pubs.acs.

org/acsaenm Article

Industrial Graphene Coating of Low-Voltage Copper Wires for

Power Distribution
Neeraj Mishra,*,⊥ Ylea Vlamidis,⊥ Leonardo Martini, Arianna Lanza, Zewdu M. Gebeyehu, Alex Jouvray,
Marco La Sala, Mauro Gemmi, Vaidotas Mišeikis, Matthew Perry, Kenneth B. K. Teo, Stiven Forti,
and Camilla Coletti*
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sı Supporting Information

ABSTRACT: Copper (Cu) is the electrical conductor of choice in many categories

of electrical wiring, with household and building installation being the major market
Downloaded via 36.68.217.12 on December 21, 2023 at 09:54:21 (UTC).

of this metal. This work demonstrates the coating of Cu wires�with diameters

relevant for low-voltage (LV) applications�with graphene. The chemical vapor
deposition (CVD) coating process is rapid, safe, scalable, and industrially
compatible. Graphene-coated Cu wires display good oxidation resistance and
increased electrical conductivity (up to 1% immediately after coating and up to 3%
after 24 months), allowing for wire diameter reduction and thus significant savings
in wire production costs. Combined spectroscopic and diffraction analysis indicates
that the conductivity increase is due to a change in Cu crystallinity induced by the
coating process conditions, while electrical testing of aged wires shows that
graphene plays a major role in maintaining improved electrical performances over
long periods of time. Finally, graphene coating of Cu wires using an ambient-
pressure roll-to-roll (R2R) CVD reactor is demonstrated. This enables the in-line production of graphene-coated metallic wires as
required for industrial scale-up.
KEYWORDS: CVD graphene, copper wires, electrical conductivity, oxidation prevention, in-line coating

1. INTRODUCTION strated that multilayer graphene can be synthesized on

The applicative realm of copper (Cu) is enormous: it is utilized cylindrical conductors by chemical vapor deposition (CVD),13
in indoor and outdoor constructions, tools, machinery, and providing antioxidation protection up to 350 °C and corrosion
portable devices, both for civil and industrial uses. In particular, inhibition in ammonium persulfate solution.18,19 Furthermore,
copper wires are commonly employed in industrial wiring and graphene-coated (Gr-coated) Cu wires with diameter ≅ 0.1 mm
interconnection technology,1 owing to their excellent advan- displayed improved surface heat dissipation, electrical con-
tages of thermal and electrical conductivity, low cost, and good ductivity, and thermal stability up to 450 °C.9,19 However, to
mechanical properties such as ductility. However, copper wires date, no work has demonstrated an industrially compatible
easily oxidize when exposed to air even at room temperature,
approach for this process, i.e., performing graphene coating of
waning their electrical performances with time in low-voltage
(LV) applications and limiting their use in high-power electronic cables complying with the following requirements: (i) process
devices and integrated circuits.2,3 Therefore, nowadays, research gases below the lower explosive limit (LEL), (ii) temperatures
efforts are devoted to develop effective processes and coatings to below 1000 °C, and (iii) ambient pressure. Addressing all of
prevent oxidation and corrosion of Cu wires, thus preserving the these points would pave the way to the in-line CVD Gr coating
electrical properties of the pristine metal over time.4,5 Graphene of metallic wires by an ambient-pressure roll-to-roll (R2R) CVD
represents an interesting candidate material for ultrathin coating system and is the object of our work. Moreover, we address the
of Cu wires, thanks to its extraordinarily high electrical and coating of LV wires, which are expected to generate the highest
thermal conductivity, flexibility, strength, and chemical inert-
ness.6−9 Moreover, graphene’s tight structure is impermeable to
gases and liquids,10,11 exhibiting remarkable performance as a Received: May 15, 2023
protective barrier in comparison to other thin-film materials.12 A Revised: May 18, 2023
number of papers have discussed the potential of graphene as a Accepted: May 19, 2023
multifunctional coating for Cu, hindering oxidation and Published: June 1, 2023
chemical etching13−15 while increasing electrical and thermal
conductivity.16,17 Concerning Cu wires, it has been demon-
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsaenm.3c00249
1937 ACS Appl. Eng. Mater. 2023, 1, 1937−1945
ACS Applied Engineering Materials pubs.acs.org/acsaenm Article

