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Cite This: ACS Appl. Mater. Interfaces 2018, 10, 41738−41746 www.acsami.org

Influence of Humidity on Contact Resistance in Graphene Devices

Arne Quellmalz,†,○ Anderson D. Smith,‡,§,○ Karim Elgammal,∥,⊥ Xuge Fan,† Anna Delin,∥,⊥,#
Mikael Ö stling,‡ Max Lemme,¶,∇ Kristinn B. Gylfason,*,† and Frank Niklaus*,†
†
Department of Micro and Nanosystems, School of Electrical Engineering and Computer Science, and ⊥Swedish e-Science Research
Center (SeRC), KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden
‡
Department of Electronics, School of Electrical Engineering and Computer Science, and ∥Department of Applied Physics, School of
Science and Engineering, KTH Royal Institute of Technology, Electrum 229, SE-16440 Kista, Sweden
§
Department of Microtechnology and Nanoscience, Chalmers University of Technology, Gothenburg 41296, Sweden
#
Department of Physics and Astronomy, Materials Theory Division, Uppsala University, Box 516, SE-75120 Uppsala, Sweden
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¶
Chair of Electronic Devices, RWTH Aachen University, Otto-Blumenthal-Str. 2, 52074 Aachen, Germany
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∇
Advanced Microelectronic Center Aachen (AMICA), AMO GmbH, Otto-Blumenthal-Str. 25, 52074 Aachen, Germany
*
S Supporting Information

ABSTRACT: The electrical contact resistance at metal−graphene interfaces can significantly degrade the properties of
graphene devices and is currently hindering the full exploitation of graphene’s potential. Therefore, the influence of
environmental factors, such as humidity, on the metal−graphene contact resistance is of interest for all graphene devices that
operate without hermetic packaging. We experimentally studied the influence of humidity on bottom-contacted chemical-vapor-
deposited (CVD) graphene−gold contacts, by extracting the contact resistance from transmission line model (TLM) test
structures. Our results indicate that the contact resistance is not significantly affected by changes in relative humidity (RH). This
%
(
behavior is in contrast to the measured humidity sensitivity 0.059 ± 0.011 % RH ) of graphene’s sheet resistance. In addition,
we employ density functional theory (DFT) simulations to support our experimental observations. Our DFT simulation results
demonstrate that the electronic structure of the graphene sheet on top of silica is much more sensitive to adsorbed water
molecules than the charge density at the interface between gold and graphene. Thus, we predict no degradation of device
performance by alterations in contact resistance when such contacts are exposed to humidity. This knowledge underlines that
bottom-contacting of graphene is a viable approach for a variety of graphene devices and the back end of the line integration on
top of conventional integrated circuits.
KEYWORDS: graphene, contact resistance, sheet resistance, humidity sensitivity, bottom-contact, integration

■ INTRODUCTION
Since its discovery,1 graphene has attracted much attention
sensitivity.4−7 Gas and humidity sensing based on graphene
have been studied intensively, whereby graphene has
because of its fascinating electronic properties. π-Bonds of demonstrated fast response and recovery times.8−13 The
neighboring carbon atoms provide delocalized electrons, which humidity sensitivity of graphene is caused by direct adsorption
account for its high conductivity and charge carrier mobility.2 of water molecules onto its surface and can therefore be
These properties lead to a wide range of potential applications
in electronics.3 Graphene’s electronic properties are eminently Received: June 15, 2018
sensitive to changes in its environment. Consequently, Accepted: November 2, 2018
graphene has been employed in sensors with outstanding Published: November 2, 2018

© 2018 American Chemical Society 41738 DOI: 10.1021/acsami.8b10033

ACS Appl. Mater. Interfaces 2018, 10, 41738−41746
ACS Applied Materials & Interfaces Research Article

