Materials Science Forum Submitted: 2018-12-05

ISSN: 1662-9752, Vol. 966, pp 404-408 Revised: 2019-05-07

doi:10.4028/www.scientific.net/MSF.966.404 Accepted: 2019-05-07
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-08-06

µSR Study with Light Irradiation of P3HT:ZnO Nanoparticles as Active

Material of Hybrid Solar Cells
Lusi Safriani1,a *, Risdiana1,b, Fitrilawati1,c, Ayi Bahtiar1,d, Annisa Aprilia1,e,
Rustam E. Siregar1,f, Maykel Manawan1,g, Dita Puspita Sari2,3,h, Julia Angel2,4,i
and Isao Watanabe2,3,4,j
1
Department of Physics, Padjadjaran University, Jl. Raya Bandung Sumedang Km. 21 Jatinangor,
Sumedang 45363, Indonesia
2
RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
3
Department of Physics, Osaka University, Toyonaka, Osaka 560-0043, Japan
4
Department of Physics, Hokkaido University, Sapporo, Hokkaido, 060-0810, Japan
a*
lusi.safriani@phys.unpad.ac.id (corresponding author), brisdiana@phys.unpad.ac.id,
c
fitrilawati@phys.unpad.ac.id, dayi.bahtiar@phys.unpad.ac.id, ea.aprilia@phys.unpad.ac.id,
f
resiregar@phys.unpad.ac.id, gmaykeltem@gmail.com, hditapuspitasari72@gmail.com,
i
julia.angel@riken.jp, jnabedon@riken.jp

Keywords: hybrid solar cells, µSR, P3HT, ZnO nanoparticles.

Abstract. Recently, hybrid solar cell that consists of a combination of organic and inorganic
materials offers a promise in increasing efficiency. Combination of conjugated polymer of Poly(3-
hexyl thiophene)/P3HT which has the highest hole mobility with inorganic materials which has high
electron mobility, good physical and chemical stability of inorganic nanocrystals, shows a better
performance of hybrid solar cells. We have conducted a measurement to investigate the charge
carrier transport in active material of hybrid solar cells by using muon spin relaxation (µSR) with
light irradiation. A bulk sample used in this study is hybrid organic-inorganic material consisting of
regio-regular P3HT and ZnO nanoparticles. Longitudinal-field µSR measurements were performed
in magnetic field ranging from 0 to 395 mT at temperature of 10 K, 15 K and 25 K. Based on µSR
measurement with light irradiation, we found that for those temperatures, longitudinal field
dependence of λ1 was proportional with C-H0.5 curve indicating three-dimensional inter-chain
diffusion. We assume that light irradiation initiates the production of exciton that increases the
number of charge carrier in the sample and transports not only along the chain of polymer (one-
dimensional) but also perpendicular to other chain of polymer (three-dimensional). With light
irradiation, the crossover temperature from one-dimensional to three-dimensional of regio-regular
P3HT and ZnO nanoparticles bulk sample was obtained at lower temperature of 10 K compared to
previous result at 25 K without light irradiation.

Introduction
Many research works related to the development of solar cells have been carried out, especially
in the improvement of the power conversion efficiency of solar cells. Even though the efficiency of
solar cells made from inorganic material has reached up to 24% [1], the production cost is very high
because it needs high purity materials and high processing techniques. An alternative technique to
produce a low cost solar cells is required. One of the solar cells technologies that is currently being
developed is organic-inorganic hybrid device which takes the advantages of both materials.
Organic materials have promising properties, such as easy to process, low cost and sustainable
materials [2]. Among various types of organic materials, conjugated polymer such as Poly-(3-
hexylthiophene) (P3HT) is one of candidates as an active material in hybrid solar cells. P3HT has
the highest hole mobility compared to other conjugated polymers [3]. On the other hand, inorganic
materials in their nanoparticles have high charge mobility, high absorption coefficients and particle

