Synthesis, Characterization, and Photovoltaic Properties of Soluble TiOPc Derivatives

We have synthesized soluble TiOPc derivatives containing alkoxy groups for use as additives in dye-sensitized solar cells (DSSCs). The DSSC devices containing these TiOPc derivatives exhibited short-circuit current densities of 8.49~10.04 mA/cm2 and power conversion efficiencies of 2.73~3.62 % under AM 1.5 illumination and 100 mW/cm2 irradiation.


Introduction
Dye-sensitized solar cells (DSSCs) constructed using dye molecules, nanocrystalline metal oxides and organic liquid electrolytes were originally developed by the research group of Gratzel et al. [1][2][3][4][5][6]. DSSCs have attracted much attention around the world, due to their high power conversion efficiency, easy fabrication, and low production cost. However, DSSCs have not been used in practical applications because many difficulties regarding their use of a liquid electrolyte remain unresolved,

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such as solvent evaporation, leakage and deterioration, which cause sealing problems and performance degradation. To solve these problems, solid-state electrolytes have been developed to replace these liquid electrolytes. Solid-state DSSCs do not need hermetic sealing, but their power conversion efficiency is lower than that of DSSCs with conventional organic liquid electrolytes. To improve their power conversion efficiency, attempts have been made to add various materials to the electrolyte [7][8][9][10][11][12]. Solid-state or quasi-solid-state electrolytes, such as hole-conducting molecular solids [13] and polymers [14], molten salts [15] and ionic liquids [16][17], have been investigated and used in place of the volatile organic solvent in DSSCs. In light of their unusual electrochemical and electronic properties, phthalocyanines (Pcs) are potentially useful additives. Pcs have attracted the attention of many researchers during the twentieth century and are still being actively studied in this century [18][19]. Many potential applications are expected for phthalocyanines (Pcs), which have high thermal and chemical stability, for instance as solar cell functional materials, gas sensors, and photodynamic therapy agents. The results concerning DSSCs using TiOPc as a co-adsorbent have been previously reported [20]. However, many of the applications of Pcs have been limited by their lack of solubility in organic solvents and water. Over the past few decades, a large variety of substituted Pc derivatives have been synthesized in order to improve their solubility [21,22].
In this study, we synthesized titanyl phthalocyanine (TiOPc) derivatives containing an alkoxy chain group with good solubility. The molecular structures of the synthesized TiOPc derivatives were characterized by Fourier Transform Infrared Spectrophotometry (FT-IR), Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) mass spectroscopy, X-ray Diffraction (XRD), and Transmission Electron Microscopy (TEM). The thermal properties of the TiOPc derivatives were analyzed by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) under a nitrogen atmosphere. The optical properties of the TiOPc derivatives were monitored by UV-vis spectrophotometry and fluorescence spectrophotometry.
We also studied the photovoltaic properties of the TiOPc derivatives. We prepared quasi-solid state dye-sensitized solar cell (DSSC) devices with TiOPc derivatives. These DSSC devices were fabricated using ruthenium (II) complex dye (N3 dye) as a photosensitizer and the TiOPc derivatives as additives in the electrolytes.

Solubility of 3a and 3b
The solubilities of 3a and 3b were examined at a ratio of compound to solvent of 100 mg/mL. Table  1 shows the solubilities of TiOPc, 3a, and 3b in a variety of common solvents. TiOPc was insoluble in almost all organic solvents. Compared with TiOPc, 3a and 3b exhibited increased solubility in various solvents, such as chloroform, chlorobenzene, and toluene, but not in methanol and acetone. In many applications, the solubility of materials is a very important problem. Therefore, the solubility of 3a and 3b in organic solvents makes them promising materials.

Optical properties of 3a and 3b
The absorption and fluorescence spectra of 3a and 3b in chloroform are shown in Figure 1. The absorption spectra of 3a and 3b showed broad bands in the region around 340 nm and sharp peaks at 704 nm and 705 nm, respectively. Weak Q-band region peaks contributed by the aggregations appear in the 620-680 nm region. The spectra show the typical Soret and Q-bands, which are characteristic of phthalocyanines. Upon excitation at 640 nm. Compounds 3a and 3b showed fluorescence emissions at 709 and 711 nm, respectively.

