KR20180053121A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device having improved driving voltage, efficiency, and lifetime. The organic light emitting device comprises: an anode; a hole transport layer; a red luminescent layer; a green luminescent layer; an electron transport layer; and a cathode.

Description

[0001] The present invention relates to an organic light emitting device,

The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifetime.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. The organic material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

In the organic light emitting device, development of an organic light emitting device having improved driving voltage, efficiency, and lifetime is continuously required.

Conventionally, red organic light emitting devices used in organic light emitting devices have been known to use n-type and amphoteric derivatives of carbazole-quinazoline bonds as the light emitting layer. However, in this case, there was a problem that the efficiency and the life span were deviated.

Alternatively, in a single element or a stacked element using two red-green light emitting layers, red light is emitted with relatively low efficiency of green light, thereby increasing the efficiency of a suitable yellow-green or white element by inducing movement of color coordinates It is known. In addition, the p-type derivative, which is the same as or different from the hole transporting layer, is deposited together with the red luminescent layer to facilitate the injection of holes into the luminescent layer and the movement of holes in the luminescent layer to facilitate hole injection into the green luminescent layer. Therefore, it is required to develop a material having a molecular weight of at least a certain level, which forms a stable interface between two light-emitting layers and has a high charge transporting ability.

Accordingly, the present invention provides a combination of the compounds represented by the derivatives shown in the claims as a constituent material combination of the organic light emitting device. Another object of the present invention is to provide an organic electroluminescent device having a low driving voltage and a long lifetime.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifetime.

The present invention provides the following organic light emitting device:

anode;

A hole transport layer;

A red luminescent layer;

A green light emitting layer;

An electron transport layer; And

A cathode,

Wherein the hole transporting material contained in the hole transporting layer and the first host included in the red light emitting layer are represented by the following general formula (1) or (2)

Wherein the second host included in the red light emitting layer is represented by the following general formula (3) or (4)

Single or stacked organic light emitting devices:

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

L ₁ , L ₂ and L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _5-60 heteroarylene containing at least one hetero atom selected from the group consisting of N, O and S,

G ₁ , G ₂ , G ₃ and G ₄ are each independently a substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S, or a substituted or unsubstituted monocyclic or polycyclic ring Lt; / RTI >

Ar ₃ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 arylalkenyl; Or substituted or unsubstituted C _5-60 heteroaryl containing at least one hetero atom selected from the group consisting of N, O and S,

R ₁₀₁ to R ₁₀₅ each independently represent hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl comprising at least one hetero atom selected from the group consisting of N, O and S,

r ₁₀₁ is an integer of 1 to 4,

r ₁₀₂ is an integer of 1 to 3,

r ₁₀₃ is an integer of 1 to 3,

r ₁₀₄ is an integer of 1 to 4,

r ₁₀₅ is an integer of 1 to 4,

When r ₁₀₁ to r ₁₀₅ are each 2 or more, the structures in parentheses of 2 or more are the same or different,

a, b and z are an integer of 0 to 4,

When a, b, and z are each 2 or more, structures in parentheses of two or more are the same or different from each other,

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

Ar < ₄ > are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; A substituted or unsubstituted C _6-60 arylalkyl group; Substituted or unsubstituted C _6-60 arylalkenyl,

_R101 to _R104 and _R106 to _R108 each independently represent hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S; Or two of R ₁₀₆ to R ₁₀₈ are bonded to each other to form a substituted or unsubstituted C _6-60 aromatic ring or a substituted or unsubstituted heteroaromatic ring selected from the group consisting of N, Form a C _5-60 heteroaromatic ring,

R ₁₀₉ is C _5-60 heteroaryl containing at least one heteroatom selected from the group consisting of hydrogen, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O, and S,

L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene;

r ₁₀₁ is an integer of 1 to 4,

r ₁₀₂ is an integer of 1 to 3,

r ₁₀₃ is an integer of 1 to 3,

r ₁₀₄ is an integer of 1 to 4,

r ₁₀₆ is an integer of 1 to 2,

r ₁₀₇ is an integer of 1 to 4,

r ₁₀₈ is an integer of 1 to 4,

When r ₁₀₁ to r ₁₀₄ and r ₁₀₆ to r ₁₀₉ are respectively 2 or more, the structures in parentheses of 2 or more are equal to or different from each other.

As described above, in the organic light emitting device according to the present invention, the combination of the hole transport layer and the red first host and the second host has advantages of voltage drop, efficiency increase, and lifetime increase regardless of various structures and shapes of the hole injection layer In particular, it has a greater effect when the hole transport layer and the first host are used in the same structure.

As a result, the red-green single light emitting device and the stacked white light emitting device have advantages in material composition and device driving, as a result of comparison between the embodiment through the combination according to the present invention and the non- I could confirm.

The organic light emitting device described above is excellent in driving voltage, efficiency, and lifetime.

1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5 and a cathode 6.
2 is a plan view of a substrate 1, an anode 2, a hole injecting layer 7, a hole transporting layer 3, a first luminescent layer 4-1, a second luminescent layer 4-2, an electron transporting layer 5, An electron injection layer 8, and a cathode 6, as shown in FIG.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

및

는 다른 치환기에 연결되는 결합을 의미한다. In the present specification,

And

Quot; means a bond connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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 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 specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

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. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. 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, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group of the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarter phenyl group, or the like, but is not limited thereto. 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.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

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

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl group, , An indole group, a carbazole group, a benzooxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.

