Journal of Photopolymer Science and Technology

Volume 27, Number 3 (2014) 409–414 © 2014SPST

Surface Characteristics of Polyethylene Terephthalate

(PET) Film Exposed to Active Oxygen Species
Generated via Ultraviolet (UV) Lights Irradiation
in High and Low Humidity Conditions
Kei Oya, Ryota Watanabe, Shunsuke Sasaki, Hajime Hiraga,
Yasutaka Ohnishi, and Satoru Iwamori

Department of Mechanical Engineering, School of Engineering,

Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292, Japan

Polyethylene terephthalate (PET) has excellent transparency, heat resistance, electrical

insulation, chemical resistance, and wear resistance. With a miniaturization and
multifunctionalization of an industrial product, control of material surface and interface has
become important. Active oxygen species were generated via 185/254 nm UV lights irradiation
under conditions of high and low humidity, and PET films were exposed to the active oxygen
species with these UV lights. Changes in their surface characteristics were evaluated. Contact
angle of water droplet on the PET film surface and surface roughness after the treatment in the
high humidity condition were higher than those in the low humidity condition, and transmittance
of the PET film within a region of the visible light after the treatment in the high humidity
condition decreased compared to that in the low humidity condition. The PET film surface can be
modified more gently in the low humidity condition than in the high humidity condition.
Keywords : poly(ethylene terephthalate); active oxygen species; UV lights irradiation;
humidity; surface characteristics

1. Introduction cause serious damages to polymer surfaces because

Polyethylene terephthalate (PET) has excellent
transparency, heat resistance, electrical insulation,
chemical resistance, and wear resistance. Various
method have been employed for the surface
modification and etching of the PET film substrate.
For instance, effects of nitrogen plasma [1],
ammonia low-temperature plasma [2], air plasma
[3], argon plasma [4], argon ion implantation [5],
carbon dioxide laser [6], and vacuum-ultraviolet
(VUV) [7] irradiations on the PET substrate have
been revealed. With a miniaturization and
multifunctionalization of an industrial product,
control of material surface and interface has
become important. Chemical functionalization and
controlling of surface morphology in micro- or
nano-level are required for the surface treatment of
the polymeric material with a minimal damage. In
the present, laser irradiation, UV ozone treatment,
and plasma irradiation are known to be effective
techniques. However, these processes sometimes
of their high energies. To overcome this problem,
we focused on the surface modification technique
using active oxygen species. The surface treatment
using active oxygen species can minimize the
damages to the polymer surface compared to
plasma and laser processes because the energies of
active oxygen species are lower than those of
plasma and laser. Therefore, the active oxygen
species can provide a mild treatment to the
polymer surface. In addition, the exposure of
active oxygen species can functionalize and
activate the polymer surface due to their oxidation
abilities.
Active oxygen species can generate via
irradiation of two wavelengths (185 and 254 nm)
of UV lamps to oxygen and water molecules. In
the generation process, many kinds of active
oxygen species, e.g., ozone, excited state singlet
oxygen atom and molecule, hydroxyl radical,
hydrogen peroxide, and hydroperoxide, are
generated and decomposed [8-16]. Since

