R2-B.3: Multi-Functional Nano-Electro-Opto-

Mechanical (NEOM) Sensing Platform

I. PARTICIPANTS

Faculty/Staff

Name Title Institution Email

Matteo Rinaldi PI NEU rinaldi@ece.neu.edu

Graduate, Undergraduate, and REU Students

Name Degree Pursued Institution Month/Year of Graduation

Yu Hui PhD NEU 2015

Zhenyun Qian PhD NEU 2017

II. PROJECT DESCRIPTION

A. Project Overview

The development of a new technology platform capable of performing multiple chemical analyses in a min-iaturized footprint is needed for the implementation of portable, ield-based analytical tools for rapid and reliable trace detection. A new multi-functional detector technology would enable a low-cost, portable, and high performance trace detection platform. This project addresses the three most important challenges as-sociated with the development of miniaturized nanoelectromechanical systems (NEMS) sensors suitable for the implementation of portable, ield-based analytical tools for rapid and reliable trace detection: (1) High resolution: 100x that of conventional sensor technologies; (2) Transduction ef iciency: Ef icient on-chip ac-tuation and sensing of vibration in ultra-low volume nanomechanical structures with a unique combination of electrical, mechanical, and optical properties; and (3) Selectivity: Selective detection of a targeted group of chemicals with very low false positive and false negative rates.

B. Biennial Review Results and Related Actions to Address

B.1. Strengths

The proposed work has the potential to achieve the true meaning of orthogonal detection. The methodology associated with this program is strong. By bringing four different sensing elements into a single device, the potential exists for bringing both sensitivity and selectivity to bear on the challenging problem of detecting explosives in complex, real-world environments. The PI has a good grasp of the relevant parameters neces-sary to maximize this technology, as well as its position within the greater scienti ic community. The project has made good progress to date. The development of uncooled, room-temperature infrared (IR) sensors, if successful, would be of great value to the trace detection industry.

B.2. Weaknesses

The PI is relatively new to the ield of explosives trace detection. These devices are in the development phase and testing on true materials and realistic conditions is needed. Equipment to perform testing on true materials and realistic conditions will be included in the budget and purchased by Year 4. Vacuum testing

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capabilities are not currently available in the PI’s lab. A radio frequency (RF) vacuum probe station with IR testing capabilities will be purchased by the end of Year 3. The capability to perform wafer level testing of the fabricated IR detector prototypes in a vacuum environment is crucial in order to characterize their actual thermal detection capabilities and compare them with the other existing technologies (uncooled IR detec-tors are in a vacuum package when used in the ield). The Owlstone Vapor Generator (OVG-4) will be pur-chased in Year 4 and used to perform testing on true materials such as pentaerythritol tetranitrate (PETN), cyclotrimethylenetrinitramine (RDX), and trinitrotoluene (TNT). The OVG-4 Vapor Generator is a compact, cost-effective calibration gas system which can generate NIST traceable, precise, repeatable, and accurate concentrations of chemicals and calibration gas standards.

C. State of the Art and Technical Approach

The performance of a sensor system for multiple analyte detection can be improved by increasing the amount of chemically orthogonal information acquired by the sensor [1]. This can be achieved by recording the ana-lyte induced variations of several independent physical, chemical, and electrical quantities such as mass, IR absorption spectrum, and temperature. Chemical sensors composed of multiple transducer modules have already been proposed but when a compact, portable, and low-power system is desirable, this hybrid solu-tion, composed of a multitude of different transducers, will be cumbersome and inef icient. In this context, the design of a multi-transducer sensor capable of ef iciently transducing different physical, chemical, and electrical changes induced by a gas sample would be ground breaking. We propose to develop an innovative, Nano-Electro-Opto-Mechanical (NEOM) sensing technology platform which integrates, in a small footprint, some of the fundamental chemical analysis typically performed in a laboratory, such as gravimetric analysis, IR spectroscopy, and thermal analysis (see Fig. 1 on the next page). The core element of the proposed technology is a Graphene-Aluminum Nitride (G-AlN) NEMS resonant multi-transducer detector coupled with an array of quantum cascade lasers (QCL) for chip scale IR spec-troscopy and integrated with a nano hot-plate for thermal analysis. The fundamental advantage of NEMS resonant sensors over other existing sensor technologies is related to the unique combination of extremely high sensitivity to external perturbations (due to their very reduced dimensions) and ultra-low noise per-formance (due to the intrinsically high quality factor, Q, of such resonant systems). The proposed technology overcomes fundamental scienti ic and engineering development challenges, enabling the implementation of a new generation of trace detectors that provide near real-time detection, high sensitivity, and high speci ic-ity for a targeted group of explosives (such as PETN, RDX and TNT) resulting in very low false positive and false negative rates.Such disruptive improvement in ield-deployable chemical sensor technology is made possible by the key innovations in gravimetric analysis, IR spectroscopy, and thermal analysis.

