Measurements of the Electrical Conductivity of Monolayer Graphene Flakes

Using Conductive Atomic Force Microscopy. Nanomaterials 2021,

The electrical conductivity of CVD-grown monolayer graphene flakes was approximately estimated to be 1.46 ±
0.82 × 106 S/m (vander Pauw method in previous studies)

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8537657/
pdf/nanomaterials-11-02575.pdf
Transfer Printing of CVD Graphene FETs on Patterned Substrates

TLM method
W=50 µm ; L=5,10,15,20,25,30 µm

Linear behavior and the intercept at zero channel length = 2R c (36.4 ± 13.6 Ω)

Normalized contact resistance (RcW )= 910 ± 340 Ω m for a Ti/Au contact

Resist-free transfer process provides a clean graphene surface that is promising for use in high sensitivity
graphene FET biosensors.

https://pubs.rsc.org/en/content/articlelanding/2015/nr/c5nr03501e
Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour
deposition

The grain boundaries (which,by definition, are defective) are expected to degrade the electrical
and mechanical properties of the resulting films.

RL ∼ 550 Ω (left grain), RR ∼ 200 Ω (right grain) and RCG ∼ 3 k Ω

(across the grain boundary), respectively.
Transmission line method

RTotal between any two contacts can be

expressed as a linear combination of RC and the
length-dependent RCH of the semiconductor in
between the contacts,

RTotal = RCH (L) + 2RC

1. The Total resistance R (including contact resistance) is a linear relationship with channel lengths (only valid if CVD gown 2D layers have uniform
quality, uniform thickness (No defects existing)).RTotal = RCH (L) + 2RC
2.The sheet resistance must be the same with the aspect ratios, but not the resistance of the channel. 
3.Grain boundaries, number of layers, folding, wrinkles and cramps (such defects, etc.) of layers will increase with channel length. In addition, the
charge carriers can be scattered defect points are liable to degrade the electrical and mechanical properties of the resulting films.
4. It would be preferable to carry out electrical measurements after annealing.
 Method of Growth No. of Electrical parameters (R, ) Ref.
layers
1 Graphena Samples (By CVD) Monolayer GFET Graphene field-effect mobility >1000 cm2/V·s https://cdn.shopify.com/s/files/
Rs= RW/L = ~ 650Ω/sq 1/0191/2296/files/2021_GFET-
W= 90 µm L=90 µm S20_TDS_05-26-2021.pdf?
v=1622043707
CVD-grown graphene Monolayer WxL=6 × 6 mm2 Rs= 1350 ± 140 Ω/sq (as-prepared ) file:///C:/Users/danie/Downloads/
Rs= 1050 ± 110Rs, Ω/sq (after annealing) nl302870x_si_001%20(1).pdf
at 170 °C for one hour in a quartz tube furnace
with a base pressure of < 2 × 10-2 Torr.
CVD-grown graphene Monolayer Rs = ∼980 Ω/sq https://pubs.acs.org/doi/10.1021/
nn201207c
CVD-grown graphene Monolayer GFET μe =78 cm2/V-s, μp =115 cm2/V-s https://pubs.acs.org/doi/10.1021/
acs.jpcc.1c10737

CVD-grown graphene Monolayer W=12 µm ; L=1 µm Rs = 103 Ω/sq file:///D:/Dr.%20Divakar

%20Botcha/Literature%20on
%20Resistance%20of%20graphene
%20and%20device%20aspect
%20ratios/
Characterization_of_CVD_graphene_
permittivity_and_.pdf
CVD-grown graphene Monolayer Not mentioned Rs = 290 ± 24Ω·sq−1 file:///D:/Dr.%20Divakar
%20Botcha/Literature%20on
%20Resistance%20of%20graphene
%20and%20device%20aspect
%20ratios/
Unveiling_the_Direct_Correlation_be
tween_the_CVD-G.pdf
CVD-grown graphene Monolayer TLM method Rc = 18.2 ± 6.8 Ω https://pubs.rsc.org/en/content/
W=50 µm ; articlelanding/2015/nr/c5nr03501e
L=5,10,15,20,25,30 µm Rs = 12.4 kΩ/sq
 Method of Growth No. of layers Electrical parameters (R, ) Ref.

