Vacuum 178 (2020) 109489

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Vacuum
journal homepage: http://www.elsevier.com/locate/vacuum

Metallic coloration on polyester fabric with sputtered copper and copper

oxides films
Mei-Lin Huang a, b, Zhen Cai b, Ying-Zhu Wu b, Sheng-Guo Lu a, *, Bao-Shan Luo b, Yong-Hong Li b
a
Guangdong Provincial Research Center on Smart Materials and Energy Conversion Devices, Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter,
School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
b
Engineering Technology Research Center for Functional Fiber and Fabric of Guangdong Province, Guangdong College Research Center of Functional Textile Engineering
and Technology, School of Textile Material and Engineering, Wuyi University, Jiangmen 529020, China

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

Keywords: Coating metal and/or metal oxides film on the surface of textile fabric to produce textiles with structural or
Textile coloration metallic colors is an efficient and environmentally benign approach. In this paper, metallic coloration with
Structural color copper (Cu) and copper oxides (CuxOy) film sputtered on polyester fabric is pursued via a direct current (DC)
Metallic color
magnetron sputtering method with different sputtering currents. The coated fabric colors are characterized in the
Copper oxide
Copper film
CIE (Commission Internationale de L’Eclairage) 1976 chromaticity space, and the impact of sputtering current on
Magnetron sputtering the optical properties was studied. Results indicate that the hue of the copper-coated fabrics varies from pale
yellow to yellow while that of the copper oxide-coated fabrics changes from brown to dark red, and further to
dark green as the color brightness decreases, which are regarded due to the intrinsic absorption of the film. The
color brightness decreases because the reflection of the visible light decreases. The absorption increases due to
the increase in the film thickness via the sputtering current. The hue of the copper oxide-coated fabrics is affected
by the contents of Cu1þ and Cu2þ ions in the films, which changes via the sputtering current. Copper oxide-
coated fabrics have good hydrophobicity, ultraviolet resistance, air permeability, and superior colorfastness to
rubbing of grade 3 or above. An approach to fabricate stable colored films on textiles by sputtering was estab­
lished to bring a new coloration strategy for the traditional textile chemical dyeing and enhance potential ap­
plications in other relevant smart textiles.

1. Introduction have used magnetron sputtering to produce structural color on textiles

Metallic coloration on plastic products has been made by dry coating
of vacuum evaporation with a silver (Ag) or aluminum (Al) films, or by
wet coating metal film with metal powder. However, these two ap­
proaches are not suitable for metallic coloration on textile fabric,
because the vacuum evaporation with high temperature steaming is not
suitable for textile with a low melting point, and the fabrication of wet
coating delivers serious pollution while the film layer is easy to peel off,
which makes the metal luster formed be not uniform and the color un­
stable. Magnetron sputtering is one of the best approaches to achieve
large area coatings. It offers high deposition rates, high uniformity, and
good structural integrity with the possibility of operating at room tem­
perature [1]. Magnetron sputtering can be implemented to textile sur­
face modification, and coatings via the properties of the film to obtain
the corresponding functionalities[T, 3]. Recently, some research works
(Fig. 1). The construction of the thin films to obtain a clear interference
structure color is primarily discussed [2–5]. However, the textile color
attained by sputtering may be an interference structural color (physical
color) or an intrinsic absorption color (also called chemical color or
pigment color), or a combination of the two. It is necessary to discuss the
influence of the original color of the substrate textile and the absorption,
transmission, and reflection of visible light to the coated textile color.
More analysis and study are needed to discover the complex coloring
mechanism that underlies the relationships between structure, compo­
nents, properties, and coloration. Manufacturing strategies for color
precise control should be promoted to simplify the magnetron sputtering
process and improve production efficiency as much as possible.
Copper (Cu) is widely used in conductive materials because it has a
lower resistance than aluminum (Al) and a lower cost than silver (Ag).
Copper oxides (CuxOy) can be invoked as semiconductors, magnetic

* Corresponding author.
E-mail address: sglu@gdut.edu.cn (S.-G. Lu).

https://doi.org/10.1016/j.vacuum.2020.109489
Received 7 March 2020; Received in revised form 16 May 2020; Accepted 18 May 2020
Available online 21 May 2020
0042-207X/© 2020 Elsevier Ltd. All rights reserved.
M.-L. Huang et al. Vacuum 178 (2020) 109489

Fig. 1. Schematic diagram of structural colored textiles prepared by sputtering [6] (Reprinted from Ref. [6] with permission).

