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Cite This: ACS Omega 2019, 4, 7628−7635 http://pubs.acs.org/journal/acsodf

Thin Film Analysis by Nanomechanical Infrared Spectroscopy

Andrea Casci Ceccacci,*,† Alberto Cagliani,† Paolo Marizza,† Silvan Schmid,‡ and Anja Boisen†
†
Department of Micro- and Nanotechnology, Technical University of Denmark, 2800 Kongens Lyngby, Denmark
‡
Institute of Sensor and Actuator Systems, TU Wien, 1040 Vienna, Austria
*
S Supporting Information

ABSTRACT: There is a fundamental need for techniques for thin film characterization. The current options for obtaining
infrared (IR) spectra typically suffer from low signal-to-noise-ratios (SNRs) for sample thicknesses confined to a few
nanometers. We present nanomechanical infrared spectroscopy (NAM-IR), which enables the measurement of a complete
infrared fingerprint of a polyvinylpyrrolidone (PVP) layer as thin as 20 nm with an SNR of 307. Based on the characterization of
the given NAM-IR setup, a minimum film thickness of only 160 pm of PVP can be analyzed with an SNR of 2. Compared to a
conventional attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) system, NAM-IR yields an SNR
that is 43 times larger for a 20 nm-thick PVP layer and requires only a fraction of the acquisition time. These results pave the
way for NAM-IR as a highly sensitive, fast, and practical tool for IR analysis of polymer thin films.

■ INTRODUCTION
The ability to engineer the chemical and physical properties of
sample thickness is much smaller than the penetration depth of
the evanescent IR wave of up to 2 μm,13 thereby effectively
surfaces using dedicated functionalization methods is of limiting the thickness range that can be studied. One
fundamental importance for the advancement in many possibility to overcome this issue is to use very long acquisition
technological fields, such as bio and chemical sensing,1 drug times,16 but this restricts the throughput of the analytical
delivery,2 tissue engineering,3 solar cells,4 thin films batteries,5 system. A multireflection ATR accessory can also be used to
and fabrication of semiconductor devices.6 In recent years, the boost the signal, but such an approach is suitable only when
possibility of engineering the chemical and physical properties the crystal is in contact with a liquid or the thin
of a surface by applying a thin polymer film has attracted functionalization layer to be studied is irreversibly attached
considerable attention due to its simplicity, robustness, and to the crystal. These drawbacks might represent an issue in
flexibility, due to the vast selection of polymer films.2,3,7−9 terms of the experimental throughput of ATR-FTIR when a
Thin polymer films can exhibit confinement-induced, peculiar large variety of thin polymer layers with high spectroscopically
physicochemical properties, such as changes in glass transition precisions have to be tested. Hence, there is a need for a fast,
temperature,10 elastic moduli,11 and crystallization.12 Charac- reliable, and nondestructive method to analyze thin films.
terizing the properties of such thin films is therefore of high Infrared reflection−absorption spectroscopy (IRRAS)20 is
relevance both technologically and scientifically. used to study the thin films and needs to be performed on a
The chemical behavior and structure of thin films are often reflective substrate.21 Due to the surface selection rule, the
characterized by infrared absorption spectroscopy13−16 or phase of the reflected beam is shifted by an amount that
other vibrational spectroscopy techniques such as surface- depends on the incident angle, polarization, and wavelength of
enhanced Raman Spectroscopy.17 Thin film IR spectroscopy is the incident light. The resulting spectra contain information on
commonly performed using attenuated total reflectance the molecules’ dipole moment perpendicular to the sur-
Fourier transform infrared spectroscopy (ATR-FTIR), with a
typical configuration with only one reflection within the ATR Received: January 30, 2019
crystal.16,18,19 An issue connected with the use of ATR-FTIR is Accepted: April 8, 2019
that the signal-to-noise-ratio (SNR) degrades quickly when the Published: April 26, 2019

