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IEEE TRANSACTIONS ON NANOTECHNOLOGY, Volume 18, 2019 879

Thermoelectric Graphene Nano-Constrictions


as Detectors of Microwave Signals
Michael R. Gasper , Student Member, IEEE, Ryan C. Toonen , Member, IEEE, Nicholas C. Varaljay,
Robert R. Romanofsky, Senior Member, IEEE, and Félix A. Miranda, Fellow, IEEE

Abstract—Microwave power detectors were realized using nano- of future deep space explorers while decreasing antenna size
constrictions fabricated from commercially-available monolayer creates an opportunity to explore new approaches for realizing
graphene, synthesized by means of chemical vapor deposition. The ultra-sensitive detectors. The use of graphene in RF detection
graphene nano-constrictions (GNCs) were fabricated so as to shunt
the inner discs to the concentric outer annuli of micrometer-scale and mixing applications has received considerable interest due
Corbino disc test structures. The test structure was fabricated to the unique rectifying characteristics [1] that result from
on a layer of electrically-insulating silicon dioxide situated on Dirac-cone bandstructure. Additionally, the nanopatterning of
an electrically-conductive, doped silicon substrate. The substrate graphene into narrow ribbons allows for the opening of an
was used as a gate for controlling the Fermi level in the nano- artificial bandgap, which can be engineered by controlling width
constriction. Probe station measurements were conducted on a
detector with nano-constriction dimensions of 500 nanometers in and crystallographic orientation [2]. Graphene has also been
width and 5 micrometers in length. The annulus of this device used in photodetection schemes as well as an absorbing material
was electrically grounded and held in thermal equilibrium with in optically transparent antennas and detectors [3]–[6]. While
chassis of the probe station. Measurements obtained with a vector photodetection at microwave frequencies has been shown at
network analyzer provided the reflection coefficient of the detector. cryogenic temperatures with suspended ultraclean graphene [7],
Using a test signal frequency of 433.92 MHz, microwave power
detection characterizations, which accounted for signal reflection, we have demonstrated room-temperature microwave detection
revealed a peak detection sensitivity of 60.25 mV/mW. The gate using on-wafer graphene processed using standard techniques.
voltage dependence of the power detection sensitivity was found In this paper, we report on improved device processing and
to be strongly correlated with that of the Mott formula used for performance over those previously explored in [8]. Microwave
calculating the Seebeck coefficient of graphene. This observation detectors based on graphene nano-constrictions (GNCs) are
suggests that localized microwave heating of the inner disc, relative
to the temperature of the outer annulus, establishes a thermal gra- integrated with Corbino-disc-style microstructures engineered
dient across the nano-constriction and results in a thermoelectric for high-frequency on-wafer probing. The concentric geometry
