WO2015029432A1 - Photoelectric conversion element - Google Patents

Abstract

This photoelectric conversion element (10) has a structure wherein a hole transport layer (40), a photoelectric conversion layer (50) and an electron transport layer (60) are sandwiched between a first electrode (30) and a second electrode (70). The photoelectric conversion layer (50) is a bulk heterojunction layer, and a fullerene or a fullerene derivative is used as an n-type organic semiconductor. An organic semiconductor represented by formula (1) is used as a p-type organic semiconductor. (In the formula, each of R¹ and R² represents a linear alkyl group or an alkyl group having a branched chain; the difference between the number of carbon atoms in the long chain of R¹ and the number of carbon atoms in the long chain of R² is 3 or less; and the total number of carbon atoms in the alkyl group of R¹ or R², which has more carbon atoms in the long chain (in cases where R¹ and R² have the same number of carbon atoms in the long chain, one that has more carbon atoms in total; and in cases where R¹ and R² have the same number of carbon atoms in total, either R¹ or R²), is 15 or less.

Description

Photoelectric conversion element

The present invention relates to a photoelectric conversion element that converts light energy into electric energy by photoelectric conversion.

Organic solar cells (photoelectric conversion elements) are considered to be promising next-generation solar cells because they are flexible and can be expected to have a large area, light weight, and a simple and inexpensive manufacturing method. At present, significant improvement in conversion efficiency is an important issue for practical application of organic solar cells.

Various donor materials are being studied in order to improve the photoelectric conversion efficiency of photoelectric conversion elements (organic solar cells). For example, Patent Document 1 discloses a p-type organic semiconductor material having a naphthobisthiadiazole (NTz) skeleton as a donor material.

International Publication Number WO2013 / 015298

Conventional photoelectric conversion elements including a p-type organic semiconductor have a photoelectric conversion efficiency as low as about 1%, and there is room for improvement for practical use.

The present invention has been made in view of these problems, and an object thereof is to provide a technique capable of improving the photoelectric conversion efficiency of a photoelectric conversion element including an organic semiconductor.

（上記式中、Ｒ^１、Ｒ^２は、直鎖状アルキル基または分岐鎖を有するアルキル基であり、Ｒ^１の長鎖炭素数とＲ^２の長鎖炭素数との差が３以内であり、かつ、Ｒ^１、Ｒ^２のうち、長鎖炭素数が長い方（長鎖炭素数が同じ場合は、合計炭素数が多い方または合計炭素数が同数の場合はいずれか一方）のアルキル基の合計炭素数が１５以下である。） One embodiment of the present invention is a photoelectric conversion element. The photoelectric conversion element includes a photoelectric conversion layer, an electron extraction electrode provided on one main surface side of the photoelectric conversion layer, a hole extraction electrode provided on the other main surface side of the photoelectric conversion layer, And the photoelectric conversion layer has an organic semiconductor having a thiazolothiazole skeleton and a naphthobisthiadiazole skeleton represented by the following formula.

(In the above formula, R ¹ and R ² are linear alkyl groups or branched alkyl groups, and the difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² is within 3 And an alkyl group having a longer long-chain carbon number among R ¹ and R ² (if the long-chain carbon number is the same, either the larger total carbon number or the total carbon number is the same). The total carbon number of is 15 or less.)

In the photoelectric conversion layer of the above aspect, the difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² may be zero. Further, both R ¹ and R ² may be 2-butyloctyl.

According to the present invention, the photoelectric conversion efficiency of a photoelectric conversion element containing an organic semiconductor can be improved.

It is a schematic sectional drawing which shows the structure of the photoelectric conversion element which concerns on embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing a configuration of a photoelectric conversion element 10 according to an embodiment. The photoelectric conversion element 10 of this Embodiment is an organic thin film solar cell which has a photoelectric converting layer containing an organic semiconductor.

