J Mater Sci: Mater Electron (2016) 27:8027–8039
DOI 10.1007/s10854-016-4799-4
Optical and electrical properties of purpurin and alizarin
complexone as sensitizers for dye-sensitized solar cells
Chaofan Sun1 • Yuanzuo Li1 • Dawei Qi1 • Huixing Li2 • Peng Song3
Received: 28 February 2016 / Accepted: 7 April 2016 / Published online: 13 April 2016
Ó Springer Science+Business Media New York 2016
Abstract The optical and electrical properties of two
dyes purpurin (1,2,4-trihydroxy-9, 10-anthracenedione)
and alizarin complexone (alizarin-3-methylimino-N,N-di-
acetic acid) as sensitizers for dye-sensitized solar cells
were investigated by using UV–Vis spectrum, FT-IR
spectrum, cyclic voltammetry and I–V (current–voltage)
characteristics. In addition, electrochemical impedance
spectroscopy was adopted to research the electrons transfer
process between each interface of the dye-sensitized solar
cell. For comparison with the experiments, the frontier
molecular orbitals, vibration analysis, the total static first
hyperpolarizability and driving force of electron injection
were calculated by using density functional theory (DFT)
with B3LYP, at 6-31G(d) basis set. Moreover, the transi-
tion properties were investigated by using time-dependent
density functional theory (TD-DFT) with PBEPBE func-
tional at 6-311?G(d,p) basis set in theory. The solvent
effect and basis set effect were taken into consideration to
investigate the excited state properties of the dyes. The
results showed that alizarin complexone had a higher
Electronic supplementary material The online version of this
article (doi:10.1007/s10854-016-4799-4) contains supplementary
material, which is available to authorized users.
& Yuanzuo Li
liyuanzuo5203@126.com; yzli@nefu.edu.cn
& Dawei Qi
Daweiqi@yahoo.com.cn
1
College of Science, Northeast Forestry University,
Harbin 150040, Heilongjiang, China
2
School of Physics and Optoelectronic Technology, Dalian
University of Technology, Dalian 116024, China
3
Department of Physics, Liaoning University,
Shenyang 110036, Liaoning, China
energy conversion efficiency of 0.27 % than that of pur-
purin (0.13 %), with higher open circuit voltage (Voc ) of
0.45 V, higher short circuit current density (Isc ) of
0.89 mA cm-2 and higher fill factor (ff) of 0.67, indicating
that the photovoltaic characteristics of alizarin excelled
that of purpurin.
1 Introduction
In recent decades, with the aggravation of environmental
pollution and acceleration fossil of energy depletion,
researchers have been working on new energy sources.
Since Gratzel et al. [1] reported that a kind of dye-sensi-
tized solar cell (DSSC) with the overall efficiency of
7.1–7.9 % under simulated solar light, a novel field is
opened up in the development of solar cells. Dye-sensitized
solar cell has attracted more and more attention due to its
abundant raw materials, low cost, no pollution, relatively
simple manufacture technology, feasible industrial pro-
duction in large scale and so on [2–5].
For dye-sensitized solar cells, the photocurrent is gen-
erated after five process in detail [6–8]: (1) the dye
molecules transfer from ground state to excited state after
irradiation of the light from the sun; (2) the electrons in
the dye molecules on excited state inject into the con-
duction band of semiconductor; (3) electrons diffuse into
the electric basement, and then into the external circuit;
(4) the dye molecules in oxidation state are deoxidized by
the electrolyte in reduction state; (5) the electrolyte in
oxidation state is deoxidized after receiving the electron at
the electrode, thereby completing a cycle. As an important
component of DSSCs, the optical and electrical property
of sensitizers is one of the main factors to determine the
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photocurrent conversion efficiency of dye-sensitized solar
cells. Some researchers have fixed attention on designing
and synthesizing novel dye sensitizers and seeking new
natural dyes as the dye sensitizers for DSSCs [9–15]. Wei
et al. [9] synthesized three organic dyes 2,6-bis (imi-
noalkyl) pyridines (DM, DE, and DP) and assembled onto
the nanocrystalline TiO2 thin films to prepare the 2,6-bis
(iminoalkyl) pyridines/N719 co-sensitized photo elec-
trodes for dye-sensitized solar cells. By co-sensitization,
the spectra response of electrodes was enhanced and the
overall conversion efficiency was increased by 28.91 %
comparing with that for DSSCs only sensitized by N719.
In addition to the research work of Wei et al. there were
researchers working on the researches of the co-sensitized
solar cells [16–19], which can provide a novel way to
improve the photo current conversion efficiency of the dye
sensitized solar cells. Li et al. [11] investigated three
natural dyes (Forsythia suspensa, Herbaviolae, and Corn
leaf) as potential sensitizers for dye-sensitized solar cells
and the highest photo electronic conversion efficiency was
0.96 % among three DSSCs. Kumara et al. [14] applied
natural pigments extracted from black tea waste to DSSC
application and found that the DSSC application with
lower pH dye had higher photo current conversion
efficiency.
In recent years, quantum chemistry method has become
a reliable way to reveal the relationship between the
structure and property of dyes, and it can provide a reliable
theoretical basis for the rapid screening of high efficiency
dye molecules [20–32]. Zhang et al. [24] designed six dyes
based on the POM conjugated zinc(II)-centered-porphyrin
and investigated the absorption spectra, electronic transi-
tion properties, and photovoltaic performance of the six
dyes for p-type dye-sensitized solar cells (DSSCs) by using
time-dependent density functional theory methods. The
results showed that the energy levels of the frontier
molecular orbitals for dyes 2–6 matched the requirements
of p-type DSSCs and the photovoltaic performances of
dyes 2–6 were suitable for high-efficiency DSSCs. Chai-
tanya et al. [26] investigated the structural and electronic
properties of five known triarylamine derived sensitizers
and their associated hypothetical dyes by using density
functional theory and time-dependent density functional
theory. The theoretical results revealed that elongating the
p-system of the sensitizers with both the benzothiadiazole
and ortho-fluorophenyl units increased the molecular
extinction coefficient, the excited state lifetime and the
light harvesting efficiency but decreased the band gap and
the reorganization energy, which will provide a valuable
reference for the strategy of inserting various p-spacers in
triarylamine sensitizers for dye sensitized solar cell appli-
cations. Novir et al. [33] studied some of new azo-based
metal-free dyes with different pi-conjugation spacers with
