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Enhanced Electrical Properties of Copper Nitride Films Deposited Via High Power Impulse Magnetron Sputtering

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nanomaterials

Article
Enhanced Electrical Properties of Copper Nitride Films
Deposited via High Power Impulse Magnetron Sputtering
Yin-Hung Chen 1,2 , Pei-Ing Lee 1 , Shikha Sakalley 2,3 , Chao-Kuang Wen 1,2 , Wei-Chun Cheng 3 , Hui Sun 4, *
and Sheng-Chi Chen 2,5, *

1 Institute of Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan
2 Department of Materials Engineering and Center for Plasma and Thin Film Technologies,
Ming Chi University of Technology, New Taipei City 243, Taiwan
3 Department of Mechanical Engineering, National Taiwan University of Science and Technology,
Taipei 106, Taiwan
4 School of Space Science and Physics, Shandong University, Weihai 264209, China
5 College of Engineering and Center for Green Technology, Chang Gung University, Taoyuan 333, Taiwan
* Correspondence: huisun@sdu.edu.cn (H.S.); chensc@mail.mcut.edu.tw (S.-C.C.)

Abstract: High Power Impulse Magnetron Sputtering (HiPIMS) has generated a great deal of interest
by offering significant advantages such as high target ionization rate, high plasma density, and the
smooth surface of the sputtered films. This study discusses the deposition of copper nitride thin
films via HiPIMS at different deposition pressures and then examines the impact of the deposition
pressure on the structural and electrical properties of Cu3 N films. At low deposition pressure, Cu-rich
Cu3 N films were obtained, which results in the n-type semiconductor behavior of the films. When
the deposition pressure is increased to above 15 mtorr, Cu3 N phase forms, leading to a change in
the conductivity type of the film from n-type to p-type. According to our analysis, the Cu3 N film
deposited at 15 mtorr shows p-type conduction with the lowest resistivity of 0.024 Ω·cm and the
Citation: Chen, Y.-H.; Lee, P.-I.;
Sakalley, S.; Wen, C.-K.; Cheng, W.-C.;
highest carrier concentration of 1.43 × 1020 cm−3 . Furthermore, compared to the properties of Cu3 N
Sun, H.; Chen, S.-C. Enhanced films deposited via conventional direct current magnetron sputtering (DCMS), the films deposited via
Electrical Properties of Copper HiPIMS show better conductivity due to the higher ionization rate of HiPIMS. These results enhance
Nitride Films Deposited via High the potential of Cu3 N films’ use in smart futuristic devices such as photodetection, photovoltaic
Power Impulse Magnetron absorbers, lithium-ion batteries, etc.
Sputtering. Nanomaterials 2022, 12,
2814. https://doi.org/10.3390/ Keywords: copper nitride (Cu3 N) thin films; High Power Impulse Magnetron Sputtering (HiPIMS);
nano12162814 peak power density; deposition pressure; conductivity type
Academic Editor: Dong-Joo Kim

Received: 5 July 2022


Accepted: 12 August 2022
1. Introduction
Published: 16 August 2022
Transition metal nitrides (TMNs) have been proved to be significant materials with
Publisher’s Note: MDPI stays neutral a myriad of uses that hugely impact our daily lives. TMNs are highly advantageous in
with regard to jurisdictional claims in that they offer good hardness [1] and high temperature stability [2], resulting in them
published maps and institutional affil- being highly recommended as a coating to protect mechanical tools [3]. Interestingly,
iations.
many of these materials possess rock–salt structures [4], due to which they can either
be metallic (like TiN [5]) or semiconductors (like ScN [6], YN [7] etc.). Among various
TMNs with semiconductor properties, researchers in a quest for new kinds of materials
possessing remarkable optoelectronic performance have put their key focus on Copper
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
Nitride (Cu3 N). Cu3 N in crystalline form has an unambiguous cubic anti-ReO3 structure
This article is an open access article
(a = 0.38 nm and α = β = γ = 90◦ ) [8]. Optical band gap is temperature-dependent, lying
distributed under the terms and within the range of 1.2 eV and 1.9 eV [9], and presenting less reflectivity [10] and high
conditions of the Creative Commons transparency in the IR region [11]. At room temperature, Cu3 N with a lattice constant
Attribution (CC BY) license (https:// lower than 38 Å possesses huge electrical resistivity [10]. Thanks to abundant resource
creativecommons.org/licenses/by/ availability, cheap manufacturing costs, non-toxicity, low deposition temperature and also
4.0/). being highly adaptable to several substrates [12,13], Cu3 N can be applied in numerous

Nanomaterials 2022, 12, 2814. https://doi.org/10.3390/nano12162814 https://www.mdpi.com/journal/nanomaterials


