KR20180133702A - Polymer and organic electronic device comprising the same - Google Patents

Abstract

The present invention relates to a compound represented by a chemical formula 1 and an organic electronic device having the same. The present specification also provides the organic electronic device comprising: a first electrode; a second electrode facing the first electrode; and at least one organic layer provided between the first electrode and the second electrode.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a compound,

The present disclosure relates to compounds and organic electronic devices comprising them.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electric device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic transistor. Hereinafter, the organic photoelectric device will be specifically described. However, in the organic electronic devices, Electron injection or transport materials, or luminescent materials act on a similar principle.

An organic photoelectric device is an element that converts light into an electric signal by using a photoelectric effect, and includes a photodiode and a phototransistor, and may be applied to an image sensor or the like. Image sensors including photodiodes are getting higher resolution as the edges are getting closer, and the pixel size is getting smaller. In the currently used silicon photodiodes, since the size of the pixels is reduced, the absorption area is reduced, so that sensitivity deterioration may occur. Accordingly, organic materials that can replace silicon have been studied.

The organic material has a high extinction coefficient and can selectively absorb light of a specific wavelength region according to the molecular structure, so that the photodiode and the color filter can be substituted at the same time, which is very advantageous for improving sensitivity and high integration.

 Polymer photovoltaic cells: Enhanced Efficiencies via Network of Internal Donor-Acceptor Heterojunctions (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995)

The present invention provides compounds and organic electronic devices comprising them.

The present invention provides a polymer comprising a unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

a, b, c and d are the same or different and each independently represents an integer of 1 to 5,

When a is 2 or more, R1 is the same or different from each other,

When b is 2 or more, R2 is the same or different from each other,

When c is 2 or more, R3 is the same or different from each other,

When d is 2 or more, R4 is the same or different from each other,

R1 to R4 are the same or different from each other and each independently hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

X1 to X4 are the same or different from each other and each independently represents O, S, CRR ', SiRR', NR, C = O, C = S, C = CRR '

R and R 'are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

Q1 is a substituted or unsubstituted monocyclic or polycyclic aromatic ring,

n is 0 or 1;

Also, the present specification discloses a plasma display panel comprising a first electrode;

A second electrode facing the first electrode; And

And at least one organic material layer provided between the first electrode and the second electrode,

Wherein at least one of the organic material layers comprises the compound.

Compounds according to one embodiment of the present disclosure provide a more effective push-pull system by delivering a non-covalent electron pair of nitrogen to a pull moiety, thereby freely modulating HOMO / LUMO energy levels .

In addition, the compound according to one embodiment of the present invention can control the charge balance when applied to an organic electronic device, and can exhibit excellent performance.

In addition, the compound according to one embodiment of the present invention has a simple molecular structure and is capable of a deposition process, which is advantageous for device application.

1 is a cross-sectional view illustrating an organic photoelectric device according to an embodiment of the present invention.
2 to 5 are cross-sectional views illustrating an organic transistor according to an embodiment of the present invention.
6 is a graph showing a result of measuring the performance of an organic photodiode according to an embodiment of the present invention.

Hereinafter, the present specification will be described in detail.

An embodiment of the specification provides a compound represented by the above formula (1).

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

Examples of such substituents are described below, but are not limited thereto.

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

As used herein, the term " substituted or unsubstituted " A halogen group; An alkyl group; An alkenyl group; An alkoxy group; Ester group; A carbonyl group; A carboxyl group; A hydroxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heterocyclic group; An arylamine group; An aryl group; A nitrile group; A nitro group; A hydroxy group; And a heterocyclic group containing at least one of N, O and S atoms, or does not have any substituent (s).