Received June 5, 2014

Accepted July 1, 2014 409
 J. Photopolym. Sci. Technol., Vol. 27, No. 3, 2014

generation process is based on the decomposition

of oxygen and water molecules and the oxidation
abilities of these active oxygen species are
different, the control of humidity environment is
important for controlling the surface modification.
Major generation technique of active oxygen
species are plasma irradiation and UV light
irradiation. However, although active oxygen
species are generated from two atmospheric
molecules, i.e., oxygen and water molecules, the
plasma irradiations such as atmospheric pressure
pulsed corona discharge and glow discharge
generate nitrogen oxides as a byproduct which
have a risk of environment pollution from nitrogen
molecules (N2) [17,18]. On the other hand, the
generation of active oxygen species via UV light
irradiation does not generate nitrogen oxides from
N2 molecules. Therefore, the active oxygen species
via UV light irradiation can be applied for green,
safe, and low-cost surface modification process.
Generation of active oxygen species via UV Fig. 1. Schematic images of controlling humidity
light irradiation is based on the decomposition of conditions in Active-Dry®: (a) high humidity condition
oxygen and water molecules in an atmospheric and (b) low humidity condition.
condition. Therefore, it is necessary to control the
humidity during the generation of active oxygen
species. In this study, the PET film was exposed to into the Active-Dry® by a pump (Fig.1a). For low
the active oxygen species generated via 185/254 humidity (<20%RH), the dry air was passed
nm UV lights irradiation under conditions of high through a warmed bottle kept at 30°C containing
and low humidity, and changes in the surface silica gels before it was introduced into the system
characteristics were evaluated. by a pump (Fig.1b). The air pumping was shut off
when the exposure of active oxygen to the PET
2. Experimental film was started. The film was exposed to active
2.1. Material oxygen species for 30 min in each humidity
Polyethylene terephthalate (PET) film with a condition.
thickness of 100 µm (COSMOSHINE® A4100,
Toyobo) was cut into 15 mm x 10 mm. The surface 2.3. Surface configuration
of the PET film was cleaned with Kimwipes® The PET film surfaces exposed to active oxygen
using acetone and dried in air. species with UV lights were observed using a
scanning probe microscope (SPM; NanoScopeIIIa,
2.2. Exposure of active oxygen generation Bruker AXS). The same analysis was carried out
An active oxygen sterilization system on unexposed films as a control. Scanning area of
(Active-Dry®, Iwasaki Electric) equipped with SPM observation was 50 µm x 50 µm. With the
three low-pressure mercury UV lamps was used for SPM observation, the roughness parameters, which
generation of active oxygen species. The total are arithmetic mean roughness (Ra) and root mean
wattage of the lamps was 16 W, comprising two 6 square (Rq), were also determined by the SPM
W lamps (GL6ZH, Sankyo Denki) and one 4 W images.
lamp (GL4ZH, Sankyo Denki). These lamps emit
simultaneously two wavelengths of UV lights, i.e., 2.4. Surface wettability
185 and 254 nm. The active oxygen species were The 10 μL of distilled water was dropped on the
generated using a system with UV light irradiation PET film surfaces after the exposure of the active
under conditions of high or low humidity. The oxygen species. The same operation was carried
temperature in the system was kept at 30°C due to out on unexposed films as a control. A photo of the
introducing warmed air continuously. For high water droplet on each film surface was taken using
humidity (>90%RH), the air was passed through a a digital camera. The contact angle of the water
water bottle kept at 30°C before it was introduced droplet at the surface of the film was measured.

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2.5. Elemental compositions of the PET film surface

Changes in the chemical composition of the PET
film surface after the exposure of the active oxygen
species were analyzed by X-ray photoelectron
spectroscopy (XPS; Quantum 2000, Ulvac-phi).
The same analysis was carried out on unexposed
films as a control. The elemental compositions and
chemical bonding states at both of the films were
analyzed. Elemental compositions and chemical
bonding states of the XPS analyses are considered
to contain the information of the depth profile
within 10 nm.

2.6. Transparency of the PET film

The transmittance of the PET films exposed to
the active oxygen species with UV lights were
measured using a UV-VIS spectrophotometer
(UV-2450, Shimadzu). The range of wavelength
was 400 nm to 600 nm. The same operation was
carried out on unexposed films as a control. In
addition, each transmittance value at 550 nm
wavelength was measured.

2.7. Statistical analysis

All data are presented as mean ± standard
deviation (SD) and were analyzed using student's
two-tailed t-test with the significance level set at P
< 0.05. In addition, multiple comparison by the
Bonferroni-Holm method was performed using the
t-test values.
Fig. 2. SPM images of PET film surfaces: (A) untreated,
(B) after exposure to active oxygen species in the low
humidity condition, and (C) after exposure in the high
humidity condition.

