Effect of polyvinyl butyral on the microstructure and laser damage threshold of

antireective silica lms

Fangting Chi
a,b
, Lianghong Yan
b,
, Haibing Lv
b
, Chengcheng Wang
b
, Xiaodong Yuan
b
a
College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
b
Research Center of Laser Fusion, China Academy of Engineering Physical, Mianyang 621900, People's Republic of China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 7 December 2009
Received in revised form 15 November 2010
Accepted 17 November 2010
Available online 27 November 2010
Keywords:
Polyvinyl Butyral
Antireective coatings
Silica
Solgel deposition
Laser induced damage threshold
Atomic Force Microscopy
Silica antireective lms modiedby polyvinyl butyral (PVB) were depositedonfused silica substrates by solgel
process. The effects of PVB on the microstructure and laser damage threshold (LIDT) of lms were investigated.
The results of the nanoparticle analyzer andscanning probe microscope revealedthat PVBmolecules surrounded
silica particles and controlled the particle growth, which resulted in a stable sol with uniformly distributed silica
particles. Therefore, the lms deposited fromthese modied sols possessed more uniformmicrostructures than
the lms without PVB. The adhesive-resistance test indicated that the strength of the modied silica lms
increased due to the bond reaction between PVB molecules and silica particles. The introduction of PVB into silica
sols had also increased the LIDT of lms. The LIDT of lms increased from 30.0 J/cm
2
to 40.1 J/cm
2
after 1.0 wt.%
PVB was added. The increase in LIDT was attributed to the increased strength and uniform microstructures of
lms as an effect of the PVB modication.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The antireective (AR) lms are widely studied and applied in
many elds [15]. To reduce the surface reection loss of laser on
transmissive optics and increase power transfer efciency, the AR
silica lms derived from solgel process have been and are being
applied on transmissive optical components of high power laser
facilities, such as the National Ignition Facility in the United States of
America and Shenguang III Facility in China. The lms have low
refractive index, low surface light scattering, high laser induced
damage threshold and relatively low production cost, which make
them attractive for use as AR lms in the laser systems [69].
The process for producing silica AR lms includes preparation of
silica sols and deposition of the sols on the substrates. The sols are
prepared by a route named as the Stber process developed more
than forty years ago [10]. In the Stber process, silica sols are formed
by the hydrolysis and condensation of silicon alkoxides in alcohol
solvents in the presence of water and a catalyst (e.g., ammonia). The
silica sols are deposited onto optical substrates by spin or dip coating
method, resulting in lms of random stacking silica colloids. The
highly porous characteristics of the lms provide the low refractive
index needed for antireection.
However, the AR lms derived fromthe simple Stber process are not
perfect, thus modied solgel processes are still the focus for the
preparation of functionalized AR lms through which the relevant lm
properties may be improved. Up to now, various types of modied silica
lms have been developed through an organic modied solgel process,
such as the organic silicate binder modication [11] and polymer
modication [12]. Through the modication methods, special functio-
nality like hydrophobicity, abrasion resistance and broadband antireec-
tion may be achieved. Among these modication techniques, polymer
modications of solgel AR silica lms are most widely used due to their
high effectiveness. Many kinds of polymers are used to improve the sol
gel silica lms in other studies. Ian M. Thomas found that the polyvinyl
alcohol modication of solgel process could increase the strength and
laser induced damage threshold of lms [13]. Yao Xu reported that
broadband antireective lms formed when a small amount of
polyvinylpyrrolidone was added into silica sols [7]. Polyvinyl butyral
(PVB) is a soluble polymer with wonderful properties, which is usually
used for applications that require strong binding, optical clarity, adhesion
to many surfaces, toughness and exibility. However, to our knowledge,
PVB modication to the solgel derived AR silica lms is rarely reported.
Inour previous work, we foundthat the additionof a small amount of
PVBintosilica sols couldsignicantlyimprovethe moisture-resistanceof
the silica lms [14]. The PVB/silica hybrid AR lms have potential
applications in the high power lasers of the Inertial Connement Fusion
facility. Thus, the present work is to systematically investigate the effects
of PVB on the microstructure and laser damage resistance of the silica
lms. It is observed that the addition of PVB into silica sols can strongly
affect the microstructure and laser damage threshold of the nal AR
lms.
Thin Solid Films 519 (2011) 24832487
Corresponding author. Tel.: +86 816 2483756.
E-mail address: yanlianghong@yahoo.cn (L. Yan).
