KR102489048B1 - Compound and organic solar cell comprising the same - Google Patents

Abstract

The present specification relates to a compound represented by Formula 1 and an organic solar cell including the same.

Description

Compound and organic solar cell containing the same {COMPOUND AND ORGANIC SOLAR CELL COMPRISING THE SAME}

The present specification relates to a compound and an organic solar cell including the same.

An organic solar cell is a device capable of directly converting solar energy into electrical energy by applying a photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells according to the materials constituting the thin film. A typical solar cell is made of a p-n junction by doping crystalline silicon (Si), an inorganic semiconductor. Electrons and holes generated by absorbing light diffuse to the p-n junction and are accelerated by the electric field to move to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit and the solar power entered into the solar cell, and has been achieved up to 24% when measured under the currently standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells already show limitations in economic feasibility and supply and demand in terms of materials, organic semiconductor solar cells that are easy to process, inexpensive, and have various functionalities are in the limelight as a long-term alternative energy source.

It is important for a solar cell to increase its efficiency so that it can output as much electrical energy as possible from solar energy. There are problems such as excessive phase separation, low absorption in the visible light region, and low thermal stability.

Accordingly, many examples of organic solar cells using non-fullerene-based compounds as electron acceptor materials have recently been published, and in particular, research on small molecule electron acceptor materials that can be designed and synthesized in various molecules is being actively conducted.

Two-layer organic photovoltaic cell (C.W.Tang, Appl. Phys. Lett., 48, 183.(1986))

The present specification provides a compound and an organic solar cell including the same.

The present specification provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

n1 and n2 are integers from 1 to 8;

[Pull1] and [Pull2] are the same as or different from each other, and each independently acts as an electron attractor,

L1 and L2 are the same as or different from each other, and each independently has the following structure,

In the above structure,

는 다른 치환기 또는 결합부에 결합되는 부위이고,

is a site bonded to another substituent or linkage,

m1 to m4 are each an integer from 0 to 3;

Y1 to Y10 are the same as or different from each other, and are each independently CRR', NR, O, SiRR', PR, S, GeRR', Se or Te,

R1 to R4, R and R' are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Another exemplary embodiment of the present specification is a first electrode;

a second electrode provided to face the first electrode; and

It is provided between the first electrode and the second electrode and includes one or more organic material layers including a photoactive layer,

At least one layer of the organic material layer provides an organic solar cell comprising the compound.

The compound according to one embodiment of the present specification may have effects of reducing a band gap and increasing an amount of light absorption. Accordingly, when applied to an organic solar cell, high current value Isc may be exhibited, and thus excellent efficiency may be exhibited.

The compound according to one embodiment of the present specification is excellent in stability while implementing high efficiency.

1 is a diagram illustrating an organic solar cell according to an exemplary embodiment of the present specification.
2 is a diagram showing the MS spectrum of Compound A-1.
Figure 3 is a diagram showing the MS measurement results of compound B-1.
4 is a diagram showing NMR measurement results of compound B-1.
5 is a diagram showing the MS measurement results of compound B-2.
6 is a diagram showing NMR measurement results of compound B-2.
7 is a diagram showing MS measurement results of Compound 1-1.
8 is a diagram showing NMR measurement results of Compound 1-1.
9 is a diagram showing current density according to voltage of an organic solar cell manufactured in one embodiment of the present specification.

Hereinafter, this specification will be described in detail.

An exemplary embodiment of the present specification provides a compound represented by Formula 1 above.

Since the compound has a structure in which a linker, which is a ladder-type plate-like structure, is bent based on spirofluorene, phase separation from the donor is prevented when applied as an acceptor compared to spherical fullerene derivatives. restrain Therefore, in addition to increasing device stability, the planar direction can be oriented in various directions, thereby improving charge transfer.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

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

Examples of substituents in the present specification are described below, but are not limited thereto.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site to be bonded to another substituent or binding part.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; imide group; amide group; carbonyl group; ester group; hydroxy group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; alkenyl group; silyl group; Siloxane group; boron group; amine group; Arylphosphine group; phosphine oxide group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto It is not.

