Patent Application
20200203615
The present invention relates to a light-emitting device.
Light-emitting devices such as organic electroluminescence devices can be suitably used for display and illumination purposes, and research and development are underway.
For example, in Patent Literature 1, a light-emitting device having an organic layer containing a polymer compound (P0-1) represented by the following formula, and a light-emitting layer containing a fluorescent compound (EM0-1) represented by the following formula is described:
For example, in Patent Literature 2, a light-emitting device having an organic layer containing a polymer compound (P0-2) comprising a constitutional unit (M0) represented by the following formula, and a light-emitting layer containing a fluorescent compound (EM0-2) represented by the following formula is described:
One having an excellent external quantum efficiency has been demanded as a light-emitting device. Accordingly, an object of the present invention is to provide a light-emitting device excellent in external quantum efficiency.
The present invention provides the following [1] to [15]:
[1] A light-emitting device comprising: an anode; a cathode; a first organic layer disposed between the anode and the cathode; and a second organic layer disposed, adjacently to the first organic layer, between the anode and the cathode, wherein:
the first organic layer is a layer containing a fluorescent low-molecular compound;
a maximum peak wavelength of an emission spectrum of the fluorescent low-molecular compound is 380 nm or larger and 750 nm or smaller;
the second organic layer is a layer containing a cross-linked form of a polymer compound comprising a cross-linking constitutional unit having a cross-linking group; and
as for each constitutional unit constituting the polymer compound, when value x obtained by multiplying molar ratio C of the constitutional unit to total mol of all constitutional units by molecular weight M of the constitutional unit, and value y obtained by multiplying the molar ratio C by number n of the cross-linking group carried by the constitutional unit are determined, a value of (Y1×1000)/X1 calculated from summation X1 of the x and summation Y1 of the y is 0.60 or more.
[2] The light-emitting device according to [1], wherein the polymer compound is a polymer compound comprising a cross-linking constitutional unit having at least one cross-linking group selected from the Group A of cross-linking group:
wherein RXL represents a methylene group, an oxygen atom or a sulfur atom; nXL represents an integer of 0 to 5; in the case where a plurality of RXL are present, they are the same or different; in the case where a plurality of nXL are present, they are the same or different; * 1 represents a position, of a bond; and these cross-linking groups optionally have a substituent.
[3] The light-emitting device according to [2], wherein the cross-linking constitutional unit is a constitutional unit represented by the formula (2) or a constitutional unit represented by the formula (2′):
wherein
nA represents an integer of 0 to 5; n represents 1 or 2; in the case where a plurality of nA are present, they are the same or different;
Ar3 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent;
LA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups optionally have a substituent; R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent; in the case where a plurality of LA are present, they are the same or different;
X represents a cross-linking group selected from the Group A of cross-linking group; and in the case where a plurality of X are present, they are the same or different, and
wherein
mA represents an integer of 0 to 5; m represents an integer of 1 to 4; c represents an integer of 0 or 1; in the case where a plurality of mA are present, they are the same or different;
Ar5 represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups optionally have a substituent;
Ar4 and Ar6 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent;
each of Ar4, Ar5 and Ar6 optionally forms a ring by bonding directly or via an oxygen atom or a sulfur atom to a group, other than the group concerned, bonded to the nitrogen atom to which the group concerned is bonded;
KA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups optionally have a substituent; R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent; in the case where a plurality of KA are present, they are the same or different;
X′ represents a cross-linking group selected from the group A of cross-linking group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent; and in the case where a plurality of X′ are present, they are the same or different, provided that at least one X′ is a cross-linking group selected from the Group A of cross-linking group.
[4] The light-emitting device according to any of [1] to [3], wherein the fluorescent low-molecular compound is a compound represented by the formula (B):
[Chemical Formula 6]
Ar1BR1B)n
wherein
n1B represents an integer of 0 to 15;
Ar1B represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and these groups optionally have a substituent; in the case where a plurality of the substituent are present, they are the same or different and are optionally bonded to each other to form a ring together with the atoms to which they are attached;
R1B represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a cycloalkynyl group, and these groups optionally have a substituent; and in the case where a plurality of R1B are present, they are the same or different and are optionally bonded to each other to form a ring together with the carbon atoms to which they are attached.
[5] The light-emitting device according to [4], wherein the n1B is an integer of 1 to 8.
[6] The light-emitting device according to [4] or [5], wherein the Ar1B is an aromatic hydrocarbon group optionally having a substituent.
[7] The light-emitting device according to [6], wherein the Ar1B is a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a triphenylene ring, a naphthacene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, an indene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthofluoranthene ring (the group optionally has a substituent).
[8] The light-emitting device according to [7], wherein the Ar1B is a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a pyrene ring, a chrysene ring, a fluoranthene ring or a benzofluoranthene ring (the group optionally has a substituent).
[9] The light-emitting device according to any of [4] to [8], wherein the R1B is an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a substituted amino group, an alkenyl group or a cycloalkenyl group (these groups optionally have a substituent).
[10] The light-emitting device according to [9], wherein the R1B is an aryl group, a substituted amino group or an alkenyl group (these groups optionally have a substituent).
[11] The light-emitting device according to any of [1] to [10], wherein the maximum peak wavelength of an emission spectrum of the fluorescent low-molecular compound is 380 nm or larger and 570 nm or smaller.
[12] The light-emitting device according to any of [1] to [11], wherein the value of (Y1×1000)/X1 is 0.85 or more and 4.0 or less.
[13] The light-emitting device according to any of [1] to [12], wherein: the first organic layer is a layer containing the fluorescent low-molecular compound and a host material; the host material is a compound represented by the formula (FH-1) or a polymer compound comprising a constitutional unit represented by the formula (Y); and the amount of the fluorescent low-molecular compound is 0.1 to 50 parts by mass with respect to 100 parts by mass in total of the fluorescent low-molecular compound and the host material:
wherein
ArH1 and ArH2 each independently represent an aryl group, a monovalent heterocyclic group or a substituted amino group and these groups optionally have a substituent;
nH1 represents an integer of 0 to 15;
LH1 represents an arylene group, a divalent heterocyclic group, or a group represented by —[C(RH11)2]nH11- and these groups optionally have a substituent; in the case where a plurality of LH1 are present, they are the same or different; nH11 represents an integer of 1 to 10; RH11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group and these groups optionally have a substituent; and a plurality of RH11 present are the same or different and are optionally bonded to each other to form a ring together with the carbon atoms to which they are attached and
[Chemical Formula 8]
ArY1 (Y)
wherein ArY1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded and these groups optionally have a substituent.
[14] The light-emitting device according to any of [1] to [13], wherein the first organic layer further contains at least one material selected from the group consisting of a hole-transporting material, a hole-injecting material, an electron-transporting material, an electron-injecting material, an antioxidant, and a light-emitting material different from the fluorescent low-molecular compound.
[15] The light-emitting device according to any of [1] to [14], wherein the second organic layer is a layer disposed between the anode and the first organic layer.
According to the present invention, a light-emitting device excellent in external quantum efficiency can be provided.
Hereinafter, preferable embodiments of the present invention will be described in detail.
The terms commonly used in the present specification have the following meanings unless otherwise specified.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.
The hydrogen atom may be a heavy hydrogen atom or may be a light hydrogen atom.
In a formula that represents a metal complex, a solid line that represents a bond to a central metal means a covalent bond or a coordinate bond.
The “polymer compound” means a polymer that has a molecular weight distribution and has a polystyrene-based number-average molecular weight of 1×103 to 1×108.
The “low-molecular compound” means a compound that does not have a molecular weight distribution and has a molecular weight of 1×104 or smaller.
The “constitutional unit” means one or more units present in a polymer compound.
The “alkyl group” may be linear or branched. The number of carbon atoms of the linear alkyl group is usually 1 to 50, preferably 3 to 30, more preferably 4 to 20, which excludes the number of carbon atoms of a substituent. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoamyl group, a 2-ethylbutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, a decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-hexyldecyl group and a dodecyl group. The alkyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the alkyl group is replaced with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like. Examples of the alkyl group having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-di-hexylphenyl)propyl group and a 6-ethyloxyhexyl group.
The number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The cycloalkyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the cycloalkyl group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like. Examples of the cycloalkyl group having a substituent include a cyclohexylmethyl group and a cyclohexylethyl group.
The “aryl group” means a remaining atomic group excluding one hydrogen atom directly bonded to an annular carbon atom from an aromatic hydrocarbon. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, more preferably 6 to 10, which excludes the number of carbon atoms of a substituent.
Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group and a 4-phenylphenyl group. The aryl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the aryl group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The “alkoxy group” may be linear or branched. The number of carbon atoms of the linear alkoxy group is usually 1 to 40, preferably 4 to 10, which excludes the number of carbon atoms of a substituent. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, which excludes the number of carbon atoms of a substituent.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group. The alkoxy group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the alkoxy group is replaced with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, which excludes the number of carbon atoms of a substituent.
Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. The cycloalkoxy group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the cycloalkoxy group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The “aryloxy group” means an atomic group in which one aryl group is bonded to an oxygen atom. The number of carbon atoms of the aryloxy group is usually 6 to 60, preferably 6 to 48, which excludes the number of carbon atoms of a substituent.
Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group and a 1-pyrenyloxy group. The aryloxy group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the aryloxy group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like.
The “p-valent heterocyclic group” (p represents an integer of 1 or larger) means a remaining atomic group excluding p hydrogen atom(s) among hydrogen atoms directly bonded to annular carbon atoms or heteroatoms from a heterocyclic compound. Among the p-valent heterocyclic groups, a “p-valent aromatic heterocyclic group” is preferable which is a remaining atomic group excluding p hydrogen atom(s) among hydrogen atoms directly bonded to annular carbon atoms or heteroatoms from an aromatic heterocyclic compound.
The “aromatic heterocyclic compound” means a compound in which a heterocyclic ring itself exhibits aromaticity, such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, or dibenzophosphole, and a compound in which an aromatic ring is condensed with a heterocyclic ring even though the heterocyclic ring itself does not aromaticity, such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, or benzopyran.
The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group and a triazinyl group. The monovalent heterocyclic group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the monovalent heterocyclic group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like.
The “halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The “amino group” optionally has a substituent and a substituted amino group is preferable. An alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable as the substituent carried by the amino group.
Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group and a diarylamino group. Specific examples of the substituted amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group and a bis(3,5-di-tert-butylphenyl)amino group.
The “alkenyl group” may be linear or branched. The number of carbon atoms of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, which excludes the number of carbon atoms of a substituent.
The number of carbon atoms of the branched alkenyl group is usually 3 to 30, preferably 4 to 20, which excludes the number of carbon atoms of a substituent.
The number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the alkenyl group and the cycloalkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group and a 7-octenyl group. The alkenyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the alkenyl group is replaced with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like. Also, the cycloalkenyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the cycloalkenyl group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The “alkynyl group” may be linear or branched. The number of carbon atoms of the alkynyl group is usually 2 to 20, preferably 3 to 20, which excludes the carbon atoms of a substituent. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, which excludes the carbon atoms of a substituent.
The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, which excludes the carbon atoms of a substituent.
Examples of the alkynyl group and the cycloalkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group and a 5-hexynyl group. The alkynyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the alkynyl group is replaced with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like. Also, the cycloalkynyl group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the cycloalkynyl group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The “arylene group” means a remaining atomic group excluding two hydrogen atoms directly bonded to annular carbon atoms from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, more preferably 6 to 18, which excludes the number of carbon atoms of a substituent.
Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a naphthacenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group and a chrysenediyl group. The arylene group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the arylene group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The arylene group is preferably groups represented by the formula (A-1) to the formula (A-20). The arylene group includes groups in which a plurality of these groups are bonded.
In the formulas, R and Ra each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. Pluralities of R and Ra present are respectively the same or different, and a plurality of Ra are optionally bonded to each other to form a ring together with the atoms to which they are attached.
The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, more preferably 4 to 15, which excludes the number of carbon atoms of a substituent.
Examples of the divalent heterocyclic group include divalent groups excluding two hydrogen atoms among hydrogen atoms directly bonded to annular carbon atoms or heteroatoms from heterocyclic compounds such as pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, azole, diazole, and triazole. The divalent heterocyclic group optionally has a substituent and can be, for example, a group in which a portion or the whole of hydrogen atoms in the divalent heterocyclic group is replaced with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The divalent heterocyclic group is preferably groups represented by the formula (AA-1) to the formula (AA-34). The divalent heterocyclic group includes groups in which a plurality of these groups are bonded.
