Synthesis and optoelectronics properties of diblock copolymer of P3HT containing thiol-side chains and its hybrid nanocomposite

Article abstract of DOI:10.1039/C6RA19895C

Although the solid-state microstructure of semiconducting polymers is well known to influence properties in optoelectronic devices, the control of desired aggregation in solution and film remains relatively rare. Here, diblock copolymer poly(3-hexylthioph

Full text of DOI:10.1039/C6RA19895C

View Article Online
View Journal
RSC Advances
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Qiao, Y. Du, Y.
Liu and Y. Li, RSC Adv., 2016, DOI: 10.1039/C6RA19895C.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
rsc.li/rsc-advances

Please do not adjust margins
RSC Advances
Page 1 of 9
View Article Online
DOI: 10.1039/C6RA19895C
RSC Advances
ARTICLE
Synthesis and optoelectronics properties of diblock copolymer of
P3HT containing thiol-side chain and its hybrid nanocomposite
Received 00th January 20xx,
Accepted 00th January 20xx
Yisha Qiao, Yixuan Du, Yinfeng Liu, Yunbo Li*
Although the solid-state microstructure of semiconducting polymers is well known to influence properties in
optoelectronic devices, the controlling desired aggregation in solution and film remains relatively few. Here, diblock
copolymer poly(3-hexylthiophene)-b-poly(3-thiophenehexanethiol) (DP-P3HT-SH) had been synthesized by simple
synthetic technique, and different aggregation states DP-P3HT-SH and their respective hybrid nanostructures DP-P3HT-S-
AuNPs had been prepared to research the influence of aggregate morphology on photoelectric performance. The diblock
copolymer DP-P3HT-SH could be prepared into different aggregation states, i.e., global (G), leaflike (L) and elliptical (E)
shape states. The DP-P3HT-S-AuNPs composites exhibited wider absorption band than DP-P3HT-SH polymer and showed
photoluminescence (PL) quenching. The amount of PL quenching of the three aggregation states were 23%, 11% and 21%,
respectively, which illustrated that the charge transfer between GDP-P3HT-SH and AuNPs was the most efficient among
these three aggregation states. In addition, the conductivity of these three aggregation states DP-P3HT-SH could be
improved by the addition of AuNPs and the increase of film thickness. Therefore, the semiconducting polymer-metal
composites could be used to design new optoelectronics material by tuning the aggregation state of diblock copolymer to
modulate device characteristics.
DOI: 10.1039/x0xx00000x
www.rsc.org/
copolymers for improving the performance of all-polymer organic
Introduction
8
photovoltaics. Among the polythiophene derivatives materials,
Polythiophene and its derivatives are important semiconducting
polymers with optoelectronic property, low cost and good
regioregular poly(3-hexylthiophene) (P3HT) has shown the good
9
performance in electricity devices. The excellent charge-transport
1
processability. The property of polythiophene derivatives is
properties of P3HT have been attributed to microstructure of
semiconductor. The solid-state microstructure of semiconducting
polymers is known to affect properties relevant for their function in
determined by its structure, regularity and self-aggregate
2
morphology. As one of the key factors, the aggregate morphology
has been studied in semiconducting materials. R. D. Mccullough had
reported that the introduction of alkyl of polythiophene contributes
to the polymer self-assembly into nanometer fiber structure which
10
optoelectronic devices.
In addition, large aggregate structures conjugated diblock
copolymers are valued in photovoltaic device in recent years.
Organic photovoltaics (OPVs) device performance depends critically
on the polymer morphology of the active layer, which ideally
3
improved the efficiency of photoelectronic device. X. Yu and co-
works reported that different self-assembled morphologies of
spheres, lamellae, worm nanofiber and crystalline nanoribbon of
promotes efficient exciton formation, charge dissociation, and
conjugated
block
copolymers
polystyrene-b-poly(3-
2b,8b
charge transport to the respective electrodes.
For example,
4
hexylthiophene)(PS-b-P3HT) effected field-effect mobility. B. A. G.
Hammer prepared nanowires and cross-linked nanowires structures
of P3HT-b-poly(3-(3-thioacetylpropyl)oxymethylthiophene) (P3TT)
which leads to different transfer and output characteristics of field-
Ryan C. Hayward group had prepared different morphologies of
perylene diimide (PDI) fibers with width of 150-500 nm or 70-200
11
nm. Todd Emrick and his coworkers prepared large size polymer
2b
P3HT-b-P3MT fibrils with width 15-25 nm and length 0.5-5.0 μm.
5
effect transistor. Seth B. Darling group reported that block
Accordingly, it is necessary to study the influence of large structures
with different morphologies on the photoelectronic performance of
organic semiconductor materials.
copolymer self-assembly can be utilized to rationally design and
6
control the shape and dimension of resulting nanostructures, such
as the application of the self-assembled P3HT-b-PLLA in organic or
In recent years, semiconducting polymer-inorganic composites
have attracted increasing interest for applications in organic
optoelectronics devices mainly due to their optical and electricity
7
hybrid solar energy devices. Verduzco, R group reported that
conjugated diblock copolymers may be useful for achieving active
layers in organic photovoltaics and light-emitting diodes, and the
important application of supramolecular conjugated block
12
properties. In particular, conjugated diblock copolymers P3HT
13
have already been used in electronic devices. Simultaneously,
many works have been done to design hybrid nanostructures based
1
4
15
on conjugated polymers bond with inorganic like CdSe and ZnO ,
and form semiconductors. Jih-Jen Wu and his colleagues
demonstrated that the introduction of Au@silica NPs could enrich
School of Materials Science & Engineering, Shanghai University, Shanghai 200072,
China
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here. Y. Li
ybli@shu.edu.cn)
(
This journal is © The Royal Society of Chemistry 20xx
RSC Advances, 2016, 00, 1-8 | 1
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 2 of 9
View Article Online
DOI: 10.1039/C6RA19895C
ARTICLE
Journal Name
1
6
3
2
0% of short-circuit current density in P3HT solar cell. Solar cells for 2.0 hours. 1.0 ml 3-bromothiophene and Ni(dppp)Cl (10.0 mg,
o
fabricated using TiO2-coated ZnO NRs and P3HT showed efficiencies 0.00002mol) at 0 C were added into the mixture. The mixture
of up to 0.76%, and a 58% improvement over TiO2-free equivalent subsequently was refluxed for 2.0 hours. 10.0 ml of 1.0 mol/L HCL
1
7
devices. Accordingly, the inorganic had important influence on and 10.0 ml distilled water was added into hydrolysis reaction
photoelectronic performance of semiconducting materials. system. The system was extracted with ether, washed to neutrality
Among them, semiconducting polymer-metal hybrid system has and dried with the combined organic phases. A light yellow product
2
1 1
been paid attention due to exciton Plasmon interactions which are was obtained after evaporate the solvent.
