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Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (1 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 1. Comparison of multistep and one-step processes to prepare inverse microstructure templates: a) a multiple-step fabrication process by
photolithography: (1) silicon substrate, (2) silicon substrate coated with photoresistor, (3) patterning of photoresistor by UV light with photomask,
(4) isotropic etching of silicon substrate, (5) silicon substrate with inverse micropyramids by removal of photoresistor. b) A one-step fabrication pro-
cess by 3D printing.
hence higher sensitivity are achieved. Meanwhile, the effective including pyramid, semisphere, and semicylinder. Upon
modulus decreases when the porous microstructured elasto- the application of external pressures, it is expected that
mers are applied as electrodes, which dramatically improves the deformation of these anisotropic microstructures with
sensitivity at the low-pressure ranges. Micrometer-scaled pyra- nonuniform cross sections can induce large changes of
mids and semispheres are two most reported microstructures contact area compared with unstructured counterparts and
for pressure sensors. As reported by Chen and co-workers in microstructures with uniform cross sections.[30] Finite ele-
2014, a piezoresistive pressure sensor with an ultrahigh sensi- ment modeling (FEM) was then used to simulate how dif-
tivity of −5.53 kPa−1 within a pressure range from 0 to 100 Pa ferent microstructures can induce the changes of effective
was obtained when an anisotropic pyramid microstructured contact area and hence large contact resistance changes.
graphene film was applied as one electrode.[30] By using two By replicating the microstructured templates, PDMS thin
layers of microdome/microsphere arrays, a high sensitivity films with microscopic contact features were obtained. A
of −15.1 kPa−1 and a minimum pressure detection of ≈0.2 Pa thin layer of conductive carbon nanofibers (CNFs) was then
were achieved.[34] However, the fabrication of these highly sen- spray-coated onto these microstructured PDMS’s thin films
sitive pressure sensors generally involves a micro/nanofabri- to impart piezoresistive capability. Finally, new pressure sen-
cation process. As illustrated in Figure 1a, in order to prepare sors were made by assembling these PDMS conductive thin
inverse silicon templates with micropyramids, a photolithog- films with a conductive electrode of indium tin oxide (ITO)–
raphy process with multiple steps including spin coating, UV coated flexible poly(ethyleneterephthalate) (PET) film. The
irradiation, etching, and cleaning is required. This process resistance changes for sensors with various microsturctures
is not only time consuming and high cost but also inacces- were investigated and compared experimentally. The sensor
sible for low-cost consumer products due to the requirement performance is highly dependent on topographic feature
of clean-room manufacturing facility. Apart from these well- of different microstructures, which was confirmed by FEM
defined microstructures by a complicated micro/nanofabri- simulation. The semicylinder microstructure was identified
cation process, large area–patterned conducting elastic thin as a new geometry to achieve the best sensor performance
films by simply copying the morphology of silk-based textiles in terms of sensitivity comparing with pyramid and semi-
also demonstrated ultrahigh sensitivity for the detection of sphere microstructures. As proof of concept, the potential
minute forces with fast response time.[35] Although substan- application of such sensors for human motion detection was
tial progress has been made by integration of various micro- demonstrated.
structures into pressure sensors, it is still unclear what effects
the geometrical features have on the sensor performance and
there is a lack of a simple and versatile method to ration- 2. Results and Discussion
ally optimize microstructures to achieve desirable sensor
performance. Comparing to the micro/nanofabrication process that involve
Here, we report a rational design and fabrication multiple steps to prepare inverse silicon templates as shown
method for highly sensitive pressure sensors by manipu- in Figure 1a,[30,31] the 3D printing method shown in Figure 1b
lating the microstructures of conductive and compress- offers a single-step process, thus overcoming high cost and
ible poly dimethylsiloxane (PDMS) electrodes. To simplify mitigating the strict clean-room conditions. In addition, the
the fabrication process, microstructured templates were ability of 3D printing to precisely adjust structure parameters
first made in one step (Figure 1b) by 3D additive printing, such as the angle of side wall of pyramids gives more flexibility
Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (2 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 2. Fabrication and characterization of microstructured PDMS thin films by replicating 3D-printed polymeric templates: a) CAD models for 3D
printing of polymeric templates including pyramids, semispheres, and semicylinders. b) Fabrication of conductive microstructured PDMS thin films
by replicating polymeric templates and spray coating of CNFs. c) Top-view optical microscope images of microstructured PDMS thin films coated with
CNFs. d) Corresponding side-view optical microscope images. e) SEM images of pyramid coated with CNFs.