XRD
The XRD patterns of 3a and 3b measured in the range of 2 theta of 10-50 degrees ( Table 2) show identical features with relatively poor crystallinity. Although the observed patterns resemble qualitatively that of the corresponding unsubstituted TiOPc, the peaks are found to be broadened with diffused intensity. This reveals that 3a and 3b were less crystalline than the unsubstituted TiOPc [24]. This may be due to the presence of the bulky substituent alkoxy chain, and seems to play a dominant role in the stacking of the metal phthalocyanine derivatives. The X-ray diffraction patterns were only used to explain the degree of crystallinity, which is qualitative. The effect of the alkoxy chain substitution can be clearly identified from the first d values of all of the complexes.

TEM studies
The size and morphology of the synthesized compounds were analyzed by TEM measurements. The TEM images of 3a and 3b are shown in Figure 2. The TEM micrography revealed that 3a and 3b consisted of irregular spherical nanoparticles with diameters ranging from 450 nm to 600 nm and that the particles were agglomerated.

AFM studies
The surface morphology of 3a and 3b films was measured by atomic force microscopy (AFM). All of the films were prepared by the spin-coating method from a chloroform solution. The difference in the root mean square (RMS) surface roughness between the two films was not very large, as depicted in Figure 3. The RMS roughnesses of 3a and 3b were 2.22 nm and 10.59 nm, respectively.

TGA and DSC studies
The TGA curves of 3a and 3b are illustrated in Figure 4. The typical TGA curve obtained with a heating rate of 10 ºC/min demonstrated high thermal stability up to 245 ºC. The initial decomposition temperatures (Tds) of 3a and 3b were observed to be 213.65 ºC and 256.11 ºC, respectively, which are less than that of TiOPc. This may be due to the substituted alkoxy chains of 3a and 3b. Figure 5 shows the DSC curves of 3a and 3b.

Photovoltaic performances of DSSC devices
The photovoltaic measurements were performed using a solar simulator under AM 1.5 illuminated conditions, and the active area of the DSSC devices was 0.25 cm 2 . The power conversion efficiency (η) of a solar cell given by: where P out is the output electrical power of the device under illumination and P in represents the intensity of the incident light (e.g., in W/m 2 or mW/cm 2 ). V oc is the open-circuit voltage, J sc is the short-circuit current density, and the fill factor (FF) is calculated from the values of V oc , J sc , and the maximum power point, P max . Figure 6 shows the I-V curves of the FTO/TiO 2 /Dye/Electrolyte/Pt device using 3a or 3b as an additive. The DSSC devices using the TiOPc derivatives showed different results according to the methyl chain length. The values of V oc , J sc , FF and the power conversion efficiency (η) are listed in Table 3. The J sc s of the devices using 3a, 3a with PEG, 3b, 3b with PEG, and PEG were 8.49, 9.84, 10.02, 10.04, and 8.98 mA/cm 2 , respectively. The power conversion efficiencies of the DSSC devices using 3a, 3a with PEG, 3b, 3b with PEG, and PEG was 2.73, 3.49, 3.19, 3.62, and 2.94 %, respectively. The DSSC devices using 3a and 3b with PEG showed higher photovoltaic performance than the devices using PEG without 3a and 3b in the same procedure. The J sc values of the DSSC devices using 3a and 3b were increased, and this can attributed to improvements in their power conversion efficiency. η = P out /P in = (J sc ×V oc ×FF)P in with FF = ( I max ×V max )/(J sc ×V oc ) = P max /(J sc ×V oc ) (1) Figure 6. I-V curves of FTO/TiO 2 /Dye/Electrolyte/Pt devices using 3a, 3a with PEG, 3b, 3b with PEG, and PEG under AM 1.5 illumination; light intensity: 100 mW/cm 2 ; active area: 0.25 cm 2 ; with mask.

Measurements
The FT-IR spectra (KBr pellets) were recorded on a Jasco FT/IR-460 Plus spectrometer. The 1 H NMR spectra (300 MHz) were recorded in CDCl 3 using a Varian Unity Plus 300 NMR spectrometer. The UV-vis absorption and fluorescence spectra of the TiOPc derivatives in chloroform solution were recorded on a UVIKON 860 spectrophotometer and Hitachi F-4500 fluorescence spectrophotometer, respectively. The TEM images were recorded on a Hitachi H-7500 Transmission Electron Microscope. Scanning Probe Microscopy was performed using a NITECH Model SPA-400. The TGA and DSC analyses were conducted on a TA instruments (TGA-Q 50 and TGA-Q 100) thermal analyser at a heating rate of 10 ºC/min under flowing nitrogen (40 mL/min and 50 mL/min). The measurement of the I-V characteristics of the solar cells was carried out using a Solar Simulator (300 W simulator, models 81150) under simulated solar light with an ARC Lamp power supply (AM 1.5, 100 mW/cm 2 ).