H NMR (500 MHz,
): 7.26 (s, 1H), 6.99 (t, 2H), 6.81 (s, 1H), 2.81 (m, 2H), 2.59(m,
exhibits enhanced radiative rates and exciton Plasmon energy 3H), 1.74(m, 2H), 1.53-1.33 (m, 4H) (ESI†, Fig. S1).
1
2a
different from its individual counterpart . This hybrid system CDCl
3
1
8
transfer due to weak coupling regimes. The semiconducting
polymer-metal nanoparticles could provide appropriate electron
donor and electron acceptor which would produce electric dipole in
the composite and form the stable electronic channels. The energy
transfer/charge separation could occur when the semiconducting
polymer-metal nanoparticles were excited. C. Fan had described the
high efficiency energy transfer from the conjugated polymer to gold
S
Br
MgBr
Br
OH
O
O
O
O
O
Br
Mg/Et O
O
O
Br
2
S
KOH, Methanol
Ni(dppp)Cl2
Scheme 1. Schematic illustration for the synthesis of the 3-[6-
4-methoxyphenoxy)hexyl]thiophene.
19
NPs. V. Ruiz had reported that the addition of gold nanoparticles
could significantly improve the conductivity of ultrathin poly(3-
(
1
2f
hexylthiophene)/gold nanoparticle blend Films.
Synthesis of 2,5-dibromo-3-(6-bromohexylthiophene). 3-[6-(4-
methoxyphenoxy)hexyl]thiophene (2.1 g, 0.007mol) was added into
a three-necked 100 mL round-bottom flask with a magnetic stirring
bar under inert atmosphere. A mixture of HBr and acetic anhydride
In this study DP-P3HT-SH has been synthesized by the simple
solution based synthetic technique and three different aggregation
states DP-P3HT-SH and their respective composites DP-P3HT-S-
AuNPs hybrid nanostructures have been prepared. Absorption and
photoluminescence spectra have been studied. In addition, the
conductivity of P3HT-S-AuNPs films made with three different
aggregation states were systematically investigated.
(
6 mL:6 mL) was added into the flask. The reaction mixture was
heated at 100 °C to reflux for 24 hours. The mixture was extracted
with ether and the solution was washed to neutrality with saturated
aqueous NaHCO
3
solution. The solution was transferred into a silica
gel column, and eluted by hexane. A colorless oil product 3-(6-
2
1
bromohexylthiophene)was obtained after removing the solvent.
-bromohexylthiophene (1.5 g, 0.006 mol) was added into a 100 mL
round-bottom flask for stirring, then the THF and acetic acid (6 mL:
mL) mixed liquid was added into the flask. n-bromosuccinimide
2.0 g, 0.011 mol) was added into the compound and heated at 30
Experimental section
3
Chemicals and Materials. Tetrahydrofuran (THF, from Sinopharm)
was
freshly
distilled
before
use.
[1,3-
6
bis(diphenylphosphino)propane]-dichloronickel(II) (Ni(dppp)Cl ), 3-
bromothiophene (97%), 2,5-Dibromo-3-hexylthiophene (99%), N-
bromosuccinimide (NBS, 99%), magnesium turnings and chloroform
2
(
o
C for an hour. Terminating reaction was carried out by distilled
water (10 ml), then the solution was extracted with diethyl ether
Isopropylmagnesium chloride (2.0 M solution in THF) and 4- (Et O) (30 ml). The organic extracts were washed by distilled water
Methoxyphenol were purchased from Aldrich Chemicals. 2-thiourea (30 ml) and saturated NaHCO solution (30 ml); then anhydrous
was purchased from TCL. 1, 6-dibromohexane was purchased from MgSO was used to dry the organic layer. After evaporating the
3
(CHCl ) were purchased from Sinopharm and used as-received.
2
3
4
Alfa Aesar. Gold(III) chloride trihydrate (HAuCl
citrate were obtained from Sinopharm.
4
) and trisodium solution, the product was transferred into a silica gel column and
eluted with petroleum ether. The final colorless product was 2,5-
2
2 1
Synthesis of 3-[6-(4-methoxyphenoxy)hexyl]thiophene. 4-
methoxyphenol (3.1 g, 0.025 mol), KOH (1.2 g, 0.021 mol), and 20
ml of dried methyl alcohol was added into a three-necked 500 mL
round-bottom flask with a magnetic stirring bar. The solution was
stirred for 1.0 hour. 1, 6-dibromohexane (10.0 g, 0.041 mol) was
added into the reaction solution and the mixture was refluxed
overnight. The mixture then was filtered to remove the KBr.
Methanol was evaporated and the mixture was redissolved in
hexane. 2.0 mol/L NaOH (aq), 1.0 mol/L NaCl (aq) and water were
prepared to wash the mixture sequentially to achieve a neutral
state. Under the condition of low pressure, the unreacted 1, 6-
dibromohexane was removed by distillation. The residue was
redissolved in hexane, and the product was filtered after the
solution was cooled down for recrystallization. The product of 1-(6-
dibromo-3-(6-bromohexylthiophene). H NMR (500 MHz, CDCl3):
.26 (s, 1H), 6.99 (t, 2H), 3.77 (s, 1H), 3.67 (t, 2H), 2.31 (t, 2H), 1.87
m, 2H), 1.25-1.53 (m, 6H) (ESI , Fig. S ).
7
(
†
2
S
O
O
HBr
S
NBS
CH3COOH, THF
S
Br
Br
(
3 2
CH CO) O
Br
Br
Scheme 2. Schematic illustration for the synthesis of the 3-(6-
bromohexylthiophene) and 2,5-dibromo-3-(6-bromohexylthio-
phene)
2
0
bromohexyl)-4-methoxybenzene was obtained. 1-(6-bromohexyl)-
-methoxybenzene (3.01 g, 0.01mol) was added into 20 ml of
4
anhydrous ether firstly and magnesium turnings (0.21 g, 0.009mol)
Synthesis of diblock copolymer poly(3-hexylthiophene)–b-
poly(3-(6-bromohexylthiophene)) (P3HT-b-P3BPT) 2,5-
were added under inert atmosphere. The mixture was then refluxed
2
| RSC Advances, 2016, 00, 1-8
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 9
RSC Advances
View Article Online
DOI: 10.1039/C6RA19895C
RSC Advances
ARTICLE
o
dibromo-3-hexylthiophene (1.63 g, 0.005 mol) and 2,5- hours at 25 C and ultrasonic 5min. Leaflike state DP-P3HT-SH (LDP-
dibromo-3-(6-bromohexylthiophene) (0.41 g, 0.001 mol) were P3HT-SH) was obtained by the following method: DP-P3HT-SH
o
separately dissolved in THF (10 ml/mg) in a 100 mL round- solution in THF was heated to 80 C for 30 min; then the solution
bottom flask. 2.0 mol/L Isopropylmagnesium chloride (0.58 g, was cooled to room temperature naturally overnight. Elliptical
0
.005 mol) and 2.0 mol/L Isopropylmagnesium chloride (0.116 shape DP-P3HT-SH (EDP-P3HT-SH) was prepared by heating the
o
g, 0.0011 mol) were separately added into the compound LDP-P3HT-SH solution to 50 C for 12 hours; then the polymer was
o
sequentially
and
refluxed
for
2
hours.
