npj | 2D materials and applications Article

Published in partnership with FCT NOVA with the support of E-MRS

https://doi.org/10.1038/s41699-025-00525-9

Layer-by-layer assembly yields thin

graphene films with near theoretical
conductivity
Check for updates
1,3 1,2,3 1 1 1
Oran Cassidy , Kevin Synnatschke , Jose M. Munuera , Cian Gabbett , Tian Carey ,
Luke Doolan 1, Eoin Caffrey 1 & Jonathan N. Coleman 1

Thin films fabricated from solution-processed graphene nanosheets are of considerable technological
interest for a wide variety of applications, such as transparent conductors, supercapacitors, and
1234567890():,;
1234567890():,;

memristors. However, very thin printed films tend to have low conductivity compared to thicker ones.
In this work, we demonstrate a simple layer-by-layer deposition method which yields thin films of
highly-aligned, electrochemically-exfoliated graphene which have low roughness and nanometer-
scale thickness control. By optimising the deposition parameters, we demonstrate films with high
conductivity (1.3 × 105 S/m) at very low thickness (11 nm). Finally, we connect our high conductivities
to low inter-nanosheet junction resistances (RJ), which we estimate at RJ ~ 1kΩ.

Owing to the unique physiochemical properties of graphene1, thin films processing can yield film conductivities beyond 105 S/m21,30, many processed
fabricated from solution-processed graphene nanosheets offer a wide array films exhibit conductivities no higher than 2.5 × 104 S/m29,31–35.
of promising device applications, such as transparent conducting films However, high-temperature processing is undesirable for flexible
(TCFs)2, supercapacitors3, memristors4, flexible electrodes5, gas sensors6, device applications, as it is incompatible with polymer substrates that have
strain gauges7,8 and antennas9. The film conductivity is a key performance low melting temperatures36,37. For example, PET38 starts to soften at
metric for many such devices, but has previously been found to display 125–130 °C and is usually not annealed above 120 °C. In addition, aggressive
values usually no larger than ~105 S/m, with such high values usually found chemical processing is best avoided if possible for a range of reasons
only for thick (>0.5 μm) graphene films5,8,10–16. Thinner films tend to have including safety, cost and environmental factors39–41. Hence, such strategies
lower conductivity due to the effects of non-uniformity, disorder and per- are unsuitable for mass-manufacture of versatile and inexpensive devices.
colation effects7,17–21. Emerging from the discussion above, there is a clear need for a means of
However, many printed applications require film conductivity to be fabricating solution-processed graphene thin films that exhibit high con-
maximized for minimal film thicknesses22 to avoid the need to deposit very ductivity ( > 105 S/m) without the requirement for aggressive processing
thick films to achieve a given sheet resistance. While higher conductivities at techniques. To maximize the conductivity of any network, it is essential to
the bulk limit for graphite (106 S/m) may also be achieved in thin films minimize the junction resistance27,28. In addition, at low film thickness,
fabricated by CVD techniques23,24, such techniques lack the ease of scal- conductivity maximisation requires the suppression of percolation effects17
ability of solution processing-based fabrication25. and the minimisation of disorder, specifically the misalignment of
In solution-processed graphene films, the typically observed con- nanosheets often found in printed nanosheet films42. In fact, these objectives
ductivity (<105 S/m) is generally somewhat lower than the reported in-plane are linked as achieving a network of highly aligned nanosheets will also lead
conductivity of graphite (~105–106 S/m)26. This is due to such films being to large area junctions and so low junction resistance.
formed from a network of graphene nanosheets, where conduction is Thus, one strategy to simultaneously minimize the junction
typically limited by the inter-nanosheet junction resistance (RJ)27,28. This resistance and disorder would involve optimization of the network
effect is even more pronounced for thin films (i.e., those with thickness morphology, i.e., developing methods to fabricate networks con-
< 50 nm), as no conductivity larger than 1.6 × 104 S/m has been observed in taining highly-aligned nanosheets which overlap their neighbours
such films without the use of complex post-processing strategies21. Such with large-area conformal junctions. The two general requirements
strategies include graphitization of the film through annealing at tempera- for this to occur are, firstly, a deposition method that directs the
tures in excess of 1000 °C29–32, or reduction of graphene oxide using strong nanosheets’ basal planes to a horizontal orientation, and secondly, the
reducing agents such as hydrazine or nitric acid21,31–35. Although post- nanosheets must possess sufficient mechanical flexibility to allow for

1
School of Physics, CRANN & AMBER Research Centres, Trinity College Dublin, Dublin, Ireland. 2Center for Advancing Electronics Dresden & Faculty of Chemistry
and Food Chemistry, TU Dresden, Dresden, 01062, Germany. 3These authors contributed equally: Oran Cassidy, Kevin Synnatschke. e-mail: [email protected]

npj 2D Materials and Applications | (2025)9:2 1

https://doi.org/10.1038/s41699-025-00525-9 Article

the formation of conformal junctions27 rather than forming jammed nanosheet networks15. Moreover, a TCF was demonstrated at a film thick-
systems with point-like junctions42. ness of 6.1 nm, showing a transparency of 82% and sheet resistance of
Such horizontally oriented films can best be achieved using Langmuir- 4.2 kΩ/□, competitive with literature values for printed graphene
type depositions, which spread nanosheets flat on top of a high surface TCFs21,29,32.
tension liquid interface43. Repeated deposition can build up films with
excellent alignment and controlled thickness44. For nanosheets to be Results and discussion
mechanically flexible enough to readily conform to each other, it has been Ink characterisation
shown that the energy cost of creating the bends required to conform to their Graphene nanosheets were prepared via electrochemical exfoliation48 as
neighbours must be balanced by the van der Waals energy of interaction described in the methods section. This process results in an ink containing
between neighbours27. For this to occur nanosheets must have lateral size to graphene nanosheets in isopropyl alcohol (IPA) at a concentration of
thickness aspect ratios above some critical value, which depends on the approximately 1 g/L. We first characterised this ink and the nanosheets
mechanical properties of the material27. Preparation of such high aspect therein using optical absorption spectroscopy and atomic force microscopy
ratio nanosheets cannot be achieved by well-known techniques such as (AFM). An optical extinction spectrum (Ext ¼  logðTÞ, where T is
liquid phase exfoliation45 but may be facilitated by intercalation-based transmittance) measured on the graphene ink is shown in Fig. 1A. It shows
exfoliation techniques, where the interlayer attraction is mitigated, such as the typical spectral profile characteristic of liquid dispersion of graphene
electrochemical or chemical exfoliation46,47. nanosheets with a peak at 270 nm, associated with a band-to-band transi-
In this work electrochemically exfoliated graphene (EEG) ink was tion and a flat region at higher wavelengths49. Previous work has showed this
deposited using a customized setup for liquid interface deposition to per- peak wavelength value to be associated with relatively thin nanosheets with
form a systematic study of the effect of the deposition parameters (ink <N > ~ 449. The ink was used to deposit nanosheets on a Si/SiO2 substrate for
concentration, nanosheet areal mass load) on the quality of the resulting AFM characterisation. Fig. 1B depicts a typical AFM image with multiple
films. Having found the ideal deposition parameters for fabricating a single graphene nanosheets. Examples of height profiles are given in the inset and
layer to be at low ink concentrations and an appropriately large areal mass the SI. The data collected by AFM allows us to extract the length and
load, thicker graphene films were fabricated by further refining the liquid thickness values for a statistically relevant number of nanosheets (see
interface deposition technique for layer-by-layer depositions. The resulting methods). The apparent nanosheet thickness is converted to layer number
films exhibited high conductivities in excess of 1.2 × 105 S/m at low film (N) using the results of step height analysis50–53 (see methods). The resultant
thicknesses (11 nm), an order of magnitude increase on the 1.6 × 104 S/m nanosheet length is plotted versus the layer number in Fig. 1C. It is clear that
record previously established for graphene nanosheet network thin films our nanosheets have N-values between 1 and 15 and maximum lateral sizes
(t < 50 nm) without aggressive post-processing21. This result is also com- approaching 10μm. The layer number is then converted to nanosheet
parable to state of the art conductivities for thicker (t > 500 nm) graphene thickness, tNS, using the crystallographic interlayer spacing