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C.1. Gravimetric analysis

The ultimate performance of a gas sensor is determined by its limit of detection (LOD) or resolution, which is the minimum value of analyte concentration that can be detected, and depends on both device sensitivity as well as the signal-to-noise ratio. For gravimetric gas sensors, the LOD is strictly related to both the sensitivity of the device’s resonance frequency to mass adsorbed per unit area (not absolute mass) and the minimum frequency shift (induced by gas molecule adsorption) that can be resolved by the sensor readout. Although the device sensitivity is in luenced exclusively by the mass and frequency of operation of the mechanical ele-ment (hence it is enhanced by scaling the device dimensions), the minimum measurable frequency shift is a function of the phase noise of the acoustic oscillator (i.e. sensor readout), hence the power handling and the dimensions of the mechanical device. Nanoscale resonators, such as nano-beams, tend to exhibit low-power handling and therefore poor phase noise, which negatively affects the sensor’s limit of detection. In addition, the greatly reduced dimensions of these devices render their transduction extremely dif icult, requiring the use of cumbersome, complex, and power inef icient read-out techniques, and limiting the area dedicated to the adsorption of the gas molecules, signi icantly decreasing the amount of mass adsorbed on the beam surface given a certain concentration of the analyte in the environment. This reduction in adsorbed mass per gas concentration limits the perfor-mance of the nano-resonant gas sensors, which should ultimately be evaluated in terms of LOD of adsorbed mass per unit area (gas concentration) rather than LOD of total adsorbed mass. In this perspective, optimal sensor performance is attained by synthesizing a transducer that occupies a relatively large area (which fa-cilitates ef icient transduction) and is very thin (which allows fabricating low mass devices with ultra-high sensitivity). Suspended membranes with thickness in the nanometer range are therefore desirable [2, 3]. In this project, by exploiting piezoelectricity in quasi two-dimensional and ultra-light weight G-AlN mem-branes, reliable electrical transduction of mechanical vibration will be employed for the making of nano-bal-ances for gravimetric analysis with sensitivities that are 100x that of conventional sensor technologies [4]. The performance of conventional piezoelectric resonant sensors in terms of sensitivity, limit of detection, and detection speed can be improved by scaling the overall thickness and reducing the overall mass of the material stack forming the resonant device while maintaining, at the same time, high values of Q factor and

Figure 1: Schematic representation (not to scale) of the envisioned sensing technology platform.

