KR102514779B1 - New acceptor-donor-acceptor triad type compound, compositions and solar cell - Google Patents

Abstract

The present invention relates to a novel A-D-A triad-type compound, a composition containing the same, and a solar cell, and more specifically, to a thiophene or fused thiophene-based donor core and an A-D-A triad containing a fullerene-based terminal unit as an acceptor. It relates to a novel compound that is an acceptor-donor-acceptor triad-type smallmolecule, a composition containing the same, and a solar cell.

Description

Novel A-D-A triad compound, composition containing the same, and solar cell

The present invention relates to a novel A-D-A triad compound and a composition and solar cell including the same.

Polymer solar cells (PSCs) are attracting great attention as next-generation generators due to their solution processability, translucency, scalability, and the like. Recently, improved power conversion efficiency (PCE) of PSCs has been reported, for example, single-junction devices with PCEs elevated up to 17% have been reported due to advances in new materials and device designs. However, prior to commercialization, the stability of the PSC device, such as thermal, optical and mechanical stability, is low, and it is necessary to develop a technology capable of improving it. BHJ (bulk-heterojunction) mixtures of donor and acceptor center (D/A) materials suffer from severe morphological instability due to strong D/A incompatibility, resulting in weak D with sharp interfaces with poor adhesion and mechanical robustness. /A junction is formed.

PSCs are highly applicable to flexible and stretchable electronic devices, and having improved mechanical durability in PSC devices is an important factor for use in electronic devices. It is known that a cohesive or adhesive fracture energy ( Gc ) of 5 Jm ^-2 or more is required to cope with mechanical stress generated in the manufacturing process and operation. However, in most fullerene and non-fullerene small molecule acceptor-based PSCs, the G c of the BHJ active layer is lower than 1-2 Jm ^-2 .

Therefore, the D/A interface of a typical BHJ PSC should have sufficient morphological stability and mechanical robustness required for fabrication and maintainable operation. To date, two major approaches have been developed to improve the morphological and thermal stability of PSCs. (1) Direct cross-linkable moiety is introduced into the donor or acceptor structure, or (2) compatibilizers are introduced into the BHJ active layer. In the cross-linking approach, donor or acceptor materials with photo- or thermally-crosslinkable units are designed to freeze the BHJ conformation to improve morphological stability under light or thermal stress. In addition, crosslinkable molecules may be introduced as additives to the BHJ active layer. However, these crosslinkable units require high-energy thermal and/or photoactive activity, which can negatively affect the photovoltaic performance of PSCs. Moreover, BHJ active materials are brittle after crosslinking and can significantly reduce mechanical ductility to PSCs.

Another way is to develop and utilize a compatibilizer capable of enhancing the physical stabilization of the D/A interface in BHJ blends. For example, a compatibilizer of amphiphilic deblock copolymers having P3HT (poly(3-hexylthiophene)) and fullerene derivatives as p-type and n-type blocks has been reported, which is Suitable for improving thermal stability. In addition, various compatibilizers such as copolymers, end-gap polymers, small molecules and in situ compatibilizers have been reported and attempts have been made to improve the thermal stability of BHJ blends. However, the reported compatibilizers are difficult to produce because they require complex synthesis steps, and the diblock copolymer-based compatibilizers contain a significant amount of insulating moiety to incorporate fullerene derivatives into the second block. This degrades free charge generation and movement in BHJ activity, and may be difficult to apply universally in other material systems because it is limited to D/A material systems.

In order to solve the above-mentioned problems, the present invention is a novel compound, an A-D-A triad type small molecule, applied as a molecular compatibilizer that can improve the performance of a solar cell as well as improve thermal and mechanical properties. is to provide

The present invention is a composition for a solar cell, which can constitute an active layer of an organic solar cell, which can improve the efficiency, stability and mechanical robustness of the organic solar cell by applying the compound according to the present invention as a molecular compatibilizer. is to provide

The present invention is to provide a polymer solar cell comprising an active layer containing the compound according to the present invention and having improved efficiency, stability and mechanical robustness.

However, the problem to be solved by the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

According to one embodiment of the present invention, it relates to a compound represented by Formula 1 below.

[Formula 1]

(Wherein fullerene ^a and fullerene ^b are selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, respectively, and Ar ¹ and Ar ² are, respectively, substituted or is selected from unsubstituted phenyl and thienyl, R ¹ to R ⁴ are each selected from -C ₁ -C ₃₀ alkyl- and -C ₂ -C ₃₀ alkenyl-, A is thiophene and fused thiophene It is selected from the open.)

According to one embodiment of the present invention, the A may include at least one or more selected from the following.

,

,

,

,

,

,

,

,

및

and

(Wherein, R ⁵ to R ¹⁴ are each selected from hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, and C ₁ -C ₃₀ alkoxy, and n and m are, respectively, 1 to 10 It is an integer of 100.)

According to one embodiment of the present invention, fullerene ^a and fullerene ^b are each selected from C60, C70, C74, C76 and C78 fullerene moieties, and R ¹ to R ⁴ are, respectively, -C ₁ -C ₂₀ alkyl-, wherein Ar ¹ and Ar ² are, respectively, unsubstituted phenyl;

또는

The A is,

or

(Where, R ⁵ to R ¹⁴ are each selected from hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy, and n and m are each 1 to 100 is an integer of).

According to one embodiment of the present invention, the A is,

(여기서, R⁶, R⁸, R¹¹ 및 R¹³은, 각각, C₅-C₁₀ 알킬에서 선택되고, n 및 m은, 각각 1 내지 10의 정수이다.)인 것일 수 있다.

(Where, R ⁶ , R ⁸ , R ¹¹ and R ¹³ are each selected from C ₅ -C ₁₀ alkyl, and n and m are integers from 1 to 10, respectively.).

According to one embodiment of the present invention, a compound represented by Formula 1 below; conjugation system donor; and a fullerene-based acceptor; It relates to a composition for a solar cell comprising a.

[Formula 1]

(Wherein fullerene ^a and fullerene ^b are selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, respectively, and Ar ¹ and Ar ² are, respectively, substituted or is selected from unsubstituted phenyl and thienyl, R ¹ to R ⁴ are each selected from -C ₁ -C ₃₀ alkyl- and -C ₂ -C ₃₀ alkenyl-, A is thiophene and fused thiophene It is selected from the open.)

According to one embodiment of the present invention, the compound represented by Formula 1 may be included in an amount greater than 0% by weight to 30% by weight in the composition.