storage media, thermoelectrics, photocatalysis, solar cells, and gas-
sensing devices because of their transparent conductivity, piezoelec­
tricity, photoelectricity, gas sensitivity, pressure sensitivity and non-
toxicity [7–10]. Copper is utilized to sputter coat textiles and make
textiles that are conductive or have electromagnetic shielding properties
[11–14]. N.Fredj et al. [15] deposited copper oxide films onto the copper
surface by an electrochemical technique and got brilliant colors. How­
ever, there are few reports about metallic coloration on textile fabrics so
far, especially by the magnetron sputtering method. Here, copper films
and copper oxides films were deposited on polyester fabrics by a
magnetron sputtering method at room temperature to produce different
colors on textile fabrics. The coloration mechanism, the impact of the
sputtering parameters, and relevant physical properties are discussed.
An innovative way of bypassing the need for traditional chemical dyeing
is offered.
2. Materials and methods
2.1. Materials
The substrate fabric is a polyester plain weave white fabric (40D/
310T, 120 � 180/inch, commercial) with a weight of 60.9 g/m2 and a
thickness of 0.13 mm. The copper target (Cu, 99.99%) was provided by
Shenzhen Morgan Sputtering Target Technology Co., Ltd. The substrates
were cleaned using ethanol and acetone successively, and dry in an oven
before deposition. Pre-sputtering of the targets was used to remove
impurities from the surface.
2.2. Films preparation
The magnetron sputtering machine (JPL-650, Zhaoqing Xielong
Machinery Manufacturing) is a custom-made setup for multiple targets
sputtering at the same time with a maximum width of 65 cm of the
substrate fabric. The fabric was rolled on the feeding roller after cleaning
and drying. The distance between the copper target and the substrate
fabric was 8.0 cm. After the base pressure was pumped down to 8.0 x
10 3 Pa, the argon (Ar. 99.99%) gas was filled in as a working gas. The
substrate fabric was then coated at a working pressure of 0.2 Pa with a
flow rate of 160 ml/min of Ar gas, and a rolling speed of 0.3 m/min to
feed the substrate fabric. For coating with copper oxides, the Ar flow rate
was set at 280 ml/min, and the oxygen flow rate at 80 ml/min. The
sputtering current varied from 1 to 7 A with an interval of 1 A. The
sputtering time is fixed as 1 min. Only the sputtering current was an
independent variable and was used to investigate its impact on the final
color of the coated samples. Other parameters like base pressure,
working gas flow rate, working pressure, and sputtering time were un­
changed. The sputtering parameters and the film thickness of each
sample which in situ measured by an online film-thickness monitor

Table 1
The sputtering current of deposition, CIE L*a*b* and K/S for the samples.
Sample Film Current/A Film thickness/nm CIE chroma metrics K/S

L* a* b*

A0 (none) 0 0 88.34 1.11 3.45 0.21

A1 copper 1 45.4 70.45 1.79 9.31 0.52
A2 2 56.5 67.2 1.49 11.63 0.68
A3 3 66.1 62.77 2.21 8.88 0.92
A4 4 79.1 61.43 1.72 8.64 0.99
A5 5 87.0 63.41 2.14 17.84 0.99
A6 6 100.2 63.88 2.54 20.77 1.02
A7 7 122.2 65.11 1.83 26.24 1.10
B0 (none) 0 0 88.34 1.11 3.45 0.21
B1 copper oxides 1 34.3 45.99 0.52 16.52 3.15
B2 2 39.2 40.87 0.02 12.7 4.29
B3 3 45.2 38.83 6.27 12.34 4.32
B4 4 50.5 36.54 1.44 7.48 4.52
B5 5 56.6 35.71 2.6 9.82 5.82
B6 6 65.2 31.66 2.53 4.63 7.58
B7 7 78.0 29.1 1.99 4.03 8.67

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M.-L. Huang et al. Vacuum 178 (2020) 109489

Fig. 2. The colors of the polyester fabrics coated with (a) copper and (b) copper oxides film. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)

(INFICON SQC-310, USA) are given in Table 1.

