Materials Research Bulletin 65 (2015) 68–72

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Formation of conductive copper lines by femtosecond laser irradiation

of copper nitride film on plastic substrates
Xiaodong Xu b , Ningyi Yuan a,b,c, * , Jianhua Qiu a,b,c , Jianning Ding a,b,c, **
a
Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu, China
b
Center for Low-Dimensional Materials, Micro-Nano Devices and Systems, Changzhou University, Changzhou 213164, Jiangsu, China
c
Jiangsu Key Laboratory for Solar Cell Materials and Technology, Changzhou University, Changzhou 213164, Jiangsu, China

A R T I C L E I N F O A B S T R A C T

Article history: In this paper, we report a simple method to form conductive copper lines by scanning a single-beam
Received 21 April 2014 femtosecond pulse laser on a plastic substrate covered with copper nitride (Cu3N) film. The Cu3N films
Received in revised form 29 October 2014 were prepared by DC magnetron sputtering in the presence of an Ar + N2 atmosphere at 100  C. The
Accepted 8 January 2015
influence of the laser power and scanning speed on the formed copper line width, surface features, and
Available online 9 January 2015
morphology was analyzed by means of optical microscopy, X-ray diffraction, non-contact 3D
profilometer, and scanning electron microscopy. The experimental results demonstrate that low laser
Keywords:
power and low scanning speed favor the formation of uniform and flat Cu lines. After process
Conductive copper lines
Copper nitride
optimization, copper lines with a width less than 5 mm were obtained, which provides an attractive
Femtosecond laser application prospect in the field of flexible electronic devices.
Plastic substrate ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction experimental band gap of 1.2–1.9 eV [7–9], is a fascinating nontoxic

Since they are disposable and low cost, flexible electronics are
highly desirable to achieve cheap and environmentally friendly
thin-film devices [1,2]. Hence, there is an ever-growing demand for
forming metal interconnections on flexible substrates, such as
plastic. The conventional and widely used techniques to fabricate
metal interconnections, consisting of complex, multistage
photolithography processes or photochemical etching and silk
(or stencil) printing, are not suitable for flexible devices. Moreover,
as devices are miniaturized, the metal interconnections have
become smaller. Due to their extremely high peak power and
minimal thermal effects, femtosecond lasers can realize precise
material processing in micro- and nanofabrication [3–5]. It has
been demonstrated that femtosecond laser irradiation processing
results in little collateral damage and a minimal heat-affected
zone.
The copper nitride (Cu3N) thin film, an indirect-bandgap
semiconductor material, with high resistivity [6] and an
and stable material at room temperature in air [10]. Furthermore,
Cu3N readily decomposes into metallic copper and nitrogen at a
slightly elevated temperature (about 100–470  C) [6,11–13]. The
facile decomposition of Cu3N, induced by heating or irradiation by
light, electrons, or ions, brings about a remarkable change in its
electrical resistivity. There are some reports about the direct
writing of a microscopic Cu dot array on a Cu3N film by electron
beam or nanosecond laser irradiation [14–16].
It is possible to form conductive copper lines from copper
nitride on plastic substrates by irradiation by a femtosecond laser,
thus benefiting from both the low temperature decomposition
characteristics of copper nitride and the minimal heat affected
zone of the femtosecond pulse laser. In this paper, we investigate
the influence of the laser power and scanning speed on the width
of the formed copper line, its surface features, morphology, and
sheet resistance.
2. Materials and methods

200-nm thick Cu3N films were grown on plastic substrates by

* Corresponding author at: Changzhou University, Jiangsu Collaborative Innova-
tion Center of Photovolatic Science and Engineering, 1 Ge Hu Road, Changzhou,
Jiangsu 213164, China. Tel.: +86 5198645008.
** Corresponding author at: Center for Low-Dimensional Materials, Micro-Nano
Devices and Systems, Changzhou University, Changzhou 213164, Jiangsu, China.
Tel.: +86 5198633008.
E-mail addresses: nyyuan@cczu.edu.cn (N. Yuan), dingjn@cczu.edu.cn (J. Ding).
DC magnetron sputtering using a copper target. The sputter
chamber system was pumped with a diffusion mechanical and
rotary pump combination to 2  10 4 Pa. The distance between the
substrates and the target was fixed to 60 mm. During the reactive
sputtering growth, the DC power was tuned to 50 W, the substrate
temperature was 100  C, and the working pressure was maintained