The substituents may be substituted or unsubstituted with an additional substituent.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, N-octyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl and cyclooctyl Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy and p- But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, and styrenyl groups.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group may be -BR ₁₀₀ R ₁₀₁ , wherein R ₁₀₀ and R ₁₀₁ are the same or different and each independently hydrogen; heavy hydrogen; halogen; A nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted, straight or branched chain alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, a fluorenyl group is a structure in which two cyclic organic compounds are connected through one atom.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing at least one of O, N and S as a hetero atom. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heteroaryl group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, a thiazolyl group, , A thiadiazolyl group, a thiadiazolyl group, a benzothiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the above heteroaryl groups.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, Naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Phenanthryloxy, 9-phenanthryloxy and the like. Examples of the arylthioxy group include phenylthio group, 2-methylphenylthio group, 4-tert-butylphenyl And the like. Examples of the aryl sulfoxy group include a benzene sulfoxy group and a p-toluenesulfoxy group, but the present invention is not limited thereto.

In the present specification, the alkyl group in the alkylthio group and the alkylsulfoxy group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, But are not limited thereto.

In the present specification, in the substituted or unsubstituted ring formed by bonding adjacent groups to each other, the "ring" means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from the examples of the cycloalkyl group or the aryl group except the univalent hydrocarbon ring.

In this specification, the aromatic ring may be monocyclic or polycyclic and may be selected from the examples of the aryl group except that it is not monovalent.

In the present specification, the hetero ring includes one or more non-carbon atoms and hetero atoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocyclic ring may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the heteroaryl group or the heterocyclic group except that the monocyclic group is not monovalent.

In one embodiment of the present invention, the formula (1) is any one of the following formulas (1-1) to (1-5).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 through 1-5 above,

a, b, c, d, R1 to R4 and X1 to X4 are the same as defined in the above formula (1)

Y1 to Y16 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, a is 1.

In one embodiment of the present disclosure, b is one.

In one embodiment of the present disclosure, c is one.

In one embodiment of the present disclosure, d is one.

In one embodiment of the present invention, the formula (1) is any one of the following formulas (1-11) to (1-13).

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

In Formulas 1-11 to 1-13,

R1 to R4, X1 to X4, n and Q1 are the same as defined in the above formula (1).

In one embodiment of the present specification, X1 to X4 are the same or different from each other and each independently O or C = O.

In one embodiment of the present invention, R 1 to R 4 are the same or different and each independently hydrogen or a substituted or unsubstituted alkoxy group.

In one embodiment of the present invention, R1 to R4 are the same or different from each other, and each independently represents hydrogen or an alkoxy group having 1 to 30 carbon atoms.

In one embodiment of the present invention, R1 to R4 are the same or different from each other, and each independently represents hydrogen or an alkoxy group having 1 to 20 carbon atoms.

In one embodiment of the present invention, R 1 to R 4 are the same or different from each other and are each independently hydrogen or an alkoxy group having 1 to 10 carbon atoms.

In one embodiment of the present invention, R 1 to R 4 are the same or different from each other and each independently OCH ₃ .

In one embodiment of the present invention, the compound represented by Formula 1 is any one selected from the following compounds.

According to one embodiment of the present disclosure, the compound has an absorption edge at 500 nm to 800 nm.

Since the compound according to the embodiment of the present invention has the absorption edge in the above range, the band gap is reduced, and the effect of absorbing light in the entire visible light region is obtained.

According to one embodiment of the present disclosure, the compound exhibits an extinction curve having a half-width of 50 nm to 100 nm in the film state.

Since the compound according to the embodiment of the present invention has a half width of the above range, it has an effect of absorbing light in the entire region of visible light.

In the present specification, the term "film state" is not a solution state, but refers to a state in which the compound represented by Formula 1 is mixed with other components that do not affect the measurement of the half width, do.

In the present specification, the half-width refers to the width of the emission peak when the maximum emission peak of light emitted from the compound represented by Formula 1 is half the maximum height.

In one embodiment of the present disclosure, the compound may have a HOMO energy level of -4.0 eV to -6.0 eV and has a band gap of 1.0 eV to 3 eV. By having HOMO level and energy band gap in the above range, it can be applied as a p-type organic layer that effectively absorbs light in the entire wavelength region, and thus can have a high external quantum efficiency (EQE) Can be improved.

Further, in one embodiment of the present invention, the compound may have a HOMO energy level of -5.0 eV to -6.0 eV and has a band gap of 1.2 eV to 2 eV.

One embodiment of the present disclosure includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound.

