JP7062284B2 - A novel porphyrin derivative, a method for producing a porphyrin derivative, a donor material, a photoelectric conversion device, and a method for manufacturing a photoelectric conversion device. - Google Patents

Description

The present invention relates to a novel porphyrin derivative, a method for producing a porphyrin derivative, a photoelectric conversion device, and a method for producing a photoelectric conversion device, and in particular, a porphyrin derivative suitable for use as a donor material, a method for producing the same, and the porphyrin derivative. The present invention relates to a photoelectric conversion device used as a donor material and a method for manufacturing the photoelectric conversion device.

As a countermeasure to the energy problem, the development of a solar cell, which is a kind of photoelectric conversion device, is attracting attention. Among them, organic thin-film solar cells having a thin film made of an organic material have been developed with a maximum efficiency of more than 13%, and some of them have begun to be put into practical use.

As the active layer of such an organic thin-film solar cell, a laminate of a donor layer (p-type layer) and an acceptor layer (n-type layer) is used, and a type (pn hetero) utilizing a heterojunction at the layer interface is used. There are two types: a type that uses a layer in which a donor and an acceptor are mixed and uses a heterojunction in the layer (called a bulk heterojunction type or a BHJ (bulk heterojunction) type). ..

Among these, in the BHJ type, since the donor and the acceptor are in an entangled state in the active layer, the area of the pn junction interface (charge separation interface) is increased, and the efficiency of charge separation can be improved. ..

The basic concept of the BHJ type was proposed in 1992, and since then it has become the mainstream configuration of organic thin-film solar cells. Among them, the coating-BHJ type, which forms an active layer by applying a solution in which a donor and an acceptor are mixed and then solidifying it, can reduce the cost of materials and manufacturing methods, and further, the active layer is large. It has a commercial advantage because it is easy to increase the area.

In the past, the coating-BHJ type often used a polymer as the donor material, but in recent years, small molecule donor materials have been attracting attention. Small molecule donor materials have the advantages of easier synthesis and purification and less variation in performance between lots than polymer donor materials. As small molecule donor materials, compounds with various skeletons such as phthalocyanine, diketopyrrolopyrrole, oligothiophene, and porphyrin are being investigated.

Among them, compounds having a porphyrin skeleton are abundant in nature, such as chlorophyll used in the photosynthetic mechanism of absorbing light energy to produce saccharides, and their structural modification is diverse and highly light-resistant. Due to its excellent properties and excellent absorbance yield, research on its application to organic EL and solar cells is progressing as well as in the field of life science.

The compound having a porphyrin skeleton has also been applied to the above-mentioned organic thin-film solar cell, and research examples of organic thin-film solar cells using a compound having a porphyrin skeleton (also referred to as a porphyrin derivative) have been known so far. Has been done.

Coating-BHJ type organic thin film solar cells using such a porphyrin derivative as a donor material are disclosed in, for example, Non-Patent Documents 1 to 7.

For example, these non-patent documents disclose an organic thin-film solar cell using a porphyrin derivative in which a diketopyrrolopyrrole (DPP) unit is linked to a porphyrin skeleton as a donor material. Some organic thin-film solar cells with conversion efficiencies of up to 9% have been reported.

Li, L .; Huang, Y .; Peng, J .; Cao, Y .; Peng, X. J. Mater. Chem. A. 2013, 1, 2144_2150. Qin, H .; Li, L .; Guo, F .; Su, S .; Peng, J .; Cao, Y .; Peng, X. Energy. Environ. Soc. 2014, 7, 1397_1401. Gao, K .; Li, L .; Lai, T .; Xiao, L .; Huang, Y .; Huang, F .; Peng, J .; Cao, Y .; Liu, F .; Russell, T. P .; Janssen , R.-A. J .; Peng, X. J. Am. Chem. Soc. 2015, 137, 7282_7285. Gao, K .; Miao, J .; Xiao, L .; Deng, W .; Kan, Y .; Liang, T .; Wang, C .; Huang, F .; Peng, J .; Cao, Y .; Liu, F .; Russell, T. P .; Wu, Hongbin, w .; Peng, X. Adv. Mater. 2016, 28, 4727_4733. Li, M .; Kao, K .; Wan, X .; Zhang, Q .; Kan, B .; Xia, R .; Liu, F .; Yang, X .; Feng, H .; ni, w .; Wang, Y .; Peng, J .; Zhang, H .; Liang, Z .; Yip, H.-L .; Peng, X .; Cao, Y .; Chen, Y. Nature Photonics. 2017, 11, 85_90 .. Hatano, J .; Obata, N .; Yamaguchi, S .; Yasuda, T .; Matsuo, Y. J. Mater. Chem. 2012, 22, 19258_19263. Ogumi, K .; Nakagawa, T .; Okada, H .; Sakai, R .; Wang, H .; Matsuo, Y. J. Mater. Chem. A. 2017, 5, 23067_23077.

The above-mentioned DPP has excellent optical characteristics and is used as a pigment or an ink, and also absorbs a wide range of wavelengths in the visible light region. It is considered that an efficient organic thin-film solar cell can be realized.

On the other hand, the coated-BHJ type organic thin-film solar cell has a structure in which the donor and the acceptor are entangled in the active layer, so that the charge transport path becomes complicated and the charge transport efficiency of electrons and holes decreases. Has been done.

Therefore, the present inventors have earnestly considered the composition of a porphyrin derivative suitable for use as a donor material in order to improve the charge transport efficiency of electrons or holes by improving the charge mobility and to improve the characteristics such as a long excitation lifetime. The study was carried out, the synthesis was successful, and the performance when used in an organic thin-film solar cell as a donor material was confirmed. In particular, by using different aryl units linked to the 10-position and 20-position of the porphyrin skeleton, we succeeded in synthesizing a porphyrin derivative with an asymmetric structure as a whole, and when used in an organic thin-film solar cell as a donor material. I confirmed the performance.

An object of the present invention is to provide a novel porphyrin derivative, a method for producing the same, and further to provide a suitable donor material for use in a photoelectric conversion device such as a solar cell. Another object of the present invention is to provide a photoelectric conversion device using the donor material and a method for manufacturing the same.