The photoelectric conversion element 10 according to the embodiment includes a substrate 20, a first electrode 30, a hole transport layer 40, a photoelectric conversion layer 50, an electron transport layer 60, and a second electrode 70.

In the present embodiment, the first electrode 30 is a positive electrode and is electrically connected to a photoelectric conversion layer 50 described later. The first electrode 30 is located on the light-receiving surface side of the photoelectric conversion layer _{50, ITO (Indium Tin Oxide)} , SnO 2, FTO (Fluorine doped Tin Oxide), ZnO, AZO (Aluminum doped Zinc Oxide), IZO It is made of a conductive metal oxide such as (Indium doped Zinc Oxide) or a thin metal film such as gold, silver, copper, or aluminum, or a transparent conductive film such as a mesh or stripe. The first electrode 30 is formed on the light-transmitting substrate 20 so as not to disturb the light receiving performance. For example, the substrate 20 may be colorless or colored glass, meshed glass, glass block, or the like, or may be colorless or colored resin having transparency. Specific examples of such resins include polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, and polymethylpentene. Etc.

The hole transport layer 40 is provided in a region between the first electrode 30 and the photoelectric conversion layer 50. The hole transport layer 40 has a function of easily moving holes from the photoelectric conversion layer 50 to the first electrode 30. The hole transport layer 40 may have a function of making it difficult for electrons to move from the photoelectric conversion layer 50 to the first electrode 30. The hole transport layer 40 includes, for example, conductive polymers such as PEDOT (polythiophene) / PSS (polystyrenesulfonate), polypyrrole, polyaniline, polyfuran, polypyridine, polycarbazole, Inorganic compounds such as MoO ₃ and WO ₃ , organic semiconductor molecules such as phthalocyanine and porphyrin, and derivatives and transition metal complexes thereof, charge transfer agents such as triphenylamine compounds and hydrazine compounds, and tetrariafulvalene (TTF) Formed of a material having a high hole mobility such as a simple charge transfer complex. The thickness of the hole transport layer is not particularly limited, but is preferably 10 to 100 nm, and more preferably 20 to 60 nm.

　上記式中、Ｒ^１、Ｒ^２は、直鎖状アルキル基または分岐鎖を有するアルキル基である。Ｒ^１の長鎖炭素数とＲ^２の長鎖炭素数との差が３以内であり（条件１）、かつ、Ｒ^１、Ｒ^２のうち、長鎖炭素数が長い方（長鎖炭素数が同じ場合は、合計炭素数が多い方または合計炭素数が同数の場合はいずれか一方）のアルキル基の合計炭素数が１５以下である（条件２）。Ｒ^１の長鎖炭素数とＲ^２の長鎖炭素数との差は０が最も好ましい。上記式で表される有機半導体の平均重量分子量は、５０００～５０００００が好ましく、１００００～１５００００がより好ましい。平均重量分子量を５０００以上とすることによりポリマー同士の配向性が向上しそのポリマーが有する高移動度を発現することができ、また、５０００００以下とすることにより溶解を容易に行うことできるため、それぞれ好ましい。式中のｎは、１より大きく、好ましくは有機半導体の平均重量分子量が５０００～５０００００となる数である。 The photoelectric conversion layer 50 of the present embodiment is a bulk heterojunction layer, and is formed by mixing a p-type organic semiconductor having electron donating properties and an n-type organic semiconductor having electron accepting properties at a nano level. As the p-type organic semiconductor, an organic semiconductor (electron donor molecule) having a structure having a thiazolothiazole naphthobisthiadiazole (TzTz-NTz) skeleton represented by the following formula is used.