In the formulas, R and Ra represent the same meanings as above.
The “cross-linking group” is a group capable of being subjected to a heating treatment, an ultraviolet irradiation, a near-ultraviolet irradiation, a visible light irradiation, an infrared irradiation, a radical reaction or the like and thereby forming a new bond and is preferably groups represented by the formula (XL-1) to the formula (XL-17) of the above-described Group A of cross-linking group.
Examples of the “substituent” include a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group and a cycloalkynyl group. The substituent may be a cross-linking group.
<Light-Emitting Device>
Next, the light-emitting device according to one embodiment of the present invention will be described.
The light-emitting device according to the present embodiment comprises an anode, a cathode, a first organic layer disposed between the anode and the cathode, and a second organic layer disposed, adjacently to the first organic layer, between the anode and the cathode. The first organic layer is a layer containing a fluorescent low-molecular compound, and the second organic layer is a layer containing a cross-linked form of a polymer compound comprising a cross-linking constitutional unit having a cross-linking group.
Examples of methods for forming the first organic layer and the second organic layer include: dry methods such as a vacuum deposition method; and wet methods such as a spin coating method and an inkjet printing method, and a wet method is preferable.
In the case of forming the first organic layer by the wet method, it is preferable to use an ink for the first organic layer (hereinafter, also referred to as a “first ink”) mentioned later.
In the case of forming the second organic layer by the wet method, it is preferable to use an ink for the second organic layer (hereinafter, also referred, to as a “second ink”) mentioned later. After formation of the second organic layer, a polymer compound of the second organic layer mentioned later, contained in the second organic layer can be cross-linked by a heating treatment or a light irradiation, and it is preferable to cross-link the polymer compound of the second organic layer mentioned later, contained in the second organic layer by a heating treatment. In the case where the polymer compound of the second organic layer mentioned later is contained in a cross-linked state (a cross-linked form of the polymer compound of the second organic layer mentioned later) in the second organic layer, the second organic layer is substantially insolubilized in a solvent. Therefore, the second organic layer can be suitably used in the lamination of the light-emitting device.
The temperature of the heating for cross-linking is usually 25 to 300° C., preferably 50 to 250° C., more preferably 150° C. to 200° C., further preferably 170° C. to 190° C. The time of the heating for cross-linking is usually 0.1 to 1000 minutes, preferably 0.5 to 500 minutes, more preferably 1 to 120 minutes, further preferably 30 to 90 minutes.
The type of the light used in the light irradiation is, for example, ultraviolet light, near-ultraviolet light, or visible light.
Examples of a method for analyzing a component contained in the first organic layer or the second organic layer include: chemical separation analysis methods such as extraction; instrumental analysis methods such as infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), and mass spectrometry (MS); and analysis methods combining chemical separation analysis methods and instrumental analysis methods.
It is possible to separate the first organic layer or the second organic layer into a component substantially insoluble in an organic solvent (insoluble component) and a component soluble in an organic solvent (soluble component) by performing solid-liquid extraction using an organic solvent such as toluene, xylene, chloroform, or tetrahydrofuran. The insoluble component can be analyzed by an infrared spectroscopy or a nuclear magnetic resonance spectroscopy, and the soluble component can be analyzed by a nuclear magnetic resonance spectroscopy or a mass spectrometry.
<First Organic Layer>
The first organic layer is a layer containing a fluorescent low-molecular compound. In the first organic layer, one fluorescent low-molecular compound may be used alone, or two or more may be contained.
[Fluorescent Low-Molecular Compound]
The “fluorescent low-molecular compound” usually means a low-molecular compound that exhibits fluorescence at room temperature (25° C.) and is preferably a low-molecular compound that exhibits light emission from a singlet excited state at room temperature.
The maximum peak wavelength of an emission spectrum of the fluorescent low-molecular compound is usually 380 nm or larger and 750 nm or smaller, preferably 380 nm or larger and 570 nm or smaller, more preferably 390 nm or larger and 540 nm or smaller, further preferably 400 nm or larger and 495 nm or smaller, particularly preferably 420 nm or larger and 480 nm or smaller.
In the present specification, the maximum peak wavelength of an emission spectrum of a compound can be evaluated by dissolving the compound in an organic solvent such as xylene, toluene, chloroform, or tetrahydrofuran to prepare a dilute solution (on the order of 1×10−6 to 1×10−3% by mass) and measuring the PL spectrum of the dilute solution at room temperature. Toluene is preferable as the organic solvent dissolving the compound.
The fluorescent low-molecular compound is preferably a compound represented by the formula (B).
[Compound Represented by Formula (B)]
n1B represents an integer of 0 to 15 and is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, further preferably an integer of 1 to 4, particularly preferably an integer of 2 to 4.
Ar1B represents an aromatic hydrocarbon group or an aromatic heterocyclic group and these groups optionally have a substituent. In Ar1B, the number of carbon atoms of the aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20 which excludes the number of carbon atoms of a substituent.
Examples of the aromatic hydrocarbon group in Ar1B include a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a triphenylene ring, a naphthacene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, an indene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthofluoranthene ring. The aromatic hydrocarbon group is preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a triphenylene ring, a naphthacene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthofluoranthene ring, more preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthofluoranthene ring, further preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthofluoranthene ring, particularly preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a biphenyl ring, a naphthalene ring, a fluorene ring, a pyrene ring, a perylene ring, a chrysene ring, a fluoranthene ring, a benzofluoranthene ring or an acenaphthotluoranthene ring, especially preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a biphenyl ring, a naphthalene ring, a pyrene ring, a chrysene ring, a fluoranthene ring or a benzofluoranthene ring, especially more preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a biphenyl ring, a pyrene ring, a chrysene ring, a fluoranthene ring or a benzofluoranthene ring, especially further preferably a group formed by removing one or more hydrogen atoms directly bonded to an annular carbon atom from a pyrene ring, a chrysene ring, a fluoranthene ring or a benzofluoranthene ring. These groups optionally have a substituent.
In Ar1B, the number of carbon atoms of the aromatic heterocyclic group is usually 2 to 60, preferably 3 to 30, more preferably 3 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the aromatic heterocyclic group in Ar1B include a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a pyrrole ring, a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a triazanaphthalene ring, an indole ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, an azacarbazole ring, a diazacarbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, an acridine ring, a 9,10-dihydroacridine ring, an acridone ring, a phenazine ring or a 5,10-dihydrophenazine ring. The aromatic heterocyclic group is preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an indole ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, a 9,10-dihydroacridine ring or a 5,10-dihydrophenazine ring, more preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a diazole ring, a triazole ring, a pyridine ring, a 1.0 diazabenzene ring, a triazine ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, a dibenzofuran ring or dibenzothiophene ring. These groups optionally have a substituent.
The substituent optionally carried by Ar1B is preferably a halogen atom, a cyano group, an aryloxy group or an amino group, more preferably a fluorine atom or a cyano group. These groups optionally further have a substituent.
Examples and a preferable range of the substituent optionally further carried by the substituent optionally carried by Ar1B are the same as examples and a preferable range of a substituent optionally carried by R1B mentioned later.
Ar1B is preferably an aromatic hydrocarbon group optionally having a substituent.
R1B represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a cycloalkynyl group, and these groups optionally have a substituent. R1B is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a substituted amino group, an alkenyl group or a cycloalkenyl group, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a substituted amino group, an alkenyl group or a cycloalkenyl group, further preferably an alkyl group, a cycloalkyl group, an aryl group, a substituted amino group, an alkenyl group or a cycloalkenyl group, particularly preferably an aryl group, a substituted amino group or an alkenyl group, especially preferably an aryl group or a substituted amino group. These groups optionally have a substituent.
In the case where R1B is an aryl group, the number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 14, which excludes the number of carbon atoms of a substituent.
In the case where R1B is an aryl group, examples of the aryl group include a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a dihydrophenanthrene ring, a naphthacene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, an indene ring, a fluoranthene ring or a benzofluoranthene ring. The aryl group is preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a fluoranthene ring or a benzofluoranthene ring, more preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a spirobifluorene ring, a fluoranthene ring or a benzofluoranthene ring, further preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, a fluorene ring or a spirobifluorene ring, particularly preferably a phenyl group or a naphthyl group. These groups optionally further have a substituent.
In the case where R1B is a monovalent heterocyclic group, the number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 3 to 30, and more preferably 3 to 20 which excludes the number of carbon atoms of a substituent.
In the case where R1B is a monovalent heterocyclic group, examples of the monovalent heterocyclic group include a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a pyrrole ring, a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a triazanaphthalene ring, an indole ring, a carbazole ring, an azacarbazole ring, a diazacarbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, an acridine ring, a 9,10-dihydroacridine ring, an acridone ring, a phenazine ring or a 5,10-dihydrophenazine ring. The monovalent heterocyclic group is preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a carbazole ring, an azacarbazole ring, a diazacarbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, a 9,10-dihydroacridine ring or a 5,10-dihydrophenazine ring, more preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring. These groups optionally further have a substituent.
In the case where R1B is a substituted amino group, an aryl group or a monovalent heterocyclic group is preferable as the substituent carried by the amino group, and an aryl group is more preferable, and these groups optionally further have a substituent. Examples and the preferable range of the aryl group as the substituent carried by the amino group are the same as the examples and the preferable range of the aryl group in R1B. Examples and the preferable range of the monovalent heterocyclic group as the substituent carried by the amino group are the same as the examples and the preferable range of the monovalent heterocyclic group in R1B.
The substituent optionally carried by R1B is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a substituted amino group or a halogen atom; more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group or a substituted amino group; and further preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group; particularly preferably an alkyl group, a cycloalkyl group or an aryl group; and especially preferably an alkyl group or a cycloalkyl group. These groups optionally further have a substituent.
Examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent optionally carried by R1B are the same as the examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group in R1B, respectively.
The substituent optionally further carried by the substituent optionally carried by R1B is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a substituted amino group or a halogen atom; more preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group; and further preferably an alkyl group or a cycloalkyl group. These groups optionally further have a substituent.
Examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent optionally further carried by the substituent optionally carried by R1B are the same as the examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group in R1B, respectively.
In the case where a plurality of R1B are present, it is preferable that they should not be bonded to each other to form a ring together with the atoms to which they are attached because the maximum peak wavelength of an emission spectrum of the compound represented by the formula (B) becomes a short wavelength.
Examples of the fluorescent low-molecular compound include compounds represented by the following formulas:
The fluorescent low-molecular compound is available from Sigma-Aldrich Co. LLC, Luminescence Technology Corp., AK Scientific, Inc., etc. Alternatively, it can be synthesized according to a method described in, for example, International Publication No. WO 2007/100010, International Publication No. WO 2008/059713, International Publication No. WO 2011/012212, International Publication No. WO 2012/096263, International Publication No. WO 2006/025273, or International Publication No. WO 2006/030527.
[Host Material]
It is preferable that the first organic layer should be a layer containing the fluorescent low-molecular compound and a host material having at least one function selected from the group consisting of a hole-injecting function, a hole-transporting function, an electron-injecting function and an electron-transporting function, because the external quantum efficiency of the light-emitting device according to the present embodiment is better. In the case where the first organic layer is a layer containing the fluorescent low-molecular compound and a host material, one host material may be contained singly, or two or more may be contained.
In the case where the first organic layer is a layer containing the fluorescent low-molecular compound and a host material, the amount of the fluorescent low-molecular compound is usually 0.05 to 80 parts by mass, preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass and further preferably 5 to 15 parts by mass with respect to 100 parts by mass in total of the fluorescent low-molecular compound and the host material.
In the case where the first organic layer is a layer containing the fluorescent low-molecular compound and a host material, it is preferable that the lowest excited singlet state (S1) possessed by the host material should have an energy level equivalent to or an energy level higher than that of S1 possessed by the fluorescent low-molecular compound because the external quantum efficiency of the light-emitting device according to the present embodiment is excellent. Specifically, it is preferable that the maximum peak wavelength of an emission spectrum of the host material should be a wavelength equivalent to or shorter than the maximum peak wavelength of an emission spectrum of the fluorescent low-molecular compound because the external quantum efficiency of the light-emitting device according to the present embodiment is excellent.
It is preferable for the host material to exhibit solubility in a solvent capable of dissolving the fluorescent low-molecular compound contained in the first organic layer, because the light-emitting device according to the present embodiment can be prepared by a solution coating process.
The host material is classified into a low-molecular compound and a polymer compound. Examples of the host material include hole-transporting materials mentioned later and electron-transporting materials mentioned later.