The present invention provides the following organic light emitting device:

anode; A hole transport layer; A red luminescent layer; A green light emitting layer; An electron transport layer; And a first host included in the hole transport layer and the first host included in the red light emitting layer are represented by Formula 1 or Formula 2 respectively and a second host included in the red light emitting layer is represented by Formula 3 > or Formula (4).

Hereinafter, the present invention will be described in detail with respect to each constitution.

Cathode and anode

The positive electrode and the negative electrode used in the present invention refer to an electrode used in an organic light emitting device.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer. Specific examples of the positive electrode material include 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; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable.

It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. 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.

Hole transport layer  And The light-

The organic light emitting device according to the present invention improves the driving voltage, efficiency, and lifetime of the organic light emitting device by controlling the substances included in the hole transporting layer and the red light emitting layer.

The hole transport layer is a layer that transports holes from the anode or the hole injection layer to the hole transport layer and transports the holes from the anode or the hole injection layer to the light emitting layer. Large materials are suitable.

In particular, the first host included in the hole transporting material and the red light emitting layer are the same or different from each other and are represented by the compound represented by the above formula (1) or (2). When the hole transporting material and the first host are the same compound, the interface resistance and the hole injecting barrier between the hole transporting layer and the red emitting layer are reduced, and holes are more easily introduced into the red light emitting layer. When the hole transport material and the first host are different from each other, holes are easily injected into the red light emitting layer based on the hole injection barrier of the compounds represented by Chemical Formulas 1 and 2 and the excellent hole transporting ability of the two compounds .

In the above formulas (1) and (2), preferably, G ₁ , G ₂ , G ₃ and G ₄ are each independently methyl or phenyl.

Preferably, L ₁ , L ₂ and L ₃ are each independently selected from the group consisting of:

In the above,

Each R < ₁ > is independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S.

More preferably, L ₁ , L ₂ and L ₃ are each independently a single bond, phenylene, biphenylene, or dimethylfluorenylene.

Preferably, Ar < ₃ > is any one selected from the group consisting of:

In the above,

R ₈ is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S;

More preferably, Ar ₃ is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, dimethylfluorenylene, dibenzofuranyl, to be.

Preferably, R ₁₀₁ to R ₁₀₅ are each independently hydrogen, phenyl, biphenyl, or naphthyl.

Representative examples of the compound represented by the above formula (1) are as follows:

The compound represented by Formula 1 may be prepared, for example, by reacting a compound represented by Formula 1 'and a compound represented by Formula 1' as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

In the above reaction formula, the definitions other than X 'are as described above, and X' is halogen, more preferably bromo. The above production method can be more specific in the production example to be described later.

Representative examples of the compound represented by the general formula (2) are as follows:

The compound represented by Formula 2 may be prepared, for example, by reacting a compound represented by Formula 2 'and a compound represented by Formula 2' as shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

In the above reaction formula, the definitions other than X 'are as described above, and X' is halogen, more preferably bromo. The above production method can be more specific in the production example to be described later.

In addition, a single host has a rather high HOMO, which results in a large barrier to holes and a desire to move electrons within the compound, resulting in a balance imbalance of the emission region. Therefore, in the present invention, the driving voltage, efficiency and lifetime of the organic light emitting device can be improved by using the second host of the hole transporting type together.

Specifically, the red luminescent layer further comprises a host represented by the above formula (3) or (4) as a second host:

In Formula 3, Ar ₄ is preferably each independently selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, naphthyl substituted phenyl , Or naphthyl substituted with phenyl.

Representative examples of the compound represented by the general formula (3) are as follows:

The compound represented by Formula 3 may be prepared, for example, by reacting a compound represented by Formula 3 'and a compound represented by Formula 3' as shown in Reaction Scheme 3 below.

[Reaction Scheme 3]

In the above reaction formula, the definitions other than Y 'and Y "are as described above, and one of Y' and Y" is halogen (more preferably bromo) and the other is B (OH) ₂ . The above production method can be more specific in the production example to be described later.

In Formula 4, preferably, L ₄ is a single bond or phenylene.

Preferably, R ₁₀₉ is hydrogen, phenyl, biphenyl, naphthyl, dimethylfluorenyl, or pyridine.

Preferably, r ₁₀₆ + r ₁₀₇ + r ₁₀₈ (sum of r ₁₀₆ , r ₁₀₇ and r ₁₀₈ ) is one.

Preferably, each of R ₁₀₆ to R ₁₀₉ is independently -L ₅ -Ar ₅ , L ₅ is a single bond, or substituted or unsubstituted C _6-60 arylene; Ar ₅ is C _5-60 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O, and S. More preferably, L < ₅ > is a single bond, or phenylene; Ar ₅ is a carbazolyl, benzocarbazolyl, dibenzothiophenyl, or dibenzofuranyl unsubstituted or substituted with phenyl, biphenylene, or terphenyline.

Representative examples of the compound represented by the formula (4) are as follows:

The compound represented by Formula 4 may be prepared, for example, by reacting a compound represented by Formula 4 'and a compound represented by Formula 4' as shown in Reaction Scheme 4 below. Can be further specified in the example.

[Reaction Scheme 4]

In the above reaction formula, the definitions other than Z 'and Z "are as described above, and one of Z' and Z" is halogen (more preferably bromo) and the other is B (OH) ₂ . The above production method can be more specific in the production example to be described later.

The weight ratio of the first host to the second host is preferably 99: 1 to 1:99.

In addition, the red light emitting layer may include a dopant material in addition to the host compound. The splittable material is not particularly limited as long as it is used for an organic light emitting device. Examples of the splittable material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex.

