KR20140068318A - Organic Photovoltaic Cells - Google Patents

Abstract

An organic solar cell device having an excellent photoelectric conversion efficiency and a long life is provided. The organic solar cell device comprises: a photoactive layer including an anode, a hole transport layer, and an electron donor; and a cathode. The hole transport layer includes a conductive polymer and a fluorinated material, and has a first surface disposed on the anode side and a second surface disposed on the photoactive layer side.

Description

BACKGROUND ART Organic photovoltaic cells

To an organic solar cell element.

At present, as interest in renewable energy is increasing worldwide, organic solar cell devices with potential and future advantages as future energy are attracting attention. The organic solar cell element can be thinned and manufactured at a low cost as compared with an inorganic solar cell element using silicon, and can be applied to various flexible devices in the future.

Conventional organic solar cell elements may include an anode, a hole extracting layer, a photoactive layer, and a cathode. The light irradiated to the organic solar cell element is separated into electrons and holes in the photoactive layer, holes are extracted through the hole extracting layer through the anode, and electrons can be extracted through the cathode.

However, the photoelectric conversion efficiency and lifetime of conventional organic solar cell devices are unsatisfactory, and improvement thereof is required.

And an organic solar cell element having excellent photoelectric conversion efficiency and long life.

According to one embodiment, the substrate 11, 21, the anodes 13, 23, the hole extraction layers 15, 25, the photoactive layers 17, 27 including an electron donor and the cathodes 19, ;

The hole extraction layer (15, 25) has a conductivity of at least 0.001 S / cm on a thickness of 100 nm;

The hole extraction layer (15, 25) includes a conductive polymer and a fluorine-based material;

The hole extraction layers 15 and 25 have a first surface 110 and a second surface 210 disposed on the anode side and a second surface 120 and 220 disposed on the side of the photoactive layer 17 and 27,

Wherein the difference between the absolute value of the work function of the second surface (120, 220) and the absolute value of HOMO (High Occupied Molecular Orbital) of the electron donor is 0.2 eV or less.

The organic solar cell element has excellent photoelectric conversion efficiency and long life, and is easy to manufacture.

1 is a schematic cross-sectional view of an organic solar cell element according to an embodiment of the present invention.
2 is a schematic cross-sectional view of an organic solar cell element according to another embodiment of the present invention.
3 is a graph showing the time-photoelectric conversion efficiency of the organic solar cell elements of Examples 1 to 4 and Comparative Example 1. Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a sectional view schematically showing a cross section of an organic solar cell element 10 according to one embodiment. The organic solar cell element 10 has a structure in which a substrate 11, an anode 13, a hole extracting layer 15, a photoactive layer 17, and a cathode 19 are sequentially stacked. The hole extracting layer 15 includes a first surface 110 disposed on the anode 13 side in contact with the anode 13 and a second surface 110 disposed on the side of the photoactive layer 17 to be in contact with the photoactive layer 17 And has a second surface 120.

As the substrate 11, a substrate used in a conventional semiconductor process can be used. For example, the substrate 11 may be formed of a material selected from the group consisting of silicon, silicon oxide, metal foil (e.g., copper foil, aluminum foil, stainless steel, etc.), metal oxide, And combinations of two or more of them. The metal foil may be made of a material which does not act as a catalyst capable of forming a graphene while having a high melting point. Examples of the metal oxide include aluminum oxide, molybdenum oxide, indium tin oxide, and the like. Examples of the polymer substrate include polytetrafluoroethylene, polyethersulphone (PES), polyacrylate (PAR) Polyetherimide (PEI), polyethyelenene naphthalate (PEN), polyethyeleneterephthalate (PET), polyphenylene sulfide (PPS), polyallylate, polyimide but are not limited to, polyimide, polycarbonate (PC), cellulose triacetate (TAC), and cellulose acetate propinonate (CAP).

For example, the substrate 11 may be a polymer substrate as described above, but is not limited thereto.

The anode 13 may be formed by providing a material for forming an anode on the substrate 11 using a deposition method, a sputtering method, or the like. The anode 13 may be selected from a material having a relatively high work function to facilitate hole extraction. The anode 13 may be a reflective electrode or a transmissive electrode. Examples of the material for forming the anode include transparent and highly conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), metal oxide / metal / metal oxide multi- graphene, and carbon nano tube may be used. (Mg), aluminum (Al), Ag, ITO, Ag / IZO, Al-Li, Ca, Mg- -Ag) or the like, the anode 13 may be formed as a reflective electrode. The anode 13 may include two different materials. For example, the anode 13 may have a two-layer structure including two different materials.

On the anode (13), a hole extracting layer (15) is formed. The hole extraction layer 15 may include a conductive polymer and a fluorine-based material.

The conductive polymer and the fluorine-based material in the hole extracting layer 15 may be uniformly mixed with each other. For example, the hole extraction layer 15 may be a single film in which the conductive polymer and the fluorine-based material are uniformly mixed with each other.

The concentration of the fluorine-based material in the second surface 120 of the hole extraction layer 15 may be greater than the concentration of the fluorine-based material in the first surface 110 of the hole extraction layer 15. For example, the conductive polymer and the fluorine-based material may be a single film having a concentration gradient. The concentration of the conductive polymer in the hole extracting layer 15 decreases along the direction from the anode 13 toward the photoactive layer 17 and the concentration of the fluorine- To the photoactive layer (17). As a result, the concentration of the fluorine-based material on the second surface 120 of the hole extracting layer 15, which is in contact with the photoactive layer 17, becomes relatively high, and the absolute value of the work function of the second surface 120, The absolute value difference of the HOMO level of the electron donor among the electron donors 17 can be further reduced.

As another example, the conductive polymer of the second surface 120 of the hole extracting layer 15 may be absent, and the fluorine-based substance may be present. For example, the interface between the hole extracting layer 15 and the photoactive layer 17 may include only the fluorine-based substance. Accordingly, only the fluorine-based material exists on the second surface 120 of the hole extracting layer 15, which is in contact with the photoactive layer 17, so that the absolute value of the work function of the second surface 120 and the absolute value of the work function of the photoactive layer 17 The absolute value difference of the HOMO level of the electron donor can be further reduced.

