WO2006041263A1

WO2006041263A1 - Chromophore compounds and organic electroluminescenc display device comprising the same

Info

Publication number: WO2006041263A1
Application number: PCT/KR2005/003424
Authority: WO
Inventors: Jong-Wook Park
Original assignee: Doosan Corporation
Priority date: 2004-10-13
Filing date: 2005-10-13
Publication date: 2006-04-20
Also published as: KR100679724B1; KR20060032930A

Abstract

The present invention relates to chromophore compounds applicable to any one of a hole injection layer (HIL)1 a hole transport layer (HTL), an emitting layer (EML), an electron transport layer (ETL) and an electron injection layer (EIL) of an organic electroluminescence display device. The compound is a derivative of phenothiazine, phenoxazine, phenoxathin, acridine, phenazasiline, or 9-aza-10- germa-anthracene. The compound has a substituent selected from the group consisting of a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl. The substituent may include at least one substituent selected from the group consisting of an alkyl, an alkoxy, a cycloalkyl, an alkenyl, an alkynyl, an aryl, a heteroaryl, a halogen such as F, Cl, Br, or I, aliphatic amine, aromatic amine, and an aryloxy.

Description

TITLE OF THE INVENTION

CHROMOPHORE COMPOUNDS AND ORGANIC ELECTROLUMINESCENCE DISPLAY DEVICE COMPRISING THE SAME

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to chromophore compounds for an electroluminescence light-emitting device and an organic electroluminescence display device including the same, and more particularly, to chromophore compounds applicable to any one of a hole injection layer (HIL), a hole transport layer (HTL), an emitting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) of an organic electroluminescence display device, and a highly efficient organic electroluminescence display device including the same.

(b) Description of the Related Art These days, as development within the information and communication industry is accelerated, higher performance display devices are required. Such display devices may be classified into luminescence types and non-luminescence types. For the former devices, a Cathode Ray Tube (CRT), an Electroluminescence Display (ELD), a Light Emitting Diode (LED), a Plasma Display Panel (PDP), etc., are exemplified.

For the latter devices, a Liquid Crystal Display (LCD), etc., are exemplified. The luminescence type and non-luminescence type display devices have basic characteristics such as working voltage, consumption power, brightness, contrast, response time, lifetime, and color display, etc. However, liquid crystal display devices, which have largely been used up till now, have some problems in terms of response time, contrast, and viewing angle among the basic characteristics described above. Displays using a luminescence diode are expected as next generation display devices that can solve the problems of liquid crystal displays since they have a much shorter response time, do not require a backlight due to having self-luminescence properties, and they also have improved brightness, etc.

An electroluminescence diode has difficulties in application to a large area electroluminescence display device because an inorganic material with crystalline form is mainly used. Furthermore, in the case of an electroluminescence display device using an inorganic material, there are disadvantages that more than 200 V of driving voltage is required and that it is expensive. Active researches on electroluminescence display devices comprising an organic materials have been undertaken since the Eastman Kodak Company firstly disclosed a device made from a material having a π-conjugated molecular structure in 1987. In the case of organic materials, there are advantages that a synthetic pathway is relatively simpler and various forms of materials can be synthesized, and thus color tuning is more easier. On the contrary, organic materials have disadvantages in that crystallization by heat occurs due to low mechanical strength.

Organic materials used in an electroluminescence display device are classified into low molecular organic materials and polymeric materials. For low molecular organic materials diamine, diamine derivatives such as N,N'-bis-(4- methylphenyl)-N,N'-bis(phenyl)benzidine (TPD), etc., perylene tetracarboxylic acid derivatives, oxadiazole derivatives, 1 ,1 ,4,4-tetraphenyl-1 ,3-butadiene (TPB), etc., are exemplified.

Generally, in the case of an organic electroluminescence display device, an evaporation method is used for producing a thin film. When applying low molecular compounds, a more uniform thin film can be obtained than when applying polymeric materials, and thus brightness and luminescence efficiency of the device are more improved. SUMMARY OF THE INVENTION The object of the present invention is to provide low molecular chromophore compounds for an electroluminescence display device that can be applied to any one of a hole injection layer (HIL), a hole transport layer (HTL), an emiting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) of an electroluminescence display device. Another object of the present invention is to provide an electroluminescence display device having a low driving voltage, various color developments, and a short response time.

The present invention provides, to achieve the objects as described above, chromophore compounds for an electroluminescence display device represented by the following formula 1 :

(chemical formula 1)

wherein, X₁ and X₂ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

A₁ and A₂ are independently selected from the group consisting of hydrogen, an unsubstituted linear or branched alkyl, an unsubstituted cycloalkyl, an unsubstituted alkenyl, an unsubstituted alkynyl, an unsubstituted alkoxy, an unsubstituted aryl, and an unsubstituted heteroaryl; and n ranges from 1 to 1000, preferably 1 to 100, more preferably 1 to 50, and still more preferably 1 to 25.

The present invention also provides an electroluminescence display device in which the chromophore compounds are applied to any one of a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, and an electron injection layer. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an organic electroluminescence display device according to the present invention.

FIG. 2a shows a ¹H-NMR spectrum of a compound according to Example 1 of the present invention.

FIG. 2b shows GC-Mass spectrum of a compound according to Example 1 of the present invention. FIG. 3a shows a ¹H-NMR spectrum of a compound according to Example 2 of the present invention.

FIG. 3b shows GC-Mass spectrum of a compound according to Example 2 of the present invention.

FIG. 4a shows a ¹H-NMR spectrum of a compound according to Example 3 of the present invention.

FIG. 4b shows GC-Mass spectrum of a compound according to Example 3 of the present invention.

FIG. 5a shows a ¹H-NMR spectrum of a compound according to Example 4 of the present invention. FIG. 5b shows GC-Mass spectrum of a compound according to Example 4 of the present invention.