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J Mater Sci: Mater Electron (2016) 27:8027–8039
density functional theory and time-dependent DFT calcu-
lations and the theoretical calculations indicated that
quantify factors such as light harvesting efficiency, electron
injection driving force and the weight of the LUMO orbital
on the carboxylic group related to the short-circuit pho-
tocurrent density and charge recombination between the
semiconductor conduction band electrons and the oxidized
dyes and/or electrolyte associated with the open-circuit
voltage.
In this work, the optical and electrical properties of two
dyes purpurin (1,2,4-trihydroxy-9,10-anthracenedione) and
alizarin complexone (alizarin-3-methylimino-N,N-diacetic
acid), hereinafter referred to as alizarin, were investigated
as the sensitizers in dye-sensitized solar cells by using
UV–Vis spectrum, FT-IR spectrum, cyclic voltammetry,
I–V (current–voltage) characteristics and electrochemical
impedance spectroscopy. The frontier molecular orbitals
and transition properties were calculated by using DFT
and TD-DFT method, respectively, and the solvent effect
and basis set effect were considered. In addition, the
vibration analysis, total static first hyperpolarizability and
driving force of electron injection and dye regeneration
were taken into account. Through the comparison between
theory and experiment, the relationship between the
structures and properties of the dye molecules was
revealed in depth.
2 Methods
The purpurin (1,2,4-trihydroxy-9,10-anthracenedione) with
a purity of greater than 98 % was obtained from Cayman
Chemical Company (USA), which was used without fur-
ther purification. The alizarin complexone (alizarin-3-
methylimino-N,N-diacetic acid) with a purity of greater
than 93 % was obtained from TCI (Shanghai) Develop-
ment Co., Ltd., which was used without further purifica-
tion. The chemical structures of the two molecules were
shown in Fig. 1. The structure of DSSCs is mainly com-
posed of electrode, dyes and electrolyte solution. The
elaborated preparation procedure is listed as following:
(a) The TiO2 electrode was prepared; adding 10 mL iso-
propyl tianate to water, and keeping hydrolysis for 3 h;
then adding HNO3 and HAC to the solution, and under
80 °C; the mixed solution was stirred until it became
transparent clear blue; later, at 200 °C hydrothermal reac-
tion was carried on at 200 °C for 12 h. After cooling, spin
steaming, centrifuging, terpineol ethyl and cellulose were
added to the ball grinder; the paste were prepared com-
pletely by ball mill, rotary steam and three roll. (b) The
application of screen printing technology was used, which
printed the TiO2 paste to the clean surface of conductive
glass, and the active area of cell was 0.16 cm2; after
J Mater Sci: Mater Electron (2016) 27:8027–8039
Fig. 1 Chemical structures of
purpurin and alizarin
complexone
ethanol bath and dry, the anode electrodes were sintered,
and then the anode electrodes were treated in TiCl4 solu-
tion. In the later of treatment, the anode electrodes were
sintered as well, after the processing, the anode was
immediately removed after the natural cooling to 80 °C,
and the anode electrodes were soaked in the natural dye
without light for 24 h. (c) The anode electrode and the
platinum plating counter electrode were assembled into the
cell, in the middle of the two electrodes, the electrolyte
solution was added (0.5 mol L-1 LiI, 0.05 mol L-1 I2
TBP, GUSCN were included). The UV–Vis spectrum were
measured with TU-1900 spectrometer (Beijing, China), and
the FT-IR spectrum were measured with FT-IR 360 spec-
trometer (Nicolet, Madison, WI, USA). Solar energy con-
version efficiency measurements were done with a solar
simulation instrument (Pecell-15, Japan), and light inten-
sity was adjusted via a reference standard Si-solar solar cell
at 1 sun light intensity of 100 mW cm-2. Cyclic voltam-
metry was tested by using CH Instruments CHI615E
Electrochemical Workstation. A three electrode system
consisting of a glassy carbon working electrode, platinum
counter electrode and Ag/AgCl reference electrode was
adopted. The scan range was between -1000 and
?1000 mV, and the initial scan potential was -1000 mV,
at a scan rate of 50 mV s-1. The supporting electrolyte was
0.1 M KNO3. Electrochemical impedance spectra (EIS) for
DSCCs were measured with an impedance/gain-phase
analyzer (PARSTAT 2273, USA). The spectra were scan-
ned in a frequency range of 2.5 9 10-1–1.0 9 106 Hz at
room temperature.
In theory, the ground state structures of purpurin and
alizarin were optimized with DFT [34, 35] using B3LYP
[36–38] functional at the 6-31G(d) basis set. Basing on the
optimized ground state structures, the highest occupied
molecular orbital (HOMO), the lowest unoccupied
molecular orbital (LUMO) and energy gaps of the two dye
molecules. In addition, the infra-red spectra of the two
molecules were simulated by using DFT//B3LYP/6-
31G(d). Meanwhile, the hyperpolarizability was calculated
basing on the optimized geometry and the total static first
hyperpolarizability can be written as following [39]:
8029
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
btol ¼ b2x þ b2y þ b2z ð1Þ
Individual static components in the above is calculated
from
1 X 
bi ¼ biii þ b þ bjij þ bjji ð2Þ
3 i6¼j ijj
where bijk (i, j, k = x, y, z) are tenser components of
hyperpolarizability. Due to Kleinman symmetry, one
finally obtains the equation that has been employed:
h 2  2
btot ¼ bxxx þ bxyy þ bxzz þ byyy þ byzz þ byxx
 2 i1=2 ð3Þ
þ bzzz þ bzxx þ bzyy
Moreover, the absorption spectrum of the two dye
molecules in vacuum were obtained by using TD-DFT [40]
with PBEPBE [41] at 6-311?G(d,p) basis set. For com-
parison, the solvent effect was considered through the
CPCM method. In addition, the basis set effect with
6-31G(d), 6-31G(d,p), 6-311G(d), 6-311?G(d) and
6-311?G(d,p) was investigated in theory. Through the
combination of theory and experiment, the relationship
between the structures and photoelectric properties of the
dye molecules was investigated more deeply. All quantum
chemical calculations were completed with Gaussian 09
package [42].
3 Results and discussion
3.1 UV–Vis absorption spectra
The measured UV–Vis absorption spectra of two dyes and
dyes with TiO2 in N,N-dimethylformamide in experiment
were showed in Fig. 2a, b and the absorption peaks were
listed in Table 1. From Fig. 2a it can be seen that the UV–
Vis absorption spectra of purpurin and purpurin with TiO2
covered the absorption band from 400 to 700 nm, which
mainly distributed in the visible region. As listed in
Table 1, the absorption peaks of Purpurin and Purpurin
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8030 J Mater Sci: Mater Electron (2016) 27:8027–8039

