KR101458690B1 - Conductive thin layer and electronic device comprising the same - Google Patents

Abstract

An electroconductive thin film and an electronic device including the same are provided.

Description

TECHNICAL FIELD The present invention relates to a conductive thin film and an electronic device including the same,

To a conductive thin film and an electronic device including the conductive thin film.

The organic light emitting device is a self light emitting type device having a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and multi-coloring.

A typical organic light emitting device may include an anode and a cathode, and an organic layer interposed between the anode and the cathode. The organic layer may include an electron injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, a cathode, and the like. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transporting layer, and electrons injected from the cathode move to the light emitting layer via the electron transporting layer. The carriers, such as holes and electrons, recombine in the light emitting layer region to produce an exiton, which is changed from the excited state to the ground state to produce light.

On the other hand, as interest in renewable energy is rising all over the world, organic solar cells having potential and future advantages as future energy are getting attention. The organic solar cell can be thinned and manufactured at a lower cost than an inorganic solar cell using silicon, and can be applied to various flexible devices in the future.

It is required to develop a conductive thin film which can easily form a film while satisfying the work function, conductivity, and the like required for each electronic device such as the organic light emitting device and the organic solar cell. This conductive thin film is a layer that improves the hole injection or extraction by complementing the low work function of ITO (4.6-4.9 eV) on a conventional transparent metal oxide electrode (eg, indium tin oxide (ITO) And can be used independently as a transparent electrode instead of a metal oxide electrode. In particular, since the indium tin oxide electrode is continuously increasing in price due to the problem of depletion of the indium resource, it is urgently required to study the material that replaces the indium tin oxide electrode.

A conductive thin film having excellent conductivity and easy work function adjustment, and an electronic device using the conductive thin film.

According to an aspect, there is provided a conductive thin film comprising a conductive polymer and a fluorine-based material containing at least one repeating unit represented by one of the following formulas (1) to (9)

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

&Lt; Formula 5 > < EMI ID =

&Lt; Formula 7 > < EMI ID =

&Lt; Formula 9 >

Among the above formulas (1) to (9)

또는

고, 상기 양이온기는 금속 이온 및 유기 이온 중 1종 이상을 포함하고, 상기 금속 이온은 Na⁺, K⁺, Li⁺, Mg⁺², Zn⁺² 또는 Al⁺³이고, 상기 유기 이온은 H⁺, CH₃(CH₂)_nNH₃ ⁺, NH₄ ⁺, NH₂ ⁺, NHSO₂CF₃ ⁺, CHO⁺, C₂H₅OH⁺, CH₃OH⁺ 또는 RCHO⁺(상기 R은 CH₃(CH₂)_n-이고; n은 0 내지 50의 정수임)임);X ₁₁ , X ₂₁ , X ₃₁ , X ₄₁ , X ₅₁ , X ₆₁ , X ₇₁ , X ₈₁ and X ₉₁ are independently of each other represented by * - [O] _p - [CH ₂ ] _q -X ₁₀₀ Wherein p is 0 or 1, q is an integer from 0 to 50, X ₁₀₀ is an ionic group containing an anionic group and a counter cation group to the anionic group, the anionic group being PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- , BO ₂ ^{2 -} ,

or

And, wherein the metal ion wherein the cationic group containing at least one kind of metal ions and organic ions are ^{Na +, K +, Li +} , Mg +2, and Zn ⁺² or Al ^+3, the organic ions are H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ^+, or RCHO ⁺ wherein R is CH ₃ (CH ₂ ) _n - and n is an integer from 0 to 50;

R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₆₁ , R ₇₁ , R ₈₁ , R ₈₂ , R ₈₃ and R ₉₁ independently represent hydrogen, , A hydroxyl group, an amino group, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group;

Y ₁₁ is S or NH;

aa, ab, ai and ao are independently of each other 1 or 2;

ac and ad are each independently an integer of 1 to 5;

ae, af, ag, ah, aj, ak, al, am and an are independently of each other an integer of 1 to 4;

q21, q31 and q41 are independently a real number in the range of 0.01 to 1, and q22, q32 and q42 are independent of each other and are a real number in the range of 0 to 0.99, and q21, q22, q31, q32, q41 and q42 represent molar ratios, Q21 + q22 = 1, q31 + q32 = 1, and q41 + q42 = 1.

According to another aspect, there is provided an electronic device including the conductive thin film. The electronic device may be an organic light emitting device or an organic solar cell.

The conductive thin film can be effectively used for various electronic devices such as an organic light emitting device and an organic solar cell because it has good conductivity and easy work function control and is easy to form.

1 is a cross-sectional view schematically showing a cross section of an embodiment of an organic light emitting device which is an example of the electronic device.
2 is a cross-sectional view schematically showing a cross section of another embodiment of the organic light emitting device, which is an example of the electronic device.
3 is a cross-sectional view schematically showing a cross section of an embodiment of an organic solar cell which is an example of the electronic device.
4 is a cross-sectional view schematically showing a cross section of another embodiment of an organic solar cell which is an example of the electronic device.

The conductive thin film includes i) a conductive polymer containing at least one repeating unit represented by one of the following formulas (1) to (9) and ii) a fluorine-based material:

&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 > < EMI ID =

&Lt; Formula 7 > < EMI ID =

&Lt; Formula 9 >

In the above formulas 1 to 9, X ₁₁ , X ₂₁ , X ₃₁ , X ₄₁ , X ₅₁ , X ₆₁ , X ₇₁ , X ₈₁ and X ₉₁ independently of one another are * - [O] _p - [CH ₂ ] _q Lt; / _RTI &gt;

In the * - [O] _p - [CH ₂ ] _q -X ₁₀₀ , p is 0 or 1, and q is an integer of 0 to 50 (for example, q is an integer of 0 to 10).