In the above formula, R ¹ and R ² are a linear alkyl group or an alkyl group having a branched chain. The difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² is 3 or less (Condition 1), and the longer long carbon number of R ¹ and R ² (long chain carbon number) In the case where the total number of carbon atoms is the same or the total number of carbon atoms is the same), the total carbon number of the alkyl group is 15 or less (condition 2). The difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² is most preferably 0. The average weight molecular weight of the organic semiconductor represented by the above formula is preferably 5,000 to 500,000, and more preferably 10,000 to 150,000. When the average weight molecular weight is 5000 or more, the orientation between polymers can be improved and the high mobility of the polymer can be expressed, and when it is 500000 or less, dissolution can be easily performed. preferable. N in the formula is larger than 1, and is preferably a number with an average weight molecular weight of the organic semiconductor of 5,000 to 500,000.

Examples of the linear alkyl group R ¹ and R ² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, among which butyl, hexyl Octyl, decyl, dodecyl and tetradecyl are preferred.

As R ¹ and R ² of the alkyl group having a branched chain, 2-ethylhexyl (EH, long-chain carbon number 6 (C6), total carbon number 8), 2-butylhexyl (BH, long-chain carbon number 6 (C6)) , Total carbon number 10), 2-ethyloctyl (EO, long chain carbon number 8 (C8), total carbon number 10), 2-butyloctyl (BO, long chain carbon number 8 (C8), total carbon number 12) 2-hexyloctyl (HO, long chain carbon number 8 (C8), total carbon number 14), 4-ethylhexyl (EH, long chain carbon number 6 (C6), total carbon number 8), 4-ethyloctyl (EO) , Long chain carbon number 8 (C8), total carbon number 10), 4-octylpentyl (OP, long chain carbon number 8 (C8), total carbon number 13), 2-heptyloctyl (long chain carbon number 8 (C8 ), Total carbon number 15) and the like.

For example, when EH is selected as R ^{1 and} BO is selected as R ² , the combination of EH long chain carbon number C6 and BO long chain carbon number C8 satisfies Condition 1, and the long chain carbon number is longer. Since the total carbon number of BO is 12, the condition 2 is satisfied.

When R ¹ and R ² are linear alkyl groups, the number of long-chain carbons and the total number of carbons are the same.

Examples of the n-type organic semiconductor include fullerene, [60] PCBM (phenyl C61 butyric acid methyl ester), bis [60] PCBM, ICMA (monoindenyl C60), ICBA (bisindenyl C60) and [70] PCBM (phenyl C71). Fullerene derivatives such as methyl butyrate), carbon nanotubes, carbon materials such as chemically modified carbon nanotubes, condensed ring aromatic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene Derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen, oxygen, and sulfur atoms (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, Norin, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazain Den, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds And the like, and the like.

The film thickness of the photoelectric conversion layer 50 is not particularly limited, but is 5 to 1000 nm, preferably 30 to 500 nm, more preferably 50 to 400 nm, and still more preferably 80 to 300 nm.

The electron transport layer 60 is provided in a region between the second electrode 70 and the photoelectric conversion layer 50. The electron transport layer 60 has a function of easily moving electrons from the photoelectric conversion layer 50 to the second electrode 70. Further, the electron transport layer 60 may have a function of making it difficult for holes to move from the photoelectric conversion layer 50 to the second electrode 70. The electron transport layer 60 is formed of a material having a high electron mobility. The material to be used is not particularly limited as long as it meets the object of the present invention. For example, organic semiconductor molecules such as phenanthroline, bathocuproin, and perylene, and organic substances such as derivatives and transition metal complexes thereof, LiF, CsF, CsO , Cs ₂ CO ₃ , TiOx (x is an arbitrary number of 0 to 2), inorganic compounds such as ZnO, and metals such as Ca and Ba. The thickness of the electron transport layer 60 is not particularly limited, but is preferably 0.1 to 100 nm, for example, and more preferably 1 to 60 nm.

The second electrode 70 is a negative electrode (electron extraction electrode) and is electrically connected to the photoelectric conversion layer 50 on the side opposite to the light receiving surface of the photoelectric conversion layer 50. The material of the second electrode 70 is not particularly limited as long as it has conductivity, but a metal such as gold, platinum, silver, copper, aluminum, magnesium, lithium, potassium, or a carbon electrode may be used. it can. The second electrode 70 can be formed by a known method such as a vacuum deposition method, an electron beam vacuum deposition method, a sputtering method, or applying metal fine particles dispersed in a solvent and volatilizing and removing the solvent.

