Compound and organic light emitting device including the same
阅读说明：本技术 化合物以及包含该化合物的有机发光器件 (Compound and organic light emitting device including the same ) 是由 郑光柱 金星秀 刘贤英 河宗陈 李锡宗 李春永 于 2019-05-30 设计创作，主要内容包括：本发明提供化合物以及包含该化合物的有机发光器件,其具有电化学稳定性以及热稳定性,因而寿命特性优秀,并在低驱动电压下,也具有高发光效率。(The present invention provides a compound and an organic light emitting device including the same, which have electrochemical stability and thermal stability, and thus have excellent life characteristics, and also have high luminous efficiency at a low driving voltage.)
1. A compound comprising at least one selected from the following chemical formulas 1 to 9,
chemical formula 1:
chemical formula 2:
chemical formula 3:
chemical formula 4:
chemical formula 5:
chemical formula 6:
chemical formula 7:
chemical formula 8:
chemical formula 9:
2. a material for an organic light-emitting device comprising the compound according to claim 1.
3. The material for organic light-emitting devices according to claim 2,
the material is used as at least one selected from a hole transport material, an electron injection material, an electron transport material, and a host material of the light-emitting layer.
4. An organic light emitting device comprising the compound of claim 1.
5. The organic light emitting device of claim 4,
the organic light emitting device comprises a first electrode, a second electrode and at least one organic layer between the first electrode and the second electrode,
the organic layer comprises the compound.
6. The organic light emitting device of claim 5,
the organic layer includes at least one of a hole transport layer, a light emitting layer, and an electron transport layer.
7. The organic light emitting device of claim 5,
the organic layer includes an electron transport layer.
8. The organic light emitting device of claim 7,
the compound is used as an electron transport material.
9. An electronic device comprising the organic light-emitting device of any one of claims 4 to 8.
Technical Field
The present invention relates to a compound and an organic light emitting device including the same.
Background
An Organic Light-Emitting Diode (OLED), which is a self-Light Emitting device, has a wide viewing angle, excellent contrast, a fast response time, excellent luminance, driving voltage, and response speed characteristics, and can realize color diversification. A general organic light emitting diode may include an anode and a cathode and an organic layer interposed between the anode and the cathode. The organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light-emitting layer through the hole-transporting layer, and electrons injected from the cathode move to the light-emitting layer through the electron-transporting layer. Carriers such as the holes and electrons are recombined in the light emitting layer region, thereby generating excitons (exiton) that generate light when they become a ground state. Generally, when an organic light emitting diode is driven, 25% of singlet state and 75% of triplet state are generated in terms of probability of excitons generated, and in the case of a fluorescent light emitting material, only light emitted from 25% of excitons of the singlet state is generated, so that the internal quantum efficiency is maintained at a level of 25% at the maximum. In order to improve such characteristics, iridium or platinum complexes that can utilize triplet energy are used and are known to have excellent quantum efficiency characteristics. However, these materials are expensive and have limited applications due to the instability of the blue light emitting material.
Disclosure of Invention
Technical problem
In view of the above, the present invention provides a compound and an organic light emitting device including the same, which have electrochemical stability and thermal stability and thus excellent life characteristics, and also have high light emitting efficiency at a low driving voltage.
Technical scheme
The present invention provides a compound comprising at least one selected from the following
Chemical formula 1:
chemical formula 2:
chemical formula 3:
chemical formula 4:
chemical formula 5:
chemical formula 6:
chemical formula 7:
chemical formula 8:
chemical formula 9:
in addition, the present invention provides a material for an organic light emitting device comprising the compound.
In addition, the present invention provides an organic light emitting device comprising the compound.
In addition, the present invention provides an electronic device including the organic light emitting device.
Effects of the invention
The compound of the present invention may be used as a hole injecting or hole transporting material, a host material, or an electron injecting or electron transporting material of an organic light emitting device. In addition, the compound is very suitable as a material for an organic light emitting device due to its excellent electron transport property, hole (hole) or exciton (exiton) blocking property, and electron injection property.
In addition, the organic light emitting device including the compound has excellent electrochemical stability and thermal stability, and thus has excellent life characteristics, and also has high luminous efficiency at a low driving voltage.
Drawings
Fig. 1 schematically shows a stacked structure of an organic light emitting device according to an embodiment of the present invention.