According to one embodiment of the present invention, the conjugated donor includes a conjugated polymer, a conjugated small molecule, or both, and the conjugated polymer and the conjugated small molecule are, respectively, a polybenzothiophene derivative, a poly It may include at least one selected from the group consisting of thiophene derivatives, poly(para-phenylene) derivatives, polyacetylene derivatives, polypyrrole derivatives, polyvinylcarbazole derivatives, polyaniline derivatives and polyphenylenevinylene derivatives.

According to one embodiment of the present invention, the conjugated donor is PTB7 ((poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene -2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]]), PTB7-Th((poly[4,8-bis(5- (2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3 ,4-b]thiophene-)-2-carboxylate-2-6-diyl)])), P3HT (poly(3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazole-4,7-diyl [4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-diyl]]),PBDB-T(poly[(2,6 -(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1 ',3'-di-2-thienyl-50,70-bis(2-ethylhexyl)benzo-[1',2'-c:4',5'-c']dithiophene-4,8-dione)) ]) and PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2- b :4,5- b ']dithiophene))- alt- (5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'- c :4' ,5′- c ′]dithiophene-4,8-dione)]) may include at least one selected from the group consisting of.

According to one embodiment of the present invention, the fullerene-based acceptor includes fullerene, a fullerene derivative, or both, and the fullerene is a group consisting of C60, C70, C74, C76, C78, C82, C84, C720 and C860 It includes at least one selected from, and the fullerene derivative may be selected from Chemical Formula 2 below.

[Formula 2]

(Wherein, fullerene is selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, Ar is selected from substituted or unsubstituted phenyl and thienyl, and R ¹ is -C ₁ -C ₂₀ alkyl-, and R ² is -OC ₁ -C ₁₂ alkyl and -OC ₁ -C ₁₂ alkyl-SH, R ² is selected from hydrogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy .)

According to one embodiment of the present invention, the fullerene-based acceptor may be included in 1% to 50% by weight of the composition.

According to an embodiment of the present invention, the mixing ratio of the compound of Formula 1 to the fullerene-based acceptor may be 0.1:1 to 1:1 (w:w).

According to one embodiment of the present invention, the ratio of the donor compound: the fullerene-based acceptor may be 1:0.001 to 20 (w:w).

According to one embodiment of the present invention, the first electrode; a second electrode; and a photoactive layer including at least one of the compounds of claim 1 formed between the first electrode and the second electrode.

The present invention provides a novel compound that is an A-D-A type small molecule, and the compound is applied to various types of BHJ blends as a molecular compatibilizer in a polymer solar cell (PSC) to improve thermal/mechanical properties and PSC performance. can improve This can satisfy the mechanical properties and optical and thermal stability required for commercialization of polymer solar cells. The compound according to the present invention can be provided as a multifunctional compound through the design of a core unit and an end group, which will provide a polymer solar cell with improved performance and stability as well as a polymer solar cell applicable to flexible and wearable devices. can

1A is a schematic representation of (a) the chemical structure of the compounds and blend system materials of the present invention and their location and function within the blend system, according to one embodiment of the present invention.
FIG. 1B shows (a) normalized thin film absorption spectra and (b) energy level diagrams of constituent materials of a compound, blend according to the present invention, according to one embodiment of the present invention.
Figure 2, according to an embodiment of the present invention, (a) JV curve, (b) diagram showing PCE distribution, (c) PTB7-Th: external quantum efficiency according to the change of 5TRh-PCBM content in PC ₇₁ BM that represents the curve.
3 shows JV curves of (a) PBDB-T:PC ₇₁ BM and (b) P3HT:PC ₆₁ BM according to changes in 5TRh-PCBM content according to an embodiment of the present invention.
Figure 4 shows (a) PTB7-Th:PC ₇₁ BM and (b) PBDBT:PC with 0 wt%, 5 wt%, and 10 wt% 5TRh-PCBM at 80 °C, according to an embodiment of the present invention. ₇₁ BM and P3HT:PC ₆₁ BM with 0 wt%, 10 wt% and 20 wt% 5TRh-PCBM at 150 °C with increasing annealing time.
5 shows (a) PTB7-Th:PC 71 BM and (a) PTB7-Th:PC ₇₁ BM with 0 wt% and 10 wt% of 5TRh-PCBM before and after thermal annealing (TA), according to an embodiment of the present invention. b) OM images of PBDB-T:PC ₇₁ BM blend, and (c) P3HT:PC ₆₁ BM blend with 0 wt % and 20 wt % of 5TRh-PCBM before and after heat treatment at 150° C. for 24 h. am.
6 shows PBDB-T:PC ₇₁ (a) not containing and (b) containing 10 wt% of 5TRh-PCBM according to an annealing time change (photon energy ¼ 284.4 eV) according to an embodiment of the present invention. The RSoXS profile of the BM blend is shown, and the RSoXS profile of the P3HT:PC ₆₁ BM blend with (d) and without (c) 20 wt% of the compatibilizer as a function of annealing time (photon energy ¼ 284.6 eV) it is shown
7 shows (a) 0 wt %, (b) 10 wt %, and (c) 20 wt % of 5TRh- annealed at 150° C. for 0 h, 12 h and 24 h, according to an embodiment of the present invention. A 2D GIXS pattern of a P3HT:PC ₆₁ BM blend with PCBM is shown.
8 shows, according to an embodiment of the present invention, (a) DCB test (Double cantilever beam test) and sample structure, (b) PTB7-Th:PC without and including 10 wt% of 5TRh-PCBM. Cohesive G c of ₇₁ BM blend and PBDB-T:PC ₇₁ BM blend.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, the terms used in this specification are terms used to appropriately express preferred embodiments of the present invention, which may vary according to the intention of a user or operator or customs in the field to which the present invention belongs. Therefore, definitions of these terms will have to be made based on the content throughout this specification. Like reference numerals in each figure indicate like elements.

Throughout the specification, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

Throughout the specification, when a certain component is said to "include", it means that it may further include other components rather than excluding other components.

Hereinafter, the novel compound of the present invention and its utilization will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

The present invention relates to a novel compound, and according to an embodiment of the present invention, the compound corresponds to a multifunctional compound designed as an A-D-A triad-type small molecule. For example, when the compound is applied as a compatibilizer, which is an additive of an organic solar cell, it may interact with a photovoltaic donor compound and an acceptor compound to improve thermal and mechanical stability and mechanical properties.

