KR20090051599A - Organometallic complex compounds for photoelectric device and photoelectric device comprising the same - Google Patents

Abstract

The present invention provides an organometallic complex compound for an organic photoelectric device represented by Formula 1, and an organic photoelectric device including the same.

[Formula 1]

Definitions of n, a, b, M, L, C ₁ to C ₃ , Y ₁ , X ₁ to X ₁₄ , and R ₁₄ in Chemical Formula 1 are as described in the detailed description of the invention. In the organometallic complex compound for an organic photoelectric device, by introducing a molecule having a bulk structure into the ligand of the organometallic complex compound, the interaction between molecules is suppressed to improve luminous efficiency and solubility.

Organic photoelectric device, organometallic complex, fluorene, carbazole, spin coating, inkjet printing, casting

Description

ORGANOMETALLIC COMPLEX COMPOUNDS FOR PHOTOELECTRIC DEVICE AND PHOTOELECTRIC DEVICE COMPRISING THE SAME}

The present invention relates to an organometallic complex compound for an organic photoelectric device, and an organic photoelectric device including the same, and more particularly to an organometallic complex compound for an organic photoelectric device having improved luminous efficiency and solubility, and an organic photoelectric device including the same. It is about.

Organic photoelectric devices are attracting attention as next generation display devices. The organic photoelectric device can be driven at a low voltage and can solve the drawbacks of the TFT-LCD, such as thinning, wide viewing angle, and fast response speed. In addition, compared to other display devices, the medium size or less may have the same or higher image quality than that of the TFT-LCD, and the manufacturing process is simple.

In the organic photoelectric device, an organic light emitting material is formed in a space between a lower plate having a form in which an ITO transparent electrode pattern is formed as a positive electrode on a transparent glass substrate and an upper plate in which a metal electrode is formed as a negative electrode on the substrate. A display device using a property that emits light while a current flows through an organic light emitting material when a predetermined voltage is applied between metal electrodes.

The organic light emitting material used in such an organic photoelectric device was developed by Eastman Kodak in 1987 for the first time to develop an organic light emitting material using a low molecular aromatic diamine and an aluminum complex as a material for forming a light emitting layer (Applied Physics Letters). 51, 913, 1987), and in 1987, CW Tang et al. Reported the first devices with practical performance (Applied Physics Letters, 51 (12), 913-915, 1987).

The organic photoelectric device is a self-luminous display device capable of driving low voltage, having a wide viewing angle, excellent contrast, and fast response speed.

Such an organic photoelectric device generally has a structure formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film layer including a light emitting region, and a cathode made of a metal electrode.

In this case, the organic thin film layer may include a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer or an electron injection layer, and may further include an electron blocking layer or a hole blocking layer due to the light emission characteristics of the light emitting layer.

When an electric field is applied to the organic photoelectric device having such a structure, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the light emitting layer through the respective hole transport layer and the electron transport layer to emit light excitons. Form. The formed light exciton emits light while transitioning to ground states, in which a light emitting layer (dopant) is doped into the light emitting layer (host) to increase the efficiency and stability of the light emitting state.

In the organic photoelectric device having the structure as described above, the light emitting material may be divided into a fluorescent material using an exciton in a singlet state and a phosphorescent material using a triplet state according to its light emitting mechanism, and not only a fluorescent light emitting material but also a phosphorescent material. Luminescent materials can also be used as luminescent materials in organic photoelectric devices (DFO'Brien et al., Applied Physics Letters, 74 (3), 442-444, 1999; MA Baldo et al., Applied Physics letters, 75 (1), 4- 6,1999).

The phosphorescence emission is a mechanism in which electrons transfer from the ground state to the excited state, and then the singlet excitons are non-luminescently transferred to the triplet excitons through intersystem crossing, and then the triplet excitons are emitted to the ground state. Is done.

At this time, the lifetime of the triplet excitons cannot be transferred directly to the ground state (spin forbidden), so the process of transition to the ground state after the flipping of the electron spin proceeds, so the lifetime (luminescence time) is higher than that of fluorescence. It has a longer characteristic.

That is, the emission duration of fluorescence emission is only several nanoseconds, but the phosphorescence emission corresponds to several micro seconds, which is a relatively long time.

