Research Article  Open Access
Photoelectric Properties of DSSCs Sensitized by Phloxine B and Bromophenol Blue
Abstract
Phloxine B and bromophenol blue as the sensitizers of dyesensitized solar cells were investigated via UVVis spectra, FTIR spectra, fluorescence spectra, and currentvoltage characteristics. The frontier molecular orbital, vibration analysis, and the first hyperpolarizability were calculated with DFT/631G(d). The dipole moment, light harvesting efficiency (LHE), and larger absolute value of driving force of electron injection () were also discussed. The calculated results were compared with the experimental results of phloxine B and bromophenol blue. It was found that, compared with bromophenol blue, bigger dipole moment of phloxine B results in larger open circuit voltage () according to the correlation between dipole moment and . At the same time, for configuration of phloxine B, it has higher LHE and , which are helpful to enhance the abilities of absorbing sunlight and electron injection. Therefore, higher LHE and for phloxine B produced a larger value of .
1. Introduction
With gradually aggravated environmental problem, it is hoped that more energies can be found to replace traditional fossil energy. Solar energy as the clean and renewable source has aroused extensive attention. Since O’Regan and Graetzel [1] developed dyesensitized solar cells (DSSCs), the phototoelectric conversion efficiency () of this type of solar cells has achieved 7.1–7.9%. Due to their friendliness and low cost of production [2–5], more attention has been paid to investigate the relationship between structure and performance and to design new DSSCs.
The band engineering of the solar cells devices is shown in Figure 1, which indicates the complete energy levels of the different materials used on the DSSCs devices. DSSCs have the characteristics of the following five aspects [6–9]: Dye molecules absorb sunlight energy, and they are excited from ground state to excited state. After the dye molecules are excited, the electrons are injected into the conduction band of semiconductor and moved into the conducting glass. The electrons diffuse into the external circuit. The dye molecules in oxidation state are deoxidized by the electrolyte in reduction. The electrolyte in oxidation state is deoxidized after receiving the electron at the conducting glass, thereby completing a cycle.
The DSSCs are mainly composed of a nanocrystalline porous semiconductor electrodeabsorbed dye, a counter electrode, and an electrolyte containing iodide and triiodide ions [10]. The dye as a sensitizer plays a key factor in absorbing sunlight and conversion solar energy into electric energy. DSSCs mainly are divided into organic dyes and inorganic dyes [11–13]. Inorganic dyes such as N3 and N719 polypyridine complexes [14] have been used as sensitizer in DSSCs. Although DSSCs of inorganic dyes have provided a relatively high efficiency, there are several shortcomings of using inorganic dyes in DSSCs. For example, some inorganic dyes are considered as resources that are limited in amount, which result in more expensive cost in the field of DSSC. By contraries, organic dyes not only are cheaper, but also have been reported to reach efficiency as high as 9.8% [15]. Nevertheless, the conversion efficiency of organic dyes was still lower than that of inorganic dyes, and it was not suitable for commercial production in comparison with silicon cell [3]. Torchani et al. [16] studied the henna and mallow (Mloukhya) as the sensitizers of DSSCs. The results showed that the filling factor of mallow solar cells is 55%, and is 0.215%. Zhou et al. [17] studied twenty natural dyes, extracted from natural materials (such as flowers, leaves, fruits, traditional Chinese medicines, and beverages), and the results showed that the open circuit voltage and of mangosteen pericarp are the highest, which are 0.686 V and 1.17%, respectively. Now several organic dyes have been utilized as sensitizers in DSSCs, such as coumarin [18], porphyrins [19–21], triphenylmethane [22, 23], indoline [24, 25], and cyanine [26, 27].
In recent years, quantum chemistry method has provided a reliable theoretical basis for the rapid screening of high efficiency dye molecules [28–32]. Kumara et al. [33] reported the black tea waste extract (BTE) as a sensitizer for DSSCs in experimental and theoretical studies. The BTE has four theaflavin analogues, and they are calculated via density functional theory (DFT) and timedependent density functional theory (TDDFT). The results showed that theaflavin and theaflavin digallate as sensitizers have well performance among four analogues. Beni and Zarandi [34] analyzed the 3amino4nitrofurazan molecule using functional theory (DFT) and MP2 methods. The geometry of the molecule in the gas phase was optimized and compared with that of the crystal. According to DFT and MP2 methods, they obtain the stable gaseous form. ElShishtawy et al. [35] studied electronic absorption spectra, ground state geometries, and electronic structures of symmetric and asymmetric squaraine dyes with DFT method, and they found that absorption of squaraine dyes can extend into NIR region by straightforward structural modification, and there are well energy match between dye and TiO_{2}. Sun et al. [36] investigated the optical and electrical properties of two dyes, purpurin and alizarin complexone, as sensitizers by using UVVis spectrum, FTIR spectrum, cyclic voltammetry, characteristics, and DFT calculation, and the results indicated that the side chain has an interesting effect on the optical and electrical properties of sensitizers. Li and coworkers [37] investigated the ground state and excited state properties of polymers BSeTT, QTT, BDTDTBTBPz (Pz), and BDTDTBTBQx (Qx) and their derivatives D1, D2, and D3 via DFT and TDDFT methods, which indicated that the molecule BDTDTBTBPz and designed molecule (D2) had the best optical and electronic properties among the investigated system. Song et al. [38] reported that electron transfer is a key process of light driven charge separation reaction in organic solar cell.
