Roberto Pezone1, Gabriele Baglioni2, Pasqualina M Sarro1, Peter G Steeneken2,3, Sten Vollebregt1. 1. Laboratory of Electronic Components, Technology and Materials (ECTM), Department of Microelectronics, Delft University of Technology, 2628 CD Delft, The Netherlands. 2. Kavli Institue of Nanoscience, Department of Quantum Nanoscience, Delft University of Technology, 2628 CD Delft, The Netherlands. 3. Department of Precision and Microsystems Engineering (PME), Delft University of Technology, 2628 CD Delft, The Netherlands.
Abstract
During the past decades micro-electromechanical microphones have largely taken over the market for portable devices, being produced in volumes of billions yearly. Because performance of current devices is near the physical limits, further miniaturization and improvement of microphones for mobile devices poses a major challenge that requires breakthrough device concepts, geometries, and materials. Graphene is an attractive material for enabling these breakthroughs due to its flexibility, strength, nanometer thinness, and high electrical conductivity. Here, we demonstrate that transfer-free 7 nm thick multilayer graphene (MLGr) membranes with diameters ranging from 85-155 to 300 μm can be used to detect sound and show a mechanical compliance up to 92 nm Pa-1, thus outperforming commercially available MEMS microphones of 950 μm with compliances around 3 nm Pa-1. The feasibility of realizing larger membranes with diameters of 300 μm and even higher compliances is shown, although these have lower yields. We present a process for locally growing graphene on a silicon wafer and realizing suspended membranes of patterned graphene across through-silicon holes by bulk micromachining and sacrificial layer etching, such that no transfer is required. This transfer-free method results in a 100% yield for membranes with diameters up to 155 μm on 132 fabricated drums. The device-to-device variations in the mechanical compliance in the audible range (20-20000 Hz) are significantly smaller than those in transferred membranes. With this work, we demonstrate a transfer-free method for realizing wafer-scale multilayer graphene membranes that is compatible with high-volume manufacturing. Thus, limitations of transfer-based methods for graphene microphone fabrication such as polymer contamination, crack formation, wrinkling, folding, delamination, and low-tension reproducibility are largely circumvented, setting a significant step on the route toward high-volume production of graphene microphones.
During the past decades micro-electromechanical microphones have largely taken over the market for portable devices, being produced in volumes of billions yearly. Because performance of current devices is near the physical limits, further miniaturization and improvement of microphones for mobile devices poses a major challenge that requires breakthrough device concepts, geometries, and materials. Graphene is an attractive material for enabling these breakthroughs due to its flexibility, strength, nanometer thinness, and high electrical conductivity. Here, we demonstrate that transfer-free 7 nm thick multilayer graphene (MLGr) membranes with diameters ranging from 85-155 to 300 μm can be used to detect sound and show a mechanical compliance up to 92 nm Pa-1, thus outperforming commercially available MEMS microphones of 950 μm with compliances around 3 nm Pa-1. The feasibility of realizing larger membranes with diameters of 300 μm and even higher compliances is shown, although these have lower yields. We present a process for locally growing graphene on a silicon wafer and realizing suspended membranes of patterned graphene across through-silicon holes by bulk micromachining and sacrificial layer etching, such that no transfer is required. This transfer-free method results in a 100% yield for membranes with diameters up to 155 μm on 132 fabricated drums. The device-to-device variations in the mechanical compliance in the audible range (20-20000 Hz) are significantly smaller than those in transferred membranes. With this work, we demonstrate a transfer-free method for realizing wafer-scale multilayer graphene membranes that is compatible with high-volume manufacturing. Thus, limitations of transfer-based methods for graphene microphone fabrication such as polymer contamination, crack formation, wrinkling, folding, delamination, and low-tension reproducibility are largely circumvented, setting a significant step on the route toward high-volume production of graphene microphones.