Fig. 1 | Characterization data for the electrochemically exfoliated graphene used shown (C) Plot of nanosheet lateral size versus nanosheet layer number and (D)
in this study. A Extinction spectrum, normalized at 750 nm, of an IPA ink made lateral size/thickness aspect ratio versus nanosheet thickness for a sample of gra-
using the EEG used in this study. B AFM image of EEG nanosheets spin coated on an phene nanosheets measured by AFM. E Histogram distribution of thickness and (F)
Si substrate inset: line profile of a typical nanosheet with its length and thickness lateral sizes of nanosheets measured by AFM.

npj 2D Materials and Applications | (2025)9:2 2

https://doi.org/10.1038/s41699-025-00525-9 Article

Fig. 2 | Schematic and photograph of the Langmuir-type setup used for the evacuated by vacuum to transfer the nanosheet film onto substrates below the
deposition parameter optimization. A Schematic of the method of liquid interface interface. Inset below: SEM image of a typical film, showing a high degree of flat
deposition used in this study, shown in cross section for clarity. A high surface nanosheet alignment. B Image of the setup used in the study, showing the apertures
tension interface is created between DI water and distilled hexane, the ink is injected into which substrates are placed, a film is formed, and then water is evacuated via
into the interface to form a film of aligned nanosheets, and the water is then tubing placed below the water line into a vacuum chamber to transfer the films.


t ðnmÞ ¼ 0:34nm  N 54 and this data is plotted in Fig. 1D as aspect ratio deposited films using a high-grade commercially available transmission

NS 
AR ¼ L=tNS versus tNS. The average aspect ratio observed was 4540 ± 180 scanner. These scans yield values for transmitted intensity (expressed in
(ranging from 125–24660), while ~90% of our nanosheets have an AR > signal intensity) for a large array of spatially resolved pixels. After calibration
1000. A histogram of nanosheet thickness is shown in Fig. 1E, which shows (detailed in Supplementary Section 1.4), these signal intensity values can be
tNS to range from 0.35 nm–4.9 nm with a mean nanosheet thickness, converted to absolute transmittance and then to optical extinction via
<t>NS = 0.97 ± 0.03 nm. Similarly, the nanosheet length histogram is given Ext ¼  logðTÞ. The resultant extinction values are averages over the visible
in Fig. 1F and is consistent with <L > = 3.18 ± 0.08 μm. This appears to be range (i.e., 380–750 nm).
typical of electrochemically exfoliated graphene, as previous studies report Shown in Fig. 3A is an optical transmission scan for a relatively poor-
measured nanosheet thicknesses ranging from 0.8 – 7 nm, and lateral sizes quality film. Although the spatial variation of extinction can be analysed57,
ranging from 1 to 40 μm48,55,56. the simplest form of analysis is to use a random sample of extinction data
from the image presented in Fig. 3A to plot a histogram as shown in Fig. 3B
(see supporting information section S1.4.1 for further details). Such histo-
Liquid-liquid interfacial deposition grams provide information about the distribution of local thicknesses within
An excellent way to achieve thin but highly aligned films of nanosheets is via the film (as Ext=εtFilm, where ε is the film extinction coefficient and tfilm is the
the liquid interface deposition method43,44. This method exploits the large local film thickness). The histogram in Fig. 3B implies the presence of
interfacial tension between two immiscible solvents, such as the water- regions of different thickness across the film, as indicated by the different
hexane system shown in Fig. 2A. To achieve this, an ink containing gra- colours of dashed rectangles in Fig. 3A which are colour-correlated with the
phene nanosheets is injected into the interface whereby the high interfacial coloured bands in Fig. 3B. These correspond to regions of uncovered sub-
tension then drives the graphene nanosheets to lie flat along the interface. strate (green), regions of thick aggregated material (blue), and flat homo-
This yields a highly aligned close-packed film of nanosheets, which can then geneous regions of nanosheets (orange), respectively.
be transferred onto any desired substrate by moving the substrate through However, for better quality, more homogeneous films, such as that
the interface. In practise, we achieve this by steadily lowering the interface by represented by the extinction map in Fig. 3C, the extinction histogram (Fig.
removing water from below the waterline as indicated in Fig. 2A. After 3D) follows a bimodal Gaussian distribution. In this example, regions of
deposition, the films are annealed at 120 °C under inert gas for 1 h. A custom covered and uncovered (i.e., around the edge) substrate can be distinguished
made, readily available setup was developed to accomplish this for fabri- from the transmission scans, which correspond to the black, and red bins in
cating multiple samples at once, using simple mill-cut PTFE parts as pic- Fig. 3D, respectively. This allows the extraction of the number of sampled
tured in Fig. 2B and detailed in Supplementary Section 1.3. pixels associated with uncovered substrate (red), Σsubstrate, and the number
of sampled pixels associated with the graphene film (black) Σfilm. In addi-
Optimization of monolayer deposition tion, we can obtain the mean substrate optical extinction, <Ext>substrate
To quantitatively assess the quality of the produced films, we have developed which allows us to correct the extinction associated with the film for the
a number of metrics using results from both optical and electrical char- optical effect of the substrate. Furthermore, the total length of all boundaries
acterisation techniques. Firstly, optical transmission scans were acquired on between domains of uncovered substrate and film, which is a measure of the

npj 2D Materials and Applications | (2025)9:2 3

https://doi.org/10.1038/s41699-025-00525-9 Article

Fig. 3 | Methods for extracting figures of merit of film quality from optical scans. extinction, <Ext>substrate is determined, such that it may be subtracted from the
A An optical scan of one of the films fabricated in the study. The differing regions average extinction in the image to yield the average film extinction <Ext>film. Also
observed in the film are highlighted, green showing uncovered substrate where shown, how the substrate pixel sum Σsubstrate is determined by integration of the
breaks in the film formed, orange showing homogeneous film coverage, and blue histogram curve, which is used to determine film coverage. E shows how the film
showing regions of material aggregation. B A histogram of extinction values cal- perimeter is determined for a sample image, by binarization of the image between
culated for a sample of 100000 pixels from the image in (A). C Image of another film film and substrate domains as shown in (F) and then using particle analysis to find
with more homogeneous film quality without full substrate coverage. D Image the sum of the perimeter of the boundary between the two regions, the result of
extinction histogram from the image in (C). Shown in the inset is how the substrate’s which can be seen in (G).