http://dx.doi.org/10.1016/j.materresbull.2015.01.029
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
 X. Xu et al. / Materials Research Bulletin 65 (2015) 68–72
at 1 Pa with a sputtering gas mixture of argon (99.999% purity) and
nitrogen (99.999% purity) (N2:Ar = 1:1).
An amplified Ti:sapphire femtosecond laser system was
employed to provide laser pulses with pulse width 35 fs and
central wavelength 800 nm. The laser pulse had a Gaussian spatial
profile and its repetition frequency was 1 kHz. The experiments
were carried out in air at room temperature (20–23  C). A very
simple experimental setup was used as shown in the schematic
diagram of Fig. 1. The incident laser irradiated the Cu3N films
through a laser collimator, a diaphragm, and a tightly focused lens.
The femtosecond laser beam was focused with a lens (f = 25 mm) in
the direction normal to the sample surfaces as depicted in Fig. 1.
The samples were put on a high-precision computer-controlled
three-dimensional electrical translational stage and positioned
near the focus plane. The scanning lines were formed by
translating the samples relative to the stationary laser beam along
the horizontal direction followed by a vertical shift. The incident
laser power was adjusted by a circular adjustable attenuator within
the range 0.5–10 mW. The scanning speed was in the range 0.05–
0.6 mm/s.
The thicknesses of the deposited Cu3N films were measured by
a profilometer (DEKTAKII). The phase composition and crystalline
structure of the samples, as deposited and after laser irradiation,
were verified by X-ray diffraction (Cu Ka radiation). The surface
morphologies were observed using an optical microscope
(BX51TRF, Olympus, Japan), a non-contact 3D profilometer
(Contour GT, Bruker, Germany), and a field-emission scanning
electron microscope (FE-SEM, Hitachi, Japan). The sheet resistan-
ces of the copper lines were measured with a Keithley 2400. Two
Ag electrodes were made on the edges of the copper lines, and the
gold-plated probes were positioned on the Ag electrodes.
3. Results and discussion
To accomplish the direct laser writing of Cu lines on the plastic
substrate, we first investigated the effect of scanning laser power
on the plastic substrate. It was found that when the scanning laser
power was lower than 8 mW, even at a scanning speed as low as
0.05 mm/s, there were no marked changes on the plastic substrate.
Therefore, in the following experiments, the laser powers were set
in the range of 0.5–8 mW and the scanning speed was set in the
range of 0.05–0.6 mm/s.
To investigate the influence of the scanning speed on the
formed Cu line width, resistance, surface features, and micromor-
phology, we used a femtosecond pulse laser with a power of
3.5 mW to scan the Cu3N film deposited on the plastic substrate.
The optical microscope (OM) picture of the sample after laser
scanning (presented in Fig. 2a) indicates that the colors of the Cu
lines after laser scanning changes from yellow variegated with dark
brown to uniform purple bronze when the laser scanning speed is
decreased from 0.6 to 0.05 mm/s. The obtained copper line surfaces
[(Fig._1)TD$IG]
Fig. 1. Schematic diagram of laser experimental setup.
69
were also observed on a 3D non-contact profilometer, as shown by
the images in Fig. 2b. It is clearly seen that the copper lines stand
out from the Cu3N film. With increasing laser power, the average
height difference between the Cu line surface and Cu3N film
surface at first increased, and then tended to maintain a stable
value. Meanwhile, the microstructures of the Cu lines became
loose and the surface rough, as shown in Fig. 2b. The line width
increased from 8.3 to 24.8 mm as shown in Fig. 2c. To investigate
the surface morphology further, field-emission scanning electron