(1) The porphyrin derivative of the present invention is a porphyrin derivative represented by the following (Chemical Formula 1).

(2) The porphyrin derivative of the present invention is a porphyrin derivative represented by the following (Chemical Formula 2).

(3) In the method for producing a porphyrin derivative of the present invention, the TIPS group of the porphyrin derivative P1 is eliminated by the first reaction of the porphyrin derivative P1 and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 1). This is a method for producing a porphyrin derivative, which produces the porphyrin derivative of the following (chemical formula 1) by the second reaction between the porphyrin derivative P1 from which the TIPS group has been removed and DPP-Br.

For example, the second reaction is a reaction using a palladium catalyst.

(4) In the method for producing a porphyrin derivative of the present invention, the TIPS group of the porphyrin derivative P2 is eliminated by the first reaction of the porphyrin derivative P2 and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 2). This is a method for producing a porphyrin derivative, which produces the porphyrin derivative of the following (chemical formula 2) by the second reaction between the porphyrin derivative P2 from which the TIPS group has been removed and DPP-Br.

For example, the second reaction is a reaction using a palladium catalyst.

(5) The donor material of the present invention is a donor material for a photoelectric conversion device having a porphyrin derivative represented by the following (Chemical formula 1) or (Chemical formula 2).

(6) The photoelectric conversion device of the present invention has a first electrode, a charge transport layer provided above the first electrode, and a second electrode provided above the charge transport layer. The charge transport layer is a layer in which a donor material and an acceptor material are mixed, and has a porphyrin derivative represented by the following (general formula 1) as the donor material. However, in the following (general formula 1), R and R'constituting the aryl unit are different.

The porphyrin derivative represented by the above (general formula 1) is a porphyrin derivative represented by the following (chemical formula 1) or (chemical formula 2).

(7) In the method for manufacturing a photoelectric conversion device of the present invention, (a) a coating layer is formed by coating a liquid having a donor material, an acceptor material, and a solvent on the first conductor layer to be the first electrode. Steps of forming, (b) a step of forming a charge transport layer having the donor material and the acceptor material by solidifying the coating layer, (c) a second electrode above the charge transport layer. It has a step of forming a second conductor layer, and the donor material is a porphyrin derivative represented by the following (general formula 1). However, in the following (general formula 1), R and R'constituting the aryl unit are different.

The porphyrin derivative represented by the above (general formula 1) is a porphyrin derivative represented by the following (chemical formula 1) or (chemical formula 2).

The porphyrin derivative represented by the above (general formula 1) is after removing the TIPS group of the porphyrin derivative by the first reaction of the porphyrin derivative and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 3). , The TIPS group is removed, and the porphyrin derivative is produced by a second reaction with DPP-Br. However, in the following (general formula 1), R and R'constituting the aryl unit are different.

The present inventors have succeeded in synthesizing a novel porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2). By using such a porphyrin derivative as a donor material, the characteristics of the photoelectric conversion device can be improved.

It is sectional drawing which shows typically the structure of the photoelectric conversion apparatus of Embodiment 1. FIG. It is sectional drawing which shows the manufacturing process of the photoelectric change apparatus of Embodiment 1. FIG. 1 ¹ HNMR spectrum of product 1. ¹³ CNMR spectrum of product 1. It is a COSY spectrum of product 1. It is an MS spectrum of product 1. ^{1 1} HNMR spectrum of product 2. ¹³ CNMR spectrum of product 2. It is a COSY spectrum of product 2. It is an MS spectrum of product 2. It is an ultraviolet-visible absorption spectrum of product 1 (MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ )). It is an ultraviolet-visible absorption spectrum of product 2 (MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ )). It is an ultraviolet-visible absorption spectrum of the comparative substance 3 (MgTEPDPP ₂ ( ₄ -hexyl-C ₆ H4) ₂ ). 3 is an AFM image of the surface of the active layer using product 1 (MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ )) as a donor material. It is an AFM image of the surface of an active layer using product 2 (MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ )) as a donor material. It is sectional drawing which shows the manufacturing process of the photoelectric conversion apparatus of Embodiment 3. FIG.

(Embodiment 1)
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, in this specification, A to B shall indicate A or more and B or less.

(Structure of photoelectric conversion device)
FIG. 1 is a cross-sectional perspective view schematically showing the configuration of the photoelectric conversion device of the present embodiment. The photoelectric conversion device of the present embodiment uses an organic material as a donor material or an acceptor material and has a thin-film active layer, and is therefore also called an organic thin-film solar cell. Donors are also referred to as electron donors, and acceptors are also referred to as electron acceptors.

The photoelectric conversion device shown in FIG. 1 includes a first electrode EL1, an active layer (also referred to as a charge transport layer) AL provided on the first electrode EL1, and a second electrode EL2 provided on the active layer AL. Have.

The active layer AL provided on the first electrode EL1 is a layer existing in a state where the donor material DO and the acceptor material AC are mixed (see FIG. 1). The active layer AL can be formed by applying a mixed solution of a donor material, an acceptor material, and a solvent (solvent) to form a coating layer, and then drying and solidifying the coating layer.

A buffer layer may be provided between the first electrode EL1 and the active layer AL. Further, a buffer layer may be provided between the active layer AL and the second electrode EL2. The first electrode EL1 and the second electrode EL2 are made of a conductive material (conductor), and at least one of the first electrode EL1 and the second electrode EL2 has light transmission. The first electrode EL1 may be provided on the substrate (support).

As the substrate, a transparent substrate can be used. As the transparent substrate, a glass substrate, a plastic film (flexible substrate), or the like can be used. As the first electrode EL1, ITO (indium tin oxide), indium zinc oxide, or the like can be used. As the second electrode EL2, a metal such as aluminum or silver, an alloy containing this metal, or the like is used. As the acceptor material, fullerenes, fullerene derivatives (fullerene compounds) and the like can be used.

(Porphyrin derivative)
Here, in the present embodiment, the porphyrin derivative represented by the following (Chemical formula 1) or (Chemical formula 2) is provided as the donor material.