The conductive polymer may be at least one selected from the group consisting of polythiophene, polyaniline, polypyrrole, polystyrene, polyethylene dioxythiophene, polyacetylene, polyphenylene, polyphenylvinylene, polycarbazole, Copolymers, derivatives thereof, or blends of two or more thereof.

The above-mentioned conductive polymer includes a copolymer in which all the different repeating units of the conductive polymer are included in the main chain, and one of the different repeating units of the conductive polymer is a graft type copolymer contained in the side chain. In addition, the polyvinyl alcohol may be a random copolymer, an alternative copolymer or a block copolymer.

The conductive polymer may include an ionic group-containing conductive polymer, a polymeric acid including an ionic group, and a conductive polymer (eg, ion-bonded) through an ionic group. Accordingly, the conductive polymer may include a self-doped conductive polymer doped with at least one of an ionic group and a polymer.

The ionic group may comprise an anionic group and a counter cationic group for the anionic group.

For example, the anionic group may be selected from the group consisting of PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- and BO ₂ ^{2 -} .

Meanwhile, the cationic group may include at least one of metal ion and organic ion. The metal ion is ^{Na +, K +, Li +} , Mg +2, Zn ⁺² and may be selected from the group consisting of Al ^+3, the organic ions are _{^{H +, CH 3 (CH 2}} ) n NH 3 + (n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ and RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer of 0 to 50) no.

The polymeric acid may be a conductive polymer in which an ionic group as described above is bonded to a side chain, which can be easily recognized from the following Polymers 1 to 26.

For example, specific examples of the conductive polymer include, but are not limited to, the following:

&Lt; Polymer 1 (PEDOT: PSS) > < Polymer 2 (PANI: DBSA) >

&Lt; Polymer 3 > < Polymer 4 (PSS-g-PANI) >

&Lt; Polymer 5 > < Polymer 6 >

<Polymer 7> <Polymer 8>

<Polymer 9 (PANI: PSS)> <Polymer 10>

&Lt; Polymer 11 > < Polymer 12 >

&Lt; Polymer 13 > < Polymer 14 >

&Lt; Polymer 15 > < Polymer 16 >

&Lt; Polymer 17 > < Polymer 18 >

&Lt; Polymer 19 > < Polymer 20 >

&Lt; Polymer 21 > < Polymer 22 >

&Lt; Polymer 23 > < Polymer 24 >

<Polymer 25>

The hole extracting layer 15 includes the conductive polymer as described above. The hole extracting layer 15 may have a conductivity of 0.01 S / cm or more on the basis of 100 nm thickness.

The fluorine-based material may be an ionomer represented by the following formula (1) (polymer having an ion group)

&Lt; Formula 1 >

In Formula 1,

0 < m? 10,000,000, 0? N <10,000,000, 0? A? 20, 0? B? 20;

A, B, A 'and B' are each independently selected from the group consisting of C, Si, Ge, Sn, and Pb;

Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' is independently hydrogen, halogen, a nitro group, a substituted or unsubstituted amino group, unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ -C ₃₀ heterocyclic alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C aryl group, a substituted or unsubstituted aryloxy-substituted C ₆ -C _30, substituted or unsubstituted C _{2 30} - for C ₃₀ heteroaryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryloxy group, a substituted or unsubstituted C ₅ -C ₂₀ in the bicyclo alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl ester group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl of S. Encircling, doedoe selected from substituted or unsubstituted aryl ester group of the unsubstituted C ₆ -C ₃₀ and, heteroaryl ester groups the group consisting of substituted or unsubstituted C ₂ -C _30, However, R _1, R _2, R _3, And R ₄ At least one of them is an ionic group or an ionic group;

The X and X 'are each independently selected from a simple bond, O, S, substituted or unsubstituted C ₁ -C ₃₀ alkylene group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkylene group, substituted or unsubstituted C ₆ - C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted heteroaryl group of C ₂ -C ₃₀ alkylene group of , A substituted or unsubstituted C ₅ -C ₂₀ cycloalkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ aryl ester group, And an unsubstituted C ₂ -C ₃₀ heteroaryl ester group,

Provided that when n is 0, at least one of R ₁ , R ₂ , R ₃ , and R ₄ may be a hydrophobic functional group containing a halogen element or may include a hydrophobic functional group.

Examples of such hydrophobic group, such as halogen atoms and C ₁ -C ₃₀ halogenated alkyl group containing at least one halogen atom, a halogenated C ₁ -C ₃₀ alkoxy group, a halogenated C ₁ -C ₃₀ heterocyclic group, C ₁ -C ₃₀ halogenated alkoxy group, a halogenated C ₁ -C ₃₀ heterocyclic alkoxy group, a halogenated C ₆ -C ₃₀ aryl group, an aryloxy group of a halogenated C ₆ -C ₃₀ arylalkyl group, a halogenated C ₆ -C ₃₀ of a halogenated C ₂ -C _A halogenated C ₂ -C ₃₀ heteroaryl group, a halogenated C ₂ -C ₃₀ heteroarylalkyl group, a halogenated C ₂ -C ₃₀ heteroaryloxy group, a halogenated C ₅ -C ₂₀ cycloalkyl group, a halogenated C ₂ -C ₃₀ heterocycloalkyl group, A halogenated C ₁ -C ₃₀ alkyl ester group, a halogenated C ₁ -C ₃₀ heteroalkyl ester group, a halogenated C ₆ -C ₃₀ aryl ester group, and a halogenated C ₂ -C ₃₀ heteroaryl ester group. For example, the hydrophobic functional group may be a halogen atom. Specifically, the hydrophobic functional group may be fluorine, but is not limited thereto.