EBF þ φSA ¼ 289:58 � 0:14 eV: (2)

2.3. Testing and characterization EFB means the BE of C 1s peak with respect to the spectrometer Fermi
level, and φSA refers to the sample work function.
Optical images under the natural light were captured by a digital
The color friction fastness of the coated samples was tested (Wenz­
camera (Olympus E-M10 Mark II, Japan) for the samples. The values of
hou Dayong YG(B) 71 II, China) in accordance with criterion GB/T
L*a*b* and K/S and the reflection spectra of visible light for the samples
3920-2008, China. The color fastness was evaluated according to criteria
were tested by spectrophotometers (X-rite Ci 7800, and PerkinElmer
GB/T 250–2008, China and GB/T 251–2008, China. The wettability of
Lambda 950, USA). The CIE (Commission Internationale de L’Eclairage)
the fabric before and after coated was conducted using a water contact
L*a*b* 1976 chromaticity space was used to characterize the sample
angle tester (Shanghai Zhongchen DA25, China). The ultraviolet (UV)
color.
absorption performance was tested via an anti-ultraviolet tester
The morphologies of the samples were observed by a scanning
(Wenzhou Dayong YG(B) 912E, China) following criterion GB/T 5453-
electron microscope (SEM) (Hirox SH-5000 M, Korea, and Zeiss Sigma
1997, China. The air permeability was measured (Wenzhou Dayong
300, Germany), and the surface elements were analyzed by an energy-
YG(B) 461-II, China) under criterion GB/T 5453-1997, China.
dispersive analysis X-ray spectroscopy (EDS) (Bruker XFlash 6, Ger­
many). The crystallization of film components was characterized by X-
3. Results and discussion
ray diffraction (XRD) (D8 Rigaku 9000, Japan).
Chemical bonding states of the coated films were characterized using
3.1. Color characterization and optical properties
X-ray photoelectron spectroscopy (XPS) (Thermo Fisher Scientific K-
Alpha, USA). Monochromatic Al K alpha radiation (hvX ray ¼1486.6 eV)
The optical pictures of the samples are shown in Fig. 2. Sample A0
was used for the X-ray source, and the anode power was set to 150 W.
and B0 are the same pristine samples without coatings. The copper-
Double beam neutralization was used and the electron incidence angle
coated fabrics are yellow in color with golden luster, while the copper
was 90� . The base pressure was 2.0 � 10 9 mbar, and the testing spot
oxide-coated fabrics have different colors.
size was 400 μm during spectra acquisition of Cu 2p, Cu LMM, O 1s, and
In CIE 1976 chromaticity space theories, color is characterized by
C 1s core levels in the constant analyzer energy mode with a voltage of
three parameters L*, a*, and b*. The position of the color in the color
15 kV, and a pass energy of 30 eV. Modified Auger parameter α}
space is represented by lightness L* and chromaticity coordinates a* and
introduced by Wagner et al. [16] was used and calculated accordingly
b*. Term L* indicates the lightness or brightness of the color with a value
for copper chemical state identification:
between 0 and 100; 0 is completely black, and 100 is completely white.
α} ¼ α’ þ hvX ray ¼ KEAuger þ BEPhotoelectron : (1) a* denotes a range from red to green with values between þ127 and
128 in which positive values indicate reddish, and negative value
Here, α is the Auger parameter, KEAuger the kinetic energy of the
’
greenish. b* indicates the range from yellow to blue with a value be­
Auger electron, and BEPhotoelectron the binding energy of the photoelectron. tween þ127 and 128 (positive yellowish, and negative blueish).
The carbon peak C 1s is a commonly used calibration of the binding Fig. 3a shows the position of the color C in the three-dimensional rect­
energy (BE) scale [17]. G. Greczynski and L. Hultman [18,19] pointed angular coordinate system of the CIE chromaticity space. Here, L* ¼ 75,
out that the use of C 1s peak of adventitious carbon (AdC) for BE scale a* ¼ 40, and b* ¼ 45, which means that the color is reddish yellowish
calibration is a flawed method. The BE value of AdC varies with the pink.
matrix material, and the variation range can reach 2.66 eV. The Fig. 3b shows the relative positions of the colors in the three-
following formula is suggested by G. Greczynski and L. Hultman to dimensional rectangular coordinate system of the CIE chromaticity
improve the BE scale calibration:

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M.-L. Huang et al. Vacuum 178 (2020) 109489

Fig. 3. The color chromaticity space and K/S values of the samples. (a) A chromaticity space schematic diagram [20]; (b) The color positions of the samples shows in
a three-dimensional map; (c) The color positions of the samples shows in a two-dimensional color plane (assuming their brightness is the same); (d) The relationship
between the sputtering current and the K/S value as well as film thickness. (For interpretation of the references to color in this figure legend, the reader is referred to
the Web version of this article.)