[Low-Molecular Host]
The low-molecular compound preferable as the host material (hereinafter, also referred to as a “low-molecular host”) will be described.
The low-molecular host is preferably a compound represented by the formula (FH-1).
Each of ArH1 and ArH2 is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group. These groups optionally have a substituent.
In the case where each of ArH1 and ArH2 is an aryl group, the number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 30, more preferably 6 to 20 and further preferably 6 to 14 which excludes the number of carbon atoms of a substituent.
In the case where each of ArH1 and ArH2 is an aryl group, examples of the aryl group include a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a dihydrophenanthrene ring, a naphthacene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring, a perylene ring, a chrysene ring, an indene ring, a fluoranthene ring or a benzofluoranthene ring. The aryl group is preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a fluorene ring, a spirobifluorene ring, a pyrene ring or a chrysene ring, more preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom from a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a fluorene ring or a spirobifluorene ring, further preferably a phenyl group, a naphthyl group or an anthracenyl group, particularly preferably a phenyl group or a naphthyl group. These groups optionally further have a substituent.
In the case where each of ArH1 and ArH2 is a monovalent heterocyclic group, the number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 3 to 30 and more preferably 3 to 20 which excludes the number of carbon atoms of a substituent.
In the case where each of ArH1 and ArH2 is a monovalent heterocyclic group, examples of the monovalent heterocyclic group include a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a pyrrole ring, a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a triazanaphthalene ring, an indole ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, an azacarbazole ring, a diazacarbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, an acridine ring, a 9,10-dihydroacridine ring, an acridone ring, a phenazine ring or a 5,10-dihydrophenazine ring. The monovalent heterocyclic group is preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an indole ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring, a 9,10-dihydroacridine ring or a 5,10-dihydrophenazine ring, more preferably a group formed by removing one hydrogen atom directly bonded to an annular carbon atom or heteroatom from a diazole ring, a triazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, a benzodiazole ring, a benzotriazole ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring. These groups optionally further have a substituent.
In the case where each of ArH1 and ArH2 is a substituted amino group, an aryl group or a monovalent heterocyclic group is preferable as the substituent carried by the amino group, and an aryl group is more preferable and these groups optionally further have a substituent. Examples and the preferable range of the aryl group as the substituent carried by the amino group are the same as the examples and the preferable range of the aryl group in ArH1 and ArH2. Examples and the preferable range of the monovalent heterocyclic group as the substituent carried by the amino group are the same as the examples and the preferable range of the monovalent heterocyclic group in ArH1 and ArH2.
The substituent optionally carried by ArH1 and ArH2 is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a substituted amino group or a halogen atom; more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group or a substituted amino group; further preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group; and particularly preferably an alkyl group, a cycloalkyl group or an aryl group. These groups optionally further have a substituent.
Examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent optionally carried by ArH1 and ArH2 are the same as the examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group in ArH1 and ArH2, respectively.
The substituent optionally further carried by the substituent optionally carried by ArH1 and ArH2 is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a substituted amino group or a halogen atom; more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group or a substituted amino group; further preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group; and particularly preferably an alkyl group or a cycloalkyl group, and these groups optionally further have a substituent.
Examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent optionally further carried by the substituent optionally carried by ArH1 and ArH2 are the same as the examples and the preferable range of the aryl group, the monovalent heterocyclic group and the substituted amino group in ArH1 and ArH2, respectively.
nH1 is preferably an integer of 0 to 10, more preferably an integer of 1 to 5 and further preferably an integer of 1 to 3.
LH1 is preferably an arylene group or a divalent heterocyclic group and more preferably an arylene group.
Examples and the preferable range of the substituent optionally carried by LH1 are the same as the examples and the preferable range of the substituent optionally carried by ArH1 and ArH2.
The arylene group in LH1 is preferably groups represented by the formula (A-1) to the formula (A-14) or the formula (A-17) to the formula (A-20), more preferably groups represented by the formula (A-1) to the formula (A-9), the formula (A-11) to the formula (A-14), the formula (A-19) or the formula (A-20), further preferably groups represented by the formula (A-1) to the formula (A-7), the formula (A-9), the formula (A-11) to the formula (A-14) or the formula (A-1.9), particularly preferably groups represented by the formula (A-1) to the formula (A-6), the formula (A-11) or the formula (A-12).
The divalent heterocyclic group in LH1 is preferably groups represented by the formula (AA-1) to the formula (AA-6), the formula (AA-10) to the formula (AA-22) or the formula (AA-24) to the formula (AA-34), more preferably groups represented by the formula (AA-1) to the formula (AA-4), the formula (AA-10) to the formula (AA-15), the formula (AA-18) to the formula (AA-21) or the formula (AA-27) to the formula (AA-34), further preferably groups represented by the formula (AA-1) to the formula (AA-4), the formula (AA-10) to the formula (AA-15) or the formula (AA-27) to the formula (AA-32).
nH11 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, further preferably 1.
It is preferable that RH11 should be a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, it is more preferable to be a hydrogen atom, an alkyl group or a cycloalkyl group, and it is further preferable to be a hydrogen atom or an alkyl group. These groups optionally have a substituent.
Examples and the preferable range of the substituent optionally carried by RH11 are the same as the examples and the preferable range of the substituent optionally carried by ArH1 and ArH2.
Examples of the compound represented by the formula (FH-1) include compounds represented by the following formulas:
[Polymer Host]
The polymer compound preferable as the host material (hereinafter, also referred to as a “polymer host”) will be described.
The polymer host is preferably a polymer compound comprising a constitutional unit represented by the formula (Y).
The arylene group represented by ArY1 is preferably groups represented by the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to the formula (A-11), the formula (A-13) or the formula (A-19), more preferably a group represented by the formula (A-1), the formula (A-7), the formula (A-9), the formula (A-11) or the formula (A-19). These groups optionally have a substituent.
The divalent heterocyclic group represented by ArY1 is preferably a group represented by the formula (AA-4), the formula (AA-10), the formula (AA-13), the formula (AA-15), the formula (AA-18) or the formula (AA-20), more preferably a group represented by the formula (AA-4), the formula (AA-10), the formula (AA-18) or the formula (AA-20). These groups optionally have a substituent.
Preferable ranges and more preferable ranges of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, represented by ArY1 are similar to the preferable ranges and the more preferable ranges of the arylene group and the divalent heterocyclic group represented by ArY1 mentioned above, respectively.
Examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, represented by ArY1 include those similar to the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, represented by ArX2 and ArX4 in the formula (X).
The substituent optionally carried by the group represented by ArY1 is preferably an alkyl group, a cycloalkyl group or an aryl group. These groups optionally further have a substituent.
Examples of the constitutional unit represented by the formula (Y) include constitutional units represented by the formula (Y-1) to the formula (Y-7), preferably a constitutional unit represented by the formula (Y-1) or the formula (Y-2) from the viewpoint of the external quantum efficiency of the light-emitting device according to the present embodiment, preferably a constitutional unit represented by the formula (Y-3) or the formula (Y-4) from the viewpoint of the electron-transporting function of the polymer host, and preferably a constitutional unit represented by the formula (Y-5) to the formula. (Y-7) from the viewpoint of the hole-transporting function of the polymer host.
In the formula, RY1 represents a hydrogen, atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of RY1 present are the same or different and adjacent groups RY1 are optionally bonded to each other to form a ring together with the carbon atoms to which they are attached.
RY1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. These groups optionally have a substituent.
The constitutional unit represented by the formula (Y-1) is preferably a constitutional unit represented by the formula (Y-1′).
In the formula, RY11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of RY11 present are the same or different.
RY11 is preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group. These groups optionally have a substituent.
In the formula, RY1 represents the same meaning as above. XY1 represents a group represented by —C(RY2)—, —C(RY2)═C(RY2)— or —C(RY2)2—C(RY2)2—. RY2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of RY2 present are the same or different, and RY2 are optionally bonded to each other to form a ring together with the carbon atoms to which they are attached.
RY2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups optionally have a substituent.
In XY1, the combination of two RY2 in the group represented by —C(RY2)2— is preferably alkyl groups or cycloalkyl groups for both, aryl groups for both, monovalent heterocyclic groups for both, or an alkyl group or a cycloalkyl group for one of them and an aryl group or a monovalent heterocyclic group for the other, more preferably an alkyl group or a cycloalkyl group for one of them and an aryl group for the other. These groups optionally have a substituent. Two RY2 present are optionally bonded to each other to form a ring together with the atoms to which they are attached, and in the case where RY2 forms a ring, the group represented by —C(RY2)2— is preferably a group represented by the formula (Y-A1) to the formula (Y-A5), more preferably a group represented by the formula (Y-A4). These groups optionally have a substituent.
In XY1, the combination of two RY2 in the group represented by —C(RY2)═C(RY2)— is preferably alkyl groups or cycloalkyl groups for both, or an alkyl group or a cycloalkyl group for one of them and an aryl group for the other, and these groups optionally have a substituent.
In XY1 each of four RY2 in the group represented by —C(RY2)2—C(RY2)— is preferably an alkyl group optionally having a substituent or a cycloalkyl group optionally having a substituent. A plurality of RY2 are optionally bonded to each other to form a ring together with the atoms to which they are attached, and in the case where the groups RY2 forms a ring, the group represented by —C(RY2)2—C(RY2)2— is preferably groups represented by the formula (Y-B1) to the formula (Y-B5), more preferably a group represented by the formula (Y-B3). These groups optionally have a substituent.
In the formulas, RY2 represents the same meaning as above.
It is preferable that the constitutional unit represented by the formula (Y-2) should be a constitutional unit represented by the formula (Y-2′).
In the formula, RY1 and XY1 represent the same meanings as above.
In the formulas, RY1 represents the same meaning as above. RY3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
RY3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group. These groups optionally have a substituent.
In the formulas, RY1 represents the same meaning as above. RY4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
RY4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group. These groups optionally have a substituent.
Examples of the constitutional unit represented by the formula (Y) include constitutional units represented by the formula (Y-11) to the formula (Y-56), preferably constitutional units represented by the formula (Y-11) to the formula (Y-55).
The constitutional unit which is a constitutional unit represented by the formula (Y) wherein Ar1 is an arylene group is preferably 10 to 100% by mol, more preferably 50 to 1.00% by mol with respect to the total content of constitutional units contained in the polymer host, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
The constitutional unit which is a constitutional unit represented by the formula (Y) wherein ArY1 is a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded is preferably 0.5 to 40% by mol, more preferably 3 to 30% by mol with respect to the total content of constitutional units contained in the polymer host because the charge-transporting function of the polymer host is excellent.
Only one constitutional unit represented by the formula (Y) may be contained in the polymer host or two or more may be contained.
It is preferable that the polymer host should further comprise a constitutional unit represented by the formula (X) because the hole-transporting function is excellent.
In the formula,
aX1 and aX2 each independently represent an integer of 0 or larger.
ArX1 and ArX3 each independently represent an arylene group or a divalent heterocyclic group and these groups optionally have a substituent.
ArX2 and ArX4 each independently represent an arylene group, a divalent heterocyclic group or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded and these groups optionally have a substituent. In the case where a plurality of ArX2 and ArX4 are present, they are the same or different.
RX1, RX2 and RX3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
In the case where pluralities of RX2 and RX3 are present, they are the same or different.
aX1 is preferably an integer of 2 or smaller, more preferably 1, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
aX2 is preferably an integer of 2 or smaller, more preferably 0, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
Each of RX1, RX2 and RX3 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group. These groups optionally have a substituent.
The arylene group represented by ArX1 and ArX3 is preferably a group represented by the formula (A-1) or the formula (A-9), more preferably a group represented by the formula (A-1). These groups optionally have a substituent.
The divalent heterocyclic group represented by ArX1 and ArX3 is preferably groups represented by the formula (AA-1), the formula (AA-2) or the formula (AA-7) to the formula (AA-26). These groups optionally have a substituent.
Each of ArX1 and ArX3 is preferably an arylene group optionally having a substituent.
The arylene group represented by ArX2 and ArX4 is preferably groups represented by the formula. (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to the formula (A-11) or the formula (A-19). These groups optionally have a substituent.
The preferable range of the divalent heterocyclic group represented by ArX2 and ArX4 is the same as the preferable range of the divalent heterocyclic group represented by ArX1 and ArX3.
The preferable range and more preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, represented by ArX2 and ArX4 are the same as the preferable range and the more preferable range of the arylene group and the divalent heterocyclic group represented by ArX1 and ArX3, respectively.
Examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, represented by ArX2 and ArX4 include groups represented by the following formulas, and these groups optionally have a substituent:
In the formulas, RXX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
Each of ArX2 and ArX4 is preferably an arylene group optionally having a substituent.
The substituent optionally carried by the group represented by ArX1 to ArX4 and RX1 to RX3 is preferably an alkyl group, a cycloalkyl group or an aryl group. These groups optionally further have a substituent.
The constitutional unit represented by the formula (X) is preferably constitutional units represented by the formula (X-1) to the formula (X-7), more preferably constitutional units represented by the formula (X-3) to the formula (X-7), further preferably constitutional units represented by the formula (X-3) to the formula (X-6).
In the formulas, RX4 and RX5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or a cyano group, and these groups optionally have a substituent. A plurality of RX4 present are the same or different. A plurality of RX5 present are the same or different, and adjacent groups RX5 are optionally bonded to each other to form a ring together with the carbon atoms to which they are attached.
The constitutional unit represented by the formula (X) is preferably 0.1 to 50% by mol, more preferably 1 to 40% by mol, further preferably 5 to 30% by mol, with respect to the total content of all constitutional, units contained in the polymer host, because the hole-transporting function is excellent.
Examples of the constitutional unit represented by the formula (X) include constitutional units represented by the formula (X1-1) to the formula (X1-19), preferably constitutional units represented by the formula (X1-6) to the formula (X1-14).
In the polymer host, only one constitutional unit represented by the formula (X) may be contained, or two or more may be contained.
Examples of the polymer host include polymer compounds (P-1) to (P-6) shown in Table 1. In this context, “Additional constitutional unit” means a constitutional unit other than the constitutional unit represented by the formula (Y) and the constitutional unit represented by the formula (X).
In Table 1, p, q, r, s and t represent the molar ratio of each constitutional unit. p+q+r+s+t=100, and 100≥p+q+r+s≥70.
Examples and the preferable range of the constitutional units represented by the formula (X) and the formula (Y) in the polymer compounds (P-1) to (P-6) are as mentioned above.
The polymer host may be any of a block copolymer, a random copolymer, an alternate copolymer, and a graft copolymer, or may be in other forms, and it is preferable to be a copolymer prepared by copolymerizing a plurality of raw material monomers.
The polystyrene-based number-average molecular weight of the polymer host is preferably 5×103 to 1×106, more preferably 1×104 to 5×105, further preferably 1.5×104 to 2×105.
[Method for Producing Polymer Host]
The polymer host can be produced using a publicly known polymerization method described in Chem. Rev., Vol. 109, p. 897-1091 (2009), etc., and examples include a method of performing polymerization through coupling reaction using a transition metal catalyst, such as Suzuki reaction, Buchwald reaction, Stille reaction, Negishi reaction and Kumada reaction.
In the above polymerization method, examples of a method for adding monomers include a method of adding the whole amount of the monomers in one portion to a reaction system, a method of adding a portion of the monomers, reacting them, and then adding the remaining monomers in one portion, continuously or in divided portions, and a method of adding the monomers continuously or in divided portions.
Examples of the transition metal catalyst include palladium catalysts and nickel catalysts.
The aftertreatment of the polymerization reaction publicly known methods is performed by using singly or in combination, for example, a method of removing water-soluble impurities by solution separation, and a method of adding the reaction solution after the polymerization reaction to a lower alcohol such as methanol, and filtering deposited precipitates, followed by drying. In the case where the purity of the polymer host is low, it can be purified by a usual method, for example, crystallization, reprecipitation, continuous extraction with a Soxhlet extractor, or column chromatography.
[First Composition]
The first organic layer may be a layer containing a composition comprising the fluorescent low-molecular compound and at least one material selected from the group consisting of the host material mentioned above, a hole-transporting material, a hole-injecting material, an electron-transporting material, an electron-injecting material, an antioxidant, and a light-emitting material (different from the fluorescent low-molecular compound) (hereinafter, also referred to as a “first composition”).
[Hole-Transporting Material]
The hole-transporting material is classified into a low-molecular compound and a polymer compound and is preferably a polymer compound. The hole-transporting material may have a cross-linking group.
Examples of the polymer compound include: polyvinylcarbazole and derivatives thereof; and polyarylene having an aromatic amine structure in the side chain or the main chain and derivatives thereof. The polymer compound may be a compound attached with an electron-accepting site. Examples of the electron-accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, and trinitrofluorenone, preferably fullerene.
In the first composition, the amount of the hole-transporting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, with respect to 100 parts by mass of the fluorescent low-molecular compound.
The hole-transporting material may be used singly, or two or more may be used in combination.
[Electron-Transporting Material]
The electron-transporting material is classified into a low-molecular compound and a polymer compound. The electron-transporting material may have a cross-linking group.
Examples of the low-molecular compound include phosphorescent compounds with 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene and diphenoquinone, and their derivatives.
Examples of the polymer compound include polyphenylene, polyfluorene, and their derivatives. The polymer compound may be doped with a metal.
In the first composition, the amount of the electron-transporting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, with respect to 100 parts by mass of the fluorescent low-molecular compound.
The electron-transporting material may be used singly, or two or more may be used in combination.
[Hole-Injecting Material and Electron-Injecting Material]
The hole-injecting material and the electron-injecting material are each classified into a low-molecular compound and a polymer compound. The hole-injecting material and the electron-injecting material may have a cross-linking group.
Examples of the low-molecular compound include metallic phthalocyanine such as copper phthalocyanine; carbon; oxides of metals such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.
Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, polythienylenevinylene, polyquinoline and polyquinoxaline, and their derivatives; and conductive polymers such as a polymer having an aromatic amine structure in the main chain or the side chain.
In the first composition, each of the amounts of the hole-injecting material and the electron-injecting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, with respect to 100 parts by mass of the fluorescent low-molecular compound.
One each of the electron-injecting material and the hole-injecting material may be used alone, or two or more each may be used in combination.
[Ion Dope]
In the case where the hole-injecting material or the electron-injecting material contains a conductive polymer, the electric conductivity of the conductive polymer is preferably 1×10−5 S/cm to 1×103 S/cm. In order to adjust the electric conductivity of the conductive polymer to such a range, the conductive polymer can be doped with an appropriate amount of an ion.
The kind of the doping ion is an anion for the hole-injecting material and is a cation for the electron-injecting material. Examples of the anion, include polystyrene sulfonate ions, alkylbenzene sulfonate ions, and camphorsulfonate ions. Examples of the cation include lithium ions, sodium ions, potassium ions, and tetrabutylammonium ions.
The doping ion may be used singly, or two or more may be used in combination.
[Light-Emitting Material]
The light-emitting material is classified into a low-molecular compound and a polymer compound. The light-emitting material may have a cross-linking group.
Examples of the low-molecular compound include naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and triplet light-emitting complexes with iridium, platinum or europium as a central metal.
Examples of the polymer compound include polymer compounds containing a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a constitutional unit represented by the formula (X), a carbazolediyl group, a phenoxazinediyl group, a phenothiazinediyl group, an anthracenediyl group, a pyrenediyl group, or the like.
The light-emitting material preferably contains a triplet light-emitting complex and/or a polymer compound.
Examples of the triplet light-emitting complex include metal complexes shown below.
In the first composition, the amount of the light-emitting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass with respect to 100 parts by mass of the fluorescent low-molecular compound.
The light-emitting material may be used singly, or two or more may be used in combination.
[Antioxidant]
The antioxidant can be a compound that is soluble in the same solvent as that for a fluorescent low-molecular compound and does not inhibit light emission and charge transport, and examples include phenol-based antioxidants and phosphorus-based antioxidants.
In the first composition, the amount of the antioxidant is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the fluorescent low-molecular compound.
The antioxidant may be used singly, or two or more may be used in combination.
[First Ink]
A composition containing the fluorescent low-molecular compound and a solvent can be used as the first ink for forming the first organic layer. The first ink can be suitably used in a wet method such as a spin coating method, a casting method, a micro-gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, a capillary coating method, or a nozzle coating method.
The viscosity of the first ink can be adjusted according to the kind of the wet method, and in the case of being applied to a printing method in which a solution passes through a discharge apparatus, such as an inkjet printing method, is preferably 1 to 20 mPa·s at 25° C. because clogging or curved flight in discharging is less likely to occur.
The solvent contained in the first ink is preferably a solvent that can dissolve or uniformly disperse solid matter in the ink. Examples of the solvent include: chlorine-based solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; ether-based solvents such as THF, dioxane, anisole, and 4-methylanisole; aromatic hydrocarbon-based solvents such as toluene, xylene, mesitylene, ethylbenzene, n-hexylbenzene, and cyclohexylbenzene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, and bicyclohexyl; ketone-based solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; ester-based solvents such as ethyl acetate, butyl acetate, ethylcellosolve acetate, methyl benzoate, and phenyl acetate; polyhydric alcohol-based solvents such as ethylene glycol, glycerin, and 1,2-hexanediol; alcohol-based solvents such as isopropyl alcohol and cyclohexanol; sulfoxide-based solvents such as dimethyl sulfoxide; and amide-based solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide. The solvent may be used singly, or two or more may be used in combination.
In the first ink, the amount of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20000 parts by mass, with respect to 100 parts by mass of the fluorescent low-molecular compound.
It is preferable that the first organic layer should be a layer that does not contain the triplet light-emitting complex mentioned above.
<Second Organic Layer>
The second organic layer is a layer containing a cross-linked form of a polymer compound comprising a cross-linking constitutional unit having a cross-linking group (hereinafter, also referred to as a “polymer compound of the second organic layer”).
In the second organic layer, the cross-linked form of the polymer compound of the second organic layer may be contained singly, or two or more may be contained.
The cross-linked form of the polymer compound of the second organic layer is obtained by preparing the polymer compound of the second organic layer into a cross-linked state by the method and the conditions, etc. mentioned above.
In the case where the second organic layer is a layer containing a cross-linked form in which one polymer compound of the second organic layer is cross-linked, as for each constitutional unit constituting the one polymer compound of the second organic layer, when value x obtained by multiplying the molar ratio C of the constitutional unit to total mol of all constitutional units constituting the one polymer compound by molecular weight M of the constitutional unit, and value y obtained by multiplying the molar ratio C by number n of the cross-linking group carried by the constitutional unit are determined, the value of (Y1×1000)/X1 calculated from the summation X1 of the values x and the summation Y1 of the values y is 0.60 or more.
In the case where the second organic layer is a layer containing a cross-linked form in which two or more polymer compounds of the second organic layer are cross-linked, a weighted average of the value of (Y1×1000)/X1 determined as to each polymer compound of the second organic layer (average value from the mixing amount ratio of two or more polymer compounds of the second organic layer) is 0.60 or more.
In the case where the second organic layer is a layer containing a cross-linked form in which one or more polymer compounds of the second organic layer are cross-linked, and a polymer compound that does not contain the cross-linking constitutional unit having a cross-linking group, a weighted average of the value of (Y1×1000)/X1 determined as to each polymer compound of the second organic layer and the value of (Y1×1000)/X1 determined as to each polymer compound that does not contain the cross-linking constitutional unit having a cross-linking group (average value from the mixing amount ratio of one or more polymer compounds of the second organic layer and one or more polymer compounds that do not contain the cross-linking constitutional unit having a cross-linking group) is 0.60 or more.
In the second organic layer, examples of the polymer compound that does not contain the cross-linking constitutional unit having a cross-linking group include a polymer compound comprising at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (Y) and a constitutional unit represented by the formula (X).
[Polymer Compound of Second Organic Layer]
It is preferable that the polymer compound of the second organic layer should be a polymer compound comprising a cross-linking constitutional unit having at least one cross-linking group selected from the above Group A of cross-linking groups, because the external quantum efficiency of the light-emitting device according to the present embodiment is excellent.
The cross-linking group selected from the above Group A of cross-linking groups is preferably cross-linking groups represented by the formula (XL-1) to the formula (XL-4), the formula (XL-7) to the formula (XL-10) or the formula (XL-14) to the formula (XL-17), more preferably a cross-linking group represented by the formula. (XL-1), the formula (XL-3), the formula (XL-9), the formula (XL-10), the formula (XL-16) or the formula (XL-17), further preferably a cross-linking group represented by the formula (XL-1), the formula (XL-16) or the formula (XL-17), particularly preferably a cross-linking group represented by the formula (XL-1) or the formula (XL-17), especially preferably a cross-linking group represented by the formula (XL-17), because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
The constitutional unit having at least one cross-linking group selected from the Group A of cross-linking groups, contained in the polymer compound of the second organic layer can be a constitutional unit represented by the formula (2) mentioned later, a constitutional unit represented by the formula (2′) mentioned later, or a constitutional unit represented by the following formula, and a constitutional unit represented by the formula (2) or a constitutional unit represented by the formula (2′) is preferable.