CVD-grown graphene Monolayer W=2-5 µm ; L=200nm-5µm RL ∼ 550 Ω (left grain), RR ∼ file:///D:/Dr.%20Divakar

200 Ω (right grain) and RCG %20Botcha/Literature%20on
∼3kΩ %20Resistance%20of%20graphene
(across the grain boundary), %20and%20device%20aspect
respectively. %20ratios/nmat3010%20(1).pdf
CVD-grown graphene Monolayer WxL=∼1x1 cm2 RS= ∼980 Ω/sq Transfer of CVD-Grown Monolayer
Graphene onto Arbitrary Substrates
file:///D:/Dr.%20Divakar
%20Botcha/Literature%20on
%20Resistance%20of%20graphene
%20and%20device%20aspect
%20ratios/nn201207c.pdf
CVD-grown graphene Monolayer W=2µm ; L=500nm, R= 1.5 kΩ Kim et al., Nanotechnology 23
W=2µm ; L=1µm, R= 2.4 kΩ (2012) 125706 (5pp)
W=2µm ; L= 2µm R= 3.8 kΩ

CVD-grown graphene Monolayer W=200µm ; L=100µm, RS= 1.75 ± 0.04 kΩ/sq https://www.beilstein-journals.org/
bjnano/content/pdf/2190-4286-4-
24.pdf
 Electrical characterization of 2D materials-based field-effect transistors

In this review, conductivity, carrier density, mobility, Schottky barrier height (SBH), contact resistance (RC) and trapped
charges are discussed as key parameters for the electrical characterization of 2D devices

https://doi.org/10.1088/2053-1583/abc187
Output characteristics Transfer characteristics

where L, W, µn, Cox, and VTH are the channel

length, channel width, channel electron mobility, oxide
capacitance, and the threshold voltage, respectively. We
discuss the use of equation to extract the
channel mobility and carrier density
 Conductivity in 2D materials and devices
In an isotropic three-dimensional (3D) material, the
electrical resistivity (ρ) and conductivity (σ) are
defined as , where R, A,
and L are the total resistance, cross-sectional area (=W × t, where W is the width and t is the thickness of the material), and
distance between the measuring points, respectively.

2-point probe measurements

2PP measurement has become a standard method of obtaining
the output and transfer characteristics of a 2D FET.

Figure 3(a) displays the individual components of the total resistances (RTotal) in a ReS2-based 2D FET; the corresponding 2PP
output characteristics at different VGS are illustrated in figure 3(b) [69]. Assuming RCH > RC along with linear ID vs.VDS
characteristics,RCH,RSH, and σ can be determined by using the following relationship:
 Noncovalent Functionalization of Graphene and Graphene Oxide for Energy Materials, Biosensing, Catalytic, and
Biomedical Applications

GO is hydrophilic, that is, easily dispersible in water. In addition, GO contains both aromatic (sp 2) and aliphatic (sp ) domains,
3

which further expands the types of interactions that can occur with the surface. GO is easily reduced to reduced
GO at high yields; however, the quality of the produced graphenes is not suitable for electronic applications or
mechanical reinforcement of polymers due to structural defects created during the synthesis of GO.

Generally, covalent functionalization compromises the sp2

structure of G lattices, thus resulting in defects and loss of the
electronic properties. In contrast, noncovalent functionalization
is largely preferred as it does not alter the structure and electronic
properties of G while it simultaneously introduces new chemical
groups on the surface.
Common examples of noncovalent functionalization include
polymer wrapping, π-π interactions, electron donor-acceptor
complexes, hydrogen bonding, and vander Waals forces (see
examples in Figure 4).
In all instances, noncovalent functionalization leads to enhanced
dispersibility, biocompatibility, reactivity, binding capacity, or
sensing properties.

