KR20140108483A - Electronic device including hybrid electrode having a high work function and conductivity - Google Patents

Abstract

An electronic device including a hybrid electrode having a high work function and high conductivity is provided. The hybrid electrode having a high work function and high conductivity has a work function-tuning layer and a conductivity-tuning layer at the same time, thereby can have excellent work function and conductivity. Thus, the electronic device including the hybrid electrode having high work function and high conductivity can have excellent light emitting efficiency and/or photoelectric conversion efficiency even if a hole-injection layer for adjusting the work function is omitted.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an electronic device including a high-work function and high-conductivity hybrid electrode,

To an electronic device.

At present, indium tin oxide (ITO) transparent electrodes are widely used as essential components in various devices such as solar cells, display devices and the like.

 Oxidized electrodes such as ITO have high electrical conductivity and transparency but they are vulnerable to bending. The resistance is increased due to the crack generated when the ITO transparent electrode is bent, and it is difficult to reuse after the crack is generated. In addition, indium, which is the main material of ITO, is not only high in price but also easy to process, and as the demand increases, the cost of raw material increases.

Accordingly, the development of other types of transparent electrode materials to replace the ITO transparent electrode material has been progressed, but the conductivity and the work function have not reached a satisfactory level.

And to provide an electronic device employing a hybrid electrode having high-work function and high-conductivity.

According to an aspect there is provided a method of fabricating a semiconductor device comprising a low-surface energy material, but not a conductive material, having a first side and a second side opposite the first side, A work function-tuning layer having a work function of 5.0 eV or more and a conductivity of 1 S / cm or more; And

Wherein the at least one low-surface energy material comprises at least one of a conductive polymer, a metallic carbon nanotube, a graphene, a reduced oxide graphene, a metal nanowire, a semiconductor nanowire, a metal grid, a metal nano dot and a conductive oxide A conductivity-tuning layer in contact with a first side of the work function-control layer;

An electronic device including a high-work function and a high-conductivity electrode is provided.

The low-surface energy material may be a fluorinated material including at least one F.

The electronic device may be an organic light emitting device, an organic solar cell, an organic transistor, an organic memory device, an organic photodetector, or an organic CMOS sensor.

The electronic device is an organic light emitting device,

The organic light emitting device includes: a substrate; A first electrode; A second electrode; And a light emitting layer interposed between the first electrode and the second electrode,

The first electrode is the high-through-function and high-conductivity hybrid electrode;

The work function-control layer among the high-work function and high-conductivity hybrid electrodes may be interposed between the light emitting layer and the conductivity-control layer.

Alternatively, the electronic device may be an organic solar cell,

The organic solar battery includes: a substrate; A first electrode; A second electrode; And a photoactive layer interposed between the first electrode and the second electrode,

The first electrode is the high-through-function and high-conductivity hybrid electrode;

The work function-control layer among the high-work function and high-conductivity hybrid electrodes may be interposed between the photoactive layer and the conductivity-control layer.

 The high-work function and high-conductivity hybrid electrodes have a work function-control layer and a conductivity-control layer at the same time, so that they can have excellent work function and conductivity. Therefore, the electronic device employing the high-work function and high-conductivity hybrid electrode can have excellent luminous efficiency and / or photoelectric conversion efficiency even if the hole injection layer for controlling work function is omitted.

1 is a view schematically illustrating a cross-section of an embodiment of an organic light emitting device, which is an example of the electronic device.
2 schematically shows the work function relationship between the substrate, the high-work function and the high-conductivity hybrid electrode (including the conductivity-control layer and the work function-control layer) and the hole transport layer of the organic light emitting element of Fig. 1 will be.
3 is a schematic view for explaining a cross section of an embodiment of an organic solar cell which is an example of the electronic device.
4 is a view schematically illustrating a cross section of an embodiment of an organic thin film transistor which is an example of the electronic device.

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

The organic light emitting device 100 of FIG. 1 includes a substrate 110, a high-work function and high-conductivity hybrid electrode 1, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, 170 and a second electrode 180.

The high-work function and high-conductivity hybrid electrode 1 includes a conductivity-control layer 120 and a work-function-control layer 130, and serves as an anode. The conductivity-control layer 120 of the high-work function and high-conductivity hybrid electrode 1 is interposed between the substrate 110 and the work function-control layer 130.

When a voltage is applied between the high-work function and high-conductivity hybrid electrode 1 and the second electrode 180 which are the anodes of the organic light emitting device 100, the high-work function and high-conductivity hybrid electrode 1 And electrons injected from the second electrode 180 pass through the electron transport layer 160 and the electron injection layer 170 to the emission layer 150 150). The carriers such as holes and electrons recombine in the light emitting layer 150 to generate an exciton, which is changed from an excited state to a ground state to generate light.

The substrate 110 may be a substrate used in a conventional semiconductor process. For example, the substrate may be a substrate, such as glass, sapphire, silicon, silicon oxide, metal foil (e.g., copper foil and aluminum foil), and a steel substrate (e.g., stainless steel) Metal oxides, polymer substrates, and combinations of two or more thereof. Examples of the metal oxide include aluminum oxide, molybdenum oxide, indium oxide, tin oxide, and indium tin oxide. Examples of the polymer substrate include a polytetrafluoroethylene (PTP), a polyethersulfone (PES) (PAR, polyacrylate), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethyleneterephthalate (PET), polyphenylene sulfide (PPS), polyarylate but are not limited to, polyallylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), and cellulose acetate propinonate (CAP).

For example, the substrate 110 may be a polymer substrate, but is not limited thereto.

On the substrate 110, a high-work function and high-conductivity hybrid electrode 1 are formed.

The work function-control layer 130 includes a low-surface energy material. By including the low-surface energy material, the work function of the second surface 130B of the work function-controlling layer 130 toward the hole transport layer 140 may be 5.0 eV or more. For example, the work function measured at the second surface 130B of the work function-control layer 130 in the hybrid electrode may be 5. eV to 6.5 eV, but is not limited thereto.

As used herein, the term "low-surface energy material" refers to a material capable of forming a film having a low surface energy, specifically, a material having a surface energy lower than that of a conductive material (included in the conductivity-control layer) Lt; / RTI >

The low-surface energy material is a material including at least one F, and may have a hydrophobicity greater than that of the conductive polymer. In addition, the low-surface energy material may be a material capable of providing a work function greater than the work function of the conductive material. For example, the low-surface energy substance, the low - has a thin film of 100nm thickness of the surface energy of less than 30mN / m made of a surface energy materials, which have a conductivity of 10 ^-1 to 10 ^-15 S / cm Lt; / RTI >

The low-surface energy material may be a material having a solubility of at least 90%, such as at least 95%, for a polar solvent. Examples of the polar solvent include water, alcohols (methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc.), ethylene glycol, glycerol, dimethylformamide (DMF), dimethylsulfoxide (DMSO) But the present invention is not limited thereto.