(a) Purpurin (c) 7500

vacuum
2.8 solvent
0.20 Purpurin with TiO2
6000

2.1 0.16

Absorption
Absorption
4500
Absorption

0.12

1.4
3000
0.08
400 450 500 550 600 650 700
Wavelength(nm)
0.7
1500

0.0 0
300 400 500 600 700 800 200 300 400 500 600 700 800 900
Wavelength(nm) Wavelength(nm)
(b) (d)
2.0 Alizarin vacuum
solvent
0.24 Alizarin with TiO2 5000

1.5 0.18
4000
Absorption

Absorption
Absorption

0.12

3000
1.0
0.06

2000
0.00
400 450 500 550 600 650 700
0.5 Wavelength (nm)
1000

0.0 0
400 500 600 700 200 300 400 500 600 700 800 900

Wavelength(nm) Wavelength(nm)

Fig. 2 a Measured UV–Vis absorption spectrum of purpurin and experiment. c Simulated UV–Vis absorption spectra of purpurin in
purpurin with TiO2 in N,N-dimethylformamide in experiment. vacuum and solvent by using TD-DFT//PBEPBE/6-311?G(d,p).
b Measured UV–Vis absorption spectrum of alizarin complexone d Simulated UV–Vis absorption spectra of alizarin complexone in
and alizarin complexone with TiO2 in N,N-dimethylformamide in vacuum and solvent by using TD-DFT//PBEPBE/6-311?G(d,p)

Table 1 Measured absorption peaks of pure dyes and dyes with TiO2 in N,N-dimethylformamide in experiment (nm)
Purpurin Purpurin with TiO2 Alizarin Alizarin with TiO2

Absorption (nm) 486.00 529.00 436.50 506.00

with TiO2 were located at 486.00 and 529.00 nm, respec- spectrum of alizarin, the absorption spectrum of alizarin
tively, in which the absorption spectrum of purpurin with with TiO2 had a red shift of about 70 nm.
TiO2 had a red shift of 43 nm compared with that of pur- Moreover, in order to further explore, the simulated
purin. Similarly, the UV–Vis absorption spectra of alizarin UV–Vis absorption spectra of purpurin and alizarin in
and alizarin with TiO2 also covered the absorption band vacuum and solvent were obtained by using TD-DFT/
from 400 to 700 nm, which were presented in Fig. 2b. The PBEPBE method with 6-311?G(d,p) basis set, which were
absorption peaks of alizarin and alizarin with TiO2 were presented in Fig. 2c, d, and the calculated data were listed
located at 436.50 and 506.00 nm, respectively, which can in Table 2. It can be seen from Table 2 that for Purpurin, at
be seen from Table 1. Comparing with absorption the first excited state S1, all the oscillator strengths were
void for vacuum and solvent, indicating that the first

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J Mater Sci: Mater Electron (2016) 27:8027–8039 8031

Table 2 Calculated transition energy and oscillator strength of purpurin and alizarin complexone in vacuum and solvent by using TD-DFT//
PBEPBE/6-311?G(d,p)
Dyes State Vacuum Solvent
E (eV) Absorption peak Contribution MO Strength E (eV) Absorption peak Contribution MO Strength
k (nm) f k (nm) f

Purpurin S1 2.1618 573.53 (0.70507)H ? L 0.0000 2.2881 541.87 (0.70559)H-1 ? L 0.0000

