Patent Application
20230165139
The present invention relates to a compound for an organic electric element, an organic electric element using same, and an electronic device thereof.
The flat panel display device plays a very important role in supporting the advanced image information society based on the Internet, which is showing rapid growth in recent years. In particular, an organic electroluminescent device (organic EL device) capable of low-voltage driving as a self-emission type has superior viewing angles and contrast ratios compared to liquid crystal displays (LCDs), which are the mainstream of flat panel display devices, and does not require a backlight, so it can be lightweight and thin, and has advantages in terms of power consumption. In addition, it is attracting attention as a next-generation display device because of its fast response speed and wide color reproduction range. In general, an organic EL device is formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode (cathode). In this case, the organic thin film comprises a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL) or an electron injection layer (EIL) in addition to an emitting layer (EML) and further include an electron blocking layer (EBL) or a hole blocking layer (HBL), and an emitting auxiliary layer due to the light emitting characteristics of the emitting layer. When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode, and the injected holes and electrons pass through the hole transport layer and the electron transport layer, respectively, and recombine in the emitting layer to form light emitting excitons. The formed luminescent excitons emit light while transitioning to ground states, at this time, in order to increase the efficiency and stability of the light emitting state, a light emitting dye (guest) is also doped into the emitting layer (host). In order to utilize such an organic electronic device in various display media, the lifespan of the element is more important than anything else, and various studies are being conducted to increase the lifespan of the organic electric element. In particular, for excellent lifespan characteristics of organic electric devices, various studies are being conducted on organic materials inserted into a buffer layer such as a hole transport layer or an emitting auxiliary layer, and to this end, a material for a hole injection layer and a hole transport layer with high uniformity and low crystallinity when forming a thin film after deposition while providing high hole transport properties from the anode to the organic layer is required.
It is necessary to develop a material for a hole injection layer and a hole transport layer not only having stable characteristics against Joule heating generated during device driving, that is, a high glass transition temperature, but also delaying the penetration and diffusion of metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifespan of organic electric devices. In addition, it is reported that the low glass transition temperature of the hole transport layer material greatly affects the device lifespan according to the characteristic that the uniformity of the thin film surface is collapsed during device driving. In addition, in the formation of OLED devices, the deposition method is the mainstream, and a material that can withstand this deposition method for a long time, that is, a material with strong heat resistance characteristics is required.
In particular, it is urgent to overcome the problems of power consumption and lifespan, as the main overcoming challenges of organic light emitting diodes are enlarged in panel sizes of mobile phones and tablet PCs.
However, as a hole transport layer material, it is difficult to overcome the driving voltage and lifetime at the same time. The reason is that, in order to lower the driving voltage, materials with excellent hole transport ability, ie, high hole mobility, have a planar structure rich in electrons in most cases. For example, naphthyl, fluorene and phenanthrene and the like.
However, when a compound with the above structure is introduced into a hole transport material as a substituent, the hole mobility increases up to a certain number and has a good effect on the lifespan, but if the number of introductions in the molecule is increased to reach the low voltage driving target required in the current industry, the driving voltage is lowered and low voltage driving is possible, but the lifespan characteristics are rapidly deteriorated.
The reason for this is that, in the case of molecules in which electron-rich planar structures are excessively introduced, holes are trapped between the plate-like structures and stabilized when a constant current is continuously supplied during device lifespan evaluation, this lowers the hole mobility and eventually increases the driving voltage to apply a constant current, resulting in a sharp deterioration in device lifespan. It is expressed by the following formula.
(J=Space Charge limited current, ε=Permissibility, μ=Mobility Coefficient, θ=Charge Trap Coefficient (Free Carrier/Total Carrier), V=Voltage, d=Thickness)
As the number of free carriers decreases due to the trap phenomenon, the θ value decreases, therefore, in the current-driven organic light emitting device that requires a constant current, the driving voltage is increased, which can have a very fatal result on the lifespan. Therefore, as described above, the introduction of an electron-rich plate-like structure capable of increasing hole mobility over a certain amount adversely affects the lifespan, so the possibility of lowering the driving voltage by using it is not great.
Accordingly, the present inventors confirmed that the compound substituted with deuterium showed many thermodynamic behaviors compared to the unsubstituted compound, and that, among these thermodynamic properties, when the iridium compound is substituted with deuterium, the properties vary according to the difference in carbon, hydrogen, and carbon and deuterium bond lengths, and that the compound composed of deuterium can have higher luminous efficiency due to the weakening of the intermolecular van der Waals force generated by the shorter bond length compared to the compound not substituted with deuterium.
However, a method of lowering the driving voltage by substituting with deuterium, that is, increasing the hole transport Mobility of the hole transport material, has not been studied much at present, and the prior art that demonstrates the effect according to a specific deuterium substitution rate has not yet been reported. Moreover, the conventionally reported general deuterium substitution method has a disadvantage in that it is difficult to control the substitution rate.