FIG. 2a is a UV-Vis spectrum of
FIG. 3a is a UV-Vis spectrum of
Fig. 4a is a UV-Vis spectrum of
FIG. 5a is a UV-Vis spectrum of
FIG. 6a is a UV-Vis spectrum of Compound 6 of the present invention, FIG. 6b is the Photoluminescence (PL) spectrum result, and FIG. 6c is the Low Temperature Photoluminescence (LTPL) spectrum result.
FIG. 7a is a UV-Vis spectrum of inventive compound 7, FIG. 7b is the Photoluminescence (PL) spectrum result, and FIG. 7c is the Low Temperature Photoluminescence (LTPL) spectrum result.
FIG. 8a is a UV-Vis spectrum of inventive Compound 8, FIG. 8b is the Photoluminescence (PL) spectrum result, and FIG. 8c is the Low Temperature Photoluminescence (LTPL) spectrum result.
FIG. 9a is a UV-Vis spectrum of inventive compound 9, FIG. 9b is Photoluminescence (PL) spectrum results, and FIG. 9c is Low Temperature Photoluminescence (LTPL) spectrum results.
FIG. 10a is a drawing of
FIG. 11a is a drawing of
FIG. 12a is a drawing of
FIG. 13a is a drawing of
FIG. 14a is a drawing of Compound 6 of the present invention1H NMR chart, FIG. 14b is13C NMR chart.
FIG. 15a is a drawing of Compound 7 of the present invention1H NMR chart, FIG. 15b is13C NMR chart.
FIG. 16a is a drawing of Compound 8 of the present invention1H NMR chart, FIG. 16b is13C NMR chart.
FIG. 17a is a drawing of Compound 9 of the present invention1H NMR chart, FIG. 17b is13C NMR chart.
FIG. 18 is a HRMS (High Resolution Mass Spectrometry) chart of
FIG. 19 is a HRMS (High Resolution Mass Spectrometry) chart of
FIG. 20 is a HRMS (High Resolution Mass Spectrometry) chart of
FIG. 21 is a HRMS (High Resolution Mass Spectrometry) chart of
FIG. 22 is a HRMS (High Resolution Mass Spectrometry) chart of Compound 6 of the present invention.
FIG. 23 is a HRMS (High Resolution Mass Spectrometry) chart of Compound 7 of the present invention.
FIG. 24 is a HRMS (High Resolution Mass Spectrometry) chart of Compound 8 of the present invention.
FIG. 25 is a HRMS (High Resolution Mass Spectrometry) chart of Compound 9 of the present invention.
Detailed Description
The present specification will be described in detail below.
Compound (I)
The present invention provides at least one compound selected from the following
Chemical formula 1:
chemical formula 2:
chemical formula 3:
chemical formula 4:
chemical formula 5:
chemical formula 6:
chemical formula 7:
chemical formula 8:
chemical formula 9:
the compound of the present invention is a bipolar compound in which three characteristic substituents, that is, a carbazolyl group, a naphthyl group, and a polycyclic aromatic hydrocarbon group, are bonded to a heterocycle, and can appropriately adjust the HOMO level or the LUMO level, and can adjust the balance of holes and electrons in one molecule, thereby adjusting efficiency and lifetime characteristics. Specifically, the compound of the present invention has excellent device lifetime characteristics due to the inclusion of a carbazolyl group, and stability of radical cations formed from carbazole under an electric field is achieved due to the inclusion of a naphthyl group, thereby having an effect of improving lifetime, and a rigid (rigid) and bulky (bulk) substituent is introduced due to the inclusion of a polycyclic aromatic hydrocarbon group, facilitating molecular stacking, thereby making excellent driving voltage improvement effect and material thermal stability improvement effect.
In addition, since the material containing the compound of the present invention is excellent in hole blocking ability and exciton (exiton) blocking ability, it is excellent in power consumption characteristics.
Substituents of the compounds may be bonded by methods known in the art, and the kind, position or number of substituents may be changed according to techniques known in the art.
The conjugation length of the compound is closely related to the band gap. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. Therefore, various substituents are introduced to the compound of the present invention, whereby compounds having various energy band gaps can be synthesized. In the present invention, various substituents are introduced into the core structure of the above structure, whereby the HOMO and LUMO levels of the compound can also be adjusted.
Further, by introducing various substituents into the core structure of the above structure, a compound having the inherent characteristics of the introduced substituents can be synthesized. For example, by introducing a substituent mainly for a hole injecting substance, a hole transporting substance, a light emitting substance, and/or an electron transporting substance, which is used in the production of an organic light emitting device, into the core structure, a substance satisfying a plurality of conditions required for each organic layer can be synthesized.
