WO2015033894A1 - カルバゾール誘導体、これを用いた有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 - Google Patents
カルバゾール誘導体、これを用いた有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 Download PDFInfo
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- 0 *c1c(*(c(c-2c(*)c(*)c3*)c3O*)N)c-2c(*)c(*)c1* Chemical compound *c1c(*(c(c-2c(*)c(*)c3*)c3O*)N)c-2c(*)c(*)c1* 0.000 description 9
- XWCJKMVFQOEGMU-UHFFFAOYSA-N C(C1c2ccccc22)=CC=CC1N2c(cc(c(c1c2cccc1)c1)[n]2-c2nc(-c3ccccc3)nc(-[n]3c(ccc(-c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)c4)c4c4ccccc34)n2)c1-[n]1c(cccc2)c2c2c1cccc2 Chemical compound C(C1c2ccccc22)=CC=CC1N2c(cc(c(c1c2cccc1)c1)[n]2-c2nc(-c3ccccc3)nc(-[n]3c(ccc(-c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)c4)c4c4ccccc34)n2)c1-[n]1c(cccc2)c2c2c1cccc2 XWCJKMVFQOEGMU-UHFFFAOYSA-N 0.000 description 1
- BAQFMRFAMFWQNT-UHFFFAOYSA-N C(c1nc(-[n](c(cccc2)c2c2c3)c2cc(-[n]2c4ccccc4c4c2cccc4)c3-[n]2c(cccc3)c3c3c2cccc3)nc(-c2cccc(-c(cc3)cc(c4c5cccc4)c3[n]5-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)c2)n1)=C1/c(ccc(-c(cc2)cc(c3c4cccc3)c2[n]4-c2ccccc2)c2)c2-c2ccccc12 Chemical compound C(c1nc(-[n](c(cccc2)c2c2c3)c2cc(-[n]2c4ccccc4c4c2cccc4)c3-[n]2c(cccc3)c3c3c2cccc3)nc(-c2cccc(-c(cc3)cc(c4c5cccc4)c3[n]5-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)c2)n1)=C1/c(ccc(-c(cc2)cc(c3c4cccc3)c2[n]4-c2ccccc2)c2)c2-c2ccccc12 BAQFMRFAMFWQNT-UHFFFAOYSA-N 0.000 description 1
- AWNPHBLOKZZIEM-UHFFFAOYSA-N CC(C)(c(cccc1)c1-c1c2)c1cc([n](c1c3)-c4ccccc4)c2c1cc(-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c3-[n]1c(cccc2)c2c2c1cccc2 Chemical compound CC(C)(c(cccc1)c1-c1c2)c1cc([n](c1c3)-c4ccccc4)c2c1cc(-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c3-[n]1c(cccc2)c2c2c1cccc2 AWNPHBLOKZZIEM-UHFFFAOYSA-N 0.000 description 1
- QNGVEVOZKYHNGL-UHFFFAOYSA-N Clc1nc(-c2ccccc2)cc(-c2ccccc2)n1 Chemical compound Clc1nc(-c2ccccc2)cc(-c2ccccc2)n1 QNGVEVOZKYHNGL-UHFFFAOYSA-N 0.000 description 1
- PXZXMMIEQSCQFU-UHFFFAOYSA-N N#Cc(cc1)ccc1-[n](c(cccc1)c1c1c2)c1ccc2-c(cc1c2c3cccc2)ccc1[n]3-c1ccccc1 Chemical compound N#Cc(cc1)ccc1-[n](c(cccc1)c1c1c2)c1ccc2-c(cc1c2c3cccc2)ccc1[n]3-c1ccccc1 PXZXMMIEQSCQFU-UHFFFAOYSA-N 0.000 description 1
- JWWRKJLEOXMFPQ-UHFFFAOYSA-N Nc(c(N)c1)cc(-c2ccccc2)c1[N+]([O-])=O Chemical compound Nc(c(N)c1)cc(-c2ccccc2)c1[N+]([O-])=O JWWRKJLEOXMFPQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Oc1ccccc1 Chemical compound Oc1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VKIUNMBRSXEUHM-UHFFFAOYSA-N c(cc1)cc(c2c3)c1[nH]c2cc(-[n]1c(cccc2)c2c2ccccc12)c3-[n]1c2ccccc2c2c1cccc2 Chemical compound c(cc1)cc(c2c3)c1[nH]c2cc(-[n]1c(cccc2)c2c2ccccc12)c3-[n]1c2ccccc2c2c1cccc2 VKIUNMBRSXEUHM-UHFFFAOYSA-N 0.000 description 1
- BYLQVKIJSWCDKG-UHFFFAOYSA-N c(cc1)cc-2c1-c1ccc(-c3cc(-[n](c4ccccc4c4c5)c4cc(-[n]4c6ccccc6c6c4cccc6)c5-[n]4c(cccc5)c5c5c4cccc5)ccc3)c3c1c-2ccc3 Chemical compound c(cc1)cc-2c1-c1ccc(-c3cc(-[n](c4ccccc4c4c5)c4cc(-[n]4c6ccccc6c6c4cccc6)c5-[n]4c(cccc5)c5c5c4cccc5)ccc3)c3c1c-2ccc3 BYLQVKIJSWCDKG-UHFFFAOYSA-N 0.000 description 1
- BYXNNGDCWAYING-UHFFFAOYSA-N c(cc1)ccc1-[n](c1c2)c(cc(c(-[n]3c(cccc4)c4c4c3cccc4)c3)-[n]4c(cccc5)c5c5ccccc45)c3c1cc1c2[s]c2ccccc12 Chemical compound c(cc1)ccc1-[n](c1c2)c(cc(c(-[n]3c(cccc4)c4c4c3cccc4)c3)-[n]4c(cccc5)c5c5ccccc45)c3c1cc1c2[s]c2ccccc12 BYXNNGDCWAYING-UHFFFAOYSA-N 0.000 description 1
- DSQNGFAXOPZMPY-UHFFFAOYSA-N c(cc1)ccc1-[n](c1c2c(-c(cc3)cc4c3c(cccc3)c3[o]4)cc(-c3cccc4c3[s]c3ccccc43)c1)c1c2c(cccc2)c2c2c1cccc2 Chemical compound c(cc1)ccc1-[n](c1c2c(-c(cc3)cc4c3c(cccc3)c3[o]4)cc(-c3cccc4c3[s]c3ccccc43)c1)c1c2c(cccc2)c2c2c1cccc2 DSQNGFAXOPZMPY-UHFFFAOYSA-N 0.000 description 1
- KDUDVWZHWNPMAF-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(cc(c(-[n]2c(cccc3)c3c3c2cccc3)c2)-[n]3c(cccc4)c4c4c3cccc4)c2c2c(cccc3)c3ccc12 Chemical compound c(cc1)ccc1-[n]1c(cc(c(-[n]2c(cccc3)c3c3c2cccc3)c2)-[n]3c(cccc4)c4c4c3cccc4)c2c2c(cccc3)c3ccc12 KDUDVWZHWNPMAF-UHFFFAOYSA-N 0.000 description 1
- CXIDESGALLWGRL-UHFFFAOYSA-N c(cc1)ccc1-[n]1c2cc(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)nc(-c(cc3)ccc3-[n]3c4ccccc4c4ccccc34)c2c2ccccc12 Chemical compound c(cc1)ccc1-[n]1c2cc(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)nc(-c(cc3)ccc3-[n]3c4ccccc4c4ccccc34)c2c2ccccc12 CXIDESGALLWGRL-UHFFFAOYSA-N 0.000 description 1
- RWUQEWZYGQVAEH-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c(cc1c(c2c3)cc(-[n]4c5ccccc5c5c4cccc5)c3-[n]3c4ccccc4c4c3cccc4)ccc1[n]2-c1ccccc1 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c(cc1c(c2c3)cc(-[n]4c5ccccc5c5c4cccc5)c3-[n]3c4ccccc4c4c3cccc4)ccc1[n]2-c1ccccc1 RWUQEWZYGQVAEH-UHFFFAOYSA-N 0.000 description 1
- PDKMRVIZYKEFMP-UHFFFAOYSA-N c(cc1)ccc1-c(cc1c(cc2-[n]3c4cnccc4c4c3cccc4)c3cc2-[n]2c4cnccc4c4c2cccc4)ccc1[n]3-c1ccccc1 Chemical compound c(cc1)ccc1-c(cc1c(cc2-[n]3c4cnccc4c4c3cccc4)c3cc2-[n]2c4cnccc4c4c2cccc4)ccc1[n]3-c1ccccc1 PDKMRVIZYKEFMP-UHFFFAOYSA-N 0.000 description 1
- SCZKERQJVOBXDJ-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n](c2ccccc2c2c3)c2cc(-[n]2c(cccc4)c4c4c2cccc4)c3-[n]2c3ccccc3c3c2cccc3)nc(-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n](c2ccccc2c2c3)c2cc(-[n]2c(cccc4)c4c4c2cccc4)c3-[n]2c3ccccc3c3c2cccc3)nc(-c2ccccc2)c1 SCZKERQJVOBXDJ-UHFFFAOYSA-N 0.000 description 1
- XDIVGLHETLKZAT-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c(cc2)ccc2-[n](c(cccc2)c2c2c3)c2cc(-[n]2c4ccccc4c4c2cccc4)c3-[n]2c(cccc3)c3c3c2cccc3)nc(-c2ccccc2)n1 Chemical compound c(cc1)ccc1-c1nc(-c(cc2)ccc2-[n](c(cccc2)c2c2c3)c2cc(-[n]2c4ccccc4c4c2cccc4)c3-[n]2c(cccc3)c3c3c2cccc3)nc(-c2ccccc2)n1 XDIVGLHETLKZAT-UHFFFAOYSA-N 0.000 description 1
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Definitions
- the present invention relates to a carbazole derivative, a material for an organic electroluminescence device using the carbazole derivative, an organic electroluminescence device using the same, and an electronic apparatus.