response that is proportional to the power level of the incident of the probing pad structure is convenient for conducting studies
microwave signal. in which both GNC width and crystallographic orientation are
Index Terms—Graphene, photodetectors, thermoelectric, mi- varied. Conventional microfabrication techniques were used to
crowave measurements, Corbino disc, lithography, electron beam produce 100 test structures per 1 cm × 1 cm die with greater
lithography, Mott formula, Seebeck coefficient. than 95% yield. Electron-beam lithography was subsequently
used to fabricate GNCs. These microwave sensing elements
I. INTRODUCTION were characterized with DC conductance vs gate voltage mea-
surements to determine the Fermi level dependence of the See-
HE next generation deep space networks will demand
T significant improvements in radio frequency (RF) receiver
performance. The desire to increase the transmission bandwidth
beck coefficient [9]. These GNC detectors were used to detect
continuous-wave signals with frequencies ranging from 10 MHz
to 10 GHz. The Fermi-level dependence of the microwave
power detection sensitivity was strongly correlated with that of
Manuscript received March 1, 2019; revised July 10, 2019; accepted August the Seebeck coefficient suggesting that the dominant physical
11, 2019. Date of publication August 20, 2019; date of current version August mechanism of detection is the thermoelectric effect. Network
27, 2019. This work was supported in part by a 2017 and 2018 NASA Glenn
Research Center Faculty Fellowship Program Award and in part by a 2018 analyzer measurements were collected in order to determine the
NASA Glenn Research Center Student Internship. The review of this paper was amount of unreflected power that was delivered to the detector.
arranged by Associate Editor SINMDC2018Portland. (Corresponding author: The sensitivity of the devices has been determined with respect
Michael R. Gasper.)
M. R. Gasper and R. C. Toonen are with the Department of Electrical and to the unreflected power, resulting in significantly higher values
Computer Engineering, University of Akron, Akron, OH 44325 USA (e-mail: than previously reported [8]. In comparison to thermoelectric
mrg41@zips.uakron.edu; rctoonen@uakron.edu). detectors based on CMOS and MEMS technologies [10]–[13]-
N. C. Varaljay is with the Space Environment Test Branch, NASA Glenn
Research Center, Cleveland, OH 44135 USA (e-mail: nicholas.c.varaljay@ which offer relatively low power detection sensitivity but are
nasa.gov). widely used in applications requiring high linearity and zero
R. R. Romanofsky and F. A. Miranda are with the Communications and Intel- DC power consumption [14]-our graphene detectors exhibit a
ligent Systems Division, NASA Glenn Research Center, Cleveland, OH 44135
USA (e-mail: robert.r.romanofsky@nasa.gov; felix.a.miranda@nasa.gov). significant improvement in power detection sensitivity (up to
Digital Object Identifier 10.1109/TNANO.2019.2935414 one order of magnitude). The improvement is three orders of