DOI: 10.1021/acs.chemrev.5b00620
• Noncovalent or supramolecular interactions are found in all types of materials that experience attractive and/or
repulsive forces between them.
• To compare the relative strength of noncovalent interactions, we consider (i) the energy range of covalent bonds
and (ii) the bond distances of single to multiple carbon bonds. The dissociation energies are ∼350 kJ mol-1 for
single, ∼611 kJ mol-1 for double, and ∼835 kJ mol-1 for triple bonds, while the bonding distances range from
1.54, 1.34, and 1.20 Å for ethane, ethene, and ethyne, respectively

It was revealed by Coleman and others that the surface tension of the solvent should be similar to the surface energy of the
material to be exfoliated, that is, a crucial factor for preparing useable quantities of 2D materials.

• The noncovalent functionalization of G and GO is mostly based on van der Waals forces
or π-π interactions with organic molecules or polymers that meet some basic criteria.
• Usually, vander Waals forces are developed between G or GO and organic molecules or
polymers with high hydrophobic character, while π-π interactions are common between
G or GO and molecules with short to highly extended π system.
• The noncovalent interactions are very important for most applications because the
extended π system of graphemic nanostructures is not interrupted, which means that
important properties such as electric conductivity or mechanical strength are not affected.
In addition, the mild and nonpermanent character of noncovalent interactions offers high
flexibility with regards to the treatment of the afforded products.
• The π-π interactions have two prevalent requirements. The first is the existence of π systems, and the second has to do
with the geometry of the interacting species. It is necessary that an overlap exists between the two components to have
a noticeable interaction, and usually this is strongly favored by the planarity of the two components. A pristine G
monolayer has a rich extended aromatic system with almost planar geometry, which prefers to interact strongly with
small aromatic molecules
• the behavior of a G nanostructure is not always similar to all
aromatic molecules. The π-π interactions are influenced by
several factors related to the aromatic molecules, among
them the electron-donating or -withdrawing ability, their
substituents, size, and planarity.
• The second stage was the exfoliation and dispersion in water
of the G/pyrene derivative hybrids. In this stage, the favorite
molecule for exfoliation is that which has the highest dipole
moment and the most asymmetric functionalization
• A simple way to utilize these properties is their incorporation in
polymer composites. A key factor for the ideal incorporation of
graphenic nanostructures into polymer matrixes is the covalent
or noncovalent interactions, which determine the homogeneity
of the composite and the extent of the cooperation between the
two components.
• The existence of π-π interactions between graphenic derivatives
and polymers that contain aromatic rings is an excellent
example in this case. A repeating aromatic polymer unit can
strongly bind graphenic
monolayers leading to highly homogeneous polymer
composites
with enhanced mechanical, electrical, and thermal properties.
• Kevlar is a characteristic polymer with aromatic
rings, which can interact strongly with G by π stacking as
presented in Figure 27.
• Lian et al. have used a Kevlar/graphene nanoribbon (GNR)
composite to reinforce polyvynil chloride (PVC).
Advantages & disadvantages of noncovalent methods

Noncovalent functionalization through electrostatic, π-effects, van der Waals forces, and hydrophobic effects,

etc., is an effective method for changing the physicochemical properties of nanofillers to improve their

interfacial interactions in a material matrix.

 Noncovalent functionalized nanomaterials containing G/GO exist in two forms: (i) nanospecies deposited onto

the G surface and (ii) nanospecies encapsulated with G/GO.

These materials have been applied in various advanced applications in the fields of energy materials, green

chemistry, environmental science, nanodevices, catalysis, photocatalytic, biosensors, bioimaging, and

biomedicine.
 How Do the Electrical Properties of Graphene Change with its Functionalization?

• Pristine graphene sheets are hydrophobic in nature, so they cannot be dissolved in polar solvents. This makes

functionalization of graphene sheets important for their future applications.