Nanomaterials 2022, 12, 2814 2 of 11

fields such as photodetectors [14], optical storage memory [15], integrated circuits [16],
tunnel junctions [17], resistive random-access memory [18], solar energy conversion [19],
photovoltaic absorber [20], diode rectifier [21], lithium-ion batteries [22], etc.
Recently, most of the attention has been focused on the formation of copper nitride
films due to potential application in numerous fields. Fabrication of Cu3 N using different
techniques results in their physical properties being able to be controlled through cer-
tain manipulations of the parameters during the fabrication process. Thus far, several
traditional techniques for the preparation of Cu3 N have been studied in depth, including
thermal oxidation [23], chemical vapor deposition [24], electrochemical lithium tuning [25],
pulsed laser deposition [16], reactive RF sputtering [26], plasma-assisted molecular beam
epitaxy [27], and DC magnetron sputtering [28]. Among these processes, magnetron sput-
tering has emerged as the most suitable process due to its tremendous uniformity across
the deposited area, high reproducibility, rapid deposition, and decent controllability of the
chemical composition [29]. However, its average degree of ionization of metallic vapor
is lower than 10% [30]; in which the condition of the existing sputtered species are often
neutral particles. With great advancement over the conventional magnetron sputtering
technique, high power impulse magnetron sputtering (HiPIMS) technology has generated
enormous interest recently as a result of the higher degree of plasma density as well as
the ionization rate of the target installed. Additionally, HiPIMS provides high voltage and
current during the deposition process and promotes a fast deposition rate. It can also be
operated at low pressure and offers high sputtering rates, even during low duty cycle. Due
to high incident target atomic energy, it increases the hardness and improves the material’s
electrical properties, smoothness, and density with excellent adhesion [31–35]. According
to our study, the ionization rate of Cu flux during deposition can achieve up to 70% in the
HiPIMS process, which is significantly superior to that of the more common DC magnetron
sputtering [36]. Although HiPIMS has many advantages in the synthesis of functional
materials, few studies have concentrated on the formation of p-type nitride films using this
technology. Besides this, sputtering atmosphere has also been confirmed as being critical
on the film’s performance. Wang et al. [37] prepared Cu3 N films while varying the nitrogen
gas at different sputtering pressure and concluded that the bandgap of the films varies
dependent upon the nitrogen gas pressure. In another study, Pierson [38] deposited Cu3 N
films using RF magnetron sputtering with Ar/N2 reactive mixtures, and the results show
an increase in the lattice constant and the electrical resistivity of the film with the increased
nitrogen flow rate in the chamber.
In this work, Cu3 N thin films were deposited via HiPIMS technology at different
deposition pressures while peak power density and the mixture of argon and nitrogen
reactive gas remained constant. The impact of the deposition pressure on the optoelectronic
properties of Cu3 N thin films was then investigated. In our previous study [21] we used
DCMS technology and changed the working pressures, and the results showed that an
increase in substitution of Cu2+ ions for Cu+ ions will lead to the creation of Cu+ vacancies
causing a transition in the conductivity type of the film from n-type to p-type. As HiPIMS
has a higher ionization rate, it can generate more Cu2+ ions, resulting in the higher substi-
tution of Cu2+ ions by replacing Cu+ ions. Moreover, upon increasing deposition pressure,
more argon ions bombard the Cu target, which can sputter more Cu ions or atoms, so
the probability of obtaining Cu2+ and Cu+ ionization states is high. It also enhances the
transmittance of the film, whereas the reflection degrades. This is primarily due to the
disappearance of the Cu-rich phase. Finally, the properties of the Cu3 N thin films prepared
via HiPIMS were compared to those of films deposited via conventional DCMS.

2. Materials and Methods


Cu3 N thin films were deposited through high power impulse magnetron sputtering
(HiPIMS) with a thickness of 100 nm on Corning Eagle XG glass and silicon substrates at
room temperature. The substrates were 6.95 mm × 6.95 mm in size, whereas the diameter
and the thickness of pure Cu metallic target are 50.8 mm and 6 mm. A constant power of
Nanomaterials 2022, 12, 2814 3 of 11

0.3 kW was supplied to the Cu target by SPIK 2000A pulse supply (Shen Chang Electric
Co., New Taipei City, Taiwan). The base pressure of the chamber was maintained below
6.7 × 10−4 Pa prior to the deposition. The reactive gas mixture flow rate of argon and
nitrogen was 30 sccm, totally. During the deposition of Cu3 N thin films, the nitrogen flow
ratio [N2 /(Ar + N2 )] of 60% was kept constant, while the deposition pressure was varied
from 5 to 25 mtorr. Meanwhile, the pulse on-time (ton ) was maintained as a constant of
50 µs and the pulse off-time (toff ) was varied between 1050~1200 µs to obtain a peak power
density of about 1000 W/cm2 (i.e., instantaneous voltage × instantaneous current/target
area). The duty cycle can be calculated as ton /(ton + toff ).
A surface profilometer (Kosaka Surfcorder ET200, Tokyo, Japan) was employed to mea-
sure the thickness of the Cu3 N thin films on glass. An X-ray diffractometer (XRD, Malvern
PANalytical Empyrean, Malvern, UK) with Grazing Incidence X-ray Diffraction (GIXRD)
using the Cu Kα radiation (the wavelength is 1.5406 Å) was used for the identification of the
phase structure. Films’ compositions were analyzed using a JEOL JXA-8200 (Tokyo, Japan)
electron probe X-ray microanalyzer (EPMA). X-ray photoelectron spectroscopy (XPS) using
a Model Sigma Probe manufactured by Thermo VG Scientific Company (Waltham, MA,
USA) was used to analyze the chemical states of the films. The films’ surface roughness was
measured by atomic force microscope (AFM, Bruker Dimension Edge, Billerica, MA, USA).
The microstructures of the films were investigated by high-resolution transmission electron
microscopy (HR-TEM, JEOL JEM-2100). Hall effect analysis (AHM-800B, Agilent Tech-
nologies, Santa Clare, CA, USA) was employed for the films’ electrical properties. Finally,
the films’ transmittance was measured by ultraviolet-visible (UV-Vis) spectrophotometer
(Jasco-V-770, Tokyo, Japan).