The porphyrin derivative represented by this (Chemical formula 1) is [5,15-bis (2,5-bis (2-ethyl-hexyl) -3,6-di-thienyl-2-yl-2,5-dihydro-pyrrolo). [3,4-c] pyrrole-1,4-dione-5'-yl-ethynyl) -10- (4-hexyl-phenylethynyl) -20- (4-trifluoromethyl-phenylethynyl) -porphyrionate] in magnesium (II) be. This may be indicated by the abbreviation of "MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ )".

The porphyrin derivative represented by this (Chemical formula 2) is [5,15-bis (2,5-bis (2-ethyl-hexyl) -3,6-di-thienyl-2-yl-2,5-dihydro-pyrrolo). [3,4-c] pyrrole-1,4-dione-5'-yl-ethynyl) -10- (4-hexyl-phenylethynyl) -20- (4-dimethylamino-phenylethynyl) -porphyrionate] in magnesium (II) be. This may be indicated by the abbreviation of "MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ )". Me is -CH ₃ .

In these porphyrin derivatives, two DDP (Diketopyrrolopyrrole) units and two annealing units are linked to the porphyrin skeleton at trans positions (5th and 15th positions, 10th and 20th positions). Each of these four units is linked to the porphyrin skeleton via an ethynyl crosslink. The porphyrin derivative can be said to be a compound in which a π-conjugated compound is linked via a triple bond.

In addition, the above-mentioned porphyrin derivative coordinates magnesium as the central metal of the porphyrin skeleton. Therefore, the porphyrin derivative can be said to be an Mg / porphyrin / DPP complex.

Further, in the porphyrin derivative having the above-mentioned structure, the π-conjugation spreads in the molecule and the entire molecule becomes planar, so that the packing structure is stabilized. That is, as the stacking density of the molecules increases, the π-π stacking between the molecules improves. When such a porphyrin derivative is used as a donor material in an active layer, it has the following advantages.

(1) By connecting the DPP unit to the porphyrin skeleton, light in the visible light region can be efficiently absorbed. Further, by adopting a DA (D = donor: porphyrin, A = acceptor: DPP) structure in the donor material, the energy band gap can be narrowed and the photoelectric conversion efficiency can be improved.

(2) As described above, the charge mobility can be improved by improving the π-π stacking between molecules.

(3) By coordinating magnesium as the central metal of the porphyrin skeleton, the excitation lifetime can be extended.

As described above, by using the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2) as a donor material, the characteristics of the photoelectric conversion device can be improved.

(4) Further, by making the two aryl units have different structures, different characteristics can be added.

(Synthesis method of porphyrin derivative)
As shown in the following (reaction formula 1), the porphyrin derivative of the above (chemical formula 1) includes a porphyrin derivative P1 (also referred to as a precursor P1 or an intermediate P1), tetrabutylammonium fluoride (TBAF), and DPP-. It can be synthesized by a chemical reaction with Br.

The TIPS (Triisopropylsilyl) of the porphyrin derivative P1 is eliminated by the reaction of the porphyrin derivative P1 with tetrabutylammonium fluoride (TBAF). Then, the DPP unit is introduced by the Sonogashira coupling. Sonogashira coupling refers to a chemical reaction in which a terminal alkyne and an aryl halide are cross-coupled by the action of a palladium catalyst, a copper catalyst, and a base to obtain an aryl halide.

As the solvent for the elimination reaction of TIPS, for example, tetrahydrofuran [THF], water ( _H2O ) or the like is used. In the case of Sonogashira coupling, for example, tetrahydrofuran [THF] or triethylamine [NET ₃ ] is used as the solvent, and the catalyst is a palladium catalyst, a copper catalyst, a base, for example, tris (dibenzylideneacetone) dipalladium. (0) [Pd ₂ (dba) ₃ ], copper (I) iodide [CuI], triphenylphosphine [PPh ₃ ] and the like are used.

As shown in the following (reaction formula 2), the porphyrin derivative of the above (chemical formula 2) includes porphyrin derivative P2 (also referred to as precursor P2 or intermediate P2), tetrabutylammonium fluoride (TBAF), and DPP-. It can be synthesized by a chemical reaction with Br. The reaction mechanism is the same as in the case of the above (chemical formula 1).

(Manufacturing method of photoelectric conversion device)
An example of a method for manufacturing a photoelectric change device (organic thin film solar cell) will be described below. FIG. 2 is a cross-sectional view showing a manufacturing process of the photoelectric change device of the present embodiment.

As shown in FIG. 2A, the first electrode EL1 is formed on the light-transmitting substrate SUB. For example, ITO (Indium Tin Oxide) is formed as a conductor layer on the substrate SUB, and the first electrode EL1 is formed by patterning.

Next, the buffer layer BUF1 is formed on the first electrode EL1. For example, a buffer layer BUF1 is formed by applying a PEDOT: PSS aqueous solution, which is a conductive polymer solution, onto a substrate and drying it.

Next, as shown in FIG. 2B, the active layer AL is formed on the buffer layer BUF1. First, the solution for forming the active layer is prepared. The donor material and acceptor material are dissolved in a solvent and additives are added as needed. Additives are used, for example, to increase the solubility of donor and acceptor materials. The solution for forming the active layer is applied onto the buffer layer BUF1 and dried to form the active layer AL. After that, if necessary, the active layer AL is subjected to an annealing treatment (heat treatment).

Next, as shown in FIG. 2 (c), the buffer layer BUF2 is formed on the active layer AL. For example, a calcium layer is formed on the active layer AL as the buffer layer BUF2 by using, for example, a vacuum vapor deposition method.

Next, the second electrode EL2 is formed on the buffer layer BUF2. For example, an aluminum layer is formed on the buffer layer BUF2 as a conductor layer for the second electrode EL2 by using, for example, a vacuum vapor deposition method.

As the donor material, the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2) is used.

As the acceptor material, for example, a fullerene derivative is used. As the solvent, for example, chlorobenzene or the like is used. As the additive, for example, ethanol, acetone, tetrahydrofuran [THF], pyrazine, triethylamine [NET ₃ ], pyridine and the like are used. The annealing temperature can be 100 ° C to 200 ° C. It is not necessary to perform annealing treatment. In particular, in the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2), as described above, the condensability (crystallinity) is good due to the improvement of π-π stacking between molecules, so the annealing treatment is omitted. can do.

Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to the examples shown below.

(Example 1)
In this example, the porphyrin derivative MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ ) represented by the above (chemical formula 1) is used in the following (reaction formula 4). It was produced by the reaction.

Under a nitrogen atmosphere, 18 mg of the porphyrin derivative P1 (also referred to as precursor P1 or intermediate P1) and 2 mL of tetrahydrofuran [THF] were placed in a 20 mL two-necked flask, and 1 mol / L tetrabutylammonium fluoride was added. 0.17 mL of the derivative [TBAF] was added, and the mixture was stirred at room temperature (about 25 ° C.) for 1 hour. Then, 20.9 mg of the DPP precursor [DPP-Br], 0.79 mg of tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ], and 4 of triphenylphosphine [PPh ₃ ]. .54 mg, 0.166 mg of copper (I) iodide [CuI], 2.19 mL of triethylamine [NET ₃ ], and 4.79 mL of tetrahydrofuran [THF] were added, and the mixture was heated and stirred at 85 ° C. for 30 minutes. .. The crude product was removed from the origin by silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 17.6 mg of product 1. The yield of product 1 was 57%. This yield was determined from the ratio of the number of moles of the porphyrin derivative P1 and the product 1.

(inspection)
It was verified as follows that the product 1 obtained by the above step was a porphyrin derivative represented by the above (chemical formula 1).

FIG. 3 is a ¹ HNMR spectrum of product 1 and FIG. 4 is a ¹³ CNMR spectrum of product 1. FIG. 5 is a COSY spectrum of product 1. FIG. 6 is an MS spectrum of product 1. In the NMR spectrum, the vertical axis shows the relative intensity of the proton signal, and the horizontal axis shows the chemical shift (δ) value.

From the NMR spectra shown in FIGS. 3 and 4, it can be confirmed that the product 1 is the porphyrin derivative represented by the above (chemical formula 1). Further, the COSY spectrum of the product 1 shown in FIG. 5 also confirms that the product 1 is the porphyrin derivative represented by the above (chemical formula 1). Further, the molecular weight (found) of the product 1 obtained from the MS spectrum of the product 1 shown in FIG. 6 is 1776.7093, which is the molecular weight (calcd) 1776.7101 of the above (Chemical formula 1). It is a good match.

As described above, the porphyrin derivative MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ ) represented by the above (Chemical Formula 1) was successfully synthesized.

(Example 2)
In this example, the porphyrin derivative MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ) represented by the above (chemical formula 2) is used in the following (reaction formula 5). It was produced by the reaction.

Under a nitrogen atmosphere, 22 mg of the porphyrin derivative P2 (also referred to as precursor P2 or intermediate P2) and 2.51 mL of tetrahydrofuran [THF] were placed in a 20 mL two-necked flask, and 1 mol / L tetrabutyl was added. 0.11 mL of ammonium fluoride [TBAF] was added, and the mixture was stirred at room temperature (about 25 ° C.) for 30 minutes. Then, 26.1 mg of the DPP precursor [DPP-Br], 0.99 mg of tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ], and 5 of triphenylphosphine [PPh ₃ ]. .67 mg, 0.206 mg of copper (I) iodide [CuI], 2.74 mL of triethylamine [NET ₃ ], and 6.03 mL of tetrahydrofuran [THF] were added, and the mixture was heated and stirred at 85 ° C. for 1 hour. .. The crude product was purified from the origin using silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 24.5 mg of product 2. The yield of product 2 was 65%.

(inspection)
It was verified as follows that the product 2 obtained by the above step was a porphyrin derivative represented by the above (chemical formula 2).

FIG. 7 is a ¹ HNMR spectrum of product 2, and FIG. 8 is a ¹³ CNMR spectrum of product 2. FIG. 9 is a COSY spectrum of product 2. FIG. 10 is an MS spectrum of product 2.

From the NMR spectra shown in FIGS. 7 and 8, it can be confirmed that the product 2 is the porphyrin derivative represented by the above (chemical formula 2). Further, the COSY spectrum of the product 2 shown in FIG. 9 also confirms that the product 2 is the porphyrin derivative represented by the above (chemical formula 2). Further, the molecular weight (found) of the product 2 obtained from the MS spectrum of the product 2 shown in FIG. 10 is 1751.7651, which is the molecular weight (calcd) 1751.7649 of the above (Chemical formula 2). It is a good match.

As described above, the porphyrin derivative MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ) represented by the above (chemical formula 2) was successfully synthesized.

(Example 3)
The ultraviolet-visible absorption spectra of products 1 and 2 obtained by the steps shown in Examples 1 and 2 were measured. For the measurement, 50 μL of each product was measured from a saturated solution of tetrahydrofuran and diluted 100-fold using two 10 mL volumetric flasks.

FIG. 11 is an ultraviolet-visible absorption spectrum of the product 1MgTEPDPP ₂ (4-hexyl-C 6H ₄ ) ( ₄ -CF ₃ -C ₆ H ₄ ). As Comparative Material 1, the two aryl units both also showed an ultraviolet-visible absorption spectrum of CF ₃ -C ₆ H ₄ . The horizontal axis represents the wavelength (Wavelength, nm), and the vertical axis represents the absorbance (Au).

As shown in FIG. 11, the product 1 MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ ) was found to have absorption over the entire visible light region. It is considered that such absorption in the visible light region is due to the introduction of the DPP unit.

Moreover, when the absorbance of the absorption band (Q band region) derived from the porphyrin skeleton was investigated, the absorbance of the product 1 MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ ) was 1. It was .303, and the absorbance of the comparative substance 1 MgTEPDPP ₂ (4-CF ₃ -C ₆ H ₄ ) ₂ was 0.987.

The absorbance in this Q-band region corresponds to the solubility of the substance, and it can be seen that the product 1 has a higher solubility than the comparative substance 1.