The photoelectric conversion element 10 can incorporate a means for blocking ultraviolet rays. The means for blocking the ultraviolet rays is not particularly limited as long as the element can be blocked from the ultraviolet rays, but examples include an ultraviolet absorbing layer, an ultraviolet reflecting layer, and a wavelength conversion layer for converting ultraviolet rays to another wavelength. The position for providing the means for blocking ultraviolet rays is not particularly limited as long as the element can be blocked from ultraviolet rays, but a layer having an ultraviolet blocking function as described above is provided on the substrate surface on the light irradiation side, or a film having an ultraviolet blocking function is pasted. Use a substrate with an ultraviolet blocking function as the light irradiation side substrate, or provide a layer having an ultraviolet blocking function between the light irradiation side substrate and the transparent conductive film. In the case of an element having a structure laminated from the electrode side, use may be made of a sealing material provided with an ultraviolet blocking function.

The wavelength region of the ultraviolet ray to be blocked is not particularly limited, but the transmittance is 10 in the wavelength region of 330 nm or less, preferably 350 nm or less, more preferably 370 nm or less, more preferably 390 nm or less, and more preferably 400 nm or less. % Or less, preferably 1% or less, more preferably 0.1% or less.

According to the photoelectric conversion element 10 according to the present embodiment, it is possible to improve the photoelectric conversion efficiency.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

(Synthesis method of organic semiconductor)
A method for synthesizing each organic semiconductor used in Examples 1 and 2 and Comparative Examples 1 to 3 will be described below.

　反応容器に化合物１（４８．４ｍｇ, ０．０５ｍｍｏｌ）、化合物２（４７．８ｍｇ, ０．０５ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）（２ｍｇ，２ｍｏｌ％）、トルエン（２ｍＬ）を加えた。反応容器をアルゴン置換した後に密封し、μ－ウェーブリアクターを用いて１８０℃で４０分間反応させた。室温まで冷却後、反応溶液をメタノール（１００ｍｌ）と塩酸（２ｍｌ）の混合溶液に注ぎ再沈殿させた。沈殿物をろ過した後、ソックスレー抽出器を用いてメタノール、ヘキサンにて洗浄後、クロロホルムにて抽出を行った。クロロホルム溶液を濃縮した後、メタノールを用いて再沈殿させることで実施例１に用いた有機半導体（Ｐ１）（６２ｍｇ，９５％）を暗紫色固体として得た。有機半導体（Ｐ１）の数平均分子量は３１０００、重量平均分子量は７１０００であった。 (Synthesis of organic semiconductor (P1))

Add Compound 1 (48.4 mg, 0.05 mmol), Compound 2 (47.8 mg, 0.05 mmol), Tetrakis (triphenylphosphine) palladium (0) (2 mg, 2 mol%), Toluene (2 mL) to the reaction vessel. It was. The reaction vessel was purged with argon, sealed, and reacted at 180 ° C. for 40 minutes using a μ-wave reactor. After cooling to room temperature, the reaction solution was poured into a mixed solution of methanol (100 ml) and hydrochloric acid (2 ml) for reprecipitation. The precipitate was filtered, washed with methanol and hexane using a Soxhlet extractor, and then extracted with chloroform. The chloroform solution was concentrated and then reprecipitated with methanol to obtain the organic semiconductor (P1) (62 mg, 95%) used in Example 1 as a dark purple solid. The number average molecular weight of the organic semiconductor (P1) was 31000, and the weight average molecular weight was 71000.