Entities:
Keywords:
MEMS; graphene; high volume production; membrane; microphone; transfer free; wafer scale
In
the past 10 years, suspended graphene has attracted the interest
of scientific and engineering communities due to the possibility of
using its unique properties for sensor devices with novel functionality
and improved performance like microphones, pressure, gas and Hall
sensors.[1] Low mass, a large surface-to-volume
ratio, high electrical conductivity, a high Young’s modulus
of 1 TPa, and a tensile strength up to 130 GPa are optimal for high
performance micro- and nano-electromechanical system (MEMS/NEMS) technologies.[1] Especially for microphones and pressure sensors,
large membranes are needed to increase the sensitivity.[2,3] Several works have explored the potential of graphene for microphone
applications. Todorović et al. demonstrated a membrane with
a 5 mm membrane diameter composed of 300 layers of chemical vapor
deposition (CVD) graphene with a 10 dB higher sensitivity than commercial
nickel-based microphones.[4] Woo et al. realized
a high-sensitivity microphone for hearing aids with a heterostructure
membrane composed of 0.6 μm of graphene and 3 μm of PMMA
on a 2.65 mm diameter membrane.[5] Wittmann
et al. reached almost similar performance as commercial silicon-based
capacitive microphones using 15× smaller membranes (diameter
2r = 40 μm) made by only few-layer graphene.[6] The high performance is mainly due to graphene’s
high flexibility, low tension, and low out-of-plane stiffness, which
results in large displacements in response to sound pressure. Significant
effort has been made to improve the process to realize free-standing
graphene by transferring the material to the target substrate by a
carrier polymer with wet, dry, or semidry methods.[7] The introduction of the inverted floating method (IFM)
by Lee et al. and Akbari et al. helped fabricate large free-standing
CVD graphene up to 2r = 500–750 μm.[8,9] A combination of hydrogen bubbling transfer with thermal annealing
by Chen et al.[10] resulted in a suspended
five-layer graphene membrane with a diameter of 1.5 mm. Carvalho et
al. developed an anthracene sublimation assisted process achieving
ten layers of CVD graphene suspended over 4 mm openings.[11] Recently, six-layer graphene and 450 nm of PMMA
were suspended over a closed cavity by HF vapor release (VHF) of the
sacrificial layer after the graphene transfer.[12] The dry release avoids liquids that usually introduce capillary
forces that pull down the suspended part introducing ruptures or breaks.[13] Moreover, exposing the graphene to wet HF might
also lead to unwanted delamination of the graphene from the substrate.[14] However, despite the very high aspect ratios
and high crystallinity of the demonstrated free-standing membranes,
the mentioned works do not provide a clear route toward industrialization
of the devices because the transfer-based methods employed are not
easily scalable toward high-volume wafer-level fabrication since no
commercial equipment for transferring suspended graphene is available,
and current methods often suffer from low yield, polymer contamination,
cracks, and folding, leading to adhesion issues, especially for nonplanarized
target substrates.[7] This work proposes
an alternative approach to overcome part of the previous limitations
with a wafer-scale transferless method where multilayer graphene (MLGr)
drums are grown and released on the same substrate. The method is
potentially less prone to contamination and degradation of the membranes
and less sensitive to topography, allowing it to be applied on nonplanarized
surfaces. The realized multilayer graphene drums made by using this
approach reach a peak mechanical compliance of ≈92 nm Pa–1 for 300 μm membranes with a yield of 18% and
of ≈9 nm Pa–1 with a 100% yield of functional
devices with diameters ranging between 85 and 155 μm. A study
of the relation between the membrane diameter (2r = 85–300 μm) and the mechanical compliance, for more
than 50 drums, demonstrates a good tension uniformity since it follows
the expected quadratic dependency.[15]
Experimental Section
Design Concept and Material
Compatibility
The device
process design utilizes multilayer (ML) transfer-free graphene and
vapor HF compatible materials to ensure the structures survive the
sacrificial layer etch. Prepatterned Mo is used as a catalyst seed
layer to locally synthesize the graphene on Si substrates along the
same procedure described in earlier studies.[16,17] ML-graphene (MLGr) is preferred here due to its higher mechanical
strength that is required to realize membranes of sufficiently large
diameter for microphone applications. Because the synthesis of the
graphene is performed at 935 °C, all the materials are selected
to have a sufficiently high melting point and mechanical stability
during graphene CVD. Thermal SiO2 and LPCVD silicon-rich
low-stress SiN are stable at these high
temperature and show an etch selectivity of 40:1 to the vapor HF based
on preliminary results and previous works on Si MEMS.[18,19] The SiN layer is used as clamping support
layer all around the edge of the graphene membrane and is also used
to protect certain parts of the SiO2 from being etched
during the silicon backside deep reactive ion etch (DRIE) and vapor
HF sacrificial layer SiO2 release etch (Figure ).