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transduction ef iciency [5]. Such performing device scaling is currently fundamentally limited by the need to use an electrically conductive (relatively thick) metal electrode to provide the excitation electrical signal to the piezoelectric nano resonator, and by the mass loading effect of chemical interactive material used to absorb the analyte on the surface of the device. We propose to develop an ultra-high resolution and fast res-onant sensor by integrating a 2D graphene layer on top of an AlN resonant nano-plate. Such a 2D graphene top layer not only represents the thinnest and lightest conductive electrode ever used to excite vibration in a piezoelectric NEMS resonator, but it also has the potential to be used as an effective chemical interactive material with the largest possible surface-to-volume ratio [6-8]. Despite the volume scaling, high values of quality factor, Q > 2000, will be attained thanks to the elimination of electrical and mechanical loading due to the metal electrode. Therefore, low noise performance even at higher frequencies of operation (i.e. ~ GHz) will be achieved, enabling the fabrication of resonant sensors with unprecedented resolution (< 10-24 g/m2). Furthermore, use of a single atomic layer graphene as a virtually massless and strain-less electrode for AlN nano-plate resonators enables an additional chemical sensing capability: the vibration amplitude of the pro-posed G-AlN Nano-Plate Resonator (NPR) is highly sensitive to the electrical conductivity of the graphene electrode. Therefore, any analyte induced variations in the graphene electrode conductivity can be ef iciently detected by monitoring the corresponding induced variations in the device vibration amplitude without the need of direct electrical probing of the graphene sensing layer. Thanks to this unique feature, two chemically orthogonal quantities, such as mass and charge of the analyte, can be simultaneously acquired by the pro-posed G-AlN NEMS resonant sensor.

C.2. IR spectroscopy

IR spectroscopy is a very well established and highly speci ic method to identify unknown gases and vapors [9, 10]. Fourier Transform Infrared (FTIR) [11] can be currently considered the most diffused technique used to perform IR spectroscopy but it suffers from fundamental limitations that prevent the implementation of compact, lightweight, and portable ield-based analytical tools for rapid and reliable identi ication of un-known hazardous gases and vapors.. The challenge in bringing FTIR spectroscopy out of the laboratory and into the ield is due to the fact that the maximum attainable spectral resolution (in cm units) of the system is inversely related to the maximum retardation (in length units) produced by the interferometer. As a result, high-resolution FTIR spectrometers require high retardation and, thus, a large amount of travel in the mov-ing mirror of the interferometer. For example, resolving spectral features with 100 MHz resolution would require a mirror travel of 3 m. Such a fundamental limitation makes FTIR inadequate for the implementation of miniaturized and high-resolution ield-based spectrometers. We propose to miniaturize IR spectroscopy by coupling a compact, low-power, and tunable (7-10 m range) QCL array to the G-AlN NEMS multi-transducer detector. The IR absorption spectrum of the gas molecules attached to the chemically interactive graphene layer will be readily detected by measuring the absorbed heat-induced resonant frequency shift of the G-AlN nanomechanical resonator. Such a nanomechanical reso-nant structure has all the fundamental features necessary for the implementation of a thermal detector with unprecedented performance. Very high sensitivity to temperature, because of material properties of G-AlN, temperature coef icient of frequency, TCF ~ 100 ppm/K, can be achieved. An extremely low thermal mass, given the nanoscaled dimension of the G-AlN nano plate, the mass of the resonant structure is < 100 pg and the corresponding thermal capacitance is Cth < nJ/K. Since the resonant nano plate is released from the silicon substrate and connected to it only through two nanoscale anchors, there is excellent isolation from the heat sink and thermal resistance Rth ~ 106 K/W, can also be achieved. Extremely low noise performance is possible by taking advantage of the high quality factor, Q > 2000, of the nanoscale resonant system; it is also possible to implement frequency sources with short term frequency stability fmin ~ ppb. For High IR absorptance, while conventional metal electrodes make the resonant structure highly re lective at IR wavelengths, the transparent nature of the atomically-thin graphene electrode employed in our proposed device enables effec-tive absorption of the incident IR radiation in the vibrating body of such a structure (the graphene, AlN and

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platinum (Pt) stack provides a Fabry-Perot like resonance). Thanks to this unique combination of thermal and electromechanical properties, the proposed G-AlN technology can deliver thermal detectors that can far exceed the state-of-the-art performance of un-cooled IR sensors [12], and rival those utilizing bulky, heavy, expensive, and inconvenient to use cryogenically cooled semiconductor photodetectors [13]; Time Constant, μs and Noise Equivalent Power, NEP pW/Hz1/2.