In the present specification, the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is 10-30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heterocyclic group includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Examples include a phenanthroline group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and each independently has the following structure.

in the structure

는 다른 치환기 또는 결합부에 결합되는 부위이고,

is a site bonded to another substituent or linkage,

m1 to m4 are each an integer from 0 to 3;

Y1 to Y10 are the same as or different from each other, and are each independently CRR', NR, O, SiRR', PR, S, GeRR', Se or Te,

R1 to R4, R and R' are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

이다.In one embodiment of the present specification, when m1 to m4 of L1 and L2 are 0, L1 and L2 are

to be.

이다.In one embodiment of the present specification, when m1 and m4 of L1 and L2 are 0 and m2 and m3 are 1, L1 and L2 are

to be.

이다.In one embodiment of the present specification, when m2 and m3 of L1 and L2 are 0 and m1 and m4 are 1, L1 and L2 are

to be.

이다.In one embodiment of the present specification, when m1 to m4 of L1 and L2 is 1, L1 and L2 are

to be.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and each independently has any one of the following structures.

in the structure

, m1, m2, Y1 내지 Y10 및 R1 내지 R4는 전술한 바와 동일하다.

, m1, m2, Y1 to Y10 and R1 to R4 are the same as described above.

이다.In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and each independently

to be.

이다.In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and each independently

to be.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently represents a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently represents a substituted or unsubstituted thiophene group.

In one embodiment of the present specification, the L1 and L2 are any one of the following structures.

In the above structure, Y1, Y2, Y5, Y6, Y9 and Y10 are the same as or different from each other, and are each independently CRR', NR, O, SiRR', PR, S, GeRR', Se or Te,

R and R' are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, Formula 1 is represented by any one of Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

[Pull1], [Pull2], [Pull1'], and [Pull2'] are the same as or different from each other, and are each independently an electron withdrawing group,

Y1, Y2, Y5, Y6, Y9, Y10, Y11, Y12, Y15, Y16, Y19, Y20, Y1', Y2', Y5', Y6', Y9', Y10', Y11', Y12', Y15' , Y16', Y19' and Y20' are the same as or different from each other, and are each independently CRR', NR, O, SiRR', PR, S, GeRR', Se or Te,

R1 to R4, R11 to R14, R1' to R4' and R11' to R14', R and R' are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 to 2-4.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,

[Pull1], [Pull2], [Pull1'] and [Pull2'] are the same as or different from each other, and each independently acts as an electron attractor,

Y1, Y2, Y5, Y6, Y9, Y10, Y11, Y12, Y15, Y16, Y19, Y20, Y1', Y2', Y5', Y6', Y9', Y10', Y11', Y12', Y15' , Y16', Y19' and Y20' are the same as or different from each other, and are each independently CRR', NR, O, SiRR', PR, S, GeRR', Se or Te,

R1 to R4, R11 to R14, R1' to R4', R11' to R14', R and R' are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, each of Y1 to Y10 is S.

In an exemplary embodiment of the present specification, each of Y1', Y2', Y5', Y6', Y9', Y10', Y11', Y12', Y15', Y16', Y19' and Y20' is S.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 3-1 to 3-4 below.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,

[Pull1], [Pull2], [Pull1'] and [Pull2'] are the same as or different from each other, and are groups each independently acting as an electron attractor.

In one embodiment of the present specification, the Pull1 and Pull2 are the same as or different from each other, and each independently has any one of the following structures.

In the above structure,

a, b and c are each an integer from 1 to 4;

When a, b, and c are each 2 or more, the structures in parentheses are the same as or different from each other,

R10 to R18 are the same as or different from each other, and each independently hydrogen; halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

이며, R17은 수소 또는 할로겐기이다.In one embodiment of the present specification, the Pull1 and Pull2 are the same as or different from each other, and each independently

And, R17 is hydrogen or a halogen group.

이며, R17은 수소이다.In one embodiment of the present specification, the Pull1 and Pull2 are identical to each other, and each

, and R17 is hydrogen.

이며, R17은 불소이다.In one embodiment of the present specification, the Pull1 and Pull2 are identical to each other, and each

, and R17 is fluorine.