space. The A-series samples are on the top of the B-series samples
because the former color brightness is generally greater than that of the
latte. Fig. 3c represents the color positions of all samples in a two-
dimensional plane formed by two dimensions of a* and b* assuming
that they have the same specific brightness. This was done to measure
the degree of the hue biased toward green, red, blue, and yellow. Color
positions of the A-series samples are relatively concentrated in the
yellowish-red position; the B-series samples are relatively scattered with
different colors.
Term L* indicates the lightness or brightness of the color in the CIE
chromaticity space. Besides, the K/S values can be used to evaluate the
color depth or gradation of the textiles. This is indicated in a simplified
form of the Kubelka-Munk function [21,22]:
K ð1 ρ∞ Þ2 A2 ð1 RÞ2
¼ ¼ ¼ (3)
S 2ρ∞ 2ð1 AÞ 2R
Here, K is the K-M absorption coefficient of the measured object, S
the K-M scattering coefficient of the measured object, ρ∞ represents the
reflectance function when the measured object is infinitely thick (means
zero transmissivity), A the absorptivity (%), and R the reflectivity (%).
The K value and S value are not calculated separately. Instead the ratio
of K/S is calculated. A larger K/S value implies a greater color depth
representing a higher concentration of colored substances. On the con­
trary, a smaller K/S value implies a lighter color depth representing a
lower concentration of colored substances. At the same time, term p∞
represents the degree of reflection of the measured object. The results
indicate that larger p∞ implies a smaller K/S; a smaller p∞ leads to a
larger K/S.
In the theory of absorption color, a larger K/S leads to better dyeing
performance. Applying this principle and characterization method, the
K/S was also used to reflect the depth or density of the substances of the
film coated on the fabric surface. Fig. 3d shows that the K/S values of
both these two series samples increase with increasing sputtering cur­
rent. The effect of the sputtering current on the copper oxide-coated
fabrics is greater than the copper-coated fabrics. A larger sputtering
current lead to more target atoms deposited on the fabric surface and
thus a thicker film, a larger K/S value, and a greater color depth. The

4
M.-L. Huang et al. Vacuum 178 (2020) 109489

Fig. 4. The optical properties of the copper oxide-coated samples. (a) The reflectivity spectra of pristine sample and copper oxide-coated samples; (b) The reflectivity,
absorptivity and transmissivity spectra of B4 (average Absorbance A ¼ 1.425); (c) The reflectivity spectra of the copper oxide-coated samples; (d) The absorbance
spectra of the B-series samples.

copper sputtering rate is greater than that of copper oxides, but the K/S
It
growth rate of copper oxide-coated fabrics is greater than that of copper- AðλÞ ¼ log T ¼ log ¼ kbc (4)
I0
coated fabrics. Therefore, the K/S value is affected by not only the film
thickness but also the absorption and reflection of the visible light; the It
two effects are different. T¼ ¼e kbc
(5)
I0
When visible light is incident on an object, part of the light is re­
flected from the surface of the object, part of the incident light is AðλÞ
selectively absorbed, part is transmitted out, and part is reflected from ɑ¼ (6)
d
the second surface. The color of an object that people see is the effect of
Here, A(λ) is the absorbance, T the light transmissivity (%), It the
the two reflected light paths interacting. Therefore, the reflection, ab­
transmitted light intensity, Io the incident light intensity, k the extinction
sorption, and transmission of incident light is taken into account. Fig. 4a
coefficient or molar absorption coefficient, b the optical path length, c
shows the reflectance spectra of the pristine fabric and copper oxide-
the light-absorbing substance concentration, ɑ the linear absorption
coated fabrics in which the reflectance of the pristine fabric is close to
coefficient and d the film thickness. Equation (4) indicates that when k
100%. When the copper oxides are coated, the reflectance is signifi­
and c are unchanged, the absorbance A(λ) increases as the thickness of
cantly reduced, causing the color brightness reduces, which is consistent
the film (b) increases, i.e., the reflectance decreases and gives rise to a
with the aforementioned decrease in L* (Fig. 3b). The color shifts to­
larger K/S and a greater color depth, which is consistent with the con­
wards the dark direction. The previous analysis mentioned that the film
clusions shown above.
thickness increases as the sputtering current increases, the reflectance is
Fig. 4c is shown that the colors of the coated fabrics are intrinsic
then reduced, i.e., ρ∞ decreases in Formula (3) indicating that the film’s
absorption colors of copper oxides and not structural colors. This is
absorption of light increases, leading to an increase in K/S. Fig. 4b dis­
concluded because there are no obvious sharp peaks with the interfer­
plays the reflectance, absorptivity, and transmittance of direct incident
ence in the reflection spectra and no iridescent effect where the colors
light to sample B4. The absorption of visible light is large, and both the
alter according to changes in the angle of vision. The absorption of the
reflectance and transmittance are small.
visible light of the substrate must be examined. It is well known that the
According to the Beer-Bouguer-Lambert law for optical absorption
refractive index of copper is around 1.1, and copper oxides are up to 3.4
[23]:

5
M.-L. Huang et al.
Fig. 5. Digital photos and SEM images of pristine sample B0 and copper oxide-coated samples B1, B3, B5, and B7.
[24]. A larger refractive index refers to a larger absorption of the light
which explains why the color brightness of the copper-coated fabrics is
generally greater than the copper oxide-coated fabrics (Fig. 3b).
Furthermore, for a thin film with a definite refractive index and
extinction coefficient, the film shows an intrinsic absorption color of the
film material when the extinction coefficient is large. With a smaller
extinction coefficient, the absorption of light is less, and increased light
energy is reflected at the second interface of the film. The interference
phenomenon is formed between the two interfaces of the film and is ever
more obvious. The film presents the interference structure color. Fig. 4c
also shows that there are two steep changes in the reflectance curves of
the samples near the wavelengths of 570 and 670 nm, respectively. The
absorbance curves of the samples are presented in Fig. 4d. As the sput­
tering current increases, the overall absorbance of a sample increases.
This is due to the absorption of the coated film, in which the steep
change of absorption means the optical absorption edge of the copper
oxides in the film, which will be discussed later in combination with the
compositional analysis.
In short, a color can be represented by a CIE Lab chromaticity system,
and its brightness can also be represented by a K/S value. We conclude
that the color brightness of the coated fabrics is influenced by the film
thickness, which increases by the increase of the sputtering current. The
film absorbs incident visible light, and the reflection decreases. Thus, the
K/S value increases, and the color brightness declines. Furthermore, the
film thickness is determined by the sputtering current when additional
parameters are not changed; thus, different colors can be adjusted by
changing the sputtering current.
3.2. Surface structure and morphology
Fig. 5 presents the surface structure and morphology of the pristine
sample B0 and the copper oxide-coated samples B1, B3, B5, and B7 by
digital photos and SEM images. The colors of these five samples are
different from those presented in Fig. 2 due to the differences in the
shooting angle and magnification. However, these colors gradually
decrease from light to dark, which is consistent with the aforementioned
6
Vacuum 178 (2020) 109489
descriptions. Among the eight samples B0 to B7, only five samples’
pictures are shown in Fig. 5, in which the pristine sample B0 without
coating shows clear gaps between the fibers. The coated samples,
however, filled into the gaps as the sputtering current increases. Surface
morphology of sample B7 (see picture B7-2) is denser than the others;
and even the fibers are almost packed into one flat plane.
Polyester fibers are cylindrical, and there are more impurities on the
fiber, even if on a pristine sample. By statistical calculation, the average
particle sizes of B0, B1, B3, B5, and B7 are 18.7, 18.4, 24.2, 14.3, and
25.8 nm, respectively. The uneven surface particles may cause a certain
degree of light scattering, which will affect the reflection and absorption
of incident visible light, and then affect the hue and brightness.
3.3. Film composition
It is known that pure copper (Cu) is purplish red, copper oxide (CuO)
is black, and cuprous oxide (Cu2O) is brick red or dark red [25,26]; thus,
the composition of the coated film should be analyzed to see how it
affects the colors. The EDS data of the pristine sample and the copper
oxide-coated samples indicate that the surface of the pristine sample
does not have elemental copper, and the copper oxide-coated samples
contain C, O, Ti, and Cu element. Ti element may be present as a trace of
impurity. The atomic percentage of Cu element proportion in B0, B1, B3,
B5, and B7 are 0, 17.43, 50.64, 55.44, and 56.49%, respectively. The
copper content increased with the increasing sputtering current and film
thickness. Further analysis was carried out to study the copper-oxygen
binding energy and crystalline phases via XPS and XRD, which are
shown below.
XPS analysis reveals the coexistence of C, O, N, and Cu elements in
the copper oxides films (Fig. 6a). Sample B1 (1A) was taken as the
reference in XPS analysis. The Cu 2p, C 1s, and O 1s peak was decon­
voluted (Fig. 6b–d) and analyzed it concerning Cu LMM curve fitting