C.3. Thermal analysis

Differential thermal analysis (DTA) is a technique widely used in chemistry laboratories to identify and quan-titatively analyze the chemical composition of substances by observing the thermal behavior of a sample as it is heated [14]. Such DTA systems have fundamental limitations in terms of size (a furnace is typically em-ployed), power consumption (10s W for the furnace), and measurement speed (typical heating rates in the order of 0.001 – 10 C/s) that prevent performing such thermal analysis of gas samples out of the laboratory and in the ield. We propose to enable compact, low-power (mW), and ultra-fast (ms) chip-scale thermal analysis by integrating a nano-scale heating element with the G-AlN NEMS multi-transducer detector. The ultra-miniaturized dimensions of the nanomechanical structure guarantees ef icient heating, temperature rise factor 10s ~ 100s C/mW, and ultra-fast heating rate ~ 106 C/s of the of the gas molecules attached to the chemically interactive graphene layer. At the same time, the very high sensitivity to temperature and the extremely low noise performance (as described in the previous section) of the G-AlN NEMS resonator allows observation of thermal behavior of the gas sample with unprecedentedly high resolution in the order of ~ μK/Hz1/2. As in conventional macro-scale DTA systems, the thermal signature of the gas sample will be mea-sured relative to that of an adjacent inert device that is not exposed to the gas sample (packaged reference NEMS device, Fig. 1).

D. Major Contributions

D.1. G-AlN NEMS resonators

Designing “ideal electrodes” that simultaneously guarantee low mechanical damping and electrical loss as well as high electromechanical coupling in ultra-low-volume piezoelectric nanomechanical structures can be considered to be a key challenge in the NEMS ield. The integration of a graphene electrode in the design of a 245 MHz piezoelectric NEMS resonator was demonstrated by the PI’s group in Year 2 [15, 16]. In Year 3, we experimentally demonstrated the remarkable manner in which this atomically-thin conductor is able to mim-ic an ideal mass-less electrode, enabling piezoelectric NEMS devices to operate at theoretically “unloaded” frequency-limits with improved electromechanical performance and reduced volume over an unprecedented range of operating frequencies, 0.2 GHz < f0 < 2.6 GHz [17]. This represents a spectacular trend inversion in the scaling of piezoelectric electromechanical resonators, opening up new possibilities for the implementa-tion of nano electro mechanical systems with unprecedented performance. Over 150 AlN resonators with Pt bottom IDE (2 μm < W0 < 20 μm) were fabricated on a single wafer. For each pitch-size, several devices were constructed with a graphene top-electrode, and reference devices with a 100 nm thick gold (Au) top-elec-trode. Compared to reference devices, there was a signi icant improvement in mass sensing capability in every single graphene-electrode device, thanks to the elimination of the mass loading and the mechanical damping associated with the conventional top metal electrode. The fabricated graphene-electrode device is characterized by: higher quality factor, Q; higher frequency, f0; reduced thickness, t; reduced mass density, ρ (see Fig. 2 on the next page).

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We also demonstrated that Graphene-AlN NEMS resonators have intrinsically high sensitivity to IR radiation without the need of additional absorbing materials (which eliminates the loading effects of the IR absorber conventionally integrated on top of the thermal detector; see Fig. 3) [18]. The achievement of high IR ab-sorptance in NEMS resonant structures with reduced volume and improved electromechanical performance addresses one of the most fundamental challenges in the NEMS ield, and can potentially lead to the devel-opment fast (~ms) and high resolution (Noise Equivalent Power ~ 1 pW/Hz1/2, Noise Equivalent Temperature Difference ~ 1 mK) uncooled IR detectors suitable for the implementation of high performance, miniaturized, and power-ef icient IR imaging systems.