When 0 < n < 10,000,000, the ionomer has a structure copolymerized with a nonionic monomer having no ionic group, so that the content of ionic groups in the ionomer is reduced to an appropriate range. As a result, Can be reduced. In this case, the content of the nonionic comonomer may be 1 mol% to 99 mol%, for example, 1 to 50 mol% based on the total monomer content required for the ionomer formation. When the content of the comonomer satisfies the above-mentioned range, it is possible to produce an ionomer containing a sufficient content of ionic groups.

R ₁ , R ₂ , R ₃ or R _{4 in the} above formula (1) May be an ionic group, or may include an ionic group. In this case, the ion group is composed of a pair of anion and cation. Examples of the anion group include PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CHOSO ₃ ^- , CH ₃ COO ^- , BO ₂ ^{2 -} Metal ions such as Na ⁺ , K ⁺ , Li ⁺ , Mg ⁺² , Zn ⁺² , and Al ⁺³ ; Or ^{_{H +, CH 3 (CH 2}} ) n NH 3 + (n is an integer of 0 to ^{_{50), NH 4 +, NH}} 2 +, NHSO 2 CF 3 +, Such as CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , CH ₃ (CH ₂ ) _n CHO ⁺ (where R is an alkyl group, ie CH ₃ (CH ₂ ) _n ^- where n is an integer from 0 to 50) Organic ions.

For example, the fluorine-based material may be an ionomer containing at least one of the repeating units represented by the following formulas (2) to (13).

(2)

Wherein M is a number from 1 to 10,000,000 and x and y are each independently a number from 0 to 10 and M ⁺ is selected from Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

(3)

Wherein m is a number from 1 to 10,000,000;

&Lt; Formula 4 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y is a number from 0 to 20, each independently, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 5 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y is a number from 0 to 20, each independently, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

(6)

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, z is a number from 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 7 >

The above formula, m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000 and, x and y are each independently a number of from 0 to 20, Y is _{^{-COO - M +, -SO 3 -}} NHSO 2 CF3 + _{^{, -PO 3 2 - (M +}} ) 2 , and one selected from a, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH 3 + (n is an integer of 0 to 50) _{^{, NH 4 +, NH 2 +}} , NHSO 2 CF 3 +, CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

(8)

Wherein m and n are 0 < m? 10,000,000 and 0? N <10,000,000, M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ 50 _{^{integer), NH 4 +, NH 2}} +, NHSO 2 CF 3 +, CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 9 >

Wherein m and n are 0 < m? 10,000,000, 0? N <10,000,000;

&Lt; Formula 10 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x is a number from 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 11 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y are each independently a number of 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 12 >

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 is a, R _f - (CF ₂ ) _z - (z is an integer of 1 to 50, excluding 2), - (CF ₂ CF ₂ O) _z CF ₂ CF ₂ - (z is an integer of 1 to 50) _{2 CF 2 CF 2 O) z} CF 2 CF 2 - (z is an integer from 1 to 50), M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH 3 + ( n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);

&Lt; Formula 13 >

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 and, x and y are each independently a number of 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - _{^{M +, -SO 3 - NHSO 2}} CF3 +, -PO 3 2 - and the (M ⁺⁾ one selected from the group consisting of _2, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH ₃ ⁺ (n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer of 0 to 50).

Meanwhile, the fluorine-based material contained in the fluorine-based substance-containing film 15 may be a fluorinated oligomer represented by the following formula (20).

(20)

XM ^f _n -M ^h _m -M ^a _r -G

In the above formula (20)

X is a terminal group;

M ^f represents a unit derived from a fluorinated monomer obtained from the condensation reaction of a perfluoropolyether alcohol, a polyisocyanate, and an isocyanate-reactive-nonfluorinated monomer;

M ^h represents a unit derived from a non-fluorinated monomer;

M ^a represents a unit having a silyl group represented by -Si (Y ₄ ) (Y ₅ ) (Y ₆ );

Y ₄ , Y ₅ and Y ₆ independently represent a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a hydrolyzable substituent, and Y ₄ , Y ₅ and Y &lt; ₆ &gt; is the hydrolyzable substituent;

G is a monovalent organic group containing a residue of a chain transfer agent;

n is a number from 1 to 100;

m is a number from 0 to 100;

r is a number from 0 to 100;

n + m + r is at least 2.

For example, in Formula 20, X may be a halogen atom, M ^f may be a fluorinated C ₁ -C ₁₀ alkylene group, M ^h may be a C ₂ -C ₁₀ alkylene group, and Y ₄ , Y ₅ and Y ₆ independently of one another may be a halogen atom (Br, Cl, F, etc.), and p may be 0. For example, the fluorinated silane-based material represented by Formula 10 may be CF ₃ CH ₂ CH ₂ SiCl ₃ , but is not limited thereto.

Specific examples of the unsubstituted alkyl groups in the present specification include linear or branched alkyl groups such as methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl and hexyl. The at least one hydrogen atom contained may be substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxy group, a nitro group, a cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ' R "is independently an alkyl group having 1 to 10 carbon atoms with each other), an amidino group, hydrazine, hydrazone or jongi, a carboxyl group, a sulfonic acid group, phosphoric acid group, a halogenated alkyl group of C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ a, A C ₁ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkynyl group, a C ₁ -C ₂₀ heteroalkyl group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ arylalkyl group, a C ₆ -C ₂₀ Or a C ₆ -C ₂₀ heteroarylalkyl group.

The heteroalkyl group in the present specification means that at least one, preferably 1 to 5 carbon atoms in the main chain of the alkyl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom and the like.

Aryl groups in this specification refer to carbocyclic aromatic systems comprising at least one aromatic ring, which rings may be attached together or fused together by a pendant method. Specific examples of the aryl group include an aromatic group such as phenyl, naphthyl, tetrahydronaphthyl and the like, and at least one hydrogen atom of the aryl group may be substituted with the same substituent as the alkyl group.

As used herein, the heteroaryl group means a ring aromatic system having 5 to 30 ring atoms, with 1, 2 or 3 heteroatoms selected from N, O, P or S and the remaining ring atoms C, Or they can be fused together. And at least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the case of the alkyl group.