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 Materials Science Forum Vol. 966 405

size induced tunability of the optical band-gap [4]. Hybrid solar cells have been fabricated in the
form of bulk heterojunction using inorganic nanoparticles with high electron mobility such as TiO2
[5] and ZnO [6,7]. ZnO nanoparticles attract much attention to be used in hybrid solar cells due to
its abundance, easy to synthesize and non-toxicity. ZnO is also used as electron acceptor to
dissociate excitons produced in the conjugated polymers [8]. Beek et al. [9] used blends of regio-
regular P3HT and ZnO nanoparticles as active components from the solution to obtain hybrid
polymer-metal oxide solar cells.
Information about charge mobility of active material is important in designing hybrid solar cell
to improve its performance. In the previous study, we have measured charge carrier transport of
blends regio-regular P3HT and ZnO nanoparticles by muon spin relaxation (µSR) [10] using
longitudinal field (LF) at various temperatures to investigate its charge carrier transport along and
perpendicular to the chain of regio-regular P3HT. Change carrier transport along the chain of
conjugated polymer is defined as one-dimensional intra-chain diffusion, while perpendicular to the
chain is defined as three-dimensional inter-chain diffusion. We have found that the dimensional
crossover temperature of regio-regular P3HT blend with ZnO nanoparticles is observed at 25 K.
In this study, we performed µSR measurement to clarify the charge carrier transport in blend of
regio-regular P3HT and ZnO nanoparticles as active material of hybrid solar cells with light
irradiation. Light illuminates the active material of hybrid solar cell, then it excites the charge
carrier from HOMO level to the LUMO level of regio-regular P3HT. The existence of ZnO in active
material of hybrid solar cells support charge carrier transfer from P3HT to electrode of the solar
cells [11].

Experiments
Regio-regular P3HT has been procured from Sigma-Aldrich, while Zn(Ac)2.2H2O and NaOH
have been purchased from Merck. All reagents were used without further purification. ZnO
nanoparticles was synthesized following the Meunleunkamp procedure with some modifications
[12]. ZnO precursor solution was prepared from 0.25M Zn(Ac)2.2H2O dissolved in methanol.
NaOH solution was dropped wisely into Zn(Ac)2.2H2O during reflux process at 64ºC followed by
stirring until a clear solution containing ZnO gel was obtained. The precipitation of ZnO gel was
washed by methanol and hexane sequentially, and after this, the ZnO nanoparticles were collected
by centrifugation. Active material of hybrid solar cells was prepared by mixing regio-regular P3HT
and ZnO nanoparticles in chlorobenzene with 3% volume of methanol to have homogeneous
solution. The mixed solution was then evaporated at 150°C to produce bulk sample of region-
regular P3HT and ZnO nanoparticles.
μSR measurement was done by mounting bulk sample on a silver plate in a cryostat. The μSR
measurements were carried out in longitudinal-field (LF) ranging from 0 to 395 mT at temperature
of 10 K, 15 K and 25 K using a pulsed positive surface muon beam [13,14] and white light source
to irradiate the bulk sample. μSR measurements were done at the RIKEN-RAL Muon Facility,
Rutherford-Appleton Laboratory, UK.
The asymmetry parameter of µSR signal A(t) at a time t is defined as:
A(t) = [F(t) – α B(t)] / [F(t) + α B(t)] (1)
where F(t) and B(t) are total muon events counted by the forward and backward counters,
respectively. α is the calibration factor reflecting the relative counting efficiencies between the
forward and backward counters [15].

Results and Discussion

The longitudinal-field (LF) dependent variation of raw asymmetry of region-regular P3HT blend
with ZnO nanoparticles at temperatures of 10 K, 15 K and 25 K measured with light irradiation is
presented in Fig. 1. All initial asymmetry shifted to the higher values with increasing field due to the
406 Functional Properties of Modern Materials II

repolarization of the muonium state [16]. The raw asymmetries at temperatures of 10 K and 300 K
show clearly both field and temperature dependencies.

30 10 K 15 K 25 K
395 mT
200 mT
Asymmetry

100 mT
50 mT
20
20 mT
10 mT
5 mT
2 mT
10
0 1 2 3 4 0 1 2 3 4 0 1 2 3 4

Time (sec)
Fig. 1 The asymmetry data of blend regio-regular P3HT and ZnO nanoparticles at temperatures of
10 K, 15 K, and 25 K for various longitudinal magnetic field with light irradiation.
The time spectra were analyzed using the two-component function as shown in Eq. 2. The results
1( sec-1)

