag nano-cubes
(c)
Ag film with nanoholes 2000
(b)
Smooth Ag film 0 (a)
R6G/PMMA 200 400 600 800 1000 1200 1400 1600 1800
AAO Glass Raman shift (cm–1)
Fig. 20 Sketches of five types of samples: (a) none of the metallic components, (b) isolated silver hole array, (c) isolated silver
cubes, (d) coupled silver cube-hole array structure [(a)–(d): all supported by the AAO substrate], (e) coupled silver nanocube-smooth
film structure supported by glass, and (f) their corresponding Raman spectra [35].
4.5107
7
810
3.6107
Enhancement factor
7107 t d
Enhancement factor
6107 2.7107
5107 1.8107
7
410
0.9107
3107
A
2107 0
(a) (b)
6107
5.3107 4.2107
Enhancement factor
7
4.610 h
Enhancement factor
D 3.5107
3.9107
3.2107 2.8107
2.5107 2.1107
7
1.810 1.4107
1.1107
0.7107
0.4107
40 60 80 100 120 140 160 10 20 30 40 50 60
Inter-hole spacing (nm) Ag film thickness (nm)
(c) (d)
Fig. 21 SERS enhancement factors with different geometrical parameters [35].
2.3.4 Coupling between LSPs and SPs for SERS distribution, so the plasmonic interaction between
enhancement and fluorescence enhancement silver nanocubes and a silver ground plane is studied
The coupling between LSPs and SPs can for SERS and fluorescence enhancement.
strongly modify the electromagnetic field In SERS experiment, a 57-nm-thick Ag film is
46 Photonic Sensors
1510 Glass
Intensity (a.u.)
20 000 1363
Height 25 000
(a)
15 000 613 12668 (a.u.)
118 5
774 20 000 EF=521
10 000
Intensity (a.u.)
613
20 000 1185 RhB doped PMMA t
774 Glass
15 000
10-nm PMMA, 0.3 s 18 000 (c)
10 000
16 000
5000 14 000 EF=19
0 12 000
0 500 1000 1500 2000
Intensity (a.u.)
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