In this way, by making the two aryl units different (different units), the intramolecular interaction was suppressed and the solubility could be improved. It is considered that such improvement in solubility is caused not by the characteristics of the substituents (R, R') of the aryl unit but by the "distortion" of the structure of the porphyrin derivative. By improving the solubility of such a substance, the film thickness of the active layer using the substance can be increased. This facilitates the manufacture of the photoelectric conversion device and can improve the characteristics of the photoelectric conversion device.

Further, by inserting aryl units having different electronic properties, the "symmetry" of the porphyrin skeleton is broken, and the peak (Q band) derived from the porphyrin skeleton is broadened as compared with the comparative substance 1.

By making the two aryl units different (different units) in this way, the electronic properties of both aryl units are different, and the absorption band (Q band region) derived from the porphyrin skeleton is widened (widened). You can see that. This makes it possible to increase the light absorption efficiency when used as a photoelectric conversion device.

FIG. 12 is an ultraviolet-visible absorption spectrum of the product 2MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ). As Comparative Material 2, the two aryl units both also showed an ultraviolet-visible absorption spectrum of NMe _{2 -} C ₆ H4.

As shown in FIG. 12, the product 2MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ) was found to have absorption over the entire visible light region. It is considered that such absorption in the visible light region is due to the introduction of the DPP unit.

Moreover, when the absorbance of the absorption band (Q band region) derived from the porphyrin skeleton was investigated, the absorbance of the product 2MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ) was 0. It was .598, and the absorbance of the comparative substance 2MgTEPDPP ₂ (4-NMe ₂ -C ₆ H ₄ ) ₂ was 0.0579.

The absorbance in this Q-band region corresponds to the solubility of the substance, and it can be seen that the product 2 has a higher solubility than the comparative substance 2.

In this way, by making the two aryl units different (different units), the intramolecular interaction was suppressed and the solubility could be improved. It is considered that such improvement in solubility is caused not by the characteristics of the substituents (R, R') of the aryl unit but by the "distortion" of the structure of the porphyrin derivative. By improving the solubility of such a substance, the film thickness of the active layer using the substance can be increased. This facilitates the manufacture of the photoelectric conversion device and can improve the characteristics of the photoelectric conversion device.

Further, by inserting aryl units having different electronic properties, the "symmetry" of the porphyrin skeleton is broken, and the peak (Q band) derived from the porphyrin skeleton is broadened as compared with the comparative substance 1.

By making the two aryl units different (different units) in this way, the electronic properties of both aryl units are different, and the absorption band (Q band region) derived from the porphyrin skeleton is widened (widened). You can see that. This makes it possible to increase the light absorption efficiency when used as a photoelectric conversion device.

As the comparative substance 3, the two aryl units both measured the ultraviolet _- visible absorption spectrum of hexyl-C ₆ H4. FIG. 13 is an ultraviolet-visible absorption spectrum of the comparative substance 3MgTEPDPP ₂ ( _{4-hexyl-C 6H 4 ) 2} , and the absorbance of the absorption band (Q band region) derived from the porphyrin skeleton was 1.166. In the case of this comparative substance 3, the absorbance is higher than that of the product 2, and it can be seen that the characteristics of the aryl unit itself are also involved in the absorbance (solubility).

Therefore, the absorbance (solubility) can be improved by selecting an annealing unit having a property of improving the absorbance (solubility) and by using different aryl units linked to the 10-position and the 20-position of the porphyrin skeleton. It is considered that this can be done (see Table 3 etc.). In addition, widening (widening) of the absorption band (Q band region) derived from the porphyrin skeleton can be expected.

(Example 4)
Devices (photoelectric conversion device, photoelectric conversion element) were prepared and evaluated using the products 1 and 2 obtained by the steps shown in Examples 1 and 2 as donor materials.

A glass substrate (FLAT ITO manufactured by Geomatec) on which a patterned ITO film (first electrode) is formed is prepared, and ultrasonically cleaned with a cleaning solution, pure water, acetone, and IPA (isopropyl alcohol) for 15 minutes each. gone. The substrate was air _- dried and UV / O3 irradiation was performed for 15 minutes. Next, a conductive polymer solution PEDOT: PSS aqueous solution (Al4083 manufactured by Clevious) was spin-coated on the substrate to a film thickness of 40 nm, unnecessary parts were wiped off, and the mixture was heated and dried at 120 ° C. for 10 minutes under air. A buffer layer was formed. The substrate was then introduced into a nitrogen-filled glove box. The concentration of water and oxygen in the glove box is less than 0.1 ppm.

The solution for forming the active layer was prepared. The liquid preparation was performed in a nitrogen-filled glove box in which the concentration of water or oxygen was less than 0.1 ppm. A mixture of product 1 obtained by the step shown in Example 1 as a donor material and a fullerene derivative as an acceptor material, as a solvent, 20 mg / mL to 40 mg / mL with respect to the total amount of the donor and the acceptor material. Dichlorobenzene was added at the ratio of the above, an additive was further added, and the mixture was heated and stirred at 80 ° C. in a glove box to dissolve the donor material and the acceptor material in a solvent to obtain a solution for forming an active layer.

This solution is cooled to room temperature (25 ° C.), filtered through a filter, the filtrate is applied onto the buffer layer by spin coating to form a coating film, and then slowly dried (solidified) in a petri dish for about 2 hours. By allowing them to form an active layer. Next, the active layer was subjected to an annealing treatment. The usual annealing is a heat treatment performed at 80 to 150 ° C. or higher for about 5 to 10 minutes. On the other hand, solvent annealing is a solvent exposure treatment performed at room temperature (25 ° C.) in a closed space for 30 seconds to 1 minute. For example, the active layer is placed in a closed container in which an organic compound (organic solvent) that volatilizes at room temperature (25 ° C.) is placed, and the active layer is exposed to the volatilized organic compound. An organic compound (for example, chloroform, tetrahydrofuran or the like can be used as the organic solvent.

Then, a calcium layer was formed on the active layer as a buffer layer with a thickness of about 20 nm using a vacuum vapor deposition machine, and then an aluminum layer was formed on the buffer layer as a second electrode with a thickness of about 80 nm. It was formed using a vacuum vapor deposition machine.