In this work, phloxine B and bromophenol blue were selected as sensitizers to investigate the optical and electrical properties of DSSCs experimentally, and the UVVis spectra, fluorescence spectra, and FTIR spectra are calculated with density functional theory (DFT) and timedependent density functional theory (TDDFT). At the same time, the absorption spectra, infrared spectra, and fluorescence spectra of phloxine B and bromophenol blue are analyzed and compared. In addition, the radiative lifetime () and total static first hyperpolarizability of the two dyes are calculated. Combined study of experiment and theory provides deep insight into the relationship between structure and performance for two DSSCS.
2. Methods
UVVis spectra were measured with TU1900 spectrometer (Beijing, China), and the FTIR spectra were measured with FTIR 360 spectrometer (Nicolet, Madison, WI, USA). Solar energy conversion efficiency measurements were done with a solar simulation instrument (Pecell15, Japan), and light intensity was adjusted via a reference standard Sisolar cell at sunlight intensity of 100 mW cm^{−2}. The ground state structures of phloxine B and bromophenol blue were optimized with DFT [39] using B3LYP [40] functional at the 631G(d) basis set. Based 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 were computed, and vibration frequencies were done at the same level. There was no imaginary vibration frequency in the minimum energy structure in the potential energy landscape. Simulation of absorption spectra was done with TDDFT at the same level. The total static first hyperpolarizability can be written as follows [41]:Individual static components in the above equation are calculated fromwhere are tenser components of hyperpolarizability. Due to the Kleinman symmetry, we finally obtain the equation that has been employed:All of the calculations were performed by using Gaussian 09 package [42].
3. Results and Discussion
3.1. The Optical Properties of the Dye
The chemical structures of bromophenol blue and phloxine B are shown in Figure 2. The experimental absorption spectra of two dyes in ethanol are presented in Figure 3(a). Absorption spectra of phloxine B showed that the absorption range was 450–600 nm, with maximum absorption peak () at around 550 nm. Absorption spectra of bromophenol blue were displayed within the range of 300–500 nm, and was 410 nm, and bromophenol blue had no other obvious absorption peaks (see Figure 3(a)).
(a)
(b)
In addition, absorption spectra of bromophenol blue and phloxine B were computed via TDDFT/631G(d) in solvent (see Figure 3(b)), and the data are listed in Table 1. Phloxine B showed the absorption region in 300–700 nm, with a of 472 nm. Bromophenol blue absorption range was 230–330 nm, while was 289 nm. The absorptions in visible and nearUV area were important areas for photovoltaic performance, so there are two important factors (the oscillator strength larger than 0.1 and absorption bands with the wavelength longer than 300 nm). The oscillator strength of the first excited state S1 of phloxine B was 0.7582 (at 472 nm), in which the oscillator strength was the strongest among the six excited states. The maximum absorption in absorption spectra was dominated by HOMO LUMO transition (contribution is about 0.70069), and the corresponding transition energy was 2.63 eV. Meanwhile, for bromophenol blue, at the first excited state S1, the oscillator strength was 0.0322. The oscillator strength of S1 was the strongest in the states, and this state is composed of HOMO LUMO electron transition.

For more indepth understanding of the electronic structure of the two dyes, the isodensity plots of the frontier molecular orbitals (MOs) of two dyes were shown in Figure 4. Phloxine B consists of two parts, namely, sodium2,3,4,5tetrachlorobenzene and sodium2,4,5,7tetrabromo6oxoxanthen3olate, respectively. The electron density of HOMO was located on the sodium2,4,5,7tetrabromo6oxoxanthen3olate group, and that of LUMO was located on conjugated bridge and sodium2,4,5,7tetrabromo6oxoxanthen3olate group. From the distribution of the above molecular orbitals of HOMO and LUMO, electron transfer was most likely to occur from sodium2,4,5,7tetrabromo6oxoxanthen3olate group unit to conjugated bridge. Electron densities of other MOs were shown in Figure 4, corresponding to the HOMO − 1, HOMO − 2, HOMO − 3, LUMO + 1, LUMO + 2, and LUMO + 3, respectively.