According to one embodiment of the present invention, the compound includes an oligothiophene-based segment as a core and a fullerene derivative as an end group, and can be applied as a functional additive, for example, a compatibilizer, in various blend systems. . For example, the oligothiophene-based segments contain thiophenes or fused thiophenes, which provide efficient, strong interactions with various types of donor compounds, and the fullerene derivatives preferentially interact with fullerene-based acceptors. can interact to improve the thermal and mechanical stability of the blend system.

According to one embodiment of the present invention, the compound may be a compound represented by Formula 1 below, an oligothiophene-rhodanine-based core and two fullerene derivative end groups at the ends. can include In other words, in order to develop an efficient compatibilizer, (1) it can be manufactured in high yield through a simple and reproducible synthetic route, and (2) it is possible to donate various photovoltaic cells so that it can be generally used in various efficient polymer solar cell (PSC) systems. and a donor and acceptor block capable of good interaction between the acceptor moieties, and also (3) contain minimal (or very few) insulating units to prevent/minimize negative effects on device performance. and (4) provide light harvesting ability that can improve the PCE of polymer solar cell (PSC) devices. In the compound of Formula 1 below, the two fullerene end groups interact non-covalently with acceptors such as PC ₆₁ BM and PC ₇₁ BM, and the oligothiophene core is π-conjugated with a π-π conjugated donor. It can provide intermolecular interactions, such as interactions and van der Waals forces, and can be located at the interface of the donor and acceptor to improve thermal stability (e.g., morphological stability to thermal stresses) and mechanical stability. there is. In addition, by providing the light-harvesting function, efficiency (eg, power conversion efficiency) and stability capable of maintaining stable performance of the PCS device may be provided.

[Formula 1]

As an example of the present invention, fullerene ^a and fullerene ^b are each selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, and fullerene ^a and fullerene ^b are the same as each other. may or may not be different. Preferably fullerene ^a and fullerene ^b may be selected from C60, C70, C74, C76 and C78 fullerene moieties, respectively.

As an example of the present invention, Ar ¹ and Ar ² are each selected from substituted or unsubstituted phenyl and thienyl, and may be the same as or different from each other. Preferably, each of Ar ¹ and Ar ² may be unsubstituted phenyl.

As an example of the present invention, R ¹ to R ⁴ are each selected from -C ₁ -C ₃₀ alkyl- and -C ₂ -C ₃₀ alkenyl-, wherein the alkyl is a straight-chain or branched-chain alkyl, and C ₁ -C _20; C ₁ -C ₁₅ ; or C ₁ -C ₁₀ alkyl. The alkenyl is straight-chain or branched-chain alkenyl, C ₂ -C ₂₀ ; C ₂ -C ₁₅ ; or C ₂ -C ₁₀ alkenyl.

As an example of the present invention, A is selected from thiophenes and fused thiophenes, and the fused thiophenes may include two or more thiophenes. For example, the A may include at least one or more selected from the following.

,

,

,

,

,

,

,

,

및

and

As an example of the present invention, each of R ⁵ to R ¹⁴ in the formula shown in the example of A may be selected from hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy. can The alkyl is straight-chain or branched-chain alkyl, C ₁ -C ₂₀ ; C ₁ -C ₁₅ ; or C ₂ -C ₁₀ alkyl. The alkenyl is straight-chain or branched-chain alkenyl, C ₂ -C ₂₀ ; C ₂ -C ₁₅ ; or C ₂ -C ₁₀ alkenyl. The alkoxy is C ₁ -C _20; C ₁ -C _15; or C ₂ -C ₁₀ alkoxy.

또는

일 수 있고, 더 바람직하게는 As an example of the present invention, n and m are, respectively, 1 to 100; 1 to 50; Or it may be selected from an integer of 1 to 10. The above-mentioned definition is selectively applied according to the description of the chemical formula given as an example of A above. Preferably, the A is

or

can be, more preferably

(Here, R ⁶ , R ⁸ , R ¹¹ and R ¹³ are each selected from C ₅ -C ₁₀ alkyl, and n and m may each be an integer of 1 to 10.).

The present invention relates to a composition comprising a compound according to the present invention. According to an embodiment of the present invention, the composition comprises a photovoltaic donor compound; acceptor compounds; And a compatibilizer additive containing at least one of the compounds according to the present invention; may be a blend of three or more components including. That is, the present invention can provide improved thermal stability and mechanical properties of a device while maintaining (or improving) high power conversion efficiency (PCE) by applying the compound according to the present invention as a compatibilizer, and commercialization of polymer solar cells. The required physical properties can be obtained.

According to one embodiment of the present invention, the compound, including one or more of the compounds represented by the formula (1), in the composition greater than 0% by weight to 30% by weight; 0.1% to 30% by weight; 0.5% to 30% by weight; Or it may be included in 1% by weight to 25% by weight. When included within the above range, a solar cell having improved stability and mechanical properties may be provided.

According to one embodiment of the present invention, the donor compound may be applied without limitation as long as it is an electron donor for photovoltaic cells applicable in the technical field of the present invention, and preferably a conjugated donor including a conjugated organic compound. am. As an example of the present invention, the conjugated donor is a conjugated polymer, a conjugated small molecule, or a conjugated donor including both, and specifically, the conjugated polymer and the conjugated small molecule are each At least one selected from the group consisting of polybenzothiophene derivatives, polythiophene derivatives, poly(para-phenylene) derivatives, polyacetylene derivatives, polypyrrole derivatives, polyvinylcarbazole derivatives, polyaniline derivatives and polyphenylenevinylene derivatives may contain more than Preferably, the conjugated donor is a thiophene-based polymer donor, for example, PTB7 ((poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5 -b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]]), PTB7-Th((poly[4,8 -bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)- 3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)])), P3HT (poly(3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazole- 4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-diyl]]), PBDB-T (poly [(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5 ,5-(1',3'-di-2-thienyl-50,70-bis(2-ethylhexyl)benzo-[1',2'-c:4',5'-c']dithiophene-4, 8-dione))]) and PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2- b : 4,5- b ']dithiophene))- alt- (5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2' -c :4',5'- c ']dithiophene-4,8-dione)]) may include at least one selected from the group consisting of.

As an example of the present invention, the donor compound is included in an amount of 1 to 50% by weight in the composition, and when included within the above content range, it can help improve the performance and stability of a solar cell.