microscope (FESEM) images were also obtained (Fig. 2a). The
deposited Cu3N film without laser irradiation (marked with a black
box 1 in Fig. 2a) has a smooth and compact surface, made up of
small grain sizes. The FESEM image of the central zone (shown as
the white box 2 in Fig. 2a) of the irradiated Cu line, which looks like
a single strand beaded with tiny nodules, presents a network
structure with obvious ablation of some parts of the deposited film.
On the other hand, a porous surface morphology is exhibited at the
edge of the line (marked with a white circle box 3 in Fig. 2a). When
the scanning speed is lower, the Cu lines (marked as a black box 4 in
Fig. 2a) become wider. However, the surfaces were flat, with tiny
and dispersed holes, as shown in the microstructure picture.
Fig. 3a shows the X-ray diffraction (XRD) results of the
deposited Cu3N film and the Cu lines after laser scanning
irradiation. It can be seen that the deposited Cu3N film on the
plastic substrate is a polycrystalline film, which belongs to the
cubic-ReO3 structure of Cu3N with a strongly preferred [111]
orientation. No other impurity phase peaks are detected. After
laser scanning, both Cu (111) and Cu (2 0 0) peaks are found. This
result suggests that laser scanning with a power of 0.35 mW can
induce a complete decomposition of the Cu3N film. Fig. 3b shows
how the sheet resistance of the Cu lines depends on scanning
speed. It indicates a sheet resistance decrease from 69.2 to 2.1 V
with a scanning speed decrease from 0.6 to 0.05 mm/s.
Fig. 4a depicts the formation process of Cu lines by femtosecond
laser scanning for different scanning speeds. When the laser power
is 3.5 mW with a 1 kHz repetition rate of the laser pulse, the
average energy per pulse is 3.5 mJ. The spatial profile of the
femtosecond laser beam is nearly Gaussian. From the microstruc-
ture, XRD, and resistance measurements of the irradiated copper
lines, it can be concluded that the decomposition energy of Cu3N
into Cu and N2 is very low. The ablation energy of Cu3N is also low.
Considering the first laser pulse that irradiates the Cu3N film, we
speculate that due to the relative high energy density in the center
of laser spot, not only does the Cu3N decompose there, but the
Cu3N film also ablates at the same time, which results in a rough
surface. However, at the boundary of the laser spot, the energy
density is lower and the ablation of Cu3N is not obvious, which
leads to a relatively flat surface. When the scanning speed is high,
the second laser spot will hit the deposited film a small distance
away from the first spot, which means that the second pulse laser-
spot center hits a zone that was not decomposed by the first laser
pulse. The second pulse will hence leave a ring with an inner rough
circle and outer flat ring. This repeated process will form a string of
beads with darker color in the middle and lighter outside. When
the scanning speed is decreased, the second laser-spot center will
hit a region that already is decomposed from Cu3N to Cu. Since the
ablation pulse energy for Cu is much larger than the used laser
energy, ablation will not happen. This phenomenon is confirmed
by the experiment results shown in Fig. 4b. The copper lines L1 and
L2 were formed first by the laser scanning on the Cu3N film, then
L3 and L4 were followed. The figure reveals that there is almost no
change in the Cu layers for repeated laser scanning with a power
less than 8 mW and scanning speed in the range of 0.05–0.6 mm/s.
Moreover, when the scanning speed is decreased, the pulse laser
boundary will cover, one by one, some zone that was not
decomposed completely after the irradiation of the prior pulse,
70 X. Xu et al. / Materials Research Bulletin 65 (2015) 68–72
[(Fig._2)TD$IG]