3. Results
The instantaneous voltage and instantaneous current at varied deposition pressures
were measured during the deposition process, as shown in Figure 1. The peak power den-
sity is numerically defined as the ratio of peak power to that of the target area. The value of
peak power density at different deposition pressures remained above 1 kW/cm2 . The instan-
taneous voltages and currents measured during the DCMS process are shown in Figure S1.
Nanomaterials 2022, 12, x FOR PEER REVIEW
The peak power density value is very different between DCMS (~0.015 kW/cm24) of 12
and
2
HiPIMS (~1 kW/cm ), which reveals that HiPIMS has a higher ionization rate than DCMS.

1. The
Figure 1.
Figure Theinstantaneous
instantaneousvoltage
voltageand current
and during
current duringthethe
HiPIMS deposition
HiPIMS process
deposition withwith
process different
dif-
deposition
ferent pressure
deposition (a) 5 mtorr,
pressure (a) 5(b) 10 mtorr,
mtorr, (b) 10(c)mtorr,
15 mtorr,
(c) (d) 20 mtorr,
15 mtorr, (d)and (e) 25 mtorr
20 mtorr, are25
and (e) represented
mtorr are
represented
by CH1 and by CH1
CH2, and CH2, respectively.
respectively.

The composition of Cu3N thin films produced via HiPIMS on silicon substrates at
various deposition pressures is shown in Figure 2. Cu content reduces with increasing
deposition pressure, while N content rises in the films. When the deposition pressure
rises from 5 mtorr to 15 mtorr, Cu and N content suddenly changes. This is due to the fact
Figure 1. The instantaneous voltage and current during the HiPIMS deposition process with dif-
Nanomaterials 2022, 12, 2814 ferent deposition pressure (a) 5 mtorr, (b) 10 mtorr, (c) 15 mtorr, (d) 20 mtorr, and (e) 25 mtorr4 are
of 11
represented by CH1 and CH2, respectively.

The composition of Cu3N thin films produced via HiPIMS on silicon substrates at
The composition of Cu N thin films produced via HiPIMS on silicon substrates at
various deposition pressures 3is shown in Figure 2. Cu content reduces with increasing
various deposition pressures is shown in Figure 2. Cu content reduces with increasing
deposition pressure, while N content rises in the films. When the deposition pressure
deposition pressure, while N content rises in the films. When the deposition pressure rises
rises from 5 mtorr to 15 mtorr, Cu and N content suddenly changes. This is due to the fact
from 5 mtorr to 15 mtorr, Cu and N content suddenly changes. This is due to the fact that
that when the deposition pressure initially increases, more nitrogen molecules or atoms
when the deposition pressure initially increases, more nitrogen molecules or atoms in the
in the chamber react with copper atoms (ions), therefore the N content in the thin film
chamber react with copper atoms (ions), therefore the N content in the thin film increases.
increases. As the deposition
As the deposition pressure pressure
exceeds 15 exceeds
mtorr,15the
mtorr, the variation
variation in N
in Cu and Cucontent
and N content
tends to
tends to moderate. Presumably, the composition of Cu 3N film has reached saturation.
moderate. Presumably, the composition of Cu3 N film has reached saturation. Likewise, the
Likewise,
deposition therate
deposition
of the Curate of the Cu3N thin film linearly declines with the increase in
3 N thin film linearly declines with the increase in the deposition
the
pressure. That is mainly due tomainly
deposition pressure. That is the factdue
thattoas
the fact
the that asof
amount the amountand
nitrogen of nitrogen and
argon within
argon within the chamber rises, additional collisions among the particles will
the chamber rises, additional collisions among the particles will shorten their mean free shorten
their
path,mean
whichfree path,the
affects which affects rate
deposition the deposition
[21]. rate [21].

Theanalysis
Figure2.2.The
Figure analysisof
ofthe
the composition
composition and deposition rate
rate of
of Cu
Cu33N
N films
filmsdeposited
depositedvia
viaHiPIMS
HiPIMSat
atdifferent
differentdeposition
depositionpressure.
pressure.

The X-ray diffractograms of Cu3 N thin films (Figure 3) deposited on glass substrates
at different deposition pressures mainly show diffraction peaks of the crystal planes of
(100), (110), (111), (200), (210), and (220). The peaks corresponding to Cu3 N phase are
associated to JCPDS: 86-2283. The two most intense XRD peaks of Cu3 N thin films are (111)
and (100) related to copper and nitrogen content; usually considered as copper-rich and
nitrogen-rich thin films, respectively [14]. Absence of impurity peaks in XRD results (like
Cu) indicates the successful Cu nitration that helps in depositing Cu3 N thin film with a
high degree of purity. A diffraction peak of the Cu3 N thin film deposited at a deposition
pressure of 5 mtorr appears between the Cu (111) peak (JCPDF: 70-3038) and the Cu3 N (111)
peak (JCPDF: 86-2283). With the further increase in the deposition pressure, the diffraction
peak (111) continues to move to lower Bragg angles until the deposition pressure exceeds
15 mtorr, which is completely matched with Cu3 N, implying the development of pure Cu3 N
thin films. Although the (100) diffraction peak that produces the N-rich (100) plane does not
appear as a result of insufficient nitrogen. Furthermore, there is a strong dominance of the
(111) plane over the (100) plane in Cu3 N at 10 mtorr, although in actuality, a small amount
of the Cu3 N (100) plane still exists, which is difficult to analyze by XRD. Additionally, the
Cu3 N (111) peak intensity declines with the rise in the deposition pressure. This may be the
result of the decline in the copper content of the film (as observed in EPMA). It can be seen
from some reports [37,39,40] that when the Cu content decrease, it will make it difficult to
generate a Cu-rich (111) peak, thus resulting in a decrease in the intensity of the (111) peak.
although in actuality, a small amount of the Cu3N (100) plane still exists, which is difficult
to analyze by XRD. Additionally, the Cu3N (111) peak intensity declines with the rise in
the deposition pressure. This may be the result of the decline in the copper content of the
film (as observed in EPMA). It can be seen from some reports [37,39,40] that when the Cu
Nanomaterials 2022, 12, 2814 content decrease, it will make it difficult to generate a Cu-rich (111) peak, thus resulting
5 of 11
in a decrease in the intensity of the (111) peak.