1,3- cooled to 40 C for 48 hours.
bis(diphenylphosphino)propane]-dichloronickel catalyst (15.0
mg, 0.00003 mol) was added into the flask reacted with the
Synthesis of gold nanoparticles (AuNPs). The gold nanoparticles in
23
water were synthesized as reported by F.M A.Carpay. Aqueous
-4
2
,5-dibromo-3-hexylthiophene Grignard for 1 hour. Then the
,5-dibromo-3-(6-bromohexylthiophene) Grignard solutions
solution of HAuCl
stirring. Then trisodium citrate (0.01 g/ml, 0.5 ml) was added into
the HAuCl aqueous solution with stirring. After 30 second the
4
(1×10 g/ml, 50 ml) was boiled under gentle
2
was added into the above reaction system and reacted for
another 1 hour. 10 ml methanol was used to quench the
polymerization. The polymer was precipitated in methanol and
centrifuged, then the solvent was decanted off and the
polymer was collected. The polymer was purified by sequential
Soxhlet extractions using methanol, hexane, and chloroform.
The chloroform fraction was dried to obtain the final polymer
4
mixed solution turned faintly blue and 2 min later the blue colour
suddenly changed into a brilliant red indicating the formation of
monodisperse spherical particles. After further vigorous stirring for
5
min, the product was collected. Next, 10 mL of hexane 10 mg of
sodium oleate were added into 10 g of the product in water
prepared above. The mixture was emulsified by vigorous stirring at
room temperature for 2 hours. Magnesium chloride (0.12 g, 0.001
mol) in 1.5 mL of water was then added with stirring. The mixture
was transformed from an emulsion into two liquid phases after 4 h
sedimentation. The hexane phase containing AuNPs was collected.
5
1
as a deep purple solid. H NMR (500 MHz, CDCl3): 6.98 (s, 1H),
.71(t, 2H), 2.82(t, 2H), 1.73(m, 2H), 1.50(m, 4H) (ESI , Fig.
S3)
3
†
.
t-butylMgCl, THF
S
S
S
Br
Br
24
S
n
m
A molecular sieve was used to remove the residual water.
Br
Br
Preparation of the hybrid particles DP-P3HT-S-AuNPs. The hybrid
particles DP-P3HT-S-AuNPs were obtained as followed: gold
nanoparticles in hexane and DP-P3HT-SH in THF were stirred for 6
hours. The hybrid particles were purified by centrifugation. Next the
precipitated was dissolved in THF. This purification procedure was
repeated for another two times. The product was dispersed in THF
finally and the concentration of DP-P3HT-S-AuNPs solution was kept
at 1.0 mg/mL.
Br
Br
Scheme 3. Schematic illustration for the synthesis of the
poly(3-hexylthiophene)–b-poly(3-(6-bromohexylthiophene))
Synthesis of diblock copolymer poly(3-hexylthiophene)-b-poly(3-
6-thiolhexylthiophene)) (DP-P3HT-SH) 0.91 g P3HT-b-P3BPT and
(
Characterization Techniques. Transmission electron microscopy
2
-thiourea (0.15 g, 0.002 mol) was dissolved in ethanol (20 mL,
5%) in a round-bottom flask and refluxed for 2 hours. KOH solution
(
TEM) images were obtained by a JEOL 200CX electron microscope
9
equipped with a Model GATAN782 CCD camera at an operating
voltage of 120 kV. The samples for TEM studies were prepared by
placing one droplet of the sample deposited onto carbon-coated
copper grids. An Agilent 8453 UV−vis spectrophotometer (Agilent
technologies, CA, USA) is utilized to analyze the UV−vis absorption
property of the sample. The slit width was 1 nm during the
(
10 ml, 0.3 mol/L) was added into the compound and refluxed for 4
hours; then 0.05ml H SO (98%) in 5 ml distilled water was added in
2
4
the reaction system to neutralize excess alkali. The solution was
extracted with hexane and washed by distilled water, and then the
4
anhydrous MgSO was used to dry the organic layer. The resulting
polymer was purified by sequential Soxhlet extractions using measurements. Fourier transform infrared (FTIR) spectra were
methanol, hexane, and chloroform. The chloroform fraction was recorded on
Nicolet 380 FTIR spectrophotometer. The
NMR photoluminescence (PL) experiments were carried out on a RF5301
): 7.00 (s, 1H), 2.70 (t, 2H), 2.59 (m, 2H), 1.73 (m, fluorescence spectrophotometer for the films and solution. The
a
5
1
dried and the obtained polymer is a deep purple solid.
500 MHz, CDCl
H), 1.25-1.70 (m, 8H), 0.85 (t, 3H) (ESI†, Fig. S4).
H
(
3
2
exciting wavelength and slit width are at 470 nm and 5 nm,
respectively. The film thickness was measured by a Surfcorder ET
S
S
2-thiourea, ethanol
reflux
KOH
S
S
1
50 profiler. All electric conductivity measurements were made
m
n
m
n
along the film plane using a VC890C+ multimeter. The samples were
prepared as followed: different aggregation states for the diblock
copolymer P3HT-SH (DP-P3HT-SH) at 1.0 mg/mL in THF with
different volume gold nanoparticles in hexane. Several fluorine-
doped tin oxide (FTO) were prepared and cleaned for further works.
The composites DP-P3HT-S-AuNPs and DP-P3HT-SH solutions were
dropped onto precleaned FTO glass to get a uniform film, and the
film thickness was controlled in the range from 0.7 μm to 2.4 μm by
adjusting the dropping layer. The substrate of the sample films for
conductivity measurement was the etched FTO glass with a channel
SH
Br
Scheme 4. Schematic illustration for the synthesis of the
poly(3-hexylthiophene)-b-poly(3-(6-thiolhexylthiophene))
Preparation of different aggregate states DP-P3HT-SH in solution.