• Despite the great application potential, it is worth mentioning that graphene itself possesses zero band gap as

well as inertness to reaction, which weakens the competitive strength of graphene in the field of

semiconductors and sensors. This is one of the reasons for the huge increase in the number of research

projects aimed at functionalization of graphene including reactions of graphene (and its derivatives) with

organic and inorganic molecules, chemical modification of the large graphene surface, and the general

description of various covalent and noncovalent interactions with graphene.

• In most cases, functionalization is the best way to achieve the best performance.
small 2013, 9, No. 3, 341–350
• Covalent functionalization of a carbon atom on graphene converts the planar sp2 lattice
point into a tetrahedral sp3 lattice-point, which breaks the potential continuum via
creation of a quantum well, leading to the introduction of a scattering site in graphene.
• Further, the removal of the π electron from the carbon atom reduces the carrier density
and can introduce a band gap (via removal of electronic states) and/or a transport
barrier.
• The functionalizing molecule can also introduce energy levels (edge states and
functionalization states) in the band structure of covalently functionalized graphene to
make it an n-type or p-type semiconductor.

Noncovalent functionalization of graphene

Covalent functionalization of graphene
Noncovalent functionalization is an attractive synthetic

The covalent chemistry of graphene, which is basically addition of method, because it offers the possibility of attaching

suitable reactive building blocks to the conjugated p-system of the functional groups to graphene without disturbing the

carbon lattice, is still in its infancy. electronic network.

Typical examples are the addition of phenyl radicals, diazonium Noncovalent or supramolecular interactions are found in all

compounds, azomethyne ylids, fluorinated phenyl nitrenes, types of materials that experience attractive and/or repulsive

carbenes, as well as Diels–Alder cycloaddition reactions. forces between them. These interactions are found in many
natural and synthetic systems for recognition or detection.
Various strategies for covalent functionalization of graphene
categorised according to mechanism.
Molecules interfacing (π −π or adsorbed) on graphene do not distort its lattice; however, quantum coupling of the interfaced molecules
enhances the effective electric field on graphene due to the dipole moment of the molecule.
This in turn introduces scattering sites by changing the local potential at the attachment site, or by creation of high-density electron–hole
puddles.
Noncovalent intermolecular interactions involving π-systems are pivotal to the stabilization of proteins, enzyme−drug complexes, DNA−
protein complexes, organic supramolecules, and functional nanomaterials.
These interactions involving π systems are most relevant in the context of nanomaterial design and fabrication of nanodevices, because subtle
changes in the electronic characteristics of the π systems can lead to dramatic effects in the structure and properties of the nanosystem.
This review outlines a detailed and integrated model to explain the factors influencing the electrical properties

of functionalized graphene (covalent bonding, adsorption, π −π interactions, and lattice incorporation).

The model explains that the electrical properties are governed via three mechanisms:

(a) conversion of the sp2-hybridized state to sp3, (b) molecular dipole interactions and the associated

quantum-capacitance-enhanced doping, and (c) hybridization of molecular orbitals with graphene's electronic

bands. Also, graphene trilayers with outer layers functionalized, graphene quantum structures, and multi-

functionalized graphene are identified as upcoming graphenic materials where further

functionalization/electrical studies are required

 Graphene field-effect transistors as bioanalytical sensors: design, operation and performance

 Graphene has received much attention for its exciting mechanical, thermal and optoelectronic properties.29
In particular, graphene was found to exhibit extremely high charge carrier mobility, as well as remarkable
sensitivity to electrostatic changes in its near environment, making it a promising material for sensing
applications
 GFETs are often described as having key advantages for biosensing applications, including easy operation,
fast response, real-time monitoring, high specificity and sensitivity with detection limits down to the
femtomolar and sub-femtomolar range, microfluidic integration and multiplexing capability
 Graphene is a particularly good choice for FET sensors because its atomically-thin geometry makes its
electrical conductance remarkably responsive to environmental effects, such as the capture or accumulation
of biological analytes near the surface.