According to one embodiment of the present invention, the acceptor compound includes a fullerene-based acceptor, and may include, for example, fullerene, a fullerene derivative, or both.

As an example of the present invention, the fullerene may include at least one selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720, and C860.

As an example of the present invention, the fullerene derivative may include at least one selected from Chemical Formula 2 below.

[Formula 2]

As an example of the present invention, in Formula 2, fullerene is selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, Ar is substituted or unsubstituted phenyl and thienyl is selected from, R ¹ is -C ₁ -C ₂₀ alkyl-, and R ² is -OC ₁ -C ₁₂ alkyl and -OC ₁ -C ₁₂ alkyl-SH, R ² is selected from hydrogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy can Preferably, the fullerene derivative is (6,6)-phenyl-C ₆₁ -butyric acid methyl ester [(6,6)-phenyl-C ₆₁ -butyric acid methyl ester; PCBM], (6,6)-phenyl-C ₇₁ -butyric acid methyl ester [(6,6)-phenyl-C ₇₁ -butyric acid methyl ester; C ₇₀ -PCBM], (6,6)-thienyl-C ₆₁ -butyric acid methyl ester [(6,6)-thienyl-C ₆₁ -butyric acid methyl ester; ThCBM], (6,6)-phenyl-C ₈₄ -butyric acid methyl ester [(6,6)-phenyl-C ₈₄ -butyric acid methyl ester; C ₈₄ -PCBM]) may include at least one selected from the group consisting of.

As an example of the present invention, the acceptor compound is included in 1 to 50% by weight of the composition, and when included within the above content range, it can help provide a solar cell with improved performance and stability.

As an example of the present invention, the mixing ratio of the compound of Formula 1 to the acceptor compound is 0.1:1 to 1:1 (w:w), and when it is included within the above range, the acceptor compound and the mixed phase are well formed, resulting in thermal and mechanical stability. It is possible to obtain the effect of improving the solar cell efficiency while maintaining the

As an example of the present invention, the ratio of the donor compound: the acceptor compound is 1: 0.001 to 20 (w: w); 1 : 0.001 to 5 (w:w); 1 : 0.01 to 5 (w:w); 1 : 0.1 to 3 (w:w); 1:1 to 3 (w:w); or 1:3 to 20 (w:w). When included within the above ratio range, the donor compound, the acceptor compound, and the compatibilizer and the mixed phase are well formed, so that mechanical properties are improved, the possibility of damage by external energy is low, and stable performance can be provided.

As an example of the present invention, the composition further includes a residual amount of an organic solvent, and the organic solvent may be applied without limitation as long as it is applicable in the technical field of the present invention without departing from the object of the present invention, for example , chlorobenzene, chloroform, paraxylene, dichlorobenzene, trichlorobenzene, hexane, THF, alcohol having 1 to 5 carbon atoms, acetone, water, and the like, but is not limited thereto.

As an example of the present invention, the composition, 50 ℃ or more; above 80 °C; Alternatively, after heat treatment at a temperature of 150 °C or higher, a critical strain energy release rate ( Gc ) value may be 1.47 Jm ^-2 or higher. That is, the composition maintains morphological stability under light and/or thermal stress by applying the compatibilizer represented by Formula 1 according to the present invention, and suppresses phase separation by strengthening the interface between the donor and the acceptor, thereby preventing phase separation. It is possible to improve the resistance to crack increase and separation according to. In addition, it is possible to improve the performance stability of the solar cell device by improving such mechanical robustness.

The present invention relates to an organic solar cell comprising the compound according to the present invention, and according to an embodiment of the present invention, the organic solar cell includes a first electrode; a second electrode; and a photoactive layer including at least one of the compounds of claim 1 formed between the first electrode and the second electrode. Components and manufacturing processes of each layer may be appropriately selected according to the above-mentioned form, provided that they do not deviate from the scope of the present invention.

As an example of the present invention, it is an inverted-type or conventional-type polymer solar cell, and the components and manufacturing process of each layer are the above-mentioned forms, provided they do not deviate from the scope of the present invention. can be selected appropriately.

As an example of the present invention, the active layer is formed on the inorganic thin film, the organic thin film or the electrode, and the active layer has a thickness of 1 nm or more; 10 nm or larger; 50 nm to 1000 nm; or 80 nm to 150 nm. For example, the organic thin film and the inorganic thin film may be applied without limitation as long as they form an electron transport layer and a hole transport layer applicable to a solar cell, or an inorganic oxide layer or a semiconductor layer.

As an example of the present invention, the electrode includes a first electrode (eg, an upper electrode) and a second electrode (eg, a lower electrode), and any electrode component applicable to an organic solar cell may be applied without limitation. The upper electrode is silver (Ag), copper (Cu), gold (Au), platinum (Pt), titanium (Ti), aluminum (Al), nickel (Ni), zirconium (Zr), iron (Fe ), it may include at least one selected from the group consisting of manganese (Mn) and magnesium (Mg). The lower electrode may include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Gallium Zinc Oxide (IGZO), Indium Tin Zinc Oxide; ITZO), Ga-doped Zinc Oxide (GZO), Al-doped Zinc Oxide (AZO), F-doped Tin Oxide (FTO), Zinc Oxide (Zinc Oxide) It may include at least one selected from the group consisting of Tin Oxide (ZTO), Indium Gallium Oxide (IGO), ZnO-Ga ₂ O ₃ , ZnO-A _{I 2} O ₃ , and SnO ₂ -Sb ₂ O ₃ However, it is not limited thereto.

As an example of the present invention, a metal oxide may be further included on the active layer. For example, Ti, Zn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, Pt, Ag, Rh, Cr, V and combinations thereof. It is an oxide of at least one metal selected from the group consisting of, more specifically, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), zinc tin oxide (Zinc Tin Oxide), gallium oxide ( Ga ₂ O ₃ ), tungsten oxide (WO ₃ ), aluminum oxide, titanium oxide, vanadium oxide (V ₂ O ₅ , VO ₂ , V ₄ O ₇ , V ₅ O ₉ , V ₂ O ₃ ) molybdenum oxide ( MoO ₃ or MoO _x ), Copper(II) Oxide: CuO), Nickel Oxide (NiO), Copper Aluminum Oxide (CAO, CuAlO ₂ ), Zinc Rhodium Oxide: ZRO, ZnRh ₂ O ₄ ), iron oxide, chromium oxide (CrO ₃ ), bismuth oxide, IGZO (Indium-Gallium Zinc Oxide), ZrO ₂ and the like, but is not limited thereto. Preferably it may be MoO ₃ , WO ₃ , V ₂ O ₅ and CrO ₃