Global state DP-P3HT-SH (GDP-P3HT-SH) was prepared as followed:
DP-P3HT-SH was dissolved in THF and kept concentration of 1.0
o
mg/mL at 20 C; then the copolymer was stirred vigorously for 20
This journal is © The Royal Society of Chemistry 20xx
RSC Advances, 2016, 00, 1-8 | 3
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 4 of 9
View Article Online
DOI: 10.1039/C6RA19895C
ARTICLE
Journal Name
1
mm wide. 2-probe methods using a VC890C+ multimeter were
employed for conductivity measurement in air. The conductivity
2
5
was calculated from Ohm’s law :
σ=Iw/Vdl
(1)
Here, I, w, V, d and l represent the current injected, width of the
channel (1 mm), voltage read out, thickness of the film in the
channel and length of the channel (1 cm), respectively.
RESULTS AND DISCUSSION
Size distribution of gold nanoparticles and FTIR spectra of P3HT-b-
P36THT, P3HT-b-P36THT/AuNPs
1
Figure 2. H NMR spectra of poly(3-hexylthiophene)-b-poly(3-(6-
Figure 1a showed the size distribution of gold nanoparticles in
hexane. The average particle diameter of gold nanoparticles is
about 22.5 nm. The smaller of the size of gold nanoparticles contain
less number atoms which could make nanometer system appeared
many new characteristics different from conventional materials.
The gold nanoparticles were used in the next work.
thiolhexylthiophene)) ( DP-P3HT-SH) in CDCl
3
P3HT-SH was the successful synthesized. The IR spectra of the DP-
P3HT-S-AuNPs hybrid particles and of DP-P3HT-SH are similar which
indicates that thiol is indeed part of the composite. What’s more,
the intensity of absorption peak of the obtained product becomes
lower compared with that of DP-P3HT-SH, which indicates that the
Figure 1b showed the FTIR spectra of the DP-P3HT-SH and DP-
P3HT-S-AuNPs hybrid particles. The polymer chain included the
27
DP-P3HT-SH polymer was thiolated gold nanoparticles.
-1
following main characteristic absorption bands: 2938 cm bands of
-
1
the C-H stretching mode of thiophene ring; 2852 cm bands of the
1
H NMR spectra of the thiol-functionalized diblock copolymers
C-H stretching mode outside of the thiophene ring side chain; 1701
(
DP-P3HT-SH)
-
1
-1
-1
cm , 1538 cm and 1465 cm bands of symmetric C=C stretching;
1
-1
Figure 2 showed the H NMR spectrum which was used to
characterize the synthesized DP-P3HT-SH. The final product had
eight main bonds of carbon–hydrogen which corresponded to
1
315 cm bands of the –CH
3
stretching mode outside of the
-1
thiophene ring side chain; 1118 cm bands of C-Br stretching mode
-1
of thiophene ring; 823 cm bands of =CH out of plane deformation;
1
1
-1
-1
peaks in H NMR spectrum. H NMR (500 MHz, CDCl ): 7.00 (s, 1H),
3
7
23 cm , 655 cm bands of C-S-C stretching mode of thiophene
-1
2.70 (t, 2H), 2.61 (m, 2H), 1.73 (m, 2H), 1.25-1.70 (m, 8H), 0.85 (t,
ring. In addition, the weak peak at about 2565 cm was the bands
3
H). The appearance of the methylene proton peaks next to thiol
of the S-H stretching mode outside of the thiophene ring side
2
6
group at 2.61 ppm could illustrate the existence of S-H bonds. The
chain. Therefore the resulting product was confirmed that DP-
1
H NMR spectrum was consistent with the studies reported by G.
Konstantatos group who had synthesized the thiol-functionalized
24
20
16
12
8
4
0
1
c
a
block copolymer P3HT-SH.
Morphology of thiol-functionalized diblock copolymer DP-P3HT-SH
and its hybrid nanoparticles
N=51
d=22.5nm
TEM analysis was used to observe the nanomorphology of DP-
P3HT-SH and their respective composites DP-P3HT-S-AuNPs. Figure
3
A and 3B showed images of GDP-P3HT-SH and hybrid particles
12
14
16
18
20
22
Diameter (nm)
24
26
GDP-P3HT-S-AuNPs. DP-P3HT-SH self-aggregated into global
nanoparticles with average diameter of about 260 nm. These
nanoparticles were uniform and stable. The gold nanoparticles
were fixed on the surface of GDP-P3HT-SH due to the side-chain
thiol leaved outside of the polymer through Au-S band and formed
b
DP-P3HT-SH
S-H
2
8
GDP-P3HT-S-AuNPs hybrid particles. The GDP-P3HT-SH polymer
and its hybrid particles GDP-P3HT-S-AuNPs were investigated in
next work.
DP-P3HT-S-AuNPs
Figure 3C and 3D showed images of LDP-P3HT-SH and hybrid
particles LDP-P3HT-S-AuNPs. The lengths of LDP-P3HT-SH were
observed to vary from ~700 to 1500 nm, with widths ranging from
4
000 3500 3000 2500 2000 150 0- 1000
50
1
Wavenumber (cm )
2
00 to 300nm. It appeared gaps in LDP-P3HT-SH polymer. This
Figure 1. Size distribution of gold nanoparticles (AuNPs) in
hexane (the inset shows the transmission electron morphology
images of gold nanoparticles) (a) and FTIR spectra of the DP-
P3HT-SH and DP-P3HTS-AuNP hybrid particles (b)
morphology polymer induced the gold nanoparticles combining
with LDP-P3HT-SH (shown in Figure 3D) and formed LDP-P3HT-S-
AuNPs hybrid particles. It could be observed that gold nanoparticles
4
| RSC Advances, 2016, 00, 1-8
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 5 of 9
View Article Online
DOI: 10.1039/C6RA19895C
RSC Advances
ARTICLE
1
2a
relatively relaxed and ordered conformations. As can be seen
from figure 3b, the absorption spectra of DP-P3HT-S-AuNPs
composites were listed. Three peaks at 515 nm, 559 nm and 609 nm
were observed. The DP-P3HT-S-AuNPs composites showed a slight
larger absorption band and stronger absorption peak compared
with conrresponding DP-P3HT-SH, respectively. It could be due to
the further increased conjugation of main chain and the stronger
1
5b
interaction between gold nanoparticles and DP-P3HT-SH.
Therefore, the DP-P3HT-S-AuNPs composites could absorb more
visible light than DP-P3HT-SH, respectively. In addition, as the
thickness is kept same for all these films, the change in the
absorption spectra is believed to be due to inter-chain interaction
of different aggregation states and the addition of gold
2
9
nanoparticles, and not because of different film thickness.