FIG. 6 shows a ¹H-NMR spectrum of a compound according to Example 5 of the present invention.

FIGs. 7 to 11 show UV-PL spectra of the compounds according to Examples 1 to 5, respectively.

FIG. 12 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/t-BPBP/Alq₃/LJF/AI) manufactured according to Example 6 of the present invention which includes a compound of Example 1 in a hole transport layer.

FIG. 13 is an EL spectrum of an electroluminescence diode (ITO/t- BPBP/Alq₃/LiF/AI) manufactured according to Example 6 of the present invention which includes a compound of Example 1 in a hole transport layer.

FIG. 14 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/t-BPTP/Alq₃/LiF/AI) manufactured according to Example 7 of the present invention which includes a compound of Example 2 in a hole transport layer. FIG. 15 is an EL spectrum of an electroluminescence diode (ITOYt-

BPTP/Alq₃/LiF/AI) manufactured according to Example 7 of the present invention which includes a compound of Example 2 in a hole transport layer.

FIG. 16 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/DP-t-BPBP/Alq₃/LiF/AI) manufactured according to Example 8 of the present invention which includes a compound of Example 3 in a hole transport layer.

FIG. 17 is an EL spectrum of an electroluminescence diode (ITO/DP-t-

BPBP/Alq₃/LiF/AI) manufactured according to Example 8 of the present invention which includes a compound of Example 3 in a hole transport layer.

FIG. 18 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/t-BPBP/NPB/Alq₃/LiF/AI) manufactured according to Example 9 of the present invention which includes a compound of Example 1 in a hole injection layer. FIG. 19 is an EL spectrum of an electroluminescence diode (ITO/t- BPBP/NPB/Alq₃/LiF/AI) manufactured according to Example 9 of the present invention which includes a compound of Example 1 in a hole injection layer. FIG. 20 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/t-BPTP/NPB/A!q₃/LiF/AI) manufactured according to Example 10 of the present invention which includes a compound of Example 2 in a hole injection layer. FIG. 21 is an EL spectrum of an electroluminescence diode (ITO/t- BPTP/NPB/Alq₃/UF/AI) manufactured according to Example 10 of the present invention which includes a compound of Example 2 in a hole injection layer. FIG. 22 is a current-voltage (I-V) characteristic of an electroluminescence diode (ITO/DP-t-BPBP/NPB/Alqs/LiF/AI) manufactured according to Example 11 of the present invention which includes a compound of Example 3 in a hole injection layer. FIG. 23 is an EL spectrum of an electroluminescence diode (ITO/DP-t-

BPBP/NPB/Alq₃/LiF/AI) manufactured according to Example 11 of the present invention which includes a compound of Example 3 in a hole injection layer.

Description of the reference numerals of the drawings

1 : substrate 2: anode 3: hole injection layer 4: hole transport layer

5: emitting layer 6: electron transport layer

7: electron injection layer 8: cathode

DETAILED DESCRIPTION OF THE INVENTION The chromophore compounds in accordance with the present invention can be applied to any one of a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, and an electron injection layer of an electroluminescence (EL) device. The compound may be an organic compound represented by the formula 1. In particular, the compounds have excellent hole injection and hole transporting properties and thus may be preferably used in a hole injection layer and a hole transport layer.

The compound is a derivative of phenothiazine (in formula 1 , either one of X₁ or X₂ is NH and the other one is S), phenoxazine (in formula 1 , either one of Xi or X₂ is NH and the other one is O), phenoxathin (in formula 1 , either one of X₁ or X₂ is O and the other one is S), acridine (in formula 1 , X₁ is NH and X₂ is CH₂), phenazasiline (in formula 1, X₁ is NH and X₂ is SiH₂), or 9-aza-10-germa-anthracene (in formula 1 , X₁ is NH and X₂ is GeH₂). The compound has a substituent selected from the group consisting of a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl. The substituent may include at least one substituent selected from the group consisting of an alkyl, an alkoxy, a cycloalkyl, an alkenyl, an alkynyl, an aryl, a heteroaryl, a halogen such as F, Cl, Br, or I, aliphatic amine, aromatic amine, and an aryloxy. In the present invention, the substituted or unsubstituted linear or branched alkyl or alkoxy may be preferably a C1 to C12 alkyl, or alkoxy, and more preferably a C1 to C7 lower alkyl or alkoxy. The cycloalkyl may be preferably a C3 to C12 cycloalkyl, and more preferably a C3 to C8 cycloalkyl. The alkenyl may be preferably a C2 to C8 alkenyl, and more preferably a C2 to C4 alkenyl. The alkynyl may be preferably a C2 to C8 alkynyl, and more preferably a C2 to C4 alkynyl. The aryl may be preferably a C4 to C20 aryl, and more preferably a C4 to C12 aryl. The heteroaryl may be preferably a C4 to C20 heteroaryl, and more preferably a C4 to C12 heteroaryl which includes 1 to 3 heteroatoms, such as N, S, P, or O, in an aromatic ring. The substituted alkyl, alkoxy, cycloalkyl, alkenyl, alkynyl, aryl, and heteroaryl means that at least one hydrogen thereof is substituted with an alkyl, a cycloalkyl, an alkoxy, an alkenyl, an alkynyl, an aryl, a heteroaryl, a halogen such as F, Cl, Br or I, aliphatic amine, aromatic amine, or an aryloxy. The alkylene may be preferably a C1 to C20 alkylene, and more preferably a C1 to C13 alkylene. In the above formula 1, X-i and X₂ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, and

X₁ and X₂ are preferably O, S, or N-R₃, and the R₃ is hydrogen, an unsubstituted linear or branched alkyl, an unsubstituted cycloalkyl, an unsubstituted alkenyl, an unsubstituted alkynyl, an unsubstituted alkoxy, an unsubstituted aryl, or an unsubstituted heteroaryl. The substituent includes an alkyl, an alkoxy, a cycloalkyl, an alkenyl, an alkynyl, an aryl, a heteroaryl, a halogen such as F, Cl, Br, or I, aliphatic amine, aromatic amine, or an aryloxy. More preferably, R₃ is hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, or an aryl or heteroaryl which is substituted with at least one substituent selected from the group consisting of an alkoxy, an aryl, and an alkyl.