For the purpose of solving the problems of the above-mentioned background art, in the present invention, deuterium is substituted in a specific ratio of 74% to 98% to an amine-based compound having long lifespan, thereby completing a device with a long lifespan, in order to realize a long-life device, which is a required characteristic of an organic electric device.
Accordingly, an object of the present invention is to provide a compound deuterated at a specific ratio, an organic electric element using same, and an electronic device thereof.
The present invention provides a 74% to 98% deuterated compound represented by Formula A.
In another aspect, the present invention provides a method for preparing the deuterated compound represented by Formula A.
In another aspect, the present invention provides an organic electric element and an electronic device comprising the compound represented by Formula A.
By using the compound according to the present invention, high luminous efficiency, low driving voltage and high heat resistance of the element can be achieved, and color purity and lifespan of the element can be greatly improved.
Hereinafter, some embodiments of the present invention will be described in detail. Further, in the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
In addition, terms, such as first, second, A, B, (a), (b) or the like may be used herein when describing components of the present invention. Each of these terminologies is not used to define an essence, order or sequence of a corresponding component but used merely to distinguish the corresponding component from other component(s). It should be noted that if a component is described as being “connected”, “coupled”, or “connected” to another component, the component may be directly connected or connected to the other component, but another component may be “connected coupled” or “connected” between each component.
As used in the specification and the accompanying claims, unless otherwise stated, the following is the meaning of the term as follows.
Unless otherwise stated, the term “halo” or “halogen”, as used herein, includes fluorine, bromine, chlorine, or iodine.
Unless otherwise stated, the term “alkyl” or “alkyl group”, as used herein, has a single bond of 1 to 60 carbon atoms, and means saturated aliphatic functional radicals including a linear alkyl group, a branched chain alkyl group, a cycloalkyl group (alicyclic), an cycloalkyl group substituted with a alkyl or an alkyl group substituted with a cycloalkyl.
Unless otherwise stated, the term “alkenyl” or “alkynyl”, as used herein, has double or triple bonds of 2 to 60 carbon atoms, but is not limited thereto, and includes a linear or a branched chain group.
Unless otherwise stated, the term “cycloalkyl”, as used herein, means alkyl forming a ring having 3 to 60 carbon atoms, but is not limited thereto.
Unless otherwise stated, the term “alkoxyl group”, “alkoxy group” or “alkyloxy group”, as used herein, means an oxygen radical attached to an alkyl group, but is not limited thereto, and has 1 to 60 carbon atoms.
Unless otherwise stated, the term “aryloxyl group” or “aryloxy group”, as used herein, means an oxygen radical attached to an aryl group, but is not limited thereto, and has 6 to 60 carbon atoms.
The terms “aryl group” and “arylene group” used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by an adjacent substituent joining or participating in a reaction.
For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.
The prefix “aryl” or “ar” means a radical substituted with an aryl group. For example, an arylalkyl may be an alkyl substituted with an aryl, and an arylalkenyl may be an alkenyl substituted with aryl, and a radical substituted with an aryl has a number of carbon atoms as defined herein.
Also, when prefixes are named subsequently, it means that substituents are listed in the order described first. For example, an arylalkoxy means an alkoxy substituted with an aryl, an alkoxylcarbonyl means a carbonyl substituted with an alkoxyl, and an arylcarbonylalkenyl also means an alkenyl substituted with an arylcarbonyl, wherein the arylcarbonyl may be a carbonyl substituted with an aryl.
Unless otherwise stated, the term “heterocyclic group”, as used herein, contains one or more heteroatoms, but is not limited thereto, has 2 to 60 carbon atoms, includes any one of a single ring or multiple ring, and may include heteroaliphadic ring and heteroaromatic ring. Also, the heterocyclic group may also be formed in conjunction with an adjacent group.
Unless otherwise stated, the term “heteroatom”, as used herein, represents at least one of N, O, S, P, or Si.
Also, the term “heterocyclic group” may include a ring including SO2 instead of carbon consisting of cycle. For example, “heterocyclic group” includes the following compound.
Unless otherwise stated, the term “fluorenyl group” or “fluorenylene group”, as used herein, means a monovalent or divalent functional group, in which R, R′ and R″ are all hydrogen in the following structures, and the term “substituted fluorenyl group” or “substituted fluorenylene group” means that at least one of the substituents R, R′, R″ is a substituent other than hydrogen, and include those in which R and R′ are bonded to each other to form a spiro compound together with the carbon to which they are bonded.
The term “spiro compound”, as used herein, has a ‘spiro union’, and a spiro union means a connection in which two rings share only one atom. At this time, atoms shared in the two rings are called ‘spiro atoms’, and these compounds are called ‘monospiro-’, ‘di-spiro-’ and ‘tri-spiro-’, respectively, depending on the number of spiro atoms in a compound.
Unless otherwise stated, the term “aliphatic”, as used herein, means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term “aliphatic ring”, as used herein, means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
Unless otherwise stated, the term “ring”, as used herein, means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a hetero ring having 2 to 60 carbon atoms, or a fused ring formed by the combination of them, and includes a saturated or unsaturated ring.