1536-125X © 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
880 IEEE TRANSACTIONS ON NANOTECHNOLOGY, Volume 18, 2019

Fig. 2. Fabrication of GNCs using electron-beam writing (a), development


leaving behind the hardened resist (b), and etching excess graphene (c). Final
device structure is shown in (d) and (e) with microscope photograph of nano-
constriction in a dogbone configuration (f). Illustrations are not to scale.

delamination of the graphene layer during device processing


and prevent exposure to ambient contaminants. The back layer
of SiO2 is removed using the same process described in [8].
The graphene is then patched in order to isolate individual
devices and allow for better adhesion of metal contacts. Positive
tone photoresist, AZ5214-E was spun on the sample at 500 rpm
for 3 seconds followed by 4000 rpm for 42 seconds. The edge
bead was removed by swabbing the corners of the sample with
AZ EBR, and the samples were soft baked at 110 ◦ C for 3 min-
utes. The samples were subsequently exposed at an intensity of
approximately 15 mW/cm2 for 20 seconds, Fig. 1 (a), followed
by a development in AZ 300 MIF for 30 seconds. The developer
Fig. 1. Photolithography to patch the graphene/Al/Al-oxide stack (a). De-
velopment and etching for patching (b) and (c). Remaining graphene patches contains tetramenthylammonium hydroxide which selectively
(d) and (e). Standard photolithographic processing of Cr/Au Corbino discs (f)–(j) etches areas of exposed Al/Al oxide, leaving only bare graphene
[8]. Microscope photograph of Corbino disc test structure after micro-fabrication Fig. 1 (b). The remaining resist acted as an etch stop [18] as
(k). Illustrations are not to scale.
the samples were placed in an reactive ion etch of O2 /Ar for
60 seconds at 100 W, Fig. 1 (c). The resist, which was left behind
after the RIE treatment, was removed with acetone. Passivated
magnitude greater when accounting for signal reflection due to graphene patches remained on the substrate, Fig. 1 (d) and (e).
impedance mismatch. The patterning of the Cr/Au contacts follows the same procedure
outlined in [8].
II. FABRICATION OF CORBINO DISCS AND GRAPHENE
Dogbone shapes with nano-constrictions were etched from the
NANO DEVICES passivated graphene situated between the inner disc and outer
With respect to previous work reported by the authors, an annuli of the Corbino disc test structures. Negative tone E-Beam
improved micro-fabrication process was developed [8]. Fig. 1 resist Dow Corning XR-1541-006 (HSQ) was used for the pro-
outlines the improved method for fabricating Corbino disc cess. The diluted resist previously used for E-Beam lithography
test structures. The process begins by cleaning commercially- was exposed too quickly, with a low dose to print, and had poor
available, CVD-grown, monolayer graphene that has been previ- resolution as a result. E-beam writing was accomplished using
ously transferred to a 300-nm thick silicon dioxide layer that was a Hitachi 2460 SEM retrofitted with a fast beam blanker and
thermally grown on a p-type silicon substrate [15], with rapid a Nabity Nanopattern Generation System. The electron beam
thermal annealing (RTA) in a forming gas (nitrogen with 4.5% lithography pattern was aligned to the micro-structures in order
hydrogen) atmosphere at 250 ◦ C for 12 minutes. The RTA is a to write lines that connected the Corbino disc contacts, Fig. 2.
critical step to reduce impurities on the graphene surface [15], The samples were exposed with a dose of 400 μC/cm2 at a
[16]. A 5 nm sacrificial layer of aluminum (Al) was deposited beam current of 10 pA at 30 kV with a working distance of
over the entire substrate and allowed to form a native oxide approximately 12 mm, Fig. 2 (a).
passivation layer [17]. This complete metallic covering was used After electron beam writing the sample was developed in AZ
to protect the graphene during photolithographic processing. 300 MIF for 4 minutes. The e-beam resist that remained on
The passivation layer deposition is necessary in order to prevent top of the graphene/Al stack hardened into glass, Fig. 2 (b).
GASPER et al.: THERMOELECTRIC GRAPHENE NANO-CONSTRICTIONS AS DETECTORS OF MICROWAVE SIGNALS 881

Fig. 4. Frequency response of GNC detector with PL = −12.9 dBm and


Vgate = 0 V (left) and reflection coefficient of GNC structure (right). Reflec-
tions decrease as frequency increases due to the capacitive design of the Corbino
disc microstructure.

Fig. 3. Drain-Source conductance as a function of Gate voltage with Drain-


Source voltage held at 100 mV (left) and derivative of conductance scaled by
resistance (right). Device displays a conductance minimum at 20 V.

However, the hardened resist acts as another layer of passivation


to protect the device. The patterned photoresist served as an
etch-stop while the unprotected graphene and remnants of Al-
oxide were dry-etched in an RIE, Fig. 2 (c). The RIE was done
in O2 /Ar for 2 minutes at 150 W. Future devices should use Fig. 5. Schematic of experimental setup. The GNC device was probed with a
a smaller amount of aluminum passivation, the Al-oxide layer Lakeshore Cryotronics CPX-VF probe station at ambient temperature, approx-
imately 20 ◦ C (293 K), and vacuum pressure of 8.7 × 10−7 Torr.
hardens during processing and can prove difficult to remove.
Fig. 2 (f) shows a photograph of a completed device.