[Constitutional Unit Represented by Formula (2)]
nA represents an integer of 0 to 5 and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 1 or 2, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
n represents 1 or 2 and is preferably 2 because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
Ar3 represents an aromatic hydrocarbon group or a heterocyclic group and is preferably an aromatic hydrocarbon group optionally having a substituent because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
The number of carbon atoms of the aromatic hydrocarbon group represented by Ar3 is usually 6 to 60, preferably 6 to 30, more preferably 6 to 18, which excludes the number of carbon atoms of a substituent.
The arylene group moiety, excluding n substituent(s), of the aromatic hydrocarbon group represented by Ar3 is preferably groups represented by the formula (A-1) to the formula (A-20), more preferably groups represented by the formula (A-1), the formula (A-2), the formula (A-6) to the formula (A-10), the formula (A-19) or the formula (A-20), further preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-7), the formula (A-9) or the formula (A-19). These groups optionally have a substituent.
The number of carbon atoms of the heterocyclic group represented by Ar3 is usually 2 to 60, preferably 3 to 30, more preferably 4 to 18, which excludes the number of carbon atoms of a substituent.
The divalent heterocyclic group moiety, excluding n substituent(s), of the heterocyclic group represented by Ar3 is preferably groups represented by the formula (AA-1) to the formula (AA-34).
The aromatic hydrocarbon group and the heterocyclic group represented by Ar3 optionally have a substituent and an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group and a cyano group are preferable as the substituent.
LA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups optionally have a substituent. R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. The number of carbon atoms of the alkylene group represented by LA is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10, which excludes the number of carbon atoms of a substituent. The number of carbon atoms of the cycloalkylene group represented by LA is usually 3 to 20, which excludes the number of carbon atoms of a substituent.
Examples of the alkylene group represented by LA include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group represented by LA optionally has a substituent, and a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom and a cyano group are preferable as the substituent. These groups optionally further have a substituent.
Examples of the cycloalkylene group represented by LA include a cyclopentylene group and a cyclohexylene group. The cycloalkylene group represented by LA optionally has a substituent, and an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom and a cyano group are preferable as the substituent. These groups optionally further have a substituent.
The arylene group represented by LA optionally has a substituent. A phenylene group or a fluorenediyl group is preferable as the arylene group, and a m-phenylene group, a p-phenylene group, a fluorene-2,7-diyl group, or a fluorene-9,9-diyl group is more preferable. An alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom, a cyano group or a cross-linking group selected from the above-described Group A of cross-linking group is preferable as the substituent optionally carried by the arylene group. These groups optionally further have a substituent.
The divalent heterocyclic group represented by LA is preferably groups represented by the formula (AA-1) to the formula (AA-34).
LA is preferably an arylene group or an alkylene group, more preferably a phenylene group, a fluorenediyl group or an alkylene group because the production of the polymer compound of the second organic layer is easy. These groups optionally have a substituent.
X represents a cross-linking group selected from the above cross-linking group A group. The cross-linking group represented by X is preferably cross-linking groups represented by the formula (XL-1) to the formula (XL-4), the formula (XL-7) to the formula (XL-10) or the formula (XL-14) to the formula (XL-17), more preferably a cross-linking group represented by the formula (XL-1), the formula (XL-3), the formula (XL-9), the formula (XL-10), the formula (XL-16) or the formula (XL-17), further preferably a cross-linking group represented by the formula (XL-1), the formula (XL-16) or the formula (XL-17), particularly preferably a cross-linking group represented by the formula (XL-1) or the formula (XL-17), especially preferably a cross-linking group represented by the formula (XL-17), because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
Only one constitutional unit represented by the formula (2) may be contained in the polymer compound of the second organic layer, or two or more may be contained.
[Constitutional Unit Represented by Formula (2′)]
mA represents an integer of 0 to 5 and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, particularly preferably 0, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
m represents an integer of 1 to 4 and is preferably 1 or 2, more preferably 2, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
c represents an integer of 0 or 1 and is preferably 0 because the production of the polymer compound of the second organic layer is easy, and the external quantum efficiency of the light-emitting device according to the present embodiment is better.
Ar5 represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded to each other. Ar5 is preferably an aromatic hydrocarbon group optionally having a substituent because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
A definition and examples of the arylene group moiety, excluding m substituent(s), of the aromatic hydrocarbon group represented by Ar5 are the same as the definition and the examples of the arylene group represented by ArX2 in the formula (X).
A definition and examples of the divalent heterocyclic group moiety, excluding m substituent(s), of the heterocyclic group represented by Ar5 are the same as the definition and the examples of the divalent heterocyclic group moiety represented by ArX2 in the formula (X).
A definition and examples of the divalent group, excluding m substituent(s), of the group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded to each other, represented by Ar5 are the same as the definition and the examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other, represented by ArX2 in the formula (X).
Ar4 and Ar6 each independently represent an arylene group or a divalent heterocyclic group and are preferably an arylene group optionally having a substituent because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
A definition and examples of the arylene group represented by Ar4 and Ar6 are the same as the definition and the examples of the arylene group represented by ArX1 and ArX3 in the formula (X).
A definition and examples of the divalent heterocyclic group represented by Ar4 and Ar6 are the same as the definition and the examples of the divalent heterocyclic group represented by ArX1 and ArX3 in the formula (X).
Each of Ar4, Ar5 and Ar6 optionally forms a ring by bonding directly or via an oxygen atom or a sulfur atom to a group, other than the group concerned, bonded to the nitrogen atom to which the group concerned is bonded. The groups represented by Ar4, Ar5 and Ar6 optionally have a substituent and an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group and a cyano group are preferable as the substituent.
KA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom. Definitions and examples of the alkylene group, the cycloalkylene group, the arylene group, and the divalent heterocyclic group represented by KA are the same as the definitions and the examples of the alkylene group, the cycloalkylene group, the arylene group, and the divalent heterocyclic group represented by LA, respectively.
It is preferable that KA should be a phenylene group or a methylene group, because the production of the polymer compound of the second organic layer becomes easy.
X′ represents a cross-linking group selected from the above Group A of cross-linking group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A definition and examples of the cross-linking group represented by X′ are the same as the definition and the examples of the cross-linking group represented by X mentioned above.
Only one constitutional unit represented by the formula (2′) may be contained in the polymer compound of the second organic layer, or two or more may be contained.
[Preferable Form of Constitutional Unit Represented by Formula (2) or (2′)]
Examples of the constitutional unit represented by the formula (2) include constitutional units represented by the formula (2-1) to the formula (2-30), and examples of the constitutional unit represented by the formula (2′) include constitutional units represented by the formula (2′-1) to the formula (2′-9). Among these, it is preferably constitutional units represented by the formula (2-1) to the formula (2-30), more preferably constitutional units represented by the formula (2-1) to the formula (2-15), the formula (2-19), the formula (2-20), the formula (2-23), the formula (2-25) or the formula (2-30), further preferably constitutional units represented by the formula (2-1) to the formula (2-9), the formula (2-20), the formula (2-22) or the formula (2-30), because the cross-linking properties of the polymer compound of the second organic layer are excellent.
[Additional Constitutional Unit]
It is preferable that the polymer compound of the second organic layer should further comprise a constitutional unit represented by the formula (X), because the hole-transporting function is excellent. It is also preferable that the polymer compound of the second organic layer should further comprise a constitutional unit represented by the formula (Y), because the external quantum, efficiency of the light-emitting device according to the present embodiment is better.
It is preferable that the polymer compound of the second organic layer should further comprise a constitutional unit represented by the formula (X) and a constitutional unit represented by the formula (Y), because the hole-transporting function is excellent, and the external quantum efficiency of the light-emitting device according to the present embodiment is better.
Definitions, examples and the preferable range of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Y) which may be contained in the polymer compound of the second organic layer are the same as the definitions, the examples and the preferable range of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Y) which may be contained in the polymer host mentioned above, respectively.
In the polymer compound of the second organic layer, each of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Y) may be contained only singly, or two or more may be contained, respectively.
Examples of the polymer compound of the second organic layer include polymer compounds (P-7) to (P-14) shown in Table 2. In this context, “Additional constitutional unit” means a constitutional unit other than the constitutional units represented by the formula (2), the formula (2′), the formula (X) and the formula (Y).
In Table 2, p′, q′, r′, s′ and t′ represent the molar ratio of each constitutional unit. p′+q′+r′+s′+t′=100, and 70≤p′+q′+r′+s′≤100.
In the polymer compounds (P-7) to (P-14), examples and the preferable range of the constitutional units represented by the formula (2), the formula (2′), the formula (X) and the formula (Y) are as mentioned above.
The polymer compound of the second organic layer may be any of a block copolymer, a random copolymer, an alternate copolymer, and a graft copolymer, or may be in other forms, and it is preferable to be a copolymer prepared by copolymerizing a plurality of raw material monomers.
The polystyrene-based number-average molecular weight of the polymer compound of the second organic layer is preferably 5×103 to 1×106, more preferably 1×104 to 5×105, further preferably 1.5×104 to 1×105.
[Method for Producing Polymer Compound of Second Organic Layer]
The polymer compound, of the second organic layer can be produced by the same method as the method for producing the polymer host mentioned above.
[Value of (Y1×1000)/X1]
The value of (Y1×1000)/X1 for the polymer compound of the second organic layer can be determined by the following method.
First, as for each constitutional unit constituting the polymer compound, the value x obtained by multiplying the molar ratio C of the each constitutional unit to total mol of all constitutional units by the molecular weight M of the constitutional unit, and the value y obtained by multiplying the molar ratio C by the number n of the cross-linking group carried by the each constitutional unit are determined. Subsequently, the summation of the value x determined as to the each constitutional unit is defined as X1, and the summation of the value y determined as to the each constitutional unit is defined as Y1.
In this respect, the value of (Y1×1000)/X1 is a value almost equal to the average number of cross-linking groups per molecular weight 1000 of the polymer compound of the second organic layer, and can be effectively used as an index that indicates the average number of cross-linking groups in the polymer compound of the second organic layer.
A specific method for calculating the average number of cross-linking groups will be described in detail by the value of polymer compound HTL-5 used in Example 1 described below.
The polymer compound HTL-5 has constitutional units derived from a compound M3, a compound M4 and a compound M5. The ratio to the total mol of all constitutional units is 0.45 for the constitutional unit derived from the compound M3, 0.05 for the constitutional unit derived from the compound M4, and 0.50 for the constitutional unit derived from the compound M5. The molecular weight of the constitutional unit derived from the compound M3 is 776.45, the molecular weight of the constitutional unit derived from the compound M4 is 240.20, and the molecular weight of the constitutional unit derived from the compound M5 is 750.51. The number of cross-linking groups carried by the constitutional unit derived from the compound M3 is 2, the number of cross-linking groups carried by the constitutional unit derived from the compound M4 is 2, and the number of cross-linking groups carried by the constitutional unit derived from the compound M5 is 0.
Accordingly, X1 is determined as follows:
(0.45×776.45)+(0.05×240.20)+(0.50×750.51)=736.67
Y1 is determined as follows:
(0.45×2)+(0.05×2)+(0.50×0)=1.00
Accordingly, the value of (Y1×1000)/X1 is determined as follows:
(1.00×1000)/736.67=1.36
In the case of containing two or more polymer compounds, the value of (Y1×1000)/X1 is determined on the basis of constitutional units constituting the each polymer compound. Also, the value of (Y1×1000)/X1 is determined as to the each polymer compound, and the value of (Y1×1000)/X1 is determined from the amount ratios of the each polymer compound.
A specific calculation method will be described about the case of mixing polymer compound HTL-1 and polymer compound HTL-2 of Comparative Example CD3 described below at a ratio of 50:50.