© 2019 American Chemical Society 7628 DOI: 10.1021/acsomega.9b00276

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face.21−23 Furthermore, studies have demonstrated that

engineered substrates equipped with antenna-like structures
can strongly enhance the light−matter interaction. These
substrates have been used to monitor nanoparticles and
protein interactions.23 Although these approaches have pushed
the limit of detection up to a single-molecule layer, the
experimental time frame is extended, and it can take up to
several hours due to the low SNR on a single acquisition.
Polarization modulation-IRRAS (PM-IRRAS) can overcome
some of the limitations of IRRAS by improving the low SNR;
however, the spectra are still dependent on the surface
selection rules, and the spectra require a complex postprocess-
ing technique.16,24,25
The combination of atomic force microscopy (AFM) and
infrared spectroscopy has emerged as a hybrid technique
known as AFM-IR, which has shown to provide a chemical
mapping of submicron polymer films.26−30 Although the
method can provide accurate spectra and overcome the spatial
resolution issue, the experimental setup needs a fine alignment
of the light sources with the AFM tip, which might limit the
throughput of method and extend the time frames.
Photothermal spectroscopy methods are based on the
transduction of the temperature change of the sample, induced
by the light absorption, into a signal that can be recorded. Figure 1. Sampling procedure and NAM-IR setup. (a) Polymer
Typically, density, pressure, or temperature changes, induced deposition method; (b) NAM-IR spectrometer comprises: a pressure-
by the wavelength specific light absorption, have been controlled chamber providing an optical access from both sides of the
exploited to obtain an IR absorption fingerprint of a sensor, a quantum cascade laser (QCL, Block Engineering) that
sample.31−34 generates a monochromatic IR light in the range from 768−1953
In the last 15 years, nanomechanical sensing has been cm−1, an optical readout system based on a laser Doppler vibrometer
exploited for biosensing purposes35−39 and material character- (Polytech MSA-500), a phase lock-in amplifier, and a piezo driver.44,45
ization.40,41 In particular, photothermal nanomechanical IR
sensing (NAM-IR) has been developed for both deflection and suffer from the typical spectral artefacts of ATR-FTIR or
resonance frequency detection schemes.32,33,42−49 absorbance-reflection techniques in the recorded spectra.13
In the present work, we have used the resonance frequency Moreover, it is insensitive to the IR light angle or polarization.
detection scheme. Our NAM-IR system used in this work consists of a thin
During the experiment, the membrane oscillates at its (100 nm) square (1 × 1 mm) prestressed (250 MPa) silicon-
mechanical natural frequency via the actuation provided by an rich silicon Nitride (SRN) membrane fabricated by standard
external piezoelectric crystal. The mechanical resonance silicon micromachining techniques.
frequency of the resonator is a function of the mechanical Membrane-like resonators have, intuitively, higher mechan-
stress, which, in turn, depends on the local temperature. ical robustness and uniform topography compared to silicon
Changes in temperature, occurring upon light absorption, nitride string resonators. Furthermore, membranes withstand
detune the resonance frequency of the resonator. Due to the typical surface functionalization treatments in liquid, including
photothermal effect,31 the absorbed light locally increases the spray coating and spin coating. As a demonstrator of the
temperature, which releases a part of the native stress in the capabilities of our NAM-IR system, we analyze polyvinylpyr-
membrane, causing the resonance frequency to drop.50 The rolidone (PVP) thin films with thicknesses down to 20 nm.
changes in the resonance frequency are recorded through a PVP polymer thin films have recently attracted much attention
lock-in detection scheme and a typical experimental setup as due to their high versatility in drug delivery devices52 and
illustrated in Figure 1.The resonance frequency shifts as a hydrogels,53 where their physical and chemical properties are
function of the wavelength specific light absorption represents crucial. The low thermal mass of our resonating membranes
the NAM-IR spectra. allows running analysis over a range of 1100 cm−1 wave-
Regardless of the detection scheme used, the samples numbers in 30 s with an SNR of up to 307, even for a polymer
examined so far using NAM-IR have been limited to airborne- film as thin as 20 nm. In Figure 1, our NAM-IR system is
deposited materials or liquids. This limitation is due to the lack illustrated. It is composed of a vacuum chamber with two
of mechanical robustness of previous nanomechanical trans- apertures, one for the IR light and one for the readout laser of
ducers, such as nanostrings45 and microcantilevers.47 More- the vibrometer. A quantum cascade laser (QCL) is used to
over, such nanomechanical structures suffer from AFM-like generate the stepwise monochromatic IR light in the range of
768−1953 cm−1 with a step of 0.5 cm−1.