A photoelectric conversion device was manufactured by the above steps. The produced photoelectric conversion device was irradiated with 1 SUN of light using a solar simulator, and the conversion efficiency (photoelectric conversion efficiency) was measured. In addition, in order to investigate the laminated state, the surface of the active layer was observed using an atomic force microscope (AFM) using a sample at the stage where the active layer was formed, and the film thickness was measured using Dektak. rice field.

In the manufacturing process of the photoelectric conversion device, conditions such as the ratio (D: A rate) of the donor material and the acceptor material, the additive, and the annealing temperature were changed according to the combinations shown in Table 1, and No. 1 to No. The device shown in No. 13 was manufactured. PC ₆₁ BM was used as the fullerene derivative. The fullerene derivative PC ₆₁ BM is a derivative of fullerene C ₆₀ [6,6] -Phenyl C ₆₁ butyric acid methyl ester. In the annealing column, the indication of "-" means that the annealing treatment has not been performed. Further, in the column of additives, the indication of "-" means that no additive is used.

The conversion efficiency PCE (%) was obtained from the product of the open circuit voltage (Voc), the short circuit current density (Jsc), and the fill factor (FF) (PCE = Voc × Jsc × FF). The results are shown in Table 1.

Further, the donor material is the product 2 obtained by the step shown in Example 2 from the product 1, and the conditions of the ratio (D: A rate) between the donor material and the acceptor material, the additive, and the annealing temperature are shown in Table 2. Change with the combination shown, and change to No. 14-No. The photoelectric conversion device (device) shown in 19 was manufactured, and the conversion efficiency was determined. The results are shown in Table 2.

FIG. 14 is an AFM image of the surface of the active layer using product 1 MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-CF ₃ -C ₆ H ₄ ) as a donor material, and FIG. 15 is an AFM image of the product. It is an AFM image of the surface of an active layer using 2MgTEPDPP ₂ (4-hexyl-C ₆ H ₄ ) (4-NMe ₂ -C ₆ H ₄ ) as a donor material. In the case of product 1, Rq = 0.901 nm, and the film thickness was 135 nm as measured using Dektak. In the case of product 2, Rq = 0.431 nm, and the film thickness was 92 nm as measured using Dektak. Rq is the root mean square height (Rq) and indicates the surface roughness. When the comparative substance 1 was used, the film thickness was about 120 nm, and it was confirmed that the film thickness could be increased by using the product 1.

(Discussion)
As shown in Tables 1 and 2, the product 1 and the product 2, that is, the porphyrin derivative represented by the following (Chemical formula 1) or (Chemical formula 2), obtained by the steps shown in Examples 1 and 2 are used. By using it as a donor material, it was possible to obtain a photoelectric conversion device (device) having a conversion efficiency of 1.20% to 4.07%.

The maximum conversion efficiency when the porphyrin derivative represented by (Chemical Formula 1) was used was 4.07%. On the other hand, the maximum conversion efficiency when the comparative substance 1 is used is 1.65% (see Non-Patent Document 7), and the aryl units linked to the 10-position and the 20-position of the porphyrin skeleton are different. It is possible that the improvement of solubility (thickening of the active layer) and the widening of the Q-band region led to an increase in conversion efficiency.

The maximum conversion efficiency when the porphyrin derivative represented by (Chemical Formula 2) was used was 3.30%. On the other hand, the maximum conversion efficiency when the comparative substance 2 is used is 2.33% (see Non-Patent Document 7), and the aryl units linked to the 10-position and the 20-position of the porphyrin skeleton are different. It is possible that the improvement of solubility (thickening of the active layer) and the widening of the Q-band region led to an increase in conversion efficiency.

Further, when the porphyrin derivative represented by (Chemical Formula 1) was used, the conversion efficiency tended to be high when the solvent annealing was performed or when the annealing treatment was not performed.

Further, as can be seen from the comparison between FIGS. 14 and 15, FIG. 14 has a large surface roughness. This is derived from the high surface energy that is a characteristic of CF ₃ , and since CF ₃ easily appears at the solid / air interface, the edge-on orientation is superior, which is a structure in which the porphyrin derivative stands up with respect to the substrate as a whole. It is probable that it became. That is, in the porphyrin derivative, when the face-on orientation in which the planar spread of the structure is parallel to the substrate is dominant, the laminated state (stacking density) becomes better and the charge transfer becomes smoother. It is considered that the conversion efficiency will be good. Therefore, regarding the aryl unit to be introduced into the porphyrin skeleton, it is considered that the conversion efficiency and other characteristics can be further improved by using a unit having a superior face-on orientation and using a different aryl unit. ..

(Embodiment 2)
In this embodiment, the synthetic raw material of the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2) will be described.

(1) First, in Example 1, the synthesis of the porphyrin derivative P1 (also referred to as precursor P1 or intermediate P1) on the left side (raw material) of the following (reaction formula 4) will be described.

This porphyrin derivative P1 can be produced, for example, by a chemical reaction (first reaction, second reaction) shown in the following (reaction formula 6).

As shown in (Reaction Formula 6), the porphyrin derivative is obtained by sonogashira coupling (first reaction) between the porphyrin derivative P3 (also referred to as precursor P3 or intermediate P3) and 4-hexylphenylacetylene which is a reactant. Synthesize P4. Next, the porphyrin derivative P1 is synthesized by sonogashira coupling (second reaction) between the porphyrin derivative P4 and the reactant trifluoromethylphenylacetylene. Toluene and triethylamine [NET ₃ ] are used as solvents, and the reaction is carried out at about 60 ° C. to 90 ° C. for about 30 minutes to 50 hours, respectively. Either of the aryl units may be introduced first.

(Example 5)
Hereinafter, the synthesis of the porphyrin derivative P1 will be described in detail based on Examples.

(First reaction)
Under a nitrogen atmosphere, 120 mg (0.146 mmol) of porphyrin derivative P3, 46.6 mL of toluene, 11.7 mL of triethylamine, 8.02 mg of tris (dibenzylideneacetone) dipalladium (0), and triphenyl in a 100 mL two-necked flask. 17.6 mg of phosphine, 7.51 mg of copper (I) iodide, and 30 μL (0.146 mmol) of 4-hexylphenylacetylene were added, and the mixture was heated and stirred at 85 ° C. for 30 hours. The crude product was removed from the origin by silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 48.56 mg of the desired product (P4). The yield of the target product (P3) was 35%.