0040-6090/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2010.11.023
Contents lists available at ScienceDirect
Thin Solid Films
j our nal homepage: www. el sevi er. com/ l ocat e/ t sf
2. Experimental details
2.1. Sample preparation
The reagents used were tetraethoxysilane (TEOS, Acros), PVB
(Mw=12,000, Acros), concentrated ammonium hydroxide (NH
3
H
2
O
Reagent Grade 2830% NH
3
), deionized water (H
2
O) and anhydrous
ethanol (EtOH, Tianjin chemicals), all of which were used without
purication. The PVB/silica sols were synthesized by controlled
hydrolysis and condensation of TEOS in an ethanol solution of PVB at
room temperature. During synthesis, two different but equal parts of
alcohol solutions were prepared. In the rst part, TEOS was added into
the anhydrous ethanol and the mixture was then sealed andkept stirred
for 30 min to achieve a completely soluble solution. The second part of
the alcohol solution was prepared by dissolving the NH
3
(aq) and
deionized water in the anhydrous ethanol. Hydrolysis and condensation
were then carried out by rapidly mixing the two parts of alcohol
solutions at vigorous stirring under atmospheric conditions. The molar
ratio of EtOH:NH
3
:H
2
O:TEOS was xed at 38:0.06:2.4:1, while the ratio
of PVB to TEOS was varied in order to produce PVB/silica sols with
different amount of PVB. As synthesized, the seven sols were named as
S0, S2, S4, S6, S10, S15 and S20, in whichPVB concentrations were 0, 0.2,
0.4, 0.6, 1.0, 1.5 and 2.0 weight percent (wt.%), respectively. All the sols
were aged for 14 days at room temperature in sealed glass containers
without stirring before use.
The sols were deposited on well cleaned fused silica glass substrates
by dip coating method. The fused silica glass substrates were ultra-
sonicated in acetone for 10 min and wiped carefully using cleanroom
wipers. Film thickness, d, was controlled to match the antireective
condition, n
f
d=/4, by adjusting the dipping speed. The desired
wavelengthwas =1053 nmandn
f
was the refractiveindexof the lms.
Films werethermallytreatedat 160 Cfor 8 hunder ambient atmosphere
and labeled as F0, F2, F4, F6, F10, F15 and F20, respectively.
2.2. Characterization
The refractive index and thickness of the silica lms were measured
using a spectroscopic ellipsometer (Sentech SE850) at 800 nm wave-
length and 70 incidence. The relative measurement errors are known to
be within 1%. The porosity of lms was calculated according to the
LorentzLorenz equation:
porosity = 1
n
2
1
n
2
d
1
; 1
where n is the refractive index of the resultant lm and n
d
=1.46 is
the refractive index of the fused silica glass. The surface morphology
of lms was observed using a scanning probe microscope (SPM)
(XE-100, PSIA) in the contact and tapping modes. The particle size
distribution of silica sols was measured on a nano particle analyzer
(Nano- ZS Malvern) at 25 C using ethanol as dispersant. The abrasion
resistance test was carried out by the method suggested by Floch et al.
[12] as follows: a dragwipe test was performed by rubbing the lm
100 times using a thin lter paper; then visual observation was used
to verify the damage degree of the lm. In addition, careful observation
was carried out under an optical microscope (Nikon eclipse LV100D) at
10 magnication.
The laser induced damage threshold (LIDT) was measured on the
lms with the set-up shown in Fig. 1. A Q-switched Nd: YAG laser
(Beijing Jiepu TrendTechnology Company) was used to provide a nearly
Gaussian-type pulse beam at 1053 nm wavelength. The maximum
output energy was 800 mJ, whose output energy stability was 2.5%.
The pulse duration was 7 ns and the repetition frequency was 1 Hz. A
xed energy attenuator was installed in the beam path to control the
output energy. Two wedges were used to pick off a portion of the beam
for a standard set of beam diagnostics that included a calorimeter
(energy measurement), a photodiode (temporal properties), and a CCD
camera (spatial prole). The laser spot on the test lms was 1.0 mm
2
.
The R: 1 testing procedure was carried out at 40 different locations that
were arranged into an 85 array. By increasing the irradiation energy
from0 to 0.5 mJ in one step, the lms were shot until damage occurred.
The damage was estimated from the visual inspection of plasma ash
and detected in situ with an interferential contrast microscope (Nikon
E600W).
3. Results and discussion
3.1. Refractive index and porosity of lms
The refractive index of lms is related to their porosity and larger
porosity produces lower refractive index. Fig. 2 shows the refractive
indices and corresponding porosities of silica lms as a function of the
PVB content. The refractive index and porosity are directly dependent
on the PVB content. The refractive index of the silica lm is 1.18 at
1053 nm, which is consistent with the result of others [15]. With the
increase of PVB content from 0 wt.% to 1.0 wt.%, the refractive index of
the lm increases from 1.18 to 1.30 and the porosity of the lm
decreases from 0.65 to 0.39. However, when the PVB content increases
beyond 1.0 wt.%, there is a decrease in refractive index and an increase
in porosity. A lling model can be used to explain this phenomenon.