Bromophenol blue is composed of three parts, namely, two identical 2,6dibromophenol groups and pyridine, respectively. The electron density of HOMO was located on two identical 2,6dibromophenol groups and conjugated bridge, and that of LUMO was located on pyridine and conjugated bridge. As the electron transition is from HOMO to LUMO, it was found that a tiny fraction of MOs for HOMO and LUMO was loaded in conjugated bridge, and more electrons were moved to pyridine. Therefore, excitation should result in electron transfer from two identical 2,6dibromophenol groups to pyridine. The HOMOs and LUMOs in the dyes indicated that the transitions at maximum absorptions had intramolecular charge transfer (ICT) character, and they played an important role in DSSCs.
3.2. Fourier Transforms Infrared Spectra
Fourier transforms infrared (FTIR) spectra of phloxine B and bromophenol blue were recorded in the 500–4000 cm^{−1} range using KBr pellets and calculated at DFT/B3LYP methods with the 631G(d) basis set. The experimental FTIR spectra were shown in Figures 5(a) and 5(b), and calculated FTIR spectra were given in Figures 5(c) and 5(d). For absorption peak vibration of bromophenol blue, the absorption peaks were distributed in ranges of 1000–2000 cm^{−1} and 3000–4000 cm^{−1}. They were 1398.75, 1472.31, 1634.19, 3440.26 cm^{−1}, and 3851.47 cm^{−1} (see Figure 5(a)), respectively. Swing vibration of two CH bonds of 2,6dibromophenol group for bromophenol blue was observed at 3243.83 cm^{−1} (see Figure 5(c)). Swing vibration of two OH bonds of two 2,6dibromophenol groups was observed at 1389.36 cm^{−1}. Stretching vibration of two CH bonds of pyridine group was observed at 1452.16 cm^{−1} and 3652.02 cm^{−1}, respectively. Pyridine group swing vibration was observed at 1632.13 cm^{−1}.
(a)
(b)
(c)
(d)
CH vibrations were studied as follows: CH swing and stretching vibration in unit 2,6dibromophenol groups were calculated in the range of 681.42, 868.79–934.34, 974.53, 1085.05–1087.63, 1205.43–1209.30, 1232.40, 1333.11–1338.06, 1388–1445.35, 1519.36–1609.41, and 1641.86–1644.21 cm^{−1} and at 3234.68–3443.83 cm^{−1}. CH swing and stretching in pyridine group were calculated in range of 718.94, 765.71–766.86, 842.82–863.99, 944.66, 993.54–999.10, 1057.47, 1108.78–1171.92, and 1452.16–1513.01 cm^{−1} and at 3192.57–322.58 cm^{−1}, respectively.
For SO, OH, and ring vibrations, results showed that SO stretching vibration was observed at 746.58 cm^{−1}, and S=O symmetric stretching was observed at 1171.92 and 1357.69 cm^{−1} in FTIR, respectively. OH swing and stretching vibration occurred in the range of 613.14, 1205.43–1209.30, 1295.17–1301.14, 1338.06 1388.22–1445.35, 1519.36–1609.41, and 3651.80–3652.02 cm^{−1}. Benzene rings stretching vibration often occurred in range of 718.94–742.42, 766.86, and 1606.85–1641.80 cm^{−1}. Benzene rings twisting vibration was found to be 765.71 cm^{−1}.
For absorption peak vibration of phloxine B, the main absorption peaks of FTIR spectra focus on 1000–2000 cm^{−1}. They were 1242.93, 1355.36, 1463.41, 1558.18 cm^{−1}, and 1634.31 cm^{−1} (see Figure 5(b)), respectively. Swing vibration of sodium2,4,5,7tetrabromo6oxoxanthen3olate group was observed at 1453.18 cm^{−1} and 1548.97 cm^{−1} (see Figure 5(d)), respectively. Two CH bonds’ stretching vibrations of sodium2,4,5,7tetrabromo6oxoxanthen3olate group were observed at 1228.48 cm^{−1} and 1356.04 cm^{−1}, respectively. C=O bond stretching vibration of sodium2,4,5,7tetrabromo6oxoxanthen3olate group was observed at 1642.66 cm^{−1}.
For CH, COONa, and ONa vibrations, it was found that CH swing and stretching vibration in sodium2,4,5,7tetrabromo6oxoxanthen3olate group were assigned in the region of 936.95, 987.30, 1008.72, 1030.88, 1204.51–1511.59, 1545.61, 1617.78, and 1665.48 cm^{−1}, respectively. The COONa symmetric stretching vibration of sodium2,4,5,7tetrabromo6oxoxanthen3olate group occurred at 910.95 and 1686.27 cm^{−1}, respectively. ONa stretching vibration was observed at 1593.03 cm^{−1}.
Furthermore, there are three benzene rings in the phloxine B. Benzene ring symmetric stretching vibration was observed in the region of 910.95–987.30, 1030.88, 1388.10, 1453.18, 1532.61, and 1572.03 cm^{−1} and at 1665.48 cm^{−1}, respectively. Benzene ring asymmetric stretching vibration was calculated in range of 1008.72, 1136.98–1204.51, 1272.62, 1290.53, 1356.04, 1382.82, 1488.37, 1511.59, and 1545.61 cm^{−1}, and inplane bending vibration was computed at 1211.25 cm^{−1}.