The normalization absorption spectra of DP-P3HT-SH films and
DP-P3HT-S-AuNPs composites films were compared in figure 4c, 4d
and 4e. Comparing with DP-P3HT-SH, DP-P3HT-S-AuNPs composites
appeared a red shifting by 7 nm, 10 nm and 9 nm at the maximum
Figure 3. TEM images of different aggregation states DP-P3HT-
SH (A, C and E) and P3HT-S-AuNPs hybrid particles (B and D).
0
0
0
.20
.15
.10
a
0.3
(Inset shows image of DP-P3HT-SH in THF without operation.)
EDP-P3HT-SH
0.05
0.00
0
0
0
.2
.1
.0
were well dispersed in LDP-P3HT-SH, revealing that the
combination between LDP-P3HT-SH and AuNPs could prevent the
aggregation of gold nanoparticles. The LDP-P3HT-SH and its
composite were researched in the following work.
4
00
600
800
Wavelength (nm)
GDP-P3HT-SH
LDP-P3HT-SH
The elliptical shape state of diblock copolymer P3HT-SH (EDP-
P3HT-SH) could be seen in figure 3E. It was prepared on the basis of
LDP-P3HT-SH and the EDP-P3HT-SH had a steady morphology. The
widths and lengths of elliptical-like polymer particles were ranging
from 1.5 um to 2.5 um and from 2.5 um to 4.0 um, respectively. It
had no image of EDP-P3HT-S-AuNPs because gold nanoparticles
couldn’t be observed clearly. EDP-P3HT-SH and EDP-P3HT-S-AuNPs
were observed by TEM and kept the same morphology after several
days. Therefore EDP-P3HT-SH and EDP-P3HT-S-AuNPs were chosen
to use in the following study.
300
450
600
750
900
Wavelength (nm)
b
0
.3
EDP-P3HT-S-AuNPs
0.2
LDP-P3HT-S-AuNPs
GDP-P3HT-S-AuNPs
0
0
.1
.0
3
00
450
600
750
900
Absorption of three different aggregation states DP-P3HT-SH film
and solution
Wavelength (nm)
c
1
0
.0
LDP-P3HT-SH
The solid state normalized UV-visible absorption spectra of different
aggregation states of diblock copolymer P3HT-SH film and DP-P3HT-
S-AuNPs composites film were shown in figure 4a, b. In addition,
the spectra of DP-P3HT-SH compared with respective P3HT-S-
AuNPs composites could be observed in figure 4c, 4d and 4e. In
figure 4a, three aggregation states of DP-P3HT-SH exhibited broad
absorption spectra between 300 nm to 800 nm including a main
absorption peak at around 510 nm and the two vibronic
.5
LDP-P3HT-S-AuNPs
1
.0
d
e
EDP-P3HT-S-AuNPs
GDP-P3HT-SH
0
1
.5
.0
EDP-P3HT-SH
0.5
GDP-P3HT-S-AuNPs
400
500
600
700
800
Wavelength (nm)
“
shoulders” at 553 nm and 605 nm. The absorption peak centered
*
at 510 nm was attributed to the π—π transition. The peak
centered at 553 nm was due to the absorption of extended
conjugation of DP-P3HT-SH in the solid film and the absorption peak
Figure 4. Solid state normalized UV-visible absorption spectra of
different aggregation states DP-P3HT-SH (a) (the inset shows the
plasmon band of pure AuNPs), respective composites DP -P3HT-
S-AuNPs hybrid particles (b) and respective DP-P3HT-SH
comparing with P3HT-S-AuNP composites films(c) (d) (e).
29
at 605 nm was caused by the interchain stacking of DP-P3HT-SH.
Compared with other two aggregation states of DP-P3HT-SH, the
GDP-P3HT-SH appeared a red shift by 11 nm that maybe arise from
This journal is © The Royal Society of Chemistry 20xx
RSC Advances, 2016, 00, 1-8 | 5
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 6 of 9
View Article Online
DOI: 10.1039/C6RA19895C
ARTICLE
Journal Name
GDP-P3HT-SH
absorption peaks, respectively. This red shifting was attributed to
the distributed of AuNPs on the surface of DP-P3HT-SH by Au-S
chemical bonds.
900
a
4
3
2
1
AuNPs
720
Figure 5 showed the UV-vis absorption spectra of three different
aggregation states DP-P3HT-SH solution and its respective DP-P3HT-
S-AuNPs hybrid nanoparticles in THF. For the spectrum of DP-P3HT-
SH solution, they showed an absorption band between 350 nm and
540
5
00
600
700
800
3
60
80
0
Wavelength (nm)
EDP-P3HT-SH
LDP-P3HT-SH
1
6
50 nm which was narrower than corresponding film varying from
00 nm to 800 nm in figure 4a. Compared the absorption band of
3
6
00
650
700
750
800
850
different aggregation states DP-P3HT-SH solution with its solid
films, it can be concluded that the DP-P3HT-SH solid state were
better to absorb sunlight due to its absorption spectrum covered
the visible light region. For the spectra of DP-P3HT-SH solution,
three peaks located at around 505 nm, 543 nm and 597 nm which
corresponded to 510 nm, 553 nm and 605 nm in the solid film,
respectively. That is to say DP-P3HT-SH solid film appeared a red
shifting to its solution state. Compared to DP-P3HT-SH, the
absorption intensity of composites DP-P3HT-S-AuNPs presented a
certain degree increase due to the addition of AuNPs.
Wavelength (nm)
7
50
b
GDP-P3HT-S-AuNPs
600
LDP-P3HT-S-AuNP
4
50
300
EDP-P3HT-S-AuNP
1
50
0
6
00
650
700
750
800
850
Wavelength (nm)
Photoluminescence of DP-P3HT-SH film
9
7
5
3
1
00
20
40
60
80
0
c
d
e
Photoluminescence spectra of films made with different
aggregation states DP-P3HT-SH and DP-P3HT-S-AuNPs composites
film were shown in Figure 6a and 6b. The PL spectra were recorded
by excitation at the wavelength that the DP-P3HT-SH has maximum
absorption. In this experiment, all the samples were excited at
wavelength of 470 nm and the PL spectra range were collected
6
00 700 800 600 700 800 600 700 800
a
EDP-P3HT-SH
Wavelength (nm)
0
0
0
0
.09
.06
.03
.00
LDP-P3HT-SH
Figure 6. Photoluminescence spectra of films made with
different aggregation states DP-P3HT-SH (inset shows
the PL spectra of pure AuNPs) (a), DP-P3HT-S-AuNPs
composites films (b) and respective DP-P3HT-SH
comparing with its composites P3HT-S-AuNPs (c) (d) (e).
GDP-P3HT-SH
3
00
450
600
750
900
from 480 nm to 900 nm. The DP-P3HT-SH films revealed similar
emission peak at 661 nm with a shoulder at 716 nm and the PL
peaks of the P3HT-S-AuNPs composites were obtained at 663 nm
and a shoulder at 718 nm.