Figure 1. (a−c) Schematic process flow of TLM device fabrication: (a) Thermal oxide (300 nm thick) was grown on a silicon substrate. (b) Metal
electrodes were deposited by evaporation and structured using a lift-off process. (c) Graphene was transferred to the substrate and etched into a
rectangular patch using O2 plasma. Bottom right: Colorized scanning electron microscopy (SEM) picture of a TLM device with gold contacts
(yellow) and a 60 μm wide graphene area (blue). (d) Manual probe station for device characterization. The inset shows a device contacted by
probe needles and the reference humidity sensor at the bottom-right. (e) Schematic illustration of water molecules adsorbing on the graphene
surface. (f) Measured resistance change of a graphene device (60 μm by 24 μm) as the relative humidity (RH) is decreased.

inhibited by a covering passivation layer. This enables influence of humidity on the metal−graphene contact
simultaneous integration of graphene-based humidity sensors resistance is of interest for all graphene devices that operate
with other graphene components.14 Similar effects and without hermetic packaging in a potentially humid environ-
preventative strategies were identified for other atomically ment because their performance might be subject to variations.
thin materials such as molybdenum disulfide (MoS2).15 Examples of such applications include electronic and spintronic
Electrical contacts to graphene are formed either by metal devices, photodetectors and modulators in optical systems,
deposition on top of graphene (top-contacting) or by nanoelectromechanical sensors, flexible and transparent
transferring graphene on top of existing metallization electronics, as well as graphene-based components for energy
(bottom-contacting). Top-contacting is the predominant storage.5,13,17,28−30 In general, experimental work on graphene
approach for experimental graphene devices. However, devices in laboratory environments is likely to be influenced by
bottom-contacting has potential advantages because it reduces variations in humidity because prototype devices are typically
the number of process steps after the graphene transfer, which neither packaged nor hermetically sealed.
reduces the risk of defect formation and potential sources of In this work, we study the influence of humidity on contact
residues on top of the graphene sheet. For the same reason, resistance in bottom-contacted chemical-vapor-deposited
bottom-contacts are advantageous for the realization of devices (CVD) graphene devices, by experimentally extracting the
with suspended graphene and enable the integration of contact resistance from transmission line model (TLM) test
graphene at the back end of the line of conventional structures at various humidity levels. To this end, we compare
semiconductor process flows on top of integrated circuits the sensitivity of graphene’s sheet resistance and contact
with metal interconnects.5,16,17 One limiting factor in resistance to variations in humidity. In addition, we employ
developing high-performance graphene devices is the contact density functional theory (DFT) simulations to investigate the
resistance at the metal−graphene interfacea high contact effect of adsorbate water molecules on the electronic structure
resistance can significantly degrade device properties.18−20 at the gold−graphene interface.
Therefore, a number of studies have investigated how to
characterize and reduce the resistance of metal−graphene
contacts.21−26 Cadore et al. found that the naturally created
■ RESULTS AND DISCUSSION
A TLM device consists of a graphene patch placed on an
heterojunction at metal−graphene contacts is modulated in an electrically insulating substrate with multiple metal electrodes
asymmetric and reversible manner by hydrogen molecules at of various spacings (Figure 1c). The measured resistances
the metal−graphene interface.27 However, to our knowledge, between neighboring electrode pairs are used for a TLM
no experimental investigation of the influence of humidity on evaluation which determines the contact resistance between
contact resistance has been reported. For top-contacts, the the graphene sheet and the metal electrodes. Furthermore, the
covering metallization impedes direct adsorption of water TLM evaluation yields the sheet resistance of the graphene
molecules onto the graphene surface, although it is plausible patch.
that molecules diffuse between the layers to the metal− Schematics of the device fabrication and a colorized SEM
graphene interface.11,27 In contrast, bottom-contacted gra- picture are shown in Figure 1a−c, while additional details are
phene is exposed to the ambient gas atmosphere and water provided in the Methods section. A layer of 300 nm SiO2
molecules certainly adsorb on its surface. The potential (silica) was formed by thermal oxidation of a p-type doped
41739 DOI: 10.1021/acsami.8b10033
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ACS Applied Materials & Interfaces Research Article