X-ray diffraction
Figure3.3.X-ray
Figure diffraction spectra
spectraofofCuCu
3 N3N
films deposited
films via HiPIMS
deposited at different
via HiPIMS deposition
at different pressure.
deposition
pressure.
The microstructure of the Cu3 N nanocrystal on glass substrates was determined
through HRTEM. The TEM sample was prepared through focused ion beam (FIB) for
The microstructure of the Cu3N nanocrystal on glass substrates was determined
structural analysis. The HRTEM images of the cross-section of Cu3 N thin films deposited
through HRTEM. The TEM sample was prepared through focused ion beam (FIB) for
at different deposition pressure were analyzed using Gatan Digital Micrograph software
structural analysis. The HRTEM images of the cross-section of Cu3N thin films deposited
(Figure 4). After inverse Fourier transformation, the interplanar d-spacing value of the
at different deposition pressure were analyzed using Gatan Digital Micrograph software
Cu3 N thin-film lattice was calculated. Under low deposition pressure (10 mtorr) (Figure 4a),
(Figure 4). After inverse Fourier transformation, the interplanar d-spacing value of the
the film appears partially amorphous, with the d-spacing value as 2.114 ± 0.04 Å of the
Cu3N thin-film lattice was calculated. Under low deposition pressure (10 mtorr) (Figure
(111) plane. As the deposition pressure increased to 15 mtorr and 20 mtorr (Figure 4b,c) the
4a), the film appears partially amorphous, with the d-spacing value as 2.114 ± 0.04 Å of
d-spacing values of the (111) plane rise to 2.254 ± 0.04 Å and 2.255 ± 0.04 Å, respectively.
Nanomaterials 2022, 12, x FOR PEER the
REVIEW 6 of 12
(111)the
Unlike plane.
(111)As the deposition
plane, pressure
the d-spacing increased
of the (100) planetoin15 mtorr
Figure and
4b,c 20 mtorr
have similar(Figure
value as
4b,c)
3.868the± d-spacing
0.04 Å andvalues
3.854 ± of0.04
the Å,
(111) plane rise From
respectively. to 2.254
the±XRD
0.04pattern
Å and 2.255 ± 0.04
(Figure 3), itÅis, clear
re-
spectively. Unlike the (111) plane, the d-spacing of the (100) plane in Figure
to see that when the deposition pressure rises from 10 mtorr to 20 mtorr, the Cu3 N (111) 4b,c have
similar
mtorr, value
the
diffraction Cu as
3N3.868
peak (111) ±diffraction
0.04 Å shifts
progressively and 3.854
peak ± 0.04angle,
Å , respectively.
to progressively
a lower shifts
whichtomeans From
a lower the
angle,
that XRD
which
the lattice pattern
means
constant
(Figure
that 3),
the it is
latticeclear to
constant see that when
gradually the deposition
increases. This pressure
further rises
confirmsfrom
gradually increases. This further confirms that the value of d-spacing increases with 10
that mtorr
the to 20
value of
the
d-spacing increases with
increasing deposition pressure. the increasing deposition pressure.

Figure
Figure4.4.The
TheHR-TEM
HR-TEM images
imagesof of
CuCu
3N films deposited via HiPIMS at deposition pressure of (a)
3 N films deposited via HiPIMS at deposition pressure of
10 mtorr, (b) 15 mtorr and (c) 20 mtorr. (For interpretation of the references to color in this figure’s
(a) 10 mtorr, (b) 15 mtorr and (c) 20 mtorr. (For interpretation of the references to color in this figure’s
legend, the reader is referred to the web version of this article).
legend, the reader is referred to the web version of this article).

The
The surface roughnessofofthe
surface roughness thedeposited
deposited thin
thin filmfilm plays
plays an essential
an essential role
role in in deter-
determining
mining the film’s quality. This characteristic of Cu 3N thin films on glass substrates (over
the film’s quality. This characteristic of Cu3 N thin films on glass substrates (over an area
an
of area
1 µmof×11µµm)
m × 1prepared
µ m) prepared by varying
by varying the deposition
the deposition pressure
pressure was analyzed
was analyzed using
using atomic
atomic force microscopy
force microscopy (AFM, (AFM,
FigureFigure 5). A significant
5). A significant reduction
reduction in thein the surface
surface rough-
roughness of
ness of the Cu N films with the increasing deposition pressure was observed.
the Cu3 N films with the increasing deposition pressure was observed. The value of the
3 The value
of the lowest
lowest surfacesurface roughness
roughness is Ra =is0.78
Ra nm
= 0.78 nm obtained
obtained at 25 This
at 25 mtorr. mtorr. This corroborates
corroborates that the
that the smoothness of the films was improved with the increase in deposition pressure.
When the deposition pressure increases, more Ar + ions strike the copper target resulting
in the high energy of the ion bombardment on the substrate due to the high peak power
density of HiPIMS, which results in a close arrangement of the incident atoms in Cu 3N
Nanomaterials 2022, 12, 2814 6 of 11