Wavelength (nm)
0
0
0
0
.15
.10
.05
.00
EDP-P3HT-S-AuNPs
LDP-P3HT-S-AuNPs
b
Figure 6c, 6d and 6e showed the photoluminescence spectra of
DP-P3HT-SH comparing with its P3HT-S-AuNPs composites,
respectively. The PL intensity of DP-P3HT-SH has reduction upon
addition of AuNPs, such as 23% for GDP-P3HT-SH, 11% for LDP-
P3HT-SH and 21% for EDP-P3HT-SH. The PL intensity reduction
reasons above all are morphological disorder and charge transfer
reaction between the polymer P3HT-SH and inorganic nanoparticles
GDP-P3HT-S-AuNPs
450 600
1
6b
3
00
750
900
AuNPs. The GDP-P3HT-SH film showed more quenching than the
films made with other aggregation states after addition of AuNPs.
The results revealed that the charge transfer reaction between
GDP-P3HT-SH and AuNPs was the most efficient among the films
made with three aggregation states, whereas the LDP-P3HT-S-
AuNPs has the least charge transfer efficient. The different amount
of PL quenching (23%, 11% and 21%) namely charge transfer
Wavelength (nm)
Figure 5. UV-visible absorption spectra of different
aggregation states DP-P3HT-SH solution (a) and its
respective DP-P3HT-S-AuNPs hybrid particles solution (b).
6
| RSC Advances, 2016, 00, 1-8
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 7 of 9
View Article Online
DOI: 10.1039/C6RA19895C
RSC Advances
ARTICLE
efficient was mainly due to the different morphological structure. It Conductivity of different aggregation states DP-P3HT-SH and DP-
could be concluded that the combination of DP-P3HT-SH and gold P3HT-S-AuNPs films
nanoparticle through Au-S band would increase charge transfer
Figure 8a showed the relationship between the conductivity and
efficient with improving electron transfer process, resulting in
1
2a
thickness of DP-P3HT-SH films. It can be observed that a monotonic
increase trend of conductivity with increased film thickness for
different aggregation state diblock copolymer DP-P3HT-SH. For
increase of the amount of PL quenching.
Figure 7 exhibited the PL spectra (λex=470 nm) of three different
aggregation states DP-P3HT-SH solution, DP-P3HT-S-AuNPs hybrid
particles solution and respective DP-P3HT-SH comparing with its
composites DP-P3HT-S-AuNPs. All the PL spectra were collected
from 480 nm to 900 nm and two peaks could be observed in DP-
P3HT-SH solution at about 658 nm and 720 nm which is similar to
DP-P3HT-SH films. The PL spectra of composites DP-P3HT-S-AuNPs
solution in Figure 7b has the similar range and peaks compared to
the films in Figure 6b. The PL intensity quenching rate shown in
Figure 7c, 7d and 7e is about 18% for GDP-P3HT-SH, 10% for LDP-
P3HT-SH and 9% for EDP-P3HT-SH, it could indicate the existence of
charge transfer between electron donors and acceptor material. In
addition, it exhibited that GDP-P3HT-SH solution has more efficient
PL quenching than the other polymer. The result indicated that the
materials used in solid film would improve PL quenching.
-4
GDP-P3HT-SH film, the conductivity increased from 0.5×10 S/cm to
-4
1
.9×10 S/cm with the film thickness varying from 0.8 μm to 2.4
μm. Both EDP-P3HT-SH film and LDP-P3HT-SH film exhibited similar
-4
-4
variation trend with the range from 0.2×10 S/cm to 1.5×10 S/cm
-4
-4
and 0.1×10 S/cm to 1.1×10 S/cm, respectively.
Although the relationship between the conductivity of P3HT and
30
film thickness has been reported, there is less report on the
relationship between conductivity of different aggregation states
P3HT with film thickness according to the best of what we have
learnt. The conductivity variation at the same thickness was
attributed to the polymer aggregation state. For GDP-P3HT-SH film,
each layer arranged closely and had large contact area which
resulted in the best conductivity property among these three
aggregation states polymer; however the LDP-P3HT-SH had large
rough surface, so it presented the worst conductivity.
a
GDP-P3HT-SH
Figure 8b showed the relationship between the conductivity of
DP-P3HT-S-AuNPs hybrid nanoparticles films with the volume of
AuNPs. The conductivity increased obviously with the addition of
AuNPs. The film thickness of 2 μm was kept by drop-casting
6
4
2
00
00
00
0
LDP-P3HT-SH
2
5
EDP-P3HT-SH
technique. It clearly exhibited that the conductivity of GDP-P3HT-
-4
-4
S-AuNPs composites increased from 1.0×10 S/cm to 5.5×10 S/cm,
-4
the conductivity of EDP-P3HT-S-AuNPs changed from 0.8×10 S/cm
-4
to 5.1×10 S/cm, and the conductivity of LDP-P3HT-S-AuNPs varied
6
00
650
700
750
800
850
-
4
-4
Wavelength (nm)
from 0.5×10 S/cm to 3.5×10 S/cm with the increasing volume of
AuNPs from 0 to 1.5 mL. Substantially the addition of gold
nanoparticles enhanced the conductivity of pure DP-P3HT-SH. Gold
nanoparticles were fixed on the surface of DP-P3HT-SH through
thiols group to form the chemical bonds Au-S and it resulted that
the gold nanoparticles distributed in polymer uniformly. In the
meantime, the combination of polymer and gold nanoparticles
could increase the contact area between interphase and contact
ability which enhanced the ability of electron conduction.
Therefore, the conductivity of composites increased with the
addition of AuNPs.
b
6
4
2
00
00
00
0
GDP-P3HT-S-AuNPs
LDP-P3HT-S-AuNPs
EDP-P3HT-S-AuNPs
650 700 750
6
00
800
850
Wavelength (nm)
In addition, the GDP-P3HT-S-AuNPs composites had the strongest
conductivity among DP-P3HT-S-AuNPs composites made by three
aggregation states and the LDP-P3HT-S-AuNPs composite had the
lowest conductivity. The conductivity of these P3HT-S-AuNPs
composites differed with each other mainly attributed to the
different aggregation states of polymer. The gold nanoparticles
distributed on the surface of GDP-P3HT-SH and integrated closely
which led to GDP-P3HT-S-AuNPs composites having the best
conductivity property. The EDP-P3HT-S-AuNPs composites had the
similar binding morphology. However the LDP-P3HT-S-AuNPs
composites were distinct from them because gold nanoparticles
had entered into its interior which could be observed through TEM
shown in figure 3D, and it resulted the worst conductivity property
of LDP-P3HT-S-AuNPs among these three aggregation states.
c
d
e
6
4
2
00
00
00
0
6
00
700
800 600 700 800 600
Wavelength (nm)
700
800
Figure 7. Photoluminescence spectra of different aggregation
states DP-P3HT-SH solution (a), DP-P3HT-S-AuNPs hybrid
particles solution (b) and respective DP-P3HT-SH comparing
with its composites DP-P3HT-S-AuNPs (c) (d) (e)
This journal is © The Royal Society of Chemistry 20xx
RSC Advances, 2016, 00, 1-8 | 7
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 8 of 9
View Article Online
DOI: 10.1039/C6RA19895C
ARTICLE
Journal Name
1.8
1.2
0.6
0.0
a
optoelectronics material to modulate efficient optoelectronics
devices by tuning different aggregation state diblock copolymer..