In addition, by introducing various substituents into the structures of the
On the other hand, the compound has a high glass transition temperature (Tg), and thus is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.
The compounds of the present invention may be prepared by a multi-step chemical reaction. A portion of the intermediate compound from which the compounds of the present invention can be prepared is first prepared. Specifically, the preparation method of the compound of the present invention can be prepared as in the examples described later.
Material for organic light-emitting device
The material for an organic light-emitting device of the present invention contains the compound.
Specifically, the material may use at least one selected from a hole blocking material, an electron injecting material, an electron transporting material, and a host material of the light emitting layer.
The compound is very suitable as a material for an organic light emitting device due to its excellent electron transport function, hole or exciton blocking property, and electron injection property. Specifically, the material for an organic light emitting device including the compound is excellent in electron injection characteristics and electron mobility (mobility), and the balance of bipolar (bipolar) characteristics of the compound, that is, the proper balance of an n-type portion and a p-type portion is properly maintained, so that a HOMO level or a LUMO level can be properly adjusted, and thus, it is excellent in lifetime characteristics, hole blocking capability and exciton (exiton) blocking capability, and thus, it is excellent in power consumption characteristics.
Organic light emitting device
The organic light emitting device of the present invention comprises the compound. When the compound of the present invention is used in an organic light emitting device, the efficiency of the organic light emitting device is improved, and the organic light emitting device has a low driving voltage and excellent life characteristics.
In the present specification, when a part is referred to as "including" a certain constituent element, another constituent element is not excluded unless specifically stated to the contrary, but it means that another constituent element may be further included.
In the present specification, when a component is referred to as being "on" another component, it does not mean that the component is adjacent to the other component, but includes a case where the other component is present between the two components.
Specifically, the organic light emitting device may include a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, and the organic layer may include the compound. Specifically, the organic layer may include at least one of a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the organic layer includes an electron transport layer, and the electron transport layer may include the compound.
The organic light emitting device may be prepared by a method and a material for preparing a general organic light emitting device, in addition to the compound described above.
Specifically, the compound of the present invention can form an organic layer not only by a vacuum deposition method but also by a solution coating method when preparing an organic light emitting device. The solution coating method includes, but is not limited to, spin coating, dip coating, inkjet printing, screen printing, spray coating, roll coating, and the like, and for example, when the compound of the present invention is used as a material for a light-emitting layer, a hole-blocking layer, an electron-transporting layer, or an electron-injecting layer, an organic layer can be formed by the solution coating method.
For example, when an organic layer is formed using the compound of the present invention, an organic layer below the organic layer is formed by a solution coating method, and an organic layer containing the compound of the present invention can be formed by a vacuum deposition method. Specifically, when the compound of the present invention is used as a material for a hole transport layer, an electron transport layer, or an electron injection layer, a light-emitting layer is formed over a first electrode, or when the hole transport layer and/or the electron transport layer and the light-emitting layer are formed over the first electrode, an organic layer containing the compound of the present invention can be formed thereon by a solution coating method and a vacuum deposition method. In this case, even if the organic layer containing the compound of the present invention is prepared by a vacuum deposition method, it can be well matched with an organic layer formed by a solution coating method at the lower portion thereof.
A stacking sequence of a cross section, electrodes, and organic layers of an organic light emitting device of an embodiment of the present invention is shown in fig. 1. However, the scope of the present invention is not intended to be limited by the foregoing drawings, and the structure of an organic light emitting device known in the art may also be applied to the present invention.
In addition, referring to fig. 1, the organic light emitting device may be stacked in the order of a first electrode, a hole injection layer, a light emitting layer, and a second electrode on a substrate, but the stacking order is not limited thereto. Specifically, the light-emitting layer or the hole injection layer in the structure of fig. 1 can contain the compound of the present invention.