In one embodiment of the present invention, the organic electronic device is selected from the group consisting of an organic photoelectric device, an organic transistor, an organic solar cell, and an organic light emitting device.

In one embodiment of the present invention, the organic electronic device may be an organic photoelectric device. Specifically, the organic electronic device includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound.

In one embodiment of the present disclosure, the organic layer includes a photoactive layer, and the photoactive layer includes an electron donor material and an electron acceptor material, and the electron donor material includes the compound.

In one embodiment of the present invention, the electron-accepting material and the n-type organic compound layer may be selected from the group consisting of fullerene, fullerene derivative, vicoproin, semiconducting element, semiconducting compound, and combinations thereof. (6,6) -phenyl-C61-butyric acid-methylester) or PCBCR ((6,6) -phenyl-C61-butyric acid-cholesteryl ester), perylene perylene, polybenzimidazole (PBI), and 3,4,9,10-perylene-tetracarboxylic bis-benzimidazole (PTCBI).

In one embodiment of the present disclosure, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ).

In the present specification, bulk heterojunction means that the electron donor material and the electron acceptor material are mixed with each other in the photoactive layer.

In one embodiment of the present invention, the organic photoelectric device can be used without limiting the materials and / or methods in the art, except that the compound represented by Formula 1 is used as the photoactive layer of the organic photoelectric device. have.

According to one embodiment of the present disclosure, the organic layer includes a p-type semiconductor layer and an n-type semiconductor layer, and the p-type semiconductor layer includes the compound.

In one embodiment of the present disclosure, the photoelectric device may be an organic photodiode. Specifically, the organic photoelectric device includes a first electrode; A second electrode facing the first electrode; And one or more organic layers disposed on the first and second electrodes, wherein at least one of the organic layers includes the compound.

An organic photoelectric device according to an embodiment of the present invention includes a first electrode, a photoactive layer, and a second electrode. The organic photoelectric device may further include a substrate, a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, an electron injection layer, and / or an electron transport layer.

According to one embodiment of the present disclosure, the organic photoelectric device may further include an additional organic layer. The organic photoelectric device can reduce the number of organic layers by using organic materials having various functions at the same time.

According to one embodiment of the present disclosure, the first electrode is an anode and the second electrode is a cathode. In another embodiment, the first electrode is a cathode and the second electrode is an anode.

According to one embodiment of the present invention, the organic photoelectric elements may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode.

In another embodiment, the organic photoelectric device may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

According to one embodiment of the present invention, the organic photoelectric device is a normal structure. In the normal structure, the substrate, the anode, the organic material layer including the photoactive layer, and the cathode may be stacked in this order.

According to one embodiment of the present invention, the organic photoelectric device is an inverted structure. In the inverted structure, the substrate, the cathode, the organic material layer including the photoactive layer, and the anode may be stacked in this order.

1, an organic photoelectric device 100 according to an embodiment of the present invention includes a first electrode 10 and / or a second electrode 20, The excitons can be generated inside the active layer 30 when the active layer 30 absorbs light in the entire wavelength range. The excitons are separated into holes and electrons in the active layer 30, and the separated holes move to the anode side, which is one of the first electrode 10 and the second electrode 20, The current flows to the cathode side which is the other of the two electrodes 20 and current flows to the organic photoelectric conversion element.

According to one embodiment of the present invention, the organic photoelectric device is a tandem structure.

In this specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in an organic electronic device. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; And conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, but are not limited thereto .

The method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . ≪ / RTI >

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming processes.

For example, the patterned ITO substrate is sequentially cleaned with a detergent, acetone, and isopropyl alcohol (IPA), and then heated on a heating plate at 100 ° C to 150 ° C for 1 minute to 30 minutes, preferably at 120 ° C for 10 minutes Dried, and the substrate surface is hydrophilically reformed when the substrate is completely cleaned.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

Pretreatment techniques for the anode electrode include a) surface oxidation using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet radiation in vacuum, and c) oxygen radicals generated by the plasma And the like.

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from the surface of the anode electrode or the substrate and to suppress the residual of moisture and organic matter as much as possible. At this time, the substantial effect of the pretreatment can be maximized.

