# Patent

## Title
Diindenothiophene derivatives and use thereof

## Abstract

A diindenothiophene derivative of the following formula (1) is disclosed:




wherein each of G1, G2, G3 and G4 is independently an unsubstituted or substituted C6-C40-aromatic group or a C1-C40-aliphatic group; A is an electron-withdrawing group; and D is an electron-donating group. The inventive diindenothiophene derivatives can be used in a dye-sensitized solar cell.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to diindenothiophene derivatives that can be used as dyes for dye-sensitized solar cells.
2. Description of the Prior Art
Rapid technological and economic advancements have fostered ever-increasing demand for energy, resulting in declining reserves of petroleum, natural gas, coal, and the like. Meeting this energy demand requires development of new resources. Solar energy is one of the most attractive and important resources for such further development as it generates little or no pollution. Of the many types of solar cells that have been developed to meet this need, dye-sensitized solar cell (DSSC) has the advantages of low manufacturing cost and potential for development.
DSSC was first developed in 1976 by Hiroshi Tsubomura et al. using porous ZnO as an electrode, and achieved a power conversion efficiency of 2.5%. The photoelectric conversion efficiency of DSSC was not substantially increased until 1991, when a Swiss team led by M. Grätzel achieved an efficiency of 7.1 ̃7.9%, opening the door for future commercialization. The DSSC developed by M. Grätzel's team in Switzerland utilized an anode produced by coating TiO2 nano-crystals onto indium-tin-oxide (ITO) glass and had Ru-complex dyes (typically, N3 and N719) absorbed by the porous structure of the porous film formed from the TiO2 nano-crystals to absorb visible light as well as a cathode of a conductive glass plated with platinum, and utilized I−/I3− solution as an electrolyte for providing the oxidation-reduction reaction necessary for the cell. N3 and N719 have the following structures:




As mentioned above, a dye-sensitized solar cell mainly consists of five parts: a cathode and anode for providing current paths, a TiO2 semiconductor layer for use as an electron transport layer, a dye layer, and an electrolyte for transporting holes. All the materials and the interfacial structures of these parts will play a role in the performance of solar cells. In particular, the dye used in the dye layer is crucial to solar cell efficiency. Therefore, the search for suitable dyes to enhance solar cell efficiency has become an important objective of solar cell development.
Dyes for dye-sensitized solar cells are normally classified into two types: those containing the above-mentioned Ru-complexes, and those comprised of organic molecules. Compared to metal complexes, organic molecules have the following advantages: (1) higher molar absorption coefficient; (2) greater flexibility in structural design and possible range of light absorption; and (3) absence of noble metals, thus eliminating dependence on limited and environmentally hazardous material sources while also reducing production costs.
In 1996, Michael Grätzel employed the natural substance coumarin as a main dye ingredient in a DSSC. However, only 0.9% photoelectric conversion efficiency was achieved, probably due to the relatively narrow absorption band of coumarin preventing efficient utilization of sunlight.
Given the above, there is ongoing demand for organic molecular materials for dyes achieving greater efficiency of sunlight absorption in dye-sensitized solar cells.
SUMMARY OF THE INVENTION
The present invention aims at providing an organic diindenothiophene derivative having a diindenothiophene structure. The diindenothiophene derivatives of the present invention have a high light absorption coefficient and can be used in solar cells as dyes. Moreover, the diindenothiophene derivatives have an absorption spectrum highly overlapping the sunlight spectrum and can obtain a high power conversion efficiency when they are utilized in dye-sensitized solar cells.
Therefore, the present invention also provides a solar cell comprising the above-mentioned diindenothiophene derivative.



BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is the absorption spectrum of the organic dye compound of formula (2) dissolved in THF according to the present invention.



DETAILED DESCRIPTION OF THE INVENTION
The diindenothiophene derivatives according to the present invention have a structure of the following formula (1):




wherein, G1, G2, G3 and G4 are each independently an unsubstituted or substituted C6-C40-aromatic group or C1-C40-aliphatic group; A is an electron-withdrawing group; and D is an electron-donating group.

According to the present invention, the preferred G1, G2, G3 and G4 are each independently an unsubstituted or substituted C6-C20-aromatic group. More preferably, G1, G2, G3 and G4 are each independently a radical selected from the group consisting of the following formula (3), formula (4), formula (5) and formula (6).




wherein, R1, R2, R3 and R4 are each independently a hydrogen atom, a C1-C8-alkyl, or a C1-C8-alkoxy; and B is CH2, NH, S, Si or O.