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[Scheme 1]

Example

(1) Synthesis of 5TRh-OH

5TRh-OH was synthesized according to the above scheme. More specifically, formyl-functionalized oligothiophene core (1, oligothiophene core), 3- (6-hydroxyhexyl) rhodamine (2, 3- (6-hydroxyhexyl) rhodamine) and phenyl-C ₆₁ -butyric acid (PC ₆₁ BA, phenyl-C ₆₁ -butyric acid) is based on previous procedures (Y. Liu, J. Zhou, X. Wan and Y. Chen, Tetrahedron 2009, 65, 5209-5215., C. Nitsche, VN Schreier, MAM Behnam, A. Kumar, R. Bartenschlager and CDKlein, J. Med. Chem. Balawi, Z. Kan, M. Wohlfahrt, E. Levillain, P. Hudhomme, PM Beaujuge, F. Laquai, C. Cabanetos and P. Blanchard, Chem. Mater. 2018, 30, 3474-3485.) . Pyridine (1 mL, Pyridine) and piperidine (0.1 mL, piperidine) were mixed with compound (1) (0.5 g, 0.54 mmol) and compound ( 2) and the resulting mixture was heated under reflux for 12 hours. The reaction solution was cooled to room temperature and poured into methanol. The precipitated solid was filtered and washed several times with methanol. After purification by silica gel column chromatography (eluent: CH ₂ Cl ₂ /MeOH=98/2, v/v), 5TRh-OH (0.7 g, 95 %) was obtained as a dark red solid. ¹ H NMR (500 MHz, CDCl3): δ (ppm) 7.76 (s, 2H), 7.14 (s, 2H), 7.11 (s, 2H), 7.11 (s, 2H), 4.11 (t, 4H), 3.65 (t, 8H), 2.81 (t, 4H), 1.74-1.66 (m, 16H), 1.41-1.27 (m, 48H), 0.86 (m, 12H); 13C NMR (125 MHz, CDCL3): δ (PPM) 192.28, 167.58, 141.10, 140.50, 139.64, 137.46, 135.77, 135.10, 132.95, 132.23, 129.95, 126.43, 125.02, 120.39, 62.78 30.6, 30.2, 29.56, 29.52, 29.47, 29.42, 29.40, 29.32, 29.26, 26.93, 26.46, 25.23, 22.69, 22.68, 14.13.

(2) Synthesis of 5TRh-PCBM

5TRh-PCBM was synthesized according to Scheme 1 above, and more specifically, 4-Dimethylaminopyridine (DMAP, 0.135 g, 1.11 mmol) was dissolved in 5TRh-OH (0.3 g, 0.22 mmol), PC ₆₁ in o-dichloromethane (o-DCB, 10 mL). BA (0.499 g, 0.56 mmol) and 1,3-dicyclohexylcarbodiimide-4-dimethylaminopyridine (DCC) (0.230 g, 1.11 mmol) added. The resulting mixture was stirred at room temperature for 36 hours. The reaction solution was poured into 200 mL of methanol, and the precipitated solid was filtered and washed with methanol. Purified dark solid 5TRh-PCBM (0.18 g, 40.8 %) was obtained through silica gel column chromatography using chloroform as an eluent. ¹ H NMR (500 MHz, CDCl3): δ (ppm) 7.92 (m, 4H), 7.76 (s, 2H), 7.54 (m, 4H), 7.48 (m, 2H), 7.22 (s, 2H), 7.15 (s, 2H), 7.11 (s, 2H), 4.09 (m, 8H), 2.91 (m, 4H), 2.81 (m, 8H), 2.52 (m, 4H), 2.18 (m, 4H), 1.70 ( br, 16H), 1.40-1.25 (br, 48), 0.86 (m, 12H); 13C NMR (125 MHz, CDCl3): δ (ppm) 192.22, 173.12, 167.49, 148.83, 147.81, 145.84, 145.16, 145.12, 145.08, 144.99, 144.75, 144.66, 144.63, 144.46, 144.39, 143.98, 143.73, 143.10, 142.99, 142.95, 192.94, 142.89, 142.87, 142.21, 142.15, 142.09, 141.18, 140.96, 140.71, 140.57, 139.70, 138.05, 137.54, 137.52, 136.78, 135.81, 135.21, 132.99, 132.30, 132.13, 130.00, 128.43, 128.24, 126.53, 125.16, 120.41, 79.88, 64.57, 51.89, 44.58, 34.20, 33.65, 31.93, 31.90, 30.62, 30.30, 29.68, 29.54 22.48, 14.16.

(3) Preparation of bulk-heterojunction (BHJ)-PSC

PSC is a conventional-type device with ITO/PEDOT:PSS (AI4083)/active layer (P3HT:PC ₆₁ BM)/Al structure and ITO/ZnO/active layer (PTB7-Th:PC71BM) or (PBDB-T:PC71BM)/MoO It was fabricated as an inverted-type device with a ₃ /Ag structure. First, organics coated with indium tin oxide (ITO) were sonicated in detergent, acetone, deionized water and isopropyl alcohol (IPA) for 20 min each. Subsequently, UV ozone plasma treatment was performed on the ITO substrate for 15 minutes. In the case of conventional-type PSC, PEDOT:PSS (AI4083) was filtered through a 0.2 um PTFE filter, spin-coated on ITO at 3000 rpm for 40 seconds, and then annealed at 165 °C for 20 minutes in an air atmosphere. . Next, the device was moved into an N ₂ -filled glove box. A blend solution of P3HT:PC ₆₁ BM of chlorobenzene (mixing ratio = 1:0.8 by weight) was prepared with various contents (0wt%, 10wt%, 20wt%) of 5TRh-PCBM as a compatibilizer. manufactured. The blend solution stored at 85 °C was spin coated at 1250 rpm for 60 seconds in PEDOT:PSS. Prior to deposition of the upper electrode, solvent vapor annealing (SVA) using IPA was performed for 20 minutes.