■
readout laser alignment issues due to their micrometer-range
lateral dimensions, which can drastically limit the final
throughput of NAM-IR. Recently, a filter-like nanomechanical RESULTS AND DISCUSSIONS
structure51 has been developed to improve the sampling In Figure 2, the NAM-IR spectra of the PVP thin films are
efficiency of airborne particles. However, the perforated compared to those of the conventional spectroscopy
geometry is not suitable for analyzing thin films. A main techniques. The three mid-IR bands of PVP recorded by
advantage of the photothermal spectroscopy is that it does not NAM-IR match well the spectra recorded by the reference
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Lambert law. Instead, NAM-IR relies on the nonradiative

decay, which is a complementary phenomenenon.56 Further-
more, the distortion of the refractive index occurring upon
absorption25 can bias a measured peak toward a lower
frequency;25,57 such phenomena can be even more pro-
nounced when the sample is a submicron film.13 Although
correction algorithms can adjust the relative peak intensities as
well as the peak positions,25,57 such methods require an a priori
knowledge on the optical properties of the film sample.
In order to maximize the IR spectrum signal-to-noise-ratio
(SNR) of our photothermal spectrometer, we looked closely at
the relation between the thermal time constant of the
membrane resonator, the minimum settling time of the IR
Figure 2. Comparison of the NAM-IR spectrum of a PVP film with source for each wavelength, and the optimal signal integration
respect to ATR and FTIR. The three main bands characterize the time.
polymer fingerprint: the signal at 1300 cm−1 referred to the C−N First, the time transient of the resonance frequency shift of
bond stretching and the CH2 ring wag mode. The band with three
the membrane sensor upon periodic IR irradiation at a fixed IR
peaks between 1400 and 1500 cm−1 corresponds to the CH2 ring wag
and the C−N stretching. The peak at 1680 cm−1 corresponds to the wavelength was characterized, in order to extract the thermal
CO stretching mode. The spectra of a 500 nm-thick PVP sample time constant of the membrane τM.58 As can be seen in Figure
are recorded. 3a, the mechanical resonance frequency of the membranes
decreases following a first-order exponential decay upon IR
methods (ATR-FTIR and transmission FTIR) as well as the absorption. Such an ON−OFF (or heating and cooling) curve
previously published results.54 The PVP carbonyl band appears has been acquired 485 times, and each of them was fitted with
to be shifted toward a higher frequency when recorded an exponential decay function,δf (t ) = Δf(1 − e−t / τM), extract-
through NAM-IR compared to the reference techniques such ing the corresponding τM. The transient was evaluated for two
as FTIR or ATR-FTIR. Photothermal spectroscopy provides a different vacuum pressures, which yielded (for a 20 nm PVP-
complementary46,55,56 technique to probe IR fingerprints of coated membrane) τM = 4.1 ± 0.08 ms at a low vacuum of 1
chemical bonds. Absorption spectroscopy relies on the Beer− mbar and τM = 17 ± 0.9 ms at a high vacuum of 10−5 mbar.

Figure 3. (a) Relative frequency shift upon periodic light absorption. The values are recorded on a 200 nm coated membrane at 1 mbar; the shades
represent the standard deviation of 485 overlapped ON−OFF curves. (b) Raw NAM-IR spectra. (c) Membrane NAM-IR spectrophotometer can
recognize the QCL steps of 0.5 cm−1. (d) Absorbed power throughout the wavelength range and relative temperature reached during a sweep on a
20 nm PVP-coated membrane in HV. On the right-hand vertical axis is the relative temperature shift established in the membrane upon absorption.
As a reference value, the baseline temperature was considered as 293.15 K.