In one embodiment of the present specification, the compound represented by Formula 1 has any one of the following structures.

An exemplary embodiment of the present specification includes a first electrode;

a second electrode provided to face the first electrode; and

It is provided between the first electrode and the second electrode and includes one or more organic material layers including a photoactive layer,

At least one layer of the organic material layer provides an organic solar cell comprising the compound.

In one embodiment of the present specification, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron donor and the electron acceptor. The generated holes are transported to the anode through the electron donating layer.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification including a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105 to be.

In one embodiment of the present specification, the organic solar cell may further include an additional organic material layer. The organic solar cell may reduce the number of organic material layers by using organic materials having multiple functions at the same time.

In one embodiment of the present specification, the organic solar cell includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transport layer and/or an electron transport layer.

In one embodiment of the present specification, the photoactive layer includes the compound.

In one embodiment of the present specification, the photoactive layer includes an electron donor and an electron acceptor, and the electron acceptor includes the compound.

In one embodiment of the present specification, the organic solar cell includes one or two or more organic material layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generating layer, an electron blocking layer, an electron injection layer, and an electron transport layer. more includes

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode. In another exemplary embodiment of the present specification, the first electrode is a cathode and the second electrode is an anode.

In one embodiment of the present specification, the organic solar cell may be arranged in the order of the substrate, cathode, photoactive layer and anode, or may be arranged in the order of the substrate, anode, photoactive layer and cathode, but is not limited thereto.

In one embodiment of the present specification, the organic solar cell has a normal structure. Specifically, in one embodiment of the present specification, when the organic solar cell has a normal structure, the organic solar cell includes a substrate, a first electrode, a hole transport layer, an organic material layer including a photoactive layer, an electron transport layer, and a second electrode. It can be a structure provided sequentially. At this time, a hole transport layer may be additionally provided between the photoactive layer and the second electrode.

In one embodiment of the present specification, the organic solar cell has an inverted structure. In one embodiment of the present specification, when the organic solar cell has an inverted structure, the organic solar cell includes a substrate, a first electrode, an electron transport layer, an organic material layer including a photoactive layer, a hole transport layer, and a second electrode sequentially. It may be a provided structure.

In one embodiment of the specification, the electron donor may use a material applied in the art, for example, poly 3-hexyl thiophene (P3HT), PCDTBT (poly[N-9' -heptadecanyl-2,7-carbazole-alt-5,5-(4'-7'-di-2-thienyl-2',1',3'-benzothiadiazole)]), PCPDTBT (poly[2,6- (4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]) , PFO-DBT (poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4,7-bis(thiophene-2-yl)benzo-2,1,3-thiadiazole)]) , 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]]), PSiF-DBT(Poly[2,7-(9,9-dioctyl-dibenzosilole)-alt-4,7-bis(thiophen- 2-yl)benzo-2,1,3-thiadiazole]), 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 at least one material selected from the group consisting of poly(benzodithiophene-benzotriazole) (PBDBT).

In one embodiment of the present specification, the electron donor and electron acceptor constitute a bulk heterojunction (BHJ). The electron donor material and the electron acceptor material may be mixed in a ratio (w/w) of 1:10 to 10:1. Specifically, the electron donor material and the electron acceptor material may be mixed in a ratio (w/w) of 1:1 to 1:10, and more specifically, the electron donor material and the electron acceptor material are 1:1 to 1:5 It can be mixed in a ratio (w / w). If necessary, the electron donor material and the electron acceptor material may be mixed in a ratio (w/w) of 1:1 to 1:3.

In one embodiment of the present specification, the photoactive layer has a bilayer structure including an n-type organic compound layer and a p-type organic compound layer, and the n-type organic compound layer includes the compound.

In the present specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is not limited as long as it is a substrate commonly used in organic solar cells. Specifically, there are glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited to this.

The first electrode may be made of a material that is transparent and has excellent conductivity, but is not limited thereto. metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The method of forming the first electrode is not particularly limited, but is applied to one surface of the substrate or in the form of a film using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. It can be formed by coating.

When the first electrode is formed on the substrate, it may undergo cleaning, moisture removal, and hydrophilic modification.