The polymer compound HTL-2 has constitutional units derived from a compound M3, a compound M4, a compound M6 and a compound M5. In the polymer compound HTL-2, the ratio to the total mol of all constitutional units is 0.05 for the constitutional unit derived from the compound M3, 0.05 for the constitutional unit derived from the compound M4, 0.40 for the constitutional unit derived from the compound M6, and 0.05 for the constitutional unit derived from the compound M5. The molecular weight of the constitutional unit derived from the compound M3 is 776.45, the molecular weight of the constitutional unit derived from the compound M4 is 240.20, the molecular weight of the constitutional unit derived from the compound M6 is 244.23, and the molecular weight of the constitutional unit derived from the compound M5 is 750.51. The number of cross-linking groups carried by the constitutional unit derived from the compound M3 is 2, the number of cross-linking groups carried by the constitutional unit derived from the compound M4 is 2, the number of cross-linking groups carried by the monomer derived from the compound M6 is 0, and the number of cross-linking groups carried by the constitutional unit derived from the compound M5 is 0. Accordingly, the value of (Y1×1000)/X1 calculated by the method mentioned above as to the polymer compound HTL-2 is 0.38.
The polymer compound HTL-1 has constitutional units derived from the compound M6 and the compound M5. In the polymer compound HTL-1, the ratios to the total mol of all constitutional units are 0.50 for the constitutional unit derived from the compound M6 and 0.50 for the constitutional unit derived from the compound M5. The molecular weight of the constitutional unit derived from the compound M6 is 244.23, and the molecular weight of the constitutional unit derived from the compound M5 is 750.51. The number of cross-linking groups carried by the constitutional unit derived from the compound M6 is 0, and the number of cross-linking groups carried by the constitutional unit derived from the compound M5 is 0. Accordingly, the value of (Y1×1000)/X1 calculated by the method mentioned above as to the polymer compound HTL-1 is 0.
In Comparative Example CD3, the polymer compound HTL-2 and the polymer compound HTL-1 are mixed at a ratio of 50:50. Accordingly, in Comparative Example CD3, the value of (Y1×1000)/X1 can be determined as 0.19 according to the following expression:
0.38×0.5+0×0.5=0.19
The values of (Y1×1000)/X1 of the polymer compound (P0-1) described in Patent Literature 1 and the polymer compound (P0-2) described in Patent Literature 2 mentioned above are calculated as 0.57 and 0, respectively.
In the present embodiment, the value of (Y1×1000)/X1 is preferably 0.69 or more, more preferably 0.85 or more, further preferably 0.95 or more, particularly preferably 1.10 or more, especially preferably 1.20 or more, because the external quantum efficiency of the light-emitting device according to the present embodiment is better. As the value of (Y1×1000)/X1 increases, the second organic layer becomes a closely packed film and the charge-transporting function of the second organic layer and/or charge injection from the second organic layer to the first organic layer is considered to be improved.
In the present embodiment, the value of (Y1×1000)/X1 is usually 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.0 or less, particularly preferably 1.50 or less. By setting the value of (Y1×1000)/X1 to this range, the effects that a flat film is obtained easily and the luminance lifetime of the light-emitting device is more improved are exerted.
In the present embodiment, the value of (Y1×1000)/X1 is preferably 0.85 or more and 4.0 or less, more preferably 0.95 or more and 3.0 or less, further preferably 1.10 or more and 2.0 or less, particularly preferably 1.20 or more and 1.50 or less, because the external quantum efficiency of the light-emitting device according to the present embodiment is better, and the luminance lifetime of the light-emitting device according to the present embodiment is more improved.
[Second Composition]
The second organic layer may be a layer containing a composition comprising the cross-linked form of the polymer compound of the second organic layer and at least one material selected from the group consisting of a hole-transporting material, a hole-injecting material, an electron-transporting material, an electron-injecting material, an antioxidant, and a light-emitting material (hereinafter, also referred to as a “second composition”).
Examples and the preferable range of the hole-transporting material, the electron-transporting material, the hole-injecting material, the electron-injecting material and the light-emitting material contained in the second composition are the same as the examples and the preferable ranges of the hole-transporting material, the electron-transporting material, the hole-injecting material, the electron-injecting material and the light-emitting material contained in the first composition.
In the second composition, each of the amounts of the hole-transporting material, the electron-transporting material, the hole-injecting material, the electron-injecting material and the light-emitting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, with respect to 100 parts by mass of the cross-linked form of the polymer compound of the second organic layer.
Examples and the preferable range of the antioxidant contained in the second composition are the same as the examples and the preferable range of the antioxidant contained in the first composition. In the second composition, the amount of the antioxidant is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the cross-linked form of the polymer compound of the second organic layer.
[Second Ink]
The second composition containing the polymer compound of the second organic layer and a solvent can be used as the second ink for forming the second organic layer. The second ink can be suitably used in the wet method described in the section of the first ink. The preferable range of the viscosity of the second ink is the same as the preferable range of the viscosity of the first ink. Examples and the preferable range of the solvent contained in the second ink are the same as the examples and the preferable range of the solvent contained in the first ink.
In the second ink, the amount of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20000 parts by mass, with respect to 100 parts by mass of the polymer compound of the second organic layer.
<Layer Configuration of Light-Emitting Device>
The light-emitting device according to the present embodiment has: an anode; a cathode; a first organic layer disposed between the anode and the cathode; and a second organic layer disposed, adjacently to the first organic layer, between the anode and the cathode. The light-emitting device according to the present embodiment may comprise a layer other than the anode, the cathode, the first organic layer and the second organic layer.
In the light-emitting device according to the present embodiment, the first organic layer is usually a light-emitting layer (hereinafter, also referred to as a “first light-emitting layer”).
In the light-emitting device according to the present embodiment, the second organic layer is usually a hole-transporting layer, a light-emitting layer (hereinafter, also referred to as a “second light-emitting layer”) or an electron-transporting layer, preferably a hole-transporting layer or the second light-emitting layer, more preferably a hole-transporting layer.
In the light-emitting device according to the present embodiment, it is preferable that the second organic layer should be a layer disposed between the anode and the first organic layer, it is more preferable to be a hole-transporting layer or the second light-emitting layer disposed between the anode and the first organic layer, and it is further preferable to be a hole-transporting layer disposed between the anode and the first organic layer, because the external quantum efficiency of the light-emitting device is better.
In the light-emitting device according to the present embodiment, in the case where the second organic layer is a hole-transporting layer disposed between the anode and the first organic layer, it is preferable to further comprise a hole-injecting layer between the anode and the second organic layer, because the external quantum efficiency of the light-emitting device is better. Also, in the case where the second organic layer is a hole-transporting layer disposed between the anode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of an electron-injecting layer and an electron-transporting layer between the cathode and the first organic layer, because the external quantum efficiency of the light-emitting device is better.
In the light-emitting device according to the present embodiment, in the case where the second organic layer is the second light-emitting layer disposed between the anode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of a hole-injecting layer and a hole-transporting layer between the anode and the second organic layer, because the external quantum efficiency of the light-emitting device is better. Also, in the case where the second organic layer is the second light-emitting layer disposed between the anode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of an electron-injecting layer and an electron-transporting layer between the cathode and the first organic layer, because the external quantum efficiency of the light-emitting device is better.
In the light-emitting device according to the present embodiment, in the case where the second organic layer is the second light-emitting layer disposed between the cathode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of a hole-injecting layer and a hole-transporting layer between the anode and the first organic layer, because the external quantum efficiency of the light-emitting device is better. Also, in the case where the second organic layer is the second light-emitting layer disposed between the cathode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of an electron-injecting layer and an electron-transporting layer between the cathode and the second organic layer, because the external quantum efficiency of the light-emitting device is better.
In the light-emitting device according to the present embodiment, in the case where the second organic layer is an electron-transporting layer disposed between the cathode and the first organic layer, it is preferable to further comprise at least one layer selected from the group of a hole-injecting layer and a hole-transporting layer between the anode and the first organic layer, because the external quantum efficiency of the light-emitting device is better. Also, in the case where the second organic layer is an electron-transporting layer disposed between the cathode and the first organic layer, it is preferable to further have an electron-injecting layer between the cathode and the second organic layer, because the external quantum efficiency of the light-emitting device is better.
Specific examples of the layer configuration of the light-emitting device according to the present embodiment include layer configurations represented by (D1) to (D14) described below. The light-emitting device usually comprises a substrate and the anode may be laminated on the substrate or the cathode may be laminated on the substrate.
(D1) Anode/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/cathode
(D2) Anode/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/cathode
(D3) Anode/hole-injecting layer/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/cathode
(D4) Anode/hole-injecting layer/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-transporting layer/cathode
(D5) Anode/hole-injecting layer/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-injecting layer/cathode
(D6) Anode/hole-injecting layer/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-transporting layer/electron-injecting layer/cathode
(D7) Anode/hole-injecting layer/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/cathode
(D8) Anode/hole-injecting layer/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-transporting layer/cathode
(D9) Anode/hole-injecting layer/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-injecting layer/cathode
(D10) Anode/hole-injecting layer/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-transporting layer/electron-injecting layer/cathode
(D11) Anode/hole-injecting layer/hole-transporting layer/second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)/electron-transporting layer/electron-injecting layer/cathode
(D12) Anode/hole-injecting layer/hole-transporting layer (second organic layer)/first light-emitting layer (first organic layer)/second light-emitting layer/electron-transporting layer/electron-injecting layer/cathode
(D13) Anode/hole-injecting layer/hole-transporting layer/first light-emitting layer (first organic layer)/second light-emitting layer (second organic layer)/electron-transporting layer/electron-injecting layer/cathode
(D14) Anode/hole-injecting layer/hole-transporting layer/first light-emitting layer (first organic layer)/electron-transporting layer (second organic layer)/electron-injecting layer/cathode
In the above (D1) to (D14), “/” means that layers before and after it are adjacently laminated. Specifically, “second light-emitting layer (second organic layer)/first light-emitting layer (first organic layer)” means that the second light-emitting layer (second organic layer) and the first light-emitting layer (first organic layer) are adjacently laminated.
The layer configurations represented by (D3) to (D12) are preferable, and the layer configurations represented by (D7) to (D10) are more preferable, because the external quantum efficiency of the light-emitting device according to the present embodiment is better.
In the light-emitting device according to the present embodiment, two or more of each of the anode, the hole-injecting layer, the hole-transporting layer, the second light-emitting layer, the electron-transporting layer, the electron-injecting layer and the cathode may be provided, if necessary.
In the case where pluralities of anodes, hole-injecting layers, hole-transporting layers, second light-emitting layers, electron-transporting layers, electron-injecting layers and cathodes are present, they are the same or different, respectively.
The thickness of each of the anode, the hole-injecting layer, the hole-transporting layer, the first light-emitting layer, the second light-emitting layer, the electron-transporting layer, the electron-injecting layer and the cathode are usually 1 nm to 1 μm, preferably 2 nm to 500 nm, further preferably 5 nm to 150 nm.
In the light-emitting device according to the present embodiment, the order, number, and thickness of layers to be laminated can be advantageously adjusted in views of the external quantum efficiency and device lifetime of the light-emitting device.
[Second Light-Emitting Layer]
The second light-emitting layer is usually the second organic layer or a layer containing a light-emitting material. In the case where the second light-emitting layer is a layer containing a light-emitting material, examples of the light-emitting material contained in the second light-emitting layer include the light-emitting material which may be contained in the first composition mentioned above. In the second light-emitting layer, one light-emitting material may be contained singly, or two or more may be contained.
In the case where the light-emitting device according to the present embodiment comprises the second light-emitting layer, and neither a hole-transporting layer mentioned later nor an electron-transporting layer mentioned later is the second organic layer, it is preferable that the second light-emitting layer should be the second organic layer.
[Hole-Transporting Layer]
The hole-transporting layer is usually the second organic layer or a layer containing a hole-transporting material. In the case where the hole-transporting layer is a layer containing a hole-transporting material, examples of the hole-transporting material include the hole-transporting material which may be contained in the first composition mentioned above. In the hole-transporting layer, one hole-transporting material may be contained singly, or two or more may be contained.
In the case where the light-emitting device according to the present embodiment comprises a hole-transporting layer, and neither the second light-emitting layer mentioned above nor an electron-transporting layer mentioned later is the second organic layer, it is preferable that the hole-transporting layer should be the second organic layer.
[Electron-Transporting Layer]
The electron-transporting layer is usually the second organic layer or a layer containing an electron-transporting material, preferably a layer containing an electron-transporting material. In the case where the electron-transporting layer is a layer containing an electron-transporting material, examples of the electron-transporting material contained in the electron-transporting layer include the electron-transporting material which may be contained in the first composition mentioned above. In the electron-transporting layer, one electron-transporting material may be contained singly, or two or more may be contained.
[Hole-Injecting Layer and Electron-Injecting Layer]
The hole-injecting layer is a layer containing a hole-injecting material. Examples of the hole-injecting material contained in the hole-injecting layer include the hole-injecting material which may be contained in the first composition mentioned above. In the hole-injecting layer, the hole-injecting material may be contained singly, or two or more may be contained.