In addition, quantum mechanically, when the holes injected from the anode and the electrons injected from the cathode recombine to form a light emitting excitons in the organic photoelectric device, the ratio of the singlet and triplet is 1: 3 and the triplet in the OLED device is generated. Luminescent excitons are generated about three times more than singlet luminescent excitons.

Therefore, in the case of fluorescence, the probability of singlet excited state is 25% (triple excited state 75%), and the luminous efficiency is limited, whereas phosphorescence can be used to triplet excited state and 75% singlet excited state. Theoretically, the internal quantum efficiency can be up to 100%. Therefore, in the case of using the phosphorescent material, there is an advantage that can achieve a light emission efficiency about three times higher than the fluorescent light emitting material.

As a molecular structure that is easy to phosphorescence emission, it is a molecular structure that is easy to intercalate to introduce heavy metals such as Ir, Pt, Rh, Pd, etc. in this case, in this case, the spin generated by the heavy atom effect (heavy atom effect) Spin-orbital coupling results in a mixture of triplet and singlet states, which allows forbidden transitions and effectively phosphorescent at room temperature.

Among these, the iridium organometallic complex is attracting attention as a material having excellent phosphorescence emission efficiency and phosphorescence emission materials using the same have been reported (Sergey Lamansky etc. Inorg. Chem., 40, 1704-1711, 2001 & J. Am. Chem. Soc., 123, 4304-4312, 2001).

The phosphorescent organic metal complex has been mainly developed for the development of low-molecular materials capable of constituting the device by vacuum deposition method, and in the case of the polymer material, the device is formed by wet processes such as spin coating, inkjet printing, and casting methods. Configure.

Wet processes using polymers are easier to fabricate devices than vacuum evaporation, and have more advantages in terms of cost and size, but have the disadvantage that polymer materials are lower than low molecular materials in terms of lifetime, luminous efficiency and color purity.

Therefore, in order to overcome such a problem, there is a demand for the development of a material capable of constituting a device by a wet process with low molecular weight and high solubility.

An object of the present invention is to provide an organometallic complex compound for an organic photoelectric device with improved luminous efficiency and solubility.

Still another object of the present invention is to provide an organic photoelectric device comprising the organometallic complex compound for an organic photoelectric device.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by the average person from the following description.

In order to achieve the above object, the present invention provides an organometallic complex compound for an organic photoelectric device represented by the following general formula (1).

[Formula 1]

(In Formula 1,

N is an integer of 1 to 3,

A and b are each independently an integer of 0 or 1,

A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aliphatic ring compound, a heteroaliphatic ring compound, an aromatic ring compound, and a heteroaromatic ring compound,

M is a metal forming an octahedral complex,

L is a monovalent anionic bidentate ligand coordinated to M through sp ² carbon and a heteroatom, or a monovalent anionic bidentate ligand coordinated to M through heteroatom and heteroatom,

C ₁ to C ₃ is -C (R ₁₇ ) _h- , h is an integer of 0 or 1,

Y ₁ is an anionic monodentate ligand coordinated to M via sp ² carbon or heteroatom,

X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2,

R ₁ to R ₅ , and R ₁₇ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted Biarylphenyl group, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si ( R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C (O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ , and

R ₁ to R ₅ are each present as an independent substituent, or are fused to each other to form a ring bonded to X ₁ to X ₁₄ ,

At least one of R ₁ to R ₅ is a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, and a substituted or unsubstituted biarylphenyl group in the group Selected,

R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

R ₁₅ is a halogen atom, a nitro group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted Or an unsubstituted acyl group having 2 to 20 carbon atoms, an amino group, and a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms).

According to another embodiment of the present invention, an organic thin film layer is disposed between a pair of electrodes, and the organic thin film layer provides an organic photoelectric device including the organometallic complex compound.

Other specific details of embodiments of the present invention are included in the following detailed description.

The organometallic complex compound for an organic photoelectric device according to the present invention is suppressed intermolecular interaction to improve the luminous efficiency and solubility.

When the organic photoelectric device is manufactured using the organometallic complex compound, due to the excellent solubility of the organometallic complex compound, the organic metal complex compound may be easily manufactured by a wet process such as spin coating, inkjet printing, and casting, thereby reducing manufacturing costs. .