Fig. 2. (a) The OM picture and FESEM images, (b) 3D non-contact profilometer, (c) the dependence of lines width on scanning speed of the sample after laser scanning. (For
interpretation of the references to color in the text, the reader is referred to the web version of this article.)

but will now further decompose. The number of pulses hitting a
particular area will increase with decreasing scanning speed,
which will increase the Cu line width. In other words, once the
second laser spot center is located in the decomposed zones, hence
containing Cu rather than Cu3N, it will not ablate Cu, and uniform
Cu lines will be formed.
The OM picture of the sample after laser scanning with power
increase from 0.5 to 8 mW at a scanning speed 0.2 mm/s is
presented in Fig. 5a. The colors of the irradiated lines also changed
from uniform purple bronze to yellow variegated with dark brown.
Meanwhile, the line width increased from 11.0 to 30.2 mm as
shown in Fig. 5b. The obtained copper line surfaces were observed

[(Fig._3)TD$IG]

Fig. 3. (a) XRD results of the as-deposited Cu3N film and the Cu lines after laser scanning, (b) the dependence of sheet resistance of Cu lines on scanning speed.
 X. Xu et al. / Materials Research Bulletin 65 (2015) 68–72 71
[(Fig._4)TD$IG]

Fig. 4. (a) The formation process of Cu lines from Cu3N by femtosecond laser scanning with different scanning speed, (b) the repeating laser scanning with a power of 8 mW
and scanning speed of 0.05 mm/s.

in a 3D non-contact profilometer, as shown by the images in Fig. 6c.
From Fig. 6c, it can be clearly seen that the copper lines stand out
from the Cu3N film. With the increase of laser power, the average
difference between the Cu line surface and Cu3N film surface first
increased and the microstructures became loose, then the average
difference maintained a stable value. However, the line surfaces
largely became rough, as shown in Fig. 5d.
[(Fig._5)TD$IG]
Fig. 6a depicts the formation process of Cu lines from Cu3N by
femtosecond laser scanning with different laser powers. Since the
Cu3N films were irradiated by a laser beam with a Gaussian
intensity distribution, when the laser power is low, the laser power
density in the center of the laser spot can decompose Cu3N to Cu,
while the laser power density in the light spot boundary region is
too small to decompose Cu3N. Under this condition, the formed Cu

Fig. 5. (a) The OM pictures (b) thedependence of lines width on scanning speed, (c) 3D non-contact profilometer, (d) the average difference between the Cu line surface and
Cu3N film surface. (For interpretation of the references to color in the text, the reader is referred to the web version of this article.)
 72 X. Xu et al. / Materials Research Bulletin 65 (2015) 68–72
[(Fig._6)TD$IG]
Fig. 6. (a) The formation process of Cu lines from Cu3N by femtosecond laser scanning with different laser powers, (b) the back to the font pattern constituted from copper
liners with a width of 4.78 mm.
line has a small width and a uniform color. When the laser power
increases, the light spot boundary region without enough energy to
decompose Cu3N becomes smaller, which results in a trend of thick
Cu lines. When the power continues to increase, the width of the
formed Cu line is the same as the size of the laser spot. Meanwhile,
in the middle of the line, the film will be seriously ablated and
the color is very dark. This means that the energy in the center of
the laser spot is enough to ablate the deposited layers. The rougher
the surface is the smaller the reflectivity is. The above experimen-
tal results demonstrate that low laser power and low scanning
speed favor the formation of uniform and flat Cu lines. Fig. 6b gives
the back to front pattern constituting of copper lines with a width
of 4.78 mm, obtained at a laser power of 0.5 mW and a scanning
speed of 0.1 mm/s.
4. Conclusion
In this paper, we demonstrated the formation of conductive
copper lines by scanning single-beam femtosecond laser pulses on
copper nitride deposited on plastic substrates. With increasing
scanning speed, the line width became thinner, while the surface
became rougher and the resistance larger. When the laser power
increased, the line width became thicker, while the surface became
rougher and the resistance larger. After a process optimization,
copper lines with a width less than 5 mm were obtained at a very
low laser power of 0.5 mW, which provides an attractive
application prospect in the field of flexible electronic devices,
since it provides a noncontact procedure requiring no sacrificial
resistance or lift-off layers. In the future work, we will change the
light path to form copper lines with submicron widths.
Acknowledgments
This work was supported by The National Natural Science
Foundation of China (51272033), Jiangsu “333” Project 223
(201041). The Privileged Development Program of Jiangsu High
Education on New Energy Material Science and Engineering,
Jiangsu Early Phase Key Laboratory for Photovolatic Engineering
and Science.
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