Furthermore, we demonstrated an innovative chemical sensing mechanism based on the effective transduc-tion of the analyte-induced variations in the electrical conductivity of the graphene electrode employed to excite mechanical vibration in an AlN NEMS resonator [17, 19]. Analyte-induced variations in the graphene electrode conductivity can be ef iciently detected by monitoring the corresponding induced variations in the

Figure 2: (Left) Schematic illustration in layered view of a contour-extensional mode AlN NEMS resonator, where the

top electrode is fabricated using mechanically transferred, CVD-synthesized graphene. (Right) Qf0/ρt is inversely

proportional to the limit of detection of NEMS gravimetric sensors; showing enhanced performance over nearly the

entire range, in graphene-electrode devices. The “spread” shown represents variations in data for each f0 value. These

metrics have been obtained from the measurements of 62 graphene-electrode devices and 65 100-nm-thick met-

al-electrode devices.

Figure 3: (Left) Measured and simulated IR absorption spectra. Three solid lines are the spectra for diff erent materials

on top of 460 nm AlN and 100 nm Pt. The dashed line is the simulated spectrum for only the AlN–Pt stack. The in-

set shows the simulated electric fi eld distribution of the fundamental mode of the Fabry–Perot resonance at 3.4 μm.

(Right) Measured frequency response of the G–AlN and reference devices exposed to a 5-μm IR radiation modulated at

1 Hz by a chopper. The G–AlN detector showed a responsivity ~ 13 × stronger than the reference device with 100 nm

Au as the top electrode.

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device vibration amplitude without the need of direct electrical probing of the graphene sensing layer (see Fig. 4). Thanks to this unique feature, two chemically orthogonal quantities, such as mass and charge of the analyte, can be simultaneously acquired by the proposed G-AlN NEMS resonant sensor.

D.2. Plasmonic Piezoelectric NEMS Resonant IR Detector

In Year 2, we demonstrated a irst prototype of an ultra-high resolution (~371 pW/Hz1/2) uncooled IR detector based on a high frequency (136 MHz) AlN piezoelectric resonant nano-plate completely released from the substrate and supported by two nanoscale Pt anchors. In Year 3, we demonstrated a new class of uncooled IR spectral sensors ideal for the implementation of low-cost handheld gas and luid analyzers with potentially revolutionary applications in medical diagnostics, homeland security, and many other markets. In particular, we used a thin piezoelectric plasmonic metasurface to form the resonant body of a nanomechanical resona-tor with simultaneously tailored optical and electromechanical properties. We experimentally demonstrate that it is possible to achieve high thermomechanical coupling between electromagnetic and mechanical res-onances in a single ultra-thin piezoelectric nano-plate. The combination of nanoplasmonic and piezoelec-tric resonances allowed the proposed device to selectively detect long-wavelength infrared (LWIR) radiation with unprecedented electromechanical performance and thermal capabilities. These attributes lead to the demonstration of a fast, high resolution, uncooled IR detector with ~80% absorption for an optimized spec-tral bandwidth around 8.8 μm (see Fig. 5 on the next page) [20].

Figure 4: (Left) Measured admittance amplitude for the same 225 MHz G-AlN NPR after three diff erent long fl uorina-

tion cycles. (Right) Raman spectra of the 225 MHz G-AlN NPR graphene top-electrode, measured on the same spot

but at diff erent stages of the fl uorination cycles. With progressive fl uorination cycles, the G and G’ peaks eventually

disappear/degenerate as a growing number of –sp2 carbon atoms transform to –sp3 attached with an F atom.

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E. Milestones

Year 3 milestones:• Demonstrated that graphene electrodes boost the performance of piezoelectric NEMS resonant sensors.• Demonstrated the irst prototype of uncooled spectral IR detector based on a piezoelectric plasmonic

NEMS resonator.The anticipated Year 4 milestones are as follows : • The demonstration of ef icient on-chip actuation and sensing of vibration in ultra-low volume nanome-

chanical structures with properly tailored electrical, mechanical, and optical properties.• Demonstrate and characterize multiple spectrally selective NEMS resonant IR detectors.• Characterize detector responsivity in vacuum.• The design and fabrication of multi-functional NEMS resonant sensors.