Figure 2. (a) Change of the device resistance during a measurement cycle. Starting from environmental conditions, dehumidified air was pumped
into the chamber for about 100 s. After closing the inlet, ambient humid air diffused into the chamber. The four datasets show the response of
graphene patches of different lengths. (b) Schematic illustration of a TLM device. Colorized regions represent graphene areas of varying length
contacted by neighboring electrodes. (c) Change in the device resistance as a function of the RH [same datasets as in (a)]. Note the linear
dependence. (d) Absolute sensitivity (Sabs) of the measured graphene device at corresponding TLM spacings. (e) TLM plots for evaluation of the
contact resistance Rc and the sheet resistance Rs of a single device at various humidity levels. The interception of the linear fit (black line) with the
Y-axis yields the contact resistance 2Rc of the two gold−graphene contacts used for probing. The slope of the linear fit and the width of the
graphene sheet determine the sheet resistance Rs. Note that the data points and linear fits are nearly indistinguishable. 20% RH: Rc = 28.2 Ω
(contact area: 4 × 60 μm2), Rs = 559.9 Ω/square, coefficient of determination R2 = 0.994.

silicon wafer. After a standard photolithographic process, layers increasing resistance with decreasing humidity.13,31,32 The
of 20 nm Ti and 80 nm gold were deposited by electron beam variation in resistance originates from changes of graphene’s
evaporation. The metal electrodes and probe pads on the electronic structure by the adsorbed water molecules on the
substrate were structured through lift-off of the underlying graphene surface. Both a shift of the Dirac point and a bending
photoresist layer. CVD graphene was transferred from copper of the energy bands around the Dirac point are plausible
foil using a wet transfer technique.5 Finally, the graphene sheet reasons for this change of the electronic structure. However,
was patterned into a rectangular patch by a second lithography the individual contribution of these effects is an interesting
and an etching step in O2 plasma. It connects the underlying research question, which is outside the scope of this work.
metal electrodes, which are oriented perpendicularly at the The acquired data in Figure 2a depict the change in
point of contact. Beyond the graphene patch, the electrodes resistance of a TLM device under variation of the humidity.
expand and form contact pads for electrical probing of the Here, each dataset corresponds to one graphene sheet length,
device. with labeling and coloration matching the schematic
Upon completion of the fabrication, the device was placed illustration in Figure 2b. Starting from environmental
inside the shielded chamber of a manual probe station for conditions, the inlet of dehumidified air was opened for a
electrical characterization (Figure 1d). A detailed description period of about 100 s, which gradually reduced the RH inside
of the setup and the procedure is given in the Methods section. the chamber to its minimum value of around 7% RH.
During characterization, dehumidified air was introduced into Consequently, the recorded resistance of the graphene device
the chamber, which allowed the gradual reduction of humidity increased. After closing the valve, ambient humid air diffused
from 20% RH down to approximately 7% RH. Probe needles into the setup and successively increased the humidity, thereby
placed on the contact pads connected the device to a causing the device resistance to decrease. Figure 2c plots the
parameter analyzer, allowing real-time measurements of the same data as in Figure 2a against the recorded RH. The change
device resistance between two electrodes. The device in resistance shows a linear dependency on the RH.
resistance is composed of the gold−graphene contact The absolute sensitivity Sabs of the TLM structure to
resistance in series with the resistance of the intermediate variation in humidity is shown in Figure 2d. Here, Sabs is
graphene sheet. defined as the ratio of the change in resistance ΔR and the
Figure 1e illustrates schematically the adsorption of water change in relative humidity ΔRH (eq 1).
molecules on the graphene surface in a humid environment. ΔR
The influence on the resistance of a graphene device with 60 Sabs =
ΔRH (1)
μm width and 24 μm spacing between the electrodes was
measured as dry air was introduced into the chamber. This The absolute sensitivity of the graphene devices increases
procedure gradually decreased the RH from 20% RH to about with the spacing of the electrodes, that is, with the length of
7% RH, whereby the device resistance increased by about 2.5 the intermediate graphene sheet (Figure 2d). This behavior is
Ω (Figure 1f). This behavior is consistent with the previously significant as it suggests that the sensitivity of graphene patches
described resistive graphene humidity sensing, which reports to humidity may be varied by geometrical design parameters.
41740 DOI: 10.1021/acsami.8b10033
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ACS Applied Materials & Interfaces Research Article

Figure 3. (a) Extraction of gold−graphene contact resistance on four TLM devices. Solid lines represent a linear fit of the square data points. (b)
Relative change in gold−graphene contact resistance Rc and sheet resistance Rs with relative humidity. Solid bold lines (orange) are the average of
the respective data sets. The shaded areas represent one standard deviation (1σ). (c) Comparison of the averaged sensitivity (S) of sheet and
contact resistance (1σ error bars).