또는

일 수 있다. 상기 양이온기는 금속 이온 및 유기 이온 중 1종 이상을 포함하되, 상기 금속 이온은 Na⁺, K⁺, Li⁺, Mg⁺², Zn⁺² 또는 Al⁺³이고, 상기 유기 이온은 H⁺, CH₃(CH₂)_nNH₃ ⁺, NH₄ ⁺, NH₂ ⁺, NHSO₂CF₃ ⁺, CHO⁺, C₂H₅OH⁺, CH₃OH⁺ 또는 RCHO⁺(상기 R은 CH₃(CH₂)_n-이고; n은 0 내지 50의 정수임)일 수 있다.On the other hand, in * - [O] _p - [CH ₂ ] _q -X ₁₀₀ , X ₁₀₀ may be an ionic group including an anion group and a counter cation group for the anion group. Wherein the anionic group is selected from the group consisting of PO ₃ ^{2 -} , SO ₃ ^- , COO ^- , I ^- , CH ₃ COO ^- , BO ₂ ^{2 -}

or

Lt; / RTI &gt; Including, but the cationic group is a metal ion and an organic ion at least one of said metal ion is ^{Na +, K +, Li +} , and Mg ^+2, Zn ⁺² or Al ^+3, the organic ions are H ^+, CH ₃ (CH ₂ ) _n NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ or RCHO ⁺ (wherein R is CH ₃ (CH ₂ ) _n - and n is an integer of 0 to 50).

For example, in the above * - [O] _p - [CH ₂ ] _q -X ₁₀₀ , p is 0 or 1, q is an integer of 0 to 10, and the anion groups in X ₁₀₀ are PO ₃ ^{2 -} , SO ₃ ^-, COO ^- or BO _{² 2} ^-, and wherein the X group of the ₁₀₀ cation Na ^+, K ^+, Li ^+, H ^+, CH ₃ (CH _{2) n} NH ₃ ^+, NH ₄ ^+, NH ₂ ^+, NHSO ₂ CF ₃ ⁺ , But is not limited to, CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ^+, or RCHO ⁺ (where n is an integer from 0 to 10).

Among R ₁ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₆₁ , R ₇₁ , R ₈₁ , R ₈₂ , R ₈₃ and R ₉₁ may independently be hydrogen, a halogen atom, a hydroxyl group, an amino group, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group. For example, the R _11, R _21, R _22, with _{R 23, R 31, R 32} , R 41, R 42, R 61, R 71, R 81, R 82, R 83 and R ₉₁ are each independently , But are not limited to, hydrogen, hydroxyl, amino, methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, butoxy or pentoxy. According to one embodiment, wherein _{R 11, R 21, R 22} , R 23, R 31, R 32, R 41, R 42, R 61, R 71, R 81, R 82, R 83 and R ₉₁ are hydrogen Lt; / RTI &gt;

In the above formula (1), Y ₁₁ may be S or NH.

Aa, ab, ai and ao in the above formulas (1) to (9) are independently of each other 1 or 2; ac and ad are each independently an integer of 1 to 5; ae, af, ag, ah, aj, ak, al, am and an may be independently an integer of 1 to 4.

A, a, a, ak, al, am, an and ao in the general formulas 1 to 9 are the same as X ₁₁ , X ₂₁ , X ₃₁ , X _{41 , X 51, X 61, X} 71, X 81, X 91, R 11, R 21, R 22, R 23, R 31, R 32, R 41, R 42, R 61, R 71, R 81, R ₈₂ , R _83, and R _91, respectively.

In the general formulas (2) to (4), q21, q22, q31, q32, q41 and q42 represent molar ratios of corresponding units. Q21, q31 and q41 are independently a real number in the range of 0.01 to 1, q22, q32 and q42 are independent of each other and are real numbers in the range of 0 to 0.99, q21 + q22 = 1, q31 + q32 = q41 + q42 = 1.

For example, the conductive polymer may be a polymer composed of the repeating units represented by Formula 4, but is not limited thereto.

The conductive polymer containing at least one repeating unit represented by any one of formulas (1) to (9) as described above may have a weight average molecular weight ranging from 1,000 to 3,000,000. When the weight average molecular weight as described above is satisfied, a conductive thin film having excellent film forming characteristics can be produced.

On the other hand, the fluorine-based material contained in the conductive thin film may be an ionomer (polymer having an ion group) represented by Chemical Formula 10:

&Lt; Formula 10 >

In Formula 10,

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} Formula 10 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 (22) to (33).

(22)

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);

&Lt; Formula 23 >

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

&Lt; EMI ID =

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 25 >

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);

(26)

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 27 >

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);

(28)

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);

(29)

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

(30)

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);

(31)

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);

(32)

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 33 >

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 chemical formula (40).

&Lt; EMI ID =

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

In the above formula (40)

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? I (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 40, 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 30 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 conductive thin film including the conductive polymer and the fluorine-based material may have excellent conductivity and work function properties. Accordingly, the conductive thin film can be used for an electronic device such as an organic light emitting device, an organic solar cell, an organic transistor, an organic memory device, an organic photodetector, or an organic CMOS sensor.

For example, the electronic device may be an organic light emitting device or an organic solar cell.

According to another embodiment, the electronic device is an organic light-emitting device, and the organic light-emitting device includes an anode; A cathode opposite to the anode; And a light emitting layer interposed between the anode and the cathode, wherein the conductive thin film is interposed between the anode and the light emitting layer.