The electron-injecting layer is a layer containing an electron-injecting material. Examples of the electron-injecting material contained in the electron-injecting layer include the electron-injecting material which may be contained in the first composition mentioned above. In the electron-injecting layer, the electron-injecting material may be contained singly, or two or more may be contained.
[Substrate/Electrode]
The substrate in the light-emitting device can form an electrode, and can be a substrate that does not chemically change in forming the organic layers, for example, a substrate made of a material such as glass, plastic, or silicon. In the case of using an opaque substrate, it is preferable that an electrode most distant from the substrate should be transparent or semitransparent.
Examples of the material of the anode include conductive metal oxides and semitransparent metals, preferably indium oxide, zinc oxide, and tin oxide; conductive compounds such as indium tin oxide (ITO) and indium zinc oxide; a composite of silver, palladium, and copper (APC); and NESA, gold, platinum, silver, and copper.
Examples of the material of the cathode include: metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, and indium; alloys composed of two or more of them; alloys composed of one or more of them and at least one selected from the group of silver, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; and graphite and graphite intercalation compounds. Examples of the alloys include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
In the light-emitting device according to the present embodiment, at least one of the anode and the cathode is usually transparent or semitransparent, and it is preferable that the anode should be transparent or semitransparent.
Examples of methods for forming the anode and the cathode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method and a lamination method.
[Method for Producing Light-Emitting Device]
In the light-emitting device according to the present embodiment, examples of a method for forming each layer such as the first light-emitting layer, the second light-emitting layer, the hole-transporting layer, the electron-transporting layer, the hole-injecting layer, or the electron-injecting layer include a vacuum deposition method from a powder and a method by film formation from a solution or a melted state in the case of using a low-molecular compound, and include a method by film formation from a solution or a melted state in the case of using a polymer compound.
The first light-emitting layer, the second light-emitting layer, the hole-transporting layer, the electron-transporting layer, the hole-injecting layer and the electron-injecting layer can be formed by a wet method such as a spin coating method or an inkjet printing method using the first ink, the second ink, and inks respectively containing the light-emitting material, the hole-transporting material, the electron-transporting material, the hole-injecting material and the electron-injecting material mentioned above.
[Purpose of Light-Emitting Device]
In order to obtain planar light emission using the light-emitting device, a planar anode and cathode can be arranged so as to overlap. In order to obtain patterned light emission, there is a method of establishing a mask provided with a patterned window on the surface of a planar light-emitting device, a method of forming a layer desired to be a non-light-emitting part as an exceedingly thick film to render the layer substantially non-light-emitting, or a method of forming an anode or a cathode, or both the electrodes in a patterned form. A segment-type display device that can display numbers, characters, etc. is obtained by forming a pattern by any of these methods and arranging some electrodes so as to switch ON and OFF independently. In order to prepare a dot matrix display device, the anode and the cathode can both be formed in a stripe state and orthogonally arranged. Partial color display or multicolor display are made possible by a method of distinctively applying a plurality of kinds of polymer compounds differing in emitted light color, or a method using a color filter or a fluorescence conversion filter. The dot matrix display device may be passively driven and may be actively driven in combination with TFT or the like. These display devices can be used in display screens of computers, televisions, portable terminals, etc. The planar light-emitting device can be suitably used as a planar light source for a backlight of a liquid-crystal display device, or a planar light source for illumination. It can also be used as a curved light source and display device as long as a flexible substrate is used.
Although the present invention will be described below in more detail with reference to Examples, the present invention is not limited by these Examples.
In Examples, the polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of a polymer compound were determined by size exclusion chromatography (SEC) (manufactured by Shimadzu Corp., trade name: LC-10Avp). The measurement conditions of SEC are as follows.
The polymer compound to be measured was dissolved in tetrahydrofuran (THF) at a concentration of approximately 0.05% by mass, and 10 μL was injected into SEC. THF was used as a mobile phase of SEC and injected at a flow rate of 2.0 mL/min. PLgel MIXED-B (manufactured by Polymer Laboratories Ltd.) was used as a column. A UV-VIS detector (manufactured by Shimadzu Corp., trade name: SPD-10Avp) was used as a detector.
In the present Examples, the maximum peak wavelength of an emission spectrum of a compound was measured at room temperature with a spectrophotometer (manufactured by JASCO Corp., trade name: FP-6500). A toluene solution in which the compound was dissolved at a concentration of approximately 0.8×10−4% by mass in xylene was used as a sample. UV light with a wavelength of 325 run was used as excitation light.
<Compounds EM-1 to EM-7, Compound EM-A1 and Compound EM-A2>
Compound EM-1 was synthesized according to the method described in International Publication No. WO 2008/059713.
Compound EM-2 was synthesized according to the method described in Japanese Unexamined Patent Publication No. 2006-176491.
Compound EM-3 was synthesized according to the method described in International Publication No. WO 2005/033051.
Compound EM-4 and compound EM-5 were purchased from Tokyo Chemical Industry Co., Ltd.
Compound EM-6 was synthesized according to the method described in International Publication No. WO 2010/013006.
Compound EM-7 was purchased from Sigma-Aldrich Co. LLC.
Compound EM-A1 was synthesized according to the method described in Japanese Unexamined Patent Publication No. 2011-105643.
Compound EM-A2 was synthesized according to the method described in International Publication No. WO 2007/058368.
The maximum peak wavelength of an emission spectrum of compound EM-1 was 441 nm.
The maximum peak wavelength of an emission spectrum of compound EM-2 was 446 nm.
The maximum peak wavelength of an emission spectrum of compound EM-3 was 453 nm.
The maximum peak wavelength of an emission spectrum of compound EM-4 was 446 nm.
The maximum peak wavelength of an emission spectrum of compound EM-5 was 404 run.
The maximum peak wavelength of an emission spectrum of compound EM-6 was 453 nm.
The maximum peak wavelength of an emission spectrum of compound EM-7 was 448 nm.
The maximum peak wavelength of an emission spectrum of compound EM-A was 454 nm.
The maximum peak wavelength of an emission spectrum of compound EM-A2 was 521 nm.
<Compounds HM-1 and HM-2>
Compound HM-1 was purchased from AK Scientific, Inc.
Compound HM-2 was synthesized according to the method described in Japanese Unexamined Patent Publication No. 2011-100942 and International Publication No. WO 2011/137922.
The maximum peak wavelength of an emission spectrum of compound HIM-1 was 425 nm.
The maximum peak wavelength of an emission spectrum of compound HM-2 was 430 nm.
<Compounds M1 to M6>
Compound M1 was synthesized according to the method described in Japanese Unexamined Patent Publication No. 2012-144721.
Compound M2 employed a commercially available product.
Compound M3 was synthesized according to the method described in International Publication No. WO 2015/145871.
Compound M4 was synthesized according to the method described in International Publication No. WO 2013/146806.
Compound M5 was synthesized according to the method described in International Publication No. WO 2005/049546.
Compound M6 was synthesized according to the method described in Japanese Unexamined Patent Publication No. 2010-189630.
(Step 1) After an inert gas atmosphere was created within a reaction container, compound M1 (1.73 g), compound M2 (0.843 g), dichlorobis[tris(2-methoxyphenyl)phosphine]palladium (2.2 mg) and toluene (40 ml) were added and heated to 105° C.
(Step 2) An aqueous solution containing 20% by mass of tetraethylammonium hydroxide (8.7 g) was added dropwise to the obtained reaction solution and refluxed for 3 hours.
(Step 3) Then, 9-bromoanthracene (64.1 mg), an aqueous solution containing 20% by mass of tetraethylammonium hydroxide (8.8 g) and dichlorobis[tris(2-methoxyphenyl)phosphine]palladium (2.2 mg) were added thereto and refluxed for 16 hours.
(Step 4) Then, an aqueous sodium diethyldithiacarbamate solution was added thereto and stirred at 80° C. for 2 hours. The obtained reaction solution was cooled and then washed twice with water, twice with an aqueous solution containing 3% by mass of acetic acid and twice with water, and as a result of adding the obtained solution dropwise to methanol, precipitates were formed. The precipitates were dissolved in toluene and purified by passing the solution through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol, and as a result of stirring, precipitates were formed. The precipitates were collected by filtration and dried to thereby obtain 0.91 g of polymer compound HP-1. Mn of the polymer compound HP-1 was 1.2×105, and Mw was 4.8×105.
The polymer compound HP-1 is a copolymer in which a constitutional unit derived from compound M1 and a constitutional unit derived from compound M2 are constituted at a molar ratio of 50:50, in terms of a theoretical value determined from the amounts of the added raw materials.
Polymer compound HTL-1 was synthesized according to the method described in International Publication No. WO 2015/194448 using compound M5 and compound M6.
Mn of the polymer compound HTL-1 was 4.5×104, and Mw was 1.5×105.
The polymer compound HTL-1 is a copolymer in which a constitutional unit derived from compound M5 and a constitutional unit derived from compound M6 are constituted at a molar ratio of 50:50, in terms of a theoretical value determined from the contents of the added raw materials. As for the polymer compound HTL-1, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.
(Step 1) After an inert gas atmosphere was created within a reaction container, compound M3 (0.130 g), compound M4 (0.0620 g), compound M6 (0.493 g), compound M5 (1.15 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.2 mg) and toluene (30 mL) were added and heated to 105° C.
(Step 2), An aqueous solution containing 20% by mass of tetraethylammonium hydroxide (8.3 mL) was added dropwise to the reaction solution and refluxed for 6 hours.
(Step 3) Then, phenylboronic acid (61.0 mg) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.1 mg) were added thereto and refluxed for 14.5 hours.
(Step 4) Then, an aqueous sodium diethyldithiacarbamate solution was added thereto and stirred at 80° C. for 2 hours. After cooling, the obtained reaction solution was washed twice with water, twice with an aqueous solution containing 3% by mass of acetic acid and twice with water, and as a result of adding the obtained solution dropwise to methanol, precipitates were formed. The obtained precipitates were dissolved in toluene and purified by passing the solution through an alumina column and a silica gel column in order. The obtained solution was added dropwise to methanol and stirred, and then, the obtained precipitates were collected by filtration and dried to thereby obtain 1.05 g of polymer compound HTL-2.
Mn of the polymer compound HTL-2 was 2.4×104, and Mw was 1.8×105.
The polymer compound HTL-2 is a copolymer in which a constitutional unit derived from compound M3, a constitutional unit derived from compound M4, a constitutional unit derived from compound M6, and a constitutional unit derived from compound M5 are constituted at a molar ratio of 5:5:40:50, in terms of a theoretical value determined from the contents of the added raw materials. As for the polymer compound HTL-2, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.38.
0.92 g of polymer compound HTL-3 was obtained by the same method as in the above synthesis of the polymer compound HTL-2 except that: (Step 1) in the synthesis of the polymer compound HTL-2 was changed to (Step 1-1) described below; (Step 2) was changed to (Step 2-1) described below; and (Step 3) was changed to (Step 3-1) described below.
(Step 1-1) After an inert gas atmosphere was created within a reaction container, compound M3 (0.311 g), compound M4 (0.0496 g), compound M6 (0.295 g), compound M5 (0.917 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.76 mg) and toluene (30 mL) were added and heated to 105° C.
(Step 2-1) An aqueous solution containing 20% by mass of tetraethylammonium hydroxide (6.7 mL) was added dropwise to the reaction solution and refluxed for 6 hours.
(Step 3-1) Then, phenylboronic acid (48.8 mg) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (0.88 mg) were added thereto and refluxed for 14.5 hours.
Mn of the polymer compound HTL-3 was 2.5×104, and Mw was 1.3×105.
The polymer compound HTL-3 is a copolymer in which a constitutional unit derived from compound M3, a constitutional unit derived from compound M4, a constitutional unit derived from compound M6, and a constitutional unit derived from compound M5 are constituted at a molar ratio of 15:5:30:50, in terms of a theoretical value determined from the contents of the added raw materials. As for the polymer compound HTL-3, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.69.
0.92 g of polymer compound HTL-4 was obtained by the same method as in the above synthesis of the polymer compound HTL-3 except that (Step 1-1) in the synthesis of the polymer compound HTL-3 was changed to (Step 1-2) described below.
(Step 1-2) After an inert gas atmosphere was created within a reaction container, compound M3 (0.518 g), compound M4 (0.0496 g), compound M6 (0.195 g), compound M5 (0.917 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (1.76 mg) and toluene (30 mL) were added and heated to 105° C.