3.3. Photovoltaic Characterization
The following formula is used to calculate the maximum power phototoelectric conversion efficiency () [43]:Here, was the intensity of the incident light; , , and FF represent short circuit density, open circuit voltage, and fill factor, respectively.
The FF was defined as the ratio of the maximum power obtained from the DSSCs and the theoretical maximum power of it [44]. Hence,Here, and were current and voltage related to the maximum power. In the experiment, we used the phloxine B and bromophenol blue as sensitizers, to measure the currentvoltage () under sunlight intensity of 100 mW cm^{−2}. And the results are shown in Figure 6, and measured characteristics of the DSSCs sensitized for the two dyes are listed in Table 2.

The DSSCs sensitized with phloxine B showed of 0.52%, with of 0.61 V, of 1.31 mA cm^{−2}, and FF of 0.65, while the DSSCs sensitized with bromophenol blue showed of 0.05%, with of 0.44 V, of 0.17 mA cm^{−2}, and FF of 0.68. The results showed that photovoltaic performance of phloxine B is greater than that of bromophenol blue. Then of the DSSCs using the phloxine B as sensitizer was more suitable. The photovoltaic performance of the phloxine B was higher than that of bromophenol blue. This improvement in the photovoltaic performance of the DSSCs with phloxine B could be attributed to the absorption spectra of solar radiations (450–600 nm) (see Figure 3(a)) [43]. This result indicated that the range of absorption spectra affected of DSSCs.
To analyze the difference of two dyes, we performed theoretical calculation to explain the well photoelectric properties (larger and ) of phloxine B. The value of was viewed as the difference between the quasiFermi level of semiconductor conduction band edge value and the electrolyte oxygen reductions. Because the electrolyte was typically I^{−}/, the redox electrolyte can be considered constant. The value of has a direct dependence on the shift of the reduction potential of the semiconductor conduction band (), and is expressed [45]:where is adsorbed on the surface concentration and is the dipole moment component perpendicular to the direction of TiO_{2} surface (where was the axis direction), is the gas permittivity, and is the dielectric constant of the organic monolayer. Obviously, according to (6), the larger the value of , the bigger the value of . The change of has direct influence on . In order to analyze and compare , we calculated , as shown in Figure 7. of phloxine B was 19.80 D, and of bromophenol blue was −1.29 D. of phloxine B was much larger than that of bromophenol blue. Therefore, the increasing for phloxine B results in the larger [46, 47].
For the dye sensitizers, the light harvesting efficiency (LHE) and oscillator strength had correlated relationship [48], which is expressed as follows:Here, is the oscillator strength. According to Table 1, we found that the first excited state of phloxine B and bromophenol blue corresponds to a dominant position in absorption, and the oscillator strength of phloxine B was larger than that of bromophenol blue. The LHE of phloxine B was 0.8255, and that of bromophenol blue was 0.0714. So the correlated relationship between the oscillator strength and light harvesting efficiency (LHE) implied that the dye with larger oscillator strength made more LHE, and thus phloxine B has well utilities of sunlight.
The sunlight absorption and electron injection were important process in DSSCs, which obviously affect the efficiency of [49]. Driving force of electron injection () means that the excited dye provided electron into semiconductor conduction band. Electron injection occurred from the excited state; could be calculated by the following equation [50]:where is the oxidation potential of the excited state of the dye, and is the reduction potential of the semiconductor conduction band. The reported = 4.0 eV [51] for TiO_{2} was adopted in this work. could be calculated as follows [52]:Here is the redox potential of the ground state, and was the absorption maximum with ICT character.
The data of phloxine B and bromophenol blue were listed in Table 3. According to the calculation results, of phloxine B (−1.82 eV) was higher than bromophenol blue (−1.49 eV), meaning that of phloxine B was easier than bromophenol blue. was an important influence factor for the electron injection efficiency. At the same time, the LHE showed that phloxine B was stronger than bromophenol blue, as discussed above. Therefore, phloxine B has improved absorption and injection abilities in comparison with bromophenol blue, which cause the larger value of .

3.4. Ground and Excited State Properties
To ensure that electrons could be effectively injected into the conduction band of TiO_{2} (about −4.0 eV) [51], LUMO energy level must be higher than the edge of the conduction band of the TiO_{2}, and HOMO energy level must be below I^{−}/ electrolyte (about −4.85 eV) [46]. Energy levels of MOs and energy gaps in solvent were studied by using DFT/B3LYP/631G(d) method. Energy levels and HOMOLUMO gap are presented in Figure 8, and the calculated data are listed in Table 4. For phloxine B, the highest occupied MO (HOMO) was −5.44 eV and the lowest unoccupied MO (LUMO) was −2.64 eV. For bromophenol blue, the HOMO was −6.63 eV and the LUMO was −1.77 eV. The band gap of phloxine B was smaller than that of bromophenol blue, meaning there is a redshifted absorption for phloxine B. From Figure 8, it seems that the LUMOs of phloxine B and bromophenol blue were all higher than the conduction band of TiO_{2}, meaning that the electron injection can occur from excited dyes into TiO_{2}, and the HOMOs of two dyes were lower than I^{−}/ (see Figure 8); therefore, two dyes can obtain electron to recovery.