III. ELECTRICAL CHARACTERIZATION OF GNCS 433.92 MHz the reflection coefficient was −0.185 dB. The
power PL delivered to the detector (an effective load) is related
DC current versus voltage traces were collected to verify to the power PS from the signal generator by
continuity of the GNC as well as locate minimum conductivity
point of the graphene. Device conductance drain-source (inner PL = PS (1 − |Γ|2 ). (2)
disc-outer disc) current versus gate voltage for varying bias
The operating frequency of 433.92 MHz was chosen for being
voltages was collected using a Keithley 4200 Semiconductor
in the middle of an unlicensed ISM band as well as being within
Characterization System. The device conductance
the frequency range before there is detection roll-off for the GNC
IDS device. A frequency sweep from 10 MHz to 10 GHz done with a
G= (1)
VDS constant power at the load of −12.9 dBm and gate voltage of 0 V
displays −3 dB roll-off on detection at 1 GHz, Fig 4. The devices
is plotted in Fig 3 along with its derivative. The data verifies
were then probed with incident microwave power through a bias
the ambipolar curve characteristic of graphene with the charge
tee, consisting of a DC Block (DCB) and RF choke (RFC), and a
neutrality point at 20 V, improved over the 30 V point shown
resulting voltage was measured directly with a digital voltmeter.
in our previous GNC devices. We attribute the improvement to
A schematic of the experimental setup is shown in Fig. 5. The
refinements made in device processing.
gate voltage was stepped from 0 V to 40 V to capture the area
The GNCs have been used to realize microwave power de-
around the charge neutrality point and the power at the load was
tectors operating from 10 MHz to 10 GHz at room temperature
swept from −54 dBm to −4 dBm. The results of the detection
and under vacuum. To determine the fraction of incident that
measurement are shown in Fig. 6.
was not reflected off of the detector, reflection coefficient Γ
Observing the measured voltage as a function of gate voltage,
measurements were collected with an Agilent E5071C vector
Fig. 7, we can see a minimum appear at the Dirac voltage. This
network analyzer. Prior to these collecting these measurements,
minimum represents a change in polarity of the measured volt-
a reference plane was defined at the probe tips by means of a
age. Plotting this data linearly, Fig. 8, shows that it is proportional
short-open-load calibration using a GGB Industries, Inc. CS-8
to the Seebeck coefficient
calibration substrate, Fig. 4. Monolayer graphene on SiO2 is
very sensitive to scattering and shows reflection very close to 1 dG
VM ∝ ∝S (3)
that of an open circuit [19]. At our operating frequency of G dVgate
882 IEEE TRANSACTIONS ON NANOTECHNOLOGY, Volume 18, 2019

Fig. 6. Raw data of measured voltage as a function of both the gate voltage
and the power delivered to the detector. Fig. 9. Measured voltage versus power delivered to the detector with Vgate =
1 V.

where the Seebeck coefficient S is given by the Mott formula,



π 2 kB
2
T 1 dG dVgate 
S=− , (4)
3|e| G dVgate dE E=EF
matching the behavior previously observed from graphene-
based photothermoelectric detectors [3], [20], [21]. The change
in polarity of the measured voltage occurs at the charge neutrality
point. The sensitivity of the detector is extracted by fitting the
linearly scaled VM and PL to
V M = SV PL . (5)
Fig. 7. Raw data of measured voltage versus gate voltage with an applied
power of 10 dBm, top, a cross section of Fig. 6. The minimum shown at The maximum sensitivity was obtained for a gate bias voltage
VGAT E = 20 V represents a change in the polarity of VM .
of approximately Vgate = 1 V and was found to be SV =
60.25 mV/mW, Fig. 9. When not accounting for impedance mis-
match, the uncompensated power detection sensitivity (relative
to PS rather than PL ) is 2.394 mV/mW.
Strong correlation between the gate-voltage dependence of
1 dG
the DC measurement of G dVgate and voltage response to inci-
dent microwave power indicates that the thermoelectric effect
is the dominant physical mechanism responsible for microwave
power detection. Incident microwave power locally heats the
inner disc (the drain node) of the Corbino disc test structure while
the outer annulus (the source node) is held in thermal contact
with probe station chassis. Thus, a temperature gradient develops
across the nano-constriction and charge carriers diffuse towards
the detectors source node, the cooler side of the constriction.
When the gate voltage is biased below the 20 V charge-neutrality
point, the Fermi level is situated below the valence band edge
of the Dirac cone and positively-charged holes are the major-
ity charge carrier in the graphene. With an accumulation of
positive charge on the source-node side of the GNC, a negative
voltage develops across the detector. Conversely, when the gate
Fig. 8. Measured voltage versus gate voltage with an applied power of 10 dBm, voltage is biased above the charge-neutrality point, negatively-
scaled linearly, showing the sign change in measured voltage due to a change
in majority carriers caused by varying the gate voltage. It can be seen that the charged electrons are the majority carrier in the graphene, and a
measured voltage is proportional to the Seebek Coefficient, VM ∝ S. negative voltage develops across the detector.
GASPER et al.: THERMOELECTRIC GRAPHENE NANO-CONSTRICTIONS AS DETECTORS OF MICROWAVE SIGNALS 883