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

According to one embodiment of the present invention, an organometallic complex compound for an organic photoelectric device represented by Formula 1 is provided.

[Formula 1]

(In Formula 1,

N is an integer of 1 to 3,

A and b are each independently an integer of 0 or 1,

A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aliphatic ring compound, a heteroaliphatic ring compound, an aromatic ring compound, and a heteroaromatic ring compound,

M is a metal forming an octahedral complex,

L is a monovalent anionic bidentate ligand coordinated to M through sp ² carbon and a heteroatom, or a monovalent anionic bidentate ligand coordinated to M through heteroatom and heteroatom,

C ₁ to C ₃ is -C (R ₁₇ ) _h- , h is an integer of 0 or 1,

Y ₁ is an anionic monodentate ligand coordinated to M via sp ² carbon or heteroatom,

X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2,

R ₁ to R ₅ , and R ₁₇ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, substituted or unsubstituted Ring biarylphenyl group, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C (O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ ,

R ₁ to R ₅ are each present as an independent substituent, or are fused to each other to form a ring bonded to X ₁ to X ₁₄ ,

At least one of the R ₁ to R ₅ is selected from the group consisting of a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, and a substituted or unsubstituted biarylphenyl group. Become,

R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

R ₁₅ is a group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Is chosen)

In this specification, a heteroatom means an atom selected from the group consisting of N, O, S, and P, and a heteroaliphatic ring compound, heteroaromatic ring compound, heteroalkyl group, or heteroaryl group is N, O, S, and P It contains 1 to 3 hetero atoms selected from the group consisting of, and the rest means an aliphatic ring compound, an aromatic ring compound, an alkyl group, or an aryl group which is carbon.

In the present specification, unless otherwise specified, the substituted is a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, an amino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted hetero atom having 2 to 30 carbon atoms. Mean substituted with a substituent selected from the group consisting of an aryl group.

A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And when C ₃ and X ₁₀ to X ₁₄ are each independently an aliphatic ring compound or a heteroaliphatic ring compound, each of X ₁ to X ₁₄ is independently C (R ₁ ) (R ₂ ), N (R ₃ ), Si (R ₅ ) (R ₆ ), O, or S, and C ₁ to C ₃ are C (R ₁₇ ). That is, h, i, j, k, o, and p are one.

In addition, the C ₁ and a ring compound consisting of X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C (R ₁ ), N (R ₃ ), Si (R ₅ ) (R ₆ ), when the ring compound consisting of C ₃ and X ₁₀ to X ₁₄ is each independently an aromatic ring compound or a heteroaromatic ring compound, O, or S, and C ₁ to C ₃ are C. That is, h, j, k, o, and p are 0 and i is 1.

X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2,

When a is 0 in Formula 1, C ₁ and X ₁ to X ₄ form a pentagonal ring compound, and when a is 1, C ₁ and X ₁ to X ₄ form a hexagonal ring compound.

In addition, when b is 0, C ₂ , Y ₁ and X ₇ to X ₉ constitute a pentagonal ring compound, and when b is 1, C ₂ , Y ₁ and X ₇ to X ₉ are hexagonal rings To form a compound.

A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aromatic ring compound and a heteroaromatic ring compound.

R ₁ to R ₅ is preferably selected from the group consisting of substituents represented by the following formulas (2) to (6).

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Chemical Formulas 2 to 6

X ₂₁ to X ₂₈ , X ₃₁ to X ₃₈ , and X ₅₁ to X ₆₆ are each independently selected from the group consisting of CR ₁₈ , and N,

R ₁₈ and R ″ are each independently a hydrogen atom, a halogen atom, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C ( O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ ,

R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

R 'is a group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Selected from

Ar ₁ to Ar ₄ is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms)

The organometallic complex compound represented by Formula 1 is preferably an organometallic complex compound selected from the group consisting of substituents represented by the following 7 to 9.