The substituted alkyl or cycloalkyl may be preferably a substituted alkyl represented by the following formula 2: (chemical formula 2)

wherein, in the above formula, X₃ is selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅ and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alky!, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

R₈ is alkylene; an aryl; alkylene substituted with an alkyl, an alkoxy, or an aryl; an aryl substituted with an alkyl, alkoxy, or an aryl, and preferably methylene, or methylene substituted with an alkyl, an alkoxy, or an aryl; or a phenyl, naphthyl, or anthracenyl substituted with an alkyl, an alkoxy, or an aryl; and

R₉ and R₁₀ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

The substituted aryl is preferably represented by the following formula 3:

(chemical formula 3)

wherein, in the above formula, X₄ is independently selected from the group consisting Of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

R₁₁ and R₁₂ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and m is an integer ranging from 1 to 4, preferably 1 to 3, and more preferably 1 to 2. Substituents may be symmetrically or unsymmetrically bound to phenyl if it does not cause a steric hindrance, and namely, may be bound at ortho, meta, or para positions.

A₁ and A₂ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, aliphatic or aromatic amine, and aliphatic or aromatic amine substituted with an aryl, and preferably the phenothiazine, phenoxazine, aromatic amine, or a derivative thereof represented by the following formula 4:

wherein, in the above formula, X₅ and X₆ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

Ri₃ and R₁₄ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl.

Suitable examples of the compound represented by the above formula 1 are a dimer of the following formula 5, a trimer of the following formula 6, and a tetramer of the following formula 7:

(chemical formula 5)

wherein, in the above formula, X₇ and X₈ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R-i to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, preferably a substituted or unsubstituted alkyl and a substituted or unsubstituted aryl, and more preferably substituted or unsubstituted phenyl;

Ri₅ and R₁₈ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

Ri6 and R₁₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, and preferably substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl: (chemical formula 6)

wherein, in the above formula, X₉ to X₁₁ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, preferably a substituted or unsubstituted alkyl and a substituted or unsubstituted aryl, and more preferably substituted or unsubstituted phenyl; and R₁₉ and R₂₃ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl: (chemical formula 7)

wherein, in the above formula, X₁₂ to X₁₅ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, preferably a substituted or unsubstituted alkyl and a substituted or unsubstituted aryl, and more preferably substituted or unsubstituted phenyl; and

R₂₄ and R₃₁ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

The compound of the following formula 8 where the basic structured compounds are bound with each other through an alkyl group and the compound of the following formula 9 where the basic structured compounds are bound with each other through an aryl group are preferable:

(chemical formula 8)

wherein, in the above formula, X₁₆ to X₁₇ are independently selected from the group consisting of CRiR₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl, preferably a substituted or unsubstituted alkyl and a substituted or unsubstituted aryl, and more preferably substituted or unsubstituted phenyl;

R₈ is an alkylene; an alkylene which is substituted with an alkylene; an aryl; an alkyl, an alkoxy, or an aryl; an aryl which is substituted with an alkyl, an alkoxy, or an aryl, and preferably methylene, methylene which is substituted with an alkyl, an alkoxy, or an aryl; or a phenyl, naphthyl, or anthracenyl which is substituted with an alkyl, an alkoxy, or an aryl; and

R₃₂to R₃₅are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl:

(chemical formula 9)

wherein, in the above formula, Xi₈ to X₂o are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, and preferably O, S, or N-R₃, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and R₃eto R₄₁ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl.

The dimer of the above formula 7 is prepared by the following process: substituents are introduced at an N position of a first monomer of the phenothiazine or phenoxazine using an Ullman coupling reaction or a Pd(O) catalyst; a halogen is introduced at a position of the first monomer where a second phenothiazine or phenoxazine monomer is bound; and a leaving group is bound with the second monomer and then is reacted with the first monomer. Examples of the leaving group may include dioxaborolan. In the case where dioxaborolan is used, the above reaction is carried out using a Suzuki coupling reaction. When only one halogen is introduced at a position of the first monomer where a second phenothiazine or phenoxazine monomer is bound, the reaction can be carried out by a Yamamoto coupling reaction using a Ni (0) catalyst, thereby synthesizing a dimer. Alternatively, the dimer can be prepared by the following process: substituents are introduced at an N position of a first monomer of the phenothiazine or phenoxazine using an Ullman coupling or a Pd(O) catalyst; a halogen is introduced at a position of the first monomer where a second phenothiazine or phenoxazine monomer is bound; the halogenated first monomer is lithiated; and the first monomer is reacted with the second monomer using a reagent such as CuCI₂ or Fe(acac)₃. In the above description, a dimer synthesis process is described but a trimer, a tetramer, an oligomer over a tetramer, or a polymer may be prepared in accordance with the above method. The chromophore compounds according to the present invention are applied between an anode made from ITO (indium tin oxide) having a large work function, which injects holes, and a cathode made from metals having various work functions, such as aluminum, lithium fluoride/aluminum, copper, silver, calcium, gold, magnesium, etc., an alloy of magnesium and silver, and an alloy of aluminum and lithium, which injects electrons. The chromophore compounds are applicable to any one of a hole injection layer (HIL), a hole transport layer (HTL), an emitting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) of an electroluminescence display device

FIG. 1 shows the sectional structure of an electroluminescence display device, where an anode 2 is formed on a substrate 1 by coating an anode material.