The obtained resistance values at various humidity levels in on top of the metallization rather than below, as in those cases.
the measurement chamber are plotted against the respective Also, Zhang et al. hint at the long-term degradation of contact
electrode spacing of the TLM device (Figure 2e). The solid resistance after exposure to air which can be reversed by
lines represent a linear fit to the resistance versus distance data. hydrogen annealing in case of nickel graphene contacts.34 The
Note that the data points and the linear fits are nearly steep slope, that is, the abnormal sheet resistance, of device 4
indistinguishable for the selected scaling. The extrapolated indicates possible defects or contamination of the graphene
residual resistance at zero contact spacing provides the contact sheet. Therefore, this device was not considered in the
resistance 2Rc of the two gold−graphene contacts connecting averaging. The relative change in contact resistance Rc and
the intermediate graphene sheet. The sheet resistance Rs of the sheet resistance Rs with change in RH is compared for three
graphene patch is calculated by multiplication of the slope of devices (Figure 3b). Solid bold lines (orange) are the average
the linear fit with the width of the graphene patch. For this of the respective data sets. The shaded areas represent one
measurement, the contact resistance at ambient humidity level standard deviation (1σ).
(20% RH) amounts to 56.4 Ω, that is, 28.2 Ω per gold− To quantify the influence of the relative humidity on Rc and
graphene contact (contact area: 4 × 60 μm2), while the sheet Rs, the averaged sensitivity S is calculated for both resistances
resistance is 559.9 Ω/square (coefficient of determination R2 = (Figure 3c). The sensitivity is derived by using eq 2 and
0.994). defined as the ratio of percent change in resistance and the
Figure 3 summarizes the resistance measurements. Only change in relative humidity in percent.
TLM devices with defect-free contacts were included in the
evaluation. Assuming similar contact resistance and a constant ΔR /R
S= × 100
sheet resistance within each TLM device, a linear relationship ΔRH (2)
between contact spacing and measured resistance is expected.
In this work, the mean sensitivity of the sheet resistance
Therefore, devices with a linear correlation coefficient R2 %
below 0.996 were neglected. The evaluation of three TLM amounts to 0.059 ± 0.011 % RH . In a previous study on similar
devices at initial conditions yields an average contact resistance %
devices, we obtained 0.31 % RH .13 Chen et al. also studied the
of Rc = 32 ± 18 Ω (1920 ± 1080 Ω μm) and an average sheet
resistance of 556.2 ± 7.6 Ω/square (Figure 3a). Our values of humidity sensitivity of the sheet resistance but defined the
the sheet resistance are in line with previous literature studying response to changes in RH as the relative change in device
current at constant bias voltage and obtained values up to
graphene on SiO2.26,33 Our measured contact resistances are
18.1% when increasing the RH from 44 to 98%.35 To directly
1.6 to 2.4 times higher than previously reported values by Passi
compare these results with our measurements, we calculated
et al. and Russo et al. for devices without additional treatment
the sensitivity according to eq 2, which yields
to reduce their contact resistance (1518 and 800 Ω μm, %
respectively).23,25 This discrepancy might be due to a 0.259 ± 0.053 % RH . We believe that our selection of devices
difference in contact design because we place the graphene with strictly ohmic behavior is the reason for the lower
41741 DOI: 10.1021/acsami.8b10033
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ACS Applied Materials & Interfaces Research Article

Figure 4. Plane-averaged charge density differences (PACDDs) computed with DFT (see Supporting Information). Left column: Data for the
gold/graphene/H2O system. Right column: Data for the quartz/graphene/H2O system. Top row: Illustrations of the geometrical configurations of
the analyzed systems. Middle row: Δρg‑s(z) (blue) and Δρm‑g‑s(z) (red). The open black circle shows the position of the central node. Data from
ref 41 are shown in green. Bottom row: The difference between Δρm‑g‑s(z) and Δρg−s(z) per adsorbed water molecule. The shaded areas indicate
the part of the systems, which is relevant for the contact resistance (interface region) and sheet resistance (graphene region), respectively.