amount and distribution of gaps in the film, may be determined by binar- extinction, <Ext>film, and its standard deviation, ΔExtfilm , which is equiva-
ization and subsequent particle analysis on the scanned film. The binar- lent to the ratio of mean film thickness and the corresponding standard
ization is achieved by applying ImageJ’s thresholding feature to the image deviation <t>Δt film . This metric gives a relative value of variation in optically
film

(Fig. 3E), below which the dark pixels (film) are defined as 0, and the light
pixels (substrate) are defined as 1, giving a binary image (Fig. 3F). ImageJ’s measured thickness across the film, with a larger value indicating a more
particle analysis feature may then be used to extract the total perimeter of all homogeneous film thickness distribution.
domains in the binary image—the film perimeter, in pixels. Further detail on Finally, the film-substrate perimeter length is obtained after binariza-
this procedure is provided in Supplementary Section 1.4.2. tion (Fig. 3E–G). To this end, perimeter lengths (in metres) were divided by
From the transmission scans we can obtain three different metrics for the total area of the film (in m2) to give a relative film perimeter length
the quality of deposited films. These are the relative film coverage, the film (m/m2). This quantifies the granularity of the film – a small perimeter length
thickness homogeneity, and the relative length of the perimeter dividing indicates a continuous film without small holes.
regions of film from bare substrate. These parameters can be generated For a systematic optimization of the deposition process, using the
quickly and easily from transmission scans and will be useful in allowing us electrochemically exfoliated graphene ink, we assess the quality of films
to systematically optimize the homogeneity of the deposition process. We produced while varying the two main deposition parameters: the ink con-
now describe how each metric is extracted and their physical meanings. centration and areal mass loading of nanosheets injected into the interface.
The relative film coverage is determined using the integral of the peaks To this end, 36 films were deposited, using 6 different concentrations
corresponding to exposed substrate (Σsubstrate), and the film (Σfilm), (0.54–0.02 g/L) and 6 different nanosheet aerial mass loads (3–21 g/m2) for
respectively.
  The coverage metric was taken from the ratio of both values each ink concentration. The optical transmission scans of each film are
1
Σsubstrate
. This quantifies the relative amount of the substrate covered by shown in Fig. 4A. Note that each box in the 6 × 6 grid corresponds to a film
Σfilm
with an area of ~4 cm2.
graphene, with the maximum, 1, indicating a film with complete coverage. From the grid in Fig. 4A, it can be seen that various regions of the
The film thickness homogeneity was produced from the extinction parameter space (e.g., top and left) yield patchy, inhomogeneous films.
histograms. As described in further detail in Supplementary Section 1.4.1, Visually, only the bottom right seems to yield uniform, homogeneous films.
the mean film extinction and its standard deviation can be generated from Below, we interrogate our various metrics to demonstrate this
the scans. The homogeneity is calculated from the ratio of the mean film quantitatively.

npj 2D Materials and Applications | (2025)9:2 4

https://doi.org/10.1038/s41699-025-00525-9 Article

Fig. 4 | Heatmaps of film deposition parameters showing optimal concentration low concentration yields films with completely contiguous films. E Heatmap of film
and mass load for homogeneous film formation. A Graph showing optical scans of conductivity homogeneity (ratio of the mean film conductivity <σ>film and the
the films formed for the ink optimisation study, with the ink concentrations (g/L) average uncertainty in film conductivity Δσfilm) measured by the transmission line
and areal mass load of nanosheets on the interface (g/m2) shown. B Heatmap of film method, showing that high areal mass load, low ink concentration yields films with
coverage of each of the films formed, showing that lower areal mass loads lead to the best film conductivity homogeneity. F SEM image of a film with medium con-
incomplete films. C Heatmap of film thickness homogeneity (ratio of the mean film centration and low areal coverage (0.0939 g/L 6.9 g/m2), showing discontinuities on
thickness and film thickness standard deviation, extracted from ratio of mean the microscale, and (G) SEM image of a film with high concentration and high areal
extinction <Ext>film and extinction standard deviation ΔExtfilm), showing high areal coverage (0.543 g/L 21 g/m2), showing the formation of aggregated, inhomogeneous
mass load, low ink concentration to yield films with best thickness homogeneity. structures on the microscale.
D Heatmap of relative film perimeter, showing that only high areal mass load and

Heatmaps of the metrics described above are shown in Fig. 4B–D. A clearly shows the lowest concentration and highest mass per unit area to
full coverage of the substrate tends to be achieved at injection masses of yield the best film.
~17–21 g/m2 over all concentrations (Fig. 4B), while the film thickness Based on the metrics, the region of high areal mass load and low ink
homogeneity (Fig. 4C) and length of nanosheet film perimeter (Fig. 4D) are concentration consistently yields films with the most desirable values for
best for the injection of 17 g/m2 at the lowest concentration (0.02 g/L). We each metric. Conversely, films produced by low areal mass load appear to
note that lower concentrations are not suitable for our deposition process as have low coverage, non-contiguous film domains, poor homogeneity in
mixing of the graphene with the water sub-phase is observed for too high ink thickness, and are least conductive. An SEM image in Fig. 4F shows the
injection volumes as required for complete substrate coverage at con- microstructure of such a film, produced using a graphene ink concentration
centrations below 0.02 g/L. This is discussed in further detail in Supple- of ~0.1 g/L, injected to an aerial mass load of 6.9 g/m2—numerous holes and
mentary Section 2. gaps are apparent between the individual nanosheets. Films produced by
In further analysis, a set of 18 gold contacts were evaporated on each high concentration, while having relatively high coverage and contiguous
deposited film to assess the spatial homogeneity of the conductivity of the film domains, appear to have even poorer thickness homogeneity and
fabricated films across different areas of the substrate. This represents a subpar conductivity homogeneity. An SEM image in Fig. 4G shows the
fourth metric for the film quality in addition to the ones extracted from microstructure of a film, produced using a graphene ink concentration of
transmission scans. We extract the “film conductivity homogeneity“ and the ~0.5 g/L, injected to an aerial mass load of 21 g/m2—shows the appearance
contact resistance using the transmission line method (see Supplementary of aggregated structures, made of folds and creases in the nanosheets.
Section 1.6 for additional details). The average film conductivity, <σ>film,
and its respective average uncertainty, Δσfilm , are used to calculate the Characterization of the optimized film
conductivity homogeneity metric as the ratio between the two values <σ> Δσfilm .
film Having found the optimal deposition parameter space for homogenously
This gives a relative value of the variation in conductivity across the film, covered films, an advanced characterization of the best film was carried out
similar to the thickness homogeneity metric, with larger values indicating (0.02 g/L, 21 g/m2), a photograph is shown in Fig. 5A, the black rectangles
more homogeneous conductivity across the film area. The heatmap corre- are gold electrodes. The substrate-corrected film extinction histogram (Fig.
sponding to the conductivity homogeneity metric is shown in Fig. 4E. This 5B) demonstrates a ΔExtfilm of 8.3 × 10−3, indicating a thickness variation

npj 2D Materials and Applications | (2025)9:2 5

https://doi.org/10.1038/s41699-025-00525-9 Article

Fig. 5 | Characterization data of an optimized graphene film. A optical image of D Raman spectrum measured for the optimal film – note the D/G ratio indicating
optimal film (0.02 g/L, 21 g/m2) with top contacted Au electrodes shown. presence of defects (E) SEM image taken for this film, showing superior coverage of
B Extinction histogram from the optical scan of the optimal film. C Extinction the substrate and microscale ordering. F A transmission line of measured resistances
spectrum measured for a similarly fabricated single layer film on fused silica. for this film.