The low-surface energy material may be at least one F-containing material. For example, the low-surface energy material may be a fluorinated polymer or fluorinated oligomer containing at least one F.

For example, the low-surface energy material may be an ionomer comprising at least one of the repeating units of 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;

≪ 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).

Alternatively, the low-surface energy material may be a fluorinated ionomer having a structure of the following formulas (14) to (19).

&Lt; Formula 14 > < EMI ID =

&Lt; Formula 16 > < EMI ID =

&Lt; Formula 18 > < Formula 19 >

Of the above formulas (14) to (19)

R ₁₁ to R _14, R ₂₁ to R _28, R ₃₁ to R _38, R ₄₁ to R _48, R ₅₁ to R ₅₈ and R ₆₁ to R ₆₈ are independently hydrogen, -F, C ₁ -C ₂₀ together An alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₁ -C ₂₀ alkyl group substituted with at least one -F, a C ₁ -C ₂₀ alkoxy group substituted with at least one -F, Q ₁ , -O- (CF _{2 CF (CF 3) -O) n} - (CF 2) m -Q 2 ( wherein, n and m are independently from 0 to 20, being an integer, n + m is 1 to each other more), and - (OCF ₂ CF ₂ ) _x -Q ₃ (where, x is selected from an integer of 1 to 20),

Wherein Q ₁ to Q ₃ are ionic groups and the ionic group comprises an anionic group and a cationic group and the anionic group is selected from PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- and BO ₂ ^{2 -} Wherein the cationic group comprises at least one of a metal ion and an organic ion and the metal ion is selected from Na ⁺ , K ⁺ , Li ⁺ , Mg ⁺² , Zn ⁺² and Al ⁺³ , is ^{_{H +, CH 3 (CH 2}} ) n1 NH 3 + ( wherein, n1 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 ⁺ wherein R is CH ₃ (CH ₂ ) _{n 2} - and n2 is an integer from 0 to 50;

At least one of R ₁₁ to R ₁₄ , at least one of R ₂₁ to R ₂₈ , at least one of R ₃₁ to R ₃₈ , at least one of R ₄₁ to R ₄₈ , at least one of R ₅₁ to R ₅₈ and R ₆₁ to R ₆₈ at least one, -F, at least in the one -F substituted C ₁ -C ₂₀ alkyl group, a substituted C ₁ -C ₂₀ alkoxy group with at least one of _{-F, -O- (CF 2 CF (CF} 3 in) -O) _n - (CF ₂ ) _m -Q ₂ and - (OCF ₂ CF ₂ ) _x -Q ₃ .

On the other hand, the low-surface energy material may be a fluorinated oligomer represented by the following chemical 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 20 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 of the heteroaryl group may be substituted with the same substituent as the alkyl group.

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

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 conductivity-controlling layer 120 may include at least one of a conductive polymer, a metallic carbon nanotube, a graphene, a reduced oxide graphene, a metal nanowire, a semiconductor nanowire, a metal grid, a metal nano dot, and a conductive oxide , The low-surface energy material is not included.

The conductivity-controlling layer 120 mainly enhances the conductivity of the high-work function and high-conductivity hybrid electrode 1, and additionally controls the scattering, reflection, and absorption so as to perform optical extraction (in the case of OLED) Or to improve light incidence (in the case of a solar cell), or to impart flexibility to improve mechanical strength.

The conductivity-control layer 120 is in contact with the first surface 130A of the work-function-control layer 130. The conductivity-

For example, the conductive polymer may be a polythiophene, a polyaniline, a polypyrrole, a polystyrene, a sulfonated polystyrene, a poly (3,4-ethylenedioxythiophene), a self-doped conductive polymer, a derivative thereof, . The derivative may mean that it may further include various sulfonic acids and the like.

For example, the conductive polymer may be selected from the group consisting of Pani: DBSA (polyaniline / dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid, see Chemical Formula), PEDOT: PSS (poly (3,4-ethylenedioxythiophene) (Polyaniline / camphor sulfonicacid) or PANI: PSS (polyaniline) / poly (4-ethylenediaminetetrafluoroethylene) styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)), and the like, but the present invention is not limited thereto.

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 metallic carbon nanotube may be a purified metallic carbon nanotube itself or a carbon nanotube having metal particles (for example, Ag, Au, Cu, Pt particles, etc.) attached to the inner wall and / Lt; / RTI &gt;

The graphene may be a graphene monolayer having a thickness of about 0.34 nm, a few layer graphene having a laminated structure of 2 to 10 graphene monolayers, or a graphene single layer having a larger number of graphenes than the water- Layer may have a multi-layer structure of graphene having a laminated structure.

The metal nanowires and the semiconductor nanowires can be, for example, Ag, Au, Cu, Pt NiSi _x (Nickel Silicide) nanowires, and composites of two or more of the same, such as alloys or core- ) Structures, etc.) nanowires, but are not limited thereto.

Alternatively, the semiconductor nanowires may be Si nanowires doped with Si, Ge, B or N, Ge nanowires doped with B or N, and complexes of two or more of them (e.g., alloys or core-shell structures) But is not limited thereto.

The diameter of the metal nanowire and the semiconductor nanowire may be 5 nm to 100 nm or less and the length may be 500 nm to 100 μm depending on the method of manufacturing the metal nanowire and the semiconductor nanowire .

The metal grid may be formed of metal wires intersecting each other by using Ag, Au, Cu, Al, Pt, or an alloy thereof, and may have a line width of 100 nm to 100 탆, Do not. The metal grid may be formed to protrude from the substrate, or may be embedded in the substrate to form a recess.

The metal nano dots may be selected from Ag, Au, Cu, Pt, and nano dots of two or more complexes (for example, an alloy or a core-shell structure), but are not limited thereto.

The metal nanowires, the surface of the semiconductor nano-wire and nano-metal point, -S (Z ₁₀₀₎ and _{-Si (Z 101) (Z 102} ) at least one moiety represented by (Z ₁₀₃₎ (here, the Z _100, Z ₁₀₁ , Z ₁₀₂ and Z ₁₀₃ are independently of each other hydrogen, a halogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group) . The -S (Z ₁₀₀₎ and _{-Si (Z 101) (Z 102} ) (Z 103) with at least one moiety represented a self-assembly (self-assembled) as a moiety, the metal nano via the moiety The bonding strength between the wire, the semiconductor nanowire and the metal nano dots, or the bonding force between the metal nanowire, the semiconductor nanowire, and the metal nano dots and the substrate 210 can be enhanced. As a result, An improved high-work function and high-conductivity hybrid electrode 1 can be manufactured.