EDP-P3HT-SH
GDP-P3HT-SH
ACKNOWLEDGMENTS
The authors thank A/Prof. D. Jin and A/Prof. H. Chen (Shanghai
University, China) for support on the measurement of TEM and UV.
This work was supported by the National Natural Science
Foundation of China (Grant no. 51203088).
LDP-P3HT-SH
2.0 2.5
0.5
1.0
1.5
Thickness (µm)
Supporting Information Available: 1 H NMR spectra of
the synthetic products.
5
.4
b
EDP-P3HT-S-AuNPs
4
3
2
1
0
.5
.6
.7
.8
.9
Notes and references
GDP-P3HT-S-AuNPs
School of Materials Science & Engineering, Shanghai University,
Shanghai 200444, China.
Email: liyunbo@shu.edu.cn
LDP-P3HT-S-AuNPs
0
.0
0.5
1.0
1.5
1. (a) Arias, A. C.; Endicott, F.; Street, R. A. Adv. Mater. 2006, 18,
Volume of AuNPs (mL)
2
900-2904; (b) Newbloom, G. M.; Weigandt, K. M.; Pozzo, D. C.
Macromolecules 2012, 45, 3452-3462; (c) Martinez, L.; Higuchi,
S.; MacLachlan, A.; Stavrinadis, A.; Miller, N.; Diedenhofen, S.
L.; Bernechea, M.; Sweetnam, S.; Nelson, J.; Haque, S.
Nanoscale 2014, 6, 10018-10026; (d) Wu, P. T.; Ren, G.; Kim, F.
S.; Li, C.; Mezzenga, R.; Jenekhe, S. A. J. Polym. Sci., Part A:
Polym. Chem. 2010, 48, 614-626; (e) Cui, J.; Martínez-Tong, D.
E.; Sanz, A.; Ezquerra, T. A.; Rebollar, E.; Nogales, A.
Macromolecules 2016, 49, 2709-2717.
Figure 8. Conductivity of DP-P3HT-SH films at different
film thickness (a) and DP-P3HT-S-AuNPs hybrid
particles films with different volume of AuNPs (b).
CONCLUSION
2
.
(a) Segalman, R. A.; McCulloch, B.; Kirmayer, S.; Urban, J. J.
Macromolecules 2009, 42, 9205-9216; (b) Hammer, B. A. G.;
Bokel, F. A.; Hayward, R. C.; Emrick, T. Chem. Mater. 2011, 23,
4250-4256; (c) Kim, D. H.; Park, Y. D.; Jang, Y.; Yang, H.; Kim, Y.
H.; Han, J. I.; Moon, D. G.; Park, S.; Chang, T.; Chang, C. Adv.
Funct. Mater. 2005, 15, 77-82; (d) Rajaram, S.; Armstrong, P. B.;
Kim, B. J.; Fréchet, J. M. Chem. Mater. 2009, 21, 1775-1777; (e)
Sivula, K.; Luscombe, C. K.; Thompson, B. C.; Fréchet, J. M. J.
Amer. Chem. Soc. 2006, 128, 13988-13989.
DP-P3HT-SH had been synthesized by the simple solution and
different aggregation states DP-P3HT-SH and their respective
composites of DP-P3HT-S-AuNPs hybrid nanostructures had been
prepared. The gold nanoparticles were attached on the surface of
DP-P3HT-SH polymer. The DP-P3HT-S-AuNPs composites exhibited
enhanced and wide range of absorption compared to the same
aggregate state of DP-P3HT-SH. However, the photoluminescence
intensity of DP-P3HT-S-AuNPs was lower than that of DP-P3HT-SH
due to the addition of gold nanoparticles. The GDP-P3HT-S-AuNPs
had the most amount of PL quenching about 23%; while the LDP-
P3HT-S-AuNPs had the least amount of PL quenching about 11%.
The charge transfer between GDP-P3HT-SH and AuNPs was the
most efficient among the films made with three aggregation states,
whereas, the LDP-P3HT-SH had the least charge transfer efficient.
3
4
5
.
.
.
Osaka, I.; McCullough, R. D. Acc. Chem. Res. 2008, 41, 1202-
1
214.
Yu, X.; Xiao, K.; Chen, J.; Lavrik, N. V.; Hong, K.; Sumpter, B. G.;
Geohegan, D. B. ACS nano 2011, 5, 3559-3567.
Hammer, B. A.; Reyes-Martinez, M. A.; Bokel, F. A.; Liu, F.;
Russell, T. P.; Hayward, R. C.; Briseno, A. L.; Emrick, T. ACS Appl
Mater Interfaces 2014, 6, 7705-11.
The relationships between conductivity and the AuNPs content in 6. Botiz, I.; Martinson, A. B.; Darling, S. B. Langmuir 2010, 26 (11),
8
756-8761.
DP-P3HT-S-AuNPs composites, and thickness of DP-P3HT-SH films
were systematically investigated. The conductivity of composites
increased with the addition of AuNPs and GDP-P3HT-S-AuNPs
composites showed the strongest conductivity among the DP-P3HT-
S-AuNPs made by three aggregation states, whereas the LDP-P3HT-
S-AuNPs composites had the lowest conductivity. In addition, every
aggregation state DP-P3HT-SH had a monotonic increase trend of
conductivity with increased film thickness.
7
8
.
.
Botiz, I.; Darling, S. B. Mater Today 2010, 13 (5), 42-51.
(a) Lin, Y.-H.; Darling, S. B.; Nikiforov, M. P.; Strzalka, J.; Verduzco,
R. Macromolecules 2012, 45 (16), 6571-6579; (b) Verduzco, R.;
Botiz, I.; Pickel, D. L.; Kilbey, S. M.; Hong, K.; Dimasi, E.; Darling,
S. B. Macromolecules 2011, 44 (3), 530-539.
(a) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000,
1
1
9
.