Analyst, 2021, 146, 403–428 | 403

 In the case of SiO2, its thickness can be as large as the order of a micrometer, or as thin as approximately
∼10–100 nm, this lower bound being to limit the occurrence of pinholes between the backgate and
graphene.
 In biosensing experiments, GFETs are most often directly operated in an electrolyte solution. In such
configuration, the gate voltage is applied using either a reference electrode immersed in the medium (Fig.
1e) or a coplanar electrode patterned on the substrate (Fig. 1f).
 Reference electrodes made of Ag/AgCl represent a common choice since their use in electrolyte buffer is
well calibrated. Others have reported immersed gate electrodes made of silver or platinum wires. Coplanar
gate electrodes are patterned on the substrate in a similar approach as for source and drain electrodes, using
deposition of metals such as platinum, silver or gold. In both cases, the gate electrode is coupled with the
graphene via an electrical double layer formed by the redistribution of ions in the electrolyte medium.
The spatial range of detection

For electrolyte-gated GFETs, it is important to take into account charge screening by mobile ions in the medium.
According to the Debye–Hückel model, charged molecules in solution are screened by mobile counter-ions such that their
electric potential is dampen exponentially with distance, with a decay constant λD called the Debye length. This constant
represents the screening length and is given by

where ε is the permittivity of the medium, kB the Boltzmann constant, T the temperature, NA the Avogadro’s number, e the
electron charge and I the ionic strength of the solution. The ionic strength is given by
where ρi and zi are respectively the density and valence of ion species i.

The Debye length represents the distance at which charges are screened; thus, charges located farther than the Debye length
are usually considered out of range for electrostatic detection by a FET sensor
 Limit of detection and sensitivity

Analytical sensitivity describes the ability of the sensor to distinguish between small differences of analyte
concentration
Limit of detection (LOD): the lowest concentration at which an analyte can be confidently detected by the
sensor.
• Sensitivity is a crucial performance metric for quantitation applications, in particular when
it’s required to identify analyte concentration with great precision.
• Sensitivity can be assessed from the calibration curve of the sensor, i.e. the evolution of a
chosen electrical metric (ex. CNP voltage, current, see section 3) as a function of analyte
concentration, as illustrated in Fig. 5a.
• Sensitivity is generally quantified as the slope S of the linear regime of the curve, given by
Electrical measurements and metrics
Change in CNP voltage:
• The CNP voltage depends on the doping level of the graphene: for intrinsic
graphene at low drain–source bias, it is expected at values close to 0 V, but in
reality, it can be either positive if the graphene is p-doped (indicating a larger
density of holes) or negative if n-doped (larger density of electrons). The doping
level depends on many factors, including the nature of the interface between
graphene and other materials (substrate, electrodes, media) and the distribution
of charged species and impurities in these materials
• The polarity depends on the interaction between analyte molecules
and the functionalized graphene layer.

Change in transconductance:
• A second type of metric in sensing with transfer curves is a change in the
transconductance gm = ∂Ids/∂Vg, which is the slope of the linear part
of the p- or n-branch of the transfer curve
• The transconductance is an important indicator of transistor performance, i.e. its
ability to convert a small change in voltage in a large change in current.
• For a given device geometry (graphene surface and gate electrode), the
transconductance is mainly dependent on the mobility μ of charge carriers.
• The mobility of charge carriers in graphene is usually an indicator of its
structural and electronic quality
Change in current:
• Electrical current being determined by the product of carrier charge, density and
velocity (I = qnv), a change in current indicates either a change in the density of
charge carriers, in scattering processes, or a combination of both.

Output curves
• The typical output curve of a GFET is represented in Fig. 3a: as the applied bias increases from zero, the amplitude of

the current increases with the same polarity as the applied bias.

• The curvature of the output curve is generally considered a good indicator of the quality of the contacts between

graphene and source/drain electrodes, and of charge transport along the graphene. With good graphene and electrical

contacts, a linear ohmic regime is usually expected at low bias.

• In practice though, a positive curvature or superlinear regime is sometimes observed due to potential barriers created by

non-ideal contacts or defect sites.

• The output conductance gds is defined as the slope of the output curve. Its amplitude is evidently a function of the gate

voltage, which modifies the carrier density.