humidity sensitivity we observed here. The graphene in these In the second row of the left column of Figure 4, we show
devices is likely to have the least material imperfections, such the plane-averaged charge density difference (PACDD) (see
as grain boundaries, wrinkles, and cracks. CVD graphene, as Supporting Information) associated with the formation of the
employed here, has intrinsic grain boundaries between gold−graphene interface of system I (Δρg‑s(z), red line).
adjacent regions of single-crystalline graphene.36,37 Also, strain Additionally, we compare it to the PACDD describing the
of the graphene layer resulting from the transfer process might charge displacement in the gold/graphene/H2O molecule
contribute to the formation of wrinkles and cracks.38 Both system referring to the situation when all three parts are
effects are likely to influence graphene’s sensitivity to isolated from each other (Δρm‑g‑s(z), blue line). The right
humidity.39 column shows the corresponding data for system II. Our
Another possible explanation for variation in humidity results suggest that the addition of a water molecule has a
sensitivity is polymer residues on the graphene originating negligible effect on the charge displacement in the interface
from the transfer and lithography processes. They affect the region between the graphene and the gold substrate, that is, the
number of surface sites available for molecule adsorption, and part of the system relevant for the contact resistancethe blue
hence varying amounts of residuals might result. Thermal and red curves are overlying. This implies that the potential
annealing has been employed to remove polymer residues from barrier which the electrons must overcome on their way
graphene;40 however, our devices were not annealed. between the graphene and the gold contacts is unaltered by the
In this work, the sensitivity of the contact resistance averages water molecule. Therefore, it is reasonable to expect that the
% contact resistance also remains unaltered, at least for the rather
to 0.000 ± 0.012 % RH implying that Rc is not significantly
low surface concentration of water molecules assumed in our
affected by changes in humidity. This behavior is in clear computation. On the other hand, earlier work by us and
contrast to the humidity sensitivity of graphene’s sheet others13,31,42,43 clearly demonstrates that water adsorption on
resistance obtained in the very same measurement. graphene on top of silica significantly changes the electronic
The electronic structure of graphene sheets is sensitive to structure of the graphene sheet, that is, the part of the system
both the choice of substrate material and the presence of relevant for the sheet resistance. Therefore, it is expected that
adsorbates.13,31,42,43 For a qualitative comparison of graphene’s water adsorption also impacts the sheet resistance significantly,
electronic structure in the contact regions and in the which agrees with the experimental data shown in Figure 3b.
intermediate regions of the TLM devices, density functional For the gold/graphene system, we also included PACDD
theory (DFT) calculations were performed on two systems: data computed with DFT by Khomyakov et al. (Figure 4,
system I, with gold as substrate (representing the contact second row, left column).41 To be able to directly compare the
regions), and system II, with α-quartz as substrate (represent- data in ref 41 with our data, we recalculated the charge q per
ing the silica in intermediate regions). The top row of Figure 4 graphene carbon atom responsible for the dipole associated
illustrates the configuration of the two systems. with the bonding between the graphene and the substrate
41742 DOI: 10.1021/acsami.8b10033
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Figure 5. Two-dimensional contour plots of the CDD in a plane cutting through the water molecule (computed with DFT, see Supporting
Information). Top row: Gold/graphene/H2O system. Bottom row: quartz/graphene/H2O system. Red and blue regions represent charge
accumulation and depletion, respectively. The isovalue is set to 0.00001 e Å−3. The CDD plots were generated by using XCrySDen visualization
program.45 The shaded areas indicate the part of the systems, which is relevant for the contact resistance (interface region) and sheet resistance
(graphene region), respectively.