The alkoxy group in the present specification refers to a radical -O-alkyl, wherein alkyl is as defined above. Specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy and hexyloxy. At least one hydrogen atom in the alkoxy group Can be substituted with the same substituents as those described above.

If the group is a substituent of heterocyclic alkoxy used in the present invention contains one or more heteroatoms, for example, except that oxygen, sulfur or nitrogen may be present in the alkyl chain essentially has the meaning of said alkoxy, for example, CH ₃ CH ₂ OCH ₂ CH ₂ O-, C ₄ H ₉ OCH ₂ CH ₂ OCH ₂ CH ₂ O-, and CH ₃ O (CH ₂ CH ₂ O) _n H.

As used herein, an arylalkyl group means that in the aryl group as defined above, some of the hydrogen atoms are replaced by a radical such as lower alkyl, such as methyl, ethyl, propyl, and the like. For example, benzyl, phenylethyl and the like. At least one hydrogen atom of the arylalkyl group may be substituted with the same substituent as the alkyl group.

In the present specification, the heteroarylalkyl group means that a part of the hydrogen atoms of the heteroaryl group is substituted with a lower alkyl group, and the definition of heteroaryl in the heteroarylalkyl group is as described above. At least one hydrogen atom of the heteroarylalkyl group may be substituted with the same substituent as the alkyl group.

The aryloxy group in this specification refers to a radical -O-aryl, wherein aryl is as defined above. Specific examples thereof include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy and the like. At least one hydrogen atom of the aryloxy group may be substituted with the same substituent as the alkyl group Do.

The heteroaryloxy group in this specification refers to a radical -O-heteroaryl, wherein the heteroaryl is as defined above.

In the present specification, specific examples of the heteroaryloxy group include benzyloxy, phenylethyloxy and the like, and at least one hydrogen atom of the heteroaryloxy group may be substituted with the same substituent as the alkyl group.

In the present specification, the cycloalkyl group means a monovalent monocyclic system having 5 to 30 carbon atoms. At least one hydrogen atom in the cycloalkyl group may be substituted with a substituent similar to that of the alkyl group.

As used herein, a heterocycloalkyl group refers to a monovalent monocyclic system of 5 to 30 ring atoms, wherein the ring atom contains C, 1, 2 or 3 heteroatoms selected from N, O, P or S, At least one hydrogen atom of the cycloalkyl group may be substituted with the same substituent as the alkyl group.

In the present specification, the alkyl ester group means a functional group having an alkyl group and an ester group bonded thereto, wherein the alkyl group is as defined above.

In the present specification, a heteroalkyl ester group means a functional group having a heteroalkyl group and an ester group bonded thereto, and the heteroalkyl group is as defined above.

In the present specification, an aryl ester group means a functional group having an aryl group and an ester group bonded thereto, wherein the aryl group is as defined above.

In the present specification, the heteroaryl ester group means a functional group in which a heteroaryl group and an ester group are bonded, wherein the heteroaryl group is as defined above.

The amino group used in the present invention is -NH ₂ , -NH (R) or -N (R ') (R "), and R' and R" are independently an alkyl group having 1 to 10 carbon atoms.

In the present specification, halogen is fluorine, chlorine, bromine, iodine, or astatine, of which fluorine is particularly preferred.

The photoactive layer 17 may include a material capable of separating holes and electrons from the irradiated light. For example, the photoactive layer 17 may comprise an electron donor and an electron acceptor. The photoactive layer 17 may have a variety of structures, including a single layer containing the electron donor and the electron acceptor, or multiple layers including the layer containing the electron donor and the layer containing the electron acceptor .

The electron donor may be a substance having an absolute value of the HOMO level of 5.1 eV or more. For example, the electron donor may comprise a p-type conjugated polymer material including a pi -electron. Examples of the electron donor include polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy-4- (0 -dispersed 1) -2,5-phenylene-vinylene), MDMO-PPV Poly [2-methoxy-5-3 (3 ', 7'-dimethyloctyloxy) -1,4-phenylenevinylene] -1,4-phenylene vinylene], PFDTBT (poly (2,7- (9,9-dioctyl) -fluorene-alt-5,5- (4 ', 7'- 2 ', 1', 3'-benzothiadiazole): poly ((2,7- (9,9-dioctyl) -fluorene) -alt- 2 ', 1'3'-benzothiadiazole), PCDTBT (Poly [[9- (1-octylononyl) -9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3 -benzothiadiazole-4,7-diyl-2,5-thiophenediyl]), polyindole, polycarbazole, polypyridazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene, polyfluorene , Polypyridine, derivatives thereof, etc. However, the present invention is not limited thereto. The electron donor may be a p- Various materials described in copper phthalocyanine (CuPc), oligo-thiopehene, Chem. Mater. 2011, 23, 470-482, etc. can be used. It is of course possible to use a combination of two or more of the specific examples of the electron donor (including blends, copolymers, etc.).

Examples of the electron acceptor include fullerenes having a high electron affinity (for example, C60, C70, C74, C76, C78, C82, C84, C720, C860, etc.); (6,6] -phenyl-C61 butyric acid methyl ester), PC70BM ([6,6] -phenyl C71-butyric acid methyl ester), C71-PCBM, C84-PCBM, bis -PCBM and the like); Perylene; Inorganic semiconductor containing nanocrystals such as CdS, CdTe, CdSe, ZnO and the like; Carbon nanotubes, carbon nanorods PBI (polybenzimidazole), PTCBI (3,4,9,10 perylenetetracarboxylic bisbenzimidazole), or mixtures thereof, but are not limited thereto.

For example, the photoactive layer 17 may be a single layer including P3HT as an electron donor and PCBM as a fullerene derivative as an electron acceptor, but the present invention is not limited thereto.

The photoactive layer 17 is irradiated with light and excitons, which are pairs of electrons and holes, are formed by photoexcitation. The excitons are generated by the difference in electron affinity between the electron donor and the electron acceptor at the interface between the electron donor and the electron acceptor, And is separated into holes.