The substrate 1 includes a material, such as a glass, a plastic, quartz, a ceramic, or silicon, which has transparency, a flat-surface, and water-repellency and is easy to handle, but is not limited thereto. The anode material may include transparent and high conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO₂), zinc oxide (ZnO), and so on.

A buffer layer exists to compensate the surface of the anode 2 and helps the injection and flow of holes. Materials used as the buffer are exemplified by high molecular materials such as doped polyaniline (PANI) and doped polyethylenedeoxythiopene (PEDOT), and low molecular materials such as alpha- CuPc. A thin film having a thickness from 20 nm to 150 nm was formed by spin coating PANI and PEDOT. Alternatively, a thin film having thickness from 20 nm to 100 nm might be formed by vacuum-deposition of alpha-CuPc.

A hole injection layer (HIL) 3 is formed on the anode or the buffer layer by coating a hole injection material using vacuum thermal deposition, or a spin coating method. Examples of the hole injection material are not particularly limited, but CuPc or a starburst-type amine such as TCTA₁ m-MTDATA, m-MTDAPB, and so on, can be used.

A hole transport layer (HTL) 4 may be formed on the hole injection layer 3 using vacuum thermal deposition or spin coating. The hole transport layer is formed using a material such as N,N'-bis(3-methylphenyl)-N_lN'-diphenyl-[1 ,1- biphenyl]-4,4'-diamine (TPD), N,N'-bis(naphthalene-1-yl)-N,N'-diphenyl- benzidine

(α-NPB), and so on..

An emitting layer (EML) 5 is formed on the hole transport layer 4 using vacuum thermal deposition or spin coating of a electroluminescence material. On the emitting, an electron transport layer (ETL) 6 is formed using vacuum deposition or spin coating. The electron transport layer may include a material such as AIq₃ or

Bu-PBD.

An electron injection layer (EIL) 7 may optionally be formed on the electron transport layer 6, but is not limited to specific materials. Examples of a material suitable for the electron injection layer (EIL) 7 may include LiF, NaCI, CsF, Li₂O,

BaO, and so on. Then, a cathode is formed on the electron injection layer (EIL) 7 by coating a cathode metal using vacuum thermal deposition to fabricate an organic

EL device. The cathode may include a metal such as lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca)₁ magnesium-indium (Mg-In)₁ magnesium-silver (Mg-Ag)₁ and so on. A front light-emitting device may be obtained by using a light-permeable cathode which contains ITO, IZO, and so on.

The chromophore compounds are applicable to any one of the hole injection layer 3, the hole transport layer 4, the emitting layer 5, the electron transport layer 6, and the electron injection layer 7 of an EL display device In particular, the compounds can preferably be applied to the hole injection layer 3 and the hole transport layer 4.

The chromophore compounds of the present invention can be used as a host or as a dopant in an emitting layer. When the compound is used as a host, it may be used with dopants such as organic compounds having conjugated double bonds. The dopants are organic compounds having conjugated double bonds and materials which have a smaller energy gap than the doped material, and thus a lower maximum wavelength value than the doped material, and good energy transfer and chromophore property. For the dopants, at least one compound selected from the group consisting of dicarbazoly! azobenzene (DCAB), fluorenyl diacetylene (FDA), perylene, carbazole, carbazole derivatives, coumarine compounds and 4-(dicyanomethylene)-2-methyl-6-(1,1 ,7,7-tetramethyljulodinyl~9- enyl)-4H-pyran (DCJT) may be used.

The dicarbazolyl azobenzene (DCAB) has the formula 10.

(chemical formula 10)

The fluorenyl diacetylene (FDA) has the formula 11 : (chemical formula 11)

wherein, in the above formula R₄₃ and R₄₄ are independently selected from the group consisting of hydrogen, an alkyl, an aryl, cycloalkyl, and acetyl. The perylene has the formula 12. (chemical formula 12)

The 4-(dicyanomethylene)-2-methyl-6-(1 ,1 ,7,7-tetramethyljulodinyl-9-enyl)- 4H-pyran has the formula 13. (chemical formula 13)

For the coumarines compounds, coumarine 6 (manufactured by EXCITON Corp.) having the formula 14 may be preferably used, (chemical formula 14)

The dopants may have more than one substituent to obtain desirable properties such as crystallization degree, thermal stability, solubility, etc.

Dicarbazolyl azobenzene (DCAB), fluorenyl diacetylene (FDA), perylene, carbazole and carbazole derivatives serve as blue dopants, coumarines compounds as green dopants, and 4-(dicyanomethylene)-2-methyl-6-(1 , 1 ,7,7- tetramethyljulodinyl-9-enyl)-4H-pyran serves as red dopant.

A combination of more than one dopant may be used.

When the chromophore compound is used as a dopant, the conventional chromophore materials may be used.

The amount of said dopants is preferably 0.1 to 30 % by weight, more preferably 5 to 30 % by weight, and most preferably 5 to 10 % by weight, based on the amount of low molecular chromophore compounds.

Examples Hereinafter, preferred embodiments of the present invention will be described. However, these are presented only for better understanding of the present invention, and the present invention is not limited thereto.