Figure 1
Main fabrication steps.
(1) Patterning of the 110 nm LPCVD SiN layer (topside) and 5 μm PECVD TEOS
layer (backside) by dry-etching. (2) Sputtered and dry-etch patterned
50 nm Mo layer. (3) Graphene synthesis at 935 °C at low pressure
of 25 mbar. (4) Evaporated 20/200 nm Cr/Au layer after lift-off patterning.
(5) Structure after sacrifical Mo wet-etch in H2O2. (6) Backside deep reactive ion etch (DRIE) of the silicon substrate.
(7) Vapor HF etching of the SiO2 finally resulting in suspended
MLGr membranes.
Main fabrication steps.
(1) Patterning of the 110 nm LPCVD SiN layer (topside) and 5 μm PECVD TEOS
layer (backside) by dry-etching. (2) Sputtered and dry-etch patterned
50 nm Mo layer. (3) Graphene synthesis at 935 °C at low pressure
of 25 mbar. (4) Evaporated 20/200 nm Cr/Au layer after lift-off patterning.
(5) Structure after sacrifical Mo wet-etch in H2O2. (6) Backside deep reactive ion etch (DRIE) of the silicon substrate.
(7) Vapor HF etching of the SiO2 finally resulting in suspended
MLGr membranes.
Drum Fabrication
A layer of 110 nm LPCVD silicon-rich
low-stress (SiH2Cl2 315 sccm/NH3 85
sccm) is deposited at 850 °C on top of 1 μm thermal oxide
on a 100 mm silicon p-type wafer. The SiN is dry-etched in defined regions on the topside and entirely removed
on the backside where a PECVD TEOS-based 5 μm is then deposited
to work as etching mask for the silicon DRIE as shown Figure (step 1). A thin film of 50
nm molybdenum is sputtered at low temperature (50 °C) and etched
by dry etching with Cl and O2 chemistry. Because of the
nature of the sputtering process, Mo covers all the steps in the topography
(Supporting Information, Figure S1a). In
this way, the CVD-grown graphene will not suffer from any discontinuities.
The positive photoresist is then removed by O2 plasma,
and all the remaining residuals are washed in N-methyl-2-pyrrolidone
(NMP) with subsequent DI water washing (Figure , step 2). At this stage, the graphene is
synthesized at 935 °C with an in-house reactor (AIXTRON Black
Magic) in 25 mbar of H2 as a reducing agent of oxidized
Mo and a CH4 step for the growth as in Figure (step 3). Next, Cr/Au 20/200
nm is evaporated by ion-beam evaporation in a vacuum and patterned
by using a lift-off technique with NMP at 65 °C for 40 min with
a final low-power sonication of 90 s (Figure , step 4). From NMP the wafer is washed in
acetone and DEMI–water. Molybdenum is chemically etched with
H2O2 for 5 min and gently washed with DEMI–water
to remove all the chemical residuals (Figure , step 5). Deep reactive etching is performed
on the backside with the graphene side facing the chuck to avoid any
exposure to the SF6 plasma that might damage the material
(Figure , step 6).
Finally, after dicing of 1 cm × 1 cm chips, the VHF etch is performed
at 45 °C with 100% anhydrous HF, N2, and EtOH in a
commercially available Primaxx μEtch system at 125 Torr shown
in Figure (step 7).