smoothness of the films was improved with the increase in deposition pressure. When the
deposition pressure increases, more Ar+ ions strike the copper target resulting in the high
energy of the ion bombardment on the substrate due to the high peak power density of
HiPIMS, which results in a close arrangement of the incident atoms in Cu3 N films. In this
way, the thin film with high deposition pressure achieved a smooth surface. In addition,
the surface quality of the Cu3 N film prepared via DCMS at 15 mtorr was also analyzed
by AFM (as shown Figure S2). Its surface roughness (1 µm × 1 µm) Ra value of about
1.96 nm is higher than the roughness of the film deposited via HiPIMS (with Ra value of
about 1.06 nm) (Figure 5c). During deposition using HiPIMS, the power density is much
higher than that in the DCMS deposition process, as shown in (Figure 1c). As a result, more
kinetic energy can be transferred from the bombarding Ar+ ions to the target atoms, which
have Cu ions combined with nitrogen to the substrate, and result in a high- density
Nanomaterials 2022, 12, x FOR PEER REVIEW 7 offilm
12
with a smooth surface. Therefore, the thin films via DCMS possessing low ionization have
relatively rough surface.

Figure 5. AFM images showing the surface (1 × 1 µm2 ) of Cu3 N films deposited by HiPIMS via
Figure 5. AFM images showing the surface (1 × 1 µ m2) of Cu3N films deposited by HiPIMS via
different deposition pressure (a) 5 mtorr, (b) 10 mtorr, (c) 15 mtorr, (d) 20 mtorr and (e) 25 mtorr.
different deposition pressure (a) 5 mtorr, (b) 10 mtorr, (c) 15 mtorr, (d) 20 mtorr and (e) 25 mtorr.
The optical properties of Cu3 N thin films deposited via HiPIMS on glass substrates
The optical properties of Cu3N thin films deposited via HiPIMS on glass substrates
were analyzed by UV-Vis spectroscopy (Figure 6a,b). The Cu3 N thin films show high
were analyzed by UV-Vis spectroscopy (Figure 6a,b). The Cu3N thin films show high
absorbance in the UV range (300–400 nm). As the wavelength increases, it starts to decrease
absorbance
gradually ininthe thevisible
UV rangerange(300–400
from 400nm).nm toAs700thenm.
wavelength
Beyond the increases, it startsit to
visible region, de-
shows
crease gradually in the visible range from 400 nm to 700 nm. Beyond
a low absorbance in the near IR range (>700 nm). Correspondingly, the Cu3 N thin films the visible region, it
shows a low absorbance in the near IR range (>700 nm). Correspondingly,
show high transmittance in the IR range (700–900 nm), and as the wavelength decreases, the Cu 3N thin

films show
it starts to high transmittance
decline gradually in in the
the visible
IR range (700–900
range fromnm), and to
700 nm as 450
the wavelength
nm wavelength. de-
creases, it starts to decline gradually in the visible range from 700
Below this region, it shows low transmittance in the near UV range (<400 nm). This nm to 450 nm wave-
length.
behavior Below
seemsthistoregion,
be veryit common
shows low in transmittance
the deposited in Cuthe near UV range (<400 nm).
3 N thin films. The deposition
This behavior seems to be very common in the deposited Cu 3N thin films. The deposition
pressure drastically affects both the absorption coefficient and the transmittance of Cu3 N
pressure
films. Whendrastically affects both
the deposition the absorption
pressure changes,coefficient
a significantandvariation
the transmittance of Cu 3N
in the absorption
films. Whenand
coefficient thethedeposition pressure
transmittance withchanges, a significant
the wavelength can bevariation
observed.inUponthe absorption
increasing
coefficient and the transmittance with the wavelength can be observed.
the deposition pressure from 5 mtorr to 15 mtorr, there is an enormous decrease in the Upon increasing
the deposition
absorption pressureand
coefficient froman5impressive
mtorr to 15increase
mtorr, there is an enormous
in transmittance. Thisdecrease in the
drastic change
absorption coefficient and an impressive increase in transmittance. This drastic
is attributable to the significant decline in the Cu content in the films. Beyond 15 mtorr, change is
attributable
the reduction to the significantcoefficient
in absorption decline in and
the Cu
thecontent in the films.
transmittance seemsBeyond 15 mtorr, the
to be weakened as a
reduction in absorption
result of little variation coefficient
in the film’sand the transmittance
composition. seemsbandgap
The optical to be weakened
(Eg ) of theasCu a re-
3N
sult of little variation in the film’s composition. The optical bandgap (Eg) of the Cu3N can
be calculated using the absorption coefficient. The Tauc method assumes that the ener-
gy-dependent absorption coefficient α can be expressed by the following equation:
αhν = A (hν – Eg) x (1)
Nanomaterials 2022, 12, 2814 7 of 11

can be calculated using the absorption coefficient. The Tauc method assumes that the
energy-dependent absorption coefficient α can be expressed by the following equation:

αhν = A (hν - Eg ) x (1)

where α is the absorption coefficient, h is the Planck constant, ν is the photon frequency, Eg
is the bandgap, and A is a constant. The power of the x-factor depends on the nature of
the electron transition, i.e., equal to 1/2 or 2 for the direct and indirect transition bandgap,
respectively (Cu3 N has the indirect transition bandgap, where x-factor is 2). Tauc plot of
Nanomaterials 2022, 12, x FOR PEER REVIEW
Cu3 N representing the SI fitting as shown in Figure S3. Here, it is observed that with 8 ofthe
12
rise in deposition pressure from 15 mtorr to 25 mtorr, the optical bandgap of p-type Cu3 N
also increases (Figure 6c).