Specific examples of the aromatic amine derivative include a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and examples thereof include pyrene, anthracene, chrysene, and ferriplantene having an arylamino group. As the styrylamine compound, A substituted arylamine group in which at least one arylvinyl group is substituted and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto. Preferably, a red dopant is used as the dopant.

Preferably, the red luminescent layer further comprises a compound represented by the following formula (5): < EMI ID =

[Chemical Formula 5]

In Formula 5,

n1 is 1 or 2,

R ' ₁ to R' ₄ are each independently hydrogen; Substituted or unsubstituted C _1-6 alkyl; Or substituted or unsubstituted C _6-60 aryl,

X-Y is an auxiliary ligand.

이다. Preferably, the XY is

to be.

Further, the red light emitting layer is provided in contact with the green light emitting layer. The green light emitting layer includes a green dopant and is not particularly limited as long as it is used in an organic light emitting device.

Electron transport layer

The electron transporting layer is a layer that receives electrons from the electron injection layer or the cathode and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. The material is suitable.

Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

In addition, the organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode, if necessary. The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are 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.

Organic light emitting device

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that the compounds of the formulas (1) to (4) are used for the hole transport layer and the red light emitting layer.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating an anode, an organic layer, and a cathode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, and / or an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the first host compound and the second host compound may be formed as a light emitting layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

In addition, the organic light emitting device according to the present invention can be used as a single type or stack type organic light emitting device. Specifically, in the case of a stacked organic light emitting device, the following organic light emitting device is provided:

anode; A hole transport layer; A red luminescent layer; A green light emitting layer; An electron transport layer; An N-type charge generating layer; A P-type charge generation layer; A hole transport layer; A hole control layer; Blue light emitting layer; An electron transport layer; Wherein the first host included in the hole transport layer and the first host included in the red light emitting layer are represented by Formula 1 or Formula 2 respectively and the second host included in the red light emitting layer is represented by Formula 3 (4).

1 and 2 schematically show the structure of the organic light emitting device according to the present invention. 1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5 and a cathode 6. FIG. 2 illustrates an example of an organic light emitting device further including a hole injection layer, a second light emitting layer, and an electron injection layer in the organic light emitting device of FIG.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Manufacturing example  One: HTM1 ~ Of HTM6  Produce

One) Of HTM1  Produce

9,9-diphenyl-9H-fluorene (19.36 g, 48.7 mmol), sodium-t- Butoxide (6.43 g, 66.9 mmol) was added to toluene, and the mixture was heated with stirring, refluxed, and [bis (tri-t-butylphosphine)] palladium (487 mg, 0.20 mmol%) was added. After the temperature was lowered to room temperature and the reaction was terminated, HTM1 (32.2 g, yield 80%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] < ⁺ > = 843.10

2) Of HTM2  Produce

(5 g, 40.3 mmol) and N - ([1,1'-diphenyl] -4-yl) -9,9-dimethyl-9H (Triphenylphosphine) -fluorene-2-amine (14.85 g, 41.1 mmol) and sodium t-butoxide (5.42 g, 56.4 mmol) were added to toluene, Palladium (41.1 mg, 0.20 mmol%). After the temperature was lowered to room temperature and the reaction was terminated, HTM2 (19.1 g, yield 70%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] < ⁺ > = 678.89

3) Of HTM3  Produce

≪ Preparation of Intermediate Al &

Amine (150 g, 716.7 mmol) was dissolved in DMF (400 mL) and then NBS (177.98 g, 716.7 mmol) was slowly added dropwise at 0 ° C. And stirred for 3 hours. After extraction with water and chloroform at room temperature, the white solid was recrystallized from hexane to give A-1 (165 g, yield 80%).

MS [M + H] < ⁺ > = 288.03

<Preparation of intermediate B1>

The intermediate Intermediate A1 (46.1 g, 159.9 mmol) and phenylboronic acid (20.1 g, 164.7 mmol) were added to dioxane (300 mL), and a 2M potassium carbonate aqueous solution (100 mL) Phenyl-phosphinopalladium (462 mg, 3.99 mmol) was added thereto, followed by heating with stirring for 10 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate aqueous solution was removed and the layers were separated. After removal of the solvent, the white solid was recrystallized from hexane to give B1 (38.8 g, yield 85%).

MS [M + H] &lt; ⁺ &gt; = 286.15

&Lt; Production of HTM3 >

(28.12 g, 70.8 mmol) and sodium-t-butoxide (9.42 g, 98 mmol) were added to a solution of Intermediate B1 (10 g, 35.0 mmol) prepared above, 2-bromo-9,9- (357 mg, 0.2 mmol%) [bis (tri-t-butylphosphine)] palladium was placed in xylene. After lowering the temperature to room temperature and terminating the reaction, HTM3 (24 g, yield 75%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; ⁺ &gt; = 919.20

4) Of HTM4  Produce

(10 g, 32.5 mmol) and N - ([1,1'-diphenyl] -4-yl) -9,9-dimethyl-9H- fluoren- (tri (t-butylphosphine)] palladium (331 mg, 0.20 mmol%) was added to toluene, Respectively. After the temperature was lowered to room temperature and the reaction was terminated, HTM4 (13.7 g, yield 72%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; ⁺ &gt; = 588.77

5) Of HTM5  Produce

&Lt; Preparation of intermediate C1 &

To the toluene was added the previously prepared B1 (11.5 g, 40.3 mmol), 2-bromotriphenylene (12.6 g, 41.1 mmol) and sodium t-butoxide (5.4 g, 56.4 mmol) And then [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (58.9 mg, 2 mol%) was added thereto. After the temperature was lowered to room temperature and the reaction was terminated, recrystallization with tetrahydrofuran and ethyl acetate gave C1 (20.7 g, yield 70%).