　実施例２に用いた有機半導体（Ｐ２）は、化合物１に対して化合物３を用いたことを除いて、有機半導体（Ｐ１）の合成と同様に作製した。得られた有機半導体（Ｐ２）の数平均分子量は４８０００、重量平均分子量は１０８０００であった。 (Synthesis of organic semiconductor (P2))

The organic semiconductor (P2) used in Example 2 was prepared in the same manner as the synthesis of the organic semiconductor (P1) except that the compound 3 was used for the compound 1. The number average molecular weight of the obtained organic semiconductor (P2) was 48,000, and the weight average molecular weight was 108,000.

　比較例１に用いた有機半導体（Ｐ３）は、化合物２に対して化合物４を用いたことを除いて、有機半導体（Ｐ１）の合成と同様に作製した。得られた有機半導体（Ｐ３）の数平均分子量は２５０００、重量平均分子量は５４０００であった。 (Synthesis of organic semiconductor (P3))

The organic semiconductor (P3) used in Comparative Example 1 was prepared in the same manner as the synthesis of the organic semiconductor (P1) except that Compound 4 was used for Compound 2. The obtained organic semiconductor (P3) had a number average molecular weight of 25,000 and a weight average molecular weight of 54,000.

　比較例２に用いた有機半導体（Ｐ４）は、化合物２に対して化合物５を用いたことを除いて、有機半導体（Ｐ２）の合成と同様に作製した。得られた有機半導体（Ｐ４）の数平均分子量は２７０００、重量平均分子量は５３０００であった。 (Synthesis of organic semiconductor (P4))

The organic semiconductor (P4) used in Comparative Example 2 was prepared in the same manner as the synthesis of the organic semiconductor (P2) except that Compound 5 was used for Compound 2. The number average molecular weight of the obtained organic semiconductor (P4) was 27000, and the weight average molecular weight was 53000.

　比較例３に用いた有機半導体（Ｐ５）は、化合物２に対して化合物５を用いたことを除いて、有機半導体（Ｐ１）の合成と同様に作製した。得られた有機半導体（Ｐ５）の数平均分子量は２９０００、重量平均分子量は５４０００であった。 (Synthesis of organic semiconductor (P5))

The organic semiconductor (P5) used in Comparative Example 3 was prepared in the same manner as the synthesis of the organic semiconductor (P1) except that Compound 5 was used for Compound 2. The number average molecular weight of the obtained organic semiconductor (P5) was 29000, and the weight average molecular weight was 54,000.

表１中、ＤＴは２－デシルテトラデシル（長鎖炭素数１４（Ｃ１４）、合計炭素数２４）を意味し、ＨＤは、２－ヘキシルデシル（長鎖炭素数１０（Ｃ１０）、合計炭素数１６）を意味する。 Table 1 shows combinations of R ¹ and R ² of each organic semiconductor used in Examples 1 and 2 and Comparative Examples 1 to 3.

In Table 1, DT means 2-decyltetradecyl (long chain carbon number 14 (C14), total carbon number 24), and HD means 2-hexyldecyl (long chain carbon number 10 (C10), total carbon number) 16).

<Example 1>
The element structure of the photoelectric conversion element of Example 1 is as follows.
Element structure: Transparent electrode (ITO) / hole transport layer (PEDOT: PSS film) / photoelectric conversion layer / electron transport layer (Ca) / counter electrode (Al)

(Method for manufacturing photoelectric conversion element)
Commercially available ITO glass (surface resistance 20Ω / sq or less) was used as the transparent electrode. On this transparent electrode, commercially available PEDOT: PSS (trade name Stark AI 4083) was mixed at a mass ratio of 1: 1 and dissolved in water so that the total concentration was 2.5 mass%. The obtained solution was formed on ITO glass by spin coating at 2000 rpm (30 seconds), then heated at 120 to 150 ° C. and dried to form a hole transport layer (PEDOT: PSS film) having a thickness of about 40 nm. did.