Example 1

Synthesis of 10.10'-bis-(4-tert-butyl-phenvO-10H, 1Q'H(3.3')biphenothiazinyl ft-BPBP)

(Reaction Scheme 1)

i) Synthesis of 10-(4-tert-butyl-phenyl)-10H-phenothiazine

3g (15mmol) of phenothiazine, 4.27g (45mmol) of sodium tert-butoxide, and

0.255g (0.45mmol) of tris(dibenzylideneacetone) dipalladium were added into a round flask of 250ml under a nitrogen condition, and thereafter, 1ml of tri-t- butylphosphine and 2.88ml (16.5mmol) of 1-bromo-t-butyl-benzene were put thereinto and then were refluxed for a reaction, while agitating them in a toluene solvent. When the reaction was complete by checking the reaction speed with a

TLC, 10ml of 1M HCI was added thereto, and thereafter, an extraction was performed by using water and chloroform. Then, second precipitations were obtained by using chloroform and methanol and thereafter, a short column was performed to gain pure 10-(4-tert-butyl-phenyl)-10H-phenothiazine. The yield of the resulting prduct was over 80%. ii) Synthesis of 3-bromo-10-(4-tert-butyl-phenvO-1QH-phenothiazine 3g (9mmol) of 10-(4-tert-butyl-phenyl)-10H-phenothiazine and 1.4g (δmmol) of N-bromo succin imide were added into a flask and agitated in a carbon tetrachloride solvent under a nitrogen atmosphere. The product was placed on a column with hexane to gain pure 3-bromo-10- (4-t-butyl-phenyl)-10H-phenothiazine. The yield of the resulting product was about 60%. iii) Synthesis of 10-(4-tert-butyl-phenyl)-3- (4,4,5,5-tetramethyl)- f 1 ,3.21dioxaborolan-2-yl)-10-phenothiazine

3g (7.3mmol) of the synthesized 3-bromo-10-(4-t-butyl-phenyl)-10H- phenothiazine was agitated under a nitrogen atmosphere in a round flask by adding tetrahydrofuran. Then, it was cooled down to -78⁰C, and 9.2ml (15mmol) of n- butyl-lithium was added thereto. The resulting product was agitated for 30 minutes, and 3ml (15mmol) of 2-lsopropoxy-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane was added thereto. After the reaction was checked by a TLC, an extraction was performed by water and diethyl ether. Then, column chromatography was performed in a condition of n-hexane:EA = 19:1 to obtain pure 10-(4-tert-butyl- phenyl)-3-(4,4,5,5- tetramethyl)-[1 ,3,2]dioxaborolan-2-yl)-10-phenothiazine. The yield of the resulting product was about 60%. iv) Synthesis of 10,10'-bis-(4-tert-butyl-phenyl)-10H.10'H (3,3')biphenothiazinyl rt-BPBP)

1g (2.5mmol) of the synthesized 3-bromo-10-(4-tert-butyl-phenyl)-10H- phenothiazine and 1.12g (2.5mmol) of 10-(4-tert-Butyl-phenyl)-3-(4,4,5,5- tetramethyl)-[1 ,3,2]dioxaborolan-2-yl)-10-phenothiazine were poured into a round flask, and 0.17g (0.83mmol) of palladium(ll)acetate and 0.1ml of tris(2- methylphenyl)phosphine were added thereto, and then agitated in a 1,2- dimethoxyethane solvent. Then, 1.7Og (12.5mmol) of K₂CO₃ was dissolved in a mixed solution of water and DME and added to the above resultant and then refluxed. When a reaction was complete by checking the reaction speed with a TLC, an extraction was performed by using water and diethyl ether, and then, second precipitations were gained by using acetone. The second precipitations were placed in a column in a condition of n-hexane : chloroform = 2:1 to obtain pure 10, 10'-bis-(4-tert-butyl-phenyl)-1 OH, 10¹H (3,3')biphenothiazinyl (t-BPB P). The yield of the resulting product was about 60%. Example 2 Synthesis of 10'-(4-tert-butyl-phenyl)-10'Hri0.3':7'10"1terphenothiazine (t-

BPTP)

(Reaction Scheme 2)

,t-BuOKt

i) Synthesis of 3,7-dibromo-10-(4-tert-butyl-phenyl)-1 OH-phenothiazine

3g (9mmol) of the synthesized 10-(4-tert-butyl-phenyl)-1 OH-phenothiazine and 3.5g (20mmol) of N-bromo succin imide were poured into a round flask and agitated in a carbon tetrachloride solvent under a nitrogen atmosphere. The resulting product was placed in a column in a condition of hexaneiCHCb = 1:1 to obtain pure 3-bromo-10-(4-t-butyl-phenyl)-1 OH-phenothiazine. The yield of the resulting product was about 60%. ii) Synthesis of 10'-(4-tert-butyl-phenvn-10'Hri0.3';7'10"lterphenothiazine (t- BPTP)

1g (2mmol) of the synthesized 3,7-dibromo-10-(4-tert-butyl-phenyl)-1 OH- phenothiazine, 1g (5mmol) of phenothiazine, and 0.255g (0.17mmol) of dipalladium were added into a round flask of 250ml under a nitrogen condition, and then, 0.2ml of tri-t-butylphosphine was added thereto while agitating them in a toluene solvent. Then, the resulting product was refluxed for a reaction.

When the reaction was complete by checking the reaction speed, 1M HCI of 10ml was added thereto. Then, an extraction was performed by using water and chloroform, second precipitations were gained by using chloroform and methanol, and thereafter, the resulting product was placed in a column to obtain pure 10'- (4- tert-butyl-phenyl)-10'H[10,3';7'10"]terphenothiazine (t-BPTP). The yield of the resulting product was more than 50%.