The conductive oxide may be one of ITO (indium tin oxide), IZO (indium zinc oxide), SnO _2, and InO ₂ .

When the high-work function and high-conductivity hybrid electrode 1 is used as a transparent electrode, the thickness of the work-function control layer 130 of the high-work function and high-conductivity hybrid electrode 1 is 20 nm to 500 nm For example, 50 nm to 200 nm. When the thickness of the work function-control layer 130 satisfies the above-described range, excellent work function characteristics, transmittance and flexible characteristics can be provided.

The conductivity of the high-work function and high-conductivity hybrid electrode 1 may be 1 S / cm or more (when the thickness of the high-work function and high-conductivity hybrid electrode 1 is 100 nm).

The high-work function and high-conductivity hybrid electrode 1 as described above is formed by forming the conductivity-control layer 120 on the substrate 110 and then forming the low-conductivity- The surface energy material, and the first solvent, and then heat-treating the mixture to form the work function-controlling layer 130.

First, a conductivity-control layer 120 is formed on the substrate 110.

According to one embodiment, on the substrate 110, a spin coating method, a casting method, an amount Muray-Blodgett method (LB), an ink-jet printing method, a nozzle printing method ), Slot-die coating, doctor blade coating, screen printing, dip coating, gravure printing, reverse offset printing, The conductive polymer may be formed using a reverse-offset printing method, a physical transfer method, a spray coating method, a chemical vapor deposition method, a thermal evaporation method, The conductivity-control layer can be formed by directly providing at least one of metallic nanotubes, metallic carbon nanotubes, graphenes, reduced oxide graphenes, metal nanowires, metal grids, carbon nanotubes, semiconductor nanowires, and metal nano dots .

According to another embodiment, the conductivity-control layer 120 may be formed of a conductive polymer, a metal carbon nanotube, a graphen, a reduced oxide graphen, a metal nanowire, a metal grid, a carbon nano dot, At least one of the nano dots and ii) the second solvent is coated on the substrate, and then the second solvent is removed by heat treatment. As an example of the second solvent, an example of a first solvent to be described later is referred to.

According to another embodiment, the conductive-control layer 120 may be formed by physically transferring a graphene sheet onto the substrate 110 when the conductive-control layer 120 may include graphene.

According to another embodiment, when the conductivity-controlling layer 120 includes the metallic carbon nanotubes, the metallic carbon nanotubes may be grown on the substrate 110, or the carbon nanotubes dispersed in the solvent may be solution- It can be formed by a printing method (for example, a spray coating method, a spin coating method, a dip coating method, a gravure coating method, a reverse offset coating method, a screen printing method, a slot-die coating method).

According to another embodiment, when the conductivity-controlling layer 120 includes a metallic grid, a metal layer is formed on the substrate 110 by vacuum deposition of metal, and patterned into various mesh patterns by photolithography. (E.g., spray coating, spin coating, dip coating, gravure coating, reverse offset coating, screen printing, slot-die coating), or by dispersing a metal precursor or metal particles in a solvent .

Next, a mixture comprising the low-surface energy material and the first solvent as described above is provided on the conductivity-controlling layer 120. The description of the low-surface energy material is given above. The first solvent is miscible with the low-surface energy material and can be easily removed by heating or the like. The first solvent can be a polar solvent, for example, water, alcohols (methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc.), formic acid, nitromethane, (N-methyl-2-pyrrolidone), N-dimethylacetamide (N-dimethylacetamide), dimethylformamide Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate (EtOAc), acetone, acetone, acetonitrile and the like. On the other hand, when selecting the first solvent, a co-solvent may be used. For example, as the first solvent, a mixture of water and an alcohol can be used.

The organic light emitting diode 100 may not include a hole injection layer. A conventional hole injection layer formed from a conductive polymer composition such as poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT: PSS) and polyaniline: poly (styrenesulfonate) The thin film conductivity is about 10 ^-6 S / cm to 10 ^-2 S / cm. For example, PEDOT: PSS of CLEVIOUS ^TM P VP AI4083 (Heraeous, formerly HC Starck) has a conductivity of 10 ^-3 S / cm, and CEDVIOUS ^TM VP VP CH8000 (Heraeous, formerly HC Starck) : PSS has a conductivity of 10 ^-6 S / cm. However, it is difficult to use PEDOT: PSS and PANI: PSS, which are used in the conventional hole injection layer, as an electrode material because the conductive polymer must have a conductivity of at least 0.1 S / cm or more in order to be used as an electrode material. The conductive polymer having a conductivity of 0.1 S / cm or more of the present invention is difficult to be used as a hole injection layer material. When the conductive polymer is used as a hole injection layer material, crosstalk between pixels of the organic light- As shown in FIG. Therefore, the conventional conductive polymer for forming a hole injection layer has been selected from materials which have a conductivity of 10 ^-2 S / cm or less and have a work function higher than that of the conventional ITO to facilitate hole injection.

FIG. 2 shows the conductivity-control layer 120 and the work function-control layer (not shown) of the high-work function and high-conductivity hybrid electrode 1 when the conductive polymer capable of dissolving or dispersing in the solvent is used as the conductivity- 130 and the hole transporting layer 140. In the drawings, FIG. When the work function-control layer dispersed in the solvent is coated on the conductive layer-control layer, the lower layer is partially melted or dispersed, thereby causing a rotting phenomenon. As a result, a gradient type electron energy level can be changed. If a material such as a graphene sheet, a metal grid, or a conductive oxide thin film which is not dispersed in a solvent is used as the conductivity-control layer, a change in the electron energy level in a gradient form as shown in Fig. 2 is not observed Stepwise energy level changes are observed for each layer. Therefore, in FIG. 2, the work function-control layer 130 has the same ionization energy as the lower surface 130A or the upper surface 130B when there is no decay.

As described above, when a conductive polymer capable of dissolving or dispersing in a solvent is used as the conductivity-control layer, the work function of the work function-control layer 130 can be determined from the work function-control layer 130 may be a variable having a slope that gradually increases along the direction from the first surface 130A to the second surface 130B. The work function of the first surface 130A of the work function-control layer 130 is Y ₁ eV and the work function of the second surface 130B is Y ₂ eV, where Y ₁ <Y ₂ . Thus, even if there is no hole injecting layer between the high-work function and high-conductivity hybrid electrode 1 serving as an anode and the hole transporting layer 140, a high-work function and high-conductivity can be obtained from the hybrid electrode 1 to the hole transporting layer 140 can be increased. That is, the high-work function and high-conductivity hybrid electrode 1 can also be interpreted to serve also as a role of the conventional anode and hole injection layers. Therefore, the organic light emitting device 100 including the high-work function and high-conductivity hybrid electrode 1 as the anode can have excellent efficiency, brightness, and lifetime characteristics without forming a hole injection layer. Therefore, the manufacturing cost of the OLED 100 can be reduced.