Figure
Figure 6. UV-Vis spectra
6. UV-Vis spectra showing
showing optical
opticalproperties
properties(a)
(a)Absorption
AbsorptionCoefficient,
Coefficient,(b)
(b)Transmittance
Transmittance
and
and (c)
(c) bandgap
bandgap of
of Cu
Cu3NN films
films deposited
deposited via
via HiPIMS
HiPIMS atat different
different deposition
deposition pressure.
pressure.

Hall
Hall measurement
measurementwas wasused
usedtotoexamine
examinethe theelectrical properties
electrical properties of of
thethe
films deposited
films depos-
on glass substrates at various deposition pressure (Figure 7), while conductivity
ited on glass substrates at various deposition pressure (Figure 7), while conductivity type type
was
confirmed through hot probe measurement. Generally, the electrical
was confirmed through hot probe measurement. Generally, the electrical properties de- properties depend
upon the composition,
pend upon phasephase
the composition, structure and vacancy
structure and vacancydefects amount.
defects By increasing
amount. By increasingthe
deposition pressure, the amount of nitrogen increases inside the reaction
the deposition pressure, the amount of nitrogen increases inside the reaction chamber. In chamber. In low
deposition pressure, the amount of nitrogen is inadequate to form Cu3 N phase, which
low deposition pressure, the amount of nitrogen is inadequate to form Cu 3N phase,
results in Cu-rich n-type Cu3 Nx film. At 5 mtorr and 10 mtorr, the carrier concentration of
which results in Cu-rich n-type Cu3Nx film. At 5 mtorr and 10 mtorr, the 22 carrier concen-
n-type Cu3 N films is found to be higher than 2.25 × 1022 cm−3 and 1.05 × 10 cm−3 , respec-
tration of n-type Cu3N films is found to be higher than 2.25 × 1022 cm−3 and 1.05 × 1022 cm−3,
tively. Their n-type conductivity occurs from the excessive electrons within Cu-rich films
respectively. Their n-type conductivity occurs from−3the excessive electrons within
with low resistivity of 8.67 × 10−5 Ω·cm and 1.42 × 10 Ω·cm, respectively. Meanwhile,
Cu-rich films with low resistivity of 8.67 × 10−5 Ω·cm and 1.42 × 10−3 Ω·cm, respectively.
the mobility decreases from 3.2 to 0.42 cm2 V−1 s−1 with 2the−1 increase in deposition pressure
Meanwhile, the mobility decreases from 3.2 to 0.42 cm V s−1 with the increase in deposi-
from 5 mtorr to 10 mtorr. Upon further increasing the deposition pressure, the N2 turns
tion pressure from 5 mtorr to 10 mtorr. Upon further increasing the deposition pressure,
to be sufficient to form p-type Cu3 N film by producing Cu+ vacancies. This conversion of
the N2 turns to be sufficient to form p-type Cu3N film by producing Cu+ vacancies. This
the electrical conductivity type was observed by hot probe measurement at the deposition
conversion of the electrical conductivity type was observed by hot probe measurement at
pressure of 15 mtorr, where the film’s resistivity and carrier concentration are 0.024 Ω·cm
the deposition
and 1.43 × 1020pressure of 15 mtorr,With
cm−3 , respectively. where the film’s
increasing resistivity
the depositionand carrier concentration
pressure, the resistivity
are 0.024 Ω·cm
increases and
and the 1.43 ×concentration
carrier 10 cm , respectively.
20 −3 With increasing
decreases gradually. At thethesamedeposition
time, thepressure,
mobility
the resistivity
increases fromincreases andcm
1.79 to 7.54 the
2 Vcarrier
−1 s−1 . concentration
After the depositiondecreases gradually.
pressure exceedsAt the same
20 mtorr,
time, the mobility increases from 1.79 to 7.54 cm 2V−1s−1. After the deposition pressure ex-
the resistivity becomes very high to the point where it exceeds the measuring limit of the
ceeds 20 This
machine. mtorr, the resistivity
variation becomesof very
in the behavior film’shigh to the
electrical point where
performance it exceedswith
is consistent the
measuring limit of the machine. This variation in the behavior of film’s electrical per-
formance is consistent with the structural change of the films as observed from XRD data.
The diffraction peak intensity becomes relatively weak as the deposition pressure in-
creases to 20 mtorr and 25 mtorr, which is due to the change in the composition of Cu3N
films. In addition, the electrical properties of Cu 3N films deposited via HiPIMS were
Nanomaterials 2022, 12, 2814 8 of 11

the structural change of the films as observed from XRD data. The diffraction peak intensity
becomes relatively weak as the deposition pressure increases to 20 mtorr and 25 mtorr,
which is due to the change in the composition of Cu3 N films. In addition, the electrical
properties of Cu3 N films deposited via HiPIMS were compared with those produced by
other conventional methods, such as DCMS and RF sputtering (Table 1). Since p-type Cu3 N
film deposited via HiPIMS at 15 mtorr presents better electrical properties, as it possesses
the lowest resistivity resulting from the high ionization rate offered by HiPIMS, we used
the same parameters to deposit Cu3 N film through DCMS. The results show that 9p-type
Nanomaterials 2022, 12, x FOR PEER REVIEW of 12
Cu3 N can be achieved, but its resistivity is above 18.82 Ω·cm (Table 1), which is excessive
compared to that of the film deposited via HiPIMS.