S2 2.3843 520.01 (0.70387)H-2 ? L 0.0000 2.4327 509.66 (0.69484)H ? L 0.1613
S3 2.5832 479.95 (0.68965)H-1 ? L 0.1102 2.5432 487.51 (0.70451)H-2 ? L 0.0000
S4 3.1911 388.53 (0.70396)H ? L?1 0.0000 3.1357 395.40 (0.67255)H-3 ? L 0.0070
S5 3.3059 375.04 (0.56816)H-3 ? L 0.0180 3.2962 376.15 (0.65743)H ? L?1 0.0386
S6 3.3224 373.17 (0.53460)H-4 ? L 0.0124 3.3515 369.94 (0.70478)H-1 ? L?1 0.0000
Alizarin S1 2.2367 554.31 (0.70604)H ? L 0.0000 1.9873 623.87 (0.70652)H ? L 0.0036
S2 2.5050 494.95 (0.60688)H-2 ? L 0.0013 2.3590 525.59 (0.70558)H-2 ? L 0.0000
S3 2.5451 487.14 (0.60472)H-3 ? L 0.0022 2.5144 493.10 (0.69007)H-1 ? L 0.1220
S4 2.6885 461.17 (0.68406)H-1 ? L 0.0831 2.6577 466.51 (0.70485)H-3 ? L 0.0001
S5 3.1869 389.05 (0.67572)H-4 ? L 0.0055 2.9908 414.55 (0.68396)H-4 ? L 0.0195
S6 3.1906 388.59 (0.70181)H ? L?1 0.0000 3.0885 401.44 (0.70437)H ? L?1 0.0075

excited state S1 could be negligible. At the second excited
state S2, the oscillator strengths were 0.0000 and 0.1613
for vacuum and solvent, respectively, in which the oscil-
lator strength for solvent was the strongest among the six
excited states. The S2 excited state for vacuum and solvent
were formed by the electrons transferring from H-2 ? L
and H ? L, respectively, whereas the transition energies
were 2.3843 and 2.4327 eV, respectively. At the third
excited state S3, the oscillator strengths were 0.1102 and
0.0000 for vacuum and solvent, in which the oscillator
strength for vacuum was the strongest among the six
excited states. The S3 excited state for vacuum and solvent
were formed by the electrons transferring from H-1 ? L
and H-2 ? L, respectively, whereas the transition energies
were 2.5832 and 2.5432 eV, respectively. At the fourth
excited state S4, the oscillator strengths were 0.0000 and
0.0070 for vacuum and solvent, respectively, indicating
that the fourth excited state S4 could also be negligible. At
the fifth excited state S5, the oscillator strengths were
0.0180 and 0.0386 for vacuum and solvent, respectively, in
which the oscillator strength for solvent was two times that
for vacuum. The S5 excited state for vacuum and solvent
were formed by the electrons transferring from H-3 ? L
and H ? L?1, respectively, whereas the transition ener-
gies were 3.3059 and 3.2962 eV, respectively. At the sixth
excited state S6, the oscillator strengths were 0.0124 and
0.0000 for vacuum and solvent, respectively. The S6
excited state for vacuum and solvent were formed by the
electrons transferring from H-4 ? L and H-1 ? L?1,
respectively, whereas the transition energies were 3.3224
and 3.3515 eV, respectively. Moreover, the simulated
absorption strength in solvent was stronger than that in
vacuum, indicating that the solvent had an interesting
effect on the absorption of dyes to light. Comparing with
the measured absorption spectrum in experiment, the
simulated absorption spectrum in solvent had a red shift of
23.66 nm.
Meanwhile, for alizarin, at the first excited state S1, the
oscillator strengths were 0.0000 and 0.0036 for vacuum
and solvent, indicating that the first excited state S1 for
vacuum could be negligible. The S1 excited state for sol-
vent was formed by the electrons transferring from H ? L,
whereas the transition energies were 1.9873 eV. At the
second excited state S2, the oscillator strengths were
0.0013 and 0.0000 for vacuum and solvent, respectively, in
which the second excited state S2 for solvent could be
negligible. The S2 excited state for vacuum was formed by
the electrons transferring from H-2 ? L, whereas the
transition energies were 2.5050 eV. At the third excited
state S3, the oscillator strengths were 0.0022 and 0.1220
for vacuum and solvent, in which the oscillator strength for
solvent was the strongest among the six excited states. The
S3 excited state for vacuum and solvent were formed by
the electrons transferring from H-3 ? L and H-1 ? L,
respectively, whereas the transition energies were 2.5451
and 2.5144 eV, respectively. At the fourth excited state S4,
the oscillator strengths were 0.0831 and 0.0001 for vacuum
and solvent, respectively, in which the oscillator strength
for vacuum was the strongest among the six excited states.
The S4 excited state for vacuum and solvent were formed
by the electrons transferring from H-1 ? L and H-3 ? L,
respectively, whereas the transition energies were 2.6885
and 2.6577 eV, respectively. At the fifth excited state S5,
the oscillator strengths were 0.0055 and 0.0195 for vacuum

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8032 J Mater Sci: Mater Electron (2016) 27:8027–8039

and solvent, respectively, and the S5 excited state for
vacuum and solvent all were formed by the electrons
transferring from H-4 ? L, whereas the transition energies
were 3.1869 and 2.9908 eV, respectively. At the sixth
excited state S6, the oscillator strengths were 0.0000 and
0.0075 for vacuum and solvent, respectively, in which the
sixth excited state S6 for vacuum could be negligible. The
S6 excited state for solvent was formed by the electrons
transferring from H ? L?1, whereas the transition energy
was 3.0885 eV. Moreover, the simulated absorption spec-
trum in solvent had a red shift of 56.60 nm compared with
the measured absorption spectrum in experiment.
3.2 Fourier transform infrared spectrum
The measured Fourier transform infrared spectra of two
dyes in the range of 400–4000 cm-1 were presented in
Fig. 3a, b, and the simulated FT-IR spectra of the two dyes
were showed in Fig. 3c, d. It can be seen from Fig. 3a that
for purpurin, the strong IR density were distributed
throughout 3000–4000 and 1000–2000 cm-1, i.e., 1269.92,
1399.66, 1457.87, 1585.99, 1622.27, 2359.97 and
3431.53 cm-1, respectively. There was a peak site of
1291.04 cm-1 showing in Fig. 3c, and it was the vibration
of two C–H on symmetrical position on the benzene ring
and O–H in the other benzene ring, as supported by the
vibration analysis in supporting materials Figure S1. The
peak site of 1367.86 cm-1 was the vibration of two O–H
on adjacent position on the benzene ring (see Figure S1).
The peak sites of 1453.32, 1538.37, 1640.13 cm-1 were
the compound vibrations of O–H and C–H on the benzene
ring (see Figure S1). In addition, there had one peak site of
3691.75 cm-1, and it was an obvious stretching vibration
of O–H on the benzene ring.