(data for gold/graphene in Figure 5 in ref 41) by numerically two-dimensional contour plots of the charge density difference
integrating the plotted data (see Supporting Information). We (CDD) (see Supporting Information) of the two systems,
then rescaled their data to obtain the value q = 0.008 e per cutting through the plane of the water molecule (Figure 5).
carbon atom which is stated in the same paper, thus making The regions of charge accumulation (red) and depletion (blue)
the data in Figure 5 in ref 41 internally consistent. Integrating are clearly different, and hence we qualitatively expect a
our own data in the same way (i.e., from the central node z0 to different effect of adsorbed water molecules on the contact and
plus or minus infinity, see Supporting Information), we find q sheet resistance, respectively.
= 0.0084 e per carbon atom, in excellent agreement with the To further clarify the effect of adsorbed water molecules on
result in ref 41. As evident from Figure 4 (second row, left the graphene surface, we plot the difference between
column), our curve and the rescaled curve from ref 41 are, Δρm‑g‑s(z) and Δρg‑s(z) for both systems (third row of Figure
overall, very similar. Some differences can be seen in the region 4). Note that in this row, the normalization is done per water
−5 to −2 Å below the graphene sheet. Because the setups of molecule instead of per carbon atom. These plots reveal that
the two calculations differ in several respects (e.g., different the net effect of the adsorbed water molecule on the charge
exchange−correlation functional and size of the supercell), displacement is very similar for both gold and quartz substrates
some discrepancies are expected. and that there is in fact a small but clearly visible change of the
It is instructive to compare the gold/graphene system with charge displacement in the interface region (−3 Å ≤ z ≤ 0). At
the quartz/graphene system. According to our calculations, the very high concentrations of water molecules on the graphene
electron transfer from the substrate/graphene system to the surface, it is therefore conceivable that a measurable effect on
adsorbed water molecule is similar for both systems (0.05 and the contact resistance emerges. We note, however, that the
0.04 e per H2O molecule for the gold/graphene and quartz/ relevant comparison is not the effect of water adsorption on
graphene system, respectively). The main difference between the two interface regions of system I and II, but rather the
the two systems is the extent of the charge displacement effect on the contact resistance in system I in relation to the
associated with the formation of the substrate-graphene effect on the sheet resistance in system II, and that these two
interface. A comparison of the two graphs in the middle row resistances emerge from the two different regions of the
in Figure 4 reveals that the charge displacement in the quartz/ systems, as already mentioned. In summary, our simulations
graphene systems is several times smaller than in the gold/ demonstrate that, overall, the electronic structure of the
graphene system. For neither system, the adsorbed water graphene sheet on top of quartz is much more sensitive to
adsorbed water molecules, compared to the charge density in
molecule causes any visible change of the charge displacement
the interface region between gold and graphene. This in turn
in the interface region between the substrate and the graphene,
suggests that the sheet resistance is expected to change much
that is, in the part of the system that affects the contact
more than the contact resistance for varying concentration of
resistance. However, as we have already shown in refs13,31,42,44
water molecules on the graphene surface. This conclusion
the electronic structure of the part of the system relevant for
agrees with the experimentally measured data in Figure 3b,
the sheet resistance, that is, the region in immediate vicinity of where the sheet resistance changes significantly with RH,
the graphene sheet, is clearly affected by adsorbed molecules. whereas the contact resistance remains virtually unaffected.

■
Because quartz is an electrical insulator, the electrons are
forced to flow in the graphene sheet only. Therefore, the
transport of electrons, or in other words the sheet resistance, is CONCLUSIONS
indeed affected by the addition of water molecules on top of We experimentally show that the gold−graphene contact
the graphene. The different effect on the electronic structure in resistance of bottom-contacts is not significantly affected by
the graphene region and in the interface region is visible in the changes in humidity. This invariance of the contact resistance
41743 DOI: 10.1021/acsami.8b10033
ACS Appl. Mater. Interfaces 2018, 10, 41738−41746
ACS Applied Materials & Interfaces Research Article

to adsorbed molecules on the graphene surface is in water molecule is relaxed on top of the substrate/graphene system in
accordance with the observation of invariable contact the two-leg down configuration, which has been demonstrated to be
resistance irrespective of the number of graphene layers and the most stable configuration for water on top of graphene.52 The
unaffected properties of graphene below the contact metal of output from the converged DFT simulations was used to compute the
charge displacement upon formation of the substrate/graphene
top-contacted devices by electrostatics.18,46 Also, this behavior system and also the effect of adding a water molecule on top of the
is in clear contrast to the humidity sensitivity of graphene’s graphene (see Supporting Information for details).