According to the present invention, the electron-withdrawing group A is selected from the group consisting of




According to the present invention, the electron-donating group D is selected from —N(S1)(S2) or —C6H4—N(S1)(S2), where S1 and S2 are each independently an unsubstituted or substituted C6-C20-aromatic group. According to an embodiment of the present invention, S1 and S2 are each independently selected from the group consisting of the following formula (7), formula (8), formula (9), formula (10), and formula (11):




wherein R5, R6, R7 and R8 are each independently a hydrogen atom, a C1-C5-alkyl or a C1-C5-alkoxy; and E is CH2, NH, S, Si or O.

According to a preferred embodiment of the present invention, D is selected from the group consisting of the following:




According to another preferred embodiment of the present invention, the G1, G2, G3 and G4 in formula (1) are each independently




more preferably





A is





and D is





more preferably





According to a preferred embodiment of the present invention, the diindenothiophene derivatives are of the following formula (2) and formula (3):




The diindenothiophene derivatives of the present invention can be used in dye-sensitized solar cells as organic dyes. The diindenothiophene derivatives will be fastened on the surface of an oxide semiconductor, such as TiO2, by adsorption. Without being limited by certain theories, it is believed that such organic dye molecules utilize the diindenothiophene group as the molecular center to become ladder-type molecules; utilize the excellent charge carrier mobilities of the thiophene ring and fix many conjugated aromatic rings so as to improve conjugation properties and charge carrier mobilities; and directly inject charges to the conduction bands of the semiconductor with the aid of the electron-donating group, electron-withdrawing group and charge transfer. Moreover, since the diindenothiophene derivatives have a broader absorption band and therefore a high absorption coefficient, they can provide an enhanced light absorption ability. In addition, since a long carbon chain, such as hexyloxyphenyl, is introduced into the molecules, the molecular stability of the molecules can be improved and the molecules will hinder electrolytes from contacting the oxide semiconductor, thereby avoiding the occurrence of dark current and therefore enhancing the efficiency of the solar cells.
The inventive diindenothiophene derivatives can be produced by any of the methods that are conventionally known to persons having ordinary skill in the art. For instance, the above-mentioned compound of formula (2) can be prepared by a method comprising the following steps:
















The resultant organic dye molecule of formula (2) has been characterized by the following physiochemcial data:
IR (KBr) ν 3444, 2926, 2855, 2211, 1692, 1606, 1579, 1507, 1493, 1419, 1177, 1153, 1030, 824, 696 cm−1;
1H NMR (CD2Cl2, 400 MHz) δ8.30 (s, 1H), 7.61 (s, 1H), 7.58 (s, 1H), 7.29-7.25 (m, 5H), 7.17-7.05 (m, 14H), 6.79-6.75 (m, 8H), 6.64 (s, 1H), 3.91 (q, J=7.06 Hz, 8H), 1.77-1.70 (m, 8H), 1.44-1.27 (m, 24H), 0.92-0.89 (m, 12H);
13C NMR (CD2Cl2, 400 MHz) δ158.5, 158.3, 156.6, 156.4, 155.9, 154.6, 153.5, 153.3, 148.3, 148.3, 147.5, 139.4, 138.1, 136.0, 135.8, 135.4, 134.3, 132.8, 132.1, 129.4, 128.9, 128.8, 123.8, 123.6, 119.0, 116.5, 116.4, 115.5, 114.5, 114.4, 94.2, 68.3, 63.2, 62.4, 32.0, 30.1, 29.6, 29.5, 26.1, 23.0, 14.2; and
TOF MS (m/z, ESI+) 1233.
In addition, as calculated according to Beer's law, the organic dye molecule of formula (2) has a greater molar absorption coefficient (ε) of 50508 M−1 cm−1 (471 nm). It can been seen from FIG. 1 that the organic dye molecule of formula (2) has a broader absorption band of from about 350 nm to about 600 nm and can utilize the visible light from sunlight more efficiently.
The present invention also provides a dye-sensitized solar cell containing at least one of the diindenothiophene derivatives of formula (1). The two substrates of the solar cell of the invention can be selected from, but are not limited to, metal such as a titanium plate or stainless plate; glass; and plastic which can be, for example, but not limited to, a polyester resin, a polyacrylate resin, a polyolefin resin, a polycycloolefin resin, a polyimide resin, a polycarbonate resin, a polyurethane resin, triacetyl cellulose (TAC), or a polylactic acid or a combination thereof, and at least one of the substrates is deposited with a transparent conducting oxide (TCO) thereon to form a conducting substrate. The conducting oxide includes, but is not limited to a fluorine-doped tin oxide (FTO), an antimony-doped tin oxide (ATO), an aluminum-doped zinc oxide (AZO), or indium tin oxide (ITO). A semiconductor oxide with a nanometer-level particle size of 2-50 nm was coated onto the conducting substrate as a film with a thickness of about 5-20 μm. When the film thickness is less than 5 μm, the solar cell could not work efficiently; and on the other hand, if the film thickness is greater than 20 μm, the film is liable to crack. The semiconductor oxides that can be used in the present invention include, but are not limited to TiO2, ZnO, ZrO2, SrTiO3, SiO2 or CdS. The electrolyte that can be used in the solar cells according to the present invention can be a liquid, a gel, or a solid and a useful catalyst can be Pt or carbon black.
The dye-sensitized solar cell according to the present invention can be produced according to any method conventionally known to persons having ordinary skill in the art. For example, it can be produced by the method comprising the following steps:

    (1) uniformly applying a titanium dioxide coating (produced by Solaronix company, Ti-Nanoxide HT) onto a FTO glass substrate (area: 1.7 cm×0.6 cm), to form a film with a thickness of about 11-12 μm;
    (2) sintering the TiO2-containing FTO glass substrate at 400° C.-600° C., to form an electrode;
    (3) screen printing platinum on another glass substrate for producing a platium electrode with a thickness of about 20 nm, as a counter electrode;
    (4) immersing the electrode obtained in step (2) in, for example, a solution of the dye compound of formula (2) (solvent: 1:1 THF/Acetonitrile) for about 12-24 hours, to allow the dye compound to be absorbed to the electrode;
    (5) injecting thereinto an electrolyte solution containing I2, LiI, 1-propyl-3-methyl-imidazolium iodide (PMII), and methylpyrrolidinone (MPN).


The dye-sensitized solar cell containing the compound of formula (2) obtained according to the above method was tested with a simulated sunlight source (AM 1.5) at a light intensity (P) of 100 mW/cm2 for measuring the current and voltage. The results are as listed in the following Table 1. The above-mentioned AM 1.5 represents an air mass 1.5 spectrum, where AM=1/cos(θ) where θ represents the tilt angle relative to the normal incidence. For testing solar cells, the average irradiance in the United States, AM 1.5 (θ=48.2°, is used to represent the average irradiance of sunlight (at 25° C.) on the earth surface with a light intensity of about 100 mW/cm2.













TABLE 1









Short-






Open-
circuit




circuit
current

Powder




photo-
density
Fill
conversion



Dye
voltagea
Jscb
factor
efficiency



compound
(Voc)
(mA/cm2)
FFc
η (%)









Formula
0.68
−15.74
0.65
6.94



(2)







aThe voltage measured when there is no external electric current.



bThe output current per area of the element when there is zero load in the solar cell.



cThe ratio of the actual maximum obtainable power to the theoretical power of the solar cell. This is a key parameter in evaluating the performance of solar cells.

## Claims

1. A diindenothiophene derivative having a structure of formula (1):



wherein, G1, G2, G3 and G4 are each independently an unsubstituted or substituted C6-C40-aromatic group or C1-C40-aliphatic group; A is an electron-withdrawing group; and D is an electron-donating group.

2. The diindenothiophene derivative of claim 1, wherein G1, G2, G3 and G4 are each independently an unsubstituted or substituted C6-C20-aromatic group.

3. The diindenothiophene derivative of claim 2, wherein G1, G2, G3 and G4 are each independently selected from the group consisting of formula (3), formula (4), formula (5), and formula (6):



wherein, R1, R2, R3 and R4 are each independently a hydrogen atom, a C1-C8-alkyl, or a C1-C8-alkoxy; and B is CH2, NH, S, Si or O.

4. The diindenothiophene derivative of claim 2, wherein G1, G2, G3 and G4 are each independently

5. The diindenothiophene derivative of claim 2, wherein G1, G2, G3 and G4 are all

6. The diindenothiophene derivative of claim 1, 4 or 5, wherein A is selected from the group consisting of

7. The diindenothiophene derivative of claim 6, wherein A is

8. The diindenothiophene derivative of claim 1, wherein D is selected from —N(S1)(S2) or —C6H4—N(S1)(S2) where S1 and S2 are each independently an unsubstituted or substituted C6-C20-aromatic group.

9. The diindenothiophene derivative of claim 8, wherein S1 and S2 are each independently selected from the group consisting of the following formula (7), formula (8), formula (9), formula (10), and formula (11):



wherein R5, R6, R7 and R8 are each independently a hydrogen atom, a C1-C5-alkyl or a C1-C5-alkoxy; and E is CH2, NH, S, Si or O.

10. The diindenothiophene derivative of claim 9, wherein D is

11. The diindenothiophene derivative of claim 10, wherein D is

12. A dye-sensitized solar cell comprising a diindenothiophene derivative as claimed in claim 1.