For example, the patterned ITO substrate is sequentially cleaned with detergent, acetone, and isopropyl alcohol (IPA), and then heated on a heating plate at 100° C. to 150° C. for 1 minute to 30 minutes, preferably at 120° C. for 10 minutes to remove moisture. After drying and when the substrate is completely cleaned, the surface of the substrate is modified to be hydrophilic.

Through the surface modification as described above, the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. In addition, when reforming, it is easy to form a polymer thin film on the first electrode, and the quality of the thin film may be improved.

Pretreatment technologies for the first electrode include a) surface oxidation method using parallel plate type discharge, b) surface oxidation method through ozone generated using UV ultraviolet rays in a vacuum state, and c) There are methods of oxidation using oxygen radicals.

One of the above methods may be selected according to the state of the first electrode or substrate. However, regardless of which method is used, it is desirable to prevent oxygen escape from the surface of the first electrode or the substrate and to suppress the remaining moisture and organic matter as much as possible. At this time, the practical effect of the pretreatment can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV may be used. At this time, after ultrasonic cleaning, the patterned ITO substrate is baked on a hot plate, dried well, put into a chamber, and a UV lamp is operated to generate oxygen gas by reacting with UV light to generate ozone. The patterned ITO substrate can be cleaned.

However, the surface modification method of the patterned ITO substrate in the present specification does not need to be particularly limited, and any method may be used as long as the method oxidizes the substrate.

The second electrode may be a metal having a low work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; It may be a multi-layered material such as LiF/Al, LiO ₂ /Al, LiF/Fe, Al:Li, Al:BaF ₂ , Al:BaF ₂ :Ba, but is not limited thereto.

The second electrode may be deposited and formed inside a thermal evaporator exhibiting a vacuum degree of 5x10 ^{- 7} torr or less, but is not limited to this method.

The material of the hole transport layer and/or the electron transport layer serves to efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material is PEDOT: PSS (Poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO _x ); vanadium oxide (V ₂ O ₅ ); nickel oxide (NiO); And tungsten oxide (WO _x ) It may be the like, but is not limited only to these.

The electron transport layer material may be electron-extracting metal oxides, and specifically, metal complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; metal complexes including Liq; LiF; Ca; titanium oxide (TiO _x ); zinc oxide (ZnO); and cesium carbonate (Cs ₂ CO ₃ ).

The photoactive layer may be formed by dissolving a photoactive material such as an electron donor and/or an electron acceptor in an organic solvent and then using a method such as spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, or the like. It is not limited to the method.

The method for preparing the compound and the preparation of an organic solar cell including the same will be described in detail in Preparation Examples and Examples below. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Preparation Example 1.

(1) Preparation of Compound A-1

Compound A (2.00 g, 4.22 mmol), bis (pinacolato) diboron (2.36 g, 9.30 mmol), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II)([1,1'-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), Pd(dppf)Cl ₂ )(0.31g, 0.42mmol), 1,1'-bis(diphenylphosphino)ferrocene ( 1,1′-bis(diphenylphosphino)ferrocene, dppf) (0.234 g, 0.42 mmol), potassium acetate (KOAc) (2.55 g, 26 mmol) and 70 mL of 1,4-dioxaen The flask was filled with nitrogen and reacted at 70° C. for 18 hours. After cooling to room temperature, the product was extracted with methylene chloride (MC) and thoroughly washed with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1 (eluent)) to obtain 1.58 g of compound A-1. (Yield: 27.6%) GC-MS: 568.2

2 is a diagram showing the MS measurement results of Compound A-1.

(2) Preparation of compound B-1

Phosphoryl chloride (POCl ₃ ) (0.56ml, 6mmol) was added to 0.54mL of dimethylformamide (DMF) and stirred for 1 hour. After dissolving compound B (5.13g, 5.0mmol) in 50mL of 1,2-dichloroethan (DCE), the POCl ₃ solution was injected at room temperature and stirred for 5 hours. The product was extracted with methylene chloride (MC) and washed sufficiently with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1 (eluent)) to obtain 2.56 g of compound B-1. (Yield: 48.7%) MALDI-TOF MS: 1046.5

Figure 3 is a diagram showing the MS measurement results of compound B-1.