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

However, the method of modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

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

The cathode may be deposited in a thermal evaporator having a degree of vacuum of 5 x 10 ^{< -7} > torr or less, but the method is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and is preferably a compound having excellent ability to form a thin film. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the electrode material and the HOMO of the surrounding organic layer. The electrode at this time may be an anode or a cathode depending on the structure. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer for transporting holes from the hole injection layer or the electrode to the photoactive layer. The hole transport material is preferably a material having high hole mobility. The electrode at this time may be an anode or a cathode depending on the structure. Specific examples of the hole transporting material include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, a metal oxide, and the like, but are not limited thereto. Specifically, examples of the hole transport layer material include BCP (bathocuproine), PEDOT: PSS (poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but the present invention is not limited thereto.

The hole blocking layer prevents holes from moving from the photoactive layer to the electron injection layer or electron injection material, and materials used in the art can be used. Specifically, TAPC (4,4'-cyclohexylidenebis [N, N-bis (4-methylphenyl) benzenamine] may be used but is not limited thereto.

The electron injecting layer is a layer for injecting electrons from the electrode, and is preferably a compound having an ability to transport electrons and having excellent thin film forming ability. The electrode at this time may be an anode or a cathode depending on the structure. Specific examples of the electron injecting material include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidenemethane, A metal complex compound thereof, and a nitrogen-containing five-membered ring derivative, but the present invention is not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The electron transporting layer is a layer that transports electrons to the photoactive layer by receiving electrons from the electrode or the electron injecting layer. As the electron transporting material, a material having high mobility to electrons is suitable. The electrode at this time may be an anode or a cathode depending on the structure. Specific examples of the electron transporting material include metal complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but the present invention is not limited thereto. The electron transporting layer can be used with any desired electrode material as used according to the prior art.

The electron blocking layer is a layer for preventing electrons from migrating into the hole injection layer or the hole injection material, and materials used in the art can be used.

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

In one embodiment of the present disclosure, the organic electronic device may be an organic transistor. Specifically, the organic electronic device includes a gate electrode; A source electrode; Drain electrodes; And one or more organic compound layers, wherein at least one of the organic compound layers includes the compound.

Specifically, in one embodiment of the present invention, the organic electronic device includes a gate electrode; A source electrode; Drain electrodes; An organic transistor including a single-layer organic material layer, wherein the organic material layer may include the compound.

In one embodiment of the present disclosure, the organic transistor may be a top gate structure. Specifically, the source electrode 70 and the drain electrode 80 may be formed first on the substrate 40, and then the organic layer 90, the insulating layer 60, and the gate electrode 50 may be sequentially formed. FIG. 2 shows the structure of the organic transistor.

In one embodiment of the present disclosure, the organic transistor may be a bottom contact structure of a bottom gate structure. Specifically, the gate electrode 50 and the insulating layer 60 are sequentially formed on the substrate 40, and then the source electrode 70 and the drain electrode 80 are formed on the insulating layer 60. Finally, An organic layer 90 may be formed on the source electrode 70 and the drain electrode 80. FIGS. 3 and 4 show the structure of the organic transistor according to the present invention.

In one embodiment of the present disclosure, the organic transistor may be a top contact structure of a bottom gate structure. Specifically, the gate electrode 50 and the insulating layer 60 are sequentially formed on the substrate 40, and then the organic layer 90 is formed on the insulating layer 60. Finally, on the organic layer 90 A source electrode 70 and a drain electrode 80 may be formed. FIG. 5 shows the structure of the organic transistor according to the present invention.

In this specification, the gate electrode may be in the form of a pattern, but is not limited thereto. The gate electrode is selected from the group consisting of Au, Ni, Cu, Ag, Al, Al-Al, Mo, Or the like.

In this specification, the gate electrode may be formed using a method selected from photolithography, offset printing, silk screen printing, inkjet printing, thermal evaporation, and a method using a shadow mask, But is not limited thereto.

The thickness of the gate electrode may be 10 nm to 300 nm, and preferably 10 nm to 50 nm.