- an organic electroluminescence (EL) element is composed of an anode, a cathode, and one or more organic thin film layers sandwiched between the anode and the cathode.
- a voltage is applied between both electrodes, electrons from the cathode side and holes from the anode side are injected into the light emitting region, and the injected electrons and holes recombine in the light emitting region to generate an excited state, which is excited.
- Light is emitted when the state returns to the ground state.
- organic EL elements can be obtained in various light emitting colors by using various light emitting materials for the light emitting layer, and therefore, researches for practical application to displays and the like are active. In particular, research on light emitting materials of the three primary colors of red, green, and blue is the most active, and intensive research has been conducted with the aim of improving characteristics.
- Patent Documents 1 and 2 disclose compounds in which carbazole is further bonded to positions 1 and 3 of carbazole.
- development of new material systems is required in order to further improve device performance.
- the present invention has been made to solve the above-described problems, and an object thereof is to provide a novel material useful as a material for an organic EL element.
- A represents a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms.
- X 1 represents N or CH
- X 2 to X 4 each represents N or CR.
- R and B 1 to B 3 each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a saturated or unsaturated ring structure. When there are a plurality of R, each may be the same or different. At least two of B 1 to B 3 are represented by the following formula (2).
- n is an integer from 0 to 4.
- L represents a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms, or a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms.
- Y represents NZ, O, S, CR′R ′′.
- R 1 to R 8 , Z, R ′ and R ′′ each independently represents a single bond, a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a saturated or unsaturated ring structure.
- R 1 and R 8 are hydrogen atoms.
- any one of R 1 to R 8 , Z, R ′, and R ′′ represents a single bond that is bonded to L, and when n is 0, the formulas (1) and (2) The bond is a single bond.
- n is 2 or more, a plurality of L may be the same or different, and L may be bonded to each other to form a saturated or unsaturated ring structure.
- a material for an organic electroluminescence device containing the carbazole derivative [2] A material for an organic electroluminescence device containing the carbazole derivative. [3] In an organic electroluminescence device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, at least one of the organic thin film layers is an organic material containing the carbazole derivative. Electroluminescence element. [4] An electronic device including the organic electroluminescence element. [5] A carbazole derivative represented by the following formula (10).
- a ′ represents a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms.
- X 1 and X 5 represent N or CH
- X 2 to X 4 and X 6 to X 8 represent N or CR, respectively.
- R and B 1 to B 6 each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a saturated or unsaturated ring structure.
- At least two of B 1 to B 3 are represented by the following formula (2).
- n is an integer from 0 to 4.
- L represents a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms, or a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms.
- Y represents NZ, O, S, CR′R ′′.
- R 1 to R 8 , Z, R ′ and R ′′ each independently represents a single bond, a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a saturated or unsaturated ring structure.
- R 1 and R 8 are hydrogen atoms.
- any one of R 1 to R 8 , Z, R ′, and R ′′ represents a single bond that is bonded to L, and when n is 0, the formulas (10) and (2) The bond is a single bond.
- n is 2 or more, a plurality of L may be the same or different, and L may be bonded to each other to form a saturated or unsaturated ring structure.
- the present invention provides a novel material useful as a material for an organic EL element and an organic EL element using the same.
- carbon number ab in the expression “substituted or unsubstituted X group having carbon number ab” represents the number of carbons when X group is unsubstituted, The carbon number of the substituent when substituted is not included. Further, when a ring is formed by adjacent substituents, the ring is separated at a position where the carbon number of one substituent is the smallest within the range of a to b, and the carbon number of the other substituent is also a Structures within the range of ⁇ b are included.
- Numberer of ring-forming carbons refers to the ring itself of a compound having a structure in which atoms or molecules are bonded in a ring (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a spiro ring compound, a carbocyclic compound, or a heterocyclic compound). Represents the number of carbon atoms among the atoms constituting When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons.
- the “ring-forming carbon number” described below is the same unless otherwise specified.
- “Number of ring-forming atoms” means the ring itself of a compound having a structure in which atoms or molecules are bonded in a ring (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a spiro ring compound, a carbocyclic compound, or a heterocyclic compound) Represents the number of atoms constituting the.
- An atom that does not constitute a ring for example, a hydrogen atom that terminates the dangling bond of an atom that constitutes a ring
- an atom contained in a substituent when the ring is substituted by a substituent is included in the number of ring-forming atoms Absent.
- the “number of ring-forming atoms” described below is the same unless otherwise specified.
- hydroxogen atom includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (deuterium) and tritium (tritium).
- an optional substituent when referred to as “substituted or unsubstituted” is an alkyl group having 1 to 50 carbon atoms (preferably 1 to 18 and more preferably 1 to 8); 3 to 50 ring carbon atoms (preferably A cycloalkyl group having 3 to 10, more preferably 3 to 8, and further preferably 5 or 6; an aryl group having 6 to 50 ring carbon atoms (preferably 6 to 25, more preferably 6 to 18); ring formation An aralkyl group having 7 to 51 (preferably 7 to 30, more preferably 7 to 20) carbon atoms having an aryl group having 6 to 50 carbon atoms (preferably 6 to 25, more preferably 6 to 18); an amino group; It is selected from an alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8) and an aryl group having 6 to 50 ring carbon atoms (preferably 6 to 25, more preferably 6 to 18).
- carbazole derivative which is one embodiment of the present invention is represented by the following (1).
- A represents a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms.
- X 1 represents N or CH
- X 2 to X 4 each represents N or CR.
- R and B 1 to B 3 each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a saturated or unsaturated ring structure. When there are a plurality of R, each may be the same or different. At least two of B 1 to B 3 are represented by the following formula (2).
- n is an integer of 0-4.
- L represents a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms, or a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms.
- Show. Y represents NZ, O, S, CR′R ′′.
- R 1 to R 8 , Z, R ′ and R ′′ each independently represents a single bond, a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a saturated or unsaturated ring structure.
- R 1 and R 8 are hydrogen atoms.
- any one of R 1 to R 8 , Z, R ′, and R ′′ represents a single bond that is bonded to L, and when n is 0, the formulas (1) and (2) The bond is a single bond.
- n is 2 or more, a plurality of L may be the same or different, and L may be bonded to each other to form a saturated or unsaturated ring structure.
- the group represented by the formula (2) is preferably any two of B 1 to B 3 , and combinations thereof are (B 1 , B 2 ), (B 1 , B 3 ). , (B 2 , B 3 ), and (B 1 , B 2 ) are preferred.
- Y is NZ.
- n is preferably 0 or 1, and 1 is more preferable.
- a carbazole derivative in which the formula (1) is represented by the following formula (3) is preferable.
- R 11 to R 18 are represented in the same manner as R 1 to R 8 above.
- carbazole derivatives of the following formula (4) or (5) are particularly preferable.
- X 11 to X 13 each independently represent CR 51 or N, provided that at least one of X 11 to X 13 is N.
- R 19 to R 20 and R 51 each independently represent a hydrogen atom or a substituent. When there are a plurality of R 51 , each may be the same or different.
- the carbazole derivative which is one embodiment of the present invention may be represented by the following formula (10).
- a ′ represents a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms.
- X 1 and X 5 represent N or CH
- X 2 to X 4 and X 6 to X 8 represent N or CR, respectively.
- R and B 1 to B 6 each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a saturated or unsaturated ring structure. When there are a plurality of R, each may be the same or different.
- At least two of B 1 to B 3 are represented by the above formula (2).
- it is preferable that at least two of B 1 to B 3 are represented by the following formula (2), and at least two of B 4 to B 6 are represented by the above formula (2).
- the carbazole derivative represented by the formula (10) is preferably represented by the following formula (11).
- X 11 to X 13 each independently represents CR 51 or N.
- R 1 to R 8 , R 11 to R 18 , R 31 to R 38 and R 41 to R 48 are: The same as R 1 to R 8 in the formula (1).
- R 51 represents a hydrogen atom or a substituent. When there are a plurality of R 51 , each may be the same or different.
- the above formula (2) is preferably represented by the following formula (2-1), more preferably represented by the following formula (2-2), and further preferably represented by the following formula (2-3). .