MS [M + H] &lt; ⁺ &gt; = 512.23

&Lt; Production of HTM5 >

To the toluene was added the above prepared C1 (10 g, 19.5 mmol), 4-bromobiphenyl (2.2 g, 19.89 mmol) and sodium-t-butoxide (2.62 g, 27.3 mmol) Bis (tri-t-butylphosphine)] palladium (149 mg, 0.29 mmol%). After the temperature was lowered to room temperature and the reaction was terminated, HTM5 (5.7 g, yield 50%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; ⁺ &gt; = 664.29

6) Of HTM6  Produce

<Preparation of Intermediate D1>

(16.46 g, 53.6 mmol) and sodium-t-butoxide (7.06 g, 73.5 mmol) were added to a solution of 9,9-dimethyl-9H- ) Was placed in toluene, and the mixture was stirred under heating, refluxed, and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (767 mg, 2 mol%) was added. After the temperature was lowered to room temperature and the reaction was terminated, D1 (20.4 g, yield 76%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; ⁺ &gt; = 456.57

&Lt; Production of HTM6 >

To a solution of D1 (10 g, 19.54 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (4.64 g, 19.9 mmol) and sodium-t-butoxide (2.61 g, 27.3 mmol) Was added to xylene, and the mixture was heated and stirred. Then, [bis (tri-t-butylphosphine)] palladium (199 mg, 0.2 mmol%) was added. After the reaction mixture was cooled to room temperature, the reaction mixture was recrystallized from tetrahydrofuran and ethyl acetate to obtain HTM6 (9.57 g, yield 74%).

MS [M + H] &lt; + &gt; = 752.97

Manufacturing example  2: Manufacture of RM1 to RM3

&Lt; Preparation of intermediates E1 and E2 >

CAS # 530-93-8, 18 g, 123 mmol) and 4-bromophenylhydrazine hydrochloride (CAS # 622-88-8, 29 g, 129 mmol) Was added to EtOH (300 mL), and a slight amount of hydrochloric acid was added thereto, followed by heating under reflux in a nitrogen stream for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting product was filtered and dried in a vacuum oven for one day to obtain 25 g (yield: 68.8%) of E1 (10-bromo-6,7-dihydro-5H-benzo [c] carbazole).

[M + H] &lt; + &gt; = 298

25 g of E1 thus prepared was placed in CH ₃ CN (400 mL), and tetrachloro-1,4-benzoquinone, chloranil, DDQ (hereinafter referred to as " CAS # 118-75-2, 21 g, 84.7 mmol) was slowly added dropwise to the same amount of E1 as the charged E1. After completion of the reaction, NaOH (10%) and water were added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with hexane to obtain 21 g (yield: 84.7%) of E2 (10-bromo-7H-benzo [c] carbazole).

[M + H] = 296

<Preparation of Intermediates F1 to F3>

1-naphthylboronic acid (CAS # 13922-41-3, 17 g, 100 mmol) and 1-chloro-2-nitrobenzene (CAS # 88-73- 3, 16 g, 100 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol. Then, potassium carbonate (CAS # 584-08-7, 41 g, 300 mmol) was dissolved in water and the mixture was heated for 30 minutes Lt; / RTI &gt; After 30 minutes, tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and the mixture was further reacted for 2 hours. After the completion of the reaction, an excess amount of water was added, and the mixture was extracted with ethyl acetate (EA (hereinafter referred to as EA) to obtain an organic layer, which was then subjected to column purification to obtain F1 (18 g, yield 75.5%).

[M + H] &lt; + &gt; = 249

20 g (80 mmol) of the above-prepared F1 was added to 200 mL of dichloromethane (CH ₂ Cl ₂ (hereinafter)) and bromine (Br ₂ , CAS # 7726-95-6, 4.3 ml, 84 mmol) was slowly added dropwise over 20 minutes. After the addition was completed, the reaction solution was stirred at room temperature for one day. After completion of the reaction, residual bromine was removed from the reaction solution with water and aqueous sodium thiosulfate (Na ₂ S ₂ O ₃ (hereinafter referred to as CAS # 10102-17-7) and extracted with dichloromethane. After the extraction, the solvent was concentrated using a rotary condenser and F2 (22.8 g, yield 86.4%) was obtained through column purification.

[M + H] &lt; + &gt; = 328

20 g of the above prepared F3 was added to triethylphosphite (P (OEt) ₃ (hereinafter referred to as CAS # 122-52-1, 42 mL) and the mixture was heated and stirred at 180 ° C for 8 hours. After completion of the reaction, the remaining P (OEt) ₃ was removed by vacuum distillation and extracted with EA. The extracted EA was dried over anhydrous magnesium sulfate (MgSO ₄ , CAS # 7487-88-9) to remove moisture and subjected to column purification to obtain 11.6 g of F3 (5-bromo-7H-benzo [c] carbazole) .

[M + H] = 296

<Preparation of Intermediates G1 to G3>

Trichloroaluminum (Aluminum chloride, AlCl ₃ (hereinafter referred to as CAS # 7446-70-0, 31.9 g, 239 mmol) was dissolved in CH ₂ Cl _{2 in the} same manner as described in U.S. Patent Publication No. 2009-0076076 And the mixture was stirred at 0 ° C for 10 minutes, and then β-tetralone (17.5 g, 120 mmol) was added thereto. Stir 20 min and Br ₂ (6.74 mL, 131 mmol) was slowly added at the same temperature. After addition of bromine, the reaction solution was further stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into an ice bath and extracted with EA. The extracted organic material was dried over MgSO ₄ and concentrated using a rotary evaporator. The concentrated solution was subjected to column purification to obtain 19 g of G1 (7-bromo-3,4-dihydronaphthalen-2 (1H) -one) (yield 71.1%).