Thanks to the high temperature and low pressure, all byproducts related
to the undoped SiO2 etching are removed by desorption[20] (Figure S4). No polymers
or tapes are involved during the final isotropic etching step since
they might trap HF molecules due to their porous nature, and they
can usually be only removed by aggressive methods such as O2 plasma or other dry-etching chemistry that can damage or remove
the suspended graphene. With this proposed approach, a lower temperature
of T > 110 °C can be used to clean all the
residuals
that originate from the LPCVD SiN growth
and vapor HF reaction,[21] which is low compared
to the T > 250 °C cleaning step typically
needed
to remove the polymer used to transfer the graphene on prepatterned
holes. The low temperature in the proposed approach is advantageous
because thermal removal of the transfer polymer residuals generally
results in a lower number of surviving membranes due to thermal expansion
coefficient mismatch of the suspended graphene and the substrate,
especially for larger membranes.[9]
Mechanical
Compliance Measurement
The input sound pressure
from a speaker is measured with a reference microphone (Sonarworks
XREF20) placed next to the sample. A Moku:Lab hardware platform from
Liquid Instruments records the signal detected by the reference microphone,
the mechanical frequency response of the graphene membrane as detected
by using a Polytec vibrometer focused at the center of the membrane,
and the output signal of the speaker. After proper correction for
the corresponding sensitivities of the vibrometer controller and reference
microphone, the mechanical compliance is obtained from the ratio of
the two signals received by the Moku:Lab.[22] Acoustic actuation at a sound pressure level of 1 Pa (≈ 94
dB SPL) is used to test the fabricated membranes.
Results and Discussion
Membrane
Fabrication Results
The topography of the
released SiO2/MLGr heterostructure (before HF etch of the
SiO2) is optically inspected by a 3D laser scanning confocal
microscope on more than 100 drums. The graphene is observed to display
out-of-plane deformation (Figure a) due to compressive stress in the SiO2 that causes the diaphragm to bend downward. This unwanted behavior
originates mainly from the difference in the thermal expansion coefficients
between the SiO2 layer and the silicon substrate.[23−25] For small diameter membranes the first buckling state of the drums
is observed (inset Figure a), whereas for drums with larger diameters 2r = 300–350 μm wavy deformations along the edge of the
membrane correspond to higher buckling modes.[26] In Figure a, the
maximum values of the out-of-plane deflection h0 of the center of the membranes are plotted, as determined
for different membrane diameters. The deflection of the heterostructures
can be modeled by the following analytical equation.[23−25]For the SiO2 layer,
the Poisson’s ratio υ = 0.2, the Young’s modulus E = 74 GPa, the thickness t = 0.95 μm,
and the radii r are reported in the legend of Figure a. With these input
values, a compressive stress σ in the SiO2 layer
σ = −275 MPa[24] is fitted to
obtain the observed correspondence that is indicated by the three
colored bands in Figure a. This analytical calculation is based on the assumption that only
the stress σ in SiO2 is considered[25] due to its considerable thickness compared to the other
materials involved.
Figure 2
Topographic analysis of the graphene membranes before
and after
SiO2 etch by using 3D laser scanning confocal microscope.
(a) Maximum out-of-plane deflection h0 of the suspended SiO2/MLGr heterostructure at the center
of the drum. The analytically predicted h0 for the different diameters, based on a compressive stress in the
SiO2 of σ = −275 MPa, is indicated by the
colored bands. The membranes with 2r < 155 μm
show an experimental behavior close to the analytical trend with a
first buckling mode (inset microscope image n = 1).
Larger membranes deviate from this trend and reveal higher order modes
of buckling (n > 1 inset microscope image). (b)
Cross
section of the wafer containing multiple membranes performed on the
released MLGr membranes after the vapor HF removal of the SiO2 layer. The membrane on the wafer have reproducible shapes
and buckling observed in (a) has disappeared with a flat suspended
membrane region. (c) Microscope image showing a Cr/Au electrode for
contacting the graphene (not used in this work) and the supported
and suspended part of the MLGr. (d) Step height measurement with the
confocal microscope along the red dashed line in (c) showing that
the MLGr is around 1.3 μm lower than the electrode. This height
difference is due to the thickness of the SiO2, SiN, and electrodes.
Topographic analysis of the graphene membranes before
and after
SiO2 etch by using 3D laser scanning confocal microscope.
(a) Maximum out-of-plane deflection h0 of the suspended SiO2/MLGr heterostructure at the center
of the drum. The analytically predicted h0 for the different diameters, based on a compressive stress in the
SiO2 of σ = −275 MPa, is indicated by the
colored bands. The membranes with 2r < 155 μm
show an experimental behavior close to the analytical trend with a
first buckling mode (inset microscope image n = 1).