In this specification, the insulating layer is composed of a single film or a multilayer film of an organic insulating film or an inorganic insulating film, or it is composed of a organic-inorganic hybrid film. As the inorganic insulating film, any one or more selected from the group consisting of a silicon oxide film, a silicon nitride film, Al ₂ O ₃ , Ta ₂ O ₅ , BST and PZT can be used. Examples of the organic insulating film include imide polymers such as CYTOP ^TM , polymethylmethacrylate (PMMA), polystyrene (PS), phenolic polymers, acrylic polymers, and polyimides, arylether polymers, amide polymers, A fluorine-based polymer, a p-xylylene-based polymer, a vinyl alcohol-based polymer, and parylene may be used, but the present invention is not limited thereto.

In this specification, the insulating layer may be formed through a solution process, and may be applied over a large area through a spin coating, a bar coating, a slit die coating, a doctor blade, or the like. Preferably, the insulating layer can be formed through spin coating, but the present invention is not limited thereto. When the insulating layer is formed, heat treatment is performed at 100 ° C to 150 ° C for 30 minutes or more to completely evaporate the used solvent.

In this specification, the source electrode and the drain electrode may be made of a conductive material, and examples thereof include carbon, aluminum, vanadium, chromium, copper, zinc, silver, gold, magnesium, calcium, sodium, potassium, titanium, indium, yttrium , Lithium, gadolinium, tin, lead, neodymium, platinum, nickel, similar metals and alloys thereof; p- or n-doped silicon; Zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide, similar tin oxide and tin oxide indium-based complex compounds; ZnO: Al, SnO _2: a mixture of oxide and metal, such as Sb; And poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophen] -dioxy) thiophene], polypyrrole, and polyaniline, but the present invention is not limited thereto.

In this specification, the organic material layer may be formed through a solution process. At this time, the organic material layer can be generally applied over a large area through spin coating, bar coating, slit die coating, doctor blade, ink jet coating or the like, but is not limited thereto.

In this specification, when a source electrode and a drain electrode are formed on the substrate, the source electrode and the drain electrode may be formed by a thermal deposition method, but the present invention is not limited thereto, and other methods known in the art As shown in FIG. In this case, the distance between the source electrode and the drain electrode is typically 2 to 100 mu m, and the channel width may be 10 to 1000 times the channel length. The source electrode and the drain electrode are usually made of gold and nickel, but other electrodes such as silver, copper, and molybdenum may be used.

In this specification, when a source electrode and a drain electrode are formed on the organic material layer, the source electrode and the drain electrode can be formed using an optical type process or a shadow mask process, but the present invention is not limited thereto. Can be formed by other known methods.

One embodiment of the present invention provides an organic image sensor including the organic electronic device.

The organic image sensor according to one embodiment of the present invention can be applied to an electronic device, for example, a mobile phone, a digital camera, and the like, but is not limited thereto.

The method for producing the above compound and the production of the organic electronic device including the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Production Example 1. Preparation of Compound 1

500mL round bottom flask the compound A 1g, Compound B 1.93g (2.5eq), tris (dibenzylideneacetone) dipalladium (0) (Tris (dibenzylideneacetone) dipalladium (0), Pd 2 dba 3) 15mg (0.05eq), 15 mg (0.05 eq) of tri-tert-butylphosphine, P (t-Bu) ₃ and 0.8 g (2.5 eq) of sodium tert-butoxide (NaOt- Are introduced into 150 mL of toluene and refluxed at 110 DEG C for 12 hours. Compound 1 was obtained after extracting the organic solvent through ethyl acetate and distilled water. _{[(1H NMR 500MHz, CDCl 3} ): 7.168 (d, 4H), 7.135 (d, 4H), 6.987 (d, 4H), 6.945 (d, 4H), 3.575 (s, 12H)]

Production Example 2. Preparation of Compound 2

15 g (0.05 eq) of Pd ₂ dba _3, 15 mg (0.05 eq) of P (t-Bu) ₃ and 0.8 g (2.5 eq) of NaOt-Bu were added to a 500 mL round- After injecting into 150 mL of toluene, reflux is carried out at 110 DEG C for 12 hours. After extracting the organic solvent through ethyl acetate and distilled water, Compound 2 was obtained. _{[(1H NMR 500MHz, CDCl 3} ): 7.325 (d, 2H), 7.314 (d, 2H), 7.305 (d, 2H), 7.257 (d, 2H), 7.214 (d, 4H), 7.206 (d, 4H ), 3.573 (s, 12 H)].