According to an embodiment, the electronic device is an organic light emitting device, and the organic light emitting device includes an anode; A cathode opposite to the anode; And a light emitting layer interposed between the anode and the cathode, wherein the anode may be the conductive thin film.

When the anode is the conductive thin film, the buffer layer and / or the hole injection layer between the anode and the light emitting layer may be omitted. Therefore, when the anode is the conductive thin film, the organic light emitting device may include i) an anode (the conductive thin film) / light emitting layer / electron transporting region (including at least one of an electron transporting layer and an electron injecting layer) ) Anode / hole transporting layer / light emitting layer / electron transporting region (including at least one of an electron transporting layer and an electron injection layer) / cathode.

According to another embodiment, the electronic device is an organic solar cell, and the organic solar cell comprises an anode; A cathode opposite to the anode; And a heterojunction layer interposed between the anode and the cathode, wherein the conductive thin film is interposed between the anode and the heterojunction layer.

According to another embodiment, the electronic device is an organic solar cell, and the organic solar cell comprises an anode; A cathode opposite to the anode; And a heterojunction layer interposed between the anode and the cathode, wherein the anode may be the conductive thin film.

When the anode is the conductive thin film, the buffer layer and / or the hole injection layer between the anode and the heterojunction layer may be omitted. Therefore, when the anode is the conductive thin film, the organic solar cell may include: i) an anode (the conductive thin film) / a hetero junction layer / an electron transport region (including at least one of an electron transport layer and an electron injection layer) Or ii) a structure of an anode (which is the conductive thin film) / a hole transporting layer / a heterojunction layer / an electron transporting region (including at least one of an electron transporting layer and an electron injecting layer) / a cathode.

1 is a view schematically showing an embodiment of an organic light emitting device 100 which is one of the electronic devices. The organic light emitting diode 100 includes a substrate 101, an anode 110, a buffer layer 130, a light emitting layer 150 as an active region that emits light of a predetermined wavelength by coupling holes and electrons, an electron transporting region 170, And a cathode 190 are stacked in this order. Here, the buffer layer 130 interposed between the anode 110 and the light emitting layer 150 may be a conductive thin film as described above. The organic light emitting diode 100 may exhibit efficiency comparable to that of a conventional organic light emitting diode including a hole transport layer.

When a voltage is applied between the anode 110 and the cathode 190 of the organic light emitting diode 100, the holes injected from the anode 110 move to the light emitting layer 150 via the buffer layer 130, The electrons injected from the electron transporting region 170 move to the light emitting layer 150 and the holes and electrons recombine in the light emitting layer 150 to generate an exiton, And the light is generated.

Although not shown in FIG. 1, the anode 110 may be formed on a substrate. As the substrate, a substrate used in a conventional semiconductor process can be used. 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).

The anode 110 may be formed by providing an anode forming material on the substrate using a deposition method, a sputtering method, or the like. The anode 110 may be selected from a material having a relatively high work function to facilitate hole injection. The anode 110 may be a reflective electrode or a transmissive electrode. As the anode forming material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like can be used which is transparent and excellent in conductivity. Alternatively, when Mg, Al, Al-Li, Ca, Mg-In and Mg-Ag are used, (110) may be formed as a reflective electrode. The anode 110 may include two different materials. For example, the anode 110 may have a two-layer structure including two different materials.

The buffer layer 130 may be a single layer in which the conductive polymer and the fluorine-based polymer are uniformly mixed.

Alternatively, the concentration of the fluorinated polymer on the light emitting layer 150 side of the buffer layer 130 may be higher than the concentration of the fluorinated polymer on the anode 110 side of the buffer layer 130.

For example, the concentration of the fluorine-based polymer in the buffer layer 130 may gradually increase along the direction from the anode 110 to the light-emitting layer 150.

As another example, the buffer layer 130 may have a two-layer structure in which a first layer including the conductive polymer and a second layer including the fluorine-based polymer are sequentially stacked from the anode 110 side.

As another example, the buffer layer 130 may include a first layer including the conductive polymer, an intermediate layer including the conductive polymer and the fluorinated polymer, and a second layer including the fluorinated polymer sequentially from the anode 110 side, Lt; / RTI &gt; structure.

The interface between the buffer layer 130 and the light emitting layer 150 has a work function of 5.0 eV or more, for example, 5.0 eV to 6.5 eV, since the buffer layer 130 includes the fluorine-based polymer as described above .

The concentration of the fluorine-based polymer in the buffer layer 130 may be 10 to 500 parts by weight, for example, 20 to 400 parts by weight per 100 parts by weight of the conductive polymer, but is not limited thereto. When the content of the fluorine-based polymer satisfies the above-described range, the buffer layer 130 may have excellent work function properties as described above.

The thickness of the buffer layer 130 may be 1 nm to 300 nm, for example, 5 nm to 100 nm. When the thickness of the buffer layer 130 satisfies the above-described range, characteristics such as an energy level gradient, excellent hole injection / extrusion characteristics, and high luminous efficiency can be achieved.

The buffer layer 130 is in contact with the anode 110 and the light emitting layer 150. Hence, the holes injected from the anode 110 reach the light emitting layer 150 via the buffer layer 130. At this time, since the buffer layer 130 has excellent conductivity by the conductive polymer as described above and can have excellent work function properties due to the fluorine-based polymer as described above, It is possible to effectively inject holes. Accordingly, the organic light emitting diode 100 as described above can have high efficiency and long life.

The buffer layer 130 may be formed by providing a first composition including the conductive polymer, the fluorine-based polymer and the solvent as described above on the anode 110, forming the first composition-film, and then heat- have.