Example 3

Synthesis of 7.7'-Diphenothiazvl-10.10'-bis-(4-tert-butvl-phenvl)- 10H.10'Hr3.3'1biphenothiazinyl ( DP-t-BPBP) (Reaction Scheme 3)

i) Synthesis of 7.7'-dibromo-10,10'-bis- (4-tert-butyl-phenvD-

10H, 1 Q'Hr3.3'1biphenothiazinyl

1g (1.5mmol) of the synthesized 10,10'-bis-(4-tert-butyl-phenyl)- 10H,10'H(3,3')biphenothiazinyl (t-BPBP) and 0.6g (3.4mmol) of N-bromo succin imide were poured into a flask and agitated in a carbon tetrachloride solvent under a nitrogen atmosphere. The obtained product was placed in a column in a condition of hexane:CHCI₃ = 1:1 to gain pure 7,7'-dibromo-10,10'-bis-(4-tert-butyl-phenyl)-

10H, 10'H[3,3']biphenothiazinyl. The yield of the resulting product was about 60%. ii) Synthesis of 7,7'-diphenothiazyl-10,10'-bis- (4-tert-butyl-phenvD- 10H, 1Q'Hr3,3'1biphenothiazinyl (DP-t-BPBP)

1g (1.2mmol) of the synthesized 7,7'-dibromo-10,10'-bis-(4-tert-butyl- phenyl)-10H,10'H[3,3']biphenothiazinyl, 0.6g (3mmol) of phenothiazine, 1.5g (16mmol) of sodium tert-butoxide, and 0.1g (0.07mmol) of tris(dibenzyliedeneacetone)dipalladium were poured into a round flask of 250ml under a nitrogen condition and agitated in a toluene solvent. Then, 1 ml of tri-t- butylphosphine was added thereto and refluxed for a reaction. When the reaction was complete by checking the reaction speed with a TLC, 10ml of 1M HCI was added thereto, and thereafter, an extraction was performed by using water and chloroform. Then, second precipitations were gained by using chloroform and methanol, and the resulting product was placed in a column in a condition of n- hexane:toluene = 2:1 to obtain pure 7,7'-diphenothiazyl-10,10'-bis-(4-tert-butyl- phenyO-IOH.IO'Hβ.a'pphenothiazinyl (DP-t-BPBP). The yield of the resulting product was more than 40%.

Example 4

Synthesis of 1 ,4-diphenothiazyl-benzene (DPB)

(Reaction Scheme 4)

1g (4.15mmol) of 1 ,4-dibromobenzene, 1.8g (9.1mmol) of phenothiazine, 2.65g (24.9mmol) of sodium tert-butoxide, and 0.228g (0.25mmol) of tris(dibenzylideneacetone) dipalladium were added into a round flask of 250ml under a nitrogen condition, and thereto, 1ml of tri-t-butylphosphine was added while agitating them in a toluene solvent and refluxed for a reaction. When the reaction was complete by checking the reaction speed with a TLC, 10ml of 1M HCI was added thereto, and an extraction was performed by using water and chloroform. Then, second precipitations were gained by using chloroform and methanol and thereafter, a short column was performed to obtain pure 1.4-diphenothiazyl-benzene (DPB). The yield of the resulting product was more than 95%.

Example 5

Synthesis of 2.9,10-diphenothiazyl-antracene (DPA)

(Reaction Scheme 5)

1g (3mmol) of 9,10-dibromoantracene, 1.31g (6.6mmol) of phenothiazine, 1.73g (18mmol) of sodium tert-butoxide, and 0.165g (0.18mmol) of tris(dibenzylideneacetone) dipalladium were added into a round flask of 250ml under a nitrogen condition, and 1 ml of tri-t-butylphosphine was added thereto, while agitating them in a toluene solvent and refluxed for a reaction. When the reaction was complete by checking the reaction speed with a TLC, 1M HCI of 10ml was added thereto and an extraction was performed by using water and chloroform. Then, second precipitations were gained by using chloroform and methanol, and thereafter, a short column was performed to obtain pure 1.4-diphenothiazyl-benzene

(DPB). The yield of the resulting product was more than 85%. Structure confirmation of a chromophore compound FIG. 2a illustrates a ¹H-NMR spectrum of 10,10'-bis- (4-tert-butyl-phenyl)- 10H,10'H(3,3')biphenothiazinyl(t-BPBP) prepared according to Example 1 , and FIG. 2b illustrates GC-Mass of the compound. FIG. 3a illustrates a ¹H-NMR spectrum of

10¹- (4-tert-butyl-phenyl)-10'H[10,3';7'10"]terphenothiazine(t-BPTP) prepared according to Example 2, and FIG. 3b illustrates GC-Mass of the compound. FIG. 4a illustrates a ¹H-NMR spectrum of 7,7'-diphenothiszyl-10,10'-bis- (4-tert-butyl- phenyl)-10H,10'H[3,3']biphenothiszyl (DP-t-BPBP) prepared according to Example 3, and FIG. 4b illustrates GC-Mass of the compound. FIG. 5a illustrates a ¹H-NMR spectrum of 1 ,4-diphenothiszylbenzene (DPB) prepared according to Example 4, and FIG. 5b illustrates GC-Mass of the compound. FIG. 6 illustrates a ¹H-NMR spectrum of 9,10-diphenothiszylanthracene(DPA) prepared according to Example 5.

Electroluminescence characteristics of chromophore compounds FIG. 7 illustrates the UV and PL spectrum of a compound prepared according to Example 1. As shown in FIG. 7, the UV-vis spectrum shows an absorption band at 338nm. The band is regarded by a TT→TΓ^* transition of a conjugated double bond. Referring to the PL spectrum, when the excitation wavelength was 338nm, a luminescent color had a maximum blue wavelength of 460nm. This corresponded to quantum energy of 2.79eV, and HOMO and LUMO values were decided by measuring CV. The HOMO value of 5.06 and LUMO value of 2.27 are appropriate to be used for a HTL or HIL.

FIG. 8 illustrates UV and PL spectra of a compound prepared according to Example 2. Referring to FIG. 8, the UV-vis spectrum was 329nm, which was slightly shifted to blue compared to that of t-BPBP shown in FIG. 7. The PL spectrum had a blue wavelength of 457nm, which came to quantum energy of

3.1 OeV.

The HOMO / LUMO values measuredby CV were 4.84/1.74 respectively. FIG. 9 illustrates the UV and PL spectra of a compound prepared according to Example 3. The UV-vis spectrum had 347nm, which was slightly shifted to red compared to that of t-BPBP shown in FIG. 7. The PL spectrum had a blue wavelength of 461 nm, which came to quantum energy of 2.94eV. HOMO/LUMO values by measuring CV of t-BPTP, DP-t-BPBP were 5.01/2.07, which were also appropriate to be used in HTL or HIL.