Production Example 3. Preparation of Compound 3

To a 500 mL round flask was added 1 g of Compound A, 1.93 g (2.5 eq) of Compound D, 15 mg (0.05 eq) of Pd ₂ dba _3, 15 mg (0.05 eq) of P (t- Bu) ₃ and 0.8 g (2.5 eq) of NaOt- After injecting into 150 mL of toluene, reflux is carried out at 110 DEG C for 12 hours. After extracting the organic solvent through ethyl acetate and distilled water, Compound 3 was obtained. _{[(1H NMR 500MHz, CDCl 3} ): 7.412 (d, 2H), 7.395 (t, 2H), 7.384 (t, 2H), 7.333 (d, 2H), 7.260 (d, 4H), 7.154 (d, 4H ), 3.475 (s, 12H)

Experimental Example 1

ITO was ultrasonically cleaned with a glass substrate (11.5 Ω / □, ITO glass) coated with a 1.5 cm × 1.5 cm bar type using distilled water, acetone and 2-propanol, and the ITO surface was exposed to ozone Respectively. Then, TAPC (4,4'-cyclohexylidenebis [N, N-bis (4-methylphenyl) benzenamine], Sigma Aldrich) was deposited on the ITO glass at a rate of 1.0 Å / s to a thickness of 30 nm. 1 and C ₆₀ (fullerene) were co-deposited at a ratio of 25:75. At this time, the deposition was carried out such that the deposition rate ratio of Compound 1 and C ₆₀ was 0.5: 1.5 Å / s, and the film thickness was 100 nm. BCP (bathocuproine, Sigma Aldrich) was then added And then Al was deposited to a thickness of 100 nm at a rate of 1.0 ANGSTROM / s to fabricate an organic photodiode.

Experimental Example 2

ITO was ultrasonically cleaned with glass substrate (11.5 Ω / □, ITO glass) coated with a 1.5 cm × 1.5 cm bar type using distilled water, acetone and 2-propanol, and the ITO surface was treated with ozone Respectively. Then, TAPC was deposited to a thickness of 30 nm on ITO glass at a rate of 1.0 Å / s, followed by co-deposition of Compound 2 and C ₆₀ prepared in Preparation Example 2 at a ratio of 25:75. At this time, the deposition was carried out such that the deposition rate ratio of compound 2 and C ₆₀ was 0.5: 1.5 Å / s, and the film thickness was 100 nm. After that, And then Al was deposited to a thickness of 100 nm at a rate of 1.0 ANGSTROM / s to fabricate an organic photodiode.

Comparative Example 1

ITO was ultrasonically cleaned with a glass substrate (11.5 Ω / □, ITO glass) coated with a 1.5 cm × 1.5 cm bar type using distilled water, acetone and 2-propanol, and the ITO surface was exposed to ozone Respectively. Then, TAPC was deposited on the ITO glass at a rate of 1.0 Å / s to 30 nm, and the following compounds Q and C60 were co-deposited at a ratio of 25:75. The deposition rate ratio of compound Q and C ₆₀ was set to 0.5: 1.5 A / s, and the film thickness was 100 nm. After that, And then Al was deposited to a thickness of 100 nm at a rate of 1.0 ANGSTROM / s to fabricate an organic photodiode.

The results of the performance measurement of the organic photodiodes prepared in Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.

Max EQE (%) @ 0V 0V
? (nm) @ -1V 1V
? (nm) @ -3V -3 V
? (nm) Example 1 19.69 360 55.40 360 78.86 360 Example 2 5.16 370 35.26 370 62.93 370 Comparative Example 1 1.00 380 19.69 380 54.02 380

Table 1 shows the result of measuring the EQE value with the reverse virus added.