- R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , R 41 to R 48 , R 51 , Z, R ′ and R ′′ are each independently preferably a hydrogen atom or a substituent selected from the following group (A), and selected from a hydrogen atom or the following group (B):
- the substituent is more preferably a hydrogen atom or a substituent selected from the following group (C).
- the group (A) is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 to 60 aryl groups (synonymous with “aromatic hydrocarbon group”, the same shall apply hereinafter), substituted or unsubstituted aralkyl groups having 7 to 61 carbon atoms, amino groups, substituted or unsubstituted alkyl groups having 1 to 50 carbon atoms, and Mono- or di-substituted amino group having a substituent selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted ring Aryloxy group having 6 to 60 carbon atoms, substituted or unsubsti
- the group (B) is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted ring group having 6 to 6 carbon atoms.
- aryl groups substituted or unsubstituted aralkyl groups having 7 to 51 carbon atoms, amino groups, substituted or unsubstituted alkyl groups having 1 to 50 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 60 ring carbon atoms
- the group (C) is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 to 60 aryl groups, substituted or unsubstituted aralkyl groups having 7 to 51 carbon atoms, amino groups, substituted or unsubstituted alkyl groups having 1 to 50 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 60 ring carbon atoms A mono- or di-substituted amino group having a substituent selected from the group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms and a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms A mono-substituted, di-substituted or tri-substituted silyl
- alkyl group having 1 to 50 carbon atoms examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group.
- Examples of the cycloalkyl group having 3 to 50 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo A heptyl group, a cyclooctyl group, an adamantyl group etc. are mentioned, A cyclopentyl group and a cyclohexyl group are preferable.
- Examples of the aryl group having 6 to 60 ring carbon atoms include, for example, a phenyl group, a naphthyl group, a naphthylphenyl group, and a biphenylyl group.
- Terphenylyl group acenaphthylenyl group, anthryl group, benzoanthryl group, aceanthryl group, phenanthryl group, benzophenanthryl group, phenalenyl group, fluorenyl group, 9,9'-spirobifluorenyl group, benzofluorenyl Group, dibenzofluorenyl group, picenyl group, pentaphenyl group, pentacenyl group, pyrenyl group, chrycenyl group, benzocricenyl group, s-indanyl group, as-indanyl group, fluoranthenyl group, benzofluoranthenyl group, tetracenyl group , Triphenylenyl group, benzotriphenylenyl group Perylenyl group, coronyl group, dibenzoanthryl group, 9,9-dimethylfluorenyl group, 9,9-dipheny
- the heteroaryl group having 5 to 60 ring atoms is at least 1, preferably 1 to 5 (more preferably 1 to 3, more preferably (Preferably 1 to 2) heteroatoms such as nitrogen, sulfur, oxygen and phosphorus atoms.
- heteroaryl group include pyrrolyl group, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group.
- Examples of the aralkyl group having 7 to 61 carbon atoms in total having an aryl group having 6 to 60 ring carbon atoms (preferably 6 to 25, more preferably 6 to 18) include the above aralkyl groups having an aryl group.
- the alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8) and the aryl group having 6 to 60 ring carbon atoms (preferably 6 to 25, more preferably 6 to 18) are selected.
- Examples of the mono-substituted or di-substituted amino group having a substituent include a mono-substituted or di-substituted amino group having a substituent selected from the above alkyl group and the above aryl group. More preferred are disubstituted amino groups having a substituent selected from the group.
- Examples of the alkoxy group having an alkyl group having 1 to 50 carbon atoms include the above alkoxy groups having an alkyl group, and for example, a methoxy group and an ethoxy group are preferable.
- Examples of the aryloxy group having an aryl group having 6 to 60 ring carbon atoms include the above aryloxy groups having an aryl group, such as a phenoxy group. Is mentioned.
- Examples of the alkylthio group having an alkyl group having 1 to 50 carbon atoms include the above alkylthio groups having an alkyl group.
- Examples of the arylthio group having an aryl group having 6 to 60 ring carbon atoms include the above arylthio groups having an aryl group.
- alkyl group having 1 to 50 carbon atoms preferably 1 to 18, more preferably 1 to 8
- an aryl group having 6 to 60 ring carbon atoms preferably 6 to 25, more preferably 6 to 18.
- Examples of the mono-substituted, di-substituted or tri-substituted silyl group having a substituent include mono-substituted, di-substituted or tri-substituted silyl groups having a substituent selected from the above alkyl group and the above aryl group.
- a trimethyl silyl group examples include triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, triphenylsilyl group, phenyldimethylsilyl group, t-butyldiphenylsilyl group, and tolylsilylsilyl group. It is done.
- haloalkyl group having 1 to 50 carbon atoms preferably 1 to 18, more preferably 1 to 8
- at least one hydrogen atom of the alkyl group is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine). And those substituted by an atom).
- alkyl group having 1 to 50 carbon atoms preferably 1 to 18, more preferably 1 to 8
- the aryl group having 6 to 60 ring carbon atoms preferably 6 to 25, more preferably 6 to 18
- the sulfonyl group having a selected substituent include a sulfonyl group having a substituent selected from the above alkyl group and the above aryl group. From the alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8) and the aryl group having 6 to 60 ring carbon atoms (preferably 6 to 25, more preferably 6 to 18).
- Examples of the disubstituted phosphoryl group having a selected substituent include a disubstituted phosphoryl group having a substituent selected from the above alkyl group and the above aryl group.
- Examples of the alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyl-substituted or aryl-substituted carbonyl group include groups each having a substituent selected from the alkyl group and the aryl group. It is done.
- a fluorine atom, a cyano group, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a disubstituted amino group are particularly preferable.
- examples of the substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms represented by A include R and B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31. Examples thereof are the same as the aryl groups of the substituents represented by -R 38 , R 41 -R 48 , R 51 , Z, R 'and R''.
- Examples of the substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms represented by A include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , R Examples similar to the heteroaryl group of the substituent represented by 41 to R 48 , R 51 , Z, R ′ and R ′′ are given.
- Examples of the substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms represented by A ′ include R, B 1 to B 3 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , A heteroarylene group in which the example of the heteroaryl group of the substituent represented by R 41 to R 48 , R 51 , Z, R ′, and R ′′ is divalent is given.
- examples of the substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms represented by L include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31.
- An arylene group in which the examples of the aryl group of the substituent represented by ⁇ R 38 , R 41 ⁇ R 48 , R 51 , Z, R ′ and R ′′ are divalent is given.
- Examples of the substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms represented by L include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , R
- Examples of the heteroaryl group as a substituent represented by 41 to R 48 , R 51 , Z, R ′ and R ′′ include a divalent heteroarylene group.
- Examples of the substituted or unsubstituted alkylene group having 1 to 50 carbon atoms represented by L include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , and R 41 to R.
- Examples of the alkyl group of the substituent represented by 48 , R 51 , Z, R ′ and R ′′ include a divalent alkylene group.
- R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , R 41 to R 48 , R 51 , Z, R ′ and R ′′ may be formed by bonding adjacent substituents to each other as a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms, substituted or unsubstituted Examples thereof include an unsubstituted heteroaryl group having 5 to 60 ring atoms.
- Examples of the substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , and R 41 to R 48.
- R 51 , Z, R ′ and R ′′ are the same examples as the aryl group of the substituent.
- Examples of the substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms include R, B 1 to B 6 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , and R 41 to R. Examples thereof are the same as the heteroaryl groups of the substituents represented by 48 , R 51 , Z, R ′ and R ′′.
- the carbazole derivative according to an embodiment of the present invention preferably has a ring structure-containing group as a substituent, and particularly preferably A has a ring structure-containing group.
- the carbazole derivative has a ring structure-containing group, when it is used as a material for an organic EL device, the organic thin film containing the material has an excellent film quality.
- ring structure-containing group examples include substituted or unsubstituted cycloalkyl groups having 5 to 60 (preferably 3 to 6, more preferably 5 or 6) ring-forming carbon atoms, and substituted or unsubstituted ring-forming carbon atoms having 6 to 60 carbon atoms.
- aryl groups substituted or unsubstituted aryl groups having 6 to 60 (preferably 6 to 24, more preferably 6 to 18) ring-forming carbon atoms
- a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms is preferable.
- the ring structure-containing group include those having a ring structure-containing group on a substituent, and specific examples of this substituent include those described above.
- A is particularly preferably a group represented by the following formula (I), more preferably a group represented by the following formula (II) or a group represented by the following formula (III).
- L 1 represents a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
- R 10 represents a hydrogen atom or a substituent.
- s is an integer of 1 to 5. When s is 2 or more, the plurality of R 10 may be the same or different. * Indicates a binding position. ]
- R 10 represents a hydrogen atom or a substituent. s is an integer of 1 to 5. When s is 2 or more, the plurality of R 10 may be the same or different. * Indicates a binding position. ]
- L 1 represents a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
- X 11 to X 13 each represent CR 51 or a nitrogen atom. However, at least one of X 11 to X 13 is N.