4 is a diagram showing NMR measurement results of compound B-1.

(3) Preparation of compound B-2

12 hours after injecting n-bromosuccinimide (NBS) (0.5 g, 2.81 mmol) into a solution of compound B-1 (2.7 g, 2.58 mmol) dissolved in 50 mL tetrahydrofuran (THF). while stirring. The product was extracted with methylene chloride (MC) and washed sufficiently with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1 (eluent)) to obtain 2.8 g of compound B-2. (Yield: 96.3%) MALDI-TOF MS: 1124.4

5 is a diagram showing the MS measurement results of compound B-2.

6 is a diagram showing NMR measurement results of compound B-2.

(4) Preparation of compound 1-1.

Compound A-1 (0.38 g, 0.67 mmol), Compound B-2 (1.70 g, 1.51 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) (0.031 g, 0.27 mmol) ), 2M potassium carbonate (K ₂ CO ₃ ) (4mL, 8mmol) and THF (16mL) were put in a flask, filled with nitrogen, and reacted at 70°C for 24 hours. After cooling to room temperature, the product was extracted with methylene chloride (MC) and thoroughly washed with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane: dichloromethane = 1: 1 (eluent)) to obtain 1.29 g of compound 1-1. (Yield: 80%) MALDI-TOF MS: 2405.3

7 is a diagram showing MS measurement results of Compound 1-1.

8 is a diagram showing NMR measurement results of Compound 1-1.

(5) Preparation of Compound 1

2mL of pyridine was added to a mixed solution of Compound 1-1 (0.36g, 0.15mmol) and Compound D (0.29g, 1.5mmol) in 20mL of chloroform (CHCl ₃ ) under a nitrogen (N ₂ ) atmosphere. . After refluxing this mixed solution for 24 hours under a nitrogen atmosphere, it was extracted with dichloromethane (CH ₂ Cl ₂ ) and washed with water. After solvent removal, recrystallization through methyl chloride (MC) / methanol, and the product is a silica gel column using hexane, ethyl acetate, and chloroform (CHCl ₃ ) as an eluent It was purified through chromatography using a gel column. The resulting solid was recrystallized through chloroform. Thereafter, washed with methanol and dried in vacuum to obtain 318 mg of Compound 1. (Yield: 77%) (MALDI-TOF MS: 2757.3 g/mol)

Preparation Example 2.

(1) Preparation of compound 2-1

Compound A-1 (0.38 g, 0.67 mmol), Compound C-1 (1.74 g, 1.51 mmol), Pd(pph ₃ ) ₄ (0.031 g, 0.27 mmol), 2M K ₂ CO ₃ (4 mL, 8 mmol) and THF (16mL) was put into a flask, filled with nitrogen, and reacted at 70°C for 24 hours. After cooling to room temperature, the product was extracted with methylene chloride (MC) and thoroughly washed with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane : dichloromethane = 1 : 1 (eluent)) to obtain compound 2-1. (Yield: %) MALDI-TOF MS: 2452.3

(2) Preparation of compound 2

2mL of pyridine was added to a mixed solution of compound 2-1 (0.32g, 0.12mmol) and compound E (0.27g, 1.2mmol) in 20mL of chloroform (CHCl ₃ ) under a nitrogen (N2) atmosphere. After refluxing this mixed solution for 24 hours under a nitrogen atmosphere, it was extracted with dichloromethane (CH ₂ Cl ₂ ) and washed with water. After solvent removal, recrystallization through methyl chloride (MC) / methanol, and the product is a silica gel column using hexane, ethyl acetate, and chloroform (CHCl ₃ ) as an eluent It was purified through chromatography using a gel column. The resulting solid was recrystallized through chloroform. Thereafter, washed with methanol and dried under vacuum conditions to obtain 321 mg of Compound 2. (Yield: 86%) (MALDI-TOF MS: 3101.2 g/mol)

Preparation Example 3.