Molecular nonlinear optical properties have a close relationship with external electric field. It reflects the characteristics of the intramolecular charge transfer (ICT), which can affect the electron injection efficiency and the light current. The first hyperpolarizability () is directly proportional to the difference in the dipole moment () between the ground state and the excited state and the transition dipole moment (), and it is inversely proportional to the transition energy. The first hyperpolarizabilities could be written as follows [53]:where and are difference in the dipole moment for ground state and excited state and the transition dipole, , is transition energy. The first hyperpolarizabilities were calculated, as listed in Table 5. The of phloxine B was higher than that of bromophenol blue. Table 1 and Figure 7 support the results of hyperpolarizabilities. Figure 7 showed that the value of for phloxine B is larger than that of bromophenol blue; at the same time, phloxine B has smaller excitation energy, so phloxine B has larger hyperpolarizabilities with obvious ICT.

3.5. Fluorescence Spectroscopy of Dyes
Radiative lifetime () played an important role in DSSCs, and it could affect charge recombination [54]. could be calculated as follows [55]:Here, is the speed of light, is the oscillator strength, and is the fluorescent energy. The experimental spectra of the phloxine B and bromophenol blue are shown in Figure 9, and the calculated fluorescence maxima , oscillator strength ( in a.u.), and relative radiative lifetime are listed in Table 6. The maximum absorption peak of phloxine B was 507 nm. The fluorescence energy, oscillator strength, and radiative lifetime were 2.45 eV, 0.6268, and 6.14 10^{−9} s, respectively. The absorption peak of bromophenol blue was 385 nm. The fluorescence energy, oscillator strength, and radiative lifetime were 3.22 eV, 0.0085, and 2.61 10^{−7} s, respectively. The radiative lifetime of bromophenol blue was higher (2.61 10^{−7} s). But phloxine B was propitious to charge recombination [54].

4. Conclusion
The absorption, molecular orbital energies, radiative lifetimes, LHE, and were addressed. The oscillator strength (0.7582), vertical dipole moment (19.80 D), and (−1.82 eV) for phloxine B were higher than those of bromophenol blue. The , , and of phloxine B were 0.61 V, 1.31 mA/cm^{2}, and 0.52%, respectively, which were higher than those of bromophenol blue. The results showed that higher dipole moment of phloxine B corresponds to larger . This means that enlarging dipole moment was a possible way to increase of DSSCs. The larger oscillator strength, higher LHE, and larger absolute value of correspond to larger . This means increasing oscillator strength and LHE and larger absolute value of were a possible way to increase . A similar trend between theory and experiment was observed. Photovoltaic performance of phloxine B was significantly higher than that of bromophenol blue.
Competing Interests
The authors declare that they have no competing interests.
Acknowledgments
This work was supported by the Fundamental Research Funds for the Central Universities (Grant no. 2572014CB31), the Heilongjiang Provincial Youth Science Foundation (Grant no. QC2013C006), the National Natural Science Foundation of China (Grant nos. 11404055 and 11374353), China Postdoctoral Science Foundation (2016M590270), Heilongjiang Postdoctoral Grant (LBHZ15002), National Undergraduate Innovative and Entrepreneurial Training Program (Grant no. 201610225099), and Academic Research Training of NEFU for Undergraduate (Grant no. KY2015020).