revenue in the copper wire and cable market in the 2021−2030 graphene layers was determined by analyzing the I2D/IG ratio, where I2D
timeframe.20 and IG are the intensities of the 2D and G peaks in the Raman spectrum,
Indeed, this work demonstrates that wires with diameters respectively.23
technologically relevant for LV applications (i.e., 1.37 and 1.74 The surface morphologies of the as-grown and aged wires were
investigated by scanning electron microscopy (SEM, ZEISS Merlin),
mm) can be effectively coated with graphene by a scalable and operating in Inlens Signal mode at 5 kV voltage and 120 pA current.
industrially compatible process: at a temperature below 1000 Additionally, atomic force microscopy (AFM) was performed with a
°C, at ambient pressure, and with rapid growth in a nonexplosive Bruker Dimension Icon in standard tapping mode. Optical microscopy
atmosphere. The Gr-coated wires, characterized by electrical (Zeiss Axioscope7 equipped with Axiocam 208 color) was employed to
measurements and microscopic and spectroscopic techniques, record bright-filed micrographs and assess Cu oxidation.
display higher electrical conductivity and improved esthetics For the X-ray diffraction (XRD) experiments, short wires (2−3 cm
than uncoated wires, allowing for a significant saving in the Cu long segments) were processed with the same parameters described in
market. Aging of Gr-coated wires is investigated, and in-depth Section 2.1, varying only the process time. In particular, analysis was
studies to correlate the electrical performances and the done for samples annealed in Ar for 5, 10, and 30 min and Gr-coated
samples annealed/grown for increasing times. To further investigate the
microstructural changes after the coating are provided. It is
effect of hydrogen on the microstructure of copper, analysis was also
found that the graphene growth process induces an improve- performed on samples annealed in Ar and then processed in H2 flow,
ment in the crystallinity of Cu wires, which is responsible for the employing the same ratio of H2/Ar as in the growth process. XRD
augmented conductivity, and that graphene coating plays a measurements were carried out on a STOE Stadi P diffractometer
major role in maintaining this improved conductivity over time. equipped with Cu Kα1 radiation (λ = 1.5406 Å) and a Ge(111)
Finally, the production of Gr-coated Cu wires with an open-end Johansson monochromator from STOE & Cie. The samples (2−3 cm
R2R pilot CVD system is demonstrated. Implementing in-line long wire segments) were mounted on a goniometer head and optically
graphene coating of metallic wires in an industrial setting is aligned with the diffractometer’s center of rotation and kept under
required. spinning during the measurements. The diffracted intensities as a
function of the scattering angle, 2θ, were acquired in the range 84−127°
by a MYTHEN2 1 K detector from Dectris. The profiles of the
2. MATERIALS AND METHODS Cu(311), (222) and (400) peaks were analyzed individually, by fitting
2.1. Sample Preparation each of them with a pseudo-Voigt function. The dependence of the
peak full- width at half-maximum (FWHM) on the sample treatment
Industrial LV Cu wires were provided by Baldassari Cavi, a
conditions was qualitatively evaluated for each of the three peak families
manufacturer of Cu wires operating in the European market.21 Rigid
and for each of the two wire thicknesses. Due to the bulk nature of the
Cu wires with diameters of 1.37 and 1.74 mm were used, and these are
samples and the peculiar experimental geometry, the position and the
technologically relevant for LV applications, especially in the Northern
intensity of the peaks do not directly provide any crystallographic
Europe. For each wire diameter size, three sets of samples were studied:
information, but the variation of the normalized FWHM with respect to
(i) pristine Cu wires (reference); (ii) Gr-coated Cu wires: annealed at a
the pristine material is indicative of the variation in the crystallite
high temperature (i.e., to increase the Cu grain size and reduce the
strain.24
surface roughness and defect density17) and then subjected to the
graphene growth process; and (iii) only annealed Cu wires (i.e., Electrical resistivity measurements on the Cu samples were