 
<ext>film
of 0.21, a relative measure of the roughness of the film equivalent to single layer of nanosheets is relatively low compared to thicker graphene
ΔExtfilm
<t>film
films which can have conductivities approaching 105 S/m27.
Using samples of the graphene film of varying thickness, achieved by
Δtfilm .
repeated interface deposition of the material onto masked glass substrates – Layer-by-layer deposition of densely packed graphene
film thicknesses are extracted from AFM height profiles (Supplementary Fig. nanosheet films
6A, C) and the film extinction is extracted from transmission scans (see Having found optimal deposition parameters for a single layer, the method
Supplementary Fig. 6B) in order to determine the extinction coefficient as was further refined for depositing films layer-by-layer to increase the film
(1.65 ± 0.03) × 107 m−1 (see Supplementary Fig. 6D). Using this extinction thickness. For this purpose, we configured the setup as described in detail in
coefficient, the mean thickness for this film can be determined as 2.9 ± 0.1 nm. Supplementary Fig. 8. In short, using a rotating stage helps with reprodu-
An extinction spectrum corresponding to a film very similar to the one cibility due to more homogenous ink injection. Hence, we change the
in Fig. 5A is shown in Fig. 5C. For the purpose of wavelength dependent geometry of the setup from the square cavities shown in Fig. 2 to a circular
extinction measurements, we deposited a film using the same conditions for cavity shown in Fig. 6A. Note that this changes the absolute injection volume
the one shown in Fig. 5A, but on fused silica. We measure an average to achieve the same aerial mass load.
extinction of (59 ± 9)×10−3 between 380 and 750 nm, which is similar to the We note that issues with the colloidal stability of our graphene ink were
average extinction extracted from the transmission scan (47 ± 9) × 10−3. observed over extended storage periods. To address this, we employed mild
In addition, we performed Raman spectroscopy on the deposited film centrifugation on the stock dispersion (cink = 1 g/L) to remove aggregates.
(Fig. 5D). The spectrum displays peaks at 1350 nm−1 and 1580 cm−1, which UV-Vis was then used to determine the concentration of the remaining
respectively correspond to the D and G bands characteristic of graphene58. supernatant, which was subsequently diluted to 0.02 g/L to match the
The D/G band intensity ratio (1.15) observed is consistent with a con- optimal ink concentration.
siderable number of basal plane defects, and is comparable to the value For multilayer deposition, each layer was deposited using the opti-
observed for reduced GO ( ~ 1.1-1.5)59, which is reported in the literature for mised protocol, as described above. In addition, we perform thermal
similar preparation protocols of EEG by anodic exfoliation55,56, indicating annealing after the deposition of each layer to improve the adhesion between
that defects are introduced during the exfoliation process. adjacent nanosheet layers. In addition, we soak the deposited and annealed
We further study the microstructure of the optimized film using SEM films briefly in acetone, to remove organic residues on the nanomaterial
imaging (Fig. 5E). The image shows a homogenous and close packing of the surface. Following this protocol, these steps can be repeated for as many
nanomaterial, with slight overlap between the individual nanosheets. This layers as desired. Transmission scans for films of deposition numbers from
confirms the high degree of nanosheet alignment associated with this 1–16 (Supplementary Fig. 8) were measured to allow for a systematic
deposition method. analysis. A sample of the resulting extinction histograms is shown in Fig. 6B.
By depositing multiple gold electrodes (Fig. 5A) we can use the The curves show a systematic shift towards higher extinction with each
transmission line method to measure both film conductivity, σ, and contact deposition as well as a broadening with increasing deposition number.
resistance, Rc. For a uniform film, we expect a well-behaved linear depen- In further analysis, we extract the mean extinction of these films,
dence between
the measured
 resistance, R, and the electrode spacing, L: <Ext>film as well as their standard deviation, ΔExtfilm. The extinction
R ¼ 2Rc þ L= σwt Film , where w is the electrode width. Fig. 5F demon- increases linearly with deposition number, indicating that each deposition
strates that this is indeed the case with linear fitting yielding σ = 84 ± 20 S/m sequentially adds layers of approximately equal thickness. In addition,
and Rc = 900 ± 700 kΩ·m, respectively. We note that this conductivity of a ΔExtfilm serves as a measure for the roughness across the deposited

npj 2D Materials and Applications | (2025)9:2 6

https://doi.org/10.1038/s41699-025-00525-9 Article

Fig. 6 | Multilayer deposition using monolayer-enriched graphene ink utilizing is supported by the distribution in Fig. 1B. D Ratio of standard deviation thickness to
the protocols developed in this study. A Schematic of the setup used to deposit mean film thickness for each film, showing a reduction in relative roughness with
multiple layers of graphene, with film formation aperture shown in cross section. deposition number. E Graph of film conductivity versus film thickness, indicating
Upon deposition of a layer, films were dried, thermally annealed, and then washed in the networks fabricated by this material and method approach a bulk conductivity of
acetone before adding subsequent layers by repeating the same process. B Extinction 1.3 × 105 S/m. F Graph of average contact resistance across the films versus
histograms of a selected sample of multilayer films from the study. C Average film deposition number. The solid line in H is related to the solid line in G
thickness versus deposition number, showing a linear scaling that indicates that a via Rc ¼ 8:4 × 107 =σ.
layer of nanosheets that are on average bilayer are added with each deposition, which