■
%
sheet resistance (in this work: 0.059 ± 0.011 % RH ) which has
been reported in a multitude of publications.13,32,47 Our ASSOCIATED CONTENT
experimental results agree well with simulations based on DFT. *
S Supporting Information
Because of the similarity of electronic properties between The Supporting Information is available free of charge on the
different metallic substrates, we expect our results to be ACS Publications website at DOI: 10.1021/acsami.8b10033.
indicative for metal−graphene bottom-contacts in general. Supplementary methods for the fabrication of TLM
This includes materials such as aluminum, titanium, and nickel devices and DFT simulations (PDF)

■
which are utilized in metal interconnect layers of conventional
complementary metal−oxide−semiconductor (CMOS) inte-
grated circuits. However, it should be noted that many of these AUTHOR INFORMATION
metals form insulating oxides at their surfaces, which degrade Corresponding Authors
the contact resistance and hence makes the usage of these *E-mail: frank.niklaus@eecs.kth.se.
metals more challenging.34 It is feasible to deposit inert gold as *E-mail: gylfason@kth.se
metallization on the top metal interconnect layer of CMOS ORCID
circuits.48,49 This approach emphasizes the suitability of Arne Quellmalz: 0000-0003-3936-818X
integrating bottom-contacted graphene at the back end of
Karim Elgammal: 0000-0002-8222-3157
the line. With regards to graphene-based devices, we thus
predict no degradation of performance by alterations in contact Anna Delin: 0000-0001-7788-6127
resistance when exposed to humidity. Taken together, our Max Lemme: 0000-0003-4552-2411
findings reinforce that bottom-contacts are suitable for reliable Frank Niklaus: 0000-0002-0525-8647
integration of graphene. However, our quantification of the Author Contributions
○
humidity sensitivity of graphene’s sheet resistance indicates the A.Q. and A.D.S. contributed equally to this work.
importance of a controlled environment in experimental work Notes
on graphene devices in general and the necessity of reporting The authors declare no competing financial interest.

■
minute details of the measurement conditions.

■ METHODS
Fabrication of TLM Devices. First, a 300 nm thick layer of SiO2
ACKNOWLEDGMENTS
This work was partially supported by the European Research
Council through the Starting Grant M&M’s (no. 277879) and
(silica) was formed by thermal oxidation of a p-type doped silicon InteGraDe (307311), by VINNOVA through grants 2016-
wafer with 100 mm diameter and 525 μm thickness (Figure 1a). An 01655 and 2017-05108, by VR through the GEMS grant
adhesion layer of 20 nm Ti and a contact layer of 80 nm gold were (2015-05112), and by the China Scholarship Council (CSC)
deposited by electron beam evaporation. Metal electrodes and probe through a scholarship grant. A.D. acknowledges financial
pads were formed using a lift-off process (Figure 1b). CVD
graphene50 (Graphenea Inc., Spain) was transferred from copper
support from Vetenskapsrådet (grant numbers VR 2015-04608
foil using a wet transfer technique.5 Next, the covering graphene sheet and VR 2016-05980) and Swedish Energy Agency (grant
was patterned into a rectangular patch by a photolithographic process number STEM P40147-1). The computations were performed
and etching in O2 plasma. Finally, the resist mask was removed in on resources provided by the Swedish National Infrastructure
acetone/isopropanol and the samples were dried in air (Figure 1c) for Computing (SNIC) at the National Supercomputer Center
(see Supporting Information for details). (NSC), Linköping University, the PDC Centre for High
Characterization and Setup. The TLM device was placed inside Performance Computing (PDC-HPC), KTH, and the High
the shielded chamber of a manual probe station (Cascade Microtech Performance Computing Center North (HPC2N), Umeå
Inc.) for electrical characterization (Figure 1d). During character- University.

■
ization, a valve-controlled inlet introduced dehumidified air into the
chamber for about 100 s, gradually reducing the RH from
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41746 DOI: 10.1021/acsami.8b10033

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