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Due to the finite thermal mass of the sensor,42,58 the thermal systems. We used an analytical model to estimate the power
time constant upon light absorption (heating) is higher than absorbed by the membranes.51 Considering a frequency noise
the cooling time constant. Instead, the difference in the τM floor of 2 ppm (see the Supporting Information), the
value is attributed to the different relative importance of the minimum power that can be detected is 5 nW for an
heat transport mechanism involved at the two vacuum levels. integration time of 7 ms and an SNR of 1. Such an absorbed
In high vacuum and at room temperature, the mean free path power corresponds to a local temperature increase in the
of the gas molecules becomes roughly 10 m, which is membrane center of 3 mK for a 20 nm PVP-coated membrane
significantly larger than the critical dimension of the nano- (see the Supporting Information). In the case of a 20 nm-
mechanical resonator. Hence, the heat transport due to natural coated membrane, the maximum absorbed power is 3.5 μW (at
convection can be neglected, and all the heat generated in the 1680 cm−1), which is about 1% of the incident QCL laser
membrane is dissipated by conduction through the body chip power at that wavelength. Such a power gives rise to a
alone. Contrary, at 1 mbar, the mean free path corresponds to temperature increase of 0.9 K in the center of the membrane
roughly 100 μm, which is comparable to the dimensions of the (see the Supporting Information), indicating that an SNR on
device, hence, allowing a part of the heat to be dissipated by the temperature estimation as high as 300 can be achieved.
conduction through the surrounding gas. Therefore, the two Finally, a calibrated power absorption spectrum is shown in
regimes have different time transient responses. The response Figure 3d, where the temperature reached at the center of the
time is also influenced by the thickness of the polymer layer, membrane throughout the entire spectrum is shown. As can be
and the corresponding values are reported in the Supporting seen, the temperature increases no more than 0.9 K compared
Information. A precise knowledge of the thermal time constant to room temperature. This ensures the noninvasiveness of the
τM is required in order to choose an optimal settling time for technique, the glass transition temperature of PVP65 being
each wavelength emitted by the QCL. The settling time was ∼448 K.
set such that the membrane would be exposed for no less than Figure 4a,b compares the NAM-IR spectra with the ATR-
3× τM for each discrete IR wavelength, in order to ensure that FTIR (Perkin−Elmer Spectrum 100) spectra for the PVP
the membrane reaches the maximum frequency shift at each sample thicknesses ranging from 20 to 500 nm. For both
wavelength step. Considering that the QCL sweeps 1185 cm−1 techniques, the comparison is done with a single-sweep
with steps of 0.5 cm−1, the total acquisition time for a 20 nm- recording. The signal acquisition parameters and postprocess-
thin polymer layer is only 28.4 s, given a τM value of ∼4 ms in ing techniques are shown in the Supporting Information. The
low vacuum. ATR-FTIR spectra were acquired at 4 and 2 cm−1 resolution;
The membranes’ transient thermal constant also influences finer resolutions did not provide any reliable results due to a
the choice of the integration time of the phase-locked loop too low SNR. When ATR-FTIR was used, the three bands of
(PLL) detection scheme. To correctly follow the resonance PVP were clearly visible for sample thicknesses higher than 100
frequency shift upon light absorption for each IR wavelength nm, but only a very broad peak corresponding to the carbonyl