3. Results
3.1. Surface observation
The scanning probe micrographs of PET films
are shown in Fig. 2. In addition, the parameters of
surface roughness determined by the SPM images,
i.e., the values of Ra and Rq, were summarized in
Figs. 3 and 4, respectively. The Ra values of the
PET films were as follows: (A) unexposed; 1.8 ±
0.1 nm, (B) exposed in the low humidity condition;
2.2 ± 0.1 nm, and (C) exposed in the high humidity
condition; 3.6 ± 0.4 nm. The Rq values of the PET
films were as follows: (A) unexposed; 2.4 ± 0.1
nm, (B) exposed in the low humidity condition; 5.7 Fig. 3. Arithmetic mean roughness (Ra) of PET film
± 0.3 nm, and (C) exposed in the high humidity surfaces: (A) untreated, (B) after exposure to active
condition; 7.0 ± 0.7 nm. Both Ra and Rq values of oxygen species in the low humidity condition, and (C)
the films after the exposure of the active oxygen after exposure in the high humidity condition. The data
species in the high humidity condition were are the mean ± SD; n=5. “†” indicates a significant
significantly larger than those in the low humidity difference by means of Student’s two-tailed t-test (P <
condition. 0.05) with Bonferroni-Holm correction.

3.2. Surface wettability

The contact angle on each PET film surface was exposed in the low humidity condition; 57.8 ±2.3 °,
summarized in Fig. 5. The value of each PET film and (C) exposed in the high humidity condition;
was as follows: (A) unexposed; 72.6 ± 1.9 °, (B) 50.6 ± 2.1 °. The values of the film exposed to

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Fig. 4. Root mean square (Rq) of PET film surfaces: (A)
untreated, (B) after exposure to active oxygen species in
the low humidity condition, and (C) after exposure in
the high humidity condition. The data are the mean ±
SD; n=5. “†” indicates a significant difference by means
of Student’s two-tailed t-test (P < 0.05) with
Bonferroni-Holm correction.
Fig. 5. Contact angles of PET film surfaces: (A)
untreated, (B) after exposure to active oxygen species in
the low humidity condition, and (C) after exposure in
the high humidity condition. The data are the mean ±
SD; n=5. “†” indicates a significant difference by means
of Student’s two-tailed t-test (P < 0.05) with
Bonferroni-Holm correction.
active oxygen species in the high humidity
condition were significantly smaller than those in
the low humidity condition.
3.3. Elemental compositions of the PET film surface
The C1s and O1s area ratios of each PET film
obtained from XPS analysis are summarized in
Table 1. The theoretical ratios of carbon and
oxygen atoms of untreated PET film are 71at% and
29at%. Carbon content of the pristine PET film
was slightly higher than that of the calculated value
412
Table 1. Ratio of chemical composition of PET film
before and after exposure to active oxygen species and
UV lights (at%).
C1s O1s
Untreated 73 27
Exposed in low humidity 65 35
Exposed in high humidity 59 41
Fig. 6. C1s XPS spectra of PET film surfaces: (A)
untreated, (B) after exposure to active oxygen species in
the low humidity condition, and (C) after exposure in
the high humidity condition.
from the molecular structure. Although this
difference is considered to be allowance limits of
error for the XPS measurement, some additives of
the PET film may affect the difference.
The C1s area ratio of the film exposed to active
oxygen species in the high humidity condition was
larger than that in the low humidity condition. The
O1s area ratio of each film increased with
decreasing of C1s area ratios. These results
indicate that the PET film is oxidized by exposure
of active oxygen species. The oxidization ability of
active oxygen species generated in the high
humidity condition is stronger than that in the low
humidity condition.
The C1s XPS spectrum of each PET film was
shown in Fig. 6. The chemical bonds of PET film,
i.e., C-C, C-O, and O=C-O, are assigned at 284.6
eV, 286.1 eV, and 288.8 eV, respectively [19]. An
obvious decrease can be recognized in the C-C and
C-O peak heights after the exposure of the active
oxygen species. On the other hand, the peak
heights of the O=C-O after the exposure of the
active oxygen species with UV lights were
increased in both of the humidity conditions. The
O=C-O peak height after the exposure of active
oxygen species in the high humidity condition was
 J. Photopolym. Sci. Technol., Vol. 27, No. 3, 2014

higher than that after the exposure in the low

humidity condition. These results indicate that the
exposure of active oxygen species with UV lights
to the PET film increases the carbonyl groups. In
addition, the exposure of the active oxygen species
generated in the high humidity condition is more
effective than that generated in the low humidity
condition.