[Formula 7]

[Formula 8]

[Formula 9]

(In the formulas 7 to 9,

N ₁ is an integer of 1 to 3, n ₂ , and n ₃ are each independently an integer of 1 to 5,

A and b are each independently an integer of 0 or 1,

A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aliphatic ring compound, a heteroaliphatic ring compound, an aromatic ring compound, and a heteroaromatic ring compound,

M is a metal forming an octahedral complex,

L is a monovalent anionic bidentate ligand coordinated to M through sp ² carbon and a heteroatom, or a monovalent anionic bidentate ligand coordinated to M through heteroatom and heteroatom,

C ₁ to C ₃ is -C (R ₁₇ ) _h- , h is an integer of 0 or 1,

Y ₁ is an anionic monodentate ligand coordinated to M via sp ² carbon or heteroatom,

X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2,

X ₁₅ to X ₃₀ are each independently selected from the group consisting of CR ₁₈ , and N,

The R ₁ to R ₅ , R ₁₇ , R ₁₈ , R '', R '''' are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, substituted Or an unsubstituted arylamine group, a substituted or unsubstituted biarylphenyl group, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C ( O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ and ,

R ₁ to R ₅ are each present as an independent substituent, or are fused to each other to form a ring bonded to X ₁ to X ₁₄ ,

R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

R ₁₅ , R ', and R''' are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted group Ring is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms)

L is preferably selected from the group consisting of ligands represented by the following Chemical Formulas 10 to 16.

[Formula 10] [Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

(In the above formula 10 to 16,

R ₁ to R ₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted biarylphenyl group , R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C (O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ ,

R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom 1 to 30 Heteroalkyl group, a substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

N ₁ is an integer of 1 to 3, n ₂ , n ₄ , and n ₅ are an integer of 1 to 4, n ₃ is an integer of 1 to 2)

The M is preferably selected from the group consisting of Group 9 elements, and Group 10 elements of the periodic table forming the octahedral complex, more preferably an element selected from the group consisting of Ir, Pt, Rh, and Pd, Even more preferred is Ir.

According to another embodiment of the present invention, an organic thin film layer is disposed between a pair of electrodes, and the organic thin film layer provides an organic photoelectric device including the polymer. The organic photoelectric device is preferably an organic light emitting device.

The organic photoelectric device includes a first electrode formed on a substrate, an organic thin film layer formed on the first electrode and including an organic metal complex compound for an organic photoelectric device, and a second electrode formed on the organic thin film layer.

The first electrode may preferably use a transparent conductive metal oxide such as indium-tin-oxide (ITO) or indium-zinc-oxide (IZO).

The substrate may preferably be a glass substrate or a flexible substrate.

Wherein the organic thin film layer is formed on the first electrode layer and the first buffer layer for injecting and transporting holes, the light emitting layer formed on the first buffer layer, formed on the light emitting layer, at least one of the second buffer layer for injecting, transporting electrons It may further comprise a layer. Layers constituting the organic thin film layer may include an organometallic complex compound according to an embodiment of the present invention.

The first buffer layer may include a layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, and a combination thereof, and the second buffer layer may be an electron injection layer, an electron transport layer, an electron blocking layer, And it may comprise a layer selected from the group consisting of a combination thereof.

The organometallic complex compound is excellent in solubility, and when the organic thin film layer is prepared using the organometallic complex, the organometallic complex compound may be easily prepared by wet processes such as spin coating, inkjet, and casting.

1 is an exploded perspective view of an organic photoelectric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic photoelectric device 1 may include a first electrode 20 made of a transparent conductive metal oxide, an organic thin film layer 100 including a light emitting region, and a second electrode 30. The structure is formed on the substrate 10.

The substrate 10 may be formed of a glass substrate or a flexible substrate having flexibility.

The first electrode 20 is formed on the substrate 10. The first electrode 20 may be formed of a transparent conductive metal oxide, and may use ITO or IZO as the transparent conductive metal oxide.

The organic thin film layer 100 is formed on the first electrode 20. The organic thin film layer 100 includes a light emitting layer 120, a first buffer layer 110, and a second buffer layer 130. At least one layer of the constituent layers of the organic thin film layer 100 includes an organometallic complex compound according to an embodiment of the present invention.