FIG. 10 illustrates the UV and PL spectra of a compound prepared according to Example 4. As shown in FIG. 10, the UV-vis spectrum showed an absorption band at 314nm. The band is regarded by a π→π^* transition of a conjugated double bond. Referring to the PL spectrum, when the excitation wavelength was 314nm, a luminescent color had a maximum blue wavelength of

445nm.

FIG. 11 illustrates UV and PL spectra of a compound prepared according to Example 5. The UV-vis spectrum was 444nm, which was shifted to red compared to that of DPB. The reason is that anthracene has a smaller band gap than benzene. The PL spectrum appeared at a red wavelength of 615nm.

Fabrication of an electroluminescence display device Examples 6 to 8

An ITO layer was formed as an anode on a glass substrate, and thereon, compounds prepared according to Examples 1 to 3 were vacuum-deposited to be 50nm thick, respectively forming a hole transport layer (HTL). Then, AIq₃ was also vacuum-deposited to form a 50nm-thick emitting layer, and thereon, 1 nm-thick LiF and a 200 nm-thick aluminum metal were vacuum-deposited to fabricate a diode.

The vacuum deposition was performed at a speed of 1 A /second under a 1 X 10^~6 torr vacuum condition to form a 9 mrf area. The thickness and growing speed of the layer during the depositions were regulated using a layer thickness monitor. Examples 9 to 11

An ITO layer was formed as an anode on a glass substrate, and then, compounds prepared according to Examples 1 to 3 were respectively vacuum- deposited to form a hole injection layer (HIL) with a thickness of 60nm. Then, NPD (N,N'-bis(naphthalene-1-yl)-N,N'-diphenylbenzidine) was vacuum-deposited to form a 15nm-thick hole transport layer, AIq₃ was also vacuum-deposited to form a 70nm- thick emitting layer, and thereafter, 1 nm-thick LiF and a 200 nm-thick aluminum metal were vacuum-deposited to fabricate a electroluminescent diode. The vacuum deposition was performed under a 1X10^"6 torr vacuum condition at a speed of 1 A /second to form a 9 mπf area. The thickness and growing speed of a layer during the deposition was regulated by a layer thickness monitor. Comparative Example 1

A electroluminescent diode was fabricated using the same method as in Examples 9 to 11 except that MTDATA (4,4',4"-tris{N-(methylphenyl)-N- phenylaminojtriphenylamine) was used as a hole transport layer.

Characteristic measurement of an electroluminescence display device

The electroluminescent diodes of Examples 6 to 11 were applied with an electric field to estimate I-V and EL characteristics. FIG. 12 shows I - V characteristics of a electroluminescent diode (ITO/t-BPBP/Alq₃/LiF/AI) of Example 6, which includes the compound of Example 1 as a hole transport layer. FIG. 13 shows EL characteristics of the diode. FIG. 14 shows I - V characteristics of a electroluminescent diode (ITO/t-BPTP/Alq₃/LiF/AI) of Example 7, which includes the compound of Example 2 as a hole transport layer. FIG. 15 shows EL characteristics of the diode. FIG. 16 shows I - V characteristics of a electroluminescent diode (ITO/DP-t-BPBP/Alq₃/LiF/AI) of Example 8, which includes the compound of Example 3 as a hole transport layer. FIG. 17 shows EL characteristics of the diode. I-V characteristics of the electroluminescent diodes were measured using Keithley SMU238. Here, a forward bias voltage of a direct current voltage was used. FIGs. 12, 14, and FIG. 16 have a curved line showing typical diode I - V characteristics and a turn-on voltage of 4-5 V.

FIGs. 13, 15, and 17 show EL spectra Of AIq₃ ranging from 507 to 520nm, accomplishing a regular device.

Brightness, color coordinates, electric power efficiency, and luminescence efficiency characteristics of a diode fabricated according to Example 6 were measured using a brightness meter, PR650. Table 1 shows the results. Table 1

Brightness, color coordinates, power efficiency, and luminescence efficiency characteristics of a diode fabricated according to Example 7 were measured using a brightness meter, PR650. Table 2 shows the results.

Table 2

Brightness, color coordinates, power efficiency, and luminescence efficiency characteristics of a diode fabricated according to Example 8 were measured using a brightness meter, PR650. Table 3 shows the results.

Table 3

FIG. 18 shows I - V characteristics of a electroluminescent diode (ITO/DP- t-BPBP/Alq₃/LiF/AI) of Example 9, which includes the compound of Example 1 as a hole transport layer. FIG. 19 shows EL characteristics of the diode. FIG. 20 shows I -V characteristics of a electroluminescent diode (ITO/DP-t-

BPBP/Alq₃/LiF/AI) of Example 9, which has the compound of Example 2 as a hole transport layer. FIG. 21 shows EL characteristics of the diode. FIG. 22 shows I - V characteristics of a electroluminescent diode (ITO/DP-t-BPBP/Alq₃/LiF/AI) of Example 9, which has the compound of Example 3 as a hole transport layer. FIG. 23 shows EL characteristics of the diode. FIGs. 18, 20, and 22 have a curved line showing typical diode I - V characteristics and a turn-on voltage of 4-5 V. FIGs. 19, 21, and 23 show AIq₃ EL spectrum results ranging 504 to 523nm, accomplishing a regular device.

Brightness, color coordinates, power efficiency, and luminescence efficiency characteristics of the electroluminescent diode according to Example 9 were measured using a brightness meter, PR650. The results are shown in the following Table 4.