The difference between the absolute value of the HOMO level of the electron donor in the photoactive layer 17 and the absolute value of the work function of the second face 200 is 0.2 eV or less, for example, 0.1 eV or less, 0.05 eV or less. For example, the absolute value of the HOMO level (high Occupied Molecular Orbital) of the electron donor in the photoactive layer 17 and the absolute value of the work function of the second face 200 may be the same. Hence, hole transport and injection from the photoactive layer 17 to the hole extraction layer 15 can be effectively performed, so that the photoelectric conversion efficiency of the organic solar cell element 10 can be improved.

The cathode 19 may use a metal, an alloy, an electrically conductive compound and a combination thereof having a relatively low work function. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- .

Although not shown in FIG. 1, an electron extracting layer (not shown in FIG. 1) may be further interposed between the photoactive layer 17 and the cathode 19 of the organic solar cell device. The electron extraction layer may serve to assist electrons generated in the photoactive layer 17 to be transported to the cathode 19. For example, the electron extraction layer may include materials such as LiF and Alq3.

One embodiment of the method for manufacturing the organic solar cell element 10 will be described below.

First, an anode 13 is formed on a substrate 11. The substrate 11 and the anode 13 are described above and various methods known in the art such as a sputtering method, A spin coating method, an ink jet printing method, or the like.

Next, after providing a mixture containing the conductive polymer, the fluorine-based material, and the solvent on the anode 13, at least a portion of the solvent may be removed to form the hole extraction layer 15.

The description of the conductive polymer and the fluorine-based material in the mixture is given above. The solvent is miscible with the conductive polymer and the fluorine-based material and can be easily removed by a process such as heat treatment. For example, examples of such solvents include water, alcohols, dimethylform (DMF), dimethylsulfoxide (DMSO), acetone, propanediol, methylpyrrolidone, sorbitol, ethylene Glycol, and the like, but are not limited thereto.

The mixture may be formed by a casting method, a volume Mu-Blow (LB) method, a spin-coating method, an ink-jet printing method, a nozzle printing method, a spray coating method, May be provided on the anode 13 using a known method such as screen printing, doctor blade coating, gravure printing, and offset printing.

Subsequently, the hole-extracting layer 15 including the conductive polymer and the fluorine-based material may be formed by removing at least a portion of the solvent by heat-treating the mixture provided on the anode 13. The conditions of the heat treatment process may vary depending on, for example, the kind and content of the conductive polymer and the fluorine-based material used, and may be selected, for example, from 100 deg. C to 250 deg. C for 5 minutes to 2 hours.

When the fluorine-based material contained in the mixture has a surface energy larger than that of the conductive polymer after the mixture is applied on the anode (13), a surface energy difference between the fluorine-based material and the conductive polymer, The fluorine-based substance can move to the surface of the mixture film. As a result, the concentration of the fluorine-based material in the second surface 120 disposed on the photoactive layer 17 side of the hole extraction layer 15 formed by heat-treating the mixture film is higher than the concentration of the fluorine- ) Of the first face 110 disposed on the side of the first face 110 side.

Next, a photoactive layer 17 including an electron donor may be formed on the hole extracting layer 15. The description of the electron donor in the photoactive layer 17 is given above. The photoactive layer 17 may be formed by various known methods such as a vapor deposition method and the like depending on the selected material.

Subsequently, the cathode 19 is formed on the photoactive layer 17 using the cathode 19 material as described above, thereby manufacturing an organic solar cell element. At this time, various modifications are possible, for example, an electron extraction layer can be further formed on the photoactive layer 17 before the cathode 19 is formed.

2 is a sectional view schematically showing a cross section of the organic solar cell element 20 according to another embodiment. The organic solar cell element 20 has a structure in which a substrate 21, an anode 23, a hole extraction layer 25, a photoactive layer 27, and a cathode 29 are sequentially stacked. The hole extracting layer 25 includes a first layer 25A and a second layer 25B which are disposed on the anode 23 side and the second layer 25B, Is disposed on the photoactive layer 27 side. The light irradiated on the organic solar cell element 20 is separated into holes and electrons in the photoactive layer 27 so that the electrons move to the cathode 29 and the holes move to the anode 23 through the hole extraction layer 25 . The first layer 25A has a first surface 210 disposed on the anode 23 side in contact with the anode 23 and the second layer 25B is disposed on the side of the photoactive layer 27 And a second surface 220 in contact with the photoactive layer 27.

A description of the conductive polymer and the fluorine-based material, the photoactive layer 27 and the cathode 29 in the substrate 21, the anode 23 and the hole extraction layer 25 in the organic solar cell element 20 is shown in FIG. See the description.

The hole extracting layer 25 includes a first layer 25A including the conductive polymer and disposed on the anode 23 side and a second layer 25B including the fluorine based material and disposed on the photoactive layer 27 side 25B.

The thickness of the first layer 25A may be 100 nm to 300 nm, for example, 20 nm to 50 nm. When the thickness of the first layer 25A satisfies the above-described range, the hole extracting layer 25 may have excellent conductivity.

The thickness of the second layer 25B may be 1 nm to 30 nm, for example, 1 nm to 10 nm. If the thickness of the second layer 25B satisfies the above-described range, hole injection from the photoactive layer 27 to the hole extraction layer 25 can be effectively performed.

The second layer 25B may further include a conductive polymer in addition to the fluorine-based material as described above. As an example of the conductive polymer that can be added to the second layer 25B, an example of the conductive polymer that can be included in the first layer 25A can be referred to. For example, the conductive polymer that may be added to the second layer 25B may be the same as the conductive polymer included in the first layer 25A.

Meanwhile, between the first layer 25A and the second layer 25B, the conductive polymer contained in the first layer 25A and the fluorine-based material contained in the second layer 25B, An intermediate layer (not shown in Figure 1) may be further intervened.