Other hetero compounds or hetero radicals other than the above-mentioned hetero compounds include, but are not limited thereto, one or more heteroatoms.
Also, unless expressly stated, as used herein, “substituted” in the term “substituted or unsubstituted” means substituted with one or more substituents selected from the group consisting of deuterium, halogen, an amino group, a nitrile group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C1-C20 alkylamine group, a C1-C20 alkylthiopen group, a C6-C20 arylthiopen group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C6-C20 aryl group substituted by deuterium, a C8-C20 arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C20 heterocyclic group, but is not limited to these substituents.
Also, unless there is an explicit explanation, the formula used in the present invention is the same as the definition of the substituent by the exponent definition of the following formula.
Here, when a is an integer of 0, the substituent R1 is absent, when a is an integer of 1, the sole substituent R1 is linked to any one of the carbon constituting the benzene ring, when a is an integer of 2 or 3, each is bonded as follows, where R1 may be the same or different from each other, when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of the hydrogen bonded to the carbon forming the benzene ring is omitted.
As used herein, the term “deuterated” refers to a compound or group in which deuterium is present at 100 times or more of its natural abundance level.
As used herein, the term “perdeuterated” refers to a compound or group in which all hydrogens have been replaced with deuterium. The term deuterated is synonymous with “100% deuterated”.
As used herein, the term “deutero-acid” refers to a compound capable of ionizing to donate deuterium ions to bronsted base. As used herein, deuterium-acids do not contain ionizable hydrogens.
Hereinafter, a compound according to an aspect of the present invention and an organic electric element including the same will be described.
The present invention is a method that can lower the driving voltage without introducing a plate-shaped molecular structure that adversely affects the lifespan by using a material with a good lifespan, and by using a method of substituting deuterium at an appropriate ratio, provides a method of lowering the driving voltage.
When substituted with deuterium, the zero point energy, that is, the energy of the ground state is lowered, and as the bond length of deuterium-carbon becomes shorter than that of hydrogen-carbon, the molecular hardcore volume decreases, accordingly, electrical polarizability can be reduced, and by weakening the intermolecular interaction, the thin film volume can be increased. This property can lower the crystallinity of the thin film, that is, create an amorphous state, and is generally very effective in implementing an amorphous state, which is essential to increase OLED lifespan and driving characteristics.
In addition, when a film is formed with a compound substituted with deuterium, the film is formed in an amorphous glass state that can greatly affect the hole mobility of the thin film, and this amorphous glass state can reduce the grain boundary through isotropic and homogeneous properties, thereby speeding up the flow of charges, that is, hole mobility.
The present invention provides a compound represented by Formula A deuterated to 74% to 98%.
In Formula A, Formula a and Formula b, each symbol may be defined as follows.
1) L1, L2 and L3 are each independently selected from the group consisting of a single bond; a C6-C60 arylene group; fluorenylene group; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; and a C2-C60 heterocyclic group;
Wherein in case L1, L2 and L3 are an arylene group, they may be preferably a C6-C30 arylene group, more preferably a C6-C24 arylene group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case L1, L2 and L3 are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, dibenzothiophen, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case L1, L2 and L3 are is a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
2) Ar1 and Ar2 are each independently selected from the group consisting of a C6-C60 aryl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; a C1-C60 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxyl group; a C6-C30 aryloxy group;
-L″-N(Ara)(Arb); a substituent represented by Formula a; and a substituent represented by Formula b;
Wherein in case Ar1 and Ar2 are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case Ar1 and Ar2 are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case Ar1 and Ar2 are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
Wherein in case Ar1 and Ar2 are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case Ar1 and Ar2 are an alkoxyl group, they may be preferably an C1˜C24 alkoxyl group.
Wherein in case Ar1 and Ar2 are an aryloxy group, they may be preferably an C6˜C24 aryloxy group.
3) Ar3 is selected from the group consisting of a C6-C60 aryl group; fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; a C1-C60 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxyl group; a C6-C30 aryloxy group; -L″-N(Ara)(Arb);
Wherein in case Ar3 is an aryl group, it may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case Ar3 is a heterocyclic group, it may be preferably a C2˜C30 heterocyclic group, more preferably a C2-C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case Ar3 is a fused ring groups, it may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
Wherein in case Ar3 is an alkyl group, it may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case Ar3 is an alkoxyl group, it may be preferably an C1˜C24 alkoxyl group.
Wherein in case Ar3 is an aryloxy group, it may be preferably an C6˜C24 aryloxy group.
4) R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; a C6-C60 aryl group; fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; a C1-C60 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxyl group; a C6-C30 aryloxy group; and -L″-N(Ara)(Arb); or in case a′, b′, c′, d′, a″, b″, c″ and d″ are 2 or more, a′, b′, c′, d′, a″, b″, c″ and d″ are each in plural being the same or different, an adjacent plurality of R1′s, or a plurality of R2′s, or a plurality of R3′s, or a plurality of R4′s, or a plurality of R1″s, or a plurality of R2″s, or a plurality of R3″s or s, a plurality of and R4″s may be bonded to each other to form a ring.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are an alkoxyl group, they may be preferably an C1-C24 alkoxyl group.