[M + H] &lt; + &gt; = 225

The above prepared G1 (20 g, 89 mmol) and phenylhydrazine hydrochloride (CAS # 59-88-1, 12.9 g, 89 mmol) were added to 300 mL of EtOH and a little hydrochloric acid was added thereto. And the mixture was heated under reflux in an air stream. After completion of the reaction, the reaction mixture was cooled to room temperature and the product was filtered and dried in a vacuum oven for one day to obtain 23 g of G2 (2-bromo-6,7-dihydro-5H-benzo [c] carbazole) (yield: 88.7%).

[M + H] &lt; + &gt; = 299

The above-prepared G2 (20 g, 67 mmol) was added to 400 mL of CH ₃ CN and added with tetrachloro-1,4-benzoquinone, chloranil, DDQ CAS # 118-75-2, 21 g, 84.7 mmol) was slowly added dropwise to the same amount of G2 as the charged G2. After completion of the reaction, NaOH (10%) and water were added to the reaction solution, and the organic layer was extracted. The reaction solution was concentrated and recrystallized with hexane to obtain 13 g of G3 (2-bromo-7H-benzo [c] carbazole) (yield 64.7%).

[M + H] = 296

<Preparation of intermediates H1 to H3>

<Production of H1>

(2,4-dichloroquinazoline, CAS # 607-68-1, 10 g, 50 mmol) and phenylboronic acid (PBA, CAS # 98-80-6, 6.10 g, 50 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol. Potassium carbonate (CAS # 584-08-7, 41 g, 300 mmol) was dissolved in water, and the mixture was heated and stirred for 30 minutes. After 30 minutes, tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and the mixture was further reacted for 2 hours. After completion of the reaction, excess water was added, and the mixture was extracted with EA to obtain an organic layer, which was then subjected to column purification to obtain H1 (8.3 g, yield 68.7%).

[M + H] &lt; + &gt; = 240

<Preparation of H2>

2,4-dichloroquinazoline (CAS # 607-68-1, 20 g, 100 mmol) and 4-biphenylboronic acid (PBA, CAS # 5122-94-1 , 20 g, 100 mmol), H2 (23.3 g, yield 73.2%) was obtained in the same manner as in the preparation of H1.

[M + H] &lt; + &gt; = 317

&Lt; Production of H3 >

2,4-dichloroquinazoline (CAS # 607-68-1, 20 g, 100 mmol) and 2-naphthyl boronic acid (CAS # 32316-92-0 , 18.1 g, 100 mmol), H3 (26.7 g, yield 91.3%) was obtained in the same manner as in the preparation of H1.

[M + H] &lt; + &gt; = 290

<Synthesis of Intermediates E2-1, F3-1 and G3-1>

<Preparation of E2-1>

Sodium hydride (NaH (hereinafter referred to as NaH (hereinafter referred to as CAS # 7646) was added to the previously prepared E2 (10 g, 33.7 mmol) in anhydrous dimethylacetamide (DMF -69-7,5 g, 35.9 mmol) was slowly added. After stirring for 1 hour at room temperature, H2 (10.9 g, 34.4 mmol) prepared above was added and stirred at room temperature for one day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain compound E2-1 (15.1 g, yield 78%).

[M + H] &lt; / RTI &gt; = 577.5

<Preparation of F3-1>

Sodium hydride (NaH (hereinafter referred to as NaH (hereinafter referred to as CAS # 7646) was added to anhydrous dimethylacetamide (DMF (hereinafter referred to as CAS # 68-12-2) -69-7,5 g, 35.9 mmol) was slowly added. After stirring for 1 hour at room temperature, the previously prepared H3 (9.95 g, 34.1 mmol) was added and stirred at room temperature for one day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain Compound F3-1 (14.1 g, yield 76.3%).

[M + H] = 551.46 &lt; RTI ID = 0.0 &gt;

&Lt; Production of G3-1 >

Sodium hydride (NaH (hereinafter referred to as NaH (hereinafter referred to as CAS # 7646) was added to the above-prepared G3 (10 g, 33.7 mmol) in anhydrous dimethylacetamide (DMF -69-7, 5g, 35.9 mmol) was slowly added. After stirring for 1 hour at room temperature, the previously prepared H1 (8.27 g, 34.4 mmol) was added and stirred at room temperature for one day. After the reaction was completed, the resulting precipitate was filtered, washed with EtOH, and then extracted with EA to obtain Compound G3-1 (12.98 g, yield 77%).

[M + H] = 501.40

1) Manufacture of RM1

(10 g, 17.3 mmol) and N-phenyl-9H-carbazole-3-yl boronic acid (CAS # 854952-58-2, 5.12 g, 17.5 mmol ) Was dissolved in 200 mL of toluene and 100 mL of ethanol. Potassium carbonate (CAS # 584-08-7, 7.12 g, 51.9 mmol) was dissolved in water, and the mixture was heated and stirred for 30 minutes. After 30 minutes, tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and the mixture was further reacted for 2 hours. After completion of the reaction, an excess amount of water was added and the mixture was extracted with EA to obtain an organic layer, which was then recrystallized from tetrahydrofuran and ethyl acetate to obtain RM1 (10.35 g, yield 82%).