step, the lock-in amplifier bandwidth has to be set sufficiently frequency at 1680 cm−1 was observable for thinner samples
high enough to follow the full dynamics of the resonance (Figure 4a). Instead, our NAM-IR spectroscopy reveals all the
frequency shift determined by τM, but at the same time, a low expected features in the spectra, resolving clearly the three PVP
bandwidth is desirable to reduce the frequency acquisition spectroscopic bands down to a 20 nm sample thickness, both
noise. The best balance was found by measuring the Allan in low and high vacuum (Figure 4c).
deviation of the frequency signal as function of the PLL To compare the performance of the ATR-FTIR and our
integration time59 (see the Supporting Information). NAM-IR system, SNRs were calculated on the baseline
Figure 3b,c shows the raw data acquired by our setup. The corrected spectra. The noise was calculated as the standard
detailed understanding of the membrane frequency behavior deviation of the spectra between 1800 and 1953 cm−1, since no
enabled us to clearly resolve each distinct IR wavelength step light absorption occurs in this range. As a signal for the
of 0.5 cm−1, since the exponential thermal response of the calculation of the SNR, we analyzed the amplitude of the
membrane frequency is clearly visible, and the signal arrives at carbonyl peak around 1680 cm−1. For all the examined
the maximum amplitude within each step. thicknesses, the SNRs of NAM-IR (Figure 5a,b) were always at
In this work, the integration time was set to 1.5 ms for low least one order of magnitude higher than the ATR-FTIR values
vacuum experiments and 7 ms for high vacuum experiments, and up to 43 times higher when compared with the high
leading to a resolvable frequency shift of 2 ppm for a vacuum recorded spectra. It is worth to note that the high
membrane coated with a 20 nm-thin PVP layer. vacuum measurements, due to the higher values of the thermal
Since different polymers,60,61 drugs,62 brush layers,63 and time constants, need a longer settling time of the QCL source
block coplymers64 can typically present phase transition for each wavelength to match the longer membrane thermal
temperatures around room temperature, it is of the highest time constant. The SNR of NAM-IR spectroscopy is nearly
importance to ensure the thermal stability of the sample independent of the total acquisition time (Figure 5b), as long
properties during the IR illumination while the spectrum is as the settling time at each IR wavelength is larger than the
recorded. Therefore, for NAM-IR to be a viable solution for membrane thermal time constant.
ultrathin organic samples, the increase in sample temperature The SNR of the ATR-FTIR spectra depends on the
during the spectrum acquisition needs to be minimized. By resolution of the acquisitions,66 which is typically 4 or 2
maximizing the SNR of the overall system, we could minimize cm−1, and the comparisons of the SNRs between the spectra
the necessary IR power and therefore achieved a spectrum with are made, considering such spectral resolutions. Although
an SNR > 200 for a change in the sample temperature below 1 FTIR-based spectrophotometers increase the SNR of spectra
K. Despite the importance of the issue, there has, to the best of by coarsening the resolution, the spectra acquired at 4 cm−1 on
our knowledge, been no previously presented any estimation of 20 and 40 nm sample thicknesses did not lead to a remarkable
the temperature rise due to the IR absorption for NAM-IR difference regarding the SNR. Considering that the NAM-IR
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NAM-IR with an ATR-FTIR spectrometer regards which