Wherein in case R1′, R2′, R3′, R4′, R1″, R2″, R3″ and R4″ are an aryloxy group, they may be preferably an C6-C24 aryloxy group.
5) a′ and b′ are each independently an integer from 0 to 5, c′, d′, a″, b″, c″ and d″ are each independently an integer from 0 to 4,
6) Any one of * is bonded to L2 or L3 of Formula A,
7) wherein L″ is each independently selected from the group consisting of a single bond; a C6-C60 arylene group; fluorenylene group; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; and a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; and wherein Ara and Arb are each independently selected from the group consisting of a C6-C60 aryl group; fluorenyl group; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; and a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; Wherein in case L″ is an arylene group, it may be preferably a C6-C30 arylene group, more preferably a C6-C24 arylene group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case L″ is a heterocyclic group, it may be preferably a C2˜C30 heterocyclic group, and more preferably a C2-C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, dibenzothiophene, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
In case L″ is fused ring groups, it may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
Wherein in case Ara and Arb are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case Ara and Arb are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2-C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case Ara and Arb are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
8) wherein the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1-C20 alkylthio group; C1-C20 alkoxyl group; C1-C20 alkyl group; C2-C20 alkenyl group; C2-C20 alkynyl group; C6-C20 aryl group; C6-C20 aryl group substituted with deuterium; a fluorenyl group; C2˜C20 heterocyclic group; C3-C20 cycloalkyl group; C7-C20 arylalkyl group; and C8-C20 arylalkenyl group; and -L″-N(Ara)(Arb); also the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C3-C60 aliphatic ring or a C6-C60 aromatic ring or a C2-C60 heterocyclic group or a fused ring formed by the combination thereof.
Also, the present invention includes compounds in which Ar3 is represented by Formula Ar-1 or Ar-2.
Wherein, each symbol may be defined as follows.
1) * means a position bonded to L1 of Formula A,
2) X1 is O, S, NRa or CRbRc,
with the proviso that when # is bonded to X1, X1 is N,
3) Y3 and Y4 are each independently single bond, O, S, NRd or CReRf, with the proviso that when # is bonded to Y3, Y3 is N,
4) Ra, Rb, Rc, Rd, Re and Rf are each independently selected from the group consisting of a C1-C50 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxyl group; a C6-C30 aryloxy group; a C6-C60 aryl group; fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; or Ra, Rb, Rc, Rd, Re and Rf are bonded to adjacent groups to form a ring.
Wherein in case Ra, Rb, Rc, Rd, Re and Rf are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case Ra, Rb, Rc, Rd, Re and Rf are an alkoxyl group, they may be preferably an C1˜C24 alkoxyl group.
Wherein in case Ra, Rb, Rc, Rd, Re and Rf are an aryloxy group, they may be preferably an C6-C24 aryloxy group.
Wherein in case Ra, Rb, Rc, Rd, Re and Rf are an aryl group, they may be preferably a C6˜C30 aryl group, more preferably a C6˜C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case Ra, Rb, Rc, Rd, Re and Rf are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2-C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
5) Ring A and ring B are each independently selected from the group consisting of a C6-C60 aryl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; and a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; or ring A and ring B may be substituted with R21.
Wherein in case ring A and ring B are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case ring A and ring B are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case ring A and ring B are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
6) R11, R12, R13, R14 and R21 are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; a C6-C60 aryl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; a C1-C50 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxy group; a C6-C30 aryloxy group; and -L″-N(Ara)(Arb); or R11, R12, R13, R14 and R21 are bonded to adjacent groups to form a ring.
Wherein in case R11, R12, R13, R14 and R21 are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case ring R11, R12, R13, R14 and R21 are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case R11, R12, R13, R14 and R21 are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
Wherein in case R11, R12, R13, R14 and R21 are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case R11, R12, R13, R14 and R21 are an alkoxy group, they may be preferably an C1˜C24 alkoxy group.
Wherein in case R11, R12, R13, R14 and R21 are an aryloxy group, they may be preferably an C6˜C24 aryloxy group.
7) wherein L″, Ara and Arb are the same as defined above,
8) q, r, s, and t are each independently an integer of 0 to 4, u and v are each independently 0 or 1, with the proviso that except when both u and v are 0, when u or v is 0, Y3 or Y4 is absent.
Also, Formula A is represented by Formula 1.
Wherein,
1) X is a single bond,
2) y is an integer of 0 or 1,
3) i) when y is 0, a and b are each independently an integer from 0 to 5,
4) c and d are each independently an integer from 0 to 4,
5) R1, R2, R3 and R4 are the same as the definition of R1′,
6) L1, L2, L3, Ar1 and Ar2 are the same as defined above, however, L1 is bonded to any one of * in Formula 1.
Also, Formula 1 is represented by any one of Formulas 2 to 4.
Wherein
1) R1, R2, R3, R4, c, d, L1, L2, L3, Ar1 and Ar2 are the same as defined above,
2) k and l are each independently an integer of 0 to 5, m and n are each independently 0 to 4, o and p are each independently 0 to 3.