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Michael R. Gasper received the B.S.E.E and M.S.E.E degrees from the Univer-
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sity of Akron, Akron, OH, USA, in 2014 and 2016, respectively. He is a graduate
[3] F. Koppens, T. Mueller, P. Avouris, A. Ferrari, M. Vitiello, and M. Polini,
student in the Department of Electrical and Computer Engineering, University
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hybrid systems,” Nature Nanotechnol., vol. 9, no. 10, p. 780, 2014.
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[5] T. Mueller, F. Xia, and P. Avouris, “Graphene photodetectors for high- Ryan C. Toonen received the M.A. degree in physics (2007), M.S. degree
speed optical communications,” Nature Photon., vol. 4, no. 5, p. 297, in electrical engineering (2005), B.S. degree in electrical engineering (2002),
2010. B.S. degree in applied mathematics, engineering and physics (1999), and Ph.D.
[6] D. Yi, X. Wei, and Y. Xu, “Transparent microwave absorber based on pat- degree in electrical engineering (2007) from the University of Wisconsin at
terned graphene: Design, measurement, and enhancement,” IEEE Trans. Madison. He is an Assistant Professor with the Department of Electrical and
Nanotechnol., vol. 16, no. 3, pp. 484–490, May 2017. Computer Engineering, University of Akron. He was previously a Post-Doctoral
[7] M. Jung, P. Rickhaus, S. Zihlmann, P. Makk, and C. Schnenberger, Research Associate with the National Institute of Standards and Technology
“Microwave photodetection in an ultraclean suspended bilayer graphene (NIST), Boulder, CO, USA, and a Research Engineer with the U.S. Army
pn junction,” Nano Lett., vol. 16, no. 11, pp. 6988–6993, 2016, Art. Research Laboratory (ARL), Aberdeen Proving Ground, MD, USA. While
no. 27704863. [Online]. Available: https://doi.org/10.1021/acs.nanolett. working at NIST, he contributed to an effort that led to the electronic re-
6b03078 definition of the Boltzmann constant. While working at ARL, he received
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F. A. Miranda, “Nanoscale fabrication of microwave detectors from Outstanding Technical Achievement. During his research career, he has gained
commercially-available CVD-grown monolayer graphene,” in Proc. IEEE expertise in the areas of applied physics, electronic devices and materials, and
13th Nanotechnol. Mater. Devices Conf. (NMDC), Oct. 2018, pp. 1–4. experimental microwave science. Prior to this career, he had worked in the
[9] T. Ihn, Semiconductor Nanostructures: Quantum States and Electronic field of mixed-signal application-specific integrated circuits (ASICs) as a design
Transport. Great Clarendon Street, Oxford OX2 6DP: Oxford University engineer. He has been awarded three U.S. patents, and he is a recipient of the
Press, 2010. 2017 and 2018 NASA Glenn Research Center Faculty Fellowship Program
[10] V. Milanovic, M. Gaitan, E. D. Bowen, N. H. Tea, and M. E. Zaghloul, Award. He has authored and co-authored a number of refereed publications
“Thermoelectric power sensor for microwave applications by commercial addressing a diverse range of topics, which include complex oxide physics,
CMOS fabrication,” IEEE Electron Device Lett., vol. 18, no. 9, pp. 450– agile microwave engineering, applied superconductivity, quantum dot transport,
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884 IEEE TRANSACTIONS ON NANOTECHNOLOGY, Volume 18, 2019