data (Fig. 6e), XPS standard spectra and binding energy data. The Auger
parameter was used and calculated accordingly for copper chemical
state identification. Built on the spectra of Cu 2p3 and Cu LMM, there
should be two Auger parameters, which are corresponding to the Auger
M.-L. Huang et al.
Fig. 6. XPS spectra of the copper oxide-coated sample B1 (1A): (a) survey spectra, (b) Cu 2p, (c) C 1s, (d) O 1s, (e) Cu LMM.
parameters of two chemical states of Cu2O (~1849 eV) and Cu(OH)2
(~1851 eV) respectively. And then peak position could be calibrated
according to the binding energy for each chemical-state: Binding energy
of Cu2O is about 932.4 eV, while Cu(OH)2 is around 934.8 eV. The
deconvolution of the Cu 2p peak in Fig. 6b indicated that it was
composed of five peaks centered at the binding energy of 932.0, 934.33,
940.32, 942.19 and 944.08 eV. By calculation with the Auger parameter
according to Formula (1), it revealed that the peaks centered at 932.0
7
Vacuum 178 (2020) 109489
and 934.33 eV originate from Cu 2p3/2 electrons in Cu2O and Cu(OH)2,
respectively. These peaks are considered to be characteristic peaks of the
above two substances. The other peaks centered at 940.32, 942.19 and
944.08 eV all correspond to Cu2þ electrons in Cu(OH)2 satellite peak.
The deconvolution of C 1s and O 1s peaks (Fig. 6c and d) also confirmed
the existence and interdependence of the two chemical bonding states of
copper, which are in agreement with the findings of M. Abidi et al. [27]
although they coated CuxO/TiO2 films on polyester cloth. These findings
M.-L. Huang et al.
Fig. 7. The stacked graph of Cu 2p spectra (a), and the proportion of Cu1þ and Cu2þ (b) of the copper oxide films.
Fig. 8. The XRD spectra of the copper oxide-coated samples (a) and the average grain size and crystallinity of the films (b).
indicate that the surface components of the films are mainly composed
of Cu2O and Cu(OH)2.
In Fig. 7a, there are differences in peak position, intensity, and half
width between the Cu 2p3/2 peaks and between the Cu 2p1/2 peaks of the
seven copper oxide films, implies a difference in the composition or
content proportion of these films. Fig. 7b manifests the content pro­
portion of Cu1þ (Cu2O) and Cu2þ (Cu(OH)2) on the copper oxide films.
The proportion of Cu2þ (Cu(OH)2) is dominant and increased slightly
with the increasing of the sputtering current.
The XRD curve denoting the main phases of the films are Cu
(PDF#70–3038), Cu2O (PDF#78–2076) and CuO (PDF#78–0428). The
diffraction peaks of Cu3þ2(CO3)2(OH)2 (azurite, PDF#11–0682) and
C2CuO4H2O (copper oxalate hydrate, PDF#48–1054) was retrieved but
weak. The seven samples all contained the last four fitting phases, while
the samples B1 (1A) and B2 (2A) did not contain the metallic copper
(Cu) phase. It can be explained that Cu was completely oxidized and
converted to other phases when the film thickness was relatively thin.
That is to say, Cu in the inner layer remains when the film thickness
reaches a certain degree. Combined with the previous EDS analysis with
the change in diffraction intensity shown in Fig. 8a, it refers that the
content of Cu increases significantly with the increase of the sputtering
current. The contents of CuO and Cu2O changes related to the increasing
sputtering current and film thickness; however, the stoichiometry was
difficult because the diffraction intensity is too low and the peaks shape
8
Vacuum 178 (2020) 109489
overlap. Some literature [28–30] revealed that oxygen partial pressure
was a crucial parameter in controlling the phase composition of CuO and
Cu2O. The possible chemical reactions and phase transformations are
discussed in later sections. Crystallinity values suggest a tiny crystalline
structure in the films, but it increased with the increasing of the sput­
tering current (Fig. 8b). The average grain size of the films is about
80–101 Å, and it shows a weak relationship with the sputtering current
and film thickness. In summary, the mixed phases and related contents
of Cu (golden), CuO (black), Cu2O (red), and Cu(OH)2 (blue) in the films
have mainly affected the hue of the film, while the crystallinity has an
impact on the brightness.
3.4. Copper oxidation
Literatures [28,31–33] mentioned that CuO and Cu2O may be con­
verted each other, and the following chemical reactions may occur:
2Cu þ O2 →2CuO (7)
4CuO → 2Cu2 O þ O2 (8)
1
Cu2 O þ O2 →2CuO (9)