nanosheet film. ΔExtfilm follows a sublinear increase with layer number, smaller effective mass load was used for the same injection volume.
saturating above about 10 layers. As shown below, that ΔExtfilm increases Additionally, a mass load below a complete film is in fact desirable for
slower than the mean extinction means the films become relatively more depositing multiple layers, as the lack of close-packing avoids the
uniform with increasing deposition number. nanosheet folds observed in Fig. 5E. Such folds contribute to the formation
The mean film extinction was converted to the average film thickness of pores in a multilayer network, and hence reduce its conductivity. As
using the extinction coefficient mentioned above. As plotted in Fig. 6C, the such, individual layers deposited with the aged material were homogenous
mean film thickness shows a linear increase with deposition number. From according to the transmission scans, but below the percolation threshold
the slope, we can extract that approximately 0.87 nm are added with each (see SI, section S1.7 for further details and AFM images).
deposited layer, consistent with each layer consisting of nanosheets each The film conductivity (Fig. 6E) is relatively low for the thinnest (low layer
with an average N of ~3. In addition, we converted ΔExtfilm to standard number) films but increases rapidly with increasing thickness, before satur-
deviation of thickness Δtfilm and calculated the ratio of Δtfilm to the mean ating at 1.3×105 S/m for thicknesses above 8 nm (layer numbers above 10).
film thickness, Δtfilm/ < t>film, as shown in Fig. 6D. This parameter is a Such thickness-dependent behaviour is as expected for thin films due to
measure of the relative roughness of the films and falls steadily with surface effects. For example, the Fuchs-Sondheimer model60 shows the
increasing deposition number. For the thickest film, this data implies the resistivity of perfectly flat thin films to increase with decreasing thickness as
standard deviation of the thickness distribution to be ~10% of the mean <tfilm > −1 because of surface scattering of electrons. A number of models61,62
thickness. have shown that for thin films with roughness or disorder on the nanoscale,
Finally, we use set electrodes to measure the I/V characteristics on each the resistivity increases with decreasing thickness can be even faster, than
film, similar to the measurements used for the optimization of the single <tfilm > −1 (see SI section S3). Such models describe the resistivity as the sum of
layer deposition (see further above, and in the SI, section S1.6 for additional a bulk-like resistivity (associated with thick films) and a term describing the
details). This allows the determination of the film conductivity and contact increase in resistivity with decreasing thickness. In the case of solution
resistance for films of each layer number. These parameters are plotted as a deposited films of nanoparticles, De et al. 17 have shown similar behaviour: the
function of film thickness in Fig. 6E, F. conductivity of thin films falls off with decreasing thickness. This paper
For the optimised multilayer deposition setup, the first two layers had describes the data in terms of two regimes: a bulk-like regime above some
near-negligible conductivity, contrary to the conductivity for single layers threshold thickness (tx) and a percolative regime, below tx. For printed gra-
in the initial optimization study. This may be due to a variety of reasons. phene films, Caffrey et al. 7 have comprehensively mapped out these regimes,
One aspect is that we observe a concentration change of the ink after accurately determining
  tx, demonstrating thickness-independent con-
prolonged storage times. We assume that partial aggregation of higher ductivity
  tFilm >tx and fitting the conductivity to a percolation scaling law
for
layer numbers occurs over time, and therefore a slight change of the for tFilm <tx . However, accurately performing such fitting requires a pro-
concentration and the monolayer content in the dispersion. Hence, a hibitively large number of conductivity versus thickness data points.

npj 2D Materials and Applications | (2025)9:2 7

https://doi.org/10.1038/s41699-025-00525-9 Article

To avoid this requirement, we show in the SI (S3) that one can apply the exact conductivity of the graphite used here, we can calculate the max-
thin film strategy of adding bulk-like and thickness-dependent resistivity imum possible junction resistance by taking the upper limit of graphite
terms used in the Fuchs-Sondheimer model60 to a system where the beha- conductivity as our value for σNS. Then, taking σB = 1.4 × 105 S/m and
viour is percolative at low thickness. This yields the following semi- tNS = 1 nm, we find RJ < 3 kΩ. However, because the graphene used her is
  for film conductivity, σ, as a function of mean film
empirical equation quite defective, its conductivity is likely somewhat below this maximal
thickness, t Film : value. For example, if we take a more realistic value of σNS = 2 × 105 S/m,
this would imply a junction resistance of ~1 kΩ. This compares to a
" " #n #1
1 tx  tc measured 3.3 kΩ value for RJ measured for a spray-cast graphene
σ ¼ σB 1þ   ð1Þ network28 and indicates that the liquid interface deposition technique
4 t Film  t c
yields networks with more conductive junctions when compared to other
printing techniques.
Here, σB is the thickness of a thick (bulklike) film, tc is the Finally, we show data for the contact resistance as a function of film
percolation threshold (the thickness below which no conduction thickness in Fig. 6F. Here we see a very sharp decrease in contact resistance
occurs), tx is defined as the thickness

where
 the film
 conductivity with increasing film thickness before saturating at thicknesses above 8 nm.
reaches 80% of the bulklike value σ tx ¼ 0:8σB while n is the This is essentially the inverse of the behaviour displayed by the conductivity.
percolation exponent. We find this equation fits the data extremely In fact, as displayed by the solid line in Fig. 6F the contact resistance is
well with fit parameters of tx = 12 nm, tc = 2 nm, σB = 1.4 × 105 S/m directly proportional to the inverse of the function used to fit the con-
and n = 3. This fit implies the transition to bulk-like conductivity to ductivity data (Rc = 8.4 × 107/σ). This implies that the contact resistance is
occur at a film thickness of 12 nm. This is a relatively low value of tx, somehow directly linked to the film resistivity, probably via the resistance
compared to others in the literature. The lowest reported value we associated with the current spreading from the contacts to flow through the
know of is that of Caffrey et al. 7 who reported tx = 120 nm. Never- entire thickness of the film.
theless, values of tx lower than 12 nm would be useful, especially for
films of semiconducting nanosheets (e.g. MoS2) in transistor appli- Key findings and interpretation of results
cations. This is because the on/off ratio is such devices is expected to We demonstrate the general methodology for a liquid-interface deposition
fall with increasing network thickness due to screening effects. Future method, and the deposition parameters required for using this method to
work will attempt to decrease tx by enhancing the deposition method deposit a homogeneous film of electrochemically exfoliated graphite
to further reduce disorder in these networks. (cink = 0.02 g/L, mass/area = 21 g/m2). We have shown that stacking of
The main advantage of this work is that it yields solution- multiple layers of graphene is possible to produce films with high con-
processed graphene films with combinations of reasonably high ductivities (1.3·105 S/m) at low thicknesses (11 nm). Such conductivities are
conductivity and relatively low thickness that surpass any previous comparable to the state of the art for graphene films in general15 and an order
reports. It should be noted that measured conductivities for solution- of magnitude increase compared to thin printed graphene films without the
graphene films comparable to the conductivities reported here— use of complex post-processing strategies21. This can all be of value to
(1.3 ± 0.2) × 105 S/m at 11.1 ± 0.2 nm - have only previously been improvements in the performance of solution-processed graphene in thin-
achieved for significantly thicker films (e.g., 1.2 × 105 film device applications. We believe that the deposition method described
S/m at a thickness of 500 nm)15 or for thin (<50 nm) films using here will be useful in a range of applications where highly conductive, yet
aggressive post-processing techniques (2.5 × 105 S/m at 15 nm after extremely thin films are required. Examples include high-performance
65% HNO3 treatment)21. For published thin films similar to those electrodes in solution-processed TFTs64, flexible transparent conductive
here (i.e., t < 50 nm without high temperature or chemical post- electrodes2 and strain gauges65 for wearable electronics, antennae66, and
processing), the record conductivity is an order of magnitude lower high-frequency electromagnetic interference shields67.
(1.6 × 104 S/m at a thickness of 15 nm)21. As such, this method More generally, this work shows a reliable route to minimizing the
demonstrates its utility for fabricating films with state-of-the-art junction resistance observed in 2D material networks, which is promising
conductivities at extremely low thicknesses. One of the thinner films for applying the method for a broader range of nanomaterials, which have
(6.1 ± 0.2 nm) fabricated in this study exhibited a transmission of previously been deposited using similar liquid-interface techniques without
82% and conductivity of (3.6 ± 0.6) × 104 S/m, which corresponds to a the optimization demonstrated here68–70. Indeed, we expect this method to
sheet resistance Rs of 4.5 kΩ/□. This is competitive with the lowest be extremely versatile and in principle applicable to a wide range of 2D
sheet resistance of a lightly-processed graphene TCF device found in materials as well as various substrates. Using this technique to overcome the
the literature (measured transmission of 85%, Rs of 4.1 kΩ/□)21. For problem of low network mobilities that have been previously observed in
further comparison to existing graphene films reported in the lit- TMD-based transistors due to large junction resistances27,68 may be parti-
erature, see Supplementary Table 1. cularly promising for the fabrication of heterostructures over large areas.
It has recently been shown that the conductivity of bulk-like nanosheet
networks is given by an equation63 which can be rewritten as: Methods
Electrochemical exfoliation