3.4. Transmittance of the PET film

Transmittance at wavelengths from 400 nm to
600nm of each PET film was shown in Fig. 7.
Change in the transmittance at 550 nm wavelength
of each film was also shown in Fig. 8. The
transmittance after the exposure of the active
oxygen species in the high humidity condition was Fig. 7. Transmittance spectra of PET film surfaces: (A)
significantly smaller than that in the low humidity untreated, (B) after exposure to active oxygen species in
condition. On the other hand, no significant the low humidity condition, and (C) after exposure in
difference between the transmittance values before the high humidity condition.
and after the exposure was observed in the low
humidity condition.

4. Discussion
It is known that active oxygen species such as
excited singlet oxygen [O(1D)], ozone (O3),
hydroxyl radicals (OH*), and hydrogen peroxide
(H2O2) have long lifetime or high oxidization
abilities [8-16]. Generation mechanisms of these
active oxygen species have already been reported
as follows [11-16]. Firstly, an oxygen molecule is
decomposed into two ground-state oxygen atoms
by irradiation with 185 nm UV light. An O3
molecule is generated by the binding one of these
atoms to another oxygen molecule. The
Fig. 8. Transmittance of PET films at the wavelength of
excited-state oxygen atom and O(1D) are generated
550 nm: (A) untreated, (B) after exposure to active
by exposure of 254 nm UV light to the O3. A OH*
oxygen species in the low humidity condition, and (C)
is generated when the O3 is decomposed and binds after exposure in the high humidity condition. The data
to a hydrogen atom. The OH* is also generated by are the mean ± SD; n=3. “†” indicates a significant
exposing water molecules to 185 nm UV light. difference by means of Student’s two-tailed t-test (P <
O(1D) and OH* were found in the atmosphere 0.05) with Bonferroni-Holm correction.
when two wavelengths (185 and 254 nm) of UV
lamps were irradiated due to analyses of an
electron spin resonance (ESR) method. low humidity condition. It is considered that the
Concentrations of O(1D) and O3 generated under amount of OH* contributed to the etching behavior
low humidity condition were much higher than of the fluorocarbon thin film [21]. In this study, the
those generated under high humidity condition, amount of OH* is also considered to contribute the
and the concentration of OH* generated under low etching behavior of the PET film substrate.
humidity condition were much lower than that Contact angle of water droplet on the PET film
generated under high humidity condition [20]. surface and surface roughness after the treatment
Furthermore, a fluorocarbon thin film deposited in the high humidity condition increased compared
onto a quartz crystal oscillator prepared by r.f. to those in the low humidity condition, and
sputtering was used for investigation of etching transmittance within a region of the visible light of
and characteristics of an organic material due to the PET film after the treatment in the high
these active oxygen species. The etching rate under humidity condition decreased compared to that in
high humidity condition was higher than that under the low humidity condition. In addition, the

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amount of C-C bonds of the PET film surface after
the treatment in the high humidity condition
decreased compared to that in the low humidity
condition. Namely, these results indicate that OH*
with two wavelengths (185 and 254 nm) of UV
lights breaks polymer chains and oxidizes the PET
film surface more easily than the O(1D) and O3.
As it is known that reaction velocity constant of
the OH* is much higher than those of the O(1D)
and O3 [22], the OH* reacts polymer chains at the
PET film surface more easily than the O(1D) and
O3. It is considered that this is one of the reasons
why the PET film surface roughness after the
treatment in the high humidity condition increased
compared to that in the low humidity condition.
5. Conclusions
Active oxygen species were generated via
185/254 nm UV lights irradiation under conditions
of high and low humidity, and polyethylene
terephthalate (PET) films were exposed to the
active oxygen species with these UV lights.
Changes in their surface characteristics were
evaluated. The PET film substrate was modified by
active oxygen species generated under high and
low humidity conditions, and we evaluated effects
of the humidity conditions on the surface
modification. The PET film surface can be
modified more gently in the low humidity
condition than in the high humidity condition, and
it is considered that the OH* with two wavelengths
(185 and 254 nm) of UV lights breaks polymer
chains and oxidizes the PET film surface more
easily than the O(1D) and O3.
Acknowledgements
This work was financially supported by a
Grant-in-Aid for A-STEP from the Japan Science
and Technology Agency (JST). The authors are
thankful to Mr. Miyamoto and Mr. Haraki of the
Technical Service Coordination Office of Tokai
University for the SPM and XPS measurements.
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