2
M.-L. Huang et al.
Fig. 9. The absorbance spectra (a) and the Tauc - hv plots (b) of the coated films excluding the influence of the substrate fabrics.
Cu2 O → CuO þ Cu (10)
Here, Reaction (7) is relatively easy. The Cu will be slowly oxidized
to CuO as long as pure copper atoms encounter oxygen atoms. A high
temperature over 1200 K is required for CuO to be converted into Cu2O
in the air (Reaction (8)). However, this temperature may not need to be
very high under a high vacuum condition in an oxygen-deficient envi­
ronment. Reaction (9) and (10) show that Cu2O can be converted into
CuO and Cu; CuO is more stable than Cu2O at room temperature.
Moreover, the following reactions would exist under certain condi­
tions [15,34]:
CuO þ H2 O→CuðOHÞ2 (11)
2Cu þ O2 þ H2 O þ CO2 →Cu2 ðOHÞ2 CO3 ; (12)
1 edges are between 652 and 826 nm for CuO and 563–590 nm for Cu2O,
Cu þ O2 þ H2 C2 O4 →C2 CuO4 H2 O: (13)
2 respectively. Research reported that a bandgap between 1.4 and 2.1 eV
Reaction (11) and (12) indicate that metallic Cu will become copper
hydroxide (Cu(OH)2) or basic copper carbonate (Cu2(OH)2CO3) (known
as patina) in a humid environment. C2CuO4H2O was the by-product of
the reaction between oxalic acid (H2C2O4) which residue during textile
processing and copper (Reaction (13)).
3.5. Optical bandgap and absorption edge
For semiconductor materials, the relationship between the optical
band gap and the absorption coefficient is [35,36].
ɑhv ¼ Bðhv Eg Þn (14)
Here, hv, ɑ, Eg, B, and n are incident photon energy, linear absorption
coefficient, optical band gap, the proportionality constant, and an
exponent, respectively. The value of n is 1/2, 3/2, 2, and 3, which
indicate the semiconductor materials are direct allowed, direct
forbidden, indirect allowed, and indirect forbidden transition, respec­
tively. According to Equations (4) and (14), another expression can be
obtained with a constant C (C¼Bd)
AðλÞ ⋅ hv ¼ Cðhv Eg Þn (15)
Here, n is 1/2 for Cu2O as a direct bandgap, 2 for CuO as an indirect
bandgap. The linear part of the Tauc plot (AðλÞ⋅hv)2 versus hv for Cu2O,
and (AðλÞ⋅hv)1/2 versus hv for CuO are plotted in Fig. 8b. The optical
band gap value Eg can be obtained in terms of extrapolating the tangents
of the plots of (AðλÞ⋅hv)2 versus hv for Cu2O, and (AðλÞ⋅ hv)1/2 versus hv
for CuO. The wavelength corresponding to the bandgap is the optical
9
Vacuum 178 (2020) 109489
Table 2
Color fastness to rubbing for the copper oxide-coated samples.
Sample Sputtering Dry rubbing fastness/ Wet rubbing fastness/
current/A grade grade
B1 1 3 3.5
B3 3 3.5 3.5
B5 5 3.5 3.5
B7 7 3.5 3.5
absorption edge, implying that the absorption suddenly changes and the
absorbance curve becomes steep after the photonic energy reaches this
level.
By calculation, the bandgap energy of CuO varies from 1.5 to 1.9 eV,
and Cu2O 2.1–2.2 eV (Fig. 9b). The corresponding optical absorption
is attained for CuO [37], and 2.0–2.6 eV for Cu2O [38]. Furthermore,
literature [10,39] reported that CuO and Cu2O have band gaps of 1.85
eV and 2.17 eV, respectively, which matches the absorption edges of
670 nm, and 571 nm. This is consistent with our previous conclusion
that the absorbance edge showed a redshift with the increasing sput­
tering current (Fig. 4c and d, and Fig. 9a). This behavior could be
explained in terms of the compositional variation and the improvement
of film crystallinity. N.W. Sangwaranatee et al. [40] have confirmed that
the absorption edge shifts to higher wavelength values as the film
crystallinity increases. Furthermore, it must be noted that the final
colors of the copper oxide-coated fabrics are dominated by the compo­
sitional variation of the films. Hsin-Chun Lu et al. [29] mentioned that
Cu2O film has high transmittance at a wavelength above 600 nm and a
high absorption coefficient at the wavelengths below. It is confirmed by
Fig. 4c in which the transmittance of B4–B7 increased at a wavelength
above 600 nm and by Figs. 4d and 8a in which the absorption of all
samples increased sharply at the wavelengths below 600 nm.
3.6. Colorfastness to rubbing
Color fastness is a basic item for textile quality. It is the resistance
ability for textiles to various environmental impacts in the daily use. The
color fastness grades are divided into 1–5. A higher grade implies better
color fastness. After testing, the color fastness at both the dry rubbing
and wet rubbing for the copper oxide-coated fabrics are above 3, sug­