Next, Al is thermally evaporated as a top electrode with a thickness of 100 nm under 3x10 ^-6 torr. For the inverted- _type device, _{the ZnO} layer was prepared by a sol-gel process, i.e. zinc acetate dihydrate ((( CH ₃ CO ₂ ) ₂ Zn(H ₂ O) ₂ , 99.9%, 1.5 g) and ethanolamine (HOCH ₂ CH ₂ NH ₂ , 99.5%, 0.405 mL) were dissolved by stirring for at least 24 hours, followed by hydrolysis reaction. (hydrolysis reaction) and aging were performed. The ZnO solution was spin-coated on the ITO substrate at 4000 rpm for 40 seconds to create a 30 nm thick ZnO layer, followed by thermal annealing in air at 215 °C for 20 minutes. After the film was heat treated, the device was transferred into an N ₂ -filled glove box. The blend solution of PTB7-Th:PC71BM (1:1.5 by weight) contained 5 vol% of chlorobenzene (total concentration: 25 mg/mL) and 1,8-diiodooctane (DIO) as an additive. ) on a 95 °C hotplate with 5 vol% of , and spin cast on an ITO/ZnO substrate at 2000 rpm for 60 seconds. A blend solution of PBDB-T:PC71BM (1:1 by weight) in o-DCB (total concentration: 20 mg/mL) with 3 vol% DIO additive was stirred at 90 °C and spun at 2000 rpm for 60 sec. has been coated Finally, 10 nm thick MoO ₃ and 120 nm thick Ag were deposited in high vacuum using thermal evaporation. The active area of the device is 0.164 cm ² .

To compare the thermal stability, the PCE of PTB7-Th:PC71BM PSC and PBDB-T:PC71BM PSC with various contents of 5TRh-PCBM (i.e., 0 to 20 wt%) were measured in a N ₂ -filled glovebox for various times. during annealing at 80 °C. In the case of P3HT:PC ₆₁ BM PSC, annealing was performed at a higher temperature of 150 °C to accelerate degradation. The BHJ active layer was spin-coated, and the device was stored under high pressure (<10 ⁻⁷ Torr) for at least 2 hours to remove residual solvent in the film.

The film was heated (at 80 ˚for the PTB7-Th:PC _{71 BM} and PBDB-T:PC ₇₁ BM PSCs and at 150 ˚for the P3HT:PC ₆₁ BM PSC), which excluded the influence of other factors related to thermal stability of the active layer shape (morphology), such as interlayer performance degradation.

ingredient

PC ₆₁ BM (PC ₇₁ BM) (Phenyl-C ₆₁ (or C71)-butyric acid methyl ester, and regio-regular (>99%)) and P3HT (poly(3-hexylthiophene-2,5-diyl)) are , were purchased from “Nano-C” and “TCI”, respectively. PTB7-Th(poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt- ((4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)] and PBDB-T (poly[(2,6-(4, 8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo-[1',2'-c:4',5'-c']dithiophene-4,8-dione))]) were each purchased from “1-Materials”.

(4) Characterization

DCB test (Double cantilever beam)

In order to measure the fracture toughness of the PSC by the DCB test, samples of the ITO glass/active layer/Au structure were fabricated. A 25 mm × 25 mm square sample was cut to a size of 8 mm × 25 mm, and then Au deposition was performed. The same ITO glass substrate was attached to the film on the ITO glass substrate using epoxy (Epo-Tek 353ND, Epoxy Technology). At ambient conditions at ~25 °C and ~30% RH, the glass-to-glass epoxy was cured for 72 hours. Next, a high-precision micromechanical test system (Delaminator Adhesion Test System, DTS Company, Menlo Park, USA) is used, load-displacement data are recorded under repetitive loading and unloading, and cohesive energy values are calculated. Calculated. The critical strain energy release rate ( Gc ) value for each a (debonded length) was calculated by the following equation.

[ceremony]

where C is specimen compliance (dδ/dp, specimen compliance), δ is the displacement of the beam tip, P _c is the critical load at which the load decreases during crack growth, E′ is the ITO glass substrate (= 76 GPa), B is the sample width (=8mm) and h is the half-height of each sample.

Characteristic analysis results are shown in FIGS. 1 to 8 . 1a shows the molecular structures of electron donors (P3HT, PTB7-Th, PBDB-T), acceptors (PC ₆₁ BM and PC ₇₁ BM) and 5TRh-PCBM compatibilizers used in the blend system of the example, ADA triad type The small molecule (5TRh-PCBM) contains an oligothiophene-rhodanine-based core and two fullerene derivatives at the ends. The 5TRh-OH molecule was synthesized with a yield of 76% through the “Knoevenagel condensation” process between compounds (1) and (2) in Scheme 1, and DCC (1,3-dicyclohexylcarbodiimide-4-dimethylaminopyridine) and DMAP (4-dimethylaminopyridine) ) was synthesized in a yield of 41% through the “Steglich esterification” process of 5TRh-OH and PC ₆₁ BA. The two fullerene end groups non-covalently interact with the PC ₆₁ BM/PC ₇₁ BM, and the oligothiophene core undergoes intermolecular interactions (i.e., π-π interactions with π-conjugated polymer donors and van der Waals forces). 5TRh-PCBM acts as a compatibilizer in the BHJ blend and is located at the D/A interface. In addition, 5TRh-PCBM exhibited a thermal decomposition temperature (T _d , decomposition temperature) at 390 °C in a N ₂ atmosphere in a TGA analysis and thus had excellent thermal stability.

In the UV-vis absorption spectrum of FIG. 1b, the compatibilizer 5TRh-PCBM shows two absorption peaks, the 520 nm peak is due to the 5TRh core, and the strong absorption peak below 400 nm is due to the PC ₆₁ BM end group. At the energy level, HOMO is influenced by the 5TRh core, and LUMO is influenced by the PC ₆₁ BM end group. That is, since oxidation occurs at the electron-rich 5TRh core and reduction occurs at the electron-poor PC ₆₁ BM moiety, which is non-conjugated. That is, the 5TRh-PCBM compatibilizer can act as a function of the third component, such as light-harvesting to form a three-component blend, and the dual function of 5TRh-PCBM can improve both device efficiency and morphological stability. .

PTB7-Th:PC ₇₁ BM PSC (ZnO/PTB7-Th:PC ₇₁ BM/MoO ₃ /Ag), PBDBT:PC ₇₁ BM PSC (ITO/ZnO/PBDB-T:PC ₇₁ BM/MoO ₃ /Ag) P3HT :PC ₆₁ BM PSC (ITO/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/P3HT:PC ₆₁ BM/Al) at AM 1.5G irradiation (100 mW cm ^-2 ) with various contents of 5TRh Table of measurement results of solar cell characteristics (open circuit voltage, short circuit current density, fill factor, PCE) in the PCBM compatibilizer and PTB7-Th:PC ₇₁ BM, PBDB-T:PC ₇₁ BM, and P3HT:PC ₆₁ BM blend systems 1 and 2 are shown.