Mn of the polymer compound HTL-4 was 2.5×104, and Mw was 3.0×105.
The polymer compound HTL-4 is a copolymer in which a constitutional unit derived from compound M3, a constitutional unit derived from compound M4, a constitutional unit derived from compound M6, and a constitutional unit derived from compound M5 are constituted at a molar ratio of 25:5:20:50, in terms of a theoretical value determined from the contents of the added raw materials. As for the polymer compound HTL-4, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.95.
Polymer compound HTL-5 was synthesized according to the method described in International Publication No. WO 2015/145871 using compound M3, compound M4 and compound M5.
Mn of the polymer compound HTL-5 was 2.3×104, and Mw was 1.2×105.
The polymer compound HTL-5 is a copolymer in which a constitutional unit derived from compound M3, a constitutional unit derived from compound M4, and a constitutional unit derived from compound M5 are constituted at a molar ratio of 45:5:50, in terms of a theoretical value determined from the contents of the added raw materials. As for the polymer compound HTL-5, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 1.36.
An ITO film was attached at a thickness of 45 nm to a glass substrate by the sputtering method to thereby form an anode. A film of a hole-injecting material ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) was formed at a thickness of 35 nm on the anode by the spin coating method. In an air atmosphere, a hole-injecting layer was formed by heating at 50° C. for 3 minutes and further heating at 230° C. for 15 minutes.
(Formation of Second Organic Layer)
Polymer compound HTL-5 was dissolved at a concentration of 0.6% by mass in xylene. A film was formed at a thickness of 20 nm on the hole-injecting layer by the spin coating method using the obtained xylene solution, and in a nitrogen gas atmosphere, a second organic layer was formed by heating at 180° C. for 60 minutes on a hot plate. The polymer compound HTL-5 became a cross-linked form by this heating.
(Formation of First Organic Layer)
Compound HM-1 and compound EM-A1 (compound HM-1/compound EM-A1=91.5% by mass/8.5% by mass) were dissolved at a concentration of 2% by mass in toluene. A film was formed at a thickness of 60 nm on the second organic layer by the spin coating method using the obtained toluene solution, and in a nitrogen gas atmosphere, a first organic layer was formed by heating at 150° C. for 10 minutes on a hot plate.
(Formation of Cathode)
The substrate with the first organic layer formed was placed in a vapor deposition machine, and after pressure reduction to 1×10−4 Pa or lower, sodium fluoride as a cathode was deposited at approximately 4 nm on the first organic layer, and subsequently, aluminum was deposited at approximately 80 nm on the sodium fluoride layer. After the deposition, the resultant was sealed using a glass substrate to thereby prepare light-emitting device D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D1. The external quantum efficiency at 200 cd/m2 was 2.99%, and the CIE chromaticity coordinate (x,y) was (0.14,0.18).
Light-emitting device D2 was prepared in the same way as in Example D1 except that polymer compound HTL-4 was used instead of the polymer compound HTL-5 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D2. The external quantum efficiency at 200 cd/m2 was 2.87%, and the CIE chromaticity coordinate (x,y) was (0.14,0.18).
Light-emitting device D3 was prepared in the same way as in Example D1 except that polymer compound HTL-3 was used instead of the polymer compound HTL-5 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D3. The external quantum efficiency at 200 cd/m2 was 2.32%, and the CIE chromaticity coordinate (x,y) was (0.14,0.17).
Light-emitting device CD1 was prepared in the same way as in Example D1 except that polymer compound HTL-2 and polymer compound HTL-3 (polymer compound HTL-2/polymer compound HTL-3=45% by mass/55% by mass) were used instead of the polymer compound HTL-5 in Example D1. As for one in which the above polymer compound HTL-2 and polymer compound HTL-3 were mixed at a ratio of 45:55, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.55.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD1. The external quantum efficiency at 200 cd/m2 was 1.77%, and the CIE chromaticity coordinate (x,y) was (0.14,0.17).
Light-emitting device CD2 was prepared in the same way as in Example D1 except that polymer compound HTL-2 was used instead of the polymer compound i-TL-5 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD2. The external quantum efficiency at 200 cd/m2 was 1.38%, and the CIE chromaticity coordinate (x,y) was (0.14,0.16).
Light-emitting device CD3 was prepared in the same way as in Example D1 except that polymer compound HTL-1 and polymer compound HTL-2 (polymer compound HTL-1/polymer compound HTL-2=50% by mass/50% by mass) were used instead of the polymer compound HTL-5 in Example D1. As for one in which the above polymer compound HTL-1 and polymer compound HTL-2 were mixed at a ratio of 50:50, the value of (Y1×1000)/X1 was calculated by the method mentioned above and was consequently 0.19.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD3. The external quantum efficiency at 200 cd/m2 was 0.89%, and the CIE chromaticity coordinate (x,y) was (0.14,0.17).
Light-emitting device CD4 was prepared in the same way as in Example D1 except that polymer compound HTL-1 was used instead of the polymer compound HTL-5 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD4. The external quantum efficiency at 200 cd/m2 was 0.75%, and the CIE chromaticity coordinate (x,y) was (0.14,0.17).
The results of Examples and Comparative Examples are shown in Table 3.
An ITO film was attached at a thickness of 45 nm to a glass substrate by the sputtering method to thereby form an anode. A film of a hole-injecting material ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) was formed at a thickness of 35 nm on the anode by the spin coating method. In an air atmosphere, a hole-injecting layer was formed by heating at 50° C. for 3 minutes and further heating at 230° C. for 15 minutes.
(Formation of Second Organic Layer)
Polymer compound HTL-5 was dissolved at a concentration of 0.6% by mass in xylene. A film was formed at a thickness of 20 nm on the hole-injecting layer by the spin coating method using the obtained xylene solution, and in a nitrogen gas atmosphere, a second organic layer was formed by heating at 180° C. for 60 minutes on a hot plate. The polymer compound HTL-5 became a cross-linked form by this heating.
(Formation of First Organic Layer)
Compound HM-1 and compound EM-1 (compound HM-1/compound EM-1=91.5% by mass/8.5% by mass) were dissolved at a concentration of 2% by mass in toluene. A film was formed at a thickness of 60 nm on the second organic layer by the spin coating method using the obtained toluene solution, and in a nitrogen gas atmosphere, a first organic layer was formed by heating at 150° C. for 10 minutes on a hot plate.
(Formation of Cathode)
The substrate with the first organic layer formed was placed in a vapor deposition machine, and after pressure reduction to 1.0×10−4 Pa or lower, sodium fluoride as a cathode was deposited at approximately 4 nm on the first organic layer, and subsequently, aluminum was deposited at approximately 80 nm on the sodium fluoride layer. After the deposition, the resultant was sealed using a glass substrate to thereby prepare light-emitting device D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D4. The external quantum efficiency at 50 cd/m2 was 2.33%, and the CIE chromaticity coordinate (x,y) was (0.16,0.22).
Light-emitting device D5 was prepared in the same way as in Example D4 except that polymer compound HTL-4 was used instead of the polymer compound HTL-5 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D5. The external quantum efficiency at 50 cd/m2 was 2.28%, and the CIE chromaticity coordinate (x,y) was (0.16,0.23).
Light-emitting device D6 was prepared in the same way as in Example D4 except that polymer compound HTL-3 was used instead of the polymer compound HTL-5 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D6. The external quantum efficiency at 50 cd/m2 was 2.06%, and the CIE chromaticity coordinate (x,y) was (0.16,0.21).
Light-emitting device D7 was prepared in the same way as in Example D4 except that compound EM-2 was used instead of the compound EM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D7. The external quantum efficiency at 50 cd/m2 was 2.03%, and the CIE chromaticity coordinate (x,y) was (0.16,0.22).
Light-emitting device D8 was prepared in the same way as in Example D4 except that compound EM-3 was used instead of the compound EM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D8. The external quantum efficiency at 50 cd/m2 was 1.63%, and the CIE chromaticity coordinate (x,y) was (0.18,0.28).
Light-emitting device D9 was prepared in the same way as in Example D4 except that compound EM-4 was used instead of the compound EM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D9. The external quantum efficiency at 50 cd/m2 was 1.53%, and the CIE chromaticity coordinate (x,y) was (0.17,0.24).
Light-emitting device D10 was prepared in the same way as in Example D4 except that polymer compound HP-1 was used instead of the compound HM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D10. The external quantum efficiency at 50 cd/m2 was 3.74%, and the CIE chromaticity coordinate (x,y) was (0.15,0.16).
Light-emitting device D11 was prepared in the same way as in Example D4 except that compound HM-2 was used instead of the compound HM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D11. The external quantum efficiency at 50 cd/m2 was 2.69%, and the CIE chromaticity coordinate (x,y) was (0.16,0.22).
Light-emitting device CD5 was prepared in the same way as in Example D4 except that polymer compound HTL-1 was used instead of the polymer compound HTL-5 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD5. The external quantum efficiency at 50 cd/m2 was 0.33%, and the CIE chromaticity coordinate (x,y) was (0.16,0.19).
The results of Examples and Comparative Example are shown in Table 4.
Light-emitting device D12 was prepared in the same way as in Example D1 except that compound EM-A2 was used instead of the compound EM-A1 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D12. The external quantum efficiency at 400 cd/m2 was 2.00%, and the CIE chromaticity coordinate (x,y) was (0.27,0.64).
Light-emitting device D13 was prepared in the same way as in Example D12 except that polymer compound HTL-4 was used instead of the polymer compound HTL-5 in Example D12.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D13. The external quantum efficiency at 400 cd/m2 was 1.69%, and the CIE chromaticity coordinate (x,y) was (0.27,0.64).
Light-emitting device CD6 was prepared in the same way as in Example D12 except that polymer compound HTL-2 and polymer compound HTL-3 (polymer compound HTL-2/polymer compound HTL-3=45% by mass/55% by mass) were used instead of the polymer compound HTL-5 in Example D12.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD6. The external quantum efficiency at 400 cd/m2 was 0.45%, and the CIE chromaticity coordinate (x,y) was (0.27,0.64).
Light-emitting device CD7 was prepared in the same way as in Example D12 except that polymer compound HTL-2 was used instead of the polymer compound HTL-5 in Example D12.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD7. The external quantum efficiency at 400 cd/m2 was 0.59%, and the CIE chromaticity coordinate (x,y) was (0.27,0.64).
Light-emitting device CD8 was prepared in the same way as in Example D12 except that polymer compound HTL-1 was used instead of the polymer compound HTL-5 in Example D12.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD8. The external quantum efficiency at 400 cd/m2 was 0.62%, and the CIE chromaticity coordinate (x,y) was (0.27,0.64).
Light-emitting device D14 was prepared in the same way as in Example D1 except that compound EM-5 was used instead of the compound EM-A1 in Example D1.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D14. The external quantum efficiency at 400 cd/m2 was 1.24%, and the CIE chromaticity coordinate (x,y) was (0.16,0.22).
Light-emitting device D15 was prepared in the same way as in Example D14 except that polymer compound HTL-3 was used instead of the polymer compound HTL-5 in Example D14.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D15. The external quantum efficiency at 400 cd/m2 was 1.07%, and the CIE chromaticity coordinate (x,y) was (0.16,0.23).
Light-emitting device CD9 was prepared in the same way as in Example D14 except that polymer compound HTL-1 was used instead of the polymer compound HTL-5 in Example D14.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device CD9. The external quantum efficiency at 400 cd/m2 was 0.60%, and the CIE chromaticity coordinate (x,y) was (0.16,0.24).
The results of Examples and Comparative Examples are shown in Table 5.
Light-emitting device D16 was prepared in the same way as in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D16. The external quantum efficiency at 1000 cd/m2 was 2.30%, and the CIE chromaticity coordinate (x,y) was (0.16,0.22).
Light-emitting device D17 was prepared in the same way as in Example D4 except that compound EM-6 was used instead of the compound EM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D17. The external quantum efficiency at 1000 cd/m2 was 1.78%, and the CIE chromaticity coordinate (x,y) was (0.14,0.18).
Light-emitting device D18 was prepared in the same way as in Example D4 except that compound EM-7 was used instead of the compound EM-1 in Example D4.
(Evaluation of Light-Emitting Device)
EL emission was observed by applying voltage to the light-emitting device D18. The external quantum efficiency at 1000 cd/m2 was 1.37%, and the CIE chromaticity coordinate (x,y) was (0.16,0.19).
According to the present invention, a light-emitting device excellent in external quantum efficiency can be provided.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-065572 | Mar 2016 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/012225 | 3/27/2017 | WO | 00 |