[M + H] = 739.89

2) Manufacture of RM2

To a solution of intermediate F3-1 (10 g, 18.2 mmol), 9H-carbazole (9H-carbazole, CAS # 86-74-8, 3.12 g, 19.3 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) Toluene, and the mixture was stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (185 mg, 0.20 mmol%) was added. After lowering the temperature to room temperature and terminating the reaction, RM2 (8.36 g, yield 71%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; + &gt; = 637.76

3) Manufacture of RM3

4-dibenzofuranylboronic acid (5.2 g, 20.35 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol, followed by the addition of potassium carbonate (CAS # 584-08-7, 7.12 g, 51.9 mmol) were dissolved in water, added to the reaction solution, and the mixture was heated with stirring for 30 minutes. After 30 minutes, tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 1.7 g, 1.5 mmol) was added and the mixture was further reacted for 2 hours. After completion of the reaction, excess water was added and extracted with EA to obtain an organic layer, which was then recrystallized from tetrahydrofuran and ethyl acetate to obtain RM3 (9.15 g, yield 78%).

[M + H] = 578.68 &lt; RTI ID = 0.0 &gt;

Manufacturing example  3: Manufacture of RM4 to RM6

<Preparation of Intermediate J1>

(Cu, CAS # 7440-50-8, 4.15 g, 60.0 mmol) in a xylene solvent was added to a solution of 3-bromo-9H-carbazole (15 g, 60.9 mmol) 64 mmol) and potassium phosphate (K ₃ PO ₄ (below), 20.4 g, 96 mmol) were charged together (under Ullmann conditions) with stirring for one day. After completion of the reaction, the reaction solution was cooled to room temperature, and excess EtOH was added to precipitate the compound. The compound was extracted with CHCl ₃ , and then recrystallized with water and EA to obtain J1 (18.9 g, yield 78%).

MS [M + H] &lt; ⁺ &gt; = 399.3

<Preparation of intermediate J2>

J2 was prepared in the same manner as in the preparation of intermediate J1 except that 4-iodophenyl was used instead of 4-iodobiphenyl.

MS [M + H] &lt; ⁺ &gt; = 475.4

<Preparation of intermediate J3>

J3 was prepared in the same manner as in the preparation of intermediate J1 except that 3-iodobiphenyl was used instead of 4-iodobiphenyl.

MS [M + H] &lt; ⁺ &gt; = 399.3

<Preparation of Intermediate K1>

Intermediate J3 (10 g, 25.1 mmol) was dissolved in THF (250 mL), the temperature was lowered to -78 ° C, 2.5M n-BuLi (14 mL) was added dropwise, and after 30 minutes, triisobutylborane 35.1 mmol) was added thereto, and the mixture was stirred at room temperature for 1 hour. 1N HCl (300 mL) was added thereto, and the mixture was stirred for 30 minutes. Then, the solvent was removed by layer separation and washed with ethyl acetate to prepare K1 (7.74 g, 85%).

MS [M + H] &lt; ⁺ &gt; = 364.22

4) Synthesis of RM4

Boronic acid (7.4 g, 25.8 mmol) was dissolved in 200 mL of toluene and 100 mL of ethanol, followed by the addition of potassium carbonate (10 g, 25.1 mmol) and (4- (9H-carbazol- , CAS # 584-08-7, 5 g, 30.2 mmol) were dissolved in water, and the mixture was heated and stirred for 30 minutes. After 30 minutes, tetrakis (triphenylphosphine) palladium (0), CAS # 14221-01-3, 2 g, 1.5 mmol) was added and the mixture was further reacted for 2 hours. After completion of the reaction, excess water was added and the mixture was extracted with EA to obtain an organic layer, which was then recrystallized from tetrahydrofuran and ethyl acetate to obtain RM3 (10.97 g, yield 78%).

MS [M + H] &lt; ⁺ &gt; = 561.7

5) Manufacture of RM5

RM5 was prepared in the same manner as in the preparation of RM4 except that intermediate J2 was used instead of intermediate J1.

MS [M + H] &lt; ⁺ &gt; = 637.8

6) Manufacture of RM6

RM6 was prepared in the same manner as in the preparation of RM4 except that Intermediate J3 was used instead of Intermediate J1 and Intermediate K1 was used instead of (4- (9H-carbazol-9-yl) phenyl) boronic acid.

MS [M + H] &lt; ⁺ &gt; = 637.8

In addition to the compounds prepared above, the structures of the compounds designated in the following Examples and Comparative Examples were as follows.

Example  One

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

The above-described P1 was thermally vacuum-deposited on the ITO transparent electrode prepared in this way to a thickness of 50 ANGSTROM to form a hole injection layer. HTM1, which is a material for transporting holes, was vacuum deposited to a thickness of 100 Å to form a hole transport layer. HTM1 as a red first host, RM1 (7: 3 weight ratio) and dopant D1 (2 wt% , Green host H 2 and H 3 (7: 3 weight ratio) and dopant D 2 (20 wt%) were vacuum deposited to a thickness of 400 Å. Next, E1 compound was deposited to a thickness of 250 Å to form an electron transport layer. Then, E2 and Li (2%) were vacuum deposited as an n-type charge generating layer to a thickness of 100 Å, To prepare an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

Example  2 to 42

Was prepared in the same manner as in Example 1 except that the materials listed in Tables 1 and 2 were used.

Comparative Example  One

An organic light emitting device was prepared in the same manner as in Example 1, except that HT1 was used instead of HTM1 as the hole transport layer and only the green light emitting layer was laminated to the same thickness without laminating the red light emitting layer.