The conductive polymer and the fluorine-based polymer in the first composition-film may be uniformly mixed. In this case, the buffer layer 130 may have a single layer structure in which the conductive polymer and the fluorine-based polymer are uniformly mixed.

On the other hand, the fluorine-based polymer may have lower surface energy than the conductive polymer. As a result, the concentration of the fluorine-based polymer in the first composition-film may have a gradually increasing gradient in the direction from the anode 110 to the light-emitting layer 150. As a result, the concentration of the fluorine-based polymer in the buffer layer 130 may gradually increase in the direction from the anode 110 to the light-emitting layer 150.

Alternatively, the buffer layer 130 may be formed by providing a second composition including the conductive polymer and a solvent on the anode 110 to form a second composition-film, and then forming a third composition- A composition may be provided to form a third composition-film, followed by heat treatment thereof. At this time, a heat treatment process may be selectively performed on the second composition-film before the third composition is provided.

By separately providing the second composition and the third composition as described above, the buffer layer 130 can have a two-layer structure including a first layer including a conductive polymer and a second layer including the fluorine-based polymer, or a two- Layer structure including the conductive polymer, an intermediate layer containing the fluorine-based polymer, and a second layer containing the fluorine-based polymer.

The first composition, the second composition and the third composition may be formed by a casting method, an LB method, a spin-coating method, an ink-jet printing method, a nozzle printing method, , Slot-die coating, spray coating, screen printing, doctor blade coating, gravure printing, and offset printing (offset printing) printing or the like on the anode 110 or the like.

The solvents in the first composition, the second composition and the third composition may be polar solvents. Examples of the solvent include water, alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, ethylene glycol, glycerol, dimethylformamide, dimethylsulfoxide, , Acetone, and the like, but are not limited thereto. The solvent may be a mixture of two or more different substances.

The heat treatment temperature and time are a temperature and a time within a range in which the buffer layer 130 can be formed by removing at least a part of the solvent as described above. The heat treatment temperature may be selected depending on the type and content of the conductive polymer, the fluorine-based polymer, and the solvent to be used, and may be selected, for example, in a temperature range of 25 ° C to 300 ° C and a time range of 1 minute to 24 hours.

The thickness of the light emitting layer 150 may be about 20 A to about 1000 A, for example, about 100 A to about 600 A. [ When the thickness of the light emitting layer 150 satisfies the above-described range, excellent light emitting characteristics can be exhibited without substantial increase in driving voltage.

The light emitting layer 150 may include a known light emitting material. For example, the light emitting layer 150 may include a known host and a dopant.

Examples of the host include Alq ₃ (Tris- (8-hydroxy-quinolinato) -aluminum) CBP (4,4'-N, N'-dicarbazole- biphenyl), PVK (poly (n-vinylcarbazole) ), 9,10-di (naphthalen-2-yl) anthracene (ADN), 4,4 ', 4 "-tris (carbazol-9-yl) -triphenylamine, TPBI (N-phenylbenzimidazole-2-yl) benzene), TBADN (3-tert-butyl-9,10- 2-yl) anthracene), E3, DSA (distyrylarylene), dmCBP (see the following chemical formula), and the like.

PVK ADN

TCTA

As the blue dopant in the dopant, the following compounds may be used, but the present invention is not limited thereto.

                                            DPAVBi

      TBPe

As the red dopant among the dopants, the following compounds may be used, but the present invention is not limited thereto. Alternatively, DCM or DCJTB described later may be used as the red dopant.

As the green dopant among the dopants, the following compounds may be used, but the present invention is not limited thereto. Or a green dopant, the following C545T can be used.

The thickness of the light emitting layer may be from about 20 A to about 1000 A, e.g., from about 100 A to about 600 A. When the thickness of the light-emitting layer satisfies the above-described range, it is possible to exhibit excellent light-emitting characteristics without substantial increase in driving voltage.

An electron transport layer for assisting electron transport and an electron injection layer for assisting electron injection may be provided between the light emitting layer 150 and the cathode 190. Accordingly, the electron transporting region 170 may include an electron transporting layer and / or an electron injecting layer. The electron transporting layer and the electron injecting layer may include a material capable of easily transporting electrons injected from the cathode 190.

For example, the electron transport layer may be a quinoline derivative, especially tris (8-hydroxyquinoline) aluminum (Alq ₃ ), bis (2-methyl-8- quinolinolato) -4- Bis (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum (Balq), bis (10-hydroxybenzo [h] quinolinato) [h] quinolinato-beryllium: Bebq ₂ ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline : BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,2 ', 2 "- (benzene-1,3,5 (2,2 ', 2 "- (benzene-1,3,5-triyl) -tris (1-phenyl-1H-benzimidazole: TPBI 4-phenyl-4-phenyl-5-tert-butylphenyl) -1,2,4-triazole -1,2,4-triazole TAZ), 4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4- 3,5-diphenyl-4H-1,2,4-triazo le: NTAZ), 2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline, diphenyl-1,10-phenanthroline: NBphen), tris (2,4,6-trimethyl-3- (pyridin- -yl) phenyl borane: 3TPYMB), phenyl-dipyrenylphosphine oxide (POPy2), 3,3 ', 5,5'-tetra [ Tri [(3-pyridyl) -phen-3-yl] biphenyl: BP4mPy), 1,3,5- (3-pyridyl) -phen-3-yl] benzene: TmPyPB), 1,3-bis [3,5- Phenyl] benzene: BmPyPhB), bis (10-hydroxybenzo [h] quinolinato) beryllium (Bis (10-hydroxybenzo Diphenylbis (4- (pyridin-3-yl) phenyl) silane (DPPS) and 1,3, (P-pyrid-3-yl-phenyl) benzene: TpPyPB), 1,3-bis [2 - (2,2'-bipyridin-6-yl) -1,3,4-oxadiazol-5-yl] benzene (1,3- (Biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -Biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2,2'-bipyridyl: BP-OXD-Bpy), but are 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 may be from about 50 ANGSTROM to about 1000 ANGSTROM, for example, from about 150 ANGSTROM to about 600 ANGSTROM. When the thickness of the electron transporting layer satisfies the above-described range, satisfactory electron transporting characteristics can be obtained without substantially increasing the driving voltage.