The first and second buffer layers 110 and 130 may include a hole injection layer, a hole transport layer, an electron transport layer, or an electron injection layer, and further include an electron blocking layer or a hole blocking layer due to light emission characteristics of the light emitting layer 120. can do.

The second electrode 30 is formed on the second buffer layer 130. The second electrode 30 may be formed of lithium (Li), magnesium (Mg), calcium (Ca), aluminum (Al), Al: Li, Ba: Li, or Ca: Li having a small work function. Can be used.

When an electric field is applied to the organic photoelectric device 1, holes and electrons are injected from the first electrode 20 and the second electrode 30, respectively, and the injected holes and electrons are light-emitting layers 120 of the organic thin film layer 100. ) And recombination to form luminescent excitons. The light emitter emits light as it transitions to ground states.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

( Organometallic complexes  Preparation of compounds)

( Example  One)

An organometallic complex compound represented by Chemical Formula 14 was prepared using the reaction of Scheme 1 below.

Scheme 1

1 g (0.9 mmol) of [Ir (ppy) ₂ Cl] ₂ , 1.64 g (2.33 mmol) of the ligand a and 1.3 g of potassium carbonate were dissolved in anhydrous glycerol, and heated and stirred at 200 ^° C. for 24 hours under a nitrogen atmosphere. Reacted.

After the completion of the reaction, the reaction was poured into distilled water, the solid was filtered and dissolved in chloroform to obtain an organometallic complex compound represented by the formula (14) using silica gel column chromatography.

(Example 2)

An organometallic complex compound represented by Chemical Formula 15 was prepared using the reaction of Scheme 2 below.

Scheme 2

An organometallic complex compound represented by Chemical Formula 15 was prepared in the same manner as in Example 1 except that ligand b was used.

( Example  3)

An organometallic complex compound represented by Chemical Formula 16 was prepared using the reaction of Scheme 3 below.

Scheme 3

An organometallic complex compound represented by Chemical Formula 16 was prepared in the same manner as in Example 1 except that ligand c was used.

( Fabrication of Organic Photoelectric Device)

A first electrode was formed on a glass substrate having a size of 15 Ω / cm ² , 1200 Å by Corning Corporation using ITO and having a size of 20 mm × 20 mm × 0.7 mm.

The substrate on which the first electrode was formed was ultrasonically cleaned for 5 minutes in isopropyl alcohol and pure water, followed by UV ozone cleaning for 30 minutes.

PEDOT (poly (ethylenedioxy) thiophene) was spin coated on the first electrode. An emission layer was formed on the PEDOT.

As the host material of the light emitting layer, a mixture of polyvinylcarbazole (PVK) and CBP (4,4'-N, N'-dicarbazolebiphenyl) in a 1: 1 ratio was used, and each of the organic compounds prepared in Examples 1 to 3 was used. The metal complex compound was used 7% as a dopant. The light emitting layer was spin coated to a thickness of 500 kPa.

BAlq (bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum) was vacuum deposited on the light emitting layer to form a hole blocking layer having a thickness of 50 Å. Subsequently, Alq ₃ (tris (8-hydroxy-quinolate) aluminum) was vacuum deposited on the hole blocking layer to form an electron transport layer having a thickness of 200 Å.

An organic photoelectric device was manufactured by sequentially vacuum depositing LiF to a thickness of 10 kW as an electron injection layer on the electron transport layer and to a thickness of 1000 kW of Al as a second electrode.

(Performance Measurement of Organic Photoelectric Device)

In order to understand the characteristics of the fabricated organic photoelectric device, the initial driving voltage (turn-on voltage), the maximum luminance (cd / m ² ), the driving voltage (V) at a luminance of 1000 cd / m ² , the current efficiency (cd / A), and power efficiency (lm / W) was measured, these results are shown in Table 1 below.

In addition, the PL intensity (photoluminescence intensity) of the organometallic complex compounds prepared in Examples 1 to 3 was measured, and the results are also shown in Table 1 below.