- R 51 and R 19 to R 20 each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a saturated or unsaturated ring structure. When there are a plurality of R 51 , each may be the same or different. * Indicates a binding position.
- adjacent substituents that may be formed by bonding to each other include a substituted or unsubstituted ring-forming carbon number of 6 to 60. Or a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms.
- R 10 R, B 1 to B 3 , R 1 to R 8 , R 11 to R 20 , R 31 to R 38 , R 41 to R 48
- R 19 to R 20 and R 51 are R, B 1 to B 3 , R 1 to R 8 , R 11 to R 18 , R 31 to R 38 , R 41 to R. 48 , Z, R ′ and R ′′ are similar.
- R 51 is more preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. More preferably, each of R 19 to R 20 independently represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 forming atoms. .
- the carbazole derivative which is one embodiment of the present invention described above is useful as a material for an organic EL device.
- the method for producing the carbazole derivative which is one embodiment of the present invention described above is not particularly limited, and those skilled in the art can easily produce the carbazole derivative by utilizing and modifying known synthetic reactions while referring to the examples of the present specification. can do.
- the material for an organic EL device includes the carbazole derivative.
- the content of the carbazole derivative in the organic EL device material of one embodiment of the present invention is not particularly limited, and may be, for example, 1% by mass or more, preferably 10% by mass or more, and 50% by mass or more. More preferably, it is more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
- the carbazole derivative and the material for an organic EL device according to an embodiment of the present invention are useful as a material in an organic EL device, for example, a host material and a dopant material in a light emitting layer of a fluorescent light emitting unit, and a light emitting layer of a phosphorescent light emitting unit. It can be used as a host material.
- the light emitting layer contains the carbazole derivative of one embodiment of the present invention and a fluorescent light emitting material or a phosphorescent light emitting material.
- an anode-side organic thin film layer provided between the anode of the organic EL element and the light emitting layer, or a cathode provided between the cathode of the organic EL element and the light emitting layer.
- a material for the side organic thin film layer that is, a material such as a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
- the “light emitting unit” refers to a minimum unit that includes one or more organic layers, one of which is a light emitting layer, and can emit light by recombination of injected holes and electrons.
- An organic EL device includes an organic thin film layer containing a light emitting layer between a cathode and an anode, and at least one of the organic thin film layers includes the above-described organic EL device material. It is characterized by that.
- the organic thin film layer containing the organic EL element material described above include an anode-side organic thin film layer (hole transport layer, hole injection layer, etc.) provided between the anode and the light emitting layer, a light emitting layer, and a cathode.
- Examples include, but are not limited to, a cathode side organic thin film layer (electron transport layer, electron injection layer, etc.), a space layer, a barrier layer and the like provided between the light emitting layer and the light emitting layer.
- the above-mentioned organic EL element material may be contained in any of the above layers.
- the organic EL device of one embodiment of the present invention may be a fluorescent or phosphorescent monochromatic light emitting device, a fluorescent / phosphorescent hybrid white light emitting device, or a simple type having a single light emitting unit.
- a tandem type having a plurality of light emitting units may be used, and among them, a phosphorescent type is preferable.
- the “light emitting unit” refers to a minimum unit that includes one or more organic layers, one of which is a light emitting layer, and can emit light by recombination of injected holes and electrons.
- typical element configurations of simple organic EL elements include the following element configurations.
- Anode / light emitting unit / cathode The above light emitting unit may be a laminated type having a plurality of phosphorescent light emitting layers and fluorescent light emitting layers. In that case, the light emitting unit is generated by a phosphorescent light emitting layer between the light emitting layers. In order to prevent the excitons from diffusing into the fluorescent light emitting layer, a space layer may be provided. A typical layer structure of the light emitting unit is shown below.
- A Hole transport layer / light emitting layer (/ electron transport layer)
- B Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer (/ electron transport layer)
- C Hole transport layer / phosphorescent layer / space layer / fluorescent layer (/ electron transport layer)
- D Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
- E Hole transport layer / first phosphorescent light emitting layer / space layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
- F Hole transport layer / phosphorescent layer / space layer / first fluorescent layer / second fluorescent layer (/ electron transport layer)
- G Hole transport layer / electron barrier layer / light emitting layer (/ electron transport layer)
- H Hole transport layer / light emitting layer / hole barrier layer (
- Each phosphorescent or fluorescent light-emitting layer may have a different emission color.
- hole transport layer / first phosphorescent light emitting layer (red light emitting) / second phosphorescent light emitting layer (green light emitting) / space layer / fluorescent light emitting layer (blue light emitting) / Examples include a layer configuration such as an electron transport layer.
- An electron barrier layer may be appropriately provided between each light emitting layer and the hole transport layer or space layer.
- a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer.
- the following element structure can be mentioned as a typical element structure of a tandem type organic EL element.
- the intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and has electrons in the first light emitting unit and holes in the second light emitting unit.
- a known material structure to be supplied can be used.
- FIG. 1 shows a schematic configuration of an example of an organic EL element according to an embodiment of the present invention.
- the organic EL element 1 includes a substrate 2, an anode 3, a cathode 4, and a light emitting unit 10 disposed between the anode 3 and the cathode 4.
- the light emitting unit 10 includes a light emitting layer 5 including at least one phosphorescent light emitting layer including a phosphorescent host material and a phosphorescent dopant (phosphorescent material).
- electron injection / transport layer (cathode-side organic thin film layer) 7 between the light-emitting layer 5 and the cathode 4 May be formed.
- an electron barrier layer may be provided on the anode 3 side of the light emitting layer 5
- a hole barrier layer may be provided on the cathode 4 side of the light emitting layer 5.
- a host combined with a fluorescent dopant is referred to as a fluorescent host
- a host combined with a phosphorescent dopant is referred to as a phosphorescent host.
- the fluorescent host and the phosphorescent host are not distinguished only by the molecular structure. That is, the phosphorescent host means a material constituting a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean that it cannot be used as a material constituting a fluorescent light emitting layer. The same applies to the fluorescent host.
- the organic EL element of one embodiment of the present invention is produced on a translucent substrate.
- the light-transmitting substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm to 700 nm of 50% or more.
- a glass plate, a polymer plate, etc. are mentioned.
- the glass plate include those using soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like as raw materials.
- the polymer plate include those using polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like as raw materials.
- the anode of the organic EL element plays a role of injecting holes into the hole transport layer or the light emitting layer, and it is effective to use a material having a work function of 4.5 eV or more.
- Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like.
- the anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When light emitted from the light emitting layer is extracted from the anode, it is preferable that the transmittance of light in the visible region of the anode is greater than 10%.
- the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 nm to 200 nm.
- the cathode plays a role of injecting electrons into the electron injection layer, the electron transport layer or the light emitting layer, and is preferably formed of a material having a small work function.
- the cathode material is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy and the like can be used.
- the cathode can be produced by forming a thin film by a method such as vapor deposition or sputtering. Moreover, you may take out light emission from the cathode side as needed.
- An organic layer having a light emitting function includes a host material and a dopant material.
- the host material mainly has a function of encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. It has a function.
- the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
- the light emitting layer employs, for example, a double host (also referred to as host / cohost) that adjusts the carrier balance in the light emitting layer by combining an electron transporting host and a hole transporting host. Also good. Moreover, you may employ
- the above light-emitting layer is a laminate in which a plurality of light-emitting layers are stacked, so that electrons and holes are accumulated at the light-emitting layer interface, and the recombination region is concentrated at the light-emitting layer interface to improve quantum efficiency. Can do.
- the ease of injecting holes into the light emitting layer may be different from the ease of injecting electrons, and the hole transport ability and electron transport ability expressed by the mobility of holes and electrons in the light emitting layer may be different. May be different.
- the phosphorescent dopant (phosphorescent material) that forms the light emitting layer is a compound that can emit light from the triplet excited state, and is not particularly limited as long as it emits light from the triplet excited state, but Ir, Pt, Os, Au, Cu, An organometallic complex containing at least one metal selected from Re and Ru and a ligand is preferable.
- the ligand preferably has an ortho metal bond.
- a metal complex containing a metal atom selected from Ir, Os and Pt is preferred in that the phosphorescent quantum yield is high and the external quantum efficiency of the light emitting device can be further improved, and an iridium complex, an osmium complex, or a platinum complex.
- iridium complexes and platinum complexes are more preferable, and orthometalated iridium complexes are particularly preferable.
- the content of the phosphorescent dopant in the light emitting layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 0.1 to 70% by mass, more preferably 1 to 30% by mass. If the phosphorescent dopant content is 0.1% by mass or more, sufficient light emission can be obtained, and if it is 70% by mass or less, concentration quenching can be avoided.
- a complex represented by the following formula (X) is preferable as the phosphorescent dopant.
- R 0 is independently a hydrogen atom or a substituent, k is an integer of 1 to 8, and t is an integer of 2 to 4. M is Ir, Os, or Pt. .)
- R 0 examples include the same examples as the substituent of formula (1).