The work function of the hole transport layer 140 may be Z eV, where Z may be a real number from 5.2 to 5.6, but is not limited thereto.

The work function value Y ₁ of the first surface 130A of the work function-control layer 130 of the high-work function and high-conductivity hybrid electrode ₁ is 4.6 to 5.2, for example, 4.7 to 4.9 Lt; / RTI &gt; The work function value Y ₂ of the second surface 130B of the work function-control layer 130 of the high-work function and high-conductivity hybrid electrode 1 is set to a value May be equal to or less than the work function of the low-surface energy material. For example, the Y ₂ may range from 5.0 to 6.5, for example, from 5.3 to 6.2, but is not limited thereto. However, when a material such as a graphene sheet, a metal grid, or a conductive oxide thin film which is not dispersed in a solvent is used as the conductivity-control layer, the gradient of the electron energy level is not observed, the change of energy level in step form is observed for each layer. Accordingly, in FIG. 2, if there is no decline in the work function-control layer 130, the first surface 130A or the second surface 130B has the same ionization energy or work function (Y _{1 =} Y ₂ ) .

The second surface 130B of the work function-control layer 130 of the high-work function and high-conductivity hybrid electrode 1 serving as the anode does not include the hole injection layer, And may contact the transport layer 140.

The hole transport layer 140 may be formed by any of various known methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. At this time, when selecting the vacuum deposition, the deposition conditions is the desired compound, varies depending on the structure and thermal properties of the layer for the purpose of, for example, the deposition temperature range, 10 ^-10 to 10 100 to 500 ℃ ^-3 torr A vacuum degree range, and a deposition rate range of 0.01 to 100 A / sec. On the other hand, when the spin coating method is selected, the coating conditions vary depending on the target compound and the structure and thermal properties of the target layer, but the coating speed ranges from 2000 rpm to 5000 rpm, the heat treatment temperature is 80 to 200 캜 Lt; RTI ID = 0.0 &gt; temperature). &Lt; / RTI &gt;

The hole transport layer 140 material may be selected from materials capable of transporting holes more efficiently than hole injection. The hole transport layer 140 may be formed using a known hole transport material, for example, an amine-based material having an aromatic condensed ring, or a triphenylamine-based material.

More specifically, the hole-transporting material may be at least one selected from the group consisting of 1,3-bis (carbazol-9-yl) benzene (MCP), 1,3,5- (Carbazol-9-yl) benzene: TCP), 4,4 ', 4 "-tris (carbazol-9-yl) triphenylamine Carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis ) biphenyl (CBP), N, N'-bis (naphthalen-1-yl) -N, N'- bis (phenyl) -benzidine: NPB), N, N'-bis (naphthalen-2-yl) -N, N'- N, N'-bis (phenyl) -benzidine:? -NPB), N, N'-bis (naphthalen- , N'-bis (phenyl) -2,2'-dimethylbenzidine:? -NPD),

N, N ', N'-diphenyl-cyclohexane: TAPC), di- [4- (N, N -ditolylamino) N'-tetra-naphthalen-2-yl-benzidine:? - TNB) and N4, N4, N4 ', N4'-tetra (9,9-dioctylfluorene-co-bis-N, N '- (4-butylphenyl) -bis-N, N'-phenyl (4-butylphenyl) diphenylamine (TFB), poly (9,9'-dioctylfluorene-co-bis-N, N'- (4-butylphenyl) -bis-N, N'-phenylbenzidine (BFB), poly (9,9-dioctylfluorene-co- phenyl-1,4-phenylenediamine (PFMO), and the like.

<NPB><MCP><TCP>

<TCTA><CBP>

< beta-NPB >< alpha -NPD >< TAPC &

<β-TNB> <TPD15>

The thickness of the hole transporting layer 140 may be 5 nm to 100 nm, for example, 10 nm to 60 nm. When the thickness of the hole transporting layer 140 satisfies the above-described range, excellent hole transporting characteristics can be obtained without increasing the driving voltage.

The light emitting layer 150 may be formed by a vacuum deposition method, a spin coating method, a casting method, an LU (Langmuir-Blodgett method), an ink-jet printing method, a nozzle printing method, Coating methods such as a die coating method, a doctor blade coating method, a screen printing method, a dip coating method, a gravure printing method, a reverse offset printing method reverse-offset printing, physical transfer method, spray coating, and the like. At this time, the deposition conditions and the coating conditions are selected within the range similar to the conditions for forming the hole transport layer 140 as described above, depending on the target compound, the structure of the target layer, the thermal properties, and the like.

The light emitting layer 150 may be made of a single light emitting material, and may include a host and a dopant.

Examples of the host include Alq ₃ , CBP (4,4'-N, N'-dicarbazole-biphenyl), 9,10-di (naphthalen-2-yl) anthracene (ADN), TCTA, TAPC, TPBI (N-phenylbenzimidazole-2-yl) benzene), TBADN (3-tert-butyl-9 , E3 (see the following chemical formula), BeBq ₂ (see the following chemical formula), and mixtures thereof, but the present invention is not limited thereto. If necessary, NPB, which is an example of the material of the hole transport layer 130, can also be used as a host.

As the known red dopant, rubrene (5,6,11,12-tetraphenylnaphthacene), PtOEP, Ir (piq) ₃ , Btp ₂ Ir (acac) and the like can be used.

Further, as a known green _{dopant, Ir (ppy) 3 (ppy} = _{phenylpyridine), Ir (ppy) 2 (} acac), Ir (mpyp) 3, C545T (10- (2- benzothiazolyl) -1,1 , 7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- [l] benzopyrano [6,7,8-ij] quinolizine- ), But the present invention is not limited thereto.

C545T

On the other hand, known blue dopants include F ₂ Irpic, (F ₂ ppy) ₂ Ir (tmd), Ir (dfppz) ₃ , ter-fluorene, 4,4'- -Tolylamino) styryl] biphenyl (DPAVBi), 2,5,8,11-tetra- tert -butylpyrylene (TBP), and the like.

The thickness of the light emitting layer 150 may be 10 nm to 100 nm, for example, 10 nm to 60 nm. When the thickness of the light emitting layer 150 is in the above range, excellent light emitting characteristics can be obtained without increasing the driving voltage.

The hole blocking layer (not shown in FIG. 2) may be formed by diffusing triplet excitons or holes of the light emitting layer 150 (for example, when the light emitting layer 150 includes a phosphorescent compound) into the second electrode 180 or the like And may be formed on the light emitting layer 150 and may be formed according to a method selected from various known methods such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, and the like. have. At this time, the deposition conditions and the coating conditions are selected within the range similar to the conditions for forming the hole transport layer 140 as described above, depending on the target compound, the structure of the target layer, the thermal properties, and the like.