to control the microstructures of PDMS thin films and hence an applied pressure of P = 300 Pa. It can be seen that for the
the sensitivity of assembled pressure sensors. same applied load, the three contactors experience different
Three microstructured templates including pyramid, semi- stress levels due to their different geometries, with the differ-
sphere, and semicylinder were designed and fabricated by ence between the semicylinder and the pyramid being more
3D printing. The schematic illustrations of the three printed than one order of magnitude. The contact area between a
polymer templates are given in Figure 2a. After printing, a pre- microscopic contactor and the flat electrode as a function of
cursor mixture of PDMS elastomer and curing agent was casted the applied pressure is summarized in Figure 3d. In the pres-
onto the printed templates, and free-standing PDMS thin films sure range of 0–2000 Pa, the contact area generally increases
were obtained by peeling off the cured PDMS (Figure 2b). Sub- with the pressure for all the three microstructures. Higher
sequently, a thin layer of CNFs was uniformly deposited onto slopes are observed at low pressure, which indicates greater
the microstructured PDMS, resulting in dark-colored PDMS sensitivity under low pressure. The stress distribution in the
films. The corresponding optical and electron microscopy contactor is nonuniform for all the three microstructures and
images of the three microstructured PDMS thin films coated is concentrated near the contacting tips due to the smaller con-
with CNFs are shown in Figure 2c–e. Regular and uniform tact area, which results in higher mechanical deformations and
microstructures of the identical feature size on the PDMS thin rapid changes of contact area. However, as the applied pressure
film can be clearly seen from Figure 2c,d for three different further increases, deformation of the microstructures tends
microstructures. A zoomed-in scanning electron microscopy to saturate, and additional pressure only induces a less rapid
(SEM) image of micropyramid in Figure 2e indicates that the change in contact area due to a larger cross-sectional area of
as-deposited CNFs are uniformly distributed on the PDMS the compressing structure. The compression sensitivity of the
substrate. microstructures decreases with pressure. It is of significant
Figure 3a–c shows the Von Mises stress field of pressure interest to note that, compared with the other two microstruc-
distribution (Pa) for the three microstructure features with tures (pyramid and semisphere), semicylinder exhibited more
Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (3 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 3. FEM analysis of different microstructures under pressure. a–c) Von Mises stress field for one single microstructure unit of a) pyramid,
b) semicylinder, and semisphere c) under a pressure of 300 Pa. d) Contact area of a sensor cell as a function of pressure. e) Sketch of electrical current
pathway through a unit microstructure of semicylinder under pressure.
pronounced change of contact area under the same pressure similar electromechanical behavior, and the changes of resist-
condition both at the low and high pressures. As illustrated ance as a function of applied pressure for three microstructures
in Figure 3e, the contract area between the conductive PDMS are summarized in Figure 4c.