- the phosphorescent host is a compound having a function of efficiently emitting the phosphorescent dopant by efficiently confining the triplet energy of the phosphorescent dopant in the light emitting layer.
- the carbazole derivative or organic EL device material of one embodiment of the present invention is useful as a phosphorescent host, but compounds other than the organic EL device material of one embodiment of the present invention can also be used as a phosphorescent host in accordance with the above purpose. It can be selected appropriately.
- the organic EL device material of one embodiment of the present invention is not limited to the application to the phosphorescent host.
- the organic EL device material of one embodiment of the present invention and other compounds may be used in combination as a phosphorescent host material in the same light emitting layer.
- the organic EL device material of one embodiment of the present invention is used as the phosphorescent host material of the layer, and a compound other than the organic EL device material of one embodiment of the present invention is used as the phosphorescent host material of another light emitting layer. Also good.
- the organic EL device material of one embodiment of the present invention can be used for an organic layer other than the light emitting layer. In that case, the organic EL device of one embodiment of the present invention is used as a phosphorescent host of the light emitting layer. A compound other than the element material may be used.
- Specific examples of compounds other than the organic EL device material of one embodiment of the present invention and suitable as a phosphorescent host include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives.
- metal complexes such as polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, etc.
- metal complexes such as polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, etc.
- examples thereof include polymer compounds.
- a phosphorescent host may be used independently and may use 2 or more types together. Specific examples include the following compounds.
- the organic EL device of one embodiment of the present invention may have a light emitting layer containing a fluorescent light emitting material, that is, a fluorescent light emitting layer.
- a fluorescent light emitting layer known fluorescent light emitting materials can be used.
- the fluorescent material is preferably at least one selected from anthracene derivatives, fluoranthene derivatives, styrylamine derivatives and arylamine derivatives, and more preferably anthracene derivatives and arylamine derivatives.
- an anthracene derivative is preferable as the host material
- an arylamine derivative is preferable as the dopant.
- suitable materials described in International Publication No. 2010/134350 and International Publication No. 2010/134352 are selected.
- the material for an organic EL device according to one embodiment of the present invention may be used as a fluorescent light emitting material of a fluorescent light emitting layer or as a host material of a fluorescent light emitting layer.
- the organic EL device of one embodiment of the present invention preferably has an electron donating dopant in the interface region between the cathode and the light emitting unit. According to such a configuration, it is possible to improve the light emission luminance and extend the life of the organic EL element.
- the electron donating dopant means a material containing a metal having a work function of 3.8 eV or less, and specific examples thereof include alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earths. Examples thereof include at least one selected from metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and the like.
- alkali metal examples include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like.
- a function of 2.9 eV or less is particularly preferable. Of these, K, Rb, and Cs are preferred, Rb and Cs are more preferred, and Cs is most preferred.
- alkaline earth metals include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), and the like. The thing below 9 eV is especially preferable.
- rare earth metals examples include Sc, Y, Ce, Tb, Yb, and the like, and those having a work function of 2.9 eV or less are particularly preferable.
- alkali metal compound examples include alkali oxides such as Li 2 O, Cs 2 O, and K 2 O, and alkali halides such as LiF, NaF, CsF, and KF, and LiF, Li 2 O, and NaF are preferable.
- alkaline earth metal compound examples include BaO, SrO, CaO, and Ba x Sr 1-x O (0 ⁇ x ⁇ 1), Ba x Ca 1-x O (0 ⁇ x ⁇ 1) mixed with these. BaO, SrO, and CaO are preferable.
- the rare earth metal compound, YbF 3, ScF 3, ScO 3, Y 2 O 3, Ce 2 O 3, GdF 3, TbF 3 and the like, YbF 3, ScF 3, TbF 3 are preferable.
- the alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as each metal ion contains at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion.
- the ligands include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl thiadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, ⁇ -diketones, azomethines, and derivatives thereof are preferred, but not limited thereto.
- the electron donating dopant it is preferable to form a layered or island shape in the interface region.
- a forming method while depositing an electron donating dopant by resistance heating vapor deposition, an organic compound (light emitting material or electron injecting material) that forms an interface region is simultaneously deposited, and the electron donating dopant is dispersed in the organic compound.
- the electron donating dopant is formed in a layered form
- the reducing dopant is vapor-deposited by a resistance heating vapor deposition method. .1 nm to 15 nm.
- the electron donating dopant is formed in an island shape
- the electron donating dopant is deposited by resistance heating vapor deposition alone, preferably The island is formed with a thickness of 0.05 nm to 1 nm.
- the electron transport layer is an organic layer formed between the light emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light emitting layer.
- an organic layer close to the cathode may be defined as an electron injection layer.
- the electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit.
- the carbazole derivative and the organic EL device material of one embodiment of the present invention can also be used as an electron transport material contained in the electron transport layer (second charge transport layer).
- an aromatic heterocyclic compound containing at least one hetero atom in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable.
- the nitrogen-containing ring derivative is preferably an aromatic ring having a nitrogen-containing 6-membered ring or 5-membered ring skeleton, or a condensed aromatic ring compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton.
- a nitrogen-containing ring metal chelate complex represented by the following formula (A) is preferable.
- R 101 to R 106 in formula (A) are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms. , An aryloxy group having 6 to 50 carbon atoms, an alkoxycarbonyl group, or an aromatic heterocyclic group having 5 to 50 ring carbon atoms, which may be substituted.
- Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
- the amino group which may be substituted include an alkylamino group, an arylamino group and an aralkylamino group.
- the alkylamino group and the aralkylamino group are represented as —NQ 1 Q 2 .
- Q 1 and Q 2 each independently represents an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 1 to 20 carbon atoms.
- One of Q 1 and Q 2 may be a hydrogen atom or a deuterium atom.
- the arylamino group is represented by —NAr 1 ′ Ar 2 ′, and Ar 1 ′ and Ar 2 ′ each independently represent a non-condensed aromatic hydrocarbon group or a condensed aromatic hydrocarbon group having 6 to 50 carbon atoms.
- Ar 1 and Ar 2 may be a hydrogen atom or a deuterium atom.
- the hydrocarbon group having 1 to 40 carbon atoms includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
- the alkoxycarbonyl group is represented as —COOY ′, and Y ′ represents an alkyl group having 1 to 20 carbon atoms.
- M is aluminum (Al), gallium (Ga) or indium (In), and is preferably In.
- L 100 is a group represented by the following formula (A ′) or (A ′′).
- R 107 to R 111 are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other are cyclic structures May be formed.
- R 112 to R 126 are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms.
- An annular structure may be formed.
- the hydrocarbon group having 1 to 40 carbon atoms represented by R 107 to R 126 in formula (A ′) and formula (A ′′) is the same as the hydrocarbon group represented by R 101 to R 106 in formula (A).
- the divalent group includes a tetramethylene group, a pentamethylene group, a hexamethylene group, and a diphenylmethane-2,2′-diyl group.
- 8-hydroxyquinoline or a metal complex of its derivative, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative is preferable.
- a metal chelate oxinoid compound containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), for example, tris (8-quinolinol) aluminum is used.
- 8-quinolinol or 8-hydroxyquinoline a metal chelate oxinoid compound containing a chelate of oxine
- tris (8-quinolinol) aluminum is used.
- an oxadiazole derivative the following can be mentioned.
- Ar 17 , Ar 18 , Ar 19 , Ar 21 , Ar 22 and Ar 25 each represent a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 carbon atoms
- Ar 17 and Ar 18 , Ar 19 and Ar 21 , Ar 22 and Ar 25 may be the same or different.
- the aromatic hydrocarbon group or the condensed aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group.
- substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyano groups.
- Ar 20 , Ar 23, and Ar 24 each represent a substituted or unsubstituted divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 60 carbon atoms, and Ar 23 and Ar 24 are identical to each other. But it can be different.
- the divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group.
- substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyano groups.
- electron transfer compounds those having good thin film forming properties are preferably used.
- Specific examples of these electron transfer compounds include the following.
- the nitrogen-containing heterocyclic derivative as the electron transfer compound is a nitrogen-containing heterocyclic derivative composed of an organic compound having the following formula, and includes a nitrogen-containing compound that is not a metal complex. Examples thereof include a 5-membered ring or 6-membered ring containing a skeleton represented by the following formula (B) and a structure represented by the following formula (C).
- X 1 represents a carbon atom or a nitrogen atom.
- Z 1 and Z 2 each independently represents an atomic group capable of forming a nitrogen-containing heterocycle.
- the nitrogen-containing heterocyclic derivative is more preferably an organic compound having a nitrogen-containing aromatic polycyclic group consisting of a 5-membered ring or a 6-membered ring. Further, in the case of such a nitrogen-containing aromatic polycyclic group having a plurality of nitrogen atoms, the nitrogen-containing compound having a skeleton in which the above formulas (B) and (C) or the above formula (B) and the following formula (D) are combined. Aromatic polycyclic organic compounds are preferred.
- the nitrogen-containing group of the nitrogen-containing aromatic polycyclic organic compound is selected from, for example, nitrogen-containing heterocyclic groups represented by the following formulae.