Figure 7. The electrical properties of Cu N films deposited via HiPIMS at different deposition pressure.
Figure 7. The electrical properties of 3Cu3N films deposited via HiPIMS at different deposition
pressure.
Table 1. Comparison of the electrical properties of Cu3 N films deposited by various sputtering techniques.

Table 1. Comparison of the electrical properties of Cu3N films deposited by various sputtering
Growth Resistivity Carrier Concentration Mobility
Material techniques. Type Year Ref.
Method (Ω cm) (cm−3 ) (cm2 V−1 s−1 )
Cu3 N RF-Sputter 1.1 × 103 Carrier
- Mobility
- n 2012 [41]
Cu3 N Growth
DC-Sputter Resistivity
20 - 2 - −1 −1 Typn 2011 [42]
Material Concentration (cm V- s Year Ref.
Cu3 N-(Zr, Cr) RF-Sputter
Method 1.65 ×
(Ω cm) 10−4 - en 2017 [43]
−3
Cu3 N-Mg RF-Sputter 1 (cm
6.8 × 10) 18 )6 n 2016 [44]
Cu
Cu3 N-Pd RF-Sputter 1.08 × 103−3 10 21 18.9 n 2013 [45]
3N RF-Sputter 1.1 ×10010 - 15 - n 2012 [41]
Cu3 N RF-Sputter 10 1 p 2016 [46]
Cu
Cu33N N DC-Sputter
RF-Sputter 20
120 -- -- n p 2011
2015 [42]
[47]
Cu
Cu3N-(Zr,3 N Cr) DC-Sputter
RF-Sputter 0.33 −4 1.29 -× 1019 1.45
- n p 2019
2017 [21]
[43]
Cu3 N DCMS
1.65×10
18.82 - - p 2022 This Study
CuCu
3N-Mg
3N RF-Sputter
HiPIMS 1
0.024 1.43×× 10
6.8
18
1020 6
1.79 n p 2016
2022 [44]Study
This
Cu3N-Pd RF-Sputter 1.08 × 10
−3
10
21
18.9 n 2013 [45]
Cu3N RF-Sputter The100comparative investigation
10
15
of the chemical
1 bonding p state in2016
Cu3 N thin [46]
films was
also performed by X-ray photoelectron spectroscopy (XPS) to confirm the change 2+
Cu3N RF-Sputter 120 - - p 2015 [47]in Cu
content within Cu3 N thin films fabricated via both DCMS and HiPIMS technology on
Cu3N DC-Sputtersilicon substrates
0.33 × 10
19
1.45 p the Cu-2p
2019 spectra[21]
(Figure1.29
8). The photoelectron emission from of Cu3 N
Cu3N DCMS thin films was
18.82 analyzed. The fitting
- curve of Cu-2p- spectra was
p compared
2022 in Figure
This Study 8a,b.
2+ +
Cu3N HiPIMS The Cu 0.024 /Cu ratio of the film deposited
1.43 × 10
20 via HiPIMS
1.79 (0.62) isp higher than that
2022 ThisofStudy
the film
deposited via DCMS (0.41), which indicates that a relatively high proportion of Cu2+ ions
exist in the Cu3 N thin films deposited via HiPIMS.
The comparative investigation of the chemical bonding state in Cu 3N thin films was
also performed by X-ray photoelectron spectroscopy (XPS) to confirm the change in Cu 2+
content within Cu3N thin films fabricated via both DCMS and HiPIMS technology on
silicon substrates (Figure 8). The photoelectron emission from the Cu-2p spectra of Cu3N
thin films was analyzed. The fitting curve of Cu-2p spectra was compared in Figure 8a,b.
The Cu2+/Cu+ ratio of the film deposited via HiPIMS (0.62) is higher than that of the film
Nanomaterials 2022, 12, x FOR PEER REVIEW 10 of 12
Nanomaterials 2022, 12, 2814 9 of 11