subjected to the same annealing conditions as those used to process performed in the DC configuration using a Keithley 2450 source
wires in point (ii)). meter. In order to minimize measurement errors, we performed all of
To facilitate the industrial translation of the process, the wires were the electrical measurements in a four-probe configuration. Such a
used as-received for all tests carried out (i.e., no additional setting reduces the variation of the contact resistance between the
pretreatment, such as etching or chemical cleaning was done before probe and the measurement clamp due to surface oxidation. Each set of
processing the samples). Copper wires 2.5 m in length were taken from samples were tested by putting the source probe at the end of the wires,
the bundle and arranged in a coil shape, in such a way that the coil could while the sensing probes were put at exactly 2 m apart through a couple
fit inside a 4 in. BM Pro AIXTRON CVD reactor where wire treatment of crocodile clips. The resistance was then measured by applying a
was performed22 (see Figure S1 in the Supporting Information for the constant DC current of 10 mA and measuring the voltage drop between
reactor setup). The coils were bound with thin, flexible copper wires the two sensing tips. Performing measurements in the DC configuration
(diameter 250 μm) to prevent them from unwrapping and thus allows us to neglect the skin effect. All measurement were performed at
touching the inner walls of the reactors during heating and cooling room temperature.” Conductivity was calculated as follows: σ = L R−1
steps. Before the growth process, argon (Ar) gas was flushed to purge A−1, where R is the resistance of the cable, A is its cross-sectional area
the reactor from air. defined by design, and L is the distance between the sensing probes (2
The optimized process was carried out between 900 and 1000 °C m for our measurements).
under an Ar pressure of 750−800 mbar. Details of the temperature Also, additional electrical resistivity measurements were performed
profile and conditions employed in the CVD process are reported in at industrial premises (i.e., Baldassari Cavi) in a commercial setup that
Figure S2. Cu wires subjected only to thermal annealing were placed in allows measurements at controlled temperature, see Figure S3 of the
the reactor and heated at 980 °C for 10 min in a flow of Ar at 2000 sccm. Supporting Information. A 2.5 m long coiled copper wire was kept
In the case of Gr-coated samples, after the initial annealing of 10 min, 2 inside the water maintained at 20 °C and firmly fixed at both ends so
sccm of methane (CH4) were flushed for 5 s in hydrogen (H2) and Ar that there was no bending or loops. A couple of wedge holders were
(20 and 2000 sccm, respectively) at 980 °C to grow graphene. After used as electrical sensors, while the wire holder at the end of the line
either annealing or growth, the samples were cooled down in Ar flow. provided the source current, with the distance between them that could
Processed copper wires were taken out from the reactor once the be precisely tuned. In this way, it was possible to measure the resistivity
temperature reached 120 °C. The process conditions were transferred of pristine and graphene-grafted wires avoiding any variation arising
from the batch reactor to the R2R CVD system. from the copper temperature or contact resistance and reducing the
uncertainty on the wire length. In addition, before the resistivity was
2.2. Sample Characterization measured, a small portion of the wire was cut and measured to check the
Raman spectroscopy was performed to assess the coverage, quality, and possible changes in diameter before and after the process. For the
number of graphene layers. A Renishaw InVia system, equipped with a electrical measurements reported, the average electrical conductivity
473 nm blue laser, a 100× objective, and an 1800 l/mm grating, was was obtained from measuring seven samples of each type. The oxidation
used. Spatially resolved Raman maps were obtained with a 1 μm step experiments were conducted within a climate chamber (Espec SH-262
while irradiating the samples with 22.3 mJ μm−2. The number of Benchtop Temperature and Humidity Chamber) at temperatures