gesting a good color fastness (Table 2).
M.-L. Huang et al.
Fig. 10. The static contact angle, UPF value and air permeability of the pristine uncoated fabric and copper oxide-coated fabrics.
3.7. Hydrophobicity, ultraviolet resistance and air permeability
The pristine uncoated fabric has a contact angle of 0� , which shows a
good wettability, but bad hydrophobicity in contrast. The copper oxide-
coated fabrics attained excellent hydrophobicity with a high static
contact angle up to 128.6� . The dense structure of the copper oxide film
prevents water molecules from entering into the fiber, so the hydro­
phobicity of the coated fabrics is greatly improved. Moreover, the hy­
drophobicity of the copper oxide-coated fabrics increased slightly with
the sputtering current increase (Fig. 10). These results are in agreement
with those previous reports [41,42] in which better hydrophobicity was
obtained by a longer sputtering treatment.
The ultraviolet protection factor (UPF) is usually used to characterize
the ultraviolet (UV) protection ability of textiles. The higher the UPF
value means the higher the UV resistance performance. The UPF of the
copper oxide-coated fabrics is much higher than that of the blank un­
coated fabric (UPF ¼ 20.5), in which the highest UPF (94.5) was
attained with the sputtering current of 7 A and the thickest film of 78
nm. It shows that higher deposition can provide perfect UV resistance
[42]. Fig. 10 also shows that the air permeability of the copper
oxide-coated fabrics increases a little compared to the uncoated fabric.
4. Conclusions
We report an efficient method for sputtering metal film or metal
oxide film on the surface of textile fabrics to produce absorption color.
The colors of the coated samples are influenced by the target material
and sputtering process—especially sputtering current. Distinct colors
have been attained by adjusting the sputtering current, while other
sputtering parameters kept unchanged. This approach provides a novel
strategy for traditional textile dyeing.
The hue of the copper-coated fabrics changes from pale yellow to
yellow, and the copper oxide-coated fabrics shifts from brown to dark
red, military green, and finally dark green as the color brightness de­
creases. The hue and brightness of the samples show a relationship with
the sputtering current. The increase in sputtering current increases the
film thickness—the absorption of visible light increases but the reflec­
tion decreases; thus, the color brightness decreases. The contents of Cu1þ
and Cu2þ on the surface of the copper oxides-coated fabrics affected the
hue, and changes in the contents can be controlled by the changes in the
10
Vacuum 178 (2020) 109489
sputtering current. The combination of film composition and film
thickness finally affects the colors. The films were noted to nicely cover
the surface of the fibers. The grade of colorfastness to rubbing of the
oxide-coated fabrics is over 3. By copper oxides coating, the hydro­
phobicity and ultraviolet resistance of the copper oxide-coated fabrics
are dramatically improved, while the air permeability is improved
slightly.
In conclusion, coloration is a comprehensive and complex science.
Achieving structural colors and metallic colors on textiles is an active
research area for green textile production. Future studies will optimize
the gradation of the hue for better smoothing. Further work is needed to
optimize the impact of the structure, surface morphology, grain size, and
the optical absorption edge of the copper oxide film on the final colors in
terms of precise control of the process parameters. The color stability
should be optimized in different applications. Also, the copper film and
copper oxide film can be utilized for the preparation of multi-functional
textiles with conductive, antibacterial, and sterilizing properties. The
use of copper and copper oxides will lead to more stylish wearable
textiles, decorations, and fashion products.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the Undergraduate Innovation and
Entrepreneurship Training Program of Wuyi University [Grant No.
S201911349106], the Natural Science Foundation of China [Grant No.
51372042, 51872053], the Guangdong Provincial Natural Science
Foundation [Grant No. 2015A030308004], and the NSFC-Guangdong
Joint Fund [Grant No. U1501246].
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