1  PNet Electrochemically exfoliated graphene was prepared according to the fol-
σB ¼ ð2Þ lowing procedure. Two pieces of graphite foil (Alfa Aesar) with dimensions
σ NS 1 þ 2t NS RJ
50 x 30 x 0.25 mm3 were connected as anode and cathode to a DC power
Where PNet is the network porosity, σNS is the conductivity of the individual supply and immersed in 100 mL of an aqueous electrolyte solution of 0.1 M
nanosheets, tNS is the mean nanosheet thickness ( ~ 1 nm here) and RJ is the (NH4)2SO4 with a separation of 2 cm between them. 10 V were applied to
mean junction resistance. For highly aligned films such as these we can the electrodes for 30 min, with a current that increased from ~1 A to ~1.8 A
approximate PNet ~ 0, allowing us to write during the process. The resulting expanded material in the electrolyte

 solution was filtered and repeatedly washed with DI water ( ~ 1 L), and then
σ 1  σ NS 1 sonicated in 100 mL of DMF for 10 min to complete the exfoliation into a
RJ  B ð3Þ dispersion of graphene nanosheets. The resulting ink was centrifuged at
2t NS
3000 rpm (940 g) for 20 min to remove incompletely exfoliated particles.
We can take σNS to be the in-plane conductivity of graphite which has The graphene sheets were sedimented at 6000 rpm (3780 g) for 90 min and
been reported in the range ~105-106 S/m26. Although we do not know the redispersed in isopropyl alcohol. This final step was repeated once more to

npj 2D Materials and Applications | (2025)9:2 8

https://doi.org/10.1038/s41699-025-00525-9 Article

remove residual DMF. The resulting 1 g/L 3780 g graphene ink in IPA was accumulations with a 100× objective. An incident power of ∼1 mW was
used for the study. used to minimise possible thermal damage.

AFM Liquid interface deposition—layer by layer

Atomic force microscopy (Bruker Multimode 8, ScanAsyst mode, non- The stock 1 g/L graphene dispersion was centrifuged at 200 g for
contact) was used to measure the nanosheet thickness and lateral dimensions 30 min in 5 sequential steps, taking the supernatant discarding the
in the size-selected graphene ink. Measurements were performed in air under sediment each time, to yield a monolayer enriched ink, which was
ambient conditions using Al-coated silicon cantilevers (OLTESPA-R3). As diluted to a concentration of 0.02 g/L using IPA. This ink was injected
detailed in the SI, to convert the apparent thickness to actual thickness, the to a water-air interface and transferred onto treated glass substrates
AFM measured height values are subtracted by 0.5 nm and divided by deposited with Au electrode arrays, using a refined setup that rotated
0.95 nm, the apparent thickness of a graphene layer. When this value is the interface as a set quantity of ink was injected at a steady rate
rounded down, this gives the number of layers in a nanosheet. This value is (100 μL/min) using an auto-injector. Following the deposition, the
multiplied by 0.34 nm, the crystallographic thickness of a graphene layer, to films were placed on a hot plate at 80 °C and covered to dry for 1 h. The
yield the actual thickness of the nanosheet54. resulting films were then annealed at 120 °C in ambient conditions for
1 h, and then briefly dipped in acetone to prepare for the deposition of a
UV-Vis spectroscopy subsequent layer. This procedure is further detailed in Supplementary
Ink characterisation. UV-Vis extinction measurements were carried out Section 1.7. Following this, we fabricated 16 samples of different
using a Cary 50 spectrophotometer, having subtracted off an IPA back- deposition numbers (1 to 16), each of which were then annealed under
ground with a sampling interval of 0.5 nm and a sample length of 4 mm. vacuum at 500 °C for 1 h. The same methods of scanning and electrical
measurements as before were then performed on the films.
Ink concentration measurements. Using the same apparatus as before,
with a sampling interval of 1 nm and a sample length of 1 mm. An Data availability
extinction coefficient of 2640 g L−1 m−1 at 660 nm was used to determine The authors declare that the data supporting the findings are available
the concentration of the measured ink from the acquired spectrum. within the paper and its supplementary information. The corresponding
authors can also provide data upon reasonable request.
Pre-treatment of glass substrates with KOH
Potassium hydroxide was dissolved in ethanol under continuous stirring Received: 1 July 2024; Accepted: 27 December 2024;
until saturation was achieved. The resulting orange solution was decanted
from the undissolved potassium hydroxide and used for substrate surface
treatment as detailed in SI section S1.2. References
1. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater. 6,
Liquid interface deposition—optimization 183–191 (2007).
Various dilutions of the resulting dispersion were prepared (1:2, 1:4, 1:5, 1:8, 2. Miao, J. & Fan, T. Flexible and stretchable transparent conductive
1:20, 1:50) and their concentrations were measured using UV-Vis spec- graphene-based electrodes for emerging wearable electronics.
troscopy as detailed above. The target substrate was immersed in particle Carbon 202, 495–527 (2023).
filtered, 18 MΩ cm−1 deionized water. ~5 mL of distilled hexane was 3. Liu, Z. et al. Water-dispersed high-quality graphene: a green solution
pipetted onto the water interface, and then a specific volume of graphene ink for efficient energy storage applications. ACS Nano 13, 9431–9441
of known concentration was pipetted onto the water-hexane interface. The (2019).
interfacial film was then transferred by vacuuming out the water from 4. Jeong, H. Y. et al. Graphene oxide thin films for flexible nonvolatile
below. The resulting films were left to dry under a cover inside a fume hood memory applications. Nano Lett. 10, 4381–4386 (2010).
for approximately 4 h, and then annealed in inert conditions at 120 °C for 5. van Hazendonk, L. S. et al. Printed stretchable graphene conductors
approximately 1 h. Multiple volumes of each of the dilutions were deposited for wearable technology. Chem. Mater. 34, 8031–8042 (2022).
by this method onto KOH-treated glass substrates. 6. Seekaew, Y. et al. Low-cost and flexible printed graphene-
PEDOT:PSS gas sensor for ammonia detection. Org. Electron. 15,
Film transmission scans 2971–2981 (2014).
The graphene films were scanned using an EPSON Perfection 750 scanner, 7. Caffrey, E. et al. Quantifying the piezoresistive mechanism in high-
and resulting images were processed to extract the film extinction dis- performance printed graphene strain sensors. ACS Appl. Mater.
tributions and film perimeter (see Fig. 3 and Supplementary Fig. 5). Interfaces 14, 7141–7151 (2022).
8. Large, M. J. et al. Large-scale surfactant exfoliation of graphene and
Conductivity measurements conductivity-optimized graphite enabling wireless connectivity. Adv.
Arrays of Au electrodes were deposited onto films/substrates with the mask Mater. Technol. 5, 2000284 (2020).
depicted in Supplemental Fig. 2B using a Temescal FC-2000 Bell Jar 9. Zhou, X. et al. A sustainable approach towards printed graphene ink
Deposition System. Electrical resistance between combinations of electrodes for wireless RFID sensing applications. Carbon 218, 118693 (2024).
along each row were measured by 2-point probe measurements across the 10. Pan, K. et al. Sustainable production of highly conductive multilayer
film using a Karl SUSS PM probe station, as depicted in Supplementary graphene ink for wireless connectivity and IoT applications. Nat.
Fig. 7A. Commun. 9, 5197 (2018).
11. He, P. et al. Screen-printing of a Highly Conductive Graphene Ink for
SEM measurements Flexible Printed Electronics. ACS Appl. Mater. Interfaces 11,
SEM was performed with a Carl Zeiss Ultra SEM operating at 2 kV with a 32225–32234 (2019).
30 μm aperture at a working distance of 5 mm. Images are acquired using 12. He, P. et al. An energy-saving structural optimization strategy for high-
the secondary electron inlens detector. performance multifunctional graphene films. Carbon 222, 118932
(2024).
Raman 13. Gang, Z. et al. High thermal conductivity and increased thickness
A WITec Raman spectrometer using a 532 nm wavelength laser is used to graphene nanosheet films prepared through metal ion-free route.
acquire spectra. The spectra for each network is averaged over 3 Ceram. Int. 48, 3711–3719 (2022).