Also, Formula 1 is represented by Formula 5 or Formula 6.
Wherein each symbols may be defined as follows.
1) R1, R2, R3, R4, a, b, c, d, L1, L2, L3, Ar2, X and y are the same as defined above,
2) R5, R6 and R7 are the same as the definition of R1,
3) e is an integer of 0 to 5, f is an integer of 0 to 3, g is an integer of 0 to 4,
4) Y1 is O, S, CR′R″ or NR′,
5) wherein R and R are each independently selected from the group consisting of a C6-C60 aryl group; a fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; and a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring; and -L″-N(Ara)(Arb); or R′ and R″ are bonded to each other to form a C6-C60 aromatic ring; a fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a C3-C60 aliphatic ring; or a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring;
Wherein in case R′ and R″ are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case ring R′ and R″ are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Wherein in case R′ and R″ are a fused ring groups, they may be preferably a fused ring group of a C3-C30 aliphatic ring and a C6-C30 aromatic ring, more preferably a fused ring group of a C3-C24 aliphatic ring and a C6-C24 aromatic ring.
6) wherein L″, Ara and Arb are the same as defined above.
Formula 1 is represented by any one of Formulas 7 to 15
1) L1, L2, L3, c, d, e, f, g, k, l, m, n, o, p and Y1 are the same as defined above,
2) R1, R2, R3, R4, R5, R6, R7, R6, R9 and R10 are the same as the definition of R1,
3) h is an integer of 0 to 5, i is an integer of 0 to 3, j is an integer of 0 to 4,
4) Y2 is O, S or CRxRy,
5) wherein Rx and Ry are each independently selected from the group consisting of a C1-C50 alkyl group; a C6-C60 aryl group; fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; or Rx and Ry are bonded to each other to form a C6-C60 aromatic ring; a fluorenyl group; a C2-C60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a C3-C60 aliphatic ring; or a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring;
Wherein in case Rx and Ry are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case Rx and Ry are an aryl group, they may be preferably a C6-C30 aryl group, more preferably a C6-C25 aryl group, for example, phenylene, biphenyl, naphthalene, terphenyl, etc.
Wherein in case Rx and Ry are a heterocyclic group, they may be preferably a C2˜C30 heterocyclic group, more preferably a C2˜C24 heterocyclic group, for example, pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazoline, dibenzofuran, benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, etc.
Also, Formula A is represented by any one of the following compounds P-1 to P-20 and P-83 to P-130.
Also, the present invention provides a method for preparing a deuterated compound represented by Formula A in which the compound represented by Formula A is synthesized by reacting a compound represented by Formula R1 or Formula R2 and a compound represented by Formula R3.
Wherein, each symbol may be defined as follows.
1) L1, L2, L3, Ar1, Ar2, R11, R12, R13, R14, ring A, ring B, q, r, s, t, u and v are the same as above,
2) R101 and R102 are each independently selected from the group consisting of a C1-C50 alkyl group; a C2-C20 alkenyl group; a C2-C20 alkynyl group; a C1-C30 alkoxyl group; and a C6-C30 aryloxy group; or R101 and R102 are bonded to adjacent groups to form a ring.
Wherein in case R101 and R102 are an alkyl group, they may be preferably a C1-C30 alkyl group, more preferably a C1-C24 alkyl group.
Wherein in case R101 and R102 are an alkoxyl group, they may be preferably an C1˜C24 alkoxyl group.
Wherein in case R101 and R102 are an aryloxy group, they may be preferably an C6˜C24 aryloxy group.
3) Z is halogen; or a triflate group;
4) w is 0 or 1.
Referring to
The organic material layer may sequentially include a hole injection layer (120), a hole transport layer (130), an emitting layer (140), an electron transport layer (150), and an electron injection layer (160) on the first electrode (110). In this case, the remaining layers except for the emitting layer (140) may not be formed. It may further include a hole blocking layer, an electron blocking layer, an emitting-auxiliary layer (220), a buffer layer (210), etc. and the electron transport layer (150) and the like may serve as a hole blocking layer. (See
The organic material layer may include 2 or more stacks including a hole transport layer, an emitting layer and an electron transport layer sequentially formed on the anode, further include a charge generation layer formed between the 2 or more stacks (see
Otherwise, even with the same core, the band gap, electrical characteristics, interface characteristics, etc. may vary depending on which position the substituent is bonded to, therefore the choice of core and the combination of sub-substituents bound thereto are also very important, and in particular, when the optimal combination of energy levels and T1 values and unique properties of materials (mobility, interfacial characteristics, etc.) of each organic material layer is achieved, a long lifespan and high efficiency can be achieved at the same time.
The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode, and after forming an organic material layer including the hole injection layer (120), the hole transport layer (130), the emitting layer (140), the electron transport layer (150) and the electron injection layer (160) thereon, it can be prepared by depositing a material that can be used as a cathode thereon.
Also, in the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, and the organic material layer provides an organic electric element comprising the compound as an electron transport material.