Table 4

Brightness, color coordinates, power efficiency, and luminescence efficiency characteristics of the electroluminescent diode according to Example 10 were measured using a brightness meter, PR650. The results are shown in the following Table 5.

Table 5

Brightness, color coordinates, electric power efficiency, and luminescence efficiency characteristics of the electroluminescent diode according to Example 11 were measured using a brightness meter, PR650. The results are shown in the following Table 6.

Table 6

Brightness, color coordinates, power efficiency, and luminescence efficiency characteristics of the electroluminescent diode according to Comparative Example 1 using MTDATA in a hole transport layer were measured using a brightness meter, PR650. The results are shown in the following Table 7.

Table 7

As shown in Tables 4 to 6, the electroluminescent diodes according to Examples 8 and 10 using t-BPBP and DP-t-BPBP in a hole transport layer, respectively showed excellent electroluminescent efficiency of more than 4 cd/A.

Particularly, the resultant efficiency (Im/W) considering a voltage was a maximum 1.82 Im/W in the case of t-BPBP indicating high electric power efficiency. On the contrary, Comparative Example 1 showed electric power efficiency of a maximum 1.54 Im/W. Therefore, the diodes according to the Examples including the compounds of the present invention showed 120 % higher efficiency values than that of the Comparative Example indicating that the diodes according to the Examples have improved performance characteristics.

The organic compound for an electroluminescence display device can be applied to one or all of a hole transport layer, a hole injection layer, an emitting layer, an electron injection layer, and an electron transport layer. The organic compound of the present invention has good hole transport properties and hole injection properties and thus is applicable to a hole transport layer and a hole injection layer. In the case that the chromophore compounds are applied, an electroluminescence display device emitting blue color can be driven at low voltage. Furthermore, suitable host or doping materials which are organic compounds with conjugated double bonds may be used along with the chromophore compounds to form a good energy transfer device which makes various color realization at low energy possible, and improves the brightness and luminescence efficiency.

The simple modifications and changes of the present invention may be made by those skilled in the art, without departing from the scope of the invention.

Claims

WHAT IS CLAIMED IS:

1. A chromophore compound for an electroluminescence display device comprising a chromophore compound represented by the following formula 1 :

(chemical formula 1)

wherein X₁ and X₂ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R-i to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

A₁ and A₂ are independently selected from the group consisting of hydrogen, an unsubstituted linear or branched alkyl, an unsubstituted cycloalkyl, an unsubstituted alkenyl, an unsubstituted alkynyl, an unsubstituted alkoxy, an unsubstituted aryl, and an unsubstituted heteroaryl; and n ranges from 1 to 1000.

2. The chromophore compound for an electroluminescence display device of claim 1, wherein the substituted alkyl is represented by the following formula 2:

(chemical formula 2)

wherein, in the above formula, X₃ is selected from the group consisting of CR₁R₂, O₁ S, N-R₃, SiR₄R₅ and GeR₆R₇, where R-i to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

R₈ is alkylene; an aryl; alkylene substituted with an alkyl, an alkoxy, or an aryl; or an aryl substituted with an alkyl, alkoxy, or an aryl; and

3. The chromophore compound for an electroluminescence display device of claim 1, wherein the substituted aryl is represented by the following formula 3:

(chemical formula 3)

R₁₁ and R₁₂ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and m is an integer ranging from 1 to 4.

4. The chromophore compound for an electroluminescence display device of claim 1 , wherein A₁ or A₂ is represented by the following formula 4: (chemical formula 4)

wherein, in the above formula, Xs and X₆ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

R₁₃ and R₁₄ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl.

5. The chromophore compound for an electroluminescence display device of claim 1 , which is represented by the following formula 5: (chemical formula 5)

wherein, in the above formula, X₇ and X₈ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

R₁₅ and Ri₈ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

R₁₆ and R₁₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

6. The chromophore compound for an electroluminescence display device of claim 1 , which is represented by the following formula 6: (chemical formula 6)

wherein, in the above formula, X₉ to Xi₁ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

R₁₉ and R₂₃ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

7. The chromophore compound for an electroluminescence display device of claim 1 , which is represented by the following formula 7: (chemical formula 7)

wherein, in the above formula, Xi₂ to X₁₅ are independently selected from the group consisting Of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R-i to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

R₂₄ and R₃i are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

8. The chromophore compound for an electroluminescence display device of claim 1, which is represented by the following formula 8: (chemical formula 8)

wherein, in the above formula, X₁₆ to X₁₇ are independently selected from the group consisting Of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;

R₈ is an alkylene; an alkylene which is substituted with an alkylene, an aryl, an alkyl, an alkoxy, or an aryl; or an aryl which is substituted with an alkyl, an alkoxy, or an aryl; and

R₃₂ to R₃₅ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl.

9. The chromophore compound for an electroluminescence display device of claim 1 , which is represented by the following formula 9: (chemical formula 9)

wherein, in the above formula, X₁₈ to X₂₀ are independently selected from the group consisting of CR₁R₂, O, S, N-R₃, SiR₄R₅, and GeR₆R₇, where R₁ to R₇ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl; and

R₃₆ to R₄₁ are independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl.

10. An organic electroluminescence display device which comprises the chromophore compound according to one claim of claims 1 to 9 in at least one selected from the group of a hole transport layer, a hole injection layer, an emitting layer, an electron injection layer, and an electron transport layer.

11. The organic electroluminescence display device of claim 10, wherein the emitting layer comprises the chromophore compound of any one of claims 1 to 9, and a dopant which is an organic compound having conjugated double bonds and materials which have a smaller energy gap than the doped material, and thus a lower maximum wavelength value than the doped material, and good energy transfer and chromophore property.

12. The organic electroluminescence display device of claim 10, wherein the emitting layer comprises a dopant comprising the chromophore compound according to any one of claims 1 to 9.