are information related to polaron diffusion in the sample. A1 and A2 are the initial asymmetries
while 1 and 2 are corresponding to the depolarization rates associated with the fast and slow
components, respectively.
A(t) = A1 exp (1t) +10AK
2 exp (2t)
15 K 25 K (2)
The raw asymmetries 100
in10Fig.
1 110were
2 then
100
fitted
101
by 10
using
2 the
100
two-component
101 102
function
103
in Eq. 2 and
the results are presented in Fig. 2 and 3. The longitudinal-field dependence of the dynamical
HLF(mT)
depolarization rate reflects the direction of charge diffusion in the polymer chain. One-dimensional
intra-chain diffusion is indicated by λ proportional to linier field of H-0.5 and three-dimensional
inter-chain diffusion
10-1 is characterized by λ ~ C-H
0.5
curve [17].
Fig. 2 and 3 show the longitudinal field (HLF) dependence of 1 and 2 of regio-regular P3HT
and ZnO nanoparticles in bulk sample measured with light irradiation. 1 is the corresponding
2( sec-1)

depolarization rates associated with the fast component, while 2 associated with the slow
10-2
component. We found that, at temperature of 10 K, 15 K and 25 K, the fitted curve displayed
λ1 ~ C-H0.5, representing the three-dimensional intra-chain diffusion in the chain of region-regular
10 K 15 K 25 K
P3HT. In the previous experiment where the µSR measurement was done without light irradiation
10-3 of 10 K, the longitudinal-field dependence of relaxation rate λ1 is associated
[11], at temperature
100 101 102 100 101 102 100 101 102 103
with λ1 ~ H-0.5 which indicating the one-dimensional intra-chain diffusion. While at temperature of
25 K, λ1 is associated with λ1 ~ C-H0.5 indicating HLF(mT)the three-dimensional inter-chain diffusion. The
crossover temperature from one-dimensional to three-dimensional diffusion for regio-regular P3HT
and ZnO nanoparticles in bulk sample at condition without light irradiation is above 25 K. For the
µSR measurements with light irradiation, we found different result. It is clear that starting from
temperature of 10 K, the diffusion of polaron is three-dimensional inter-chain diffusion. We assume
that three-dimensional diffusion of polaron take place at lower temperature was related to the
increasing number of charge carrier because of light irradiation. The existence of ZnO nanoparticles
also gives contribution to the facilitate the charge carrier transport along (one-dimensional intra-
chain) and perpendicular (three-dimensional inter-chain) in the regio-regular P3HT and ZnO
nanoparticles in bulk sample [18]. The implication of knowing the three-dimensional inter-chain
diffusion starting from the temperature of 10 K is to ensure that P3HT:ZnO nanoparticles could be
used as active material of hybrid solar cells at wide range temperatures. These results also indicate
that P3HT:ZnO nanoparticles has the potential to be used as an active material on solar power
system that are needed for future planetary science missions where temperature changes are very
large and extreme.
 AsymmetryAsy
395 mT
10 mT
200 mT
5 mTmT
100
2 mT
50 mT
10
Materials Science Forum Vol. 966 407
20
0 1 2 3 4 0 1 2 3 4 0 1 2 3 4 20 mT

Time (sec) 10 mT
5 mT
2 mT
10
0 1 2 3 4 0 1 2 3 4 0 1 2 3 4

Time (sec)

1( sec-1) 1( sec-1)

10 K 15 K 25 K

100 101 102 100 101 102 100 101 102 103

HLF(mT)
10 K 15 K 25 K
Fig. 2. The longitudinal-field dependence of relaxation rate λ1 of regio-regular P3HT and ZnO
0
10-1 10
nanoparticles at temperature 101 10 K,
of 102 15 10
K0 and1025
1 2
100
K 10measured 101 light
with 102 irradiation.
103

HLF(mT)
2( sec-1) 2( sec-1)

-2
10-1
10

10 K 15 K 25 K
-3
10-2
10
100 101 102 100 101 102 100 101 102 103

H (mT)
10 K 15 KLF 25 K

10-3
100 101 102 100 101 102 100 101 102 103

HLF(mT)

Fig. 3. The longitudinal-field dependence of relaxation rate λ2 of regio-regular P3HT and ZnO
nanoparticles at temperature of 10 K, 15 K and 25 K measured with light irradiation.

Conclusion
We have carried out µSR measurements with light irradiation of regio-regular P3HT and ZnO
nanoparticles as active material of hybrid solar cells to investigate charge carrier transport. We
found that starting from the lowest temperature of 10 K, charge carrier transport is three-
dimensional inter-chain diffusion, which is different with the µSR measurements in condition
without light irradiation at 25 K.

Acknowledgement
This study was funded through the project Academic Leadership Grant (ALG) of Direktorat
Riset, Pengabdian pada Masyarakat dan Inovasi (DRPMI) Universitas Padjadjaran with project no.
7397/UN6.D/LT/2018.

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