1938 https://doi.org/10.1021/acsaenm.3c00249
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Figure 1. Morphological properties of pristine and Gr-coated Cu cables. Pictures of (a, i) pristine and (e, m) Gr-coated Cu wires arranged in coils.
Optical micrographs of (b, j) pristine and (f, n) Gr-coated Cu wires. SEM micrographs of (c, k) pristine and (g, o) Gr-coated Cu wires. AFM
topography images of (d, l) pristine and (h, p) Gr-coated Cu wires. All data are reported for both 1.37 and 1.74 mm wire diameters.

between 40 and 90 °C, humidity levels between 80 and 100%, and times Figure 1 shows the appearance of the pristine (panels a, i) and
between 20 s and 24 h. Gr-coated (panels e, m) Cu wires, arranged in a coil shape. After
the CVD process, the Gr-coated wires display higher malleability
3. RESULTS AND DISCUSSION and appear shinier and smoother when compared to the pristine
ones. The optical characterization of the wire surface, shown in
3.1. Gr-Coated Cu Wires via Industrially Compatible CVD: Figure 1 (panels b, f, j, n), reveals no evident oxidation signs,
Properties both for the pristine and for the as-processed wires. It can be
Preliminary studies were performed to identify the process further observed that the Gr-coated wires display a smoother
conditions to obtain graphene-coated Cu wires while satisfying and more homogeneous surface compared to the pristine
the following requirements: (i) process gases below the LEL, (ii) counterparts, for both diameters.
temperatures below 1000 °C, and (iii) ambient pressure. A To study in detail the surface morphology, SEM and AFM
summary of such preliminary investigations is reported in the characterizations for all the samples were performed. Figure 1c,d
Supporting Information (SI) (Figures S4 and S5). Notably, and and k, l reports the SEM and AFM micrographs of pristine Cu
different from what is reported in the literature until now, the wires, 1.74 and 1.37 mm diameters, respectively. For both
optimized process shown herein has a volume percentage of diameters, an inhomogeneous surface can be observed, with
explosive gases, which complies with LEL requirements. Indeed, RMS roughness values of 6.5 and 5.6 nm for 1.37 and 1.74 mm
H2 and CH4 used during the process were at 1 and 0.1% (over areas of 1 μm2), respectively. SEM micrographs of the Gr-
concentrations, respectively, and this is significantly below the coated wires display instead a smoother wire surface decorated
LEL (i.e., 4 and 5% for H2 and CH4, respectively). This allows with particles of ∼160 nm size. We verified that the presence of
this process to operate in safe conditions, and this can be easily particles could be avoided by introducing a wire pretreatment
implemented in an industrial setting (see the SI). Optimized step, i.e., Cu electropolishing25 (see Figure S6). AFM micro-
process temperature and pressure were 980 °C and 780 mbar, graphs reveal the presence of atomic terraces, typically observed
respectively. Notably, no wire pretreatment was necessary, after the growth of graphene with good crystallinity and
besides reactor annealing, prior to graphene growth. This is also thickness homogeneity.25−28 The RMS roughness values
relevant as most of the work reported to date requires some form measured from 1 μm2 micrographs for the 1.37 and 1.74 mm
of chemical pretreatment, thus introducing additional complex- wires are ∼3.9 and 4.6 nm, respectively.
ity and significant cost to the implementation of this graphene Raman spectroscopy confirmed the presence of graphene
coating process at industrial premises. Table S1 presents a films on the wires of both diameters. As seen in Figure 2c, sharp
comparison between this work and those present in the G (∼1590 cm−1) and 2D bands (2720 cm−1) could be
literature with respect to sample chemical pretreatment, process visualized. The average I2D/IG ratios over an area of 30 × 30
temperature, and gas LEL. μm2 were found to be ∼0.9 and ∼0.80 for 1.37 and 1.74 mm
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Figure 2. Spectroscopic and electrical properties of Gr-coated Cu wires. Representative Raman 30 × 30 μm2 maps (with relative histograms in the
insets) reporting the (a, d) FWHM (2D) and (b, e) intensity ratio of 2D/G bands for both thicknesses. (c) Representative Raman spectra for 1.37 and
1.74 mm wires. (f) Electrical conductivity improvement of Gr-coated wires with respect to pristine ones. Error bars indicate the standard deviation of
the mean (SDM).

Figure 3. Characterization performed after aging of pristine and Gr-coated Cu wires.(a) Optical image of pristine and Gr-coated wires after 24 months.
Raman spectra taken on different areas (indicated by arrows in the insets) of (b and d) pristine copper wires and (c and e) Gr-coated copper wires, for
both thicknesses after 24 months. (f) Electrical conductivity improvement of 1.37 and 1.74 mm Gr-coated wires with respect to that of pristine wires
from 6 to 24 months of aging.

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Figure 4. (a) Electrical conductivity improvement of annealed and Gr-coated Cu with respect to pristine wires from 6 to 24 months of age. (b) Raman
spectra of annealed Cu taken in different areas of the wire (see the inset) after 24 months of aging in the CuxO range. (c, d) FWHM evolution of (400),
(222), and (311) diffraction peaks for Cu wires that were annealed, Gr-coated, and annealed plus H2-treated; both diameters were considered.