(a) (c)
85 Purpurin

Purpurin
2000
80
Transmittance %

1500
75
IR activity

1000
70

500
65

500 1000 1500 2000 2500 3000 3500 4000 0

0 1000 2000 3000 4000
Wavenumbers(cm-1)
-1
Frequency(cm )
(b) (d)
90
Alizarin Alizarin
1400
85
1200
Transmittance %

80 1000
IR activity

75 800

600
70
400
65
200

60 0
500 1000 1500 2000 2500 3000 3500 4000 4500 0 1000 2000 3000 4000
Wavenumbers(cm-1) Frequency(cm-1)

Fig. 3 a Measured FT-IR spectrum of purpurin in experiment. b Measured FT-IR spectrum of alizarin complexone in experiment. c Simulated
IR spectrum of purpurin in theory. d Simulated IR spectrum of alizarin complexone in theory

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From Fig. 3b one can see that for Alizarin, the strong IR
density were distributed throughout 3000–4000 and
1000–2000 cm-1, i.e., 715.78, 1286.89, 1342.81, 1637.15,
3448.44, 3630.02, 3650.88, 3676.69, 3822.22 and
3854.61 cm-1, respectively. Moreover, there was a peak
site of 707.69 (see Fig. 3d) and it was a vibration of O–H
on the carboxyl groups attached to the nitrogen atom, as
supported by the vibration analysis in supporting materials
Figure S2. The peak site of 1299.33, 1348.77,
1649.21 cm-1 were the compound vibration of O–H and
C–H on the benzene ring and carboxyl groups (see Fig-
ure S2). Meanwhile, there had two peak sites of 3679.77,
3686.94 cm-1 and they were stretching vibration of O–H
on the different carboxyl groups, respectively.
3.3 Photovoltaic characterization
Here, I–V (current–voltage) characteristics of the DSSCs
sensitized with the two dyes were listed in Table 3, in
which consisted of open circuit voltage (Voc ), short circuit
current density (Isc ), fill factor (ff) and energy conversion
efficiency (g%).
The maximum energy conversion efficiency was cal-
culated by using the following formula [43]:
significantly greater than that of purpurin, indicating that
the photovoltaic characteristics of alizarin excelled that of
purpurin.
3.4 Electrochemical properties
The electrochemical properties of the two dyes were
investigated by using cyclic voltammetry, and the cyclic
voltammograms of the two dyes were showed in Fig. 4a, b.
The research of electrochemical properties for dyes could
provide the probability of electrons transferring from the
excited state of dyes to the conduction band of semicon-
ductor and the ability of dye recovery. The HOMO energy
level of dyes is corresponding to the first oxidation potential,
and the first oxidation potential of two dyes were 0.51 V for
purpurin and 0.28 V for alizarin, respectively. When an Ag/
AgCl electrode was used as the reference electrode, the
HOMO energy level can be calculated by using the
Purpurin
(a)
10
5

ISC  VOC  ff 0
g¼ ð4Þ
Current (μΑ)

P
-5
where P is the intensity of the incident light.
The fill factor (ff) was defined as the ratio of the max- -10

imum power obtained from the DSSC and the theoretical -15
maximum power. Hence,
-20
I m  Vm
ff ¼ ð5Þ
ISC  VOC -25
-1.0 -0.5 0.0 0.5 1.0
where Im and Vm are current and voltage related to the Potential (V versus Ag/AgCl)
maximum power, respectively.
As listed in Table 3, the DSSC sensitized with Purpurin Alizarin
showed energy conversion efficiency of 0.13 %, with open (b)
circuit voltage (Voc ) of 0.44 V, short circuit current density 6
(Isc ) of 0.51 mA cm-2 and fill factor (ff) of 0.60. While,
4
the DSSC sensitized with Alizarin showed energy con-
version efficiency of 0.27 %, with open circuit voltage 2
Current (μΑ)

(Voc ) of 0.45 V, short circuit current density (Isc ) of

0
0.89 mA cm-2 and fill factor (ff) of 0.67, in which the
DSSC sensitized with alizarin was two times that of pur- -2
purin and the short circuit current density of alizarin was
-4

-6
Table 3 Current–voltage characteristics of purpurin and
alizarincomplexone -8
Dye Voc (V) Isc (mA cm-2) ff g% -1.0 -0.5 0.0 0.5 1.0
Potential (V versus Ag/AgCl)
Purpurin 0.44 0.51 0.60 0.13
Alizarin 0.45 0.89 0.67 0.27 Fig. 4 a Cyclic voltammogram of purpurin. b Cyclic voltammogram
of alizarin complexone