(1) Preparation of compound 3-1

Compound A-2 (0.41 g, 0.50 mmol), Compound B-2 (3.38 g, 3.00 mmol), Pd(pph ₃ ) ₄ (0.035 g, 0.03 mmol), 2M K ₂ CO ₃ (4 mL, 8 mmol) and THF (16mL) was put into a flask, filled with nitrogen, and reacted at 70°C for 24 hours. After cooling to room temperature, the product was extracted with methylene chloride (MC) and thoroughly washed with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Thereafter, purification was performed by silica gel column chromatography (hexane:dichloromethane = 1:2 (eluent)) to obtain 570 mg of compound 3-1. (Yield: 25%) MALDI-TOF MS: 4493.5

(2) Preparation of compound 3

2mL of pyridine was added to a mixed solution of Compound 3-1 (0.36g, 0.08mmol) and Compound D (0.15g, 0.80mmol) in 40mL of chloroform (CHCl ₃ ) under a nitrogen (N ₂ ) atmosphere. . After refluxing this mixed solution for 24 hours under a nitrogen atmosphere, it was extracted with dichloromethane (CH ₂ Cl ₂ ) and washed with water. After solvent removal, recrystallization through methyl chloride (MC) / methanol, and the product is a silica gel column using hexane, ethyl acetate, and chloroform (CHCl ₃ ) as an eluent It was purified through chromatography using a gel column. The resulting solid was recrystallized through chloroform. Thereafter, washed with methanol and dried in vacuum to obtain 280 mg of Compound 3. (Yield: 67%) (MALDI-TOF MS: 5198.5 g/mol)

Preparation Example 4.

(1) Preparation of compound 4-1

Compound A-2 (0.37 g, 0.45 mmol), Compound C-1 (3.10 g, 2.70 mmol), Pd (pph ₃ ) ₄ (0.035 g, 0.03 mmol), 2M K ₂ CO ₃ (4 mL, 8 mmol) and THF (16mL) was put into a flask, filled with nitrogen, and reacted at 70°C for 24 hours. After cooling to room temperature, the product was extracted with methylene chloride (MC) and thoroughly washed with water. The extracted organic matter was dried using anhydrous MgSO ₄ . Then, it was purified by silica gel column chromatography (hexane : dichloromethane = 1 : 2 (eluent)) to obtain 420 mg of Compound 4-1. (Yield: 19%) MALDI-TOF MS: 5037.4

(2) Preparation of compound 4

2mL of pyridine was added to a mixed solution of Compound 4-1 (0.30g, 0.06mmol) and Compound E (0.14g, 0.60mmol) in 40mL of chloroform (CHCl ₃ ) under a nitrogen (N ₂ ) atmosphere. . After refluxing this mixed solution for 24 hours under a nitrogen atmosphere, it was extracted with dichloromethane (CH ₂ Cl ₂ ) and washed with water. After solvent removal, recrystallization through methyl chloride (MC) / methanol, and the product is a silica gel column using hexane, ethyl acetate, and chloroform (CHCl ₃ ) as an eluent It was purified through chromatography using a gel column. The resulting solid was recrystallized through chloroform. Thereafter, washed with methanol and dried in vacuum to obtain 210 mg of Compound 4. (Yield: 59%) (MALDI-TOF MS: 5885.7 g/mol)

Example 1.

A composite solution was prepared by dissolving Compound 1 prepared in Preparation Example 1 and the following Compound K in a 1:1 ratio in chlorobenzene (CB). At this time, the concentration was adjusted to 2.0wt%, and the organic solar cell had a structure of ITO/ZnO/photoactive layer/MoO ₃ /Ag. The ITO-coated glass substrate was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was treated with ozone for 10 minutes, followed by spin-coating with a ZnO precursor solution and heat treatment at 120° C. for 10 minutes. Thereafter, the composite solution of Compound 1 and Compound K was filtered through a 0.45 μm PTFE syringe filter and then spin-coated to form a photoactive layer. Thereafter, MoO ₃ was deposited on the photoactive layer in a thermal evaporator at a rate of 0.4 Å/s to a thickness of 5 nm to 20 nm to prepare a hole transport layer. An organic solar cell was prepared by depositing Ag to a thickness of 10 nm at a rate of 1 Å/s in a thermal evaporator on the hole transport layer.