Specifically, the organic light emitting device may have a substrate/a first electrode/a light emitting layer/a second electrode; substrate/first electrode/hole injection layer/light emitting layer/second electrode; substrate/first electrode/hole transport layer/light emitting layer/second electrode; substrate/first electrode/luminescent layer/electron transport layer/second electrode; substrate/first electrode/hole injection layer/hole transport layer/light emitting layer/second electrode; substrate/first electrode/luminescent layer/electron transport layer/second electrode; substrate/first electrode/luminescent layer/electron injection layer/second electrode; substrate/first electrode/luminescent layer/hole blocking layer/second electrode; substrate/first electrode/luminescent layer/hole transport layer/electron injection layer/second electrode; substrate/first electrode/luminescent layer/hole barrier layer/electron transport layer/second electrode; substrate/first electrode/luminescent layer/hole barrier layer/electron transport layer/electron injection layer/second electrode; substrate/first electrode/hole injection layer/hole transport layer/luminescent layer/electron transport layer/electron injection layer/second electrode; substrate/first electrode/hole injection layer/hole transport layer/electrode barrier layer/luminescent layer/electron transport layer/electron injection layer/second electrode; a substrate/a first electrode/a hole injection layer/a hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a second electrode, etc., in which case at least one organic layer, such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or an electron injection layer, between the first electrode and the second electrode may include the compound of the present invention.
Specifically, the compound of the present invention can be used as a material for a light-emitting layer, a hole-blocking layer, an electron-transporting layer, or an electron-injecting layer in a device of the above structure. More specifically, the compound of the present invention can be used as a material for an electron transport layer in a device of the above structure.
In another embodiment, the organic light emitting device may include a charge generation layer including the compound of the present invention. For example, the organic light emitting device may include a light emitting layer including at least two light emitting units, and a charge generation layer may be provided between adjacent two light emitting units. As another example, the organic light emitting device includes at least one light emitting unit, and a charge generation layer may be provided between the light emitting unit and the first electrode or between the light emitting unit and the second electrode.
In this case, since the charge generation layer containing the compound of the present invention can function as an n-type charge generation layer, the charge generation layer containing the compound of the present invention can be provided in contact with a p-type organic layer.
The light emitting unit may be formed of only the light emitting layer, and may further include at least one organic layer, which is a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, or the like, as necessary.
For example, the organic light emitting device may have a substrate/a first electrode/a light emitting unit/a charge generation layer (n-type)/a charge generation layer (p-type)/a light emitting unit/a second electrode; substrate/first electrode/charge generation layer (n-type)/charge generation layer (p-type)/light emitting unit/second electrode; substrate/first electrode/light emitting unit/charge generation layer (n-type)/charge generation layer (p-type)/second electrode, etc. At this time, the number of the light emitting units may include at least 2 or 3 as necessary. The light emitting unit may include a light emitting layer, and may further include at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, as necessary.
In particular, the compound of the present invention may be used as a material for a light emitting layer, a hole blocking layer, an electron transport layer, or an electron injection layer in the organic light emitting device.
When the compound of the present invention is used as a material for a light emitting layer, the compound of the present invention may function as a light emitting host, and in this case, the light emitting layer may further include a dopant. For example, the compounds of the present invention may be used as n-type phosphorescent hosts.
In addition, dopants that can be used with the compounds shown in the present invention may be used as known in the art. For example, when the compound of the present invention is used as a phosphorescent host, the phosphorescent dopant used together may be a complex of a transition metal (complex). Specifically, the phosphorescent dopant may be a complex of iridium (Ir), platinum (Pt), osmium (Os), gold (Au), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), or thulium (Tm)More specifically, it may be selected from Ir (ppy)3、Ir(ppy)2(acac)、Ir(mppy)3、Ir(mpp)2(acac)、F2Irpic、(F2ppy)2Ir(tmd)、Ir(ppy)2tmd、Ir(pmi)3、Ir(pmb)3、FCNIr、FCNIrpic、FIr6、FIrN4、FIrpic、PtOEP、Ir(chpy)3、P0-01(C31H23IrN2O2S2)、Ir(ppz)3And Ir (dfppz)3But is not limited thereto.
The organic light emitting device may be prepared by materials and methods known in the art, except that the compound of the present invention is included in at least one organic layer. In addition, the compound of the present invention may form at least one layer of organic layers of the organic light emitting device alone. However, it may be mixed with other substances and form an organic layer as necessary.
In the organic light emitting device, although materials other than the compound of the present invention are shown below, these are for example only, not for limiting the scope of the present invention, and may be substituted by materials known in the art.
In particular, the first electrode may be an anode and the second electrode may be a cathode.
As the anode material, a material having a large work function can be used, and a transparent conductive oxide, a metal, a conductive polymer, or the like can be used. As specific examples of the anode material, there are metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO); such as ZnO Al or SnO2A combination of metal and oxide of Sb; such as poly (3-methylthiophene), poly [3, 4- (ethylene-1, 2-dioxy) thiophene]Conductive Polymers of (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
As the cathode material, a material having a small work function can be used, and a metal, a metal oxide, a conductive polymer, or the like can be used. Specific examples of the cathode material include magnesium, calcium, sodium, and magnesium,Metals of potassium, titanium, indium, yttrium, lithium, ytterbium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; such as LiF/Al, LiO2Multi-layer structure material of/Al, LiF/Mg: Ag/Ag, etc., but not limited thereto.