The second layer 25B containing the fluorine-based substance as described above is interposed between the first layer 25A and the photoactive layer 27 so that the lower part of the photoactive layer 27, that is, the photoactive layer 27 and the hole extraction (<30%) of the conductive polymer is present at the interface between the conductive polymer and the layer 25, so that only the fluorine-based material capable of providing high work-function properties is present or provides high work-function properties (> 70%) of the above-mentioned fluorine-based materials. The difference between the absolute value of the HOMO level of the electron donor of the photoactive layer 27 and the absolute value of the work function of the second surface 220 is 0.2 eV or less, for example, 0.1 eV or less, And can be 0.05 eV or less. That is, since the absolute value of the HOMO level of the electron donor in the photoactive layer 27 is substantially equal to the work function of the second surface 220, the hole transport from the photoactive layer 27 to the anode 23 Can be effectively achieved. Thus, photoelectric conversion efficiency and lifetime of the organic solar cell device can be improved.

The hole extracting layer 25 is formed as a double layer of a first layer 25A including the conductive polymer and a second layer 25B containing a fluorine substance so that the hole extracting layer 25 is formed on the side of the photoactive layer 27 The difference between the absolute value of the work function of the second surface 220 and the absolute value of the HOMO level of the electron donor in the photoactive layer 27 is effectively reduced because the concentration of the fluorine- .

An embodiment of the method of manufacturing the organic solar cell element 20 will be described below.

First, after a cathode 23 is formed on a substrate 21, a first mixture containing a conductive polymer and a first solvent is provided on the anode 23, and then at least a portion of the first solvent is removed The first layer 25A can be formed. The method of forming the anode 23 on the substrate 21 will be described with reference to FIG.

The description of the conductive polymer in the first mixture is given above. The first solvent is miscible with the conductive polymer and can be easily removed by a process such as heat treatment. For example, examples of the first solvent include water, alcohols, dimethylform (DMF), dimethylsulfoxide (DMSO), acetone, propanediol, methylpyrrolidone, sorbitol, And the like, but the present invention is not limited thereto.

The first mixture may be formed by a casting method, an LB method, a spin-coating method, an ink-jet printing method, a nozzle printing method, a spray coating method, May be provided on the anode 23 using known methods such as screen printing, doctor blade coating, gravure printing, and offset printing. have.

Next, a first layer 25A including the conductive polymer may be formed by removing at least a portion of the first solvent by heat-treating the first mixture provided on the anode 23. The conditions of the heat treatment process may vary depending on the type and content of the conductive polymer used, and may be selected from, for example, 120 deg. C to 220 deg. C for 1 minute to 1 hour.

Thereafter, a second mixture containing a fluorine-based material and a second solvent is provided on the first layer 25A, and a part or more of the second solvent is removed to form the second layer 25B, The hole extraction layer 25 including the first layer 25A and the second layer 25B can be formed.

A detailed description of the fluorine-based material is given above. The second solvent may be selected from a solvent which is miscible with the fluorine-based material and is substantially not reactive with the conductive polymer, and can be easily selected depending on the selected conductive polymer and fluorine-based material. Examples of the second solvent include, but are not limited to, water, methanol, dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethylene glycol and the like.

Next, a second mixture containing the fluorine-based material and the second solvent is applied to the substrate by a casting method, a volume Mu-Blow (LB) method, a spin-coating method, an ink-jet printing method, A known method such as spray coating, screen printing, doctor blade coating, gravure printing, and offset printing may be used to form the above- May be provided on the first layer 25A.

By heat-treating the second mixture provided on the first layer 25A, a part or more of the second solvent may be removed to form the second layer 25B. The conditions of the heat treatment process may be selected within the range of heat treatment conditions for forming the first layer 15A, depending on the kind and content of the fluorine-based material used.

When a solvent which is miscible with the conductive polymer contained in the first layer 25A is selected as the second solvent for forming the second layer 25B, a part of the conductive polymer on the surface of the first layer 25A already formed The conductive polymer contained in the first layer 25A and the conductive polymer contained in the second layer 25B may be disposed between the first layer 25A and the second layer 25B, An intermediate layer including a fluorine-based material included in the first interlayer insulating film 25B may be further formed.

Next, a photoactive layer 27 including an electron donor may be formed on the second layer 25B. A description of the electron donor in the photoactive layer 27 is given above. The photoactive layer 27 may be formed by various known methods such as a deposition method and the like depending on the selected material.

Subsequently, the cathode 29 is formed on the photoactive layer 27 using the cathode 29 material as described above, thereby manufacturing an organic solar cell element. At this time, various modifications are possible, for example, an electron extraction layer may be further formed on the photoactive layer 27 before the cathode 29 is formed.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

 [Example]

Example  One

ITO substrate (glass substrate coated with ITO) was prepared, and PEDOT: PSS (CLEVIOS PH manufactured by Heraeus Co., Ltd.) was spin-coated on the ITO anode and then heat-treated at 200 ° C for 5 minutes to form a first layer having a thickness of 30 nm . The polymer 100 was dispersed in an amount of 5 wt% in a mixture of water and alcohol (water: alcohol = 4.5: 5.5 (v / v)), ) Was diluted to 1/30 in methanol, spin-coated, and then heat-treated at 200 ° C for 10 minutes to form a second layer having a thickness of 3 nm. Thus, a hole extracting layer (hole extracting layer Weight ratio of PEDOT: PSS: Polymer 100 was 1: 2.5: 0.73 and work function was 5.4 Ev). PCDTBT (1material Inc., HOMO = -5.3 eV by Ultraviolet Photoelectron Spectroscopy), PC ₇₀ BM (nano-C Inc.) and 1,2-dichlorobenzene (Sigma-Aldrich Inc., Anhydrous ) (7 mg: 28 mg: 1 mL) was dissolved at 60 ° C for 8 hours and then cooled at room temperature. The resulting mixture was spin-coated and then heat-treated at 70 ° C for 8 minutes to form a 75- . Then, an organic solar cell was fabricated by depositing Ca of 3 nm thickness and Al of 100 nm thickness on the photoactive layer to form a cathode.