diameters, respectively (Figure 2b,e). Similarly, the average Raman spectroscopy, and electrical measurements was carried
FWHM (2D) values were measured as 65 and 63 cm−1 for 1.37 out. The effect of aging on the chemical properties was
and 1.74 mm diameters, respectively (Figure 2a,d). Combined investigated at different time points, from 6 to 24 months after
analysis of FWHM (2D) and I(2D)/I(G) indicated that the the CVD process.
average number of layers is 2−3.29,30 Furthermore, the as-grown Figure 3a shows a picture of pristine and Gr-coated Cu wires
samples exhibited a negligible D peak (see Figure 2c), indicating after 24 months of aging: color darkening�a clear sign of
a negligible number of defects. No sp2-related bands are oxidation�is very evident in uncoated wires, while the Gr-
observed for pristine and annealed wires in the same coated ones maintain a shiny and new appearance. Figure S8
wavenumber range. confirms a similar trend for both kinds of wires also at
The electrical conductivity of Gr-coated wires measured at intermediate aging times. It is well known that Cu wires tend to
controlled temperature with a commercial system at industrial become darker over time: this is usually thought as an indication
premises is reported in Figure 2f as a percentage variation with of “poor quality” and causes significant sale returns, which
respect to pristine wires. Immediately after growth, Gr-coated negatively affects Cu wire manufacturers and retailers. Graphene
wires displayed average improvements of 0.98% and 0.74% for coating offers a viable solution to this issue, providing an esthetic
1.37 and 1.74 mm wires, respectively. Improvement of this advantage.
magnitude could not be only related to the presence of the Optical microscopy analysis might apparently contradict the
graphene conductive layer since in our geometry the conduction resistance to oxidation of Gr-coated wires since oxidation spots
in graphene represents less than 10−6 the one in the copper, (observed as green areas) can be found on both pristine and Gr-
different from those in Kashani et al.9 and Kang et al.,16 where coated wires (see the insets in Figure 3b−e). However, Raman
the copper cross section is three orders of magnitude smaller. It analysis confirms that Gr-coated wires have a higher oxidation
should be mentioned that already a 0.6% conductivity
resistance. Raman spectra were recorded in the copper oxide
improvement would lead to a wire diameter reduction
(CuxO) range (between 150 and 800 cm−1),14,32,36 on both the
corresponding to a Cu cost reduction of 200€/Ton,31,32 an
green and bright areas (Figure 3b−d, c−e). Remarkable
appealing saving for Cu cable manufacturers. In addition, we
differences can be observed when comparing the uncoated
verified the mechanical resistance of graphene to manual
handling by collecting Raman maps before and after rolling and Gr-coated samples. The pristine wires (Figure 3b,d) display
and unrolling operations of the coated wires. We did not observe a very high intensity of CuxO peaks both in the green and bright
any measurable variation in graphene quality and homogeneity, areas, demonstrating extended oxidation, which involves the
confirming the mechanical stability of the graphene coating (see entire surface of the wire. On the contrary, in the case of Gr-
Figure S7). coated wires (Figure 3c,e) CuxO peaks with a significantly lower
intensity than those found in pristine wires are measured in the
3.2. Aging of Gr-Coated Cu Wires green areas, with the rest of the surface having a negligible CuxO
To assess the performances of aged Cu wires, a complete signal. Indeed, we notice that preferential paths for oxidation
characterization of the samples by means of optical microscopy, upon aging and/or exposure to extreme environmental
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Figure 5. Characterization of Cu wires Gr-coated in an R2R prototype reactor. Representative Raman 25 × 25 μm2 maps (with relative histograms in
the insets) reporting the (a) FWHM(2D) and intensity ratio of (b) 2D/G and (c) D/G bands. (d) Representative Raman spectrum of graphene grown
on 1.74 mm Cu wire. (e) Comparison of FWHM evolution of (400), (222), and (311) diffraction peaks for Cu wires coated with graphene in the lab
and the in-line reactor. (f) Optical image with the SEM micrograph in the inset.