The hole blocking material may be arbitrarily selected from known hole blocking materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and the like can be used.

The thickness of the hole blocking layer may be about 5 nm to 100 nm, for example, 10 nm to 30 nm. When the thickness of the hole blocking layer satisfies the above range, excellent hole blocking characteristics can be obtained without increasing the driving voltage.

The electron transport layer 160 may be formed by a method selected from various known methods such as a vacuum deposition method, a spin coating method, a nozzle printing method, a casting method, a gravure printing method, a slot die coating method, a screen printing method, 150) or on the hole blocking layer. At this time, the deposition conditions and the coating conditions are selected within the range similar to the conditions for forming the hole transporting layer as described above, depending on the target compound, the structure of the target layer and the thermal properties, and the like.

For example, the electron transport layer may be a quinoline derivative, particularly tris (8-hydroxyquinoline) aluminum (Alq), or tris ₃ ), bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (Balq), bis 10-hydroxybenzo [h] quinolinato) beryllium (Bebq ₂ ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrol 4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline Bphen), 2,2 ', 2 "- (benzene-1,3,5-triyl) -tris (1-phenyl-1H- benzimidazole) , 3,5-triyl) -tris (1-phenyl-1H-benzimidazole: TPBI), 3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ) (Naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole : NTAZ), 2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-naphthalen- -1,10-phenanthroline: NBphen), tris (2,4,6-trimethyl-3- (pyridin- yl) phenyl) borane: 3TPYMB), phenyl-dipyrenylphosphine oxide (POPy2), 3,3 ', 5,5'-tetra [(m-pyridyl) (3,3 ', 5,5'-tetra [(m-pyridyl) -phen-3-yl] biphenyl: BP4mPy), 1,3,5-tri [ 3-yl] benzene: TmPyPB), 1,3-bis [3,5-di (pyridin-3-yl) phenyl] ] Benzene (BmPyPhB), bis (10-hydroxybenzo [h] quinolinato) beryllium (Bis (10-hydroxybenzo [ Diphenylbis (4- (pyridin-3-yl) phenyl) silane: DPPS) and 1,3,5-diazabicyclo [ - (P-pyrid-3-yl-phenyl) benzene: TpPyPB), 1,3-bis [2- (2,2 -Bipyridin-6-yl) -1, 3, 4-oxadiazol-5-yl] Oxadiazo-5-yl] benzene: Bpy-OXD), 6,6'-bis [5- (biphenyl-4-yl) -1,3,4- , Biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2,2'-bipyridyl: BP-OXD-Bpy ), But the present invention is not limited thereto.

<Alq ₃ ><TPBI>

<PBD><BCP>

<Bphen><Balq><Bpy-OXD>

<BP-OXD-Bpy><TAZ>

<NTAZ><NBphen><3TPYMB>

<POPy2><BP4mPy><TmPyPB>

<BmPyPhB> <Bepq2>

<Bebq2><DPPS>

<TpPyPB>

The thickness of the electron transporting layer 160 may be about 5 nm to 100 nm, for example, 15 nm to 50 nm. When the thickness of the electron transporting layer 160 satisfies the above-described range, excellent electron transporting characteristics can be obtained without increasing the driving voltage.

An electron injection layer 170 may be formed on the electron transport layer 160. As the electron injecting layer forming material, known electron injecting materials such as iF, NaCl, NaF, CsF, Li ₂ O, BaO, BaF ₂ , Cs ₂ CO ₃ , Liq (lithium quinolate) The deposition conditions of the injection layer 170 vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer 130.

The thickness of the electron injection layer 170 may be about 0.1 nm to 10 nm, for example, 0.5 nm to 5 nm. When the thickness of the electron injection layer 170 satisfies the above-described range, satisfactory electron injection characteristics can be obtained without substantially increasing the driving voltage.

In addition, the electron injection layer may include one or more of LiF, NaCl, CsF, NaF, and Li ₂ O in an amount of 1 to 50% based on the electron transport layer materials such as Alq ₃ , TAZ, Balq, Bebq ₂ , BCP, TBPI, TmPyPB, and TpPyPB. , A metal oxide of BaO or Cs ₂ CO ₃ and doped with a metal such as Li, Ca, Cs, Mg, etc.

The second electrode 180 serves as a cathode. As the material of the second electrode 180, a metal, an alloy, an electrically conductive compound, or a combination thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . ITO, IZO, or the like may also be used to obtain a front light emitting element.

The organic light emitting device 100 includes the above-described high-work function and high-conductivity hybrid electrode 1 as an anode, and can have a very high hole injection efficiency without forming a hole injection layer, Further, since electrons can be prevented from flowing into the high-work function and high-conductivity hybrid electrode 13 via the hole transporting layer 140, the organic light emitting device 100 can have excellent electrical characteristics, If a flexible substrate is employed as the substrate 110, the organic light emitting device 100 may have a flexible characteristic.

The organic light emitting device 100 of FIG. 2 has a structure in which a hole transport layer 140 is interposed between a high-work function and high-conductivity hybrid thin film 1 which is an anode and a light emitting layer 150, The second face 130B of the work function-control layer 130 of the anode-high work function and high-conductivity hybrid electrode 1 can be in contact with the light emitting layer 150, and the like, .

Figure 3 schematically illustrates an embodiment of an organic solar cell comprising a high-work function electrode as described above.

The organic solar cell 200 of Figure 3 includes a substrate 210, a high-work function and high-conductivity hybrid electrode 2, a photoactive layer 240, an electron transport region 250 and a second electrode 260 do. The light irradiated to the organic solar cell 200 is separated into holes and electrons in the photoactive layer 240 so that the electrons move to the second electrode 260 through the electron transporting region 250 and the holes move to the high- - conductive hybrid electrode (2).

The high-work function and high-conductivity hybrid electrode 2 includes a conductivity-control layer 220 and a work-function-control layer 230, and is formed between the photoactive layer 240 and the conductivity- The work function-control layer 230 is interposed.

The description of the substrate 210 and the high-work function and high-conductivity hybrid electrode 2 in FIG. 3 is based on the substrate 110 and the high-work-function and high-conductivity hybrid- See the description.

The photoactive layer 240 may include a material capable of separating holes and electrons from the irradiated light. For example, the photoactive layer 240 may include an electron donor and a hole acceptor. The photoactive layer 240 may have a variety of structures including a single layer including the electron donor and the hole acceptor or multiple layers including the layer including the electron donor and the layer including the hole acceptor .