Larger membranes deviate from this trend and reveal higher order modes
of buckling (n > 1 inset microscope image). (b)
Cross
section of the wafer containing multiple membranes performed on the
released MLGr membranes after the vapor HF removal of the SiO2 layer. The membrane on the wafer have reproducible shapes
and buckling observed in (a) has disappeared with a flat suspended
membrane region. (c) Microscope image showing a Cr/Au electrode for
contacting the graphene (not used in this work) and the supported
and suspended part of the MLGr. (d) Step height measurement with the
confocal microscope along the red dashed line in (c) showing that
the MLGr is around 1.3 μm lower than the electrode. This height
difference is due to the thickness of the SiO2, SiN, and electrodes.Whereas this model captures the deflection of the small membranes
quite well, the deflection h0 measured
on experimental the large diameter drums (2r = 300–350
μm) is relatively far from theory, which is attributed to the
presence of higher buckling modes.[26] Once
the SiO2 is etched, the graphene restores its original
flat shape in the suspended region by adhesion to the unetched silicon
substrate along its circumference (Figure b–d and Figure S1b). We verify its flatness by measuring the step height between
the surface of the Cr/Au electrode and the Si surface of the suspended
MLGr (Figure d), which
is ≈1.3 μm, equal to sum of the thickness of the SiO2, SiN and the electrode. As can
be seen in Figure b, the membranes survive the processing. We quantify the yield using
optical inspection in Table , where membranes with diameters of 85–155 μm
show a 100% yield with all 132 suspended devices surviving after the
vapor HF release. Large SiO2/MLGr heterostructures with
diameters of 300–350 μm show a 37% yield on 117 fabricated
drums after the DRIE. After SiO2 etching, the same drums
decrease their yield from 37% to 18%. After 1 week of storage and
handling, the small membranes still show 100% of yield, and the survival
rate of large membranes decreased to 8%. The difference in yield for
the studied drum sizes can be attributed to the high deformations
that cause wrinkles, distortions, and even cracks in the oxide (Figure S2). They may negatively affect the graphene
integrity creating randomly distributed tears and localized stress.
During the vapor HF, handling, and storing they might be a source
of crack propagations leading to final membrane breakage. Gas pressure
on the membrane during handling and storage might also play a role
and account for the yield reduction in the larger membranes. This
yield reduction might be mitigated in future processes by tuning the
stress and thickness of the oxide layer or by using strain compensation
measures like suspending the MLGr from a SiN frame that generates tensile stress.[27]
Survived at the mentioned step without
ruptures or cracks.
Survived at the mentioned step without
ruptures or cracks.
Graphene Characterization
The crystallinity of the
MLGr is investigated through a Horiba HR800 Raman spectrometer equipped
with a 514.5 nm Ar+ laser maintained at 5 mW to minimize
any possible damages by laser heating. A 100× objective with
a numerical aperture of 0.9 is used, giving a spot size of about 696
nm. The graphene properties are mainly characterized by two Raman
bands: The first is the G band, which is characteristic of all the
graphitic sp2-type structures and typically centers at
1580 cm–1 when the material is in a stress and doping-free
state. The second band is the 2D band, which is centered at 2700 cm–1 and mainly gives information about the number and
stacking order of the layers. In Figure a, which shows an example of the Raman spectrum
of a MLGr trampoline after VHF normalized to the G band, a third prominent
D band is observed that has an intensity of ≈0.68 presenting
evidence for the presence of defects. In fact, the D band is related
to any kind of defect that distorts the graphene lattice, like edges,
wrinkles, Stone–Wales defects, and vacancies. The relatively
large D band intensity shows the invasiveness of the process on the
graphene compared to previous works where lower defect intensity was
reported for the same material.[16,17] This increased defectivity
source is mainly attributed to the lift-off step where N-methylpyrrolidone (NMP) is used for the Cr/Au electrode fabrication.