For example, the electron injecting layer, may include LiF, NaCl, CsF, NaF, Li ₂ O, BaO, Cs ₂ CO ₃ etc., but is not limited to this. 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.

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. , BaO, and Cs ₂ CO ₃ , and the electron transport layer material may be formed to have a thickness of 1 nm to 100 nm, which is doped with a metal such as Li, Ca, Cs, or Mg.

The cathode 190 may be formed of a metal, an alloy, an electrically conductive compound, or a combination thereof. 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 cathode 190 may have a single layer or a multi-layer structure. For example, the cathode 190 may include an electron injection layer and a metal-containing layer.

2 is a view schematically showing an organic light emitting device 100 'which is another embodiment of the electronic device. The organic light emitting diode 100 includes a substrate 101, an anode 110, a buffer layer 130, a hole transport layer 140, an emission layer 150 as an active region for emitting light of a predetermined wavelength by coupling holes and electrons, The electron transporting region 170 and the cathode 190 are sequentially stacked. Here, the buffer layer 130 interposed between the anode 110 and the light emitting layer 150 may be a conductive thin film as described above.

The description of the substrate 101, the anode 110, the buffer layer 130, the light emitting layer 150, the electron transporting region 170, and the cathode 190 of the organic light emitting device 100 ' do.

The hole transport layer 140 of the organic light emitting device 100 'promotes hole transport between the buffer layer 130 and the light emitting layer 150. The hole transporting layer material may be a substance whose hole mobility under the same electric field is higher than electron mobility. The hole transport layer 140 may be formed using a known hole transport material. For example, 1,3-bis (carbazol-9-yl) benzene ) benzene: MCP), 1,3,5-tris (carbazol-9-yl) benzene: TCP), 4,4 ' Tris (carbazol-9-yl) triphenylamine (TCTA), 4,4'-bis (carbazol-9-yl) biphenyl (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (N, N'- N'-di (1-naphthyl) -N, N'-diphenylbenzidine), (N, N'- bis (naphthalen- , N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -2,2'-dimethylbenzidine bis (phenyl) -2,2'-dimethylbenzidine: alpha-NPD) N-phenylcarbazole, N, N'- Phenyl] -4,4'-diamine (TPD), an amine derivative having an aromatic condensed ring such as TCTA, TAPC (1,1-bis [4- [N, N'- Such as triphenylamine-based materials such as 1,1-bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] Cyclohexane) Materials can be used. However, it is not limited. Among them, for example, in the case of TCTA, besides the hole transporting role, it can also prevent the excitons from diffusing from the light emitting layer 140.

<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 130 satisfies the above-described range, excellent hole transporting characteristics can be obtained without increasing the driving voltage.

1 and 2 can be modified so that the anode 110 on the substrate 101 is a conductive thin film as described above and the buffer layer 130 is omitted. That is, when the anode 110 is the conductive thin film, the anode 110 may be deformed to contact the light emitting layer 150 (see FIG. 1) or to contact the hole transporting layer 140 (see FIG. 2).

When the anode 110 is a conductive thin film as described above, it is possible to improve the conductivity of the anode, improve optical characteristics, and provide a surface plasmon effect between the substrate 101 and the anode 110 A conductive thin film auxiliary layer (not shown in FIGS. 1 and 2) may be provided.

The conductive thin film auxiliary layer may be formed by a method such as spin coating, casting, Langmuir-Blodgett (LB), ink-jet printing, nozzle printing, 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 method) the conductive polymer has a conductivity of 100 (mass%), a thickness of 100 nm, a thickness of 100 nm, a thickness of 100 nm, S / cm or more), metallic carbon nanotubes, graphene, reduced graphene oxide, metal nanowires, metal grids, carbon nanodots, semiconductor nanowires, And at least one of the metal nano dots By providing me on the substrate 110, it may be formed.

Wherein the conductive thin film auxiliary layer comprises i) at least one of a conductive polymer, a metallic carbon nanotube, graphene, reduced graphene oxide, a metal nanowire, a carbon nano-point, a semiconductor nanowire, and a metal nano- Is coated on a substrate, and then the substrate is heat-treated to remove the solvent. Reference is made to the examples of solvents described herein as examples of such solvents.

According to one embodiment, if the conductive thin film auxiliary layer comprises graphene, the conductive thin film auxiliary layer can be formed by physically transferring the graphene sheet onto the substrate 210, 212.

According to another embodiment, when the conductive thin film auxiliary layer includes the metallic carbon nanotubes, the metallic carbon nanotubes may be grown on the substrates 210 and 212, or the carbon nanotubes dispersed in the solvent may be subjected to solution- Coating method, 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) An auxiliary layer can be formed.

According to another embodiment, when the conductive thin film auxiliary layer includes a metallic grid, metal is vacuum deposited on the substrate 210, 212 to form a metal film, and patterned in various mesh patterns by photolithography Or by dispersing a metal precursor or a metal particle in a solvent and applying the dispersion 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 conductive thin film auxiliary layer can be formed.

3 is a schematic cross-sectional view of an organic solar cell 200 which is another example of the electronic device.