In Table 1, @ 0V is the maximum EQE value in the state of applying the reverse virus of 0V, 0V is the absorption wavelength at this time, @ -1V is the maximum EQE value when the reverse virus of -1V is applied, 1V λ means the absorption wavelength at this time, @ -3V means the maximum EQE value when the inverted virus is applied at -3V, and -3V means the absorption wavelength at this time. For example, in the case of Embodiment 1, the maximum EQE value at 0 V is 19.69%, and the absorption wavelength at this time is 360 nm. Also, it can be seen that the EQE value of the same device with the -3 V reverse virus added is 78.86%, and the maximum wavelength at this time is 360 nm.

From the results shown in Table 1, it can be seen that Examples 1 and 2 exhibited higher EQE values than Comparative Example 1 devices, and therefore, superior devices were realized.

Fig. 6 shows the performance measurement results of Example 1, Example 2, and Comparative Example 1. Specifically, the external quantum efficiency curve measured at a voltage of -3 V is shown.

From Table 1 and FIG. 6, it can be seen that the example in which a compound not containing an aryl group between 3,6-dibromofuro [3,2-b] furan-2,5-dione and N is applied is 3,6-dibromofuro [ -b] furan-2,5-dione and N in comparison with the comparative example comprising an aryl group.

10: first electrode
20: Second electrode
30: photoactive layer
40: substrate
50: gate electrode
60: Insulating layer
70: source electrode
80: drain electrode
90: organic layer
100: organic photoelectric device

Claims (14)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
a, b, c and d are the same or different and each independently represents an integer of 1 to 5,
When a is 2 or more, R1 is the same or different from each other,
When b is 2 or more, R2 is the same or different from each other,
When c is 2 or more, R3 is the same or different from each other,
When d is 2 or more, R4 is the same or different from each other,
R1 to R4 are the same or different from each other and each independently hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
X1 to X4 are the same or different from each other and each independently represents O, S, CRR ', SiRR', NR, C = O, C = S, C = CRR '
R and R 'are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
Q1 is a substituted or unsubstituted monocyclic or polycyclic aromatic ring,
n is 0 or 1; The method according to claim 1,
Wherein the formula 1 is any one of the following formulas 1-1 to 1-5:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 through 1-5 above,
a, b, c, d, R1 to R4 and X1 to X4 are the same as defined in the above formula (1)
Y1 to Y16 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1,
Wherein R1 to R4 are the same or different from each other and each independently hydrogen or a substituted or unsubstituted alkoxy group. The method according to claim 1,
Wherein X1 to X4 are the same or different from each other and each independently O or C = O. The method according to claim 1,
Wherein the compound of Formula 1 is any one of the following Formulas 1-11 to 1-13:
[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

In Formulas 1-11 to 1-13,
R1 to R4, X1 to X4, n and Q1 are the same as defined in the above formula (1). The method according to claim 1,
Wherein the compound represented by the formula (1) is any one selected from the following compounds:

A first electrode;
A second electrode facing the first electrode; And
And at least one organic material layer provided between the first electrode and the second electrode,
Wherein at least one of the organic layers comprises a compound according to any one of claims 1 to 6. The method of claim 7,
Wherein the organic electronic device is selected from the group consisting of an organic photoelectric device, an organic transistor, an organic solar cell, and an organic light emitting device. The method of claim 7,
The organic electronic device includes a first electrode;
A second electrode facing the first electrode; And
And at least one organic material layer provided between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises the compound. The method of claim 9,
Wherein the organic layer comprises a photoactive layer,
Wherein the photoactive layer comprises an electron donor material and an electron acceptor material,
Wherein the electron donor material comprises the compound. The method of claim 10,
Wherein the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ). The method of claim 9,
The organic photoelectric device includes a first electrode;
A second electrode facing the first electrode; And
An organic photodiode including at least one organic layer provided between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises the compound. The method of claim 7,
The organic electronic device includes a gate electrode; A source electrode; Drain electrodes; And at least one organic material layer,
Wherein at least one of the organic material layers comprises the compound. An organic image sensor comprising an organic electronic device according to claim 7.

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