Here, the porphyrin derivative P3 and 4-hexylphenylacetylene were added so as to have the same equivalent amount. As described above, the equivalent of the first aryl unit to be introduced is 1 equivalent or less with respect to 1 equivalent of the porphyrin derivative P3.

(Second reaction)
Then, in a 50 mL two-necked flask under a nitrogen atmosphere, 46 mg (0.048 mmol) of the porphyrin derivative P4, 18.4 mL of toluene, 4.6 mL of triethylamine, Tris (dibenzylideneacetone) dipalladium (0) 5.27 mg, and triphenyl 11.6 mg of phosphine, 4.94 mg of copper (I) iodide, and 78 μL (0.48 mmol) of 4-trifluoromethylphenylacetylene were added, and the mixture was heated and stirred at 85 ° C. for 30 hours. The crude product was removed from the origin by silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 29.4 mg of the desired product (P1). The yield of the target product (P1) was 59%.

Here, 4-trifluoromethylphenylacetylene was added in excess (here, 10 equivalents) to the porphyrin derivative P4. As described above, the equivalent of the second aryl unit to be introduced is 1 equivalent or more, more preferably 2 equivalents or more, with respect to 1 equivalent of the porphyrin derivative P4.

(2) Next, the synthesis of the porphyrin derivative P3 (also referred to as precursor P3 or intermediate P3) will be described. The porphyrin derivative P3 can be produced, for example, by a chemical reaction shown in the following (reaction formula 7).

As shown in (Reaction equation 7), the porphyrin derivative P3 can be synthesized through a 4-step reaction from TIPS acetylene, which is a raw material MT. The first step (St1) is a step of changing the acetylene terminal to an aldehyde, and the second step (St2) is a step of forming a porphyrin ring skeleton. The third step (St3) is a step of inserting magnesium, and the fourth step (St4) is a step of dibromoization.

(3) Next, in Example 2, the synthesis of the porphyrin derivative P2 (also referred to as precursor P2 or intermediate P2) on the left side (raw material) of the following (reaction formula 5) will be described.

This porphyrin derivative P2 can be produced, for example, by a chemical reaction (first reaction, second reaction) shown in the following (reaction formula 6').

As shown in (reaction formula 6'), porphyrin is obtained by sonogashira coupling (first reaction) between the porphyrin derivative P3 (also referred to as precursor P3 or intermediate P3) and 4-hexylphenylacetylene which is a reactant. Derivative P4 is synthesized. Next, the porphyrin derivative P1 is synthesized by Sonogashira coupling (second reaction) between the porphyrin derivative P4 and the reactant 4-dimethylaminophenylacetylene. Toluene and triethylamine [NET ₃ ] are used as solvents, and the reaction is carried out at about 60 ° C. to 90 ° C. for about 30 minutes to 50 hours, respectively. Either of the aryl units may be introduced first.

(Example 6)
Hereinafter, the synthesis of the porphyrin derivative P2 will be described in detail based on Examples.

(First reaction)
Under a nitrogen atmosphere, 120 mg (0.146 mmol) of porphyrin derivative P3, 46.6 mL of toluene, 11.7 mL of triethylamine, 8.02 mg of tris (dibenzylideneacetone) dipalladium (0), and triphenyl in a 100 mL two-necked flask. 17.6 mg of phosphine, 7.51 mg of copper (I) iodide, and 30 μL (0.146 mmol) of 4-hexylphenylacetylene were added, and the mixture was heated and stirred at 85 ° C. for 30 hours. The crude product was removed from the origin by silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 48.56 mg of the desired product (P4). The yield of the target product (P3) was 35%.

Here, the porphyrin derivative P3 and 4-hexylphenylacetylene were added so as to have the same equivalent amount. As described above, the equivalent of the first aryl unit to be introduced is 1 equivalent or less with respect to 1 equivalent of the porphyrin derivative P3.

(Second reaction)
Then, under a nitrogen atmosphere, 29 mg (0.03 mmol) of the porphyrin derivative P4 was placed in a 20 mL two-necked flask, 11.6 mL of toluene, 2.9 mL of triethylamine, tris (dibenzylideneacetone) dipalladium (0) 3.33 mg, and triphenyl. 7.24 mg of phosphine, 2.09 mg of copper (I) iodide, and 33 mg (0.23 mmol) of 4-dimethylaminophenylacetylene were added, and the mixture was heated and stirred at 85 ° C. for 30 hours. The crude product was removed from the origin by silica gel column chromatography and then purified by GPC (gel permeation chromatography) to obtain 21.6 mg of the desired product (P2). The yield of the target product (P2) was 71%.

Here, 4-dimethylaminophenylacetylene was added in excess (here, 7.6 equivalents) with respect to the porphyrin derivative P4. As described above, the equivalent of the second aryl unit to be introduced is 1 equivalent or more, more preferably 2 equivalents or more, with respect to 1 equivalent of the porphyrin derivative P4.

(4) The porphyrin derivative P3 can be produced, for example, by the chemical reaction shown in the above-mentioned (reaction formula 7).

As described above, by chemically modifying the synthetic raw material of the porphyrin derivative in advance, the porphyrin derivative as the donor material can be given a further function. In particular, by introducing two types of aryl units, it is possible to improve the absorbance (solubility) and widen the absorption band (Q band region) derived from the porphyrin skeleton.

That is, by using the porphyrin derivative represented by the following (general formula 1) as the donor material, the characteristics of the photoelectric conversion device can be further improved. In the following (general formula 1), R and R'constituting the aryl unit are different.

As R and R'of the above general formula, for example, R1 to R7 shown in Table 3 can be combined. In the case of the porphyrin derivative represented by the above (chemical formula 1), R and R'are "-(CH ₂ ) ₅ CH ₃ " shown in the column of "R2" and "-CF ₃ " shown in the column of "R3", respectively. It becomes. The corresponding reactants (X, X') are 4-hexylphenylacetylene and trifluoromethylphenylacetylene, respectively.