As another specific example, the compound of the same or different types of the compound represented by Formula A is mixed and used in the organic material layer. Also, the present invention provides an emitting auxiliary layer composition comprising the compound represented by Formula A, and provides an organic electric element including the emitting auxiliary layer.
Also, the present invention provides a hole transport layer composition comprising the compound represented by Formula A, and provides an organic electric element including the hole transport layer.
Also, the present invention provides an electronic device comprising a display device including the organic electric element; and a control unit for driving the display device; In another aspect, the organic electric element is at least one of an organic electroluminescent device, an organic solar cell, an organic photo conductor, an organic transistor, and a device for monochromatic or white lighting. At this time, the electronic device may be a current or future wired/wireless communication terminal, and covers all kinds of electronic devices including mobile communication terminals such as mobile phones, a personal digital assistant(PDA), an electronic dictionary, a point-to-multipoint(PMP), a remote controller, a navigation unit, a game player, various kinds of TVs, and various kinds of computers.
Hereinafter, a synthesis example of the compound represented by Formula A of the present invention and a manufacturing example of an organic electric element of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
The compound (final product 1-1) represented by Formula 1 according to the present invention is prepared by reacting Sub 1 with Sub 2 as shown in Scheme 1.
The deuterated compound of compound (final product 1-1) represented by Formula 1 according to the present invention is prepared by dissolving in perdeuterated benzene (benzene-D6), adding deuterium-triflic acid (CF3SO3D), and reacting at a temperature of 80° C. for 3 hours to 18 hours, and more preferably 3 hours.
Sub 1-1 (7.8 g, 22.2 mmol), Sub 2-1 (7.5 g, 22.2 mmol), Pd2(dba)3 (0.6 g, 0.7 mmol), t-BuONa (4.3 g, 44.5 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (130 mL), then P(t-Bu)3 (50 wt % Sol.) (0.54 mL, 1.3 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 10.8 g (yield: 75%) of P 1-1.
P 1-1 (10.8 g, 16.6 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (126.0 g, 1,495.9 mmol) and CF3SO3D (12.5 g, 83.1 mmol) was added thereto, followed by a temperature of 80° C. reacted for 3 hours to form a deuterated material. Periodically take a sample, measure the degree of deuterium by LC-MS, and after the deuterium exchange reaction is completed at a desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and concentrate the organic solvent. Recrystallization using toluene and acetone solvent gave 10.3 g (yield: 92%) of deuterated compound P-1. The final mass was determined by LC-MS to confirm to be 87.1% deuterated.
Sub 1-2 (9.0 g, 25.5 mmol), Sub 2-2 (8.9 g, 25.5 mmol), Pd2(dba)3 (0.7 g, 0.8 mmol), t-BuONa (4.9 g, 51.0 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (150 mL), then P(t-Bu)3 (50 wt % Sol.) (0.62 mL, 1.5 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 13.6 g (yield: 80%) of P 1-2.
P 1-2 (13.6 g, 20.4 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (154.7 g, 1,838.4 mmol) and CF3SO3D (15.3 g, 102.1 mmol) was added thereto, followed by reacting a temperature at 80° C. for 3 hours to form a deuterated material. Periodically take a sample, measure the degree of deuteration by LC-MS, and after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 13.3 g (yield: 94%) of deuterated compound P-2. The final mass was determined by LC-MS to confirm to be 87.1% deuterated.
Sub 1-2 (7.8 g, 22.1 mmol), Sub 2-1 (7.4 g, 22.1 mmol), Pd2(dba)3 (0.6 g, 0.7 mmol), t-BuONa (4.3 g, 44.2 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (130 mL), then P(t-Bu)3 (50 wt % Sol.) (0.54 mL, 1.3 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 11.4 g (yield: 79%) of P 1-3.
P 1-3 (11.4 g, 17.5 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (132.5 g, 1,574.1 mmol) and CF3SO3D (13.1 g, 87.5 mmol) was added thereto, followed by reacting a temperature at 80° C. for 3 hours to form a deuterated material. Periodically take a sample, measure the degree of deuteration by LC-MS, and after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 10.7 g (yield: 90%) of deuterated compound P-3. The final mass was determined by LC-MS to confirm to be 87.8% deuterated.
Sub 1-4 (9.6 g, 27.2 mmol), Sub 2-4 (10.1 g, 27.2 mmol), Pd2(dba)3 (0.8 g, 0.8 mmol), t-BuONa (5.2 g, 54.4 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (180 mL), then P(t-Bu)3 (50 wt % Sol.) (0.66 mL, 1.6 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH21C2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 15.1 g (yield: 81%) of P 1-4.
P 1-4 (15.1 g, 22.1 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (167 g, 1,988.7 mmol) and CF3SO3D (16.6 g, 110.5 mmol) was added thereto, followed by reacting a temperature at 80° C. for 3 hours to form a deuterated material. Periodically take a sample, measure the degree of deuteration by LC-MS, and after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 13.8 g (yield: 87%) of deuterated compound P-4. The final mass was determined by LC-MS to confirm to be 83.7% deuterated.