<Polymer 100>

(Of the polymer 100, x = 1300, y = 200, x = 1)

The HOMO level of the electron donor PCDTBT in the photoactive layer is -5.3 eV, and the work function of the surface of the second layer of the hole extraction layer is -5.3 eV.

Example  2

Except that the hole extraction layer was formed by adjusting the weight ratio of PEDOT: PSS: polymer 100 in the hole extraction layer to 1: 2.5: 0.37 to form the hole extraction layer. Respectively.

Example  3

Except that the hole extraction layer was formed by controlling the weight ratio of PEDOT: PSS: Polymer 100 in the hole extraction layer to 1: 2.5: 0.19 to form the hole extraction layer. Respectively.

Example  4

Except that a hole extraction layer was formed by controlling the weight ratio of PEDOT: PSS: polymer 100 in the hole extraction layer to 1: 2.5: 0.1 so as to form a hole extraction layer. Respectively.

Comparative Example  One

At the time of forming the hole extraction layer, a mixture of PEDOT: PSS (CLEVIOS PH manufactured by Heraeus Co., Ltd.) and a 100-polymer-containing mixture of Example 1 at a weight ratio of 8: 1 was spin-coated on the ITO anode, An organic solar cell device was fabricated using the same method as in Example 1 except that a 35 nm thick monolayer hole extraction layer (work function = 5.46 eV) was formed by heat treatment.

Comparative Example  2

Upon formation of the photoactive layer, a mixture (concentration = 40 mg / 1.5 ml) containing 1,2-dichlorobenzene, P3HT and PCBM (weight ratio of P3HT and PCBM of 1: 1) was spin-coated on the hole extraction layer And then heat-treated at 150 DEG C for 30 minutes to form a 210 nm thick photoactive layer.

Evaluation example  One

The voltage-current density characteristics of the organic solar cell devices of Examples 1 to 4 and Comparative Example 1 were evaluated, and the results are summarized in Table 1. Voltage-current density characteristic evaluation, the light source is a xenon lamp (Xenon lamp) using the (solar condition (AM1.5) of the xenon lamp is also corrected using a standard solar cell device) in the light of 100mW / cm ² Were irradiated to each organic solar cell element.

On the other hand, the photoelectric conversion efficiency (PCE) (%) is calculated from the measured short-circuit current (J _SC ), open-circuit voltage (V _OC ) and fill factor (FF) .

Open-circuit voltage
(V _OC )
(V) Short-circuit current
(J _SC )
(mA / cm ² ) Fill factor
(FF)
(%) Photoelectric conversion efficiency
(PCE)
(%) Comparative Example 1 0.9 11.6 57.4 6.00 Example 1 0.9 11.7 60.2 6.33 Example 2 0.897 11.7 60.3 6.3 Example 3 0.880 11.9 59.7 6.3 Example 4 0.810 11.5 53.3 5.0

It can be seen from Table 1 that the organic solar cell elements of Examples 1 to 4 have superior characteristics to those of the organic solar cell element of Comparative Example 1. [

Further, the light of 100 W / cm ² was continuously irradiated (at 25 캜) to each organic solar cell element, and the change of the photoelectric conversion efficiency was evaluated. The results are shown in Fig.

From FIG. 3, it can be seen that the organic solar cell elements of Examples 1 to 4 have excellent thermal stability as compared with the organic solar cell element of Comparative Example 1, and photoelectric conversion can be effectively performed for a long time.

10, 20: organic solar cell element
11, 21: substrate
13, 23: anode
15, 25: hole extraction layer
25A: First layer
25B: Second layer
17, 27: photoactive layer
19, 29: cathode

Claims (14)

A positive electrode, a hole extraction layer, a photoactive layer including an electron donor, and a negative electrode;
The hole extraction layer has a conductivity of 0.01 S / cm or more on a 100 nm thickness basis;
Wherein the hole extracting layer comprises a conductive polymer and a fluorine-based substance;
The hole extraction layer has a first surface disposed on the anode side and a second surface disposed on the side of the photoactive layer;
Wherein a difference between a work function of the second surface and an absolute value of a HOMO (High Occupied Molecular Orbital) level of the electron donor is 0.1 eV or less. The method according to claim 1,
Wherein the conductive polymer and the fluorine-based material in the hole extraction layer are uniformly mixed with each other. The method according to claim 1,
Wherein the concentration of the fluorine-based substance in the second surface of the hole extracting layer is larger than the concentration of the fluorine-based substance in the first surface of the hole extracting layer. The method according to claim 1,
Wherein the hole extraction layer includes a first layer including the conductive polymer and disposed on the anode side and a second layer including the fluorine based material and disposed on the side of the photoactive layer. 5. The method of claim 4,
Wherein an intermediate layer containing a conductive polymer contained in the first layer and a fluorine-based substance contained in the second layer is interposed between the first layer and the second layer. The method according to claim 1,
Wherein the conductive polymer is at least one selected from the group consisting of polythiophene, polyaniline, polypyrrole, polystyrene, polyethylene dioxythiophene, polyacetylene, polyphenylene, polyphenylvinylene, polycarbazole, Or a blend of two or more thereof. The method according to claim 1,
The conductive polymer includes a self-doped conductive polymer doped with at least one of an ionic group and a polymeric acid,
Said ionic group comprising an anionic group and a counter cationic group for said anionic group,
The anionic group is selected from the group consisting of PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- and BO ₂ ^{2 -}
The cationic group includes at least one of a metal ion and an organic ion,
Wherein the metal ion is selected from the group consisting of Na ⁺ , K ⁺ , Li ⁺ , Mg ⁺² , Zn ⁺² and Al ⁺³ and the organic ion is selected from the group consisting of H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ Is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ Wherein R is selected from the group consisting of CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ and RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50). The method according to claim 1,
Wherein the fluorine-based material is an ionomer represented by the following Formula 1:
&Lt; Formula 1 >