The electron donor may include a p-type conductive high molecular material including a [pi] -electron. Examples of the electron donor include P3HT (poly (3-hexylthiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy- Phenylene-vinylene), MEH-PPV (poly- [2-methoxy-5- (2'-ethoxyhexyloxy) - (2'-ethylhexyloxy) -1,4-phenylene vinylene], MDMO-PPV (poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) Phenylene vinylene]), PFDTBT (poly (2,7- (9,9-dioctyl) -fluorene] poly ((2,7- (9,9-dioctyl) -2,5-dihydro- -fluorene-alt-5,5- (4 ', 7'-di-2-thienyl-2', 1 ', 3'- benzothiadiazole), PCPDTBT (poly [N'-O'-heptadecanyl- (4 ', 7'-di-2-thienyl-2', 1 ', 3'- benzothiazole), polyindole, polycarbazole, Diazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene, polyphosphate Examples of the electron donor include, but are not limited to, rhenylene, polypyridine, CuPc (Copper Phthalocyanine), SubPc (subphthalocyanine), ClAlPc (Chloro-aluminum phthalocyanine) It is of course also possible to use combinations (including blends, copolymers, etc.).

Examples of the hole receptor include fullerenes having a high electron affinity (for example, C60, C70, C74, C76, C78, C82, C84, C720, C860, etc.); Fullerene derivatives (for example, PCBM ([6,6] -phenyl-C61 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 240 may be a single layer including P3HT as an electron donor and PCBM as a hole receptor, but is not limited thereto.

The photoactive layer 240 is irradiated with light, and excitons, which are pairs of electrons and holes, are formed by photoexcitation. The excitons act on the electrons and holes due to the difference in electron affinity between the electron donor and the hole acceptor at the interface between the electron donor and the hole acceptor. And is separated into holes.

The electron transport region 250 may include an electron transport layer and an electron extraction layer. The electron transport layer serves to help transport electrons generated in the photoactive layer 240 to the second electrode 260.

As the electron transport layer material, refer to the electron transport layer 160 material of FIG.

The electron extraction layer may assist in transferring electrons generated in the photoactive layer 240 to the second electrode 260. Examples of the electron extraction layer material include, but are not limited to, LiF, NaCl, CsF, NaF, Li ₂ O, BaO, Cs ₂ CO ₃ and the like. The thickness of the electron injection layer may be from about 1 A to about 100 A, and from about 3 A to about 90 A. When the thickness of the electron injection layer satisfies the above-described range, satisfactory electron injection characteristics can be obtained without substantially increasing the driving voltage.

Further, the electron extraction layer may contain LiF, NaCl, CsF, NaF, and Li ₂ O in an amount of 1 to 50% in the electron transport layer materials such as Alq ₃ , TAZ, Balq, Bebq ₂ , BCP, TBPI, TmPyPB, and TpPyPB. , A metal oxide of BaO or Cs ₂ CO ₃ and doped with a metal such as Li, Ca, Cs, Mg, etc.

The photoactive layer 240 and the electron transport region 250 in the organic solar cell may be fabricated by a vacuum deposition and solution process. The vacuum deposition is typically performed by thermal evaporation, and the solution process may be carried out by spin coating, ink-jet printing, nozzle printing, spray coating, A screen printing method, a doctor blade coating method, a gravure printing method and an offset printing method may be used.

The second electrode 260 may use a metal, an alloy, an electrically conductive compound, or 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- .

Since the organic solar cell 200 employs the high-work function and high-conductivity hybrid electrode 2 as described above, the holes generated in the photoactive layer 240 can be easily converted into high-work function and high- To the electrode (2). Therefore, excellent electrical characteristics can be provided.

The organic solar cell 200 of FIG. 3 does not include a hole extracting layer, but a hole is formed between the high-work function and high-conductivity hybrid electrode 2 and the photoactive layer 240 of the organic solar cell 200 of FIG. A variety of modifications are possible, for example, an extraction layer can be further intervened. As the hole extracting layer material, the hole transporting layer 140 material of FIG. 1 can be used.

FIG. 4 schematically shows an embodiment of an organic thin film transistor including a hybrid electrode having a stacked structure having the high-work function and high-conductivity.

The organic thin film transistor 300 of FIG. 4 includes a substrate 311, a gate electrode 312, an insulating layer 313, an organic semiconductor layer 315, and source and drain electrodes 314a and 314b. At least one of the gate electrode 312 and the source and drain electrodes 314a and 314b may be a high-work function and high-conductivity hybrid electrode as described above.

For the description of the substrate 311, refer to the description of the substrate 110. A gate electrode 312 of a predetermined pattern is formed on the substrate 311. The gate electrode 312 may be a high-work function and high-conductivity hybrid electrode as described above. Or an alloy of metals such as Au, Ag, Cu, Ni, Pt, Pd, Al, Mo, or Al: Nd, Mo: W alloy or the like, but is not limited thereto.

An insulating layer 313 is formed on the gate electrode 312 to cover the gate electrode 312. The insulating layer 313 may be formed of an inorganic material such as a metal oxide or a metal nitride, or may be formed of an organic material such as a flexible organic polymer.

An organic semiconductor layer 315 is formed on the insulating layer 313. The organic semiconductor layer 315 may be formed of one selected from the group consisting of pentacene, tetracene, anthracene, naphthalene, alpha-6-thiophene, alpha-4-thiophene, perylene, And derivatives thereof, rubrene and derivatives thereof, coronene and derivatives thereof, perylene tetracarboxylic diimide and derivatives thereof, perylene tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride and derivatives thereof, perylene tetracarboxylic dianhydride and derivatives thereof, tetracarboxylic dianhydride and derivatives thereof, polythiophene and derivatives thereof, polyparaphenylene vinylene and derivatives thereof, polyparaphenylene and derivatives thereof, polyfluorene and derivatives thereof, polythiophene and derivatives thereof, polythiophene and derivatives thereof, Oligopeptides of the naphthalene and derivatives thereof, oligothiophenes and derivatives thereof of alpha-5-thiophene, phthalocyanines containing and not containing metals and derivatives thereof, Pyromellitic diimides, derivatives thereof, and the like, but the present invention is not limited thereto.

Source and drain electrodes 314a and 314b are formed on the organic semiconductor layer 315, respectively. As shown in FIG. 4, the source and drain electrodes 314a and 314b may be formed so as to overlap with the gate electrode 312, but the present invention is not limited thereto. The source and drain electrodes 314a and 314b may be high-work function and high-conductivity hybrid electrodes as described above. Alternatively, the source and drain electrodes 314a and 314b may be formed of a noble metal such as Au, Pd, Pt, Ni, Rh, Ru, or the like in consideration of the work function of the material forming the organic semiconductor layer. , Ir, Os, and combinations of two or more of them may be used.