- R ′ ′′ represents an aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 40 carbon atoms, an aromatic heterocyclic group or condensed aromatic heterocyclic group having 3 to 40 carbon atoms, carbon An alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, n 1 is an integer of 0 to 5, and n 1 is an integer of 2 or more, a plurality of R ′ ′′ They may be the same or different.
- preferred specific compounds include nitrogen-containing heterocyclic derivatives represented by the following formula (D1). HAr-L 101 -Ar 101 -Ar 102 (D1)
- HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group having 3 to 40 carbon atoms
- L 101 is a single bond, substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms.
- HAr is selected from the following group, for example.
- L 101 is selected from the following group, for example.
- Ar 101 is selected from, for example, groups represented by the following formulas (D2) and (D3).
- R 201 to R 214 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number.
- Ar 103 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, a condensed aromatic hydrocarbon group or a substituted or unsubstituted aromatic group having 3 to 40 carbon atoms It is a heterocyclic group or a condensed aromatic heterocyclic group.
- Ar 102 is selected from the following group, for example.
- the following compounds are also preferably used as the nitrogen-containing aromatic polycyclic organic compound as the electron transporting compound.
- R 211 to R 214 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic group having 3 to 20 carbon atoms.
- X 21 and X 22 each independently represents an oxygen atom, Represents a sulfur atom or a dicyanomethylene group.
- the following compounds are also preferably used as the electron transfer compound.
- R 221 , R 222 , R 223 and R 224 are the same or different groups, and are an aromatic hydrocarbon group or a condensed aromatic hydrocarbon group represented by the following formula (D6) It is.
- R 225 , R 226 , R 227 , R 228 and R 229 are the same or different from each other, and are a hydrogen atom, a saturated or unsaturated C 1-20 alkoxyl group, saturated or An unsaturated alkyl group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms. At least one of R 225 , R 226 , R 227 , R 228 and R 229 is a group other than a hydrogen atom.
- the electron transfer compound may be a polymer compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative.
- the electron transport layer of the organic EL device of one embodiment of the present invention particularly preferably contains at least one nitrogen-containing heterocyclic derivative represented by the following formulas (E) to (G).
- Z 201 , Z 202 and Z 203 each independently represents a nitrogen atom or a carbon atom.
- R 301 and R 302 each independently represents a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, substituted or unsubstituted carbon An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.
- v is an integer of 0 to 5, and when v is an integer of 2 or more, the plurality of R 301 may be the same as or different from each other. Two adjacent R 301s may be bonded to each other to form a substituted or unsubstituted hydrocarbon ring.
- Ar 201 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.
- Ar 202 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted Alternatively, it is an unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.
- Ar 201 and Ar 202 are a substituted or unsubstituted condensed aromatic hydrocarbon ring group having 10 to 50 ring carbon atoms or a substituted or unsubstituted condensed aromatic group having 9 to 50 ring atoms. It is a heterocyclic group.
- Ar 203 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms.
- L 201 , L 202 and L 203 are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a divalent divalent having 9 to 50 ring atoms which are substituted or unsubstituted.
- aryl group having 6 to 50 ring carbon atoms examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, chrysenyl group, pyrenyl group, biphenyl group, terphenyl group, tolyl group, fluoranthenyl group, fluorenyl Group and the like.
- heteroaryl group having 5 to 50 ring atoms examples include pyrrolyl group, furyl group, thienyl group, silolyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, imidazolyl group, pyrimidyl group, carbazolyl group, selenophenyl Group, oxadiazolyl group, triazolyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinoxalinyl group, acridinyl group, imidazo [1,2-a] pyridinyl group, imidazo [1,2-a] pyrimidinyl group and the like.
- Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
- Examples of the haloalkyl group having 1 to 20 carbon atoms include groups obtained by substituting one or more hydrogen atoms of the alkyl group with at least one halogen atom selected from fluorine, chlorine, iodine and bromine.
- Examples of the alkoxy group having 1 to 20 carbon atoms include groups having the above alkyl group as an alkyl moiety.
- Examples of the arylene group having 6 to 50 ring carbon atoms include groups obtained by removing one hydrogen atom from the aryl group.
- Examples of the divalent condensed aromatic heterocyclic group having 9 to 50 ring atoms include groups obtained by removing one hydrogen atom from the condensed aromatic heterocyclic group described as the heteroaryl group.
- the thickness of the electron transport layer is not particularly limited, but is preferably 1 nm to 100 nm. Moreover, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative as a component of the electron injection layer that can be provided adjacent to the electron transport layer. If the electron injection layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved.
- an insulator it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved.
- preferable alkali metal chalcogenides include, for example, Li 2 O, K 2 O, Na 2 S, Na 2 Se, and Na 2 O
- preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS and CaSe.
- preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl.
- preferable alkaline earth metal halides include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 and BeF 2 , and halides other than fluorides.
- the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film. If the electron injection layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides.
- the preferred thickness of the layer is about 0.1 nm to 15 nm. Moreover, even if the electron injection layer in the organic EL element of one embodiment of this invention contains the above-mentioned electron-donating dopant, it is preferable.
- an organic layer close to the anode may be defined as a hole injection layer.
- the hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit.
- the carbazole derivative and the organic EL device material of one embodiment of the present invention can also be used as a hole transport material contained in the hole transport layer (first charge transport layer).
- an aromatic amine compound for example, an aromatic amine derivative represented by the following formula (H) is preferably used.
- Ar 211 to Ar 214 are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 50 ring carbon atoms or condensed aromatic hydrocarbon groups, substituted or unsubstituted ring forming atoms having 5 to 5 atoms.
- L 211 represents a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring forming atom number of 5 to 5. Represents 50 aromatic heterocyclic groups or condensed aromatic heterocyclic groups.
- An aromatic amine represented by the following formula (J) is also preferably used for forming the hole transport layer.
- the hole transport layer of the organic EL device of one embodiment of the present invention may have a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).
- the thickness of the hole transport layer is not particularly limited, but is preferably 10 to 200 nm.
- a layer containing an acceptor material may be bonded to the positive hole transport layer or the anode side of the first hole transport layer. This is expected to reduce drive voltage and manufacturing costs.
- the acceptor material a compound represented by the following formula (K) is preferable.
- R 311 to R 316 may be the same as or different from each other, and each independently represents a cyano group, —CONH 2 , carboxyl group, or —COOR 317 (R 317 has 1 to 20 carbon atoms) Represents an alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, provided that one or two or more pairs of R 311 and R 312 , R 313 and R 314 , and R 315 and R 316 are taken together— A group represented by CO—O—CO— may be formed.)
- R 317 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
- the thickness of the layer containing the acceptor material is not particularly limited, but is
- n doping is a method of doping a metal such as Li or Cs into an electron transport material
- p doping is F 4 TCNQ (2, 3, 5, 6) as a hole transport material.
- the space layer is a fluorescent layer for the purpose of adjusting the carrier balance so that excitons generated in the phosphorescent layer are not diffused into the fluorescent layer. It is a layer provided between the layer and the phosphorescent light emitting layer.
- the space layer can be provided between the plurality of phosphorescent light emitting layers. Since the space layer is provided between the light emitting layers, a material having both electron transport properties and hole transport properties is preferable. In order to prevent diffusion of triplet energy in the adjacent phosphorescent light emitting layer, the triplet energy is preferably 2.6 eV or more. Examples of the material used for the space layer include the same materials as those used for the above-described hole transport layer.
- the material for an organic EL device of one embodiment of the present invention can also be used.
- the organic EL device of one embodiment of the present invention preferably has a barrier layer such as an electron barrier layer, a hole barrier layer, or a triplet barrier layer in a portion adjacent to the light emitting layer.
- the electron barrier layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer
- the hole barrier layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer. is there.
- the organic EL device material of one embodiment of the present invention can also be used.
- the triplet barrier layer prevents the triplet excitons generated in the light emitting layer from diffusing into the surrounding layers, and confins the triplet excitons in the light emitting layer, thereby transporting electrons other than the light emitting dopant of the triplet excitons. It has a function of suppressing energy deactivation on the molecules of the layer.
- the triplet energy of the phosphorescent dopant in the light emitting layer is E T d and the triplet energy of the compound used as the triplet barrier layer is E T TB , E T d ⁇ If the energy level relationship of E T TB is satisfied, the triplet exciton of the phosphorescent dopant is confined (cannot move to other molecules) due to the energy relationship, and the energy deactivation path other than light emission on the dopant is interrupted. It is assumed that light can be emitted with high efficiency.
- the organic EL element material of one embodiment of the present invention can be used as a material for a triplet barrier layer having a TTF element configuration described in International Publication WO2010 / 134350A1.
- the electron mobility of the material constituting the triplet barrier layer is preferably 10 ⁇ 6 cm 2 / Vs or more in the range of the electric field strength of 0.04 to 0.5 MV / cm.
- the electron mobility is determined by impedance spectroscopy.