thin films and ITO electrode increases with the applied load, The pressure response curves of pressure sensors with
causing the total resistance to decrease. different microstructures shown in Figure 4c can be gener-
A typical assembly of pressure sensor with semicylinder ally divided into two regions: high-sensitivity at low-pressure
microstructure is illustrated in Figure 4a. The pressure sensor values (0–200 Pa) and a low sensitivity at pressures above
consists of two halves placed face to face: one part is a thin 200 Pa. The observation of a distinct difference in sensitivity
conductive PDMS film with microstructured features while between two pressure ranges can be explained by the corre-
the other part is a flat conductive ITO–PET film. Applying sponding change of contact area. As discussed in the above
an external pressure would cause the microscopic features of FEM analysis (Figure 3), for the three microstructures, ani-
PDMS to deform, causing the contact area between the two sotropic morphological features, and nonuniform stress dis-
conducting surfaces to increase, which in turn reduces the tribution resulted in larger change of contact area and hence
electrical resistance. The geometry of the contacting features higher sensitivity of resistance change at the low pressure
plays an important role in their deformation responses and, range. As the contact area change tends to saturate at high
thus, the electrical behavior under external forces. To charac- pressures, the sensitivity of the sensors decreased accord-
terize the effect of the microstructure geometries on the sensor ingly. Sensors with semicylinder microstructure exhibited the
sensitivity, changes of the sensor output resistance (ΔR/R0) highest sensitivity of −3.6 kPa−1, which is comparable to most
were measured as a function of the applied pressure, where pressure sensors decorated with smaller microstructures by
R0 is the initial total resistance without loading and ΔR is the the micro/nanofabrication process.[25,30,33,34] The sensitivity
total resistance change upon loading. Taking the semicylinder of pressure sensors based on 3D printing in this work even
microstructure as an example, the output resistance change as outperforms these made from printed organic transistors
a function of the applied pressure is shown in Figure 4b. It can with 3D self-organized organic semiconductor microstruc-
be clearly seen that the change of resistance (ΔR/R0) induced tures (1.07 kPa−1),[36] ultrathin gold nanowires (1.14 kPa−1),[27]
by external pressure increased with pressure. When the pres- and silk-molded microstructured e-skin (1.8 kPa−1).[35] A
sure was released, the semicylinder structures recovered due table (Table S1) has been added in the Supporting Informa-
to the elastic property of PDMS, resulting in complete recovery tion to compare sensing performance of different pressure
of the electrical resistance. The response time of the pressure sensors. As a comparison, sensors with unstructured flat
sensor to detect the application and removal of pressure load PDMS as the top electrode showed a much lower sensitivity
was estimated to be in the range of 20–50 ms for all the micro- (−0.046 kPa−1) due to very small change of contact area under
structure types (Figure S1, Supporting Information). The other stress. The sensitivities of the other two sensors with semi-
two microstructures, semisphere and pyramid, also exhibited sphere and pyramid microstructures are −1.5 and −1.0 kPa−1
Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (4 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (5 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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(a) 3. Conclusion
0.0
A new method based on a simple 3D
-0.2 printing technology to fabricate highly sen-
sitive pressures sensors has been developed
∆R/R0
-0.3
∆R/R0
4. Experimental Section
Preparation of Conductive PDMS Thin Films with Different
Microstructures: Polymer templates with arrays of inverse
microstructures including pyramids, semispheres, and semicylinders
were designed and prepared by 3D printing (ProJet 3500 HDMax).
Their feature sizes in terms of base length of pyramids, diameter of
semispheres, and diameter of semicylinders were 1 mm. After printing,
the templates were cleaned by ethanol and isopropanol, respectively,
and then dried by compressed air. In order to facilitate demolding,
the templates were coated with a hydrophobic layer of 1H,1H,2H,2H-
perfluorodecyltrichlorosilane (PFDTS, Sigma) by chemical vapor
deposition (CVD) after treating the surface of printed templates with
O2 plasma for 10 min.
Liquid mixtures of PDMS precursors (Sylgard 184, Dow Corning)
Figure 6. a) Small pressures can be detected by the semicylinder micro- including elastomer and its cross-linker (10:1 w/w) were casted onto
structured pressure sensor. b) The curve shows the resistance change the templates and then put in an oven for 3 h at 65 °C after degassing.
with the loading and unloading of a rice grain (20 mg) from the sensor The cured PDMS thin films were then peeled off from polymer
with an area of 1 cm2, corresponding to a pressure of about 2 Pa. c) Meas- templates.
ured pulse pressure waveform of a human subject with a resting heart CNFs (Pyrograf-III, grade PR-24-XT-HHT, Applied Sciences Inc.) were
rate of 70 b.p.m. over a 10 s period. d) Magnified electrical resistance dispersed in isopropanol (1 mg mL−1) with poly(4-vinylpyridine) (P4VP,
signal clearly representing pulse pressure (P1) and late systolic augmen- Mn = 10 000, Sigma, 1 wt% based on CNFs) as the dispersing agent.
tation (P2). Probe sonication was applied to the mixture for 30 min. Using a spray
Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (6 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Adv. Mater. Interfaces 2018, 5, 1800403 1800403 (7 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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