As the hole injecting Material, known hole injecting materials can be used, and for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429 or starburst-type amine derivatives described in the document Advanced Material, 6, p.677 (1994)) such as tris (4-carbazol-9-ylphenyl) amine (TCTA), 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA), 1,3, 5-tris [4- (3-methylphenylphenylamino) phenyl ] benzene (m-MTDAPB), soluble conductive polymer polyaniline/dodecylbenzene sulfonic acid (polyaniline/dedylbenzenesulfonic acid) or poly (3,4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (poly (3, 4-ethylenedioxythiophene)), polyaniline/camphorsulfonic acid (polyaniline/camphorsulfonic acid) or polyaniline/poly (4-styrene sulfonate), etc., but are not limited thereto.
As the hole transport material, a pyrazoline derivative, an aromatic amine derivative, a stilbene (stilbene) derivative, a triphenyldiamine derivative, or the like can be used, and a low molecular or high molecular material can also be used, but not limited thereto.
As the electron transport material, oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and the like can be used, and not only low molecular substances but also high molecular substances can be used, but not limited thereto.
As the electron injecting material, for example, LiF is representatively used in the art, but not limited thereto.
As the light emitting material, a red, green, or blue light emitting material can be used, and at least two light emitting materials can be used in combination as needed. As the light-emitting material, a fluorescent material may be used, but a phosphorescent material may also be used. As the light-emitting material, a material which emits light by combining holes and electrons injected from the anode and the cathode, respectively, may be used alone, but a material in which a host material and a dopant material participate in light emission together may be used.
The organic light emitting device may be a top emission type, a bottom emission type, or a double-sided emission type, depending on the material used.
The compound of the present invention can also function in organic electronic devices such as organic solar cells, organic photoconductors, organic transistors, and the like, on a principle similar to that applied to organic light emitting devices.
Electronic device
In addition, the electronic device of the present invention includes the organic light emitting device.
For example, the electronic device may be a display, and particularly, may be a display having at least one structure selected from among an RGB OLED, a white OLED, a soluble OLED, and a QLED, but is not limited thereto.
The RGB OLED, as an organic light emitting display device including a sub-pixel for emitting red (R) light, a sub-pixel for emitting green (G) light, and a sub-pixel for emitting blue (B) light in a light emitting layer, may include an electron injection layer, an electron transport layer, a light emitting layer, a hole injection layer, a hole transport layer, and the like. For example, the RGB OLED may include a form in which an electron injection layer, an electron transport layer, an emission layer, a hole transport layer, and a hole injection layer are stacked in this order. As another example, the rgb oled may include a state in which a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially stacked.
In addition, the white oled (woled) is a full color display device using a thin light source, a backlight of a liquid crystal display device, or a color filter as a white organic light emitting display device. For example, the white OLED is generally formed of a tandem (stack) structure, and the light emitting layer included in each stack may be composed of a plurality of layers having different colors from each other. In this case, an electron transport layer is applied to each light emitting layer unit, two electron transport layers may be applied in the case of two stacks, and three electron transport layers may be applied in the case of three stacks. In addition, the function of the common layer is particularly important according to the difference in Charge injection characteristics of CGLs (Charge generation layers) formed in respective stacks. In particular, the electron transport layer forms a junction with the n-CGL, thereby giving a large influence on the electron injection characteristics, and thus, the device characteristics.
In addition, the soluble OLED was developed as a representative next generation model of a large area OLED panel together with the WOLED, and the hybrid type is typical. In the mixed type soluble OLED, a soluble material is applied from an anode to a light emitting layer and prepared by a solution process, and a deposition material may be used from an electron transport layer to a cathode. In particular, the interface characteristics between the solution-processed light emitting material and the deposition-type electron transport material are one of important technical problems in device characteristics. Therefore, it is important to develop an electron transport material suitable for the solution process.
In addition, the QLED is a display device which realizes full color by forming a light emitting layer with quantum dots (quantum dots). Also, the common layer material other than the light emitting layer is composed of a concept (concept) similar to the OLED device, and the driving principle is also similar.
In addition, the electronic device may be a mobile phone, a Television (TV), or the like and have various sizes.
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