123
8034
following formula: HOMO ¼ eðEOX þ 4:40ÞðeVÞ [44].
So the calculated HOMO energy levels of purpurin and
alizarin were -4.91 and -4.68 eV, respectively, which
were different from the following theoretical values. The
calculated HOMO, LUMO energy levels and band gaps of
two dyes in vacuum and solvent were listed in Table 4. The
lower the HOMO level, the higher the ability of dyes
donating electron.
3.5 Electrochemical impedance spectrum
Electrochemical impedance spectrum (EIS) is a very useful
method to investigate the electrons transfer process
between the each interface of the dye-sensitized solar cell,
such as the transfer and recombination of electrons in the
TiO2/dye/electrolyte interface, the transfer of electrons in
the TiO2 electrode and the electron transfer in the electrode
[45, 46]. So the photovoltaic performances of the two dyes
were described by the analysis of electrochemical impe-
dance spectrum of the DSSCs. The electrochemical impe-
dance spectrum, represented as the Nyquist plot, of the two
DSSCs were shown in Fig. 5. The large semicircle dis-
tributing at the low frequency region of Nyquist plot cor-
responded to the charge recombination rooting in electrons
in the TiO2 film recombining with the I3- ion in the
electrolyte, and the small semicircle in the high frequency
region corresponded to the electron transfer from the Pt
counter electrode to the oxidized species in the electrolyte.
From Fig. 5 it can be seen that the impedance of the two
DSSCs in the high frequency region had little to no change,
which was due to the application of same electrolyte and Pt
electrode for the two DSSCs. In contrast, there was a very
clear difference in the impedance of the low frequency
region. The radius of large semicircle of alizarin was
greater than that of purpurin, implying that the recombi-
nation impedance of electrons in the TiO2 film recombin-
ing with the I3- ion in the electrolyte was greater than that
of purpurin. The biggish recombination impedance made
the lower recombination rate of electrons in the TiO2 film
recombining with the I3- ion in the electrolyte, resulting in
the greater open circuit voltage of alizarin [47]. These
results were consistent with the order of the open circuit
voltage in the previous experiment.
Table 4 Energy levels of HOMO, LUMO and energy gaps in vac-
uum and solvent (eV)
Purpurin Alizarin
Vacuum Solvent Vacuum Solvent
H -5.84 -5.93 -6.11 -6.23
L -2.37 -2.62 -2.42 -2.72
DH–L 3.47 3.31 3.69 3.51
123
J Mater Sci: Mater Electron (2016) 27:8027–8039
100 Purpurin
Alizarin
90
80
70
60
-Z'' (Ω)
50
40
30
20
10
0
0 20 40 60 80 100 120 140 160 180 200 220 240
Z' (Ω)
Fig. 5 The Nyquist plots of the two DSSCs
3.6 Calculated ground and excited states properties
In order to further study the relationship between the
structure and optical and electrical properties of the dyes,
the frontier molecular orbital energies and energy gaps
were investigated by using DFT//B3LYP/6-31G(d) method
with the inclusion of vacuum and solvent effect of N,N-
dimethylformamide, and the calculated data were listed in
Table 4. It can be seen form Table 4 that the calculated
energy levels of HOMO and LUMO of Purpurin in gas
were -5.84 and -2.37 eV, respectively, whereas in sol-
vent were -5.93 and -2.62 eV, respectively. And for
alizarin, the energy levels of HOMO and LUMO in gas
were -6.11 and -2.42 eV, respectively, whereas in sol-
vent were -6.23 and -2.72 eV, respectively. The differ-
ence of energy level of HOMO and LUMO indicated that
the energy level of HOMO and LUMO decreased in sol-
vent. The band gaps of purpurin in gas and solvent were
3.47 and 3.31 eV, respectively, and the band gaps of ali-
zarin in gas and solvent were 3.69 and 3.51 eV, respec-
tively, indicating that the band gaps of the dyes in solvent
became smaller than that in gas due to the value of LUMO
decreased more than that of HOMO.
In order to make the charge can be effectively injected
into the conduction band of TiO2, the LUMO levels of dyes
need to be higher than the conduction band edge of TiO2
(about -4.0 eV) and in order to make the molecules that
lost electrons could be effectively restored by getting
electrons from electrolyte, the HOMO levels of dyes must
be lower than that of I-/I3- (about -4.8 eV) [48, 49]. The
energy levels of the two dyes were presented in Fig. 6. As
shown in Fig. 6, the LUMO energy levels of the two dyes
all were higher than the conduction band edge of TiO2,
indicating that the charge can be effectively injected into
the conduction band of TiO2. Meanwhile, the HOMO
J Mater Sci: Mater Electron (2016) 27:8027–8039 8035

HOMO 6-31G(d,p), 6-311G(d), 6-311?G(d) and 6-311?G(d,p),

LUMO
Purpurin Alizarin respectively. Comparing with the absorption peak
-2 vacuum (486.00 nm) in experiment, there were red shifts of 21.34,
vacuum
solvent solvent
21.87, 22.07, 23.61, 23.66 nm for using basis set 6-31G(d),
-3
Energy level (eV)

6-31G(d,p), 6-311G(d), 6-311?G(d) and 6-311?G(d,p),

-4
-5
-6
-7
Fig. 6 Energy levels of purpurin and alizarin complexone in vacuum
and solvent
energy levels of the two dyes all were lower than I-/I3-,
indicating that the dyes that lost electrons could be effec-
tively restored by getting electrons from electrolyte.
On the base of optimized ground state structures, the
absorption spectra were simulated taking the solvent effect
into account by using TD-DFT//PBEPBE/6-311?G (d,p).
For comparison, the basis set effect with 6-31G(d),
6-31G(d,p), 6-311G(d), 6-311?G(d) and 6-311?G(d,p)
basis sets was also applied to investigate the excited state
properties. The calculated absorption peaks and oscillator
strengths of the dyes purpurin and alizarin were listed in
Table 5, and the simulated absorption spectra were shown
in Fig. 7a, b. From Table 5 it can be seen that for purpurin,
the maximum absorption peaks were corresponding to the
excited state S2 and the results were 507.34, 507.87,
508.07, 509.61, 509.66 nm for the basis sets 6-31G(d),
respectively. In addition, from Table 5 it can be seen that
E CB(ΤιΟ2)
for Alizarin, the maximum absorption peaks were corre-
− −
E(Ι ⁄Ι3 ) sponding to the excited state S3 and the peaks were 489.23,
489.69, 491.37, 493.32, 493.10 nm for the basis sets
6-31G(d), 6-31G (d,p), 6-311G(d), 6-311?G(d) and
6-311?G(d, p), respectively. Compared with the experi-
mental result (436.50 nm), there were red shifts of 52.73,
53.19, 54.87, 56.82, 56.60 nm for using basis set 6-31G(d),
6-31G(d,p), 6-311G(d), 6-311?G(d) and 6-311?G(d,p),
respectively.
The nonlinear optical properties of molecules have a
relationship with the response of molecular to external
electric field, which can be used to determine the charac-
teristics of the intramolecular charge transfer (ICT) and is
very important for improving the electron injection effi-
ciency and the light current response [28, 50, 51]. The
static first hyperpolarizability can be written as follows [52,
53]:
 2
Dleg leg
b/ 2
ð6Þ
Eeg
where Dleg is the difference in the dipole moment for
ground state and excited state, leg is the transition dipole
and Eeg is transition energy. Basing on the optimized
ground state geometry, the static first hyperpolarizabilities
of the two dyes in vacuum and solvent were calculated and
listed in Table 6. It can be seen that all the bxxx value of