- the electron injection layer is desirably 10 ⁇ 6 cm 2 / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm. This facilitates the injection of electrons from the cathode into the electron transport layer, and also promotes the injection of electrons into the adjacent barrier layer and the light emitting layer, thereby enabling driving at a lower voltage.
- the method for forming each layer of the organic EL element of the present invention is not particularly limited. Conventionally known methods such as vacuum deposition and spin coating can be used.
- the organic thin film layer containing the compound of the present invention used in the organic EL device of the present invention can be prepared by vacuum deposition, molecular beam deposition (MBE method), dipping of a solution obtained by dissolving the compound of the present invention in a solvent, spin It can be formed by a known method such as a coating method, a casting method, a bar coating method, a roll coating method or the like.
- the film thickness of each organic layer of the organic EL device of the present invention is not particularly limited. Generally, if the film thickness is too thin, defects such as pinholes are likely to occur. Conversely, if it is too thick, a high applied voltage is required and the efficiency is deteriorated. Therefore, the range of several nm to 1 ⁇ m is usually preferable.
- a method for forming a layer containing the compound of the present invention for example, a method of forming a film of a solution comprising the compound of the present invention and other materials such as a dopant as required is preferable.
- a known coating method can be used effectively.
- spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, slit coating method, wire bar examples thereof include a coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet method, and a nozzle printing method.
- a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable. Film formation by these methods can be performed under conditions well known to those skilled in the art.
- heating upper limit 250 ° C.
- drying under vacuum may be performed to remove the solvent, and polymerization reaction by light or high temperature heating exceeding 250 ° C. is unnecessary. Therefore, it is possible to suppress deterioration of the performance of the element due to light or high temperature heating exceeding 250 ° C.
- the film-forming solution only needs to contain at least one kind of the compound of the present invention, and includes additives such as other hole transport materials, electron transport materials, light-emitting materials, acceptor materials, solvents, and stabilizers. You may go out.
- the film-forming solution contains additives for adjusting the viscosity and / or surface tension, such as thickeners (high molecular weight compounds, etc.), viscosity reducing agents (low molecular weight compounds, etc.), surfactants, and the like. May be.
- antioxidants which do not influence the performance of organic EL elements, such as a phenolic antioxidant and phosphorus antioxidant.
- the content of the compound of the present invention in the film-forming solution is preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the whole film-forming solution.
- High molecular weight compounds that can be used as thickeners include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, copolymers thereof, poly Examples thereof include photoconductive resins such as —N-vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
- Examples of the solvent for the film-forming solution include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; tetrahydrofuran, dioxane, dioxolane, anisole and the like.
- Ether solvents aromatic hydrocarbon solvents such as toluene and xylene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, etc.
- Aliphatic hydrocarbon solvents such as acetone, methyl ethyl ketone, cyclohexanone, benzophenone and acetophenone; ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate; ethylene Glycol, ethylene glycol Polyhydric alcohols such as butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof; methanol, Examples thereof include alcohol solvents such as ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as
- aromatic hydrocarbon solvents aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferable from the viewpoints of solubility, film formation uniformity, viscosity characteristics, and the like.
- An organic electroluminescence element includes a display component such as an organic EL panel module, a display device such as a television, a mobile phone, or a personal computer, and an electronic device such as a light emitting device for lighting or a vehicle lamp. Can be used for
- Example 1 A glass substrate with an ITO transparent electrode of 25 mm ⁇ 75 mm ⁇ thickness 1.1 mm (manufactured by Geomatic Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. The thickness of the ITO transparent electrode was 100 nm.
- the glass substrate with the ITO transparent electrode line after washing is attached to the substrate holder of the vacuum evaporation apparatus, and the following compound (HA1) is first coated so as to cover the transparent electrode on the surface on which the ITO transparent electrode line is formed.
- the HA1 film having a thickness of 10 nm was formed by vapor deposition to form a hole injection layer.
- the following compound HT1 was vapor-deposited as a first hole transport material so as to cover the transparent electrode on the hole injection layer to form a first hole transport layer having a thickness of 40 nm.
- the following compound HT2 was deposited as a second hole transport material to form a second hole transport layer having a thickness of 10 nm.
- the compound 1 as a host material and the following compound YD1 as a phosphorescent material were co-evaporated to form a phosphorescent layer having a thickness of 20 nm.
- the concentration of YD1 in the light emitting layer was 12% by mass. This co-deposited film functions as a light emitting layer.
- the following compound ET1 was formed to a film thickness of 45 nm.
- This compound ET1 film functions as a first electron transport layer.
- LiF was used as an electron injecting electrode (cathode) at a film forming rate of 0.1 ⁇ / sec, and the film thickness was 1 nm.
- Metal Al was vapor-deposited on this LiF film, and a metal cathode was formed with a film thickness of 80 nm to produce an organic EL device.
- the compounds used in Examples and Comparative Examples are shown below.
- the lifetime was measured as follows. The 80% lifetime (time until the luminance is reduced to 80% of the initial luminance by low current driving) at an initial luminance of 10,000 cd / m 2 was determined.
- Example 2 an organic EL device was produced in the same manner except that the compound 2 and the compound 3 were used in place of the compound 1 as the host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1. Comparative Example 1 In Example 1, an organic EL device was produced in the same manner except that the following comparative compound 1 was used instead of compound 1 as the host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1.
- Example 4 In Example 1, when forming the light emitting layer, the above compound 1 and the following PG1 were used as the host material, the following compound YD1 was co-evaporated as the phosphorescent light emitting material, and a phosphorescent light emitting layer having a thickness of 20 nm was formed. Similarly, an organic EL device was produced. Similar to Example 1, the evaluation results are shown in Table 1. The concentration of PG1 in the light emitting layer was 44% by mass, and the concentration of YD1 was 12% by mass.
- Example 5 In Example 4, an organic EL device was produced in the same manner except that the compound 2 was used in place of the compound 1 as a host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1. Comparative Example 2 In Example 4, an organic EL device was produced in the same manner except that the comparative compound 1 was used in place of the compound 1 as the host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1.
- Example 6 In Example 1, when forming the first hole transport layer, the film was formed to have a film thickness of 20 nm, and when forming the light emitting layer, the above compound 6 was used as the host material, and the following compound was used as the phosphorescent light emitting material.
- a phosphorescent light emitting layer is formed so as to have a film thickness of 40 nm by co-evaporation with RD1 (the concentration of RD1 in the light emitting layer is 5% by mass), and when the first electron transport layer is formed, the film thickness is 40 nm.
- An organic EL element was produced in the same manner except that the film was formed so that The results evaluated in the same manner as in Example 1 are shown in Table 1.
- Example 7 In Example 6, an organic EL device was produced in the same manner except that the compound 7 was used instead of the compound 6 as a host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1.
- Example 8 In Example 6, an organic EL device was produced in the same manner except that the compound 8 was used as the host material of the phosphorescent layer and the compound RD2 was used as the phosphorescent material. Similar to Example 1, the evaluation results are shown in Table 1.
- Comparative Example 3 In Example 6, an organic EL device was produced in the same manner except that the comparative compound 1 was used in place of the compound 6 as the host material of the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1.
- Comparative Example 4 an organic EL device was produced in the same manner except that the comparative compound 1 was used instead of the compound 8 as a host material for the phosphorescent light emitting layer. Similar to Example 1, the evaluation results are shown in Table 1.
- Comparative Compound 1 was used for the organic EL device using the carbazole derivative of one embodiment of the present invention. It can be confirmed that the lifetime of the organic EL element is long.