Nicholas C. Varaljay received his B.S.E.E.T degree from Cleveland State Félix A. Miranda (M’91–SM’98–F’14) is the Deputy Chief of the Commu-
University and Journeyman certificate in Electronic Systems Mechanic from nications and Intelligent Systems Division, NASA Glenn Research Center,
NASA Glenn (1984). He is currently Lead Micro-Fabrication Engineering Cleveland, OH, USA. Dr. Miranda is a fellow of the Institute of Electrical
Technologist with the Communications Division Clean Room and has supported and Electronics Engineers (IEEE), a member of the American Institute of
the Antenna and Optical systems Branch along with the Electron and Opto- Aeronautics and Astronautics (AIAA), a member of the American Physical
Electronic-Devices Branch since 1984. He has been instrumental in the process Society (APS), and a member of the Forum of Industrial and Applied Physicists
engineering and fabrication of many prototype radio-frequency (RF) circuits (FIAP). He has authored or co-authored more than 200 journal and conference
such as RFMEMS (RF microelectromechanical system) switches, for which publications in his areas of expertise, has written several book chapters, is the
he received a NASA Craftsmanship Award and the Ferroelectric Phased Array co-editor for several conference proceeding volumes on ferroelectric materials
Antenna. He has co-authored several publications in microwave device technol- and devices, and is the co-editor for the book Advanced Nanomaterials for
ogy along with numerous acknowledgments. He is a recipient of the QASAR Aerospace Applications (Pan Stanford Publishing, 2014). His areas of expertise
(Quality and Safety Achievement Recognition) award for the implementation of are antenna technology and microwave components, and circuits and devices
PECVD (plasma enhanced chemical vapor deposition) in the clean room, and a for space- and ground-based communications. He is the co-inventor of 15 U.S.
recipient of 2 IR&D awards (2010, 2015). In addition, he has received several patents. He is a recipient of the 2007 NASA Exceptional Service Medal for
group achievement awards along with letters of commendation. Some current outstanding technical and managerial leadership in antenna and microwave
research supports include thin film graphene technology, phased array antennas, technologies for space communications. He received the 2007 R&D100 award
and high-temperature wireless communication. from the R&D Magazine for the development of an antenna near-field probe
station scanner. He is also a recipient of the 2010 R&D100 Award from the
R&D Magazine for the development of a thin film ferroelectric high-resolution
scanning reflectarray antenna for aerospace communications and received the
Robert R. Romanofsky has been employed by the NASA Glenn Research 2015 R&D100 Award for the development of a polyimide aerogel-based antenna.
Center for approximately 30 years. In addition, he has been an Adjunct Profes-
sor with Cleveland State University since 2000. From October, 2010 through
September, 2011, he was detailed to the National Security Space Office in
Washington, DC and served as an acting Chief of Advanced Concepts. He
was appointed as Senior Technologist with the Communications and Intelligent
Systems Division in 2016. He was also detailed to the NASA headquarters
in 1990 as Program Manager for superconductivity and RF communications
and subsequently served a 3-month collateral assignment in the White House
Office of Science and Technology Policy. He has authored over 120 technical
publications and holds seven patents. His expertise is in the fields of microwave
device technology and antennas, cryogenic electronics and high-temperature
superconductivity, and microwave applications of thin ferroelectric films. He
has authored chapters in Low Temperature Electronics (Academic Press, 2000),
Antenna Engineering Handbook (McGraw-Hill, 2007, 2019), and Ferroelectric
Thin Films at Microwave Frequencies (Research Signpost, 2010). He is a
recipient of the NASA’s Exceptional Service Medal, National Stellar Space
Award, NASA’s Exceptional Technology Achievement Medal, two IR&D 100
Awards, and the Air Force Exemplary Civilian Service Medal. Dr. Romanofsky
was inducted into the Space Technology Hall of Fame in 2013.

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