TABLE 1

compound PL intensity (nm) Initial drive voltage (V) Characteristics at luminance 1000 cd / m ² Maximum luminance (cd / m ² ) Drive voltage (V) Current efficiency (cd / V) Power Efficiency (lm / W) Color coordinates (x, y) Example 1 505 4.2 8.4 25.94 9.7 0.30, 0.60 10,690 Example 2 510 4.4 8.8 18.75 6.7 0.29, 0.59 11,810 Example 3 510 4.6 10.2 6.94 2.14 0.29, 0.57 10,500

Referring to Table 1, although the organometallic complex compound used in the organic thin film layer is an organic photoelectric device manufactured by a spin coating method, which is a wet process rather than a vacuum deposition method, in Example 1 it is about 26cd at 1000cd / m ² High efficiency of / A, all materials have a maximum brightness of 10,000 cd / m ² or more.

In addition, the initial drive voltage was measured to be 4.2 to 4.6 V, and the drive voltage at 1000 cd / m ² was measured to be 8.4 to 10.2 V.

Accordingly, the organometallic complex compound according to one embodiment of the present invention is different from Ir (ppy) ₃ or Ir (mppy) ₃ , which is known to have an excellent effect among green phosphorescent organic metal complex compounds, such as toluene, chloroform, or chlorobenzene. The organic solvent also exhibits excellent solubility characteristics due to the reduction of the intermolecular van der Waals force, it can be seen that the organic photoelectric device can be easily produced by the wet process using the organometallic complex compound.

As such, by introducing a bulky substituent into the organometallic complex compound according to the embodiment of the present invention, the intermolecular distance is increased, thereby decreasing crystallinity and increasing solubility. That is, the intermolecular interaction can be suppressed to improve luminous efficiency and electrical characteristics.

Therefore, the organometallic complex compound according to one embodiment of the present invention can be usefully used as a phosphorescent material of an organic photoelectric device.

1 is an exploded perspective view of an organic photoelectric device according to an embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

1: organic photoelectric device 10: substrate

20: first electrode 30: second electrode

100 organic thin film layer 110 first buffer layer

120 emitting layer 130 second buffer layer

Claims (12)

An organometallic complex compound for an organic photoelectric device represented by the following formula (1). [Formula 1]

(In Formula 1, N is an integer of 1 to 3, A and b are each independently an integer of 0 or 1, A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aliphatic ring compound, a heteroaliphatic ring compound, an aromatic ring compound, and a heteroaromatic ring compound, M is a metal forming an octahedral complex, L is a monovalent anionic bidentate ligand coordinated to M through sp ² carbon and a heteroatom, or a monovalent anionic bidentate ligand coordinated to M through heteroatom and heteroatom, C ₁ to C ₃ is -C (R ₁₇ ) _h- , h is an integer of 0 or 1, Y ₁ is an anionic monodentate ligand coordinated to M via sp ² carbon or heteroatom, X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2, R ₁ to R ₅ , and R ₁₇ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted Biarylphenyl group, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si ( R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C (O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ , and R ₁ to R ₅ are each present as an independent substituent, or are fused to each other to form a ring bonded to X ₁ to X ₁₄ , At least one of the R ₁ to R ₅ is selected from the group consisting of a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, and a substituted or unsubstituted biarylphenyl group. Become, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, R ₁₅ is a group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Is selected from, The substituted Iran hydrogen atom is a substituent selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, an amino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. Substituted) The method of claim 1, The R ₁ to R ₅ are each independently selected from the group consisting of substituents represented by the formula 2 to 5 organometallic complex compound for an organic photoelectric device. [Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Chemical Formulas 2 to 6 X ₂₁ to X ₂₈ , X ₃₁ to X ₃₈ , and X ₅₁ to X ₆₆ are each independently selected from the group consisting of CR ₁₈ , and N, R ₁₈ and R ″ are each independently a hydrogen atom, a halogen atom, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C ( O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ , R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, R 'is a group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Selected from Ar ₁ to Ar ₄ is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, The substituted Iran hydrogen atom is a substituent selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, an amino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. Substituted) The method of claim 1, The substituent represented by Formula 1 is selected from the group consisting of substituents represented by the following 7 to 9 organometallic complex compound for an organic photoelectric device. [Formula 7]

[Formula 8]

[Formula 9]