Further, in the case of the porphyrin derivative represented by the above (chemical formula 2), R and R'are "-(CH ₂ ) ₅ CH ₃ " shown in the column of "R2" and "-NMe" shown in the column of "R4", respectively. It becomes ₂ ". The corresponding reactants (X, X') are 4-hexylphenylacetylene and 4-dimethylaminophenylacetylene, respectively.

In addition to these, by introducing R1 to R7 shown in Table 3 in combination, a porphyrin derivative having good characteristics can be obtained.

Further, in Table 3 above, R and R'constituting the aryl unit have been described, but the R and R'may be those bound to thiophene (thiophene compound). For example, any of R1 to R7 shown in Table 3 and T1 to T7 shown in Table 4 can be combined. For example, by combining R2 and T2, there is a high possibility that the absorbance (solubility) can be improved and the characteristics can be improved by widening the Q band region. Further, when used in a photoelectric conversion device, the face-on orientation becomes dominant, and there is a high possibility that the conversion efficiency and the like will be good.

As described above, by using the porphyrin derivative represented by the above (general formula 1) as a donor material, it is possible to improve the characteristics of the photoelectric conversion device (improve the conversion efficiency and the like). Further, by introducing various groups as R and R', the physical properties can be adjusted.

Here, the porphyrin derivative represented by the above (general formula 1) is desorbed from the TIPS group of the porphyrin derivative by the first reaction of the porphyrin derivative and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 3). After that, it is produced by a second reaction between the porphyrin derivative from which the TIPS group has been removed and DPP-Br.

(Embodiment 3)
In this embodiment, a method of manufacturing a photoelectric conversion device using a continuous coating method called roll-to-roll will be described.

FIG. 16 is a cross-sectional view showing a manufacturing process of the photoelectric conversion device of the present embodiment. As shown in FIG. 16, the flexible substrate 10 is horizontally conveyed from the roller 11 to the roller 12. A first electrode and a buffer layer (not shown) are preliminarily formed on the flexible substrate 10 by using a continuous coating method or the like.

Then, between the rollers, a solution for forming the active layer (for example, the solution described in Examples 1 and 2) is applied from the slit coater 13, and the coating film is annealed by the cylindrical heater 14. As a result, the active layer AL is formed on the flexible substrate 10 and is wound around the roller 12.

After that, a buffer layer and a second electrode are formed on the active layer AL by using a continuous coating method or the like.

As described above, the active layer using the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2) described in the first and second embodiments can be formed by a continuous coating method, and the device manufacturing cost can be reduced. The cost can be reduced, and the area of the active layer can be easily increased.

Further, as described above, in the porphyrin derivative represented by the above (Chemical formula 1) or (Chemical formula 2), the solubility in the solvent is improved, so that the coating process can be easily adjusted and the thickness of the active layer is increased. Membrane formation is possible.

Although the invention made by the present inventor has been specifically described above based on the embodiment, the present invention is not limited to the above embodiment and can be variously modified without departing from the gist thereof. Needless to say.

For example, in the above embodiment, Mg is coordinated as the central metal of the porphyrin skeleton, but the central metal of the porphyrin skeleton may be Zn. Further, it may be another divalent metal (M), for example, Ca or Fe.

10 Flexible substrate 11 Roller 12 Roller 13 Slit coater 14 Heater AC acceptor material AL Active layer (charge transport layer)
BUF1 Buffer layer BUF2 Buffer layer DO Donor material EL1 1st electrode EL2 2nd electrode SUB substrate

Claims (10)

The porphyrin derivative represented by the following (Chemical formula 1).

The porphyrin derivative represented by the following (Chemical formula 2).

The porphyrin from which the TIPS group was removed after the TIPS group of the porphyrin derivative P1 was removed by the first reaction between the porphyrin derivative P1 and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 1). A method for producing a porphyrin derivative, which produces the porphyrin derivative of the following (chemical formula 1) by the second reaction of the derivative P1 and DPP-Br.

In the method for producing a porphyrin derivative according to claim 3,
The second reaction is a reaction using a palladium catalyst, which is a method for producing a porphyrin derivative. The porphyrin from which the TIPS group was removed after the TIPS group of the porphyrin derivative P2 was removed by the first reaction of the porphyrin derivative P2 and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 2). A method for producing a porphyrin derivative, which produces the porphyrin derivative of the following (chemical formula 2) by the second reaction of the derivative P2 and DPP-Br.

In the method for producing a porphyrin derivative according to claim 5.
The second reaction is a reaction using a palladium catalyst, which is a method for producing a porphyrin derivative. A donor material for a photoelectric conversion device having a porphyrin derivative represented by the following (Chemical formula 1) or (Chemical formula 2).

It has a first electrode, a charge transport layer provided above the first electrode, and a second electrode provided above the charge transport layer.
The charge transport layer is a layer in which a donor material and an acceptor material are mixed.
A photoelectric conversion device having a porphyrin derivative represented by the following (general formula 1) as the donor material. However, the following (general formula 1) is a porphyrin derivative represented by the following (chemical formula 1) or (chemical formula 2) .

(A) A step of forming a coating layer by coating a liquid having a donor material, an acceptor material, and a solvent on the first conductor layer to be the first electrode.
(B) A step of forming a charge transport layer having the donor material and the acceptor material by solidifying the coating layer.
(C) A step of forming a second conductor layer to be a second electrode above the charge transport layer.
Have,
The method for manufacturing a photoelectric conversion device, wherein the donor material is a porphyrin derivative represented by the following (general formula 1). However, the following (general formula 1) is a porphyrin derivative represented by the following (chemical formula 1) or (chemical formula 2) .

In the method for manufacturing a photoelectric conversion device according to claim 9 ,
The porphyrin derivative represented by the above (general formula 1) is after removing the TIPS group of the porphyrin derivative by the first reaction of the porphyrin derivative and tetrabutylammonium fluoride (TBAF) shown in the following (reaction formula 3). A method for producing a photoelectric conversion device, which is produced by a second reaction between the porphyrin derivative from which the TIPS group has been removed and DPP-Br .

Images