The graphene on Mo is exposed for 40 min at 65 °C with a final
low-power ultrasonic bath of 90 s to strip the cross-linked photoresist
(PR). Intercalation of NMP into the stacked layers and the short ultrasonic
bath have probably negatively affected the quality of the material,
as already reported in other works.[28−30] We exclude that the
DRIE is invasive since the graphene is not exposed to the plasma etch
from the backside of the wafer and instead faces the tool’s
chuck. VHF is also not considered a possible defective source because
the ID/IG ratio
does not show any significant change after the release (Figure b). Upon comparison of the
G and 2D peak positions of the material before and after the suspension,
a prominent red-shift or softening is reported. Shifts of νG from 1582.1 to 1574.1 cm–1 and ν2D from 2696.3 to 2682.8 cm–1 are found after
the VHF removal of the SiO2 from the suspended MLGr (Figure d). These shifts
might be attributed to phonon softening due to the graphene stress
going from a compressive to a more tensile state during the removal
of the buckled SiO2 layer as illustrated schematically
in Figure a,b. These
results align with previous works reported in the literature on monolayer,
few-layer graphene, and graphite.[31−33] Finally, it can be seen
that the Raman 2D-peak ratios are representative for multilayer graphene,[34] as shown in Figure a where I2D/IG < 1 ratios are measured. An atomic force
microscope (AFM) from Cypher Asylum Research is used in semicontact
mode for the graphene thickness measurement, and a value of ≈7
± 2 nm is found, where the standard deviation of 2 nm represents
its nonuniformity as shown by the variations in the line scans in Figure c. Because it is
not feasible to directly measure the step height of the carbon layers
on the SiN, the reported AFM thickness
measurements are obtained on graphene which is processed with all
the reported steps except the VHF and then wet-transferred in DI water
on a clean thermally oxidized silicon chip. The graphene needs to
be transferred because SiN is partially
etched during the Mo patterning and the VHF exposure and can therefore
not be regarded as a flat reference point. The small wrinkles observed
in Figure c are generally
attributed to the small grains of the Mo catalyst surface that arise
during the CVD synthesis temperature of 935 °C, whose topography
is imprinted into the graphene.[35]Figure e shows a suspended
membrane that is patterned in a trampoline geometry with a diameter
of 300 μm. At the supports of the MLGr trampoline it is evident
that the Cr–Au/SiN/Si interface
acts as a clamping support for the suspended graphene.
Figure 3
Graphene characterization.
(a) Raman spectrum from 1100 to 3200
cm–1 of the trampoline MLGr in the suspended region
after the VHF release. (b) Comparison of the Raman peak ratio ID/IG before and
after the VHF treatment in the suspended region for 25 drums. (c)
Thickness measurement of the MLGr graphene after transfer by AFM in
semicontact mode. (d) Raman peak frequencies of the G and 2D bands
before and after VHF etch in the free-suspended area. (e) Scanning
electron microscope pictures made by a SEM Hitachi Regulus 8230 of
suspended graphene trampoline with a diameter of 2r = 300 μm. Cr/Au electrodes and SiN substrate clamp the suspended graphene membrane.
Graphene characterization.
(a) Raman spectrum from 1100 to 3200
cm–1 of the trampoline MLGr in the suspended region
after the VHF release. (b) Comparison of the Raman peak ratio ID/IG before and
after the VHF treatment in the suspended region for 25 drums. (c)
Thickness measurement of the MLGr graphene after transfer by AFM in
semicontact mode. (d) Raman peak frequencies of the G and 2D bands
before and after VHF etch in the free-suspended area. (e) Scanning
electron microscope pictures made by a SEM Hitachi Regulus 8230 of
suspended graphene trampoline with a diameter of 2r = 300 μm. Cr/Au electrodes and SiN substrate clamp the suspended graphene membrane.
Resonance Frequency and Mechanical Compliance
The first
mode of the resonance frequency is measured by a digital holographic
microscope (LynceeTec) using a laser with a wavelength of 666 nm and
a 10× objective lens. The interference between the reflected
laser beam from the sample and the reference path provides the intensity
and phase of each pixel defining the 3D topography. The measurements
are performed in a chamber connected to a vacuum pump at 10–4 kPa to reduce air damping effects. The samples are actuated by shaking
them with a piezoelectric element below the chip that is actuated
by using a voltage-controlled stage with a 0.5 V sine wave in the
frequency range f = 50–350 kHz where the fundamental
resonance frequency is given by eq .[36]Here n0 is the
pretension (N/m) of the graphene, ρ the mass density, and t the thickness of the graphene. In this relation, the contribution
of the bending rigidity is neglected since its is estimated to be
small.[37] The inspected membranes show fundamental
frequencies over a range of ≈156–218 kHz for diameters
of 2r = 120–155 μm (see Figure a) and ≈92 kHz for trampolines
with diameters of 2r = 300 μm. These measured
values show lower resonance frequencies compared to previous results
obtained for monolayer and bilayer graphene of similar diameter.[9] Using a graphene thickness of 7 nm, a density
of 2260 kg/m3, and a diameter range 120–155 μm,
the experimental results fit the analytical values in a pretension
window of n0 = 0.03–0.05 N/m (see Figure a). The deviations
between experimental and theoretical resonance frequencies might be
caused by variations in pretension that can be attributed to small
nonuniformities in the graphene boundary conditions due to variations
in hole geometries from a perfect circular shape in the holes made
by using the DRIE etch, differences in the clamping electrode geometries,
mass density variations, or unetched SiO2 residuals between
the graphene and the silicon substrate. When the membrane is actuated
at its resonance frequency, its mechanical mode shape is captured
by the LynceeTec via the optical phase shifts that result from the
oscillating membrane (Figure b and Movie S1).