Comparative Example  2

In Example 1, an organic light emitting device was manufactured in the same manner except that HT1 was used instead of HTM1 as the hole transporting layer and the first host.

Comparative Example  3

An organic light emitting device was prepared in the same manner as in Comparative Example 2 except that the ratio of the first host to the second host was changed to 5: 5 instead of 7: 3.

The materials used in Examples 1 to 42 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below.

Example  43

P2 was thermally vacuum deposited on the ITO transparent electrode prepared in the same manner as in Example 1 to a thickness of 50 ANGSTROM to form a hole injection layer. HTM1, which is a material for transporting holes, was vacuum deposited to a thickness of 100 Å to form a hole transport layer. HTM1 as a red first host, RM5 (7: 3 weight ratio) and dopant D1 (2 wt% , Green host H 2 and H 3 (7: 3 weight ratio) and dopant D 2 (20 wt%) were vacuum deposited to a thickness of 400 Å. Next, E1 compound was deposited to a thickness of 250 Å to form an electron transport layer. Then, E2 and Li (2%) were vacuum deposited as an n-type charge generating layer to a thickness of 100 Å, To prepare an organic light emitting device. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

Example  44 to 84

Was prepared in the same manner as in Example 43, except that the materials listed in Tables 3 and 4 were used.

Comparative Example  4

An organic light emitting device was fabricated in the same manner as in Example 43, except that HT1 was used instead of HTM1 as the hole transport layer, and only the green light emitting layer was laminated to the same thickness without laminating the red light emitting layer.

Comparative Example  5

An organic light emitting device was prepared in the same manner as in Example 43, except that HT1 was used instead of HTM1 in the hole transport layer and the first host.

Comparative Example  6

An organic light emitting device was prepared in the same manner as in Comparative Example 5 except that the ratio of the first host to the second host was changed to 5: 5 instead of 7: 3.

The materials used in Examples 43 to 84 and Comparative Examples 4 to 6 are shown in Tables 3 and 4 below.

Example  85

The above-described HTM3 was thermally vacuum-deposited on the ITO transparent electrode prepared in the same manner as in Example 1 to a thickness of 100 Å to form a hole injection layer. The compound P3 was doped with a doping concentration of 3%, and a hole transporting material HTM3 was vacuum-deposited to a thickness of 100 Å to form a hole transport layer. HTM1 as a red first host, RM2 (weight ratio of 7: 3) and dopant D1 (2 wt%) as a second host were vacuum deposited Green host H 2 and H 3 (weight ratio 7: 3) and dopant D 2 (20 wt%) were vacuum deposited to a thickness of 400 Å. Next, E1 compound was deposited to a thickness of 250 Å to form an electron transport layer. Then, E2 and Li (2%) were vacuum deposited as an n-type charge generating layer to a thickness of 100 Å, To prepare an organic light emitting device. In this process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

Example  86 to 126

An organic light emitting device was prepared in the same manner as in Example 85, except that the materials listed in Tables 5 and 6 were used.

Comparative Example  7

An organic light emitting device was prepared in the same manner as in Example 85 except that HT1 was used instead of HTM1 as the hole injecting layer and the hole transporting layer, and only the green light emitting layer was laminated to the same thickness without laminating the red light emitting layer.

Comparative Example  8

An organic light emitting device was prepared in the same manner as in Example 85 except that HT1 was used instead of HTM1 in the hole injecting layer, the hole transporting layer, and the first host.

Comparative Example  9

An organic light emitting device was prepared in the same manner as in Comparative Example 8 except that the ratio of the first host to the second host was changed to 5: 5 instead of 7: 3.

The materials used in Examples 85 to 126 and Comparative Examples 7 to 9 are shown in Tables 5 and 6.

[White EL device]

Example  127

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

&Lt; Formation of green light emitting element &

The above-described P1 was thermally vacuum-deposited on the ITO transparent electrode prepared in this way to a thickness of 50 ANGSTROM to form a hole injection layer. HTM1, which is a material for transporting holes, was vacuum deposited to a thickness of 100 Å to form a hole transport layer. HTM1 as a red first host, RM1 (7: 3 weight ratio) and dopant D1 (2 wt% , Green host H 2 and H 3 (7: 3 weight ratio) and dopant D 2 (20 wt%) were vacuum deposited to a thickness of 400 Å. Then, E1 compound was deposited to a thickness of 250 ANGSTROM to form an electron transport layer. Then, E2 and Li (2%) were vacuum deposited as an n-type charge generating layer to a thickness of 100 ANGSTROM. Subsequently, Was formed to a thickness of 50 angstroms.

&Lt; Formation of blue light emitting element &

Blue was formed as the second light emitting unit following the charge generating layer. HTM1, which is a material for transporting holes on the charge-generating layer, was vacuum-deposited to a thickness of 900Å to form a HTL, HT2 as a hole-controlling layer, and then host H4 and dopant D3 (4 wt% Vacuum deposition was performed. Subsequently, an E3 compound was formed as an electron transport layer at a thickness of 300 ANGSTROM with Alq3 at a ratio of 1: 1, followed by sequentially depositing lithium fluoride (LiF) having a thickness of 10 ANGSTROM and aluminum having a thickness of 800 ANGSTROM to form a cathode. . In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec. The structure of the material used was as follows.

Example  128 to 142 and Comparative Example  10-12

An organic light emitting device was fabricated in the same manner as in Example 127 except that the materials listed in Table 7 were used.

The materials used in Examples 127 to 142 and Comparative Examples 10 to 12 are shown in Table 7. The characteristics of the respective organic light emitting devices were evaluated, and the results are shown in Table 7.