The compound represented by Formula A according to the present invention (final product 2) is prepared by a reaction according to Reaction Scheme 2.
The deuterated compound of the compound represented by Formula A (final product 2) according to the present invention is dissolved in perdeuterated benzene (benzene-D6), deuterium-triflic acid (CF3SO3D) is added, and prepared by reacting at the temperature of 80° C. for 3 hours to 18 hours, preferably 3 hours to 18 hours, and more preferably 3 hours.
Sub 1-84 (10.0 g, 23.7 mmol), Sub 2-84 (4.3 g, 23.7 mmol), Pd2(dba)3 (0.7 g, 0.7 mmol), t-BuONa (4.6 g, 47.4 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (119 mL), then P(t-Bu)3 (50 wt % Sol.) (0.6 mL, 1.4 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 10.0 g (yield: 78%) of P 1-84.
P 1-84 (10.0 g, 18.5 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (132 g, 1,568.7 mmol) and CF3SO3D (13.1 g, 87.2 mmol) was added thereto, followed by reacting a temperature at 80° C.
Samples were taken periodically for 3 hours and the degree of deuteration was measured by LC-MS, after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 9.7 g (yield: 93%) of deuterated compound P-72. The final mass was determined by LC-MS to confirm to be 80.6% deuterated.
Sub 1-106 (10.0 g, 20.8 mmol), Sub 2-106 (3.8 g, 20.8 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), t-BuONa (4.0 g, 41.5 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (104 ml, then P(t-Bu)3 (50 wt % Sol.) (0.5 mL, 1.3 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane CH2Cl2=4:1) to obtain 10.1 g (yield: 77%) of P 1-106.
P 1-106 (10.1 g, 16 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (120.7 g, 1,434.2 mmol) and CF3SO3D (12.0 g, 79.7 mmol) was added thereto, followed by reacting a temperature at 8000.
Samples were taken periodically for 3 hours and the degree of deuteration was measured by LC-MS, after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 9.8 g (yield: 94%) of deuterated compound P-106. The final mass was determined by LC-MS to confirm to be 74.3% deuterated.
Sub 1-119 (10.0 g, 19.0 mmol), Sub 2-119 (3.5 g, 19.0 mmol), Pd2(dba)3 (0.5 g, 0.6 mmol), t-BuONa (3.6 g, 38.0 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (95 mL), then P(t-Bu)3 (50 wt % Sol.) (0.5 mL, 1.1 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 10.1 g (yield: 78%) of P 1-119.
P 1-119 (10.1 g, 14.8 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (112.7 g, 1,339.0 mmol) and CF3SO3D (11.2 g, 74.4 mmol) was added thereto, followed by reacting a temperature at 80° C.
Samples were taken periodically for 3 hours and the degree of deuteration was measured by LC-MS, after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 9.8 g (yield: 93%) of deuterated compound P-119. The final mass was determined by LC-MS to confirm to be 84.2% deuterated.
Sub 1-124 (10.0 g, 30.7 mmol), Sub 2-119 (5.8 g, 30.7 mmol), Pd2(dba)3 (0.8 g, 0.9 mmol), t-BuONa (5.9 g, 1.8 mmol) were placed in a round-bottom flask and dissolved in anhydrous Toluene (154 mL), then P(t-Bu)3 (50 wt % Sol.) (2.1 mL, 1.8 mmol) was added and heated and stirred at 110° C. for about 4 hours. After confirming the completion of the reaction by TLC, cooled to room temperature and extracted with CH2Cl2 and water. The separated organic layer was dried over MgSO4, concentrated, and the resulting compound was recrystallized using silicagel column (Hexane:CH2Cl2=4:1) to obtain 15.7 g (yield: 72.4%) of P 1-124.
P 1-124 (15.7 g, 22.2 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (168.4 g, 2,001.6 mmol) and CF3SO3D (16.7 g, 111.2 mmol) was added thereto, followed by reacting a temperature at 80° C.
Samples were taken periodically for 3 hours and the degree of deuteration was measured by LC-MS, after the deuterium exchange reaction is completed at the desired substitution rate, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 15.2 g (yield: 93%) of deuterated compound P-124. The final mass was determined by LC-MS to confirm to be 82.8% deuterated.
[Synthesis of Comparative Compound A-1]
P 1-1 (10.0 g, 15.4 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (116.5 g, 1,385.1 mmol) and CF3SO3D (11.6 g, 77.0 mmol) was added thereto, followed by reacting at a temperature of 50° C. for 20 hours to form a deuterated material. After the reaction is completed, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 9.2 g (yield: 91%) of deuterated compound A-1. The final mass was determined by LC-MS to confirm to be 22.6% deuterated.
[Synthesis of Comparative Compound A-2]
P 1-84 (9.0 g, 15.7 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (118.8 g, 1,411.8 mmol) and CF3SO3D (11.8 g, 78.4 mmol) was added thereto, followed by reacting at a temperature of 50° C. for 20 hours to form a deuterated material. After the reaction is completed, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 8.5 g (yield: 94%) of deuterated compound A-2. The final mass was determined by LC-MS to confirm to be 22.6% deuterated.