In Formula 1,
0 < m? 10,000,000, 0? N <10,000,000, 0? A? 20, 0? B? 20;
A, B, A 'and B' are each independently selected from the group consisting of C, Si, Ge, Sn, and Pb;
Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' is independently hydrogen, halogen, a nitro group, a substituted or unsubstituted amino group, unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ -C ₃₀ heterocyclic alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C aryl group, a substituted or unsubstituted aryloxy-substituted C ₆ -C _30, substituted or unsubstituted C _{2 30} - for C ₃₀ heteroaryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryloxy group, a substituted or unsubstituted C ₅ -C ₂₀ in the bicyclo alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl ester group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl of S. Encircling, is selected from substituted or unsubstituted aryl ester group of the unsubstituted C ₆ -C ₃₀ and, a heteroaryl group consisting of ester group of a substituted or unsubstituted C ₂ -C _30, However, R _1, R _2, R _3, And R ₄ At least one of them is an ionic group or an ionic group;
The X and X 'are each independently selected from a simple bond, O, S, substituted or unsubstituted C ₁ -C ₃₀ alkylene group, a substituted or unsubstituted C ₁ -C ₃₀ heteroalkylene group, substituted or unsubstituted C ₆ - C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a substituted or unsubstituted heteroaryl group of C ₂ -C ₃₀ alkylene group of , A substituted or unsubstituted C ₅ -C ₂₀ cycloalkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ aryl ester group, And an unsubstituted C ₂ -C ₃₀ heteroaryl ester group,
Provided that when n is 0, at least one of R ₁ , R ₂ , R ₃ , and R ₄ is a hydrophobic functional group containing a halogen element or includes a hydrophobic functional group. 9. The method of claim 8,
Said ionic group comprising an anionic group and a counter cationic group for said anionic group,
The anionic group is selected from the group consisting of PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- and BO ₂ ^{2 -}
The cationic group includes at least one of a metal ion and an organic ion,
Wherein the metal ion is selected from the group consisting of Na ⁺ , K ⁺ , Li ⁺ , Mg ⁺² , Zn ⁺² and Al ⁺³ and the organic ion is selected from the group consisting of H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ Is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ Wherein R is selected from the group consisting of CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ and RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50). 8. The method of claim 7,
Wherein the hydrophobic functional group is a halogen element. The method according to claim 1,
Wherein the fluorine-based substance is an ionomer containing at least one of repeating units represented by the following formulas (2) to (13):
(2)

Wherein M is a number from 1 to 10,000,000 and x and y are each independently a number from 0 to 10 and M ⁺ is selected from Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
(3)

Wherein m is a number from 1 to 10,000,000;
&Lt; Formula 4 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y is a number from 0 to 20, each independently, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 5 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y is a number from 0 to 20, each independently, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
(6)

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, z is a number from 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 7 &gt;

The above formula, m and n are 0 <m ≤ 10,000,000, 0 ≤ n <10,000,000 and, x and y are each independently a number of from 0 to 20, Y is _{^{-COO - M +, -SO 3 -}} NHSO 2 CF3 + _{^{, -PO 3 2 - (M +}} ) 2 , and one selected from a, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH 3 + (n is an integer of 0 to 50) _{^{, NH 4 +, NH 2 +}} , NHSO 2 CF 3 +, CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
(8)

Wherein m and n are 0 < m? 10,000,000 and 0? N <10,000,000, M ⁺ is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ 50 _{^{integer), NH 4 +, NH 2}} +, NHSO 2 CF 3 +, CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 9 >

Wherein m and n are 0 < m? 10,000,000, 0? N <10,000,000;
&Lt; Formula 10 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x is a number from 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 11 >

The above formula, m and n are 0 <m ≤ 10,000,000, and 0 ≤ n <10,000,000, x and y are each independently a number of 0 to 20, M ⁺ is ^{Na +, K +, Li +} , H +, CH ₃ (CH ₂ ) _n NH ₃ ⁺ (n is an integer from 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 12 >

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 is a, R _f - (CF ₂ ) _z - (z is an integer of 1 to 50, excluding 2), - (CF ₂ CF ₂ O) _z CF ₂ CF ₂ - (z is an integer of 1 to 50) _{2 CF 2 CF 2 O) z} CF 2 CF 2 - (z is an integer from 1 to 50), M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH 3 + ( n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer from 0 to 50);
&Lt; Formula 13 >

The above formula, m and n are 0 ≤ m <10,000,000, 0 < n ≤ 10,000,000 and, x and y are each independently a number of 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - _{^{M +, -SO 3 - NHSO 2}} CF3 +, -PO 3 2 - and the (M ⁺⁾ one selected from the group consisting of _2, M ⁺ is ^{Na +, K +, Li +} , H +, CH 3 (CH 2) n NH ₃ ⁺ (n is an integer of 0 to 50), NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ , RCHO ⁺ (R is CH ₃ (CH ₂ ) _n -; n is an integer of 0 to 50). The method according to claim 1,
Wherein the fluorine-based substance is a fluorinated oligomer represented by the following formula (20):
(20)
XM ^f _n -M ^h _m -M ^a _r -G
In the above formula (20)
X is a terminal group;
M ^f represents a unit derived from a fluorinated monomer obtained from the condensation reaction of a perfluoropolyether alcohol, a polyisocyanate, and an isocyanate-reactive-nonfluorinated monomer;
M ^h represents a unit derived from a non-fluorinated monomer;
M ^a represents a unit having a silyl group represented by -Si (Y ₄ ) (Y ₅ ) (Y ₆ );
Y ₄ , Y ₅ and Y ₆ independently represent a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group or a hydrolyzable substituent, and Y ₄ , Y ₅ and Y < ₆ > is the hydrolyzable substituent;
G is a monovalent organic group containing a residue of a chain transfer agent;
n is a number from 1 to 100;
m is a number from 0 to 100;
r is a number from 0 to 100;
n + m + r is at least 2. The method according to claim 1,
Wherein the absolute value of the HOMO level of the electron donor is at least 5.1 eV. The method according to claim 1,
Wherein the electron donor comprises a p-type conductive polymer containing? -Electrons.

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