The organic solar cell 200 includes a substrate 201, an anode 210, a buffer layer 230, a photoactive layer 250 that is an active region for separating light into holes and electrons, an electron transport region 270, ). The light incident on the photoactive layer 250 is separated into holes and electrons and holes are transferred to the anode 210 via the buffer layer 230 and electrons are transferred to the cathode 290 via the electron transporting region 270. [ Lt; / RTI &gt; The buffer layer 230 is a conductive thin film as described above.

A detailed description of the substrate 201, the anode 210 and the buffer layer 230 used in the organic solar cell 200 can be applied to the substrate of the organic light emitting diode 100, the anode 110 and the buffer layer 130 See the description.

Since the buffer layer 230 includes the conductive polymer and the fluorine-based material as described above, the buffer layer 230 can have both good conductivity and work-function characteristics, and can efficiently extract holes from the photoactive layer 250 to the anode 210 . Accordingly, the organic solar cell 200 can have high photoelectric conversion efficiency and operating life efficiency.

The photoactive layer 250 may include a material capable of separating holes and electrons from the irradiated light. For example, the photoactive layer 250 may include an electron donor and a hole acceptor. The photoactive layer 250 may have a variety of structures, including a single layer including the electron donor and the hole acceptor, or multiple layers including the electron donor-containing layer 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, (poly (1-methoxy- (Vinylene), MEH-PPV (poly- [2-methoxy-5- (2'-ethoxyhexyloxy) (3 ', 7'-dimethyloctyloxy) -1,4-phenylene vinylene]), MDMO-PPV (poly [ : poly [2,7- (9,9-dioctyl) -fluorene-aldehyde], PFDTBT Poly ((2,7- (9,9-dioctyl) -fluorene (1, 3'-benzothiadiazole) ) -alt-5,5- (4 ', 7'-di-2-thienyl-2', 1 ', 3'- benzothiadiazole)), PCPDTBT (poly [N', 0'-heptadecanyl- (4 ', 7', di-2-thienyl-2 ', 1', 3'-benzothiazole), polyindole, polycarbazole, , Polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene, polyfluorene, polypyridine, But are not limited to, CuPc (Copper Phthalocyanine), SubPc (subphthalocyanine), ClAlPc (Chloro-aluminum phthalocyanine), TAPC and derivatives thereof. Merging, etc.) is also possible of course.

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 250 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 250 is irradiated with light. The exciton, which is a pair of electrons and holes, is formed by photoexcitation, and the exciton forms electrons and holes by 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 270 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 250 to the cathode 290. As the electron transporting layer material, the same materials as those used in the organic light emitting elements 100 and 100 'can be used. The electron extraction layer may assist in transporting electrons generated in the photoactive layer 250 to the cathode 290. Examples of the electron extraction layer material include, but are not limited to, LiF, NaCl, CsF, 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.

The electron extraction layer may be formed of a material selected from the group consisting of LiF, NaCl, CsF, NaF, and Li ₂ O in an amount of about 1% to 50% in the electron transport layer materials such as Alq ₃ , TAZ, Balq, Bebq ₂ , BCP, TBPI, TmPyPB, and TpPyPB. O, BaO, and Cs ₂ CO ₃ , and the electron transport layer material may be a layer having a thickness of 1 nm to 100 nm doped with a metal such as Li, Ca, Cs, or Mg.

The light emitting layer, the hole transporting layer, the electron transporting layer, the electron injecting layer and the photoactive layer, the hole transporting layer, the electron transporting layer and the electron extracting layer in the organic light emitting device can be prepared by 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, slot-die coating, Spray coating, screen printing, doctor blade coating, gravure printing, and offset printing may be used.

The cathode 290 may use a metal, an alloy, an electrically conductive compound having a relatively low work function, or a combination thereof. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- .

4 is a schematic cross-sectional view of an organic solar cell 200 ', which is another example of the electronic device.

The organic solar cell 200 includes a substrate 201, an anode 210, a buffer layer 230, a hole transport layer 240, a photoactive layer 250 as an active region for separating light into holes and electrons, 270 and a cathode 290. Light incident on the photoactive layer 250 is separated into holes and electrons and holes are transferred to the anode 210 via the hole transport layer 240 and the buffer layer 230 and electrons are transported through the electron transport region 270 And is transmitted to the cathode 290. The buffer layer 230 is a conductive thin film as described above.

A description of the substrate 201, the anode 210, the buffer layer 230, the photoactive layer 250, the electron transport region 250, and the cathode 290 in the organic solar cell 200 ' .

A description of the hole transport layer 240 of the organic solar cell 200 'will be described with reference to the description of the hole transport layer 140 of the organic light emitting device 100' of FIG.

3 and 4 can be modified so that the anode 210 on the substrate 201 is a conductive thin film as described above and the buffer layer 230 is omitted. That is, when the anode 210 is the conductive thin film, the anode 210 may be deformed to contact the heterojunction layer 250 (see FIG. 3) or to be in contact with the hole transport layer 240 (see FIG. 4) have.

When the anode 210 is a conductive thin film as described above, it is possible to improve the conductivity of the anode, improve optical characteristics, and provide a surface plasmon effect between the substrate 201 and the anode 210 A conductive thin film auxiliary layer (not shown in FIGS. 3 and 4) may be provided. The description of the conductive thin film auxiliary layer refers to the description of the above description of Figs.

In addition to the conductive polymer and the fluorine-based material, the conductive thin film may include carbon nanotubes, graphene, reduced graphene, metal nanowires, metal carbon nanotubes, semiconductor quantum dots, semiconductor nanowires, And at least one additive selected from metal nano dots. By the additive, the conductivity of the conductive thin film can be further improved.