Table 5 Calculated absorption peaks and oscillator strength of purpurin and alizarincomplexone in solvent by using TD-DFT/PBEPBE method
with different basis sets
6-31G(d) 6-31G(d, p) 6-311G(d) 6-311?G(d) 6-311?G(d,p)
Purpurin Alizarin Purpurin Alizarin Purpurin Alizarin Purpurin Alizarin Purpurin Alizarin

S1 546.01 604.75 546.67 606.91 540.39 609.94 541.56 619.76 541.87 623.87
(0.0000) (0.0026) (0.0000) (0.0027) (0.0000) (0.0029) (0.0000) (0.0034) (0.0000) (0.0036)
S2 507.34 529.53 507.87 530.08 508.07 523.57 509.61 525.27 509.66 525.59
(0.1523) (0.0000) (0.1523) (0.0000) (0.1654) (0.0000) (0.1658) (0.0000) (0.1613) (0.0000)
S3 491.42 489.23 491.84 489.69 486.88 491.37 487.39 493.32 487.51 493.10
(0.0000) (0.1175) (0.0000) (0.1173) (0.0000) (0.1197) (0.0000) (0.1240) (0.0000) (0.1220)
S4 387.45 469.76 387.68 469.94 388.80 464.01 394.85 465.96 395.40 466.51
(0.0073) (0.0001) (0.0074) (0.0001) (0.0056) (0.0000) (0.0070) (0.0001) (0.0070) (0.0001)
S5 371.51 409.91 372.48 410.76 377.08 409.45 375.72 414.05 376.15 414.55
(0.0307) (0.0093) (0.0302) (0.0089) (0.0325) (0.0135) (0.0394) (0.0193) (0.0386) (0.0195)
S6 365.84 401.02 366.71 401.56 368.03 400.45 369.01 399.02 369.94 401.44
(0.0000) (0.0090) (0.0000) (0.0094) (0.0000) (0.0038) (0.0000) (0.0072) (0.0000) (0.0075)

123
8036 J Mater Sci: Mater Electron (2016) 27:8027–8039

3257.931
3165.522
956.639
941.224
(a)
7500
6-31G(d)

btot
6-31G(d,p)
6-311G(d)
6000 6-311+G(d)
6-311+G(d,p)

0.0009
10.654

13.633
0.021
Absorption

4500

bzzz
3000

0.101
-0.043
0.138
-30.430
byzz
1500

87.544

138.938
-1.448

-3.317
0
300 400 500 600 700 800

bxzz
Wavelength (nm)

(b)
6000

37.088

127.991
-0.008

0.236
6-31G(d)
6-31G(d,p)

byyz
6-311G(d)
6-311+G(d)
4500
6-311+G(d,p)

207.457
0.004

2.006
59.329
Absorption

bxyz
3000

-0.090
7.914
18.210
63.114
1500

bxxz
Table 6 Static first hyperpolarizability of purpurin and alizarincomplexone in vacuum and solvent

-396.919
-124.864
-4.757

-1448.261
300 400 500 600 700 800
Wavelength (nm)
byyy

Fig. 7 a Simulated UV–Vis absorption spectra of purpurin in solvent

in theory by using TD-DFT/PBEPBE method with different basis
-27.378

41.860
-356.143

-1207.029
sets. b Simulated UV–Vis absorption spectra of alizarin complexone
in solvent in theory by using TD-DFT/PBEPBE method with
different basis sets
bxyy

Purpurin in vacuum and solvent are larger than that of

Alizarin, and all the first hyperpolarizability of purpuirn in
190.301
-291.023
556.024
-906.443

vacuum and solvent are also larger than that of alizarin,

bxxy

indicating that there is an obvious difference in the dipole

moment.
967.280
-371.307
3190.662
-1003.082

3.7 Molecular electronic calculations

bxxx

To gain insight into the geometrical electronic structures of

the dyes, the electron clouds at selected energy levels of
the dyes purpurin and alizarin in solvent were shown in
Purpurin

Purpurin
Alizarin

Alizarin

Fig. 8, and the electron clouds distributed on the different

location of the dye molecules at different energy levels
(see Fig. 8). For the dyes Purpurin, it can be seen that the
molecule structure consists of three parts: a benzene ring,
Vacuum