npj 2D Materials and Applications | (2025)9:2 9

https://doi.org/10.1038/s41699-025-00525-9 Article

14. Qian, W. et al. Scalable assembly of high-quality graphene films via 38. Torres-Huerta, A. M. et al. Morphological and mechanical properties
electrostatic-repulsion aligning. Adv. Mater. 34, 2206101 (2022). dependence of PLA amount in PET matrix processed by single-screw
15. Clifford, K. et al. Emergent high conductivity in size-selected extrusion. Polym. Plast. Technol. Eng. 55, 672–683 (2016).
graphene networks. Carbon 218, 118642 (2024). 39. Gilles, D. G. & Loehr, R. C. Waste generation and minimization in
16. Mirkhani, S. A. et al. Reduction of electrochemically exfoliated semiconductor industry. J. Environ. Eng. 120, 72–86 (1994).
graphene films for high-performance electromagnetic interference 40. Shin, C.-H. et al. Recovery of nitric acid from waste etching solution
shielding. ACS Appl. Mater. Interfaces 13, 15827–15836 (2021). using solvent extraction. J. Hazard. Mater. 163, 729–734 (2009).
17. De, S., King, P. J., Lyons, P. E., Khan, U. & Coleman, J. N. Size effects 41. Shen, C. W., Tran, P. P., Ly, P. T. M. Chemical waste management in
and the problem with percolation in nanostructured transparent the U.S. Semiconductor industry. Susutainability 10, 1545 (2018).
conductors. Acs Nano 4, 7064–7072 (2010). 42. Gabbett, C. et al. Quantitative analysis of printed nanostructured
18. Gao, Y., Shi, W., Wang, W., Leng, Y. & Zhao, Y. Inkjet printing patterns networks using high-resolution 3D FIB-SEM nanotomography. Nat.
of highly conductive pristine graphene on flexible substrates. Ind. Eng. Commun. 15, 278 (2024).
Chem. Res. 53, 16777–16784 (2014). 43. Neilson, J., Avery, M. P. & Derby, B. Tiled monolayer films of 2D
19. Parvez, K., Worsley, R., Alieva, A., Felten, A. & Casiraghi, C. Water- molybdenum disulfide nanoflakes assembled at liquid/liquid
based and inkjet printable inks made by electrochemically exfoliated interfaces. ACS Appl. Mater. Interfaces 12, 25125–25134 (2020).
graphene. Carbon 149, 213–221 (2019). 44. Vićentić, T., Andrić, S., Rajić, V. & Spasenović, M. Reliable fabrication
20. Marković, Z. M. et al. Semi-transparent, conductive thin films of of transparent conducting films by cascade centrifugation and
electrochemical exfoliated graphene. RSC Adv. 6, 39275–39283 Langmuir–Blodgett deposition of electrochemically exfoliated
(2016). graphene. Beilstein J. Nanotechnol. 13, 666–674 (2022).
21. Parvez, K. et al. Electrochemically exfoliated graphene as solution- 45. Backes, C. et al. Equipartition of energy defines the size-thickness
processable, highly conductive electrodes for organic electronics. relationship in liquid-exfoliated nanosheets. Acs Nano 13, 7050–7061
ACS Nano 7, 3598–3606 (2013). (2019).
22. Suriani, A. B. et al. Synthesis, transfer and application of graphene as a 46. Yang, Y. et al. Electrochemical exfoliation of graphene-like two-
transparent conductive film: a review. Bull. Mater. Sci. 43, 310 (2020). dimensional nanomaterials. Nanoscale 11, 16–33 (2019).
23. Wu, W. et al. Control of thickness uniformity and grain size in graphene 47. Le, T.-H., Oh, Y., Kim, H. & Yoon, H. Exfoliation of 2D materials for
films for transparent conductive electrodes. Nanotechnology 23, energy and environmental applications. Chem. A. Eur. J. 26,
035603 (2012). 6360–6401 (2020).
24. Bae, S. et al. Roll-to-roll production of 30-inch graphene films for 48. Abdelkader, A. M., Cooper, A. J., Dryfe, R. A. W. & Kinloch, I. A. How to
transparent electrodes. Nat. Nanotechnol. 5, 574–578 (2010). get between the sheets: a review of recent works on the
25. Wang, S. et al. High mobility, printable, and solution-processed electrochemical exfoliation of graphene materials from bulk graphite.
graphene electronics. Nano Lett. 10, 92–98 (2010). Nanoscale 7, 6944–6956 (2015).
26. Nakamura, S., Miyafuji, D., Fujii, T., Matsui, T. & Fukuyama, H. Low 49. Backes, C. et al. Spectroscopic metrics allow in situ measurement of
temperature transport properties of pyrolytic graphite sheet. mean size and thickness of liquid-exfoliated few-layer graphene
Cryogenics 86, 118–122 (2017). nanosheets. Nanoscale 8, 4311–4323 (2016).
27. Kelly, A. C., O’Suilleabhain, D., Gabbett, C. & Coleman, J. N. The 50. Synnatschke, K. et al. Sonication-assisted liquid phase exfoliation of
electrical conductivity of solution-processed nanosheet networks. two-dimensional CrTe3 under inert conditions. Ultrason. Sonochem.
Nat. Rev. Mater. 7, 217–234 (2022). 98, 106528 (2023).
28. Gabbett, C. et al. Understanding how junction resistances impact the 51. Synnatschke, K. et al. Sonication-assisted liquid exfoliation and size-
conduction mechanism in nano-networks. Nat. Commun. 15, 4517 dependent properties of magnetic two-dimensional α-RuCl3. J. Phys.
(2023). D: Appl. Phys. 56, 274001 (2023).
29. Kymakis, E., Stratakis, E., Stylianakis, M. M., Koudoumas, E. & 52. Synnatschke, K. et al. Liquid exfoliation of Ni2P2S6: structural
Fotakis, C. Spin coated graphene films as the transparent characterization, size-dependent properties, and degradation. Chem.
electrode in organic photovoltaic devices. Thin Solid Films 520, Mater. 31, 9127–9139 (2019).
1238–1241 (2011). 53. Gosch, J., Synnatschke, K., Stock, N. & Backes, C. Comparative
30. Zheng, Q.-B., Shi, L.-F. & Yang, J.-H. Langmuir-Blodgett assembly of study of sonication-assisted liquid phase exfoliation of six layered
ultra-large graphene oxide films for transparent electrodes. Trans. coordination polymers. Chem. Commun. 59, 55–58 (2023).
Nonferrous Met. Soc. China 22, 2504–2511 (2012). 54. Paton, K. R. et al. Scalable production of large quantities of defect-free
31. Becerril, H. A. et al. Evaluation of solution-processed reduced few-layer graphene by shear exfoliation in liquids. Nat. Mater. 13,
graphene oxide films as transparent conductors. ACS Nano 2, 624–630 (2014).
463–470 (2008). 55. Mei, J. et al. Insights into the conductive network of electrochemical
32. Wang, S. J., Geng, Y., Zheng, Q. & Kim, J.-K. Fabrication of highly exfoliation with graphite powder as starting raw material for graphene
conducting and transparent graphene films. Carbon 48, 1815–1823 production. Langmuir 39, 4413–4426 (2023).
(2010). 56. Achee, T. C. et al. High-yield scalable graphene nanosheet production
33. Xu, Y. et al. Polymer photovoltaic devices with transparent graphene from compressed graphite using electrochemical exfoliation. Sci.
electrodes produced by spin-casting. Carbon 48, 3308–3311 (2010). Rep. 8, 14525 (2018).
34. Wöbkenberg, P. H. et al. Reduced graphene oxide electrodes for large 57. Finn, D. J., Lotya, M. & Coleman, J. N. Inkjet printing of silver nanowire
area organic electronics. Adv. Mater. 23, 1558–1562 (2011). networks. Acs Appl. Mater. Interfaces 7, 9254–9261 (2015).
35. Eda, G., Fanchini, G. & Chhowalla, M. Large-area ultrathin films of 58. Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers.
reduced graphene oxide as a transparent and flexible electronic Phys. Rev. Lett. 97, 187401 (2006).
material. Nat. Nanotechnol. 3, 270–274 (2008). 59. Buglione, L., Chng, E. L. K., Ambrosi, A., Sofer, Z. & Pumera, M.
36. Katiyar, A. K. et al. 2D materials in flexible electronics: recent Graphene materials preparation methods have dramatic influence
advances and future prospectives. Chem. Rev. 124, 318–419 (2024). upon their capacitance. Electrochem. Commun. 14, 5–8 (2012).
37. Schranghamer, T. F., Sharma, M., Singh, R. & Das, S. Review and 60. Fuchs, K. The conductivity of thin metallic films according to the
comparison of layer transfer methods for two-dimensional materials electron theory of metals. Math. Proc. Camb. Philos. Soc. 34, 100–108
for emerging applications. Chem. Soc. Rev. 50, 11032–11054 (2021). (1938).