Although the electronic device has been described with reference to Figs. 1 to 4 and its modifications, it is not limited thereto.

The conductive thin film of the present invention can be used not only as an organic light emitting device and an organic solar cell but also as a buffer layer and an electrode for other organic electronic devices such as an organic memory, an organic transistor, an organic photodetector or an organic CMOS sensor.

[Example]

Evaluation example  1: Evaluation of conductive thin film

&Lt; Conductive thin film formation &

(Synthesized according to the procedure reported in the article of self-doped polyaniline (PANBUS (100), Eunkyoung Kim et al. J. Electrochem. Soc., 141, 3 (1994)) self-doped with sulfuric acid A polymer 100-containing solution and a polymer 200-containing solution (a polymer 200 was dispersed in 5% by weight in a mixture of water and alcohol (water: alcohol = 4.5: 5.5 (v / v) (100 wt%) was prepared. Here, the mixing ratio of the polymer 100-containing solution and the polymer 200-containing solution was adjusted so that the content of the polymer 200 (based on the solid content) was 1.6 parts by weight per 1 part by weight of the polymer 100.

<Polymer 100>

<Polymer 200>

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

The composition for forming a conductive thin film was spin-coated on a glass substrate, and then heat-treated at 200 ° C for 10 minutes to form a conductive thin film 1 having a thickness of 50 nm.

Then, the mixture ratio of the polymer 100-containing solution and the polymer 200-containing solution was adjusted to 3.2 parts by weight, 6.3 parts by weight, 12.7 parts by weight and 25.4 parts by weight per 100 parts by weight of the polymer 100, The conductive thin films 2, 3, 4 and 5 (the surface of the conductive thin film, which is in contact with the glass substrate, are formed on the glass substrate by the same method as the method of manufacturing the conductive thin film 1, Plane, and the surface opposite to the 1A plane is a 2A plane).

On the other hand, for comparison, the thin film A was formed using the same method as that for the conductive thin film 1, except that the polymer 200 was not used.

< Work function  Evaluation>

The ionic potentials of the conductive thin films 1 to 5 and the thin film A were evaluated using an ultraviolet photoelectron spectroscopy in air (manufacturer: Niken Keiki, model name is AC2) Respectively.

Polymer 100 / Polymer 200 (weight ratio) Ionization potential (eV) Thin film A 1/0 5.22 Conductive thin film 1 1 / 1.6 5.53 Conductive thin film 2 1 / 3.2 5.61 Conductive thin film 3 1 / 6.3 5.70 Conductive thin film 4 1 / 12.7 5.73 Conductive thin film 5 1 / 25.4 5.91

Example  One

A 15 Ω / cm 2 (1200 Å) ITO glass substrate of Corning was prepared and cut to a size of 2 × 2 mm, and the ITO surface was UV-ozone treated for 15 minutes. A conductive thin film 5 (buffer layer) was formed on the ITO anode using the same method as described in Evaluation Example 1, and NPB was thermally deposited on the conductive thin film 5 to form a hole transporting layer having a thickness of 20 nm. Bebq ₂ and C545T (weight ratio of 98: 2) were co-deposited on the hole transport layer to form a 70 nm light emitting layer, and Bebq ₂ was deposited on the light emitting layer to form an electron transport layer having a thickness of 20 nm. Thereafter, Liq (Lithium quinoline) and Al were sequentially deposited on the electron transport layer to sequentially form an electron injection layer with a thickness of 1 nm and a cathode with a thickness of 130 nm to form an organic light emitting device (ITO anode / conductive thin film 5 50 nm) / NPB hole transporting layer (20 nm) / light emitting layer (70 nm) / Bebq ₂ (Electron transport layer) (20 nm) / Liq (1 nm) / Al (cathode)).

Comparative Example  One

Except that the thin film A was formed in the same manner as described in Evaluation Example 1, instead of the conductive thin film 5. The same procedure as in Example 1 was carried out to prepare an organic light emitting device (ITO anode / thin film A (50 nm) / An NPB hole transporting layer (20 nm) / a light emitting layer (70 nm) / Bebq2 (electron transporting layer) (20 nm) / Liq (1 nm) / Al (cathode)).

Evaluation example  2: Device evaluation

The luminous efficiencies of the organic luminescent devices of Example 1 and Comparative Example 1 were evaluated using a Keithley 236 source measuring instrument and a Minolta CS 2000 spectro radomet. The results are shown in Table 2 below.

Efficiency (cd / A) Example 1 19.5 Comparative Example 1 13.7

It can be seen from Table 2 that the organic light emitting device of Example 1 has better light emitting efficiency than the organic light emitting device of Comparative Example 1. [

100, 100 ': Organic light emitting device
200, 200 ': Organic solar cell
101, 201: substrate
110, 210: anode
130, 230: buffer layer
140, 240: hole transport layer
150: light emitting layer
250: photoactive layer
170, 270: electron transport region
190, 290: cathode

Claims (18)

A conductive thin film including an ion-type conductive polymer and a fluorine-based material containing at least one repeating unit represented by one of the following formulas (1) to (9)
&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >< EMI ID =