Figure 4
Resonance frequency and
mechanical compliance measurements. (a)
Resonance frequency as a function of diameter for MLGr membranes with
120–155 um diameters inspected by a LynceeTec holographic microscope.
Comparison to eq suggests
the tension in the membranes is n0 = 0.04
N/m. (b) Three first modes of the trampoline membranes recorded by
a LynceeTec microscope at resonance frequencies of 92, 136, and 195
kHz. Blue and red colors indicate the phase of the motion, corresponding
to upward and downward moving parts of the membrane. The color saturation
is a measure for the motion amplitude. (c) Comparison of the mechanical
compliance of the MLGr membranes with a commercial MEMS microphone
MP23DB01HP, MP34DT04 STMicroelectronics (purple pentagon). MLGr shows
comparable and higher mechanical compliance despite its smaller dimension.
Large membranes are more sensitive due to their larger diameter. The
experimental measurements are also compared with the ideal analytical
trend of eq with different
pretension values, suggesting that the pretension reduces for larger
membranes.
Resonance frequency and
mechanical compliance measurements. (a)
Resonance frequency as a function of diameter for MLGr membranes with
120–155 um diameters inspected by a LynceeTec holographic microscope.
Comparison to eq suggests
the tension in the membranes is n0 = 0.04
N/m. (b) Three first modes of the trampoline membranes recorded by
a LynceeTec microscope at resonance frequencies of 92, 136, and 195
kHz. Blue and red colors indicate the phase of the motion, corresponding
to upward and downward moving parts of the membrane. The color saturation
is a measure for the motion amplitude. (c) Comparison of the mechanical
compliance of the MLGr membranes with a commercial MEMS microphone
MP23DB01HP, MP34DT04 STMicroelectronics (purple pentagon). MLGr shows
comparable and higher mechanical compliance despite its smaller dimension.
Large membranes are more sensitive due to their larger diameter. The
experimental measurements are also compared with the ideal analytical
trend of eq with different
pretension values, suggesting that the pretension reduces for larger
membranes.Finally, we characterize the acoustic
membrane displacement in
the presence of sound at a frequency of 1 kHz at a sound pressure
level of 94 dB. The compliance or sensitivity in nm/Pa of the fabricated
graphene membranes is determined optically by using a single point
laser Doppler vibrometer (LDV) (OFV-5000 Polytec GmbH) at the center
of the membrane. Details of the experimental setup and procedure can
be found in ref (22) and the Experimental Section. The experimental
mechanical compliance at 1 kHz are compared again with the analytical
results based on eq , which relates the applied pressure to the maximum deflection of
the membranes.[3] Far below the resonance
frequency in the linear regime (such that cubic terms in z can be neglected), the membrane displacement z is
related[3] to the sound pressure level ΔP by the equationThus, a quadratic relation is expected between
the mechanical compliance, or sensitivity , and radius r for a constant
sound pressure level ΔP. The reported mechanical
compliances of 76 drums shown in Figure c range from ≈3–10 nm Pa–1 for the smaller membranes with 2r = 85–155 μm and ≈43–92 nm Pa–1 for large membranes with 2r = 300 μm. Figure c also shows a MEMS
microphone with a membrane diameter of 950 μm, which is measured
by using the same procedure resulting in a value of S = 3 nm Pa–1.The graphene data are fit by eq , showing that different pretensions n0 are needed to fit the large (2r = 300
μm) and small membranes. Large membranes are closer to the analytical
results obtained with lower pretension n0 = 0.1 N/m, whereas the smaller membranes yield n0 = 0.2 N/m. This could be attributed to a lower pretension
due to the larger suspended region where membrane sagging might be
more profound. Moreover, the tension is also affected by the graphene
clamping geometry, where for the same diameter of 300 μm the
trampoline shows an even higher mechanical compliance (by a factor
1.4) due to lower tension of n0 = 0.07
N/m compared to the fully clamped geometry.[2] The mechanical compliance of drums with different sizes and geometries,
over the entire audible range, is also reported (Figure S3). When comparing the pretension extracted from eqs and 3, we note that different values of n0 are obtained as in Figure c. These differences might be caused by uncertainty in the
mass and thickness that affect eq , gas damping and permeation effects at 1 kHz that
affect eq , and differences
in the deflected mode shapes from theory. More study is needed to
quantitatively account for these differences. We note that the higher
pretensions extracted from eq are the most relevant for device operation as microphone.