Fig. 1. Schematic of laser damage testing apparatus at 1053 nm.
2484 F. Chi et al. / Thin Solid Films 519 (2011) 24832487
When PVB is progressively increased to ll the pores of the lminitially,
the porosity would decrease until the pores are full and consequently
the refractive index increases. A further addition of PVB leads to an
increase in interparticle distance and the packing density decreases,
resulting in a lower refractive index.
3.2. Film strength
The solgel derived AR silica lms are easily abraded because
no chemical bond exists between the individual silica particles and
with the substrate surface. The nature of the lms is such that they
are kept intact only by physical forces between independent colloids
and the abrasion resistance is therefore low. The lms are irreversibly
damaged when physically touched or wiped. Fortunately, it is found
that increasing lm strength is achieved by the incorporation of
polymer binders into lm composition [16]. The properties required
for such a polymer are as follows: 1, must be soluble in ethanol;
2, should not occulate the silica sol; and 3, should readily be
compatible with the silica particles. PVB is found to be satisfactory for
this application. In the solgel process, the silica particles are formed
by the hydrolysis and condensation of TEOS in alcohol solvents in the
presence of NH
3
and H
2
O as the following chemical reactions:
SiOC
2
H
5

4

4
H
2
OSiOH
4

4
C
2
H
5
OH: 2
nSiOH
4
nSiO
2
2nH
2
O: 3
However, not all the hydroxyl groups on the silicon atom react
with each other. Thus the silica particles contain a large number of
hydroxyl groups on their surfaces. The PVB molecules also involve the
hydroxyl groups. The silica particles can be connected by the PVB
binder owing to the existence of the hydroxyl groups in both the PVB
binders and the silica particles [17]. The PVB modication of lm
enables us to physically touch AR lms without any microscopic
damage since the AR lms become stronger. The abrasion resistance
test was performed by a dragwipe test. It is observed that the abrasion
resistance of lms increases with the increase of PVB content. After
rubbing the lms 100 times, the lms without PVB physically damaged
seriously. However, lms with 2.0 wt.% PVB show no visible damage
under anoptical microscope. Alarger amount of PVBis not recommended
because it will occulate the silica sol. During the deposition process, the
occulated silica sol is not stable, which makes the sol not suitable for
coating.
3.3. LIDT of lms
It is well known that solgel derived silica AR lms possess very high
LIDT [8,18]. Fig. 3 gives the LIDTs measured at 1053 nm for all the lms,
which correspond to the highest energies at which no damage occurred.
The LIDT values for the lms with different PVB contents are 30.0, 34.1,
35.5, 37.2, 40.1, 38.1, and 35.1 J/cm
2
, corresponding to F0, F2, F4, F6, F10
,
F15 and F20 respectively. With the increase of PVB content, the LIDT of
silica lms increases rstly from30.0 J/cm
2
(F0) to 40.1 J/cm
2
(F10), and
thendecreases quickly to 35.1 J/cm
2
. The lmF10has the highest LIDT, in
which the PVP content is 1.0 wt.%. It shows that the addition of a suitable
amount of PVB can improve the laser damage resistance of silica lms,
but the excessive PVB reduces the LIDT. The increase in LIDT may mainly
result from the increase in lm strength induced by the enhanced
particle-to-particle bond strength due to the PVB binder. The silica lms
are normally prepared from organic reagents, thus organic impurities
and other contaminants possibly remained in the nal lms. When some
of these organic impurities andother contaminants are rapidly vaporized
bythelaser irradiation, thelms woulddamage. Therefore, it is suspected
that lm weakness can contribute to laser damage and higher LIDT of
lms can be obtained when the lms are strengthened. However, PVB
itself can act as organic impurity and excessive amount of PVB has a
negative effect on the LIDT. In addition, it suggests that lm F6 modied
with suitable PVB content has the most uniform structure among all the
lms, which will be discussed in Section 3.4. The representative
morphologies of the damaged areas for the lms with and without PVB
addition are shown in Fig. 4. All samples show similar annular damage
spots induced by the laser surface burning of lms. At the center of the
damage spots the lm materials have been entirely removed. Beyond a
certain distance from the center, no material loss can be observed. This
suggests that the damages of lms may be caused by laser-induced
ablation processes. In Fig. 4, the different surface morphologies indicate
that the lm without PVB suffered the most serious damage while the
lm prepared with 1.0 wt.% PVB has the mildest damage. It shows that
the PVB content has a positive effect on the LIDT of the lms.