[Synthesis of Comparative Compound A-3]
P 1-119 (10.0 g, 14.7 mmol) obtained in the above synthesis was dissolved in perdeuterated benzene (C6D6) (111.6 g, 1,325.7 mmol) and CF3SO3D (11.1 g, 73.7 mmol) was added thereto, followed by reacting at a temperature of 50° C. for 20 hours to form a deuterated material. After the reaction is completed, cool to room temperature, quench by adding Na2CO3 in D2O, and the organic solvent is concentrated. Recrystallization using toluene and acetone solvent gave 9.4 g (yield: 93%) of deuterated compound A-3. The final mass was determined by LC-MS to confirm to be 21.1% deuterated.
As can be seen from the results of Comparative Synthesis Examples 1 to 3, it can be seen that the conventionally known general deuterium substitution method has a long reaction time and is difficult to control the substitution rate with a significantly lower deuterium substitution rate compared to the manufacturing method of the present invention. In the manufacturing method described in the present invention, it is possible to reduce the reaction time by reacting at a high temperature compared to the existing reaction temperature for a certain time, preferably 3 hours, and to obtain a deuterated compound having an improved substitution rate.
Meanwhile, FD-MS (Field Desorption-Mass Spectrometry) values of the compounds of the present invention prepared according to the above synthesis examples are shown in Table 1.
Manufacturing Evaluation of Organic Electric Elements
After vacuum deposition of 2-TNATA to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, NPB was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Then, the compound P-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form an emitting auxiliary layer, and then 9,10-di(naphthalen-2-yl)anthracene as a host and BD-052X (manufactured by Idemitsu Kosan) as a dopant were used in a weight ratio of 96:4 on the emitting auxiliary layer to form an emitting layer with a thickness of 30 nm. Subsequently, (1,1′-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole blocking layer, and then on the hole blocking layer, bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq2) was vacuum-deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then AI was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.
An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 2 was used instead of the compound P-1 of the present invention as a emitting auxiliary layer material.
An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compounds 1 to 6 described in Table 2 were used instead of Compound P-1 of the present invention as an emitting auxiliary layer material
By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 20, Comparative Examples 1 to 6 of the present invention, Electroluminescence (EL) characteristics were measured with PR-650 from Photoresearch, and the T95 lifetime was measured using a lifetime measuring device manufactured by McScience at 500 cd/m2 standard luminance, and the measurement results are shown in Table 2.
As can be seen from the results in Table 2, it can be seen that when a blue organic light emitting device is manufactured by using the material for an organic electroluminescent device of the present invention as an emitting auxiliary layer material, the lifespan of the organic electroluminescent device can be significantly improved compared to Comparative Examples using Comparative Compounds 1 to 6. In detail, compared to Comparative Compound 1, Comparative Compound 3, and Comparative Compound 5 in which were not substituted with deuterium, Comparative compound 2, comparative compound 4, and comparative compound 6 in which were partially substituted with deuterium showed improved device results with improved driving voltage, efficiency, and lifespan, and Compared to Comparative Compound 2, Comparative Compound 4, and Comparative Compound 6, the compound of the present invention in which 74% or more of the total hydrogen was substituted with deuterium showed superior device results in terms of lifespan.
When deuterium is substituted, as the bond length of deuterium-carbon becomes shorter than that of hydrogen-carbon, the molecular hardcore volume is reduced, and thus electrical polarizability can be reduced. For this reason, the effect of lowering the crystallinity of the thin film, that is, an amorphous state can be made, and consequently, hole mobility can be increased.
It can be seen that, in particular, the compound of the present invention deuterated at a substitution rate of 74% to 98%, which is higher than the existing substitution rate, increases the BDE (Bond Dissociation Energy) compared to the comparative compound, thereby maximizing the bond stability of the structure, and as a result, the stability of the molecules in the device is improved, so that the results are remarkably excellent in terms of lifespan.
This suggests that even though they have a similar structure, the physical properties, and properties of the compound, and results of the device may be significantly different depending on the substitution rate of deuterium.
In the case of the emitting auxiliary layer, it is necessary to understand the correlation between the hole transport layer and the emitting layer (host), and even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics exhibited by the emitting auxiliary layer in which the compound of the present invention is used.
In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied only to the emitting auxiliary layer has been described, but the compound of the present invention may be applied to the hole transport layer or both the hole transport layer and the emitting auxiliary layer may be applied.
Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Therefore, the embodiment disclosed in the present invention is intended to illustrate the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiment. The scope of the present invention shall be construed on the basis of the accompanying claims, and it shall be construed that all of the technical ideas included within the scope equivalent to the claims belong to the present invention.
According to the present invention, it is possible to manufacture an organic device having excellent device characteristics of high luminance, high light emission and long life, and thus has industrial applicability.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0044003 | Apr 2020 | KR | national |
| 10-2021-0034201 | Mar 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/004434 | 4/8/2021 | WO |