Synthesis of TiOPc derivatives 3a and 3b
In the first step, alkoxyphthalonitriles were formed from 4-hydroxyphthalonitrile and 1-bromohexadecane or 1-bromotetradecane. 4-Hydroxyphthalonitrile (0.72 g, 5 mmol) and dry potassium carbonate (5.52 g, 40 mmol) was stirred for 30 min under N 2 gas in NMP, then a solution of 1bromohexadecane or 1-bromotetradecane (10 mmol) in NMP was added and the mixture was stirred for 12 h at room temperature. The reaction mixture was filtered and purified by chromatography on a silica column with dichloromethane as the eluent. Yield: 92 % (2a) and 79 % (2b). The second step was the base catalyzed cyclotetramerization of the phthalonitriles. A mixture of alkoxyphthalonitrile (4 mmol), Ti(OBu) 4 (0.37 g, 1.1 mmol), urea (0.12 g, 2 mmol), and 1-octanol was heated at 150 ºC under N 2 for 24 h. After the addition of methanol to the reaction mixture followed by refluxing for 30 min, the resulting deep green blue crystals were collected by filtration, washed with methanol, and then dried in a vacuum oven at 100 ºC. Yield: 24 % (3a) and 21 % (3b).

Fabrication of DSSC devices
We prepared DSSC devices using a quasi-solid state electrolyte containing 3a or 3b as an additive sandwiched with TiO 2 adsorbed dyes and Pt-coated electrode as the two electrodes. The structure of the DSSC device is shown in Figure 7. The FTO/TiO 2 /Dye/Electrolyte/Pt device was fabricated using the following procedure; a volume of ca. 10 µL/cm 2 of the transparent paste (Ti-Nanoxide HT) was spread on FTO glass by the doctor blade method. After heating the FTO glass covered with TiO 2 nanoparticles successively at ca. 100 ºC and ca. 450 ºC for about 30 min each, the sintering process was completed and the TiO 2 deposited electrode was cooled down from 100 ºC to ca. 60 ºC at a controlled cooling rate (5 ºC/min) to avoid the cracking of the glass. A Pt counter electrode was fabricated by spreading on FTO glass using the doctor blade method. After heating the FTO glass spread Pt catalyst T/SP at 100 ºC for 10 min, it was fired at 400 ºC for 30 min. N3 dye was dissolved in absolute ethanol at a concentration of 20 mg per 100 mL of solution. Nanoporous TiO 2 film was dipped in this solution at room temperature for 24 hours. Afterwards, the dye-sensitized TiO 2 electrode was rinsed with absolute ethanol and dried in air. Without a sealant, the electrolyte solution was cast onto the TiO 2 electrode impregnated with N3 dye and then dried at 55 ºC for 2 hours. The electrolyte solution was composed of 24 mg of I 2 , 72 mg of TBAI, 80 mg of PMImI as an ionic liquid, 0.32 mL of EC/0.08 mL of PC (EC/PC=4/1 as volume ratio) and 3a or 3b in acetonitrile solution.

Conclusions
We have synthesized two kinds of TiOPc derivatives containing alkoxy groups, 3a and 3b, and analyzed them by FT-IR, UV-vis and Fluorescence spectroscopy, XRD, and TEM. The optical properties of 3a and 3b were measured by UV-vis and fluorescence spectrophotometry. Both 3a and 3b showed high solubility in organic solvents such as chloroform, chlorobenzene, and dichloromethane. The quasi-solid DSSC devices prepared with a polymer electrolyte using 3a or 3b as an additive showed higher photovoltaic performance than the devices with a polymer electrolyte without 3a or 3b, due to their increased J sc values. The best result obtained for the DSSC devices was a power conversion efficiency of 3.62 in the case of the DSSC device using PEG with 3b. Its Voc, J sc , and FF were 0.66 V, 10.04 mA/cm 2 and 0.54, respectively.