F. Future Plans

• Demonstrate and characterize multiple spectrally selective NEMS resonant IR detectors (spectral range

Figure 5: (a) Mock-up view: an aluminum nitride nano-plate is sandwiched between a bottom metallic interdigitated

electrode and a top nanoplasmonic metasurface. The incident IR radiation is selectively absorbed by the plasmonic

metasurface and heats up the resonator, shifting its resonance frequency from f0 to f’ due to the temperature depen-

dence of its resonance frequency. (b) SEM images of the fabricated resonator, metallic anchors, and nanoplasmonic

metasurface. The dimensions of the resonator are: L = 200 μm, W = 75 μm, W0 = 25 μm (19 μm + 6 μm), L

A = 20 μm,

and WA = 6.5 μm. The dimensions of the unit cell of the plasmonic metasurface are: a = 1635 nm, and b = 310 nm. (c)

Simulated and measured absorption spectra of the fabricated plasmonic piezoelectric nanomechanical resonator. The

dimensions of the Au patches which compose the metasurface area = 1635 nm, b = 310 nm, and the thickness of the

Au, AlN, and Pt layers are 50nm, 500nm, and 100nm, respectively. (d) Measured response of the plasmonic piezoelec-

tric resonator and a conventional AlN MEMS resonator to a modulated IR radiation emitted by a 1500 K globar (2 -16

μm broadband spectral range).

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8-10 m, compatible with EOS Photonics’ tunable QCLs).• Demonstrate IR signature detection capability.

III. RELEVANCE AND TRANSITION

A. Relevance of Research to the DHS Enterprise

• A new multi-functional sensing technology platform which integrates, in a small footprint, some of the fundamental chemical analysis typically performed in a chemistry laboratory, such as gravimetric analy-sis, IR spectroscopy and thermal analysis, is being developed.

• By ef iciently transducing different physical, chemical, and electrical changes induced by a gas sample, the proposed technology will lead to the development of low-cost, portable, and high performance (i.e. 100x that of conventional sensor technologies) trace detection platforms.

• Heterogeneous integration of this multi-functional detector technology with state-of-the-art QCLs will enable the fabrication of ultra-miniaturized and power ef icient frequency domain IR spectrometers, which will lead to disruptive improvement in ield-deployable systems for trace detection and imaging.

B. Potential for Transition

Proof of concept will be shared with the identi ied potential customers to explore technology transition. Po-tential users and commercialization partners are identi ied in the following lists.• DHS• DARPA Microsystems Technology Of ice, Troy Olsson, Dev Palmer• Air Force Of ice of Science Research, Kenneth Goretta, Gernot Pomrenke, and Harold Weinstok• Analog Devices, Inc.• Qualcomm• RF Micro Devices, Inc.• Eos Photonics• Avago• Apple• Google

C. Data and/or IP Acquisition Strategy

The PI holds intellectual property for the technology relevant to the project: a patent application has been iled under the Patent Cooperation Treaty (PCT), application no. PCT/US14/35015, January 2015. A US pro-

visional patent application has been iled, application no. 62/132,755, March 2015. US Patent application 14/969,948 (publication no. US 2016/0099701 A1) related to the “plasmonic piezoelectric resonant IR de-tector” has been examined by the United States Patent and Trademark Of ice and allowed for issuance as a patent on 4/1/2016 (Notice of Allowance 19815-225, all claims have been allowed).

D. Transition Pathway

Proof of concept will be shared with the above list of potential users and commercialization partners to explore technology transition.

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E. User and Potential Commercialization Partner Connections

See section III.B above. Analog Devices (Dr. Eugene Hwang).