vibrational modes can be excited by the IR light in case the
sample is a thin film that presents good molecular order-
ing.13,16,57 ATR-FTIR probes the surface sample with the IR
beam obliquely oriented to the normal of the sample surface
with a nearly fixed angle. Therefore, the IR radiation is probing
the perpendicular as well as the horizontal (with respect to the
surface) molecular vibrational modes. In this case, the resulting
spectra contain both the information about the horizontal as
well as the perpendicular modes, calling for precautions in the
interpretation of spectra from thin layers ordered at the
molecular level. Moreover, the ATR-FTIR spectra further
depend on the reflection occurring at the substrate and sample
interface.13 In fact, when the sampling depth is higher than the
sample thickness, the evanescent wave is partially reflected by
the substrate, leading to an extinction of the transversal mode
and enhancement of the longitudinal ones.13,67 Similar
artefacts are also present in adsorption−reflectance-based
systems.16,20 On the other hand, the infrared spectrum
obtained by NAM-IR is not influenced by the distortion of
the refractive index, which would shift the position of the peaks
to lower frequencies. ATR-IR suffers from these artefacts,
which need to be corrected through advanced correction
algorithms.57
Thus, the NAM-IR approach is much more flexible, and the
IR light can probe the sample with any angle and any
polarization. This flexibility simplifies the interpretation of the
spectra for samples where molecules follow a specific
orientation on the surface, such as self-assembled monolayers,
Langmuir block monolayers, or partially crystallized polymer
layers. A spectrum acquired with the IR light impinging the
sample surface perpendicularly would contain information only
on the vibrational modes that have a component of the dipole
moment parallel to the sample surface. Changing the
impinging angle of the IR light, the vibrational modes with a
dipole moment component orthogonally oriented to the
sample surface will also be probed.
These advantages and the much higher SNR for the sub-50
Figure 4. (a) ATR spectra, (b) NAM-IR spectra at 1 mbar, and (c) nm layers make membrane-based NAM-IR a very strong
close up of 20 nm PVP layer at 1 and 10−5 mbar and ATR-FTIR candidate for a new generation of single-molecule layer IR
spectra. For the sake of comparison, all the spectra were offset, and spectroscopy tools.
the NAM-IR spectra are represented as absolute values of the Membrane resonator-based NAM-IR spectroscopy enabled
resonance frequency shift. new possibilities for performing IR spectroscopy on sub-50 nm
organic films. The SNR of 307 obtained on a 20 nm PVP
spectra recorded on a 20 nm-thick PVP layer showed an polymer layer, combined with a detection limit in the attomole
impressive SNR of 307 in high vacuum, we are confident that range, positions membrane-based NAM-IR as a possible
this technique is now capable of recording the IR spectrum of a technique for a single-molecule layer analysis. The NAM-IR
single-molecule PVP layer. In fact, extrapolating the SNR spectroscopy measurements were performed in less than 30 s
versus thickness relation toward smaller thicknesses (see the on a 20 nm PVP layer, whereas in using a commercial ATR-
Supporting Information) and considering an SNR of 2 as the FTIR technique, the same SNR would be achieved with an
lowest value needed to clearly recognize a spectral feature of acquisition time 43 times longer or an SNR 43 times lower. If
PVP, the limit of detection regarding mass per unit area for we consider the acquisition performed under low vacuum
NAM-IR is 0.13 fg/μm2 (femtogram per square micrometer). conditions, the SNR is still 25 times higher compared to that of
This mass per unit area limit corresponds to an equivalent the commercial ATR-FTIR technique.
thickness of 160 pm of PVP, approximately corresponding to 4 Moreover, the vibrational modes in ordered organic thin
attomoles of PVP spread over the laser spot area (diameter, layers can be potentially selectively probed, since the IR light
100 μm). These data strongly indicate that single-molecule can hit the surface with virtually any angle, overcoming the
layers can be probed with NAM-IR, with very high effects of the interaction of the electric field in the case of
performances regarding SNR and short acquisition time. reflection of the incident beam at the substrate sample
NAM-IR spectroscopy not only outperforms ATR-FTIR in interface.13
terms of SNR but potentially also in terms of simplicity in the In terms of the mechanical robustness, the membranes
interpretation of the spectrum. In fact, another important comply better with the experimental conditions typical of the
feature to bear in mind when comparing our photothermal surface functionalization experiments compared to micro-
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Figure 5. (a) Comparison of SNR between NAM-IR spectroscopy and ATR-FTIR for different thicknesses. (b) SNR of 200 nm PVP-coated
membrane for different acquisition times. The SNR is not sensitive to a prolonged acquisition time; instead, ATR-FTIR spectrophotometer
increments the SNR for an increased number of scans.