Solvent

1,2,4-trihydroxybenzene unit and middle part. It can be

seen from Fig. 8 that for HOMO, the electron clouds

123
J Mater Sci: Mater Electron (2016) 27:8027–8039 8037

Purpurin Alizarincomplexone whole molecular structure for the LUMO, LUMO ? 1 and
HOMO-2 energy levels.
For alizarin, it can be seen that the molecule structure
consists of three parts: a benzene ring, 1,2-dihydroxyben-
zene unit and N-methyleneiminodiacetic acid unit. For
HOMO and HOMO-1, the electron clouds were mainly
LUMO+1 distributed on the 1,2-dihydroxybenzene unit and the N-
LUMO+1 methyleneiminodiacetic acid unit, respectively. For
HOMO-2, the electron clouds were mainly localized on the
middle part of the molecular backbone, and for HOMO-3,
the electron clouds spread over the whole molecular
structure. Meanwhile, for HOMO-4, the electron clouds
LUMO were mainly distributed on the benzene ring. For LUMO
LUMO and LUMO ? 1, the electron clouds spread over the
molecular main structure for the two energy levels. Cor-
responding to the electron transition of the maximum
absorption peak, the electron transferred from the N-
methyleneiminodiacetic acid unit to the main molecule
chain, which was an intramolecular charge transfer (ICT)
HOMO HOMO state. Intramolecular charge transfer is beneficial to the
excited state electron injection into the conduction band of
the semiconductor, which is one of the essential elements
of the photosensitive dyes [54, 55].

HOMO-1 HOMO-1 3.8 Driving force of electron injection and dye

regeneration

Research shows that the short circuit current density of the

DSSCs is related to the driving force of the dye excited
state electron injection and regeneration of dye [25,
HOMO-2 56].The dyes not only have a well optical response with the
HOMO-2 UV visible spectrum, but also the absorbed photon energy
can efficiently transfer to the conduction band of semi-
conductor. Thermodynamically, driving force of the elec-
tron injection process can be described as:
ox ox
ETDF ¼ Eex  Ecb , where Eex and Ecb are the excited state
oxidation potential and the conduction band edge, respec-
HOMO-3 HOMO-3 tively. According to the Rehm and Weller equation [57,
ox
58], Eex can be calculated as following:
ox ox
Eex ¼ Egr  E00 ð7Þ
ox ox
where Eex and Egr are the excited and ground state oxi-
dation potentials, respectively, E00 is the electronic tran-
HOMO-4 sition energy, and the Egr ox
value is calculated from the
ox
HOMO energy. After calculation, the Eex value of Purpurin
Fig. 8 Electron densities of the selected HOMO and LUMO of the
two dyes in solvent and Alizarin are -1.001 and -1.010 V, respectively,
which are more negative than the conduction band edge of
TiO2 [0.5 V vs. normal hydrogen electrode (NHE)] [59].
mainly localized on the 1,2,4-trihydroxybenzene unit. Moreover, the electron injection of alizarin is more easily
Meanwhile, for HOMO-1 and HOMO-3, the electron than that of Purpurin because of the bigger difference
clouds mainly distributed among the middle part of the dye between the excited state oxidation potentials and the
molecule. However, the electron clouds distributed on the conduction band edge of TiO2.

123
8038
In addition, the driving force of dye regeneration was
defined by using the following equation [26, 60]:
DGreg ¼ Eredox  Edye ð8Þ
where Eredox and Edye are the redox potential of I-/I3- and
ground state oxidation potential of dye, respectively. The
Eredox of I-/I3- was -4.6 eV [61] and Edye was the
HOMO energy level of dye. By calculation, the driving
force of dye regeneration for purpurin and alizarin were
-1.33 and -1.63 eV, respectively, indicating that the
driving force of dye regeneration for alizarin was stronger
than that of purpurin. In conclusion, the higher driving
force of electron injection and dye regeneration of alizarin
resulted in the bigger short circuit current density than
that of purpurin.
4 Conclusion
In this work, the optical and electrical properties of two
dyes purpurin (1,2,4-trihydroxy-9,10-anthracenedione) and
alizarin complexone (alizarin-3-methylimino-N,N-diacetic
acid) as sensitizers for dye-sensitized solar cells (DSSCs)
were investigated by using UV–Vis spectrum, FT-IR
spectrum, cyclic voltammetry, I–V (current–voltage)
characteristics and electrochemical impedance spec-
troscopy. The results showed that alizarin complexone had
a higher energy conversion efficiency of 0.27 %, with
higher open circuit voltage (Voc ) of 0.45 V, higher short
circuit current density (Isc ) of 0.89 mA cm-2 and higher
fill factor (ff) of 0.67, and Purpurin showed energy con-
version efficiency of 0.13 %, with open circuit voltage
(Voc ) of 0.44 V, short circuit current density (Isc ) of
0.51 mA cm-2 and fill factor (ff) of 0.60, indicating that
the photovoltaic characteristics of alizarin excelled that of
purpurin. For comparison, the frontier molecular orbitals,
transition properties, vibration analysis, the total static first
hyperpolarizability and driving force of electron injection
were calculated by using DFT and TD-DFT methods in
theory. The results showed that alizarin complexone had
lower HOMO and higher LUMO than that of purpurin
considering the solvent effect, resulting in the wider band
gap for alizarin complexone. Moreover, the electron
injection of alizarin is more easily than that of purpurin
because of the bigger difference between the excited state
oxidation potentials and the conduction band edge of TiO2.
Electrochemical impedance spectroscopy analysis revealed
that alizarin complexone had the greater recombination
impedance of electrons in the TiO2 film recombining with
the I3- ion in the electrolyte. In a conclusion, the side chain
has an interesting effect on the optical and electrical
properties of sensitizers.
123
J Mater Sci: Mater Electron (2016) 27:8027–8039
Acknowledgments This work was supported by the Fundamental
Research Funds for the Central Universities (Grant No.
2572014CB31), the Heilongjiang Provincial Youth Science Founda-
tion (Grant No. QC2013C006), the National Natural Science Foun-
dation of China (Grant Nos. 11404055 and 11374353) and
Heilongjiang Postdoctoral Grant (LBH-Z15002).
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