conditions are defective regions such as those found in the increase in electrical conductivity could be induced by
correspondence of grain boundaries,14,18 Cu particles, or other microstructural changes in the Cu wires due to processing
types of defects that can open up percolative paths for conditions rather than from the presence of the thin layer of
contaminants (see Figures S9 and S10). It is to be noted that graphene itself. Indeed, on millimeter-sized wires, it is quite
defective graphene (even 2/3 layer thick) is not effective in unlikely that a thin layer of graphene could have such a
preserving Cu wires from oxidation and might even be remarkable effect on the electrical properties, although such an
counterproductive, owing to galvanic coupling, as previously explanation has been provided for thinner wires.9 In order to
reported in refs.34,35 The electrical properties of the wires at assess the influence of thermal annealing on the electrical
room temperature were also investigated for different aging properties of Cu wires, the electrical conductivity of annealed
times by recording their resistance at 10 mA. The relative wires over time was investigated. Despite exhibiting a shiny
improvement of the electrical conductivity, calculated with appearance (Figure S11) and improved conductivity at t = 0, it
respect to the pristine Cu wires at the same aging stage, is was found that the conductivity improvement over time is lower
reported in Figure 3f. The different electrical behavior for wires than that measured for Gr-coated wires (see Figure 4a). Hence,
with and without graphene coatings over 6 to 24 months is the presence of graphene seems pivotal for maintaining
apparent. After 12 months, a gradual worsening of the electrical augmented electrical performances. Indeed, Raman analyses
properties for the pristine wires was observed, while the (as well as optical imaging) of aged wires indicate that oxidation
resistivity of the Gr-coated Cu wires remained comparable to progresses in annealed cables in a similar fashion to that in
that of the as-grown ones. This result further confirms that the pristine ones (see Figures 3b and 4b). After 24 months, annealed
presence of graphene significantly reduces the deterioration of wires appear significantly darker than the Gr-coated wires, and
Cu properties. Remarkably, after 24 months, relative improve- CuxO peaks are comparable to those measured for pristine wires
ments in conductivity of 3.0 and 3.6% are observed for the 1.37 of the same age (Figure S12). With the aim of further
and 1.74 mm Gr-coated samples, respectively. The waning of investigating qualitative microstructural differences in pristine,
electrical conductivity in the pristine wires is associated to the annealed, and Gr-coated wires, XRD measurements were
oxidation of Cu discussed above.18,33 Furthermore, the graphene performed. The qualitative assessment of the XRD peaks further
coating was found to be effective in preserving the wires from clarifies the role of annealing and graphene growth steps in the
significant oxidation even at high temperatures (up to 90 °C) conductivity of copper. The histograms in Figure 4c,d report the
and humidity levels (up to 100%) (see Figure S9). relative variation (in %) of the FWHM of each peak with respect
to the pristine samples, against the total duration of thermal
3.3. Effect of Wire Annealing and Hydrogen Treatment on treatment (the XRD patterns are shown in the SI, Figure S13).
Wire Microstructure
The annealed wires display narrower FWHM compared to the
From the analyses reported above, it appears that Gr-coated pristine Cu wires, and further FWHM reduction is observed
wires have the following advantages with respect to pristine upon Gr growth. The FWHM is sensitive to the variation in
ones: (i) increased electrical conductivity at time zero and over microstructure (crystallinity, presence of defects, and grain size)
time and (ii) oxidation protection. One can argue that the and stress−strain accumulation in the material.37 During the
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annealing and recovery process, the improved atomic diffusion 4. CONCLUSIONS