strings or perforated geometries for airborne particles, allowing increased to 250 ms to allow the membrane to reach the steady
the user to prepare the samples in an ample kind of methods. value of the resonant frequency shift at each cycle.
The high capability to dissipate the heat makes the response ATR Spectra Acquisition. The ATR spectra were
one order of magnitude faster compared to microstrings.43 recorded with Perkin−Elmer Spectrum 100, providing a
Finally, the readout of the membrane motion can be constant power throughout the spectral range of 5 mW. The
integrated using a more advanced design, creating a compact spectra were acquired in samples composed of a silicon nitride
yet extremely sensitive, versatile, and fast IR spectroscopy tool substrate and a PVP layer, prepared in the same way as the
for ultrathin organic layers. membrane resonator. The PVP layer is placed in tight contact

■
with a single reflection ZnSe crystal. The gauge force of the
EXPERIMENTAL SECTION crystal was set to its optimal value, achieving the highest signal
intensity. For all the spectra, at least three signals were
Membrane Fabrication. The details of the membrane
recorded for each sample thickness. A single acquisition
fabrication process are described in the Supporting Informa-
spectrum is acquired at the spectral resolution of 2 and 4 cm−1.
tion.
The amplitude of the acquired spectra is then corrected to
Sample Preparation. The polymer solution was prepared
compensate the different absorption amplitudes throughout
by dissolving polyvinylpyrrolidone powder (PVP, Sigma-
the spectral range using the built-in function of the software.

■
Aldrich Mw = 360,000) in an aqueous solution of hydrogen
peroxide) (H2O2, 30% w/v) in two different concentrations (1
and 5 wt %). The deposition on the membrane was performed
ASSOCIATED CONTENT
by spin coating: the solution (4 mL) was poured on a silicon *
S Supporting Information

wafer containing the membrane chip and then spun at various The Supporting Information is available free of charge on the
rotational speeds. The sample was allowed to dry at room ACS Publications website at DOI: 10.1021/acsome-
temperature and atmospheric pressure. Ellipsometry was used ga.9b00276.
to measure the thickness of the polymer layers. The spinning Details on the membrane resonator fabrication, sample
curves, standard deviations, and details of the sample preparation, thermal time constant calculations, Allan
preparation are provided in the Supporting Information. deviation (noise) measurement, QCL laser power curve,
NAM-IR Spectra Recording. The NAM-IR signal was NAM-IR linearity studies, infrared spectroscopy data
recorded through a lock-in scheme. The membrane resonator postprocessing, NAM-IR absorption power, details of
is placed in a vacuum chamber that guarantees an optical the finite element modeling, and limit of the detection
access from the top and from the bottom side of the sensor of calculation (PDF)

■
the membrane. The resonance frequency of the membrane
resonator is probed optically (Polytech MSA-500), and the
infrared light is provided by a tunable quantum cascade laser AUTHOR INFORMATION
(QCL, Block Engineering 768−1953 cm−1) and collimated by Corresponding Author
a parabolic mirror on the membrane resonator providing a *E-mail: [email protected].
laser spot size of 100 μm. A lock-in amplifier records the ORCID
frequency shift. The phase detector bandwidth was 500 Hz for Andrea Casci Ceccacci: 0000-0002-1740-0807
the LV (10−3 mbar) measurement and 200 Hz for the HV
(10−5 mbar) measurement, and the sampling rate was set at Notes
The authors declare no competing financial interest.

■
3600 Hz. The thermal time constant was determined by
irradiating the membrane resonator periodically at a certain
wavelength as described elsewhere.58 The IR radiation was ACKNOWLEDGMENTS
mechanically chopped providing an irradiation time of 50 ms The research is funded by the Danish National Research
for the LV measurement. In HV mode, the irradiation time was Foundation (grant no. DNRF122), the Villum Fonden (grant
7633 DOI: 10.1021/acsomega.9b00276
ACS Omega 2019, 4, 7628−7635
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no. 9301), and the European Research Council (grant no. (21) Jiang, E. Y. Advanced FT-IR Spectroscopy; Thermo Electron
320535, “HERMES”). Corporation, 2003.

■
(22) Fan, J.; Trenary, M. Symmetry and the Surface Infrared
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7635 DOI: 10.1021/acsomega.9b00276

ACS Omega 2019, 4, 7628−7635