References
 B. O'Regan and M. Graetzel, “A lowcost, highefficiency solar cell based on dyesensitized colloidal titanium dioxide films,” Nature, vol. 353, no. 6346, pp. 737–740, 1991. View at: Publisher Site  Google Scholar
 M. Grätzel, “Photoelectrochemical cells,” Nature, vol. 414, no. 6861, pp. 338–344, 2001. View at: Publisher Site  Google Scholar
 D. Wei, “Dye sensitized solar cells,” International Journal of Molecular Sciences, vol. 11, no. 3, pp. 1103–1113, 2010. View at: Publisher Site  Google Scholar
 M. K. Nazeeruddin, C. Klein, P. Liska, and M. Grätzel, “Synthesis of novel ruthenium sensitizers and their application in dyesensitized solar cells,” Coordination Chemistry Reviews, vol. 249, no. 1314, pp. 1460–1467, 2005. View at: Publisher Site  Google Scholar
 B. Li, L. Wang, B. Kang, P. Wang, and Y. Qiu, “Review of recent progress in solidstate dyesensitized solar cells,” Solar Energy Materials and Solar Cells, vol. 90, no. 5, pp. 549–573, 2006. View at: Publisher Site  Google Scholar
 N. Robertson, “Optimizing dyes for dyesensitized solar cells,” Angewandte Chemie, vol. 45, no. 15, pp. 2338–2345, 2006. View at: Publisher Site  Google Scholar
 A. Sasani, A. Baktash, K. Mirabbaszadeh, and B. Khoshnevisan, “Structural and electronic properties of Mg and MgNb codoped TiO_{2} (101) anatase surface,” Applied Surface Science, vol. 384, pp. 298–303, 2016. View at: Publisher Site  Google Scholar
 S. E. Gledhill, B. Scott, and B. A. Gregg, “Organic and nanostructured composite photovoltaics: an overview,” Journal of Materials Research, vol. 20, no. 12, pp. 3167–3179, 2005. View at: Publisher Site  Google Scholar
 M. Magni, P. Biagini, A. Colombo, C. Dragonetti, D. Roberto, and A. Valore, “Versatile copper complexes as a convenient springboard for both dyes and redox mediators in dye sensitized solar cells,” Coordination Chemistry Reviews, vol. 322, pp. 69–93, 2016. View at: Publisher Site  Google Scholar
 M. Grätzel, “The advent of mesoscopic injection solar cells,” Progress in Photovoltaics: Research and Applications, vol. 14, no. 5, pp. 429–442, 2006. View at: Publisher Site  Google Scholar
 A. Mishra, M. K. R. Fischer, and P. Büuerle, “Metalfree organic dyes for dyeSensitized solar cells: from structure: property relationships to design rules,” Angewandte Chemie, vol. 48, no. 14, pp. 2474–2499, 2009. View at: Publisher Site  Google Scholar
 Z. Ning and H. Tian, “Triarylamine: a promising core unit for efficient photovoltaic materials,” Chemical Communications, vol. 45, no. 37, pp. 5483–5495, 2009. View at: Publisher Site  Google Scholar
 S. M. Zakeeruddin and M. Grätzel, “Solventfree ionic liquid electrolytes for mesoscopic dyesensitized solar cells,” Advanced Functional Materials, vol. 19, no. 14, pp. 2187–2202, 2009. View at: Publisher Site  Google Scholar
 H. Chang and Y.J. Lo, “Pomegranate leaves and mulberry fruit as natural sensitizers for dyesensitized solar cells,” Solar Energy, vol. 84, no. 10, pp. 1833–1837, 2010. View at: Publisher Site  Google Scholar
 G. Zhang, H. Bala, Y. Cheng et al., “High efficiency and stable dyesensitized solar cells with an organic chromophore featuring a binary πconjugated spacer,” Chemical Communications, no. 16, pp. 2198–2200, 2009. View at: Publisher Site  Google Scholar
 A. Torchani, S. Saadaoui, R. Gharbi, and M. Fathallah, “Sensitized solar cells based on natural dyes,” Current Applied Physics, vol. 15, no. 3, pp. 307–312, 2015. View at: Publisher Site  Google Scholar
 H. Zhou, L. Wu, Y. Gao, and T. Ma, “Dyesensitized solar cells using 20 natural dyes as sensitizers,” Journal of Photochemistry and Photobiology A: Chemistry, vol. 219, no. 23, pp. 188–194, 2011. View at: Publisher Site  Google Scholar
 Z.S. Wang, Y. Cui, K. Hara, Y. DanOh, C. Kasada, and A. Shinpo, “A highlightharvestingefficiency coumarin dye for stable dyesensitized solar cells,” Advanced Materials, vol. 19, no. 8, pp. 1138–1141, 2007. View at: Publisher Site  Google Scholar
 C.L. Wang, C.M. Lan, S.H. Hong et al., “Enveloping porphyrins for efficient dyesensitized solar cells,” Energy and Environmental Science, vol. 5, no. 5, pp. 6933–6940, 2012. View at: Publisher Site  Google Scholar
 M. J. Griffith, K. Sunahara, P. Wagner et al., “Porphyrins for dyesensitised solar cells: new insights into efficiencydetermining electron transfer steps,” Chemical Communications, vol. 48, no. 35, pp. 4145–4162, 2012. View at: Publisher Site  Google Scholar
 W. M. Campbell, A. K. Burrell, D. L. Officer, and K. W. Jolley, “Porphyrins as light harvesters in the dyesensitised TiO_{2} solar cell,” Coordination Chemistry Reviews, vol. 248, no. 1314, pp. 1363–1379, 2004. View at: Publisher Site  Google Scholar
 K. Kudo, H. Yageta, S. Kuniyoshi, and K. Tanaka, “Surface pressure variation in triphenylmethane dye adsorbed merocyanine monolayers at the airwater interface,” Japanese Journal of Applied Physics, vol. 32, no. 4, pp. 1775–1778, 1993. View at: Publisher Site  Google Scholar