00, 2537-2574; (b) Babel, A.; Jenekhe, S. A. Synth. Met. 2005,
48, 169-173.
Accordingly, aggregation state ultimately impacted the 10. Fronk, S. L.; Mai, C.-K.; Ford, M.; Noland, R. P.; Bazan, G. C.
optoelectronic properties in solid state and the addition of gold Macromolecules 2015, 48, 6224-6232.
nanoparticles could improve optoelectronics performance. 11. Bu, L.; Dawson, T. J.; Hayward, R. C. ACS nano 2015, 9 (2), 1878-
885.
1
Therefore this work could play an important role in achieving new
1
2. (a) Jana, B.; Bhattacharyya, S.; Patra, A. Phys. Chem. Chem. Phys.
8
| RSC Advances, 2016, 00, 1-8
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
RSC Advances
Page 9 of 9
View Article Online
DOI: 10.1039/C6RA19895C
RSC Advances
ARTICLE
2
015, 17, 15392-15399; (b) Jiang, G.; Susha, A. S.; Lutich, A. A.; 21. Bäuerle, P.; Würthner, F.; Heid, S. Angew. Chem. Int. Ed. 1990, 29,
Stefani, F. D.; Feldmann, J.; Rogach, A. L. ACS nano 2009, 3, 419-420.
127-4131; (c) Wight, A.; Davis, M. Chem. Rev. 2002, 102, 22. Zhai, L.; Pilston, R. L.; Zaiger, K. L.; Stokes, K. K.; McCullough, R.
589-3614; (d) Shenhar, R.; Rotello, V. M. Acc. Chem. Res. 2003, D., Macromolecules 2003, 36, 61-64.
6, 549-561; (e) Templeton, A. C.; Wuelfing, W. P.; Murray, R. 23. Frens, G. Nature 1973, 241, 20-22.
4
3
3
W. Acc. Chem. Res. 2000, 33, 27-36; (f) Ruiz, V.; Nicholson, P. G.; 24. Li, B.; Ni, C.; Li, C. Y. Macromolecules 2008, 41 (7), 2754-2754.
Jollands, S.; Thomas, P. A.; Macpherson, J. V.; Unwin, P. R. J. 25. Chen, J. Y.; Chen, Z. B.; Qu, Y. P.; Lu, G. H.; Ye, F.; Wang, S. S.; Lv, H.
Phys. Chem. B 2005, 109, 19335-19344; (g) Banerjee, S.; Pillai,
S. C.; Falaras, P.; O’shea, K. E.; Byrne, J. A.; Dionysiou, D. D. J. 26. Xiao, X.; Hu, Z.; Wang, Z.; He, T. J. Phys. Chem. B 2009, 113 ,
Phys. Chem.Lett. 2014, 5, 2543-2554; (h) 14604-14610.
Martinez, L.; Higuchi, S.; MacLachlan, A. J.; Stavrinadis, A.; 27. Li, Y.; Song, L.; Qiao, Y. RSC Adv. 2014, 4 (101), 57611-57614; (b)
Y.; Yang, X. N. RSC Adv. 2015, 5, 1777-1784.
Miller, N. C.; Diedenhofen, S. L.; Bernechea, M.; Sweetnam, S.;
Nelson, J.; Haque, S. A.; Tajima, K.; Konstantatos, G. Nanoscale
Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R. J.
Chem. Soc., Chem. Commun. 1994, (7), 801-802.
2
014, 6, 10018-10026.
28. Mayeda, M. K.; Kuan, W.-F.; Young, W.-S.; Lauterbach, J. A.; Epps
III, T. H. Chem. Mater. 2012, 24, 2627-2634.
1
3. (a) Li, G.; Shrotriya, V.; Huang, J.; Yao, Y.; Moriarty, T.; Emery, K.;
Yang, Y. Nature mater. 2005, 4, 864-868; (b) Jo, J.; Na, S. I.; Kim, 29. Ramani, R.; Alam, S. Polymer 2013, 54, 6785-6792.
S. S.; Lee, T. W.; Chung, Y.; Kang, S. J.; Vak, D.; Kim, D. Y. Adv. 30. Li, W.; Hendriks, K. H.; Roelofs, W.; Kim, Y.; Wienk, M. M.;
Funct. Mater. 2009, 19, 2398-2406; (c) Zardalidis, G.; Pipertzis,
A.; Mountrichas, G.; Pispas, S.; Mezger, M.; Floudas, G.
Macromolecules 2016, 49, 2679-2687.
Janssen, R. A. Adv. Mater. 2013, 25, 3182-3186.
14. Heinemann, M. D.; von Maydell, K.; Zutz, F.; Kolny-Olesiak, J.;
Borchert, H.; Riedel, I.; Parisi, J. Adv. Funct. Mater. 2009, 19,
3
788-3795; (b) Radychev, N.; Lokteva, I.; Witt, F.; Kolny-Olesiak,
J.; Borchert, H.; Parisi, J. J. Phys. Chem. C. 2011. 115, 14111–
4122.
5. (a) Beek, W. J.; Wienk, M. M.; Janssen, R. A. Adv. Mater. 2004,
1
1
1
2
6, 1009-1013; (b) Li, F.; Du, Y. H.; Chen, Y. W. Thin Solid Films
012, 526, 120-126; (c) Beek, W. J.; Wienk, M. M.; Janssen, R.
A. Adv. Funct. Mater. 2006, 16, 1112-1116.
16. Liao W P, Su Y H, Huang Y K, et al. P3HT-based nanoarchitectural
fano solar cells. Acs Appl. Mater. Interfaces, 2014, 6: 17993-
1
8000.
1
7. Li Y, Lu P, Jiang M, et al. Femtosecond Time-Resolved
Fluorescence Study of TiO2-Coated ZnO Nanorods/P3HT
Photovoltaic Films. J. Phys. Chem. C, 2012, 116: 25248-25256.
8. Achermann, M. J. Phys. Chem.Lett. 2010, 1, 2837-2843.
9. Fan, C.; Wang, S.; Hong, J. W.; Bazan, G. C.; Plaxco, K. W.; Heeger,
A. J. Proc. Natl. Acad. Sci. 2003, 100 , 6297-6301.
1
1
20. Miyanishi, S.; Tajima, K.; Hashimoto, K. Macromolecules 2009,
4
2, 1610-1618.
For Table of Contents use only
DP-P3HT-SH in global, leaflike and elliptical shape states exhibiting broad absorption spectra between 300 nm to 650 nm and the
conductivity values of DP-P3HT-S-AuNPs hybrid nanoparticles film as a function of the weight content AuNPs.
This journal is © The Royal Society of Chemistry 20xx
RSC Advances, 2016, 00, 1-8 | 9
Please do not adjust margins