3.4. Relation between microstructure and LIDT of lm
Themicrostructureof PVB/silicaARlms shouldalsobeconsideredin
order to understand the effect of PVB on LIDT. The colloidal particles
producedby the solgel process have sphere structure andsubsequently
formlms withporous structure bypackingthesesilica spheres [19]. The
microstructure of the silica lm is controlled by several factors such as
the reaction condition, the intrinsic microstructure of silica particles and
the deposition process. It is known that the microstructure of the solgel
lm has a signicant effect on the LIDT of the lms [20]. Solgel lms
possess porous structure formed by particle stacking, which provides
Fig. 2. Variation of refractive indices and porosity of lms with PVB content.
Fig. 3. Laser induced damage threshold of lms with different amount of PVB.
2485 F. Chi et al. / Thin Solid Films 519 (2011) 24832487
good LIDT. Solgel lms have a good space capability to accommodate
thermal expansionwhichoccurs during laser irradiationprocess because
of the absorption of laser energy by the lm. Thus the microstructure of
thelmis alsoa keyfactor totheLIDT. Scanningprobe microscope(SPM)
analysis is an effective tool to investigate the microstructure of the lm,
thus we characterize the silica lms using a SPMand relate the results of
SPMto the laser induced damage behavior of the lms froma particular
view.
Fig. 5 shows the two-dimensional SPM images of lms F0, F10 and
F20, indicating the different porous structures and the different
surface roughness. It is distinctly observed that the surface of the lm
without PVB modication is composed of silica particles and rather
rough as given in Fig. 5(a). In contrast, the lm F10 with 1.0 wt.% PVB
modication is dense and the surface is smooth as shown in Fig. 5(b).
It indicates that tighter structures are formed in PVB/silica lms and
that the tightness is improved with the PVB modication. However,
when the PVB content increases in excess of 1.0 wt.%, the silica
particles become larger, leading to a rougher lm. The observation is
consistent with the results of refractive index and porosity of lm. The
root-mean-square (RMS) roughness values of lms were analyzed
with a SPM. The RMS values of the lms F0, F10 and F20 are 5.12, 3.25,
and 4.61 nm, respectively. The results indicate that a suitable amount
PVB modication can decrease the surface roughness, and surface
roughness increases as the PVB content exceeds an optimal value. As
shown in Section 3.3, the LIDT values of lms showthe same trends as
the microstructures of the lms. From the results derived from the
SPM, it could suspect that the LIDT of the lm is positively dependent
Fig. 4. Laser induced damage morphologies of the annealed lms with Nikon microscope:
(a) lm without PVB, (b) lm with 1.0 wt.% PVB, and (c) lm with 2.0% PVB.
Fig. 5. Two-dimensional SPM images of annealed lms: (a) lm without PVB, (b) lm with
1.0 wt.% PVB, and (c) lm with 2.0% PVB.
2486 F. Chi et al. / Thin Solid Films 519 (2011) 24832487
on the microstructures of the lms. When the lm composed of
uniform silica particles has a uniform microstructure, it may have a
stable structure and possesses a higher LIDT.
The zetasizer nano particle analyzer was used to investigate the
microstructures of silica particles in the sols. Fig. 6 shows the particle
size distributions of silica sols S0, S10, S20, corresponding to PVB
contents of 0 wt.%, 1.0 wt.% and 2.0 wt.%, respectively. The particle
size distributions are narrower in the PVB/silica sols than those
without PVB, and the particles are smaller in the PVB/silica sols. The
results indicate that PVB has the ability to inhibit the growth of silica
particles. It agrees well with the results of SPM, in which the lm
derived from sol S10 has a more uniform structure. During the
deposition process, the small particles may be stacked tightly so that
the tightness of the lm can be enhanced.
4. Conclusion
PVB modied silica AR lms were prepared through the addition of
PVB to the solgel precursor solution. The addition of PVB to silica sols
was found to increase the LIDT of the lms prepared from the sols. The
increase in LIDT was due to the increase in lmstrength and uniformity
of lm microstructures. Adhesive-resistance test showed that the
strength of the lm was enhanced by the incorporation of PVB into
lms. Suchlmwas more difcult todamage by the laser irradiationdue
to its improved physical strength. Furthermore, the result of the nano
particle analyzer showed that the growth of the silica particles was
controlled by the addition of the optimal amount of PVB, and a stable
silica sol was obtained in which the size of sol particles was more
uniform. As a result, the lm deposited from such silica sols possessed
more uniform microstructures. The uniform microstructures made the
lm have a good space capability to accommodate thermal expansion
which occurred during laser irradiation process.
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Fig. 6. Particle size distributions of the PVB modied silica sols: (a) sol without PVB,
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2487 F. Chi et al. / Thin Solid Films 519 (2011) 24832487