IV. PROJECT ACCOMPLISHMENTS AND DOCUMENTATION

A. Peer Reviewed Journal Articles

1. Y. Hui, J. S. Gomez-Diaz, Z. Qian, A. Alu’ and M. Rinaldi. “Plasmonic Piezoelectric Nanomechanical Res-onator for Spectrally Selective Infrared Sensing.” Nature Communications, 7:11249, 15 April 2016. DOI: 10.1038/ncomms11249

2. Z. Qian, Y. Hui, F. Liu, S. Kar and M. Rinaldi. “Graphene-Aluminum NEMS Resonant Infrared Detector.” Nature Microsystems & Nanoengineering, Vol. 2, p. 16026, 2016. DOI: 10.1038/micronano.2016.26

B. Other Publications

1. Y. Hui and M. Rinaldi. “MEMS Resonant Infrared Sensors” in Encyclopedia of Nanotechnology, B. Bhu-shan, Ed., ed: Springer, 17 February 2016, pp. 1-9, ISBN:978-94-007-6178-0. DOI:10.1007/978-94-007-6178-0_100962-1, http://dx.doi.org/10.1007/978-94-007-6178-0_100962-1

C. Peer Reviewed Conference Proceedings

1. Z. Qian, Y. Hui and M. Rinaldi. “Effects of Volume Scaling in AlN Nano Plate Resonators on Quality Fac-tor.” Proceedings of the IEEE International Frequency Control Symposium (IFCS 2016), New Orleans, LA, 9-12 May 2016.

2. Z. Qian, Y. Hui, F. Liu, S. Kar and M. Rinaldi. “Chemical Sensing based on Graphene-Aluminum Nitride Nano Plate Resonators.” Proceedings of the IEEE Sensors 2015 Conference, Busan, Korea, 1-4 Novem-ber 2015, pp. 1-4. DOI: 10.1109/ICSENS.2015.7370507

D. Other Presentations

1. Seminarsa. “Hybrid MEMS/NEMS for Advanced Sensing and Wireless Communications.” 2016 CMOS Emerg-

ing Technologies Research Symposium, Montreal, QC, Canada, 26 May 2016, Invited Talk.b. “Plasmonic Piezoelectric NEMS Resonant Infrared Detectors.” IEEE Sensors 2015 Conference, Bu-

san, Korea, 2 November 2015, Invited Talk.

V. REFERENCES

[1] C. Jin, P. Kurzawski, A. Hierlemann, and E. T. Zellers, “Evaluation of Multitransducer Arrays for the Determination of Organic Vapor Mixtures,” Analytical Chemistry, vol. 80, pp. 227-236, 2008/01/01 2007.

[2] M. Rinaldi, C. Zuniga, and G. Piazza, “ss-DNA functionalized array of ALN Contour-Mode NEMS Resonant Sensors with single CMOS multiplexed oscillator for sub-ppb detection of volatile organic chemicals,” in IEEE 24th International Conference on Micro Electro Mechanical Systems (MEMS 2011), 2011, pp. 976-979.

[3] M. Rinaldi, “NEMS Resonant Chemical Sensors, Encyclopedia of Nanotechnology,” B. Bhushan, Ed., ed: Springer Netherlands, 2012, pp. 1888-1895.

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[4] M. Li, H. X. Tang, and M. L. Roukes, “Ultra-sensitive NEMS-based cantilevers for sensing, scanned probe and very high-frequency applications,” Nature Nanotechnology, vol. 2, pp. 114-120, 2007.

[5] M. Rinaldi and G. Piazza, “Effects of volume and frequency scaling in AlN contour mode NEMS resonators on oscillator phase noise,” in 2011 Joint Conference of the IEEE International Frequency Control and the European Frequency and Time Forum (FCS), 2011, pp. 1-5.

[6] F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake, M. I. Katsnelson, and K. S. Novoselov, “Detection of individual gas molecules adsorbed on graphene,” Nat Mater, vol. 6, pp. 652-655, 2007.

[7] Y. Lu, B. R. Goldsmith, N. J. Kybert, and A. T. C. Johnson, “DNA-decorated graphene chemical sen-sors,” Applied Physics Letters, vol. 97, pp. 083107-3, 2010.

[8] S. Rumyantsev, G. Liu, M. S. Shur, R. A. Potyrailo, and A. A. Balandin, “Selective Gas Sensing with a Single Pristine Graphene Transistor,” Nano Letters, vol. 12, pp. 2294-2298, 2012/05/09 2012.