npj 2D Materials and Applications | (2025)9:2 10

https://doi.org/10.1038/s41699-025-00525-9 Article

61. Namba, Y. Resistivity and temperature coefficient of thin metal films performed deposition experiments, did transmission scans, performed
with rough surface. Jpn. J. Appl. Phys. 9, 1326-& (1970). extinction measurements, analysed the data, and wrote the initial draft of the
62. Zhou, T. J., Zheng, P. Y., Pandey, S. C., Sundararaman, R. & Gall, D. manuscript. O.C. programmed python routines. C.G., L.D., O.C., and K.S.
The electrical resistivity of rough thin films: a model based on electron performed SEM measurements, performed and evaluated electrical mea-
reflection at discrete step edges. J. Appl. Phys. 123, 155107 (2018). surements. C.G., L.D., O.C., E.C., and K.S. evaluated and discussed
63. Gabbett C. et al. Understanding how junction resistances impact the transmission scans. K.S. and J.N.C. conceived the idea, led, oversaw the
conduction mechanism in nano-networks. Nat. Commun. 15, 4517 (2024) project, and finalized the manuscript.
64. Kim, J. et al. All-solution-processed van der Waals heterostructures
for wafer-scale electronics. Adv. Mater. 34, e2106110 (2022). Competing interests
65. Neilson, J., Cataldi, P. & Derby, B. Graphene-based transparent The authors declare no competing interests.
flexible strain gauges with tunable sensitivity and strain range. ACS
Appl. Nano Mater. 6, 21763–21774 (2023). Additional information
66. Tripathi, S. K., Kumar, M. & Kumar, A. Graphene based tunable and Supplementary information The online version contains
wideband terahertz antenna for wireless network communication. supplementary material available at
Wirel. Netw. 25, 4371–4381 (2019). https://doi.org/10.1038/s41699-025-00525-9.
67. Wei, Q. et al. Superhigh electromagnetic interference shielding of
ultrathin aligned pristine graphene nanosheets film. Adv. Mater. 32, Correspondence and requests for materials should be addressed to
e1907411 (2020). Jonathan N. Coleman.
68. Carey, T. et al. High-mobility flexible transistors with low-temperature
solution-processed tungsten dichalcogenides. ACS Nano 17, Reprints and permissions information is available at
2912–2922 (2023). http://www.nature.com/reprints
69. Lee, K. et al. Highly conductive and long-term stable films from liquid-
phase exfoliated platinum diselenide. J. Mater. Chem. C. 11, 593–599 Publisher’s note Springer Nature remains neutral with regard to
(2023). jurisdictional claims in published maps and institutional affiliations.
70. Shcherbakov, A. et al. Solution-processed NiPS3 thin films from liquid
exfoliated inks with long-lived spin-entangled excitons. ACS Nano 17, Open Access This article is licensed under a Creative Commons
10423–10430 (2023). Attribution-NonCommercial-NoDerivatives 4.0 International License,
which permits any non-commercial use, sharing, distribution and
Acknowledgements reproduction in any medium or format, as long as you give appropriate
We acknowledge the European Commission through the HORIZON-CL4- credit to the original author(s) and the source, provide a link to the Creative
2023-DIGITAL-EMERGING-01-CNECT project 2D-PRINTABLE (GA- Commons licence, and indicate if you modified the licensed material. You
101135196). We have also received support from the Science Foundation do not have permission under this licence to share adapted material
Ireland (SFI) funded centre AMBER (SFI/12/RC/2278_P2) and availed of the derived from this article or parts of it. The images or other third party
facilities of the SFI-funded AML and ARL labs. K.S. acknowledges financial material in this article are included in the article’s Creative Commons
support by the Deutsche Forschungsgemeinschaft (DFG) through SY 217/2- licence, unless indicated otherwise in a credit line to the material. If material
1 and CRC-1415 - 417590517 and Professor Xinliang Feng for granting is not included in the article’s Creative Commons licence and your intended
access to his laboratory and instrumentation. use is not permitted by statutory regulation or exceeds the permitted use,
you will need to obtain permission directly from the copyright holder. To
Author contributions view a copy of this licence, visit http://creativecommons.org/licenses/by-
J.M. and T.C. performed electrochemical exfoliation and Raman nc-nd/4.0/.
meausrements, K.S. designed and refined the setup and performed
centrifugation-based size selection and did AFM analysis. O.C. and K.S. © The Author(s) 2025

npj 2D Materials and Applications | (2025)9:2 11