In addition, according to another embodiment, the work function-control layers 130 and 230 of the high-work function and high-conductivity hybrid electrodes 1 and 2 may be provided with carbon nanomaterials A metal nanowire, a metal carbon nanotube, a semiconductor quantum dot, a semiconductor nanowire, and a metal nano-dot. By the additive, the conductivity of the high-work function and high-conductivity hybrid electrodes 1 and 2 can be further improved.

As examples of the electronic device, an organic light emitting device, an organic solar cell, and an organic thin film transistor have been described with reference to Figs. 1 to 4, but the electronic device is not limited thereto.

For example, the high-work function and high-conductivity hybrid electrode may be used as the second electrode 190 of the organic light emitting device of FIG. 1 or the second electrode 260 of the organic solar cell of FIG. 3, . At this time, the work function-control layer may be disposed in a direction toward or opposite to the light emitting layer of the organic light emitting element or the photoactive layer of the organic solar cell, and the high-work function and high-conductivity hybrid electrode may be formed on the base film And then transferred onto the electron injection layer 170 of the organic light emitting device or the electron transporting region 250 of the organic solar cell by using, for example, Laser Induced Thermal Imaging (LITI) or Transfer Printing process. .

In addition, the high-work function and high-conductivity hybrid electrode can be used for manufacturing an inverted organic light emitting device or an organic solar cell.

The electronic device may include an organic memory device, an organic photodetector, or an organic CMOS sensor, as well as an organic light emitting device, an organic solar cell, and an organic thin film transistor.

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  1: high- Work function  And high-conductivity hybrid  Electrode production

<Conductivity Control layer  Formation>

 A mixture containing PEDOT: PSS (PH500 from HC Starck) as a conductivity-control layer and 5 wt% DMSO was prepared. The mixture was spin-coated on a PET substrate and then heat-treated at 200 ° C for 10 minutes to form a thin film having a thickness of 100 nm. The conductivity of the conductive polymer layer 1 was 300 S / cm (measured with a 4-point probe).

< Work function Control layer  Formation>

The polymer 100 was dispersed in 5% by weight in a solution of the following polymer 100 (a mixture of water and alcohol (water: alcohol = 4.5: 5.5 (v / v)) as a work function-control layer, manufactured by Aldrich Co.) Was diluted to 5% by weight with isopropyl alcohol (purity of JT Baker Co., Ltd., CMOS grade).

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

The mixture was spin-coated on the conductive polymer layer 1 at 5000 rpm for 90 seconds and then heat-treated at 150 캜 for 10 minutes to form an electrode 1.

Comparative Example  A

Except that a thin film was formed from a mixture containing PEDOT: PSS (PH500 of HC Starck Co.) and 5% by weight of DMSO, without coating the work function control layer with the electrode 1, except that the conductive polymer layer 1 The electrode A was manufactured using the same method as the production method of the electrode A.

Evaluation example  1: high- Work function  And high-conductivity hybrid  Electrode evaluation

<High- Work function  And high-conductivity hybrid  Electrode Work function  And conductivity evaluation>

For the electrode 1 and the electrode A, the work function was evaluated using ultraviolet photoelectron spectroscopy in air (manufactured by Nikken Keiki, model name is AC2), and the conductivity was measured with a 4-point probe Respectively. The results are shown in Table 1.

The work function (eV) Conductivity (S / cm) Electrode 1 5.80 150 Electrode A 4.73 300

While the polymer 100 provides a high work function, it can be seen that the conductivity is reduced because the polymer 100 is an insulator.

Example  2: OPV Production

According to Example 1, an electrode 1 was formed as an anode on an organic substrate, and then a 80 nm-thick PCDTBT: PC70BM photoactive layer was spin-coated on the electrode 1 to form a 1 nm thick Ca electron extraction layer and a 100 nm thick Of Al cathode were sequentially formed (using the vacuum evaporation method) to prepare OPV 1.

Comparative Example  One

OPV A was fabricated in the same manner as in Example 2, except that the electrode A of Comparative Example A was used instead of the electrode 1.

Comparative Example  2

The upper (15Ω / ㎠ (1200Å) ITO glass substrate of Corning Incorporated (Corning)) ITO electrode PEDOT: PSS solution ^{(CLEVIOS TM P VP AI4083 / PEDOT} 1 parts by weight per PSS is 6 parts by weight) was spin-coated, 200 ℃ For 10 minutes to form a 30 nm thick PEDOT: PSS hole extraction layer. A PCDTBT: PC70BM photoactive layer with a thickness of 80 nm, a Ca electron extraction layer with a thickness of 1 nm, and an Al cathode with a thickness of 100 nm were sequentially formed on the hole injection layer (using the vacuum evaporation method).

Evaluation example  3: OPV  evaluation

(PCE), short-circuit current (J _SC ), open-circuit voltage (V _OC ), and fill factor (FF) for OPV 1 and OPV A to B using the Keithley 2400 source measuring instrument, Newport 69907 power supply and digital exposure controller operation ) Were evaluated. The results are shown in Table 2. From Table 2, it can be seen that OPV 1 shows excellent short circuit current (J _SC ), open circuit voltage (V _OC ) and efficiency (PCE) compared to OPV A to B.

OPVA OPV B OPV 1 Fitted V _OC (V) 0.838 0.856 0.878 Fitted J _SC (mA / cm 2) 10.4 10.9 11.2 FF (%) 47.0 57.4 56.5 PCE (%) 4.1 5.5 5.6

Example  3: OLED Production

After the glass substrate, forming the above-described embodiment the first electrode 1 as an anode in accordance with the mechanism how the, above the TAPC hole transport layer, TCTA of 5nm _{thickness: Ir (ppy) 3 (Ir} (ppy) 3 was 3% by weight ), A 5 nm thick CBP: Ir (ppy) ₃ (Ir (ppy) ₃ is 4 wt%) luminescent layer, a 65 nm thick TPBI electron transport layer, a 1 nm thick LiF electron injection layer and a 110 nm thick Al cathode (Using a vacuum evaporation method) to fabricate OLED 1.

Comparative Example  3

OLED A was fabricated in the same manner as in Example 3, except that the electrode A of Comparative Example A was used instead of the electrode 1 as the anode.

Comparative Example  4

The upper (15Ω / ㎠ (1200Å) ITO glass substrate of Corning Incorporated (Corning)) ITO electrode PEDOT: PSS solution ^{(CLEVIOS TM P VP AI4083 / PEDOT} 1 parts by weight per PSS is 6 parts by weight), spin coated and then, 150 ℃ For 30 minutes to form a 50 nm thick PEDOT: PSS hole injection layer. Ir (ppy) ₃ (Ir (ppy) ₃ is 3 wt%) and a 5 nm thick CBP: Ir (ppy) ₃ (Ir (ppy) ) ₃ was 4 wt%), a 65 nm thick TPBI electron transport layer, a 1 nm thick LiF electron injection layer, and a 110 nm thick Al cathode were sequentially formed (using the vacuum evaporation method).