It can be seen from FIG. 2 and Table 1 that the device performance significantly increased at 5 wt% and 10 wt% 5TRh-PCBM. The PTB7-Th:PC71BM:5TRh-PCBM blend shows higher PCE values of 10.09% (5 wt% 5TRh-PCBM) and 9.72% (10 wt% 5TRh-PCBM) than before addition of 5TRh-PCBM. The Jsc value also increased slightly from 17.88 ± 0.12 to 18.63 ± 0.04 (5 wt% 5TRh-PCBM) and 18.91 ± 0.23 mA cm ^-2 (10 wt% 5TRh-PCBM) due to the addition of light absorption by 5TRh-PCBM. The increased Jsc can be confirmed again in EQE (external quantum efficiency), and the EQE spectrum increases within the wavelength range of 300-400 nm and 500-600 nm, and shows two main absorption peaks by 5TRh-PCBM.

[Table 1]

Figure 3 shows the JV curves of (a) PBDB-T:PC ₇₁ BM and (b) P3HT:PC ₆₁ BM according to the change in 5TRh-PCBM content according to an embodiment of the present invention. In the curves, the PCE of the PBDB-T:PC ₇₁ BM and P3HT:PC ₆₁ BM blend systems showed improved light absorption, which was confirmed to have a positive effect on the PCE of various PSC systems due to the addition of 5TRh-PCBM.

The thermal stability of PSC by the addition of 5TRh-PCBM in FIG. 4 was evaluated, and in PTB7-Th:PC ₇₁ BM and PBDBT:PC ₇₁ BM PSCs containing various 5TRh-PCBM contents (0 wt% to 10 wt%) PCE annealed the film at 80 °C at various time intervals in a N ₂ -filled glove box, and P3HT:PC ₆₁ BM PSC annealed at 150 °C.

In (a) of FIG. 4, the PCE (annealed at 80 °C for 120 h) of the PTB7-Th:PC ₇₁ BM two-component system (not including 5TRh-PCBM) was reduced by 6 1% compared to the initial PCE. On the other hand, the PTB7-Th:PC ₇₁ BM device containing 5TRh-PCBM shows excellent thermal stability after the same annealing conditions. The PCE of PTB7-Th:PC ₇₁ BM with 5 wt% and 10 wt% of 5TRh-PCBM only decreased by 31% and 16%, respectively. In (b) and (c) of FIG. 4 , the PBDB-T:PC ₇₁ BM and P3HT:PC ₆₁ BM devices show improved thermal stability according to the addition of 5TRh-PCBM. The PCE of P3HT:PC ₆₁ BM with 20 wt% of 5TRh-PCBM only decreases by 6% after 120 h annealing and remains similar after annealing at 150 °C higher, but the P3HT:PC ₆₁ BM binary blend shows 64 decreased by %.

5 and 6, in order to confirm the thermal stability of the PSC by the addition of 5TRh-PCBM, optical microscopy (OM), resonant soft X-ray scattering (RSoXS) and grazing incidence Xray scattering (GIXS) of the active layer Film morphological characteristics were measured in nanometers to tens of microns.

In the OM images of (a) and (b) of FIG. 5, when 5TRh-PCBM is not added after annealing at 80 ° C, dark spots caused by PCBM aggregation and the occurrence and growth of a large number of aggregates according to the increase in annealing time appear, which results in phase separation of the two components. In (c) of FIG. 5, different morphological characteristics are shown depending on whether or not 5TRh-PCBM is added. For example, when 5TRh-PCBM is not added, various shapes such as aggregation of PCBM are found. That is, it can be confirmed that the 5TRh-PCBM compatibilizer provides high thermal stability in various PSC systems, stabilizes the blend shape, and suppresses phase separation.

In the RSoXS profile of FIG. 6 , it can be seen that the value of distance (d) increases rapidly after annealing at 80 ° C in the RSoXS profile of the PBDB-T:PC ₇₁ BM that does not contain 5TRh-PCBM. This is due to the diffusion of PC ₇₁ BM molecules into the PC ₇₁ BM rich phase by annealing. Morphological stability can be confirmed by the addition of 5TRh-PCBM to P3HT:PC ₆₁ BM. When 20 wt% of 5TRh-PCBM compatibilizer is added, no scattering peak shift or increase in intensity is observed after annealing at 150 °C and 48 h.

7 shows (a) 0 wt %, (b) 10 wt %, and (c) 20 wt % of 5TRh- annealed at 150° C. for 0 h, 12 h and 24 h, according to an embodiment of the present invention. 2D GIXS patterns of P3HT:PC ₆₁ BM blends with PCBM are shown. In the GIXS pattern of FIG. 7 _, 5TRh- It can be confirmed that the morphological stability of PCBM is improved, and q = about 0.7 and 1.4 Å ^-1 related to PC ₆₁ BM crystals in the P3HT:PC ₆₁ BM blend system without 5TRh-PCBM after annealing.

Fabrication of a PSC with high mechanical robustness is a prerequisite for stable operation of the device and for use in flexible and wearable generators. In FIG. 8, the DCB measurement method was used to measure G c (cohesive fracture energy) depending on whether or not 5TRh-PCBM was applied, and the G c of the as-cast PTB7-Th:PC ₇₁ BM film was 10 wt% of 5TRh-PCB The addition increased from 1.68 ± 0.33 J m ^-2 to 2.25 ± 0.25 J m ^-2 without annealing. After annealing of the film, it increased from 1.47 ± 0.13 J m ^-2 to 2.73 ± 0.47 J m ^-2 with 5TRh-PCBM.

The pristine PTB7-Th:PC ₇₁ BM tends to break the film more easily due to strong phase separation, and when the compatibilizer according to the present invention is added, the D/A interface can be strengthened and macroscopic phase separation can be suppressed. there is. If the PBDB-T:PC ₇₁ BM blend system has a similar trend, the G c value after annealing in the PBDB-T:PC ₇₁ BM film is 1.06 ± 0.14 J m ^-2 to 2.93 after addition of 10 wt% 5TRh-PCBM. ± 0.15 J m ^-2 (2.8-fold increase) increased. The selective localization of 5TRh-PCBM at the D/A interface modifies the weak D/A interface to reduce the interface tension. This feature can increase the resistance to crack growth and separation between the two phases and improve the mechanical PSC robustness.