 S. Cleinmensen, J. C. Jensen, N. J. Jensen, O. Meyer, P. Olsen, and G. Würtzen, “Toxicological studies on malachite green: a triphenylmethane dye,” Archive Für Toxikologie, vol. 56, no. 1, pp. 43–45, 1984. View at: Publisher Site  Google Scholar
 G. Li, M. Liang, H. Wang et al., “Significant enhancement of opencircuit voltage in indolinebased dyesensitized solar cells via retarding charge recombination,” Chemistry of Materials, vol. 25, no. 9, pp. 1713–1722, 2013. View at: Publisher Site  Google Scholar
 H. W. Ham and Y. S. Kim, “Theoretical study of indoline dyes for dyesensitized solar cells,” Thin Solid Films, vol. 518, no. 22, pp. 6558–6563, 2010. View at: Publisher Site  Google Scholar
 X. Ma, J. Hua, W. Wu et al., “A highefficiency cyanine dye for dyesensitized solar cells,” Tetrahedron, vol. 64, no. 2, pp. 345–350, 2008. View at: Publisher Site  Google Scholar
 J. Tang, W. Wu, J. Hua, J. Li, X. Li, and H. Tian, “Starburst triphenylaminebased cyanine dye for efficient quasisolidstate dyesensitized solar cells,” Energy & Environmental Science, vol. 2, no. 9, pp. 982–990, 2009. View at: Publisher Site  Google Scholar
 Y. Li, T. Pullerits, M. Zhao, and M. Sun, “Theoretical characterization of the PC60BM:PDDTT model for an organic solar cell,” The Journal of Physical Chemistry C, vol. 115, no. 44, pp. 21865–21873, 2011. View at: Publisher Site  Google Scholar
 Ü. Ceylan, G. Ö. Tarı, H. Gökce, and E. Ağar, “Spectroscopic (FTIR and UVVis) and theoretical (HF and DFT) investigation of 2EthylN[(5nitrothiophene2yl)methylidene]aniline,” Journal of Molecular Structure, vol. 1110, pp. 1–10, 2016. View at: Publisher Site  Google Scholar
 E. B. Sas, M. Kurt, M. Can, N. Horzum, and A. Atac, “Spectroscopic studies on 9Hcarbazole9(4phenyl) boronic acid pinacol ester by DFT method,” Journal of Molecular Structure, vol. 1118, pp. 124–138, 2016. View at: Publisher Site  Google Scholar
 S. Soleimani Amiri, S. Makarem, H. Ahmar, and S. Ashenagar, “Theoretical studies and spectroscopic characterization of novel 4methyl5((5phenyl1,3,4oxadiazol2yl)thio)benzene1,2diol,” Journal of Molecular Structure, vol. 1119, pp. 18–24, 2016. View at: Publisher Site  Google Scholar
 A. G. AlSehemi, A. Irfan, A. M. Asiri, and Y. A. Ammar, “Synthesis, characterization and DFT study of methoxybenzylidene containing chromophores for DSSC materials,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 91, pp. 239–243, 2012. View at: Publisher Site  Google Scholar
 N. T. R. N. Kumara, M. R. R. Kooh, A. Lim et al., “DFT/TDDFT and experimental studies of natural pigments extracted from black tea waste for DSSC application,” International Journal of Photoenergy, vol. 2013, Article ID 109843, 8 pages, 2013. View at: Publisher Site  Google Scholar
 A. S. Beni and M. Zarandi, “Application of DFT and MP2 calculations on structural and waterassisted proton transfer in 3amino4nitrofurazan,” Russian Journal of Physical Chemistry A, vol. 90, no. 2, pp. 374–382, 2016. View at: Publisher Site  Google Scholar
 R. M. ElShishtawy, S. A. Elroby, A. M. Asiri, and K. Mullen, “Optical absorption spectra and electronic properties of symmetric and asymmetric squaraine dyes for use in DSSC solar cells: DFT and TDDFT studies,” International Journal of Molecular Sciences, vol. 17, no. 4, p. 487, 2016. View at: Publisher Site  Google Scholar
 C. F. Sun, Y. Z. Li, D. W. Qi, H. X. Li, and P. Song, “Optical and electrical properties of purpurin and alizarin complexone as sensitizers for dyesensitized solar cells,” Journal of Materials Science: Materials in Electronics, vol. 27, no. 8, pp. 8027–8039, 2016. View at: Publisher Site  Google Scholar
 Y. Z. Li, C. F. Sun, D. W. Qi, P. Song, and F. C. Ma, “Effects of different functional groups on the optical and charge transport properties of copolymers for polymer solar cells,” RSC Advances, vol. 6, no. 66, pp. 61809–61820, 2016. View at: Publisher Site  Google Scholar
 P. Song, Y. Li, F. Ma, T. Pullerits, and M. Sun, “Photoinduced electron transfer in organic solar cells,” Chemical Record, vol. 16, no. 2, pp. 734–753, 2016. View at: Publisher Site  Google Scholar
 W. Kohn and L. J. Sham, “Quantum density oscillations in an inhomogeneous electron gas,” Physical Review, vol. 137, no. 6, pp. A1697–A1705, 1965. View at: Publisher Site  Google Scholar
 C. Lee, W. Yang, and R. G. Parr, “Development of the ColleSalvetti correlationenergy formula into a functional of the electron density,” Physical Review B: Condensed Matter, vol. 37, no. 2, pp. 785–789, 1988. View at: Google Scholar
 D. A. Kleinman, “Nonlinear dielectric polarization in optical media,” Physical Review, vol. 126, no. 6, pp. 1977–1979, 1962. View at: Publisher Site  Google Scholar
 M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., Gaussian 09, Gaussian Inc., Wallingford, Conn, USA, 2009.