[9] D. Levy and E. G. Diken, “Field Identifi cation of Unknown Gases and Vapors Via IR Spectroscopy for Homeland Security and Defense,” Sensors Journal, IEEE, vol. 10, pp. 564-571, 2010.

[10] L. Mariey, J. P. Signolle, C. Amiel, and J. Travert, “Discrimination, classifi cation, identifi cation of microorganisms using FTIR spectroscopy and chemometrics,” Vibrational Spectroscopy, vol. 26, pp. 151-159, 2001.

[11] K. Gerwert and C. Kötting, “Fourier Transform Infrared (FTIR) Spectroscopy,” in eLS, ed: John Wiley & Sons, Ltd, 2001.

[12] F. Niklaus, C. Vieider, and H. Jakobsen, “MEMS-based uncooled infrared bolometer arrays: a re-view,” pp. 68360D-68360D, 2007.

[13] A. Rogalski, “Infrared detectors: status and trends,” Progress in Quantum Electronics, vol. 27, pp. 59-210, 2003.

[14] R. C. Mackenzie and B. D. Mitchell, “Differential thermal analysis. A review,” Analyst, vol. 87, pp. 420-434, 1962.

[15] Z. Qian, Y. Hui, F. Liu, S. Kar, and M. Rinaldi, “245 MHz graphene-aluminum nitride nano plate res-onator,” in Solid-State Sensors, Actuators and Microsystems (TRANSDUCERS & EUROSENSORS XXVII), 2013 Transducers & Eurosensors XXVII: The 17th International Conference on, 2013, pp. 2005-2008.

[16] Z. Qian, Y. Hui, F. Liu, S. Kar, and M. Rinaldi, “Single transistor oscillator based on a Graphene-Alu-minum Nitride nano plate resonator,” in European Frequency and Time Forum & International Fre-quency Control Symposium (EFTF/IFC), 2013 Joint, 2013, pp. 559-561.

[17] Z. Qian, F. Liu, Y. Hui, S. Kar, and M. Rinaldi, “Graphene as a Massless Electrode for Ultrahigh-Fre-quency Piezoelectric Nanoelectromechanical Systems,” Nano Letters, vol. 15, pp. 4599-4604, 2015/07/08 2015.

[18] Z. Qian, Y. Hui, F. Liu, S. Kai, and M. Rinaldi, “1.27 GHz Graphene-Aluminum Nitride nano plate resonant infrared detector,” in 2015 Transducers - 2015 18th International Conference on Solid-State Sensors, Actuators and Microsystems (TRANSDUCERS), 2015, pp. 1429-1432.

[19] Z. Qian, Y. Hui, F. Liu, S. Kar, and M. Rinaldi, “Chemical sensing based on graphene-aluminum ni-tride nano plate resonators,” in SENSORS, 2015 IEEE, 2015, pp. 1-4.

[20] Y. Hui, J. S. Gomez-Diaz, Z. Qian, A. Alu, and M. Rinaldi, “Plasmonic piezoelectric nanomechanical resonator for spectrally selective infrared sensing,” Nat Commun, vol. 7, 2016.

[21] M. Rinaldi, Y. Hui, C. Zuniga, A. Tazzoli, and G. Piazza, “High frequency AlN MEMS resonators with integrated nano hot plate for temperature controlled operation,” in Frequency Control Sympo-sium (FCS), 2012 IEEE International, 2012, pp. 1-5.

[22] Y. Hui and M. Rinaldi, “Fast and high resolution thermal detector based on an aluminum nitride

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Appendix A: Project Reports Thrust R2: Trace & Vapor Sensors

Project R2-B.3

piezoelectric microelectromechanical resonator with an integrated suspended heat absorbing ele-ment,” Applied Physics Letters, vol. 102, pp. 093501-4, 2013.

ALERT Phase 2 Year 3 Annual Report

Appendix A: Project Reports Thrust R2: Trace & Vapor Sensors

Project R2-B.3