1: substrate 2: anode
3: hole transport layer 4: light emitting layer
4-1: First light emitting layer 4-2: Second light emitting layer
5: electron transport layer 6: cathode
7: Hole injection layer 8: Electron injection layer

Claims (11)

anode;
A hole transport layer;
A red luminescent layer;
A green light emitting layer;
An electron transport layer; And
A cathode,
Wherein the hole transporting material contained in the hole transporting layer and the first host included in the red light emitting layer are represented by the following general formula (1) or (2)
Wherein the second host included in the red light emitting layer is represented by the following general formula (3) or (4)
Single or stacked organic light emitting devices:
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
L ₁ , L ₂ and L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _5-60 heteroarylene containing at least one hetero atom selected from the group consisting of N, O and S,
G ₁ , G ₂ , G ₃ and G ₄ are each independently a substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S, or a substituted or unsubstituted monocyclic or polycyclic ring Lt; / RTI &gt;
Ar ₃ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _6-60 arylalkenyl; Or substituted or unsubstituted C _5-60 heteroaryl containing at least one hetero atom selected from the group consisting of N, O and S,
R ₁₀₁ to R ₁₀₅ each independently represent hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl comprising at least one hetero atom selected from the group consisting of N, O and S,
r ₁₀₁ is an integer of 1 to 4,
r ₁₀₂ is an integer of 1 to 3,
r ₁₀₃ is an integer of 1 to 3,
r ₁₀₄ is an integer of 1 to 4,
r ₁₀₅ is an integer of 1 to 4,
When r ₁₀₁ to r ₁₀₅ are each 2 or more, the structures in parentheses of 2 or more are the same or different,
a, b and z are an integer of 0 to 4,
When a, b, and z are each 2 or more, structures in parentheses of two or more are the same or different from each other,
(3)

[Chemical Formula 4]

In the above formulas (3) and (4)
Ar &lt; ₄ &gt; are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; A substituted or unsubstituted C _6-60 arylalkyl group; Substituted or unsubstituted C _6-60 arylalkenyl,
_R101 to _R104 and _R106 to _R108 each independently represent hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S; Or two of R ₁₀₆ to R ₁₀₈ are bonded to each other to form a substituted or unsubstituted C _6-60 aromatic ring or a substituted or unsubstituted heteroaromatic ring selected from the group consisting of N, Form a C _5-60 heteroaromatic ring,
R ₁₀₉ is C _5-60 heteroaryl containing at least one heteroatom selected from the group consisting of hydrogen, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O, and S,
L ₄ is a single bond; Substituted or unsubstituted C _6-60 arylene;
r ₁₀₁ is an integer of 1 to 4,
r ₁₀₂ is an integer of 1 to 3,
r ₁₀₃ is an integer of 1 to 3,
r ₁₀₄ is an integer of 1 to 4,
r ₁₀₆ is an integer of 1 to 2,
r ₁₀₇ is an integer of 1 to 4,
r ₁₀₈ is an integer of 1 to 4,
When r ₁₀₁ to r ₁₀₄ and r ₁₀₆ to r ₁₀₉ are respectively 2 or more, the structures in parentheses of 2 or more are equal to or different from each other.
The method according to claim 1,
Wherein the hole transport material and the first host are the same or different from each other,
Organic light emitting device.
The method according to claim 1,
G ₁ , G ₂ , G ₃ and G ₄ are each independently methyl,
Organic light emitting device.
The method according to claim 1,
L ₁ , L ₂ and L ₃ are each independently any one selected from the group consisting of:
Organic Light Emitting Device:

In the above,
Each R &lt; ₁ &gt; is independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S;
The method according to claim 1,
Ar ₃ is any one selected from the group consisting of:
Organic Light Emitting Device:

In the above,
R ₈ is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Hydroxy; Carbonyl; ester; Imide; amides; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _6-60 arylalkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkoxy; A substituted or unsubstituted C _6-60 aryloxy group; Substituted or unsubstituted C _1-60 alkylthio; Substituted or unsubstituted C _6-60 arylthioxy; Substituted or unsubstituted C _1-6 alkylsulfoxy; A substituted or unsubstituted C _6-60 arylsulfoxy group; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted silyl; Substituted or unsubstituted boron; A substituted or unsubstituted amine; Substituted or unsubstituted phosphine oxides; Substituted or unsubstituted C _6-60 aryl; Or C _5-60 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S;
The method according to claim 1,
R ₁₀₁ to R ₁₀₅ in the general formulas (1) and (2) are each independently hydrogen, phenyl, biphenyl or naphthyl,
Organic light emitting device.
The method according to claim 1,
The compound represented by the formula (1) is any one selected from the group consisting of
Organic Light Emitting Device:

The method according to claim 1,
Wherein the compound represented by Formula 2 is any one selected from the group consisting of
Organic Light Emitting Device:

The method according to claim 1,
Wherein the compound represented by the formula (3) is any one selected from the group consisting of
Organic Light Emitting Device:

The method according to claim 1,
The compound represented by the formula (4) is any one selected from the group consisting of
Organic Light Emitting Device:

The method according to claim 1,
Wherein the red light emitting layer further comprises a compound represented by the following general formula (5)
Organic Light Emitting Device:
[Chemical Formula 5]

In Formula 5,
n1 is 1 or 2,
R ' ₁ to R' ₄ are each independently hydrogen; Substituted or unsubstituted C _1-6 alkyl; Or substituted or unsubstituted C _6-60 aryl,
XY is an ancillary ligand.

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