 S. Kushwaha and L. Bahadur, “Enhancement of power conversion efficiency of dyesensitized solar cells by cosensitization of Phloxine B and Bromophenol blue dyes on ZnO photoanode,” Journal of Luminescence, vol. 161, pp. 426–430, 2015. View at: Publisher Site  Google Scholar
 W. Li, J. Wang, J. Chen, F.Q. Bai, and H.X. Zhang, “Theoretical investigation of triphenylaminebased sensitizers with different πspacers for DSSC,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 118, pp. 1144–1151, 2014. View at: Publisher Site  Google Scholar
 M. Liang and J. Chen, “Arylamine organic dyes for dyesensitized solar cells,” Chemical Society Reviews, vol. 42, no. 8, pp. 3453–3488, 2013. View at: Publisher Site  Google Scholar
 S. Rühle, M. Greenshtein, S.G. Chen et al., “Molecular adjustment of the electronic properties of nanoporous electrodes in dyesensitized solar cells,” The Journal of Physical Chemistry B, vol. 109, no. 40, pp. 18907–18913, 2005. View at: Publisher Site  Google Scholar
 Z. Ning, Y. Fu, and H. Tian, “Improvement of dyesensitized solar cells: what we know and what we need to know,” Energy & Environmental Science, vol. 3, no. 9, pp. 1170–1181, 2010. View at: Publisher Site  Google Scholar
 J. Preat, D. Jacquemin, and E. A. Perpète, “Towards new efficient dyesensitised solar cells,” Energy and Environmental Science, vol. 3, no. 7, pp. 891–904, 2010. View at: Publisher Site  Google Scholar
 T. Marinado, D. P. Hagberg, M. Hedlund et al., “Rhodanine dyes for dyesensitized solar cells: spectroscopy, energy levels and photovoltaic performance,” Physical Chemistry Chemical Physics, vol. 11, no. 1, pp. 133–141, 2009. View at: Publisher Site  Google Scholar
 J. Preat, C. Michaux, D. Jacquemin, and E. A. Perpète, “Enhanced efficiency of organic dyesensitized solar cells: triphenylamine derivatives,” Journal of Physical Chemistry C, vol. 113, no. 38, pp. 16821–16833, 2009. View at: Publisher Site  Google Scholar
 J. B. Asbury, Y.Q. Wang, E. Hao, H. N. Ghosh, and T. Lian, “Evidences of hot excited state electron injection from sensitizer molecules to TiO_{2} nanocrystalline thin films,” Research on Chemical Intermediates, vol. 27, no. 45, pp. 393–406, 2001. View at: Publisher Site  Google Scholar
 R. Katoh, A. Furube, T. Yoshihara et al., “Efficiencies of electron injection from excited N_{3} dye into nanocrystalline semiconductor (ZrO_{2}, TiO_{2}, ZnO, Nb_{2}O_{5}, SnO_{2}, In_{2}O_{3}) Films,” Journal of Physical Chemistry B, vol. 108, no. 15, pp. 4818–4822, 2004. View at: Publisher Site  Google Scholar
 G. Olbrechts, T. Munters, K. Clays, A. Persoons, O.K. Kim, and L.S. Choi, “Highfrequency demodulation of multiphoton fluorescence in hyperRayleigh scattering,” Optical Materials, vol. 12, no. 2, pp. 221–224, 1999. View at: Publisher Site  Google Scholar
 C.R. Zhang, L. Liu, J.W. Zhe et al., “The role of the conjugate bridge in electronic structures and related properties of tetrahydroquinoline for dye sensitized solar cells,” International Journal of Molecular Sciences, vol. 14, no. 3, pp. 5461–5481, 2013. View at: Publisher Site  Google Scholar
 T. Le Bahers, T. Pauporté, G. Scalmani, C. Adamo, and I. Ciofini, “A TDDFT investigation of ground and excited state properties in indoline dyes used for dyesensitized solar cells,” Physical Chemistry Chemical Physics, vol. 11, no. 47, pp. 11276–11284, 2009. View at: Publisher Site  Google Scholar
Copyright
Copyright © 2016 Penghui Ren et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.