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Abstract
Description
また、有機EL素子は、発光層に種々の発光材料を用いることにより、多様な発光色を得ることが可能であることから、ディスプレイなどへの実用化研究が盛んである。特に赤色、緑色、青色の三原色の発光材料の研究が最も活発であり、特性向上を目指して鋭意研究がなされている。
しかしながら、有機EL素子の分野においては、さらなる素子性能の向上を目指すため、新たな材料系の開発が求められている。
[1]下記式(1)で表されるカルバゾール誘導体。
X1は、N又はCH、X2~X4は、それぞれN又はCRを示す。
R及びB1~B3は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。Rが複数ある場合、それぞれは同一であっても異なっていてもよい。
B1~B3の少なくとも2つは、下記式(2)で表される。
nは0~4の整数。Lは、置換もしくは無置換の環形成炭素数6~60のアリーレン基、置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基、置換もしくは無置換の炭素数1~50のアルキレン基を示す。
Yは、NZ、O、S、CR’R''を示す。
R1~R8、Z、R’及びR''は、それぞれ独立に、単結合、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
ただし、YがNZのとき、R1とR8は水素原子である。
また、R1~R8、Z、R’及びR''のうちいずれか1つはLと結合する単結合を表し、nが0の場合は、式(1)と式(2)との結合が単結合であることを表す。nが2以上の場合は、複数のLは同一であっても異なっていてもよく、L同士で互いに結合して飽和又は不飽和の環構造を形成してもよい。)]
[3]陰極と陽極間に少なくとも発光層を含む一層又は複数層からなる有機薄膜層が挟持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも1層が、前記カルバゾール誘導体を含有する有機エレクトロルミネッセンス素子。
[4]前記有機エレクトロルミネッセンス素子を備える電子機器。
[5]下記式(10)で表されるカルバゾール誘導体。
X1及びX5は、N又はCH、X2~X4及びX6~X8は、それぞれN又はCRを示す。
R及びB1~B6は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
B1~B3の少なくとも2つは下記式(2)で表される。
nは0~4の整数。Lは、置換もしくは無置換の環形成炭素数6~60のアリーレン基、置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基、置換もしくは無置換の炭素数1~50のアルキレン基を示す。
Yは、NZ、O、S、CR’R''を示す。
R1~R8、Z、R’及びR''は、それぞれ独立に、単結合、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
ただし、YがNZのとき、R1とR8は水素原子である。
また、R1~R8、Z、R’及びR''のうちいずれか1つはLと結合する単結合を表し、nが0の場合は、式(10)と式(2)との結合が単結合であることを表す。nが2以上の場合は、複数のLは同一であっても異なっていてもよく、L同士で互いに結合して飽和又は不飽和の環構造を形成してもよい。)]
また、隣接する置換基同士で環を形成する場合は、一方の置換基の炭素数がa~bの範囲内で最小となる箇所で当該環を切り離して、他方の置換基の炭素数もa~bの範囲内となる構造が含まれる。
これらの置換基は、さらに上述の任意の置換基により置換されていてもよい。
X1は、N又はCH、X2~X4は、それぞれN又はCRを示す。
R及びB1~B3は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。Rが複数ある場合、それぞれは同一であっても異なっていてもよい。
B1~B3の少なくとも2つは、下記式(2)で表される。
nは0~4の整数である。Lは、置換もしくは無置換の環形成炭素数6~60のアリーレン基、置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基、置換もしくは無置換の炭素数1~50のアルキレン基を示す。
Yは、NZ、O、S、CR’R''を示す。
R1~R8、Z、R’及びR''は、それぞれ独立に、単結合、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
ただし、YがNZのとき、R1とR8は水素原子である。
また、R1~R8、Z、R’及びR''のうちいずれか1つはLと結合する単結合を表し、nが0の場合は、式(1)と式(2)との結合が単結合であることを表す。nが2以上の場合は、複数のLは同一であっても異なっていてもよく、L同士で互いに結合して飽和又は不飽和の環構造を形成してもよい。
また、式(2)において、Yが、NZであるものが好ましい。また、nが0又は1が好ましく、1がより好ましい。
さらに、式(1)が下記式(3)で表されるカルバゾール誘導体が好ましい。
R19~R20及びR51は、それぞれ独立に、水素原子又は置換基を示す。R51が複数ある場合、それぞれは同一であっても異なっていてもよい。)
X1及びX5は、N又はCH、X2~X4及びX6~X8は、それぞれN又はCRを示す。
R及びB1~B6は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。Rが複数ある場合、それぞれは同一であっても異なっていてもよい。
B1~B3の少なくとも2つは上記式(2)で表される。
式(10)において、B1~B3の少なくとも2つは下記式(2)で表され、B4~B6の少なくとも2つは上記式(2)で表されると好ましい。
R51は、水素原子又は置換基を示す。R51が複数ある場合、それぞれは同一であっても異なっていてもよい。)
以上の置換基の中でも、具体的には、置換もしくは無置換のフェニル基、置換もしくは無置換のビフェニリル基、置換もしくは無置換のターフェニリル基、置換もしくは無置換のナフチル基、置換もしくは無置換のフェナントリル基、置換もしくは無置換のフルオレニル基、置換もしくは無置換の9,9’-スピロビフルオレニル基、置換もしくは無置換のクリセニル基、置換もしくは無置換のトリフェニレニル基、置換もしくは無置換の9,9-ジメチルフルオレニル基、置換もしくは無置換の9,9-ジフェニルフルオレニル基、置換もしくは無置換のピリジル基、置換もしくは無置換のピリミジニル基、置換もしくは無置換のトリアジニル基、置換もしくは無置換のベンゾフラニル基、置換もしくは無置換のイソベンゾフラニル基、置換もしくは無置換のキノリル基、置換もしくは無置換のイソキノリル基、置換もしくは無置換のキナゾリニル基、置換もしくは無置換のベンゾチオフェニル基、置換もしくは無置換のイソベンゾチオフェニル基、置換もしくは無置換のインドリジニル基、置換もしくは無置換のジベンゾフラニル基、置換もしくは無置換のジベンゾチオフェニル基、置換もしくは無置換のカルバゾリル基、置換もしくは無置換のアザトリフェニレニル基、置換もしくは無置換のジアザトリフェニレニル基、置換もしくは無置換のキサンテニル基、置換もしくは無置換のアザカルバゾリル基、置換もしくは無置換のアザジベンゾフラニル基、及び置換もしくは無置換のアザジベンゾチオフェニル基からなる群から選ばれる基であると好ましい。
前記炭素数1~50(好ましくは1~18、より好ましくは1~8)のアルキル基及び環形成炭素数6~60のアリール基(好ましくは6~25、より好ましくは6~18)から選ばれる置換基を有するモノ置換又はジ置換アミノ基としては、上記アルキル基及び上記アリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基が挙げられ、該ジ置換アミノ基が好ましく、上記アリール基から選ばれる置換基を有するジ置換アミノ基がさらに好ましい。
前記環形成炭素数6~60(好ましくは6~25、より好ましくは6~18)のアリール基を有するアリールオキシ基としては、上記アリール基を有するアリールオキシ基が挙げられ、例えば、フェノキシ基等が挙げられる。
前記環形成炭素数6~60(好ましくは6~25、より好ましくは6~18)のアリール基を有するアリールチオ基としては、上記アリール基を有するアリールチオ基が挙げられる。
前記炭素数1~50(好ましくは1~18、より好ましくは1~8)のハロアルキル基としては、上記アルキル基の水素原子の1以上が、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)により置換されたものが挙げられる。
前記炭素数1~50(好ましくは1~18、より好ましくは1~8)のアルキル基及び前記環形成炭素数6~60(好ましくは6~25、より好ましくは6~18)のアリール基から選ばれる置換基を有するジ置換ホスフォリル基としては、上記アルキル基及び上記アリール基から選ばれる置換基を有するジ置換ホスフォリル基が挙げられる。
前記アルキルスルホニルオキシ基、アリールスルホニルオキシ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルキル置換又はアリール置換カルボニル基としては、それぞれ、上記アルキル基及び上記アリール基から選ばれる置換基を有する基が挙げられる。
以上の置換基の中でも、特に、フッ素原子、シアノ基、アルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、ジ置換アミノ基が好ましい。
Aの示す置換もしくは無置換の環形成原子数5~60のヘテロアリール基としては、上記R、B1~B6、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のヘテロアリール基と同様の例が挙げられる。
式(10)において、A’の示す置換もしくは無置換の環形成炭素数6~60のアリーレン基としては、上記R、B1~B3、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のアリール基の例を2価としたアリーレン基が挙げられる。
A’の示す置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基としては、上記R、B1~B3、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のヘテロアリール基の例を2価としたヘテロアリーレン基が挙げられる。
Lの示す置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基としては、上記R、B1~B6、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のヘテロアリール基の例を2価としたヘテロアリーレン基が挙げられる。
Lの示す置換もしくは無置換の炭素数1~50のアルキレン基としては、上記R、B1~B6、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のアルキル基の例を2価としたアルキレン基が挙げられる。
置換もしくは無置換の環形成炭素数6~60のアリール基としては、上記R、B1~B6、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のアリール基と同様の例が挙げられる。
置換もしくは無置換の環形成原子数5~60のヘテロアリール基としては、上記R、B1~B6、R1~R8、R11~R20、R31~R38、R41~R48、R51、Z、R’及びR''で表される置換基のヘテロアリール基と同様の例が挙げられる。
カルバゾール誘導体が環構造含有基を有することにより、有機EL素子用材料として用いた場合に、該材料を含む有機薄膜の膜質が良好となるなどの効果を奏する。
上記環構造含有基としては、置換基上に環構造含有基を有するものも包含され、この置換基の具体例としては、上述したものが挙げられる。
[式(I)において、L1は、単結合、又は、置換もしくは無置換の環形成炭素数6~30のアリーレン基を示す。R10は水素原子又は置換基を示す。sは、1~5の整数である。sが2以上の場合、複数のR10は同一であっても異なっていてもよい。*は結合位置を示す。]
なお、前記式(III)における、R51、R19~R20のうち隣接する置換基同士が互いに結合して形成してもよい環としては、置換もしくは無置換の環形成炭素数6~60のアリーレン基、又は置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基が挙げられる。
上記式(III)において、R19~R20及びR51としては、上述のR、B1~B3、R1~R8、R11~R18、R31~R38、R41~R48、Z、R’及びR'' と同様の例が挙げられる。R51としてより好ましくは、水素原子、置換もしくは無置換の環形成炭素数6~30のアