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Mechanisms and applications of terahertz

Cite this: Nanoscale, 2017, 9, 13864
metamaterial sensing: a review
Wendao Xu, †a Lijuan Xie †a and Yibin Ying *a,b

Terahertz (THz) technology has attracted great worldwide interest and novel high-intensity THz sources
Published on 24 August 2017. Downloaded on 10/12/2022 6:00:43 AM.

Received 30th May 2017,
Accepted 23rd August 2017
DOI: 10.1039/c7nr03824k
rsc.li/nanoscale
and plasmonics are two of the most active fields of recent research. Being situated between infrared light
and microwave radiation, the absorption of THz rays in molecular and biomolecular systems is dominated
by the excitation of intramolecular and intermolecular vibrations. This indicates that THz technology is an
effective tool for sensing applications. However, the low sensitivity of free-space THz detection limits the
sensing applications, which gives a great opportunity to metamaterials. Metamaterials are periodic artificial
electromagnetic media structured with a size scale smaller than the wavelength of external stimuli. They
present localized electric field enhancement and large values of quality factor (Q factor) and show high
sensitivity to minor environment changes. In the present work, the mechanism of THz metamaterial
sensing and dry sample and microfluidic sensing applications based on metamaterials are introduced.
Moreover, new directions of THz metamaterial sensing advancement and introduction of two-dimen-
sional materials and nanoparticles for future THz applications are summarized and discussed.

1. Introduction vibrations, including weakly bound molecular entities with

The terahertz (THz) wave, lying between 0.1 and 10 THz, is the
last part of the electromagnetic wave to be explored. Being situ-
ated between infrared and microwave radiation, the absorption
of THz rays in molecular and biomolecular systems is domi-
nated by the excitation of intramolecular and intermolecular
a
School of Biosystems Engineering and Food Science, Zhejiang University,
866 Yuhangtang Road, Hangzhou 310058, P.R. China. E-mail: ibeying@zju.edu.cn
b
Zhejiang A&F University, Hangzhou, Zhejiang 311300, China
† These authors contributed equally to this work.
hydrogen bonds and weak interactions such as van der Waals
forces,1,2 which is significant for molecule and biomolecule
detection. Because of the absorption, some chemicals like
illicit drugs,3 antibiotics,4,5 pesticides,6,7 amino acids,8 geneti-
cally modified organisms,9 melamine,10 and other harmful
residues have been identified by detection through pressing
powder samples into pellets.11 However, this method is suit-
able for studying the feasibility of THz detection, not for trace
amount analysis. To obtain better sensitivity of THz detection,
THz attenuated total reflection (ATR) spectroscopy,12 terahertz
differential time-domain spectroscopy,13 waveguides,14 and

Wendao Xu is a Ph.D. student Lijuan Xie is a professor at the

at the College of Biosystems
Engineering and Food Science,
Zhejiang University, China, and
has worked as a visiting student
at Massachusetts Institute of
Technology and Kyoto University.
He obtained his bachelor degree
from Zhejiang University in 2013.
His current research interests are
in terahertz sensing and imaging
applications.
Wendao Xu
College of Biosystems Engineering
and Food Science, Zhejiang
University, China. She obtained
her Ph.D. degree from Zhejiang
University in 2009 and then
worked as a visiting researcher
at the Department of Electrical
and Computer Engineering,
Rice University, USA. Her current
research focuses on terahertz
devices and the optical proper-
Lijuan Xie ties of materials.

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metamaterials15,16 have been developed. Among them, THz
metamaterial sensing is not only signal-enhancing but also
easy to operate, which attracts significant attention from
researchers in diverse fields.
Metamaterials are periodic artificial electromagnetic media
structured with a size scale smaller than the wavelength of
external stimuli, presenting properties that cannot be found in
Nature. They were first developed to realize fascinating pro-
perties such as negative refraction index17,18 and cloaking.19,20
Within the rapid progress in recent decades, the development
of metamaterial research lies in diverse aspects that have been
reported in some reviews, such as all-dielectric metamater-
ials,21 reconfigurable metamaterials,22,23 flexible metamater-
ials,24 metadevices,25 graphene metamaterials,26 tunable meta-
materials,27 and metasurfaces.28 THz metamaterials, as firstly
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sensor applications. We also discuss the trend and challenges
of THz metamaterial sensing including novel metamaterial
design and introduction of nanomaterials into metamaterial
sensing, graphene plasmonics, graphene metamaterial devices
and topological insulator induced THz surface plasmons.
2. The mechanism of THz
metamaterial sensing
Metals, such as gold and silver, which commonly show surface
plasmon polaritons (SSP) in the visible part of the spectrum,
have significantly different physical properties in the THz
regime that make them hard to sustain SPPs at a flat metal

intersurface. As the THz frequency is far below metals’ plasma

reported by Prof. Xiang Zhang’s group,15 have received a great
deal of interest and have become a popular topic in THz
science and technology, including metamaterial modu-
lators,16,29 metamaterial polarizers,30 THz wave generation,31
THz wave absorbers,32 compressing imaging,33 etc. In recent
years, metamaterial based sensors have shown their potential
in diverse applications, which can be found in some review
articles.34–36 These metamaterials are suitable for sensing
applications as they provide spoof surface plasmons37 with
localized electric field enhancement and large values of
quality factor (Q factor) which show high sensitivity to minor
environment changes. Our review is specially focused on THz
metamaterials as they are easier to fabricate than mid-infrared
metamaterials, near-infrared metamaterials, and visible meta-
materials. Because of their potential detection abilities, THz
metamaterial-based sensing technology is expected to provide
a wide range of applications in the near future. In this paper,
we reveal the mechanism of THz metamaterial sensing, includ-
ing typical metasurface based sensing, metallic mesh device
(MMD) based sensing, metamaterial absorber based sensing,
and thin film sensing. As THz metamaterial-based sensing
research has progressed rapidly in the past decade, we divide
its applications into several aspects including molecule
sensors, biomolecule sensors and biosensors, and microfluidic
frequency, these materials have very high conductivity which
makes them resemble a perfect electric conductor (PEC) to a
greater extent.38 Thus the SPP’s electric field only slightly pene-
trates the metal, exhibiting poor confinement, thereby losing
plenty of advantages. To overcome this poor penetration of the
THz wave, one suitable solution is to use metals with a tex-
tured surface so that the electric field can effectively go further
into the metal side. Therefore, these engineered metal surfaces
can support SPP-like modes and metamaterials are an excel-
lent example.
As mentioned in the introduction, there are several types
of metamaterials, including metasurfaces, metamaterial
absorbers, MMDs, all dielectric metamaterials, graphene meta-
materials, etc. Among them, metasurfaces, metamaterial
absorbers, and MMDs are the most commonly used types
serving as sensors in the THz region. Thereby, we will mainly
focus on the sensing mechanisms based on them, as well as
show the mechanism of metamaterial-based thin film sensing.
We also show a comparative table of the performance of the
metamaterial sensors regarding the current state of the art as
Table 1.
2.1. THz metasurfaces
Metasurfaces (as shown in Fig. 1a),39 consisting of single-layer
or few-layer stacks of planar structures, can be readily fabri-

Yibin Ying is a professor at the

College of Biosystems Engineering Table 1 A comparative table of the performance of the metamaterial
sensors with respect to the current state of the art
and Food Science, Zhejiang
University, China. He obtained
Method Sensitivity Other advantages Limitations
his Ph.D. degree in 1999. And his
research interests lie in the broad Fluorescent High Easy operation, Photobleaching
rapid detection
areas of advanced material
Colorimetric Low Simple preparation, Interference from
technology, and intelligent equip- rapid detection sample
ment, including nanotechnology, SPRa High Label-free, real time High cost of the
visible/near-infrared and terahertz detection instrument
spectroscopy, biosensors, artificial THz High Fruitful structure Complex
intelligence and robotics. metamaterials design, rapid fabrication
detection process
Yibin Ying
a
SPR is short for surface plasmon resonance.

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Fig. 1 Typical metamaterial sensing. (a) Metasurface. Reprinted with permission from ref. 39. Copyright (2014) Nature. (b) Metamaterial absorber.
Reprinted with permission from ref. 42. Copyright (2017) Elsevier. (c) Metallic mesh device (MMD). Reprinted with permission from ref. 50. Copyright
(2014) American Chemical Society. (d) Red shift of the resonant peak caused by external sensing targets.
cated using lithography and nanoprinting technologies.28 The
ultrathin thickness in the wave propagation direction can
greatly suppress the undesirable losses caused by the resonant
responses and the use of metallic structures. As the meta-
material atoms are much smaller than the incident wave-
length, they are not resolved by the electromagnetic wave to
behave as a new material or medium. The reflection and trans-
mission properties of a boundary between two homogeneous
media are determined by the continuity of field components at
the boundary. When adding to the interface some periodic
subwavelength resonators of negligible thickness to form a
metasurface, the reflection and transmission coefficients will
be dramatically changed due to the boundary condition modi-
fication caused by the periodic subwavelength resonators.28
The incident electromagnetic wave couples into the surface
electromagnetic wave propagating back and forth along the
surface of resonators and is accompanied by the charge oscil-
lations inside the resonators. These coupled surface electro-
magnetic wave and oscillating charges are well known as
surface plasmons. In the THz regime, spoof surface plasmons
are used to explain the mechanism of metamaterials.37 The
localized electric field enhancement caused by THz meta-
surfaces enables a great improvement in sensitivity of external
target detection because a tiny change of the environment will
result in the change of resonant peaks, including the resonant
frequency and the Q value of the resonant peak.
2.2. THz metamaterial absorber
Typical metamaterial absorbers are bi-layered metal structures
spaced by a dielectric film; they were firstly reported in 2008.40
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The demonstration of metamaterial absorbers represents one
of the most significant applications as the oft-overlooked loss
components of the optical constants have much potential and
meaningful use when manipulated to create an effective absor-
ber. As an effective medium, the effective impedance of a
metamaterial absorber can be defined as
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ZðωÞ ¼ μðωÞ=εðωÞ: ð1Þ
When the effective impedance of a metamaterial absorber
matches the free space impedance Z0, the reflection is mini-
mized. It will then behave like an absorber at a certain fre-
quency.41 By designing a new structure of the metamaterial,
the frequency of the near unity absorption peak can be tuned.
The localized magnetic and electric resonant field enhance-
ment in the impedance matching metamaterial absorber
shows strong interaction with an external sensing target,
which can be used in ultrasensitive target analysis and bio-
sensing applications (Fig. 1b).42 Further, a metamaterial absorber
based sensing scheme in the THz regime displays significantly
enhanced sensitivity which outweighs that of planar meta-
surfaces.43 The enhanced sensitivity of the metamaterial absor-
bers is mainly induced by the strong resonant electric and
magnetic field enhancement in the absorber cavity, which may
be extremely attractive in sensing applications.
Flexible materials are suitable for targets of unshaped sur-
faces and hold potential applications in various cases. A THz
sensing platform based on a highly flexible, ultrathin meta-
material absorber with thickness down to 50 μm was develo-
ped for sensing applications as presented in Fig. 2a.44 Its
maximum frequency sensitivity was numerically achieved at
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Fig. 2 (a) Scanning electron microscope (SEM) image of the fabricated metamaterial absorber with a schematic cross-section of the sample (top
right) and the fabricated metamaterial absorber is caught between two fingers to illustrate its large flexibility (bottom right). Reprinted with per-
mission from ref. 44. Copyright (2015) AIP. (b) Thickness dependence of dielectric films on calculated transmission properties of the metallic mesh.
Reprinted with permission from ref. 61. Copyright (2009) The Japan Society of Applied Physics. (c) Schematic showing the location of the sample
under measurement by a THz near-field system. Reprinted with permission from ref. 64. Copyright (2012) OSA. (d) Experimental setup of a THz
spectroscopy system using a Tsurupica lens to focus the THz waves on the annular nanogap sample. Normally incident THz waves illuminate the
sample from the substrate side. (e) Schematic diagram of an Al2O3 ultrathin layer on an annular gap array in a 150 nm thick gold film on a glass sub-
strate. (Inset) Enlarged illustration of the Al2O3 overlayer on the nanogap, which is filled with Al2O3. Panels (d–e) are reprinted with permission from
ref. 65. Copyright (2015) American Chemical Society.

139.2 GHz RIU−1 (RIU is short for refractive index unit). By
decreasing the spacer thickness to 15 μm, the sensitivity of the
sensor was not dramatically enhanced comparing to the pre-
vious case as mentioned (50 μm thick spacer), which indicated
that the thickness of the spacer was not the major effect of very
thin film detection but the architectures of the resonators were.
A general metamaterial absorber had only one resonance
absorption with a single patterned structure. To obtain a multi-
band perfect absorber, multiple different metallic patterns were
needed. However, a simple design consisting of only an asym-
metric cross was presented as a triple-band terahertz absorber,45
which was sensitive to the tiny change of the external dielectric
environment with a maximal sensitivity of up to 1.6 THz RIU−1.
2.3. THz metallic mesh devices
MMDs, as presented in Fig. 1c, are generally composed of well-
distributed square holes and exhibit anomalous transmission
properties. As a kind of subwavelength aperture,46 MMDs with
grid intervals ranging from tens to hundreds of micrometers
have shown specific transmission Fano like dips in the THz
regime, where the dipped frequency can be controlled by the
size of the MMD.47 This dip is reported as being attributed to
splitting of the first-order surface plasmon polariton mode. Due
to the structure of MMDs and the oblique wave incidence, the
Fano-like dip occurs, forming a sensitive sensor accompanied
by a high Q factor resonance.36 The sensing modality of MMDs
is revealed by the frequency shift (red shift) of the dip with the
addition of external analyte layers as shown in Fig. 1d, which
have attracted a large amount of attention and interest owing to
their applications as label-free biosensors.48–51
2.4. THz metamaterial-based thin film sensing
Thin film sensing is one of the simplest cases in THz meta-
material applications as the thin film is flat with given optical
properties. With the employment of simulation as well as
experiment, thin film simulation and detection can be suitably

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used to display the sensing properties of THz metamaterial
applications.
The split ring resonator (SRR) is a well-known and widely
used type of THz metamaterial application. It is reported that
with the increased thickness of photoresist on the top of the
metamaterial, the frequency shift of the resonant peak grew
but with a slower speed as a result of the decay of the electric
field above the space of the SRRs.52 With the addition of a
16 μm dielectric overlayer, a nearly 120 GHz frequency shift
could be observed, which is in line with the simulation results.
Moreover, with the increase of the height of the SRR thickness,
the frequency shift was enlarged, and thereby pointing out a
new potential approach for signal enhancing. The effects of
dielectric overlayer thickness on planar THz metamaterials
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(double SRR structure) were studied using THz time-domain
spectroscopy (THz-TDS).53 By evaluating the effects of uniform
dielectric overlayers ranging from 100 nm to 16 μm, the limit-
ations and obstacles of THz metamaterial based sensing were
revealed with an overlayer of 100 nm that is quickly approach-
ing the limit of detectability. Some frequency selective surface
(FSS) consisting of asymmetric double split ring (aDSR) also
showed a promising sensitivity.54 With the addition of asym-
metry, this FSS presented a Fano like resonant peak, which
was extremely sensitive to external overlayers, showing a 4 GHz
frequency shift by covering 10 nm of sample. As high Q factor
resonances are extremely advantageous for ultrasensitive THz
metamaterial designs, a low loss dual band metasurface was
fabricated with high Q Fano and quadrupole resonances.55
The sensitivities were evaluated by the red shifts of the two res-
onances when coating the analyte on the surface of a meta-
material. The refractive index sensitivity of the Fano resonance
(2.06 × 104 nm RIU−1) with a higher Q factor was much better
than that of the quadrupole resonance (5.07 × 103 nm RIU−1).
Singh and his colleagues56 presented similar trends with sensi-
tivity levels of 7.75 × 103 nm RIU−1 for a quadrupole resonance
and 5.70 × 104 nm RIU−1 for a Fano resonance where the sensi-
tivity could be further enhanced by employing a thinner sub-
strate. As traditional SRR structures were sensitive to the polar-
ization of incident THz radiation, polarization-insensitive
metamaterial devices,57 which were composed of square ring
resonators, were especially suitable to work together with the
linear polarized femtosecond laser pumped THz radiation
with a minimal resolution of 17.7 μmol L−1 in the detection of
bovine serum albumin.
Like metasurfaces, a metal hole array (MHA) was also used
to study the effect of dielectric film sensing by Miyamaru and
his colleagues.58 The reflection dip shifted to lower frequen-
cies with increasing dielectric film thickness (the smallest
thickness of this study was 50 μm), which indicates the poten-
tial to be applied in highly sensitive THz applications. In their
work, the dependance of the reflection spectrum on the
MHA’s thickness and the side to which the dielectric film was
attached were also investigated. The sensitivity of the THz
MHA sensing of the illuminated side of the array outweighed
the opposite side of the array as the contribution from the illu-
minated surface to the reflection spectrum was much stronger
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compared with that from the opposite surface. And in their
study, using a thinner MHA could obtain a better sensitivity,
which indicated that the reflection characteristic of the thin
MHA could be applied to highly sensitive THz detections. A
fishnet structure based circular hole array59 was also intro-
duced into THz sensing as a polarization insensitive sensor. In
their work, the frequency shift and the amplitude modulation
were investigated as a function of the refractive index and the
thickness of the overlayer, showing promising sensing capa-
bilities for the refractive index changes with a sensitivity reach-
ing 128 GHz RIU−1. Moreover, due to the cutoff effect of the
metal holes and the mismatch of the resonant frequency of
the two sides,60 the transmission peak of MHAs decreased sig-
nificantly (the minimal thickness of the dielectric film was set
as 50 μm), which made it difficult to measure the resonant
peak and decreased the signal-to-noise ratio (SNR).
Metamaterials, which hold the sensitivity to the thickness
of thin films, inspire the application of thickness detection.
The thickness of poly(ethylene terephthalate) (PET) was
detected using MMD and a 1 μm thickness difference could be
recognized (the thicknesses of the samples are 3 μm, 4 μm,
and 5 μm as shown in Fig. 2b).61 Two-dimensional images of
MMD with thin film attached on its surface were also recorded
and the differences between images of various thin film thick-
nesses could also be easily distinguished. A similar method
had been applied to SiO2 film thickness detection62 by MMDs,
where the sensitivity could reach sub-mm-thick SiO2 layers.
With the introduction of Fano resonances to metamaterials,
the minimum thickness resolution of Si further reached
12.5 nm which is 1/16 000 times the wavelength of the incident
THz wave.63 Moreover, a near-field THz system was constructed
to reduce the spot size for THz metamaterial sensing.64 By
placing the metasurface sensing platform close to a sub-diffr-
action THz source (the distances were 25 and 50 μm in their
study), the number of the resonators and the minimal sensing
film area were significantly reduced, presenting a smaller
inter-cell coupling strength and a remarkably increased
Q factor compared to that of far field THz systems as demon-
strated in Fig. 2c. An area of only 3 × 3 resonators (0.2 × 0.2λ)
could be excited, which was much smaller than the area
excited by the far field system. By combining a near field
source and metamaterial sensing, the sensitivity could be
improved to a λ/375-thick dielectric film. As the excited area
and the thickness of target were much smaller than the tra-
ditional THz far field system, THz near field based meta-
material detection demonstrated promising potential in bio-
molecular detection. The most extreme sensitivity of THz
metamaterial based thin film detection reached down to 1 nm
which was 1/106 of the incident THz wavelength as shown in
Fig. 2d.65 In this work, a nanogap was used to confine THz
waves into sub-10 nm metallic gaps, which can detect the
refractive index changes caused by only a 1 nm thick Al2O3
layer with as much as 5% shift in the peak position as demon-
strated in Fig. 2e. The THz wave excited electric field was
extremely strong in the nanogap, which contributed to the
enhanced sensitivity.
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A THz plasmonic waveguide was also introduced into THz
nanofilm sensing.66 In this work, a high-aspect-ratio metallic rod
array (MRA) was demonstrated to generate and propagate THz
surface plasmonic waves and realize nanofilm sensing. The sensi-
tive MRA THz waveguide sensor could detect 300nm-thick SiO2
and ZnO nanofilms coated on a 100 μm-thick polypropylene film.
Thin film sensing is fundamental and of great scientific sig-
nificance, which reveals basic sensing properties such as the
effects of refractive index, volume of the sensing target, reson-
ance type, the thicknesses of the substrate of the metasurface,
and spacer of the metamaterial absorber. The sensing pro-
perties of metamaterial detection are of extreme importance to
further structure design, target sensing, and biosensing.
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In this section, we will introduce recent trends of meta-
material-based applications with respect to molecule sensors,
biomolecule sensors, biosensors, microfluidic sensors and
some other applications.
3.1. Molecule detection
In 2011, a paper-based planar metamaterial device was fabri-
cated for glucose detection as shown in Fig. 3a.67 In their
work, they presented glucose detection with a sensitivity reach-
ing 3.0 mmol L−1 as presented in Fig. 3b. As the normal con-
centration of glucose in human blood ranges from 3 mmol L−1
to 30 mmol L−1, this device holds the potential for further
practical applications. As inexpensive and abundant paper-
based biosensors could be more accessible to average users,

the paper-based THz metamaterial sensor was promising and

3. THz metamaterial-based sensing
applications
The THz metamaterial sensing method has been utilized in
many dynamic fields based on the theory as mentioned above.
could be fabricated as a lab-on-a-chip device. A highly sensitive
and selective sugar detection method was reported using
nano-antennas which operated in the THz frequency range
(0.5–2.5 THz) (Fig. 3c).68 The strongly localized and enhanced
THz transmission by this metamaterial sensing tool could

Fig. 3 (a) Schematic of the micrometer-sized metamaterial resonators sprayed on paper substrates with a predefined microstencil. (Bottom left)
Photograph of a paper-based terahertz metamaterial sample. (Bottom right) Optical microscopy image of one portion of an as-fabricated paper
metamaterial sample. (b) Experimentally measured transmission spectra of the paper metamaterial samples coated with a series of glucose solutions
with varying concentrations. Panels (a–b) are reprinted with permission from ref. 67. Copyright (2011) Wiley. (c) Schematic of the THz detection of
sugar molecules using a nano-antenna array-based sensing chip. The small cubes represent crystallized molecules of sugar and the THz wave is nor-
mally incident on the chip. Inset is a microscopic image of the nano-slot-antenna array for fructose. (d) Normalized THz spectra measured with the
glucose antenna for D-glucose and (e) sucrose molecules. (f ) Normalized THz transmittances using a nano-antenna array with a fundamental reson-
ance at 1.7 THz are shown for Coca-Cola Zero, Coca-Cola Light, Coca-Cola Classic, Pepsi-Cola, and Sprite. Panels (c–f ) are reprinted with
permission from ref. 69. Copyright (2015) Nature. (g) Schematic of the metasurface structure with kanamycin sulfate molecules deposited on the
surface. (Top left and bottom left) SEM images of the metasurface. (Bottom right) Kanamycin sulfate molecular structure. (h) Fractional change
of transmittance versus frequency for kanamycin sulfate. Panels (g–h) are reprinted with permission from ref. 73. Copyright (2015) Nature.
(i) Schematic of spoof plasmon sensing using a linear array of subwavelength grooves with guided THz wave. Panel (i) is reprinted with permission
from ref. 77. Copyright (2014) American Chemical Society.

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effectively increase molecular absorption. When the absorp-
tion peak of carbohydrate molecules and the transmission
peak of nano-antennas were matched, the absorption of the
sensing target was enhanced, which enabled selective detec-
tion at low concentrations, as shown in Fig. 3d and e.68,69 For
instance, the intensity of the transmission peak at 1.4 THz
would be obviously damped with the addition of external
D-glucose molecules which had a strong absorption peak at
1.4 THz, and sucrose could not induce such damping of the
transmission peak. This novel method could also be extended
to the utilization of the discrimination of different popular
drinks including Coca-Cola Zero, Coca-Cola Light, Coca-Cola
Classic, Sprite, and Pepsi-Cola Classic (Fig. 3f ).
Food security and safety, two major global public health
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issues, are receiving increasing worldwide attention with the
growth in population.70–72 As external harmful additions, such
as pesticide and antibiotics, show fingerprints in the THz
region,4–7 THz spectroscopy shows great feasibility in food
safety applications. To further improve the sensitivity of THz
detection, metamaterials have been introduced into food
quality and safety control in recent years. The research group
at Zhejiang University, China, employed THz metamaterials in
food safety applications. A metasurface consisting of square-
shaped slits on a high resistance silicon substrate with extra-
ordinary optical transmission resonance at ∼0.3 THz was used
for kanamycin sulfate detection as presented in Fig. 3g.73
Extraordinary sensitivity had been reached with the minimal
detectable concentration down to 100 pg L−1 (Fig. 3h),
showing a dramatic ∼1010 times enhancement with the utiliz-
ation of metasurfaces as a consequence of the existence of THz
electric field amplification, comparing to the lowest detectable
concentration of kanamycin sulfate on bare silicon (∼1 gram
per L). Swiftly, a circle slit-shaped metasurface was used for
tetracycline hydrochloride (TCH) detection with a minimal
detectable concentration as small as 0.1 mg L−1.74 In TCH
detection, ∼105 times sensitivity improvement was obtained
with the utilization of metasurfaces when compared to
sensing on a bare silicon substrate only. Pesticides have also
been widely used and have become a global concern partly
because of the harmful effects on human health and the
environment. A THz metamaterial absorber was reported for
the detection of pesticides, namely chlorpyrifos-methyl.42
Sensitivity improvement could be accessed by comparing the
sensing performances of THz metamaterial absorbers and
Teflon plates. In their work, the limit of detection (LOD) was
calculated to be 0.204 mg L−1 which was lower than the World
Health Organization’s provisional guideline limit for chlorpyri-
fos-methyl in vegetables (1 mg L−1). THz metamaterial absor-
ber based sensing indicated the potential applications in food
quality and safety control. Additionally, THz metamaterials
with SRR structure could be used in the tiny refractive index
difference between transgenic product and non-transgenic
ones with clearly distinguished SRR response peaks,75 indicat-
ing the possibility in identifying transgenic products.
By using a scattering edge coupling method, THz waves
could be guided onto the surface of metamaterials.76,77 As
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illustrated in Fig. 3i, they showed that broadband spectral data
could be experimentally extracted from corrugated metallic
surfaces consisting of a linear array of subwavelength
grooves.77 The enhanced light–matter interactions that occur
in the vicinity of the spoof plasmon surface allowed for a more
efficient use of the limited power of current terahertz sources
and could detect lactose at 300 ng mm−2. A THz plasmonic
sensor using a hybrid planar waveguide composed of a subwa-
velength plastic ribbon waveguide and a diffraction grating
was also employed in THz sensing.78 Within localized and
enhanced THz plasmonic fields, the minimum detectable
amount of analytes (Bi2CuISe3) in powdered form reached
17.3 nmol mm−2.
3.2. Biomolecule detection and THz biosensing
THz technology has attracted a large breadth of interest in the
biomedical context as the collective vibration modes of protein
and DNA molecules are predicted in the THz regime.79,80 Thus
protein detection and THz biosensing applications are of great
significance to extend the utilization of THz technology. As the
detection of trace amounts of protein is needed, THz meta-
materials are suitable for the signal amplification in those
applications.
Detection of small amounts of horseradish peroxidase was
demonstrated using a highly sensitive MMD sensor by Yoshida
and his colleagues.81 To evaluate the sensitivity of the MMD
sensor, horseradish peroxidase was printed on the surface of
MMD with the utilization of a commercially available printer.
As a result, a distinct shift of the transmission dip occurred
with horseradish peroxidase at a concentration of 500 pg mm−2
(11 fmol), presenting a significantly high sensitivity of this
MMD sensor for the femtomole level of sensing targets.
Planar wallpaper-based metamaterials were also utilized for
protein detection. The metamaterial structures varied includ-
ing both hexagonal and square unit cells.82 Multiple methods,
including the theory, simulations, and experiments, were used
to characterize these metamaterials with different patterns. By
applying these novel structures, the resonant peaks can reach
a good match with biotin’s which may help to increase the
sensitivity of biotin. Furthermore, a thin-slab metamaterial
structure enhanced the THz absorption signal of an ultrathin
adsorbed layer as demonstrated in Fig. 4a, thus serving as a
signal amplifier.83 By matching the absorption peak of bovine
serum albumin (BSA) and the resonant peak of the meta-
material at 4.8 THz, the absorption of BSA molecules was
enhanced with a concentration of 300 mM (Fig. 4b). While
using other molecules like Rhodamine 6G (Rh6G) and 3,3′-di-
ethylthiatricarbocyanine iodide (DTTCI), no significant absorp-
tion signal was observed. This study indicated that with the
improvement in structure design of a metamaterial device,
they could show selectivity by matching the absorption peak of
sensing targets and the resonant peak of metamaterial
devices. Thereby, THz metamaterial sensing could improve the
sensitivity and, in some cases, the selectivity could also be
maintained.
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Fig. 4 (a) Schematic illustrations of the metamaterial sample. (b) (Top plot) Normalized transmittance spectrum of a submicron-thick BSA protein
layer (black circles) and the transmittance of the metamaterial sample (red circles) show the matching of the protein signal and metamaterial reson-
ance. (Bottom plot) Normalized transmittance spectra of an ultrathin layer of BSA molecules absorbed on the metamaterial sample and a reference
sapphire substrate. Panels (a–b) are reprinted with permission from ref. 83. Copyright (2016) Nature. (c) Schematic of a THz metamaterial sensor
with different shapes of sensing targets. Reprinted with permission from ref. 85. Copyright (2015) OSA. (d) The schematic diagram of label-free THz
measurement for cell apoptosis. Reprinted with permission from ref.86. Copyright (2016) AIP. (e) Schematic diagram of THz metamaterial bio-
sensing. Top-left shows the SEM of SRRs without and with biomolecules for comparison. Reprinted with permission from ref. 90. Copyright (2013)
Elsevier.

Microorganisms have frequently been researched in THz
metamaterial sensing applications partly due to the comparable
size of a microorganism to the size of a THz metamaterial
atom. Slot antenna arrays were used to demonstrate individual
yeast cell detection by Park and his colleagues,84 where the
addition of yeast cells caused a shift in the resonant frequency
of metamaterials. Their simulated and experimental results also
indicated that sensors fabricated on relatively low permittivity
substrates (like quartz) presented higher sensitivity and vertical
range of the effective sensing volume than that on high permit-
tivity substrates (like silicon). The field enhancement effect was
confirmed when sensing yeast films on metamaterials with
different sizes of slot widths, showing that the sensitivity was
higher for smaller slot widths (metamaterial with a 2 μm slot
width causing ∼13 GHz frequency shift when deposited a 4 μm
yeast film). As the shapes of microorganisms varied in sensing
applications, the sensitivity of the shape dependence was one
important consideration. Therefore, THz metamaterial sensing
of samples with different shapes was studied, where different
shapes of polystyrene microbeads were selected as targets
(Fig. 4c).85 In their work, spherical, ovular, lens-shaped, and
star-shaped structures of polystyrene microbeads were studied.
Star-shaped microbeads presented the best sensitivity in the
low-density regime which was three times that of spherical
ones, implying the field enhancement effects in this work. The
frequency shift saturated at 60–80 GHz when the gap area was
full of microbeads. In practice, monitoring the cell status
during natural growth or after some treatment was very essential
and label-free sensors were among the best choices. As the
metamaterial sensor was sensitive to the number of the external
cells, this type of sensors could be used in label-free measure-
ments of cell apoptosis. A flexible metamaterial fabricated on a
10μm-thick polyimide substrate was constructed, consisting of a
planar array of five concentric subwavelength gold ring resona-
tors (Fig. 4d), which was sensitive to the external tiny change of
the dielectric environment.86 In their work, oral cancer cells
with and without a sanative drug were tested and a linear
relationship between cell apoptosis measured by flow cytometry
and the relative changes of resonant frequencies of THz meta-
materials were observed and further analyzed. As the cell
number of cured oral cancer cell samples was obviously smaller
than that of control ones, the frequency shift of the meta-
material resonant peak with cured oral cancer cell samples was
much smaller than that with uncured ones. This work was of
general importance in developing cheap, label-free, real-time,
and in situ detection tools.
A label-free THz biosensing platform for living body-related
molecular binding was demonstrated using a thin MMD,

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showing that the dip frequency shift and transmittance attenu-
ation of the dip frequency were dependent on the bonding
amount of sensing targets.87 As a basic and effective bonding,
the avidin–biotin interaction was selected as an example and a
small amount of biotin (0.17 pg mm−2) was detected through
this method. A similar MMD was used for single- and double-
stranded DNA detection with a polyvinylidene difluoride
(PVDF) membrane for adding DNA samples.88 Free-space THz
measurement could not recognize the optical properties of a
small amount of DNA molecules due to the low absorption of
such targets. However, MMD devices provided an enhanced
sensitivity as they were sensitive to the tiny refractive index
difference between single- and double-stranded DNA at the
concentration of 2 μg mm−2, showing a potential approach to
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tion as shown in Fig. 4e.90 Both the low and high frequency
resonant modes of the metamaterials were found useful in
detecting SA with a frequency shift up to 6.76 GHz (non-
diluted SA solution, extent of labeling ≥1 mg ml−1). SRR pat-
terned metamaterials were also used for fast and accurate
detection of microorganisms, such as fungi and bacteria.39
Extremely small amounts of the microorganisms were detected
as their sizes were on the same scale as the micro-gaps of the
THz metamaterials. A blue shift of the resonant peak was
observed with the addition of 0.019 μm−2 Escherichia coli
(E. coli) because the refractive index of water was greater than
that of E. coli cells. As the excited electric field was at the
several tens of micrometer level, the absorption of water was
not strong, thereby making this metamaterial sensor usable in

the analysis of biologically relevant DNA samples. Alkanethiol
molecules were detected by using metamaterials with an SRR
pattern.89 A differential transmission (DT) interrogation
method was applied to measure the resonant peak difference
of metamaterials with and without sensing targets, where the
DT signal mainly came from the interaction between alkane-
thiols and metamaterials by electron transfer and/or the
variation of the dielectric constants. The carbon chain length
dependence of the alkanethiol molecules was studied in this
work, indicating that metamaterials offer a promising way to
read out the carbon number in the self-assembled alkanethiol
molecular monolayers. Further, numerical simulations also
confirmed that the strong electric field at the gap and corner
regions of this kind of metamaterials had shown large
enhancement of the sensitivity. A label-free and specific meta-
material biosensor, which was decorated by octadecan thiols
and biotins, was employed for streptavidin–agarose (SA) detec-
liquid sensing with the most sensitive area locating at the gap
of the SRR structure which was not easy for free space THz
sensing.
3.3. Metamaterial based microfluidic applications
The initial step towards THz metamaterial based microfluidic
applications was the detection of liquid samples. Planar SRR
structure arrays were fabricated for 50 nm thin liquid layer
sensing, where both the circular current driven and linear
polarization induced resonances presented red-shifted reson-
ances.91 When acquiring the reflection of a metamaterial
using THz radiation, the reflection signal came from the sub-
strate (GaAs) part and the metamaterial (SRR) part formed two
pulses in the received time domain spectrum as shown in
Fig. 5a and b.92 Therefore, the THz spectra of the reference
and sensing signal could be collected in a single measurement
from different intersurfaces of the substrate. An ethanol–water

Fig. 5 (a) Schematic diagram of the experimental arrangement in reflective geometry for a metamaterial with aqueous solutions. (b) Typical reflec-
tive THz time-domain waveforms from split ring resonators (SRRs)/GaAs. Panels (a–b) are reprinted with permission from ref. 92. Copyright (2013)
AIP. (c) Optical configuration of the experimental setup around the complementary split ring resonator (CSRR) sample. (Right plot) A photograph of
a CSRR used in the experiments. Reprinted with permission from ref. 93. Copyright (2013) Springer. (d) Schematic of the fluidic THz metamaterial
device for the sensing of aqueous solutions. (Right plot) Photograph of the fluidic metamaterial device. Reprinted with permission from ref. 94.
Copyright (2016) Royal Society of Chemistry. (e) Schematic diagram of the metamaterial absorber integrated microfluidic sensor. The microfluidic
channel is sandwiched between the metal microstructure array and the metal reflector. The metal microstructure array is attached on the cap and
the metal reflector is on the substrate. The analyte in the channel flows in from the inlet and out from the outlet. A THz beam is incident from the
cap side and the reflected terahertz beam is measured for sensing. Reprinted with permission from ref. 95. Copyright (2016) Wiley.

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mixture (ethanol 30%, 50%, 70%, and 100%) and an aqueous
solution of NaCl (0.666, 1.202, and 1.903 mol L−1) were investi-
gated and the peak–valley value near the resonant region
depended linearly on the solution concentration, which came
from the variation of the dielectric environment near the inter-
face between the metamaterials and the aqueous sample.
Complementary split ring resonators (CSRRs), as demon-
strated in Fig. 5c, were fabricated to achieve better reflection
energy than SRRs for the detection of glycerol–water mix-
tures.93 The reflected resonant dip frequency changed sharply
with glycerol concentration, showing detection sensitivity
about 8 times higher when compared to the case on a silicon
substrate. By depositing a dielectric film on a metamaterial,
the resonant frequency shifted but saturated at a specific thick-
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ness as a result of the limited sensing volume of the meta-
material;94 thereby, the dielectric constant of various polymers
could be extracted. In this work, they demonstrated a micro-
fluidic channel based on metamaterials to address the real
dielectric constants for a polar liquid solution partly due to
the fact that the resonance shift was mainly caused by the real
dielectric constants of the liquid solution (Fig. 5d).94 As an
instance, the dielectric constants of sodium chloride and pot-
assium chloride solutions had been determined with various
concentrations. THz metamaterial absorbers trapped incident
THz waves into a thin layer, forming strong attenuation of the
incident THz waves, showing an extremely strong electric field
enhancement in the thin layer, and, thereby being suitable for
sensitive detection. In 2016, an array-dielectric–metal micro-
structure was constructed where the dielectric layer of the
structure was hollow and acted as the microfluidic channel,
serving as a highly sensitive sensor for label-free refractive
index sensing (Fig. 5e).95 By the novel design of the electro-
magnetic parameters of the metamaterial absorber, the
electromagnetic fields could be strongly confined in the
channel, which resulted in the significantly enhanced inter-
action between the sensing targets and the incident THz wave.
Compared to the traditional THz metamaterial absorber
sensor, this new type of THz metamaterial absorber sensor
achieved a high sensitivity up to 3.5 THz RIU−1. The proposed
idea of combining metamaterial and microfluid with a great
light–matter interaction could be extended to other frequency
regions and showed promise in sensing and biosensing
applications.
A THz artificial material composed of MRA also was suc-
cessfully incorporated into microfluidics as a miniaturized
waveguide with an extended optical-path-length for label free
fluidic sensing.96 The detection limit of a liquid analyte was
demonstrated to be less than 0.1 mmol which indicated that
this type of phase sensitive sensor had good adaptability in
lab-chip technology. In recent years, THz surface plasmon
resonance using prism-coupling and periodically grooved metal
films was used for refractive index sensing.97–99 The gap dis-
tance between the prism and the metal film and the incident
angle have great effect on the performance of sensing. The sen-
sitivity could reach up to 2.57 THz RIU−1 when using a second-
order mode sensing by simulation.98 This device could also be
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employed to differ different kinds of liquids, such as gasoline,
liquid paraffin, glycerin and water.99
3.4. Other applications
The large wavelength associated with THz radiation severely
hindered its interaction with nano-objects, including nano-
particles, nanorods, and large biological molecules; however,
by fabricating THz metamaterials with a gap achieving the
nanometer level, the electric field could be strongly enhanced
as shown in Fig. 6a.100 The THz dipole nanoantennas spaced
by nanogaps of 20 nm allowed retrieving the spectroscopic sig-
nature of a monolayer of cadmium selenide quantum dots at
5.65 THz, presenting a Fano-like interference between the fun-
damental antenna mode and the phonon resonance of the
quantum dots with an absorption enhancement factor greater
than one million (Fig. 6b). Therefore, trapping a THz wave into
nanovolumes might develop sensitive as well as selective
sensors in the future. The extraordinary transmission of a THz
wave through an array of nanogaps with varying dimensions
and periodicities was employed for the THz sensing of thin
film single-walled carbon nanotubes (CNTs) (Fig. 6c).101 As
CNTs behaved like conductors which could strongly change
the electric field excited by metamaterials, a 10 nm-thick film
of single-walled CNTs over the gaps led to 43% extinction of
THz waves. Compared to polar liquids such as water and
ethanol, oil does not show significant absorption in the THz
region, enabling easy oil detection even in free space THz
detection. SRR patterned THz metamaterials were also used as
a sensor for discriminating gasoline of 93# and 97#, indicating
the potential applications of gasoline identification.102 The
experimental and simulated results showed that the red shift
of the high frequency resonant peak was larger than that of
the low frequency one.
4. Conclusion and perspective
4.1. Novel metamaterial design
In recent years, the sensitivity of metamaterial detection has
been improving partly due to the improvement of meta-
material structures. Increasing the excited electric field or uti-
lizing the high electric field for sensing are two plausible solu-
tions. In the literature, we find that sensing applications using
a Fano-like structure, metamaterial absorber, and squeezing
incident THz wave into a nanovolume (the common method is
shortening the gap to the nanometer level as a result, enhan-
cing the electric field) are possible ways toward ultra-sensitive
applications. Novel metamaterial designs are still of great sig-
nificance as the requirement for low-cost and fast sensors
increases.
In addition to sensitivity, another crucial consideration for
metamaterial design is the selectivity of the device.68,69 In
recent years, Fano coupling of the sensing targets and the
metamaterial device has been observed when the absorption
peak of sensing target and the resonance of the metamaterials
are well matched.100 Therefore, applying metamaterials in
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Fig. 6 (a) (Left plot) Sketch of the THz nanoantenna array and definition of geometrical antenna parameters. (Right plot) SEM detail of a nanogap
region (upper panel); two-dimensional surface plot of the field amplitude enhancement factor around the gap region at the quantum dot (QD)
resonance frequency (lower panel). (b) Transmittance of the array for THz polarization set along the nanoantenna long axis and without QDs over
the surface (green curve); transmittance of the same array covered with a QD monolayer, for THz polarization set along the y (black curve) and x
(red curve) axis. Panels (a–b) are reprinted with permission from ref. 100. Copyright (2015) American Chemical Society. (c) Schematic diagram of
THz transmission coupled to a single-walled carbon nanotube film on 2 nm-wide metallic nanogap arrays. Reprinted with permission from ref. 101.
Copyright (2015) Royal Society of Chemistry.

sensing applications can improve the sensitivity as well as pre-
serve the fingerprint signal of sensing targets. However, the
Fano-like resonance does not always occur in the THz regime
when matching the absorption peak of the sensing target and
the resonance of the metamaterials, which is partly due to the
weak and broad absorption of sensing targets in the THz
band. Therefore, novel designs of metamaterials are needed
when detecting targets with a broad absorption band.
4.2. Introducing nanomaterials into metamaterial sensing
Nanomaterials, such as gold nanoparticles, quantum dots,
etc., are attractive in various sensing applications.103,104
However, the plasmons of those nanoparticles do not lie in
the THz region, which limits their use in many sensing appli-
cations. As mentioned above, quantum dots have been used
in THz metamaterial sensing, showing that THz metamater-
ials can sense ultrathin films with thickness down to the
nanometer level.100 This inspires us to introduce those nano-
particles into THz metamaterial sensing. Nanoparticles, such
as gold, can be functionalized and used in many applications;
therefore, introducing them into THz sensing will lead to
fruitful practices. Hence, introducing nanoparticles to THz
metamaterial sensing may open up a new avenue for
researchers in the development of new embranchments of
THz detection.
4.3. Graphene plasmonics and graphene metamaterial
devices
Graphene plasmonics have been found tunable and less lossy
compared to metal induced plasmonics.105 In recent years,
graphene plasmonics have been successfully used in protein
sensing and the fingerprint detection of external molecule in
the mid-infrared region.106,107 The addition of external mole-
cules on the surface of graphene metamaterials will induce
two major phenomena, red shift of the graphene resonant
peak and external molecule induced doping of graphene,
which moves the Fermi level of CVD grown graphene toward
the Dirac point, accompanying a decrease of the carrier
density of graphene and red shift of the resonant peak of the
graphene plasmonics. Therefore, graphene plasmonic based
sensing may be a new research theme as the addition of the
external sensing target induced doping of graphene also con-

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tributes to the red shift of the resonant peak, which enhances
the sensitivity.
Graphene-metamaterial heterostructures have been
reported as active THz wave modulators in recent years, where
the external electric voltage induced doping of graphene con-
tributes to the modulation ability.108–112 As is well known,
many methods can be used to induce the doping of graphene,
including the addition of external molecules. Therefore, intro-
ducing graphene metamaterials to THz sensing technology
may produce new sensing strategies as the external molecule
induced doping of graphene that significantly changes the
electromagnetic environment near the surface of metamater-
ials as compared to the case of metamaterial sensing only
which is sensitive to the refractive index of the sensing targets.
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Two-dimensional (2D) materials other than graphene, such
as molybdenum disulfide (MoS2), have also been introduced
into THz metamaterial technology.113 As 2D materials show
similar physical properties, this inspires us that more and
more 2D materials will be utilized in THz metamaterial
technology in the near future. Like graphene, other 2D
materials also have been widely employed as sensors.114–119
Therefore, more and more 2D materials may be introduced
into THz metamaterial sensing technology, which could be an
effective contribution to future THz sensing and biosensing
technology.
4.4. Topological insulator induced THz surface plasmon
Like an ordinary insulator, a topological insulator has a bulk
energy gap separating the highest occupied electronic band
from the lowest empty band; the surface or edge in two dimen-
sions of a topological insulator, however, necessarily has
gapless states.120 In short, they are unique states of matter
having a conducting Dirac surface and underlying bulk. In
recent years, topological insulators have been introduced in
THz plasmon generation,121,122 plasmon modulation,123 non-
linearity,124 and Fano dynamics.125 These properties of the
topological insulator show great potential in future THz plasmo-
nics sensing.
From the above, it is clear that more experimental studies
are needed for the field of THz metamaterial based sensing.
As a metamaterial is sensitive to the tiny change of the dielec-
tric environment near the surface (the sensing limit is around
several tens of micrometers), the refractive index of the
sensing target can be recognized. However, detecting the
refractive index only is not of great interest to a large group of
researchers from vast fields, calling for the need for biosensors
that are able to capture targets in a complex environment. At
present, the quantity of THz metamaterial based biosensing
applications is still far from sufficient, limiting the practical
applications where THz metamaterials serve as biosensors.
In addition, as the sensing volume of metamaterials is
limited, the damping of THz metamaterials is limited, too.
Therefore, the absorption of polar liquids such as water could
be compressed to an acceptable extent, indicating a feasible
method for microfluidics. As we mentioned above, there are
some THz metamaterial based microfluidic applications and
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the sensitivity has been improved through the strongly con-
fined electromagnetic fields in the channel, resulting in the
significantly enhanced interaction between the sensing targets
and the incident THz wave. However, this type of device is still
a refractive index sensor at present as the selectivity of those
devices is low, calling for the need for biosensing applications
which has been employed in metamaterial sensing in other
bands.126
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors gratefully acknowledge the financial support pro-
vided by the National Natural Science Foundation of China
(no. 31671573).
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