Example 2.

An organic solar cell was prepared in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1 in Example 1.

Example 3.

An organic solar cell was prepared in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1 in Example 1.

Example 4.

An organic solar cell was prepared in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1 in Example 1.

The photoelectric conversion characteristics of the organic solar cells prepared in Examples 1 to 4 were measured under the condition of 100 mW/cm ² (AM 1.5), and the results are shown in Table 1 below.

photoactive layer material V _OC
(V) J _SC
(mA/cm ² ) FF
(%) PCE
(%) Example 1 Compound 1:Compound K = 1:1 0.84 10.47 47.2 4.15 Example 2 Compound 2: Compound K = 1:1 0.80 9.75 51.2 4.00 Example 3 Compound 3: Compound K = 1:1 0.89 10.70 57.4 5.45 Example 4 Compound 4: Compound K = 1:1 0.82 8.81 45.5 3.28

The current density according to the voltage of the organic solar cells prepared in Examples 1 and 3 is shown in FIG. 9 .

From Table 1 and FIG. 9, it can be confirmed that the compound according to an exemplary embodiment of the present specification can be applied as a material for a photoactive layer of an organic solar cell.

101: substrate
102: first electrode
103: hole transport layer
104: photoactive layer
105: second electrode

Claims (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
n1 and n2 are each 1 or 2;
[Pull1] and [Pull2] are the same as or different from each other, and each independently

ego,
R17 is hydrogen or a halogen group,
b is an integer from 1 to 4;
L1 and L2 are the same as or different from each other, and each independently has the following structure,

In the above structure,

is a site bonded to another substituent or linkage,
m1 to m4 are each 0 or 1;
Y1 to Y10 are S,
R1 to R4 are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The method of claim 1,
A compound wherein L1 and L2 are the same as or different from each other, and each independently has any one of the following structures:

in the structure

is a site bonded to another substituent or linkage,
Y1 to Y10 are S,
R1 to R4 are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The method of claim 1,
Formula 1 is a compound represented by any one of Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
[Pull1], [Pull2], [Pull1'] and [Pull2'] are the same as or different from each other, and each independently

ego,
R17 is hydrogen or a halogen group,
b is an integer from 1 to 4;
Y1, Y2, Y5, Y6, Y9, Y10, Y11, Y12, Y15, Y16, Y19, Y20, Y1', Y2', Y5', Y6', Y9', Y10', Y11', Y12', Y15' , Y16', Y19' and Y20' are S,
R1 to R4, R11 to R14, R1' to R4', and R11' to R14' are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The method of claim 1,
Formula 1 is a compound represented by any one of Formulas 2-1 to 2-4:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,
[Pull1], [Pull2], [Pull1'] and [Pull2'] are the same as or different from each other, and each independently

ego,
R17 is hydrogen or a halogen group,
b is an integer from 1 to 4;
Y1, Y2, Y5, Y6, Y9, Y10, Y11, Y12, Y15, Y16, Y19, Y20, Y1', Y2', Y5', Y6', Y9', Y10', Y11', Y12', Y15' , Y16', Y19' and Y20' are S,
R1 to R4, R11 to R14, R1' to R4', and R11' to R14' are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The method of claim 1,
Formula 1 is a compound represented by any one of Formulas 3-1 to 3-4:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,
[Pull1], [Pull2], [Pull1'] and [Pull2'] are the same as or different from each other, and each independently

ego,
R17 is hydrogen or a halogen group,
b is an integer from 1 to 4; delete The method of claim 1,
A compound represented by Formula 1 is any one of the following structures:

a first electrode;
a second electrode provided to face the first electrode; and
It is provided between the first electrode and the second electrode and includes one or more organic material layers including a photoactive layer,
An organic solar cell wherein at least one layer of the organic material layer contains the compound according to any one of claims 1 to 5 and 7. The method of claim 8,
The photoactive layer includes an electron donor and an electron acceptor,
The electron acceptor is an organic solar cell comprising the compound. The method of claim 8,
The organic solar cell further comprises one or two or more organic material layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generation layer, an electron blocking layer, an electron injection layer, and an electron transport layer. .

Images