Evaluation example  3: OLED  evaluation

For OLED 1 and A to B, the efficiency was evaluated using a Keithley 236 source measuring instrument and a Minolta CS 2000 spectro radomet, and the results are shown in Table 3, respectively. The light emitting efficiency of Example 3 was as high as 83.1 lm / W. The light emitting efficiency of Comparative Example 2 was 25.2 lm / W. The light emitting efficiency of Comparative Example 3 was 68.0 lm / W. From this, it can be confirmed that the organic light emitting device of Example 3 has a higher luminous efficiency than the organic light emitting device of Example 3.

OLEDA OLED B OLED1 Power luminous efficiency (lm / W) 25.2 68 83.1

110, 210: substrate
1, 2: High-work function and high-conductivity hybrid thin film
120, 220: conductivity-control layer
130, 230: work function-control layer
130A, 230A: a first side of the work function-control layer (130, 230)
130B, 230B: a second surface of the work function-control layer 130,

Claims (12)

A semiconductor device comprising: a substrate having a first surface and a second surface opposite the first surface, the second surface having a work function of less than 5.0 eV, A work function-tuning layer; And
Wherein the low-surface energy material comprises at least one of a conductive polymer, a metallic carbon nanotube, a graphene, a reduced oxide graphene, a metal nanowire, a semiconductor nanowire, a carbon nano-dot, a metal nano dot and a conductive oxide, A conductivity-tuning layer, wherein the conductivity-control layer is in contact with a first side of the work function-control layer;
Having a conductivity of at least 1 S / cm, including a high work function and a high-conductivity hybrid electrode. The method according to claim 1,
Wherein the low-surface energy material is a fluorinated material comprising at least one F. The method according to claim 1,
Wherein the low-surface energy material is an ionomer comprising at least one of the repeating units of 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 low-surface energy material is a fluorinated ionomer having the structure of formulas (14) to (19) or a fluorinated low molecule of formula (20).
&Lt; Formula 14 >< EMI ID =

&Lt; Formula 16 &gt;&lt; EMI ID =

&Lt; Formula 18 >< Formula 19 >

Of the above formulas (14) to (19)
R ₁₁ to R _14, R ₂₁ to R _28, R ₃₁ to R _38, R ₄₁ to R _48, R ₅₁ to R ₅₈ and R ₆₁ to R ₆₈ are independently hydrogen, -F, C ₁ -C ₂₀ together An alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₁ -C ₂₀ alkyl group substituted with at least one -F, a C ₁ -C ₂₀ alkoxy group substituted with at least one -F, Q ₁ , -O- (CF _{2 CF (CF 3) -O) n} - (CF 2) m -Q 2 ( wherein, n and m are independently from 0 to 20, being an integer, n + m is 1 to each other more), and - (OCF ₂ CF ₂ ) _x -Q ₃ (where, x is selected from an integer of 1 to 20),
Wherein Q ₁ to Q ₃ are ionic groups and the ionic group comprises an anionic group and a cationic group and the anionic group is selected from PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- and BO ₂ ^{2 -} Wherein the cationic group comprises at least one of a metal ion and an organic ion and the metal ion is selected from Na ⁺ , K ⁺ , Li ⁺ , Mg ⁺² , Zn ⁺² and Al ⁺³ , is ^{_{H +, CH 3 (CH 2}} ) n1 NH 3 + ( wherein, n1 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 ⁺ wherein R is CH ₃ (CH ₂ ) _{n 2} - and n2 is an integer from 0 to 50;
At least one of R ₁₁ to R ₁₄ , at least one of R ₂₁ to R ₂₈ , at least one of R ₃₁ to R ₃₈ , at least one of R ₄₁ to R ₄₈ , at least one of R ₅₁ to R ₅₈ and R ₆₁ to R ₆₈ at least one, -F, at least in the one -F substituted C ₁ -C ₂₀ alkyl group, a substituted C ₁ -C ₂₀ alkoxy group with at least one of _{-F, -O- (CF 2 CF (CF} 3 in) -O) _n - (CF ₂ ) _m -Q ₂ and - (OCF ₂ CF ₂ ) _x -Q ₃ .
(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.
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. The method according to claim 1,
Wherein the conductive polymer is selected from the group consisting of a polythiophene, a polyaniline, a polypyrrole, a polystyrene, a sulfonated polystyrene, a poly (3,4-ethylenedioxythiophene), a self-doped conductive polymer, a derivative thereof, . The method according to claim 1,
At least one moiety represented by -S (Z ₁₀₀ ) and -Si (Z ₁₀₁ ) (Z ₁₀₂ ) (Z ₁₀₃ ) on the metal nanowire, the semiconductor nanowire, the carbon nano- Wherein Z ₁₀₀ , Z ₁₀₁ , Z ₁₀₂ and Z ₁₀₃ are independently of each other hydrogen, a halogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group) Electronic device. The method according to claim 1,
Wherein the conductive oxide is one of ITO (indium tin oxide), IZO (indium zinc oxide), SnO _2, and InO ₂ . The method according to claim 1,
Wherein the work function observed at the second side of the work function-control layer in the hybrid electrode is selected in the range of 5.0 eV to 6.5 eV. The method according to claim 1,
Wherein the work function-control layer is at least one selected from the group consisting of carbon nanotubes, graphenes, reduced graphene, metal nanowires, metal carbon nanotubes, semiconductor quantum dots, semiconductor nanowires, Electronic devices, including further additives The method according to claim 1,
An organic light emitting device, an organic solar cell, an organic transistor, an organic memory device, an organic photodetector or an organic CMOS sensor. The method according to claim 1,
Wherein the electronic device is an organic light emitting device,
The organic light emitting device comprising: a substrate; A first electrode; A second electrode; And a light emitting layer interposed between the first electrode and the second electrode,
The first electrode is the high-through-function and high-conductivity hybrid electrode;
Wherein a work function-control layer of the high-through-function and high-conductivity hybrid electrodes is interposed between the light-emitting layer and the conductivity-control layer. The method according to claim 1,
Wherein the electronic device is an organic solar cell,
The organic solar cell comprising: a substrate; A first electrode; A second electrode; And a photoactive layer interposed between the first electrode and the second electrode,
The first electrode is the high-through-function and high-conductivity hybrid electrode;
Wherein a work-function layer of the high-work function and high-conductivity hybrid electrodes is interposed between the photoactive layer and the conductivity-control layer.

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