Figure 8. XPS spectra of Cu2 p core levels of Cu3 N films deposited using (a) DCMS and (b) HiPIMS
Figure 8. XPS spectra of Cu2p core levels of Cu3N films deposited using (a) DCMS and (b) HiPIMS
modes. (For interpretation of the references to color in this figure legend, the reader is referred to the
modes. (For interpretation of the references to color in this figure legend, the reader is referred to
web
the version
web of this
version article).
of this article.).
4. Discussion
4. Discussion
Based on the conductivity type mechanism of NiO thin films, holes get generated by
Based two
replacing on theNiconductivity
2+ cations with type
twomechanism of NiO
Ni3+ cations, thinresult
which films,inholes
Ni2+ get generated
vacancies by
[48,49].
replacing two Ni 2+ cations with two Ni 3+ cations, which result in Ni 2+ vacancies [48,49].
This theory suits the best as proof to describe the conductivity type transition mechanism
This
of Cutheory suits the best as proof to describe the conductivity type transition mechanism +
3 N (as shown in Figure S4). The above findings confirm that the replacement of Cu
ofions
Cu3by
N (asCu shown
2+ in Figure
ions are S4). Thein
more evident above
HiPIMSfindings confirm
than that that thewhich
in DCMS, replacement
results in ofmore
Cu+
ions
Cu by
+ Cu ions
2+
vacancies are more
during evident in HiPIMS
the deposition than that
using HiPIMS in DCMS,
process. which
It could results to
contribute in higher
more
Cu + vacancies during the deposition using HiPIMS process. It could contribute to higher
p-type carrier concentration in the films deposited via HiPIMS technology, which helps in
p-type
reducingcarrier concentration
the electrical in theoffilms
resistivity deposited
the films via HiPIMS
as compared technology,
to DCMS. which clearly
These results helps
inshow
reducing the electrical resistivity of the films as compared to DCMS.
the potential of Cu3 N films deposited through HiPIMS technology to be applied in These results
clearly
future show the potential
optoelectronic of This
devices. Cu3Ntechnique
films deposited
helps in through
obtainingHiPIMS
a flatter technology
interface when to be
the
applied
multilayerin future
films areoptoelectronic
coated, which devices. This technique
can improve the devicehelps in obtaining
performance [50]. a flatter in-
terface when the multilayer films are coated, which can improve the device performance
5. Conclusions
[50].
Cu3 N thin films were deposited via HiPIMS technology at different deposition pres-
5.sures,
Conclusions
while peak power density and the mixture of argon and nitrogen reactive gas
remained
Cu3N constant.
thin filmsAtwere
lowerdeposited
depositionviapressure,
HiPIMS thetechnology
existence ofatCu-rich phase
different enhances
deposition
the film’s while
pressures, n-typepeak
conductivity. Uponand
power density increasing
the mixturethe deposition
of argon and pressure,
nitrogenthe deposition
reactive gas
rate and surface roughness decrease while nitrogen content in
remained constant. At lower deposition pressure, the existence of Cu-rich phase en- the film increases with
the reduction
hances in the
the film’s copper
n-type content in the
conductivity. Uponfilm.increasing
At the higher deposition pressure,
the deposition pressures,the the
existence of a Cu
deposition rate and N phase is confirmed to increase the film’s transmittance
3 surface roughness decrease while nitrogen content in the film in- and its optical
bandgap,
creases withwhile also enhancing
the reduction in thethe resistivity
copper contentof in
thethe
Cufilm.
3 N film.
At theIn addition, the study
higher deposition
compares the
pressures, the existence
chemical of bonding
a Cu3Nstate, quality,
phase and electrical
is confirmed properties
to increase of Cu
the film’s 3 N deposited
transmittance
through HiPIMS and DCMS methods. Beneficial due to its higher ionization
and its optical bandgap, while also enhancing the resistivity of the Cu3N film. In addition, rate and
peak power density, HiPIMS offers lower roughness of the films and a higher Cu 2+ /Cu+
the study compares the chemical bonding state, quality, and electrical properties of Cu 3N
ratio, which resultsHiPIMS
in moreand +
Cu DCMS
vacancies. This indicates
deposited through methods. Beneficialthat dueHiPIMS technology
to its higher is an
ionization
ideal
rate andtechnology
peak power to achieve
density,better electrical
HiPIMS offersproperties of Cu3 Nof
lower roughness films
the in comparison
films and a higherto the
transitional DCMS methods.
Cu2+/Cu+ ratio, which results in more Cu+ vacancies. This indicates that HiPIMS tech-
nology is an ideal technology to achieve better electrical properties of Cu 3N films in
Supplementary Materials: The following supporting information can be downloaded at: https://
comparison to the transitional DCMS methods.
www.mdpi.com/article/10.3390/nano12162814/s1, Figure S1: The instantaneous voltage and current
during the (a) HiPIMS and (b) DCMS process are represented by CH1 and CH2, respectively.;
Supplementary Materials: The following supporting 2information can be downloaded at:
Figure S2: AFM images showing the surface (1 × 1 µm ) of Cu N films deposited by DCMS at
www.mdpi.com/xxx/s1, Figure S1: The instantaneous voltage and3current during the (a) HiPIMS
15 mtorr.; Figure S3: Tauc plot of Cu3 N representing the SI fitting.; Figure S4: The p-type conductivity
and (b) DCMS process are represented by CH1 and CH2, respectively.; Figure S2: AFM images
mechanism of Cu3 N.
showing the surface (1 × 1 µ m2) of Cu3N films deposited by DCMS at 15 mtorr.; Figure S3: Tauc plot
of Cu3N representing the SI fitting.; Figure S4: The p-type conductivity mechanism of Cu3N.
Nanomaterials 2022, 12, 2814 10 of 11

Author Contributions: Conceptualization, H.S. and S.-C.C.; formal analysis, Y.-H.C. and P.-I.L.;
investigation, Y.-H.C., P.-I.L. and C.-K.W.; writing—original draft preparation, S.S. and Y.-H.C.;
writing—review and editing, S.S. and H.S.; supervision, W.-C.C. and S.-C.C.; funding acquisition,
S.-C.C. and H.S. All authors have read and agreed to the published version of the manuscript.
Funding: We gratefully acknowledge the Ministry of Science and Technology of Taiwan (No. 109-
2221-E-131-018), the National Natural Science Foundation of China (No. 62004117) for their finan-
cial support.
Acknowledgments: We also thank H.-C. Lin and C.-Y. Kao of the Instrumentation Center, National
Taiwan University for their assistance with EPMA experiments.
Conflicts of Interest: The authors declare no conflict of interest.

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