(In the formulas 7 to 9, N ₁ is an integer of 1 to 3, n ₂ , and n ₃ are each independently an integer of 1 to 5, A and b are each independently an integer of 0 or 1, A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently selected from the group consisting of an aliphatic ring compound, a heteroaliphatic ring compound, an aromatic ring compound, and a heteroaromatic ring compound, M is a metal forming an octahedral complex, L is a monovalent anionic bidentate ligand coordinated to M through sp ² carbon and a heteroatom, or a monovalent anionic bidentate ligand coordinated to M through heteroatom and heteroatom, C ₁ to C ₃ is -C (R ₁₇ ) _h- , h is an integer of 0 or 1, Y ₁ is an anionic monodentate ligand coordinated to M via sp ² carbon or heteroatom, X ₁ to X ₁₄ are each independently C (R ₁ ) _i (R ₂ ) _j , N (R ₃ ) _k , Si (R ₄ ) _o (R ₅ ) _p , O, or S, wherein i, j, k, o, and p are each independently an integer of 0 or 1, i + j, and o + p are each independently an integer of 1 or 2, X ₁₅ to X ₃₀ are each independently selected from the group consisting of CR ₁₈ , and N, The R ₁ to R ₅ , R ₁₇ , R ₁₈ , R '', R '''' are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, substituted Or an unsubstituted arylamine group, a substituted or unsubstituted biarylphenyl group, R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C ( O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ and , R ₁ to R ₅ are each present as an independent substituent, or are fused to each other to form a ring bonded to X ₁ to X ₁₄ , R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, R ₁₅ , R ', and R''' are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted group It is selected from the group consisting of an alkylene group having 1 to 20 ring carbon atoms, The substituted Iran hydrogen atom is a substituent selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, an amino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. Substituted) The method of claim 1, A cyclic compound consisting of C ₁ and X ₁ to X ₅ ; Cyclic compounds consisting of C ₂ , Y ₁ and X ₆ to X ₉ ; And C ₃ and X ₁₀ to X ₁₄ are each independently a cyclic compound selected from the group consisting of an aromatic ring compound and a heteroaromatic ring compound. The method of claim 1, The L is an organometallic complex compound for an organic photoelectric device that is selected from the group consisting of ligand represented by the following formula (10 to 16). [Formula 10] [Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

(In the above formula 10 to 16, R ₁ to R ₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted biarylphenyl group , R ₁₆ , OR ₁₆ , N (R ₁₆ ) ₂ , P (R ₁₆ ) ₂ , P (OR ₁₆ ) ₂ , POR ₁₆ , PO ₂ R ₁₆ , PO ₃ R ₁₆ , SR ₁₆ , Si (R ₁₆ ) ₃ , Si (CH ₃ ) ₂ R ₁₆ , Si (Ph) ₂ R ₁₆ , B (R ₁₆ ) ₂ , B (OR ₁₆ ) ₂ , C (O) R ₁₆ , C (O) OR ₁₆ , C (O) N (R ₁₆ ) ₂ , CN, NO ₂ , SO ₂ , SOR ₁₆ , SO ₂ R ₁₆ , and SO ₃ R ₁₆ , R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group 1 to 30 30 heteroalkyl group, substituted or unsubstituted aryl group having 3 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, N ₁ is an integer of 1 to 3, n ₂ , n ₄ , and n ₅ are an integer of 1 to 4, n ₃ is an integer of 1 to 2, The substituted Iran hydrogen atom is a substituent selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, an amino group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. Substituted) The method of claim 1, M is an organometallic complex compound for an organic photoelectric device which is an element selected from the group consisting of Group 9 elements of the Periodic Table, and Group 10 elements. The method of claim 1, M is an organometallic complex compound for an organic photoelectric device that is an element selected from the group consisting of Ir, Pt, Rh, and Pd. The method of claim 1, M is an organometallic complex compound for an organic photoelectric device that is Ir. An organic thin film layer positioned between the pair of electrodes, The organic thin film layer includes an organic metal complex compound according to any one of claims 1 to 8. The method of claim 9, The organic thin film layer is an organic photoelectric device comprising a light emitting layer. The method of claim 9, The organic thin film layer further comprises a layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, and a combination thereof. The method of claim 9, The organic thin film layer is an organic photoelectric device further comprises a layer selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and combinations thereof.

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