&Lt; Formula 7 &gt;&lt; EMI ID =

&Lt; Formula 9 >

Among the above formulas (1) to (9)
X ₁₁ , X ₂₁ , X ₃₁ , X ₄₁ , X ₅₁ , X ₆₁ , X ₇₁ , X ₈₁ and X ₉₁ are independently of each other represented by * - [O] _p - [CH ₂ ] _q -X ₁₀₀ Wherein p is 0 or 1, q is an integer from 0 to 50, X ₁₀₀ is an ionic group containing an anionic group and a counter cation group to the anionic group, wherein the anionic group is PO ₃ ^2- , SO ₃ ^- , COO ^{- _{, I -, CH 3 COO -}} , BO 2 2-,

or

And, wherein the metal ion wherein the cationic group containing at least one kind of metal ions and organic ions are ^{Na +, K +, Li +} , Mg +2, and Zn ⁺² or Al ^+3, the organic ions are H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ^+, or RCHO ⁺ wherein R is CH ₃ (CH ₂ ) _n - and n is an integer from 0 to 50;
R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₆₁ , R ₇₁ , R ₈₁ , R ₈₂ , R ₈₃ and R ₉₁ independently represent hydrogen, , A hydroxyl group, an amino group, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group;
Y ₁₁ is S or NH;
aa, ab, ai and ao are independently of each other 1 or 2;
ac and ad are each independently an integer of 1 to 5;
ae, af, ag, ah, aj, ak, al, am and an are independently of each other an integer of 1 to 4;
q21, q31 and q41 are independently a real number in the range of 0.01 to 1, and q22, q32 and q42 are independent of each other and are a real number in the range of 0 to 0.99, and q21, q22, q31, q32, q41 and q42 represent molar ratios, and, q21 + q22 = 1, satisfies the q31 + q32 = 1 and q41 + q42 = 1, the CH ₃ (CH _{2) n} NH ₃ ⁺ in n is an integer from 0 to 50. The method according to claim 1,
P is 0 or 1 and q is an integer from 0 to 10;
The anionic group in X ₁₀₀ is PO ₃ ^2- , SO ₃ ^- , COO ^- or BO ₂ ^2- ;
The cation in X ₁₀₀ is selected from Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _n NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ or RCHO ⁺ . Conductive thin films:
In the CH ₃ (CH ₂ ) _n NH ₃ ⁺ , n is an integer from 0 to 50;
In RCHO ⁺ , R is CH ₃ (CH ₂ ) _n - and n is an integer of 0 to 50. The method according to claim 1,
Wherein R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₆₁ , R ₇₁ , R ₈₁ , R ₈₂ , R ₈₃ and R ₉₁ independently of one another are hydrogen, An amino group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group. The method according to claim 1,
Wherein the fluorine-based material is an ionomer represented by Chemical Formula 10:
&Lt; Formula 10 >

In Formula 10,
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. 5. The method of claim 4,
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,
The metal ion is ^{Na +, K +, Li +} , Mg +2, Zn ^+2, and is selected from the group consisting of Al ^+3, the organic ions are ^{_{H +, CH 3 (CH 2}} ) n NH 3 +, NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , A conductive thin film 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)
In CH ₃ (CH ₂ ) _n NH ₃ ⁺ , n is an integer of 0 to 50. 5. The method of claim 4,
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 (22) to (33):
(22)

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);
&Lt; Formula 23 >

Wherein m is a number from 1 to 10,000,000;
&Lt; EMI ID =

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 25 &gt;

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);
(26)

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 27 &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 ⁺⁾ is 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 from 0 to 50);
(28)

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);
(29)

Wherein m and n are 0 &lt; m? 10,000,000, 0? N <10,000,000;
(30)

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);
(31)

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);
(32)

The above formula, m and n are 0 ≤ m and <10,000,000, 0 <n ≤ 10,000,000 , R f = - (CF 2) z - (z is from 1 to 50 integer, except for 2), - (CF ₂ CF _{2 O) z CF 2 CF 2} - (z is an integer of 1 to _{50), - (CF 2 CF} 2 CF 2 O) z CF 2 CF 2 - and (z is an integer of 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 33 &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 0 to 20, Y are, each _{^{independently, -SO 3 - M +, -COO}} - M ^+, -SO ₃ ^- NHSO _2, and _{^{CF3 +, -PO 3 2- (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 chemical formula 40:
&Lt; EMI ID =
XM ^f _n -M ^h _m -M ^a _r -G
In the above formula (40)
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. delete The method according to claim 1,
A conductive thin film further comprising at least one additive selected from carbon nanotubes, graphenes, reduced oxide graphenes, metal nanowires, metal carbon nanotubes, semiconductor quantum dots, semiconductor nanowires and metal nano dots. delete delete Anode; A cathode opposite to the anode; And a light emitting layer interposed between the anode and the cathode,
Wherein the conductive thin film of any one of claims 1 to 8 and 10 is interposed between the anode and the light emitting layer. Anode; A cathode opposite to the anode; And a light emitting layer interposed between the anode and the cathode,
Wherein the anode is the conductive thin film of any one of claims 1 to 8 and 10. 15. The method of claim 14,
A conductive polymer, a metal carbon nanotube, a graphene, a reduced graphene oxide, a metal nanowire, a metal grid, a carbon nanodot ), A conductive thin film auxiliary layer containing at least one selected from the group consisting of semiconductor nanowires and metal nano dots. Anode; A cathode opposite to the anode; And a heterojunction layer interposed between the anode and the cathode,
Wherein the conductive thin film of any one of claims 1 to 8 and 10 is interposed between the anode and the heterojunction layer. Anode; A cathode opposite to the anode; And a heterojunction layer interposed between the anode and the cathode,
Wherein the anode is the conductive thin film according to any one of claims 1 to 8 and 10. 18. The method of claim 17,
A conductive polymer, a metal carbon nanotube, a graphene, a reduced graphene oxide, a metal nanowire, a metal grid, a carbon nanodot ), A conductive thin film auxiliary layer containing at least one selected from the group consisting of semiconductor nanowires and metal nano dots.

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