Furthermore, we demonstrate that music can be recorded by a MLGr drum
with 2r = 300 μm by monitoring the motion of
the graphene membrane using the Polytec vibrometer[22] (Supporting Information, Audio
S1). The output signal from the polytec in response to an arbitrary
sound file is recorded with a sampling frequency of 20 kHz to detect
the sound waveform, and the measured trace is then reconverted to
an audio file with Python.The proposed wafer-scale transfer-free
multilayer graphene performances
are visually compared in Figure with the transfer-based graphene and graphene heterostructures
condenser microphones reported in the literature. It mostly shows
higher performance of the presented membranes due to the absence of
any polymer supports, leading to higher deflection under sound pressure
with also a new fabrication method that is more prone to mass production.
Moreover, in these works, the microphone sensitivity S, defined as open-circuit sensitivity,[38] is measured by an electrical read-out. Theoretically, it is equal
to the product between the electrical sensitivity S and the mechanical sensitivity S contribution by the equation[38]For this reason, the respective
mechanical
compliances are indirectly calculated by using eq and eqs , 3 as also described by Baglioni et
al.[22] where the input values S (m V Pa–1 or dB),
pretension (N/m), resonance frequency (Hz), the distance membrane–bottom
electrode g0 (m), and V (V) are obtained from the reported
works.[4,5,11,12,39−43] For most of the presented data (electrical read-out), the mechanical
compliance is indirectly calculated from eq . Thus, Figure may show limitations in the comparison with the results
obtained by optical read-out (this work). This may be due to the presence
of a V (bias voltage),
resulting in an underestimation of the extrapolated reported mechanical
compliance.
Figure 5
Comparison of the mechanical compliance normalized by the area
of graphene microphone. The extrapolated mechanical compliances related
to the principal graphene microphone works,[4,5,11,12,39−43] and the proposed results are presented. The values are normalized
by area of the suspended graphene to have an accurate correlation
within the different works.
Comparison of the mechanical compliance normalized by the area
of graphene microphone. The extrapolated mechanical compliances related
to the principal graphene microphone works,[4,5,11,12,39−43] and the proposed results are presented. The values are normalized
by area of the suspended graphene to have an accurate correlation
within the different works.
Conclusions
With this work, we present an efficient transferless
method to
fabricate wafer-scale graphene drums with diameters from 2r = 85 to 300 μm. Large arrays of graphene drums with
diameters up to ∼155 μm are fabricated with a high yield
of 100% by using a CMOS-compatible process flow without any transfer
steps. These graphene membranes are shown to operate as microphones,
detecting sound with mechanical compliances as high as 92 nm Pa–1, which is much higher than that of commercial MEMS
microphones that typically have a compliance of 3 nm Pa–1. The graphene attains this high sensitivity by using a membrane
area that is 10 times smaller than that of the MEMS device. This demonstrates
the great potential of graphene for microphone applications. The fabrication
route for trampoline designs offers the possibility to invent and
engineer new suspended graphene geometries for realizing very high
mechanical compliances at the wafer scale. When integrated with electrodes
and read-out electronics, it can enable next-generation, high volume,
wafer-scale graphene microphone technologies.
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