at high temperatures enables the release of the stored strain In this work, we report an industrially compatible CVD process
energy of the extruded wires. The decrease of XRD peak to coat with graphene electrical Cu wires with diameters relevant
broadening is suggestive of a decrease of crystallite strain, which to LV applications. The Gr-coated wires display improved
can explain the enhanced conductivity of Cu after annealing. aesthetics and enhanced electrical conductivity with respect to
The growth step implies a remarkable decrease in peak width uncoated (pristine) wires. Specifically, the conductivity is 1%
regardless of the annealing time (see the SI, Figure S14). This higher than that of pristine wires immediately after graphene
observation suggests that the conditions used for graphene coating and 3% higher after 24 months. Structural analyses
coating relieve crystallite strain much more effectively than performed via XRD indicate that the exposure to high
annealing in Ar does. temperatures and the presence of hydrogen during graphene
The aforementioned microstructural observations, as well as growth cause an increase in Cu crystallinity, which is a
the increased malleability and smoothness, confirm that the reasonable explanation for the observed increase in electrical
enhanced conductivity is due to a more radical and deep change conductivity. Combined electrical and chemical character-
in the bulk copper crystallinity occurring during the growth izations show that graphene efficiently acts as a barrier against
treatment rather than to the presence of graphene itself. Since oxidation (even under different environmental conditions),
the growth step employs a mixture of H2/CH4, the effect of which is beneficial to preserve the augmented conductivity in
hydrogen on the microstructure of copper was investigated, time. The reported increase in electrical conductivity potentially
analyzing samples annealed in Ar and then processed in H2 flow. allows for a reduction in wire diameter with consequent savings
The details of the samples and process conditions are reported in in wire production costs. Building on such promising premises,
Table S2 of the SI. As demonstrated by the histograms reported we demonstrate that the developed process can be adopted in a
in Figure 4 for a process where the standard annealing was R2R CVD reactor for in-line coating of metallic wires, which
associated with subsequent hydrogen treatment for 5 s (without builds a road towards the realistic translation of the graphene
concomitant graphene growth), the peak widths are comparable coating technology in industrial settings. The extension of such
to those obtained after 5 s growth or possibly even narrower in coating technology also to flexible Cu cables and wires adopted
the case of 1.37 mm wires. in automotive and aerospace industries could lead to a
Additional XRD measurements were performed for different significant decrease in the overall amount of Cu weight, leading
annealing and hydrogen treatment times (see Figure S14 and to lighter vehicles with a lower impact on the environment.
Table S2), which further confirm that high-temperature H2
treatment positively affects Cu crystallinity.38 In conclusion, we
can identify the hydrogen gas present in the CVD process during
■
*
ASSOCIATED CONTENT
sı Supporting Information
graphene growth as the main player in the improvement of Cu
crystallinity and the consequent enhanced electrical properties; The Supporting Information is available free of charge at
however, the structural, chemical, and electrical measurements https://pubs.acs.org/doi/10.1021/acsaenm.3c00249.
performed for the different wires indicate that graphene is Experimental and measurement setups, including photo-
necessary for maintaining enhanced electrical properties over graphs of the experimental setup and Cu wires, tables,
time. optical images, XRD patterns, SEM images, and Raman
3.4. Gr-Coated Cu Wires with an Ambient-Pressure R2R CVD analysis results (PDF)
Reactor
The results above show that graphene coating of Cu wires is
instrumental to obtaining combined improved electrical
conductivity over time and oxidation resistance. This makes
■ AUTHOR INFORMATION
Corresponding Authors
graphene an appealing coating for LV Cu wires, while graphene Neeraj Mishra − Center for Nanotechnology Innovation@
coating of metals might be of interest also for other applications NEST, Istituto Italiano di Tecnologia, 56126 Pisa, Italy;
spanning from nautical, electrical vehicles to aerospace.39−42 Graphene Labs, Istituto Italiano di Tecnologia, 16163 Genova,
However, the scalable coating of metallic wires with graphene Italy; orcid.org/0000-0002-7740-9168;
can be enabled only by the development of an ambient-pressure Email: neeraj.mishra@iit.it
R2R CVD reactor. In this work, the properties of Gr-coated Cu Camilla Coletti − Center for Nanotechnology Innovation@
wires obtained with such an R2R CVD reactor developed by NEST, Istituto Italiano di Tecnologia, 56126 Pisa, Italy;
AIXTRON Ltd. are presented. Using this in-line R2R CVD Graphene Labs, Istituto Italiano di Tecnologia, 16163 Genova,
system, graphene was grown successfully onto a 1.74 mm Cu Italy; orcid.org/0000-0002-8134-7633;
wire, and the relevant characterizations are reported in Figure 5. Email: camilla.coletti@iit.it
Raman spectroscopy indicates a uniform few-layer graphene
film. The FWHM (2D) averages at ∼68 cm−1, the 2D/G Authors
intensity ratio is found to be ∼0.64. and the D/G intensity ratio Ylea Vlamidis − Center for Nanotechnology Innovation@
is ∼0.33 (see Figure 5a−c). XRD measurements reveal an NEST, Istituto Italiano di Tecnologia, 56126 Pisa, Italy;
increased Cu crystallinity, comparable to that of Gr-coated wires Graphene Labs, Istituto Italiano di Tecnologia, 16163 Genova,
processed in a batch reactor (see Figures 4d and 5e). Optical and Italy
SEM characterizations confirm the presence of a uniform Leonardo Martini − Center for Nanotechnology Innovation@
coating across the surface (Figure 5f). These results indicate that NEST, Istituto Italiano di Tecnologia, 56126 Pisa, Italy;
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■ ACKNOWLEDGMENTS
The research leading to these results has received funding from
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