Next, [60] PCBM and p-type organic semiconductor (P1) are added to a chlorobenzene solvent at a mass ratio of 1: 2 to prepare a 10% by mass coating solution, and this coating solution is placed on the hole transport layer at 500 rpm ( 30 seconds). Thereafter, drying was performed to form a photoelectric conversion layer having a thickness of about 200 nm.

On the obtained photoelectric conversion layer, after forming Ca to form a film thickness of about 10 nm by a vacuum deposition method and forming an electron transport layer, the film thickness is further about 100 nm by a vacuum deposition method. In this way, a counter electrode was formed by depositing Al.

Photoelectric conversion elements of Example 2 and Comparative Examples 1 to 3 were produced in the same manner as Example 1 except that the above-described organic semiconductors (P2) to (P5) were used as p-type organic semiconductors.

For the photoelectric conversion elements of Examples 1 and 2 and Comparative Examples 1 to 3, Jsc (short circuit current density), Voc (open voltage), FF (Fill factor) while irradiating 1000 W / m ² pseudo sunlight at room temperature, respectively. Was measured, and PCE (photoelectric conversion efficiency) was calculated according to the following formula.
PCE (%) = Jsc (mA / cm ² ) × Voc (V) × FF

The results obtained for PCE are shown in Table 1. As shown in Table 1, it was confirmed that the photoelectric conversion elements of Examples 1 and 2 had higher PCE (%) than the photoelectric conversion elements of Comparative Examples 1 to 3. In particular, it was confirmed that the PCE (%) was remarkably increased in Example 1 where both R ¹ and R ² were 2-butyloctyl.

Even if the long chain carbon number difference (| C1-C2 |) is within 3 as in Comparative Example 3, when the long chain side total carbon number is more than 15, the effect of increasing the PCE (%) is achieved. It was confirmed not to. On the other hand, as in Example 2, when the long chain carbon number difference (| C1-C2 |) is within 3 and the long chain side total carbon number is 15 or less, the PCE (%) is It was confirmed that there was an effect of increasing.

The present invention is not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art. Embodiments to which such modifications are added Can also be included in the scope of the present invention.

For example, in the photoelectric conversion element 10 according to the embodiment, the electron transport layer 60 is provided between the photoelectric conversion layer 50 and the second electrode 70, and the positive electrode is provided between the photoelectric conversion layer 50 and the first electrode 30. Although the hole transport layer 40 is provided, the position of the hole transport layer 40 and the position of the electron transport layer 60 can be interchanged. When the electron transport layer 60 is provided in a region between the first electrode 30 and the photoelectric conversion layer 50, and the hole transport layer 40 is provided in a region between the second electrode 70 and the photoelectric conversion layer 50. The first electrode 30 is a cathode, and the second electrode 70 is an anode. Further, either one or both of the hole transport layer 40 and the electron transport layer 60 may be omitted.

10 photoelectric conversion element, 20 substrate, 30 first electrode, 40 hole transport layer, 50 photoelectric conversion layer, 60 electron transport layer, 70 second electrode

The present invention can be used for a photoelectric conversion element.

Claims (3)

A photoelectric conversion layer;
An electron extraction electrode provided on one main surface side of the photoelectric conversion layer;
A hole extraction electrode provided on the other main surface side of the photoelectric conversion layer;
With
A photoelectric conversion element comprising an organic semiconductor having a thiazolothiazole skeleton and a naphthobisthiadiazole skeleton, wherein the photoelectric conversion layer is represented by the following formula.

(In the above formula, R ¹ and R ² are linear alkyl groups or branched alkyl groups, and the difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² is within 3 And an alkyl group having a longer long-chain carbon number among R ¹ and R ² (if the long-chain carbon number is the same, either the larger total carbon number or the total carbon number is the same). The total carbon number of is 15 or less.) The photoelectric conversion element according to claim 1, wherein the difference between the long chain carbon number of R ^{1 and} the long chain carbon number of R ² is zero. The photoelectric conversion device according to claim 2, wherein R ¹ and R ² are both 2-butyloctyl.

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