The present invention provides a novel multifunctional compatibilizer (5TRh-PCBM) based on an acceptor-donor-acceptor (ADA) type structure that is very effective in improving thermal and mechanical stability when applied to various efficient polymer solar cells (PSCs). can provide The molecular compatibilizer is composed of a 5T (pentathiophene)-based D core and a fullerene derivative-based A terminal unit, and various polymer donors including thiophene and/or fused thiophene units and fullerene-based acceptors can interact preferentially. In order to demonstrate the broad usefulness of the 5TRh-PCBM compatibilizer, the present invention not only includes the existing P3HT:PC ₆₁ BM, but also efficiently PTB7-Th:PC ₇₁ BM and PBDB-T:PC ₇₁ BM-based PSCs It has been successfully applied to various types of PSCs, including Addition of 5TRh-PCBM from 5 wt% to 20 wt% significantly improved the thermal stability and mechanical properties of all these PSC systems. For example, the PCE of P3HT:PC ₆₁ BM PSC containing 20 wt% of 5TRh-PCBM maintained 94% of the initial value after 120 hours at 150 °C. In the case of P3HT:PC ₆₁ BM PSCs without 5TRh-PCBM, it was reduced by 64%. In addition, the cohesive G c values of the PTB7-Th:PC ₇₁ BM and PBDB-T:PC ₇₁ BM blends were improved 1.3-fold and 2.1-fold, respectively, by adding 10 wt% of 5TRh-PCBM. Unlike previously reported compatibilizers, the addition of 5TRh-PCBM at 5 wt% and 10 wt% in the present invention greatly improves the thermal and mechanical stability of all tested PSCs, especially PTB7-Th:PC ₇₁ BM The addition of 5 wt% 5TRh-PCBM to the blend shows an increase in PCE from 9.37% to 10.09%, which is due to the addition of light harvesting effect. The effect of the 5TRh-PCBM compatibilizer according to the present invention can be confirmed on the optical, morphological and photovoltaic properties of PSC.

As described above, although the embodiments have been described with limited examples and drawings, those skilled in the art can make various modifications and variations from the above description. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a different form than the described method, or substituted or replaced by other components or equivalents. Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

Claims (13)

A compound represented by Formula 1 below:

[Formula 1]

wherein fullerene ^a and fullerene ^b are selected from the C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, respectively;
Ar ¹ and Ar ² are each selected from unsubstituted phenyl and thienyl;
R ¹ to R ⁴ are each selected from -C ₁ -C ₃₀ alkyl- and -C ₂ -C ₃₀ alkenyl-;
A includes at least one selected from the following.)

,

,

,

and

(Wherein, R ⁵ to R ¹⁴ are each selected from hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, and C ₁ -C ₃₀ alkoxy, and n and m are, respectively, 1 to 10 It is an integer of 100.)
delete According to claim 1,
wherein fullerene ^a and fullerene ^b are selected from C60, C70, C74, C76 and C78 fullerene moieties, respectively;
R ¹ to R ⁴ are each -C ₁ -C ₂₀ alkyl-;
Ar ¹ and Ar ² are each unsubstituted phenyl;

The A is,

or

(Where, R ⁵ to R ¹⁴ are each selected from hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy, and n and m are each 1 to 100 is an integer of).
compound.
According to claim 1,
The A is,

(Where, R ⁶ , R ⁸ , R ¹¹ and R ¹³ are each selected from C ₅ -C ₁₀ alkyl, n and m are each an integer of 1 to 10,
R ⁹ and R ¹⁰ are each hydrogen),
compound.
A compound represented by Formula 1 of claim 1;
conjugation system donor; and
fullerene-based acceptor;
A composition for a solar cell comprising a.
According to claim 5,
The compound represented by Formula 1,
Which is contained in more than 0% by weight and less than 30% by weight of the composition,
A composition for a solar cell.
According to claim 5,
The conjugated donor includes a conjugated polymer, a conjugated small molecule, or both,
The conjugated polymer and the conjugated small molecule are, respectively, polybenzothiophene derivatives, polythiophene derivatives, poly(para-phenylene) derivatives, polyacetylene derivatives, polypyrrole derivatives, polyvinylcarbazole derivatives, polyaniline derivatives and poly To include at least one selected from the group consisting of phenylene vinylene derivatives,
A composition for a solar cell.
According to claim 5,
The conjugated donor,
PTB7((poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[ (2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]]), PTB7-Th((poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1, 2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2- 6-diyl)])), P3HT (poly(3-hexylthiophene)), PCPDTBT (Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta [2,1-b:3,4-b']dithiophene-2,6-diyl]]),PBDB-T(poly[(2,6-(4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-50,70- bis(2-ethylhexyl)benzo-[1',2'-c:4',5'-c']dithiophene-4,8-dione))]) and PM6 (poly[(2,6-(4, 8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2- b :4,5- b ']dithiophene))- alt- (5,5-(1 ',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'- c :4',5'- c ']dithiophene-4,8-dione) ]), which includes at least one selected from the group consisting of
A composition for a solar cell.
According to claim 5,
The fullerene-based acceptor,
containing fullerenes, fullerene derivatives or both;
The fullerene includes at least one selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720 and C860,
The fullerene derivative is selected from Formula 2 below, a composition for a solar cell:

[Formula 2]

(Wherein, fullerene is selected from C60, C70, C74, C76, C78, C82, C84, C720 and C860 fullerene moieties, Ar is selected from substituted or unsubstituted phenyl and thienyl, and R ¹ is -C ₁ -C ₂₀ alkyl-, and R ² is -OC ₁ -C ₁₂ alkyl and -OC ₁ -C ₁₂ alkyl-SH, R ² is selected from hydrogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl and C ₁ -C ₃₀ alkoxy .)
According to claim 5,
The fullerene-based acceptor,
Which is included in 1% to 50% by weight of the composition,
A composition for a solar cell.
According to claim 5,
The mixing ratio of the compound of Formula 1 to the fullerene acceptor is
0.1: 1 to 1: 1 (w: w),
A composition for a solar cell.
According to claim 5,
The ratio of the donor compound: the fullerene acceptor is
1: 0.001 to 20 (w: w), the composition for a solar cell.
a first electrode;
a second electrode; and
a photoactive layer comprising at least one of the compounds of claim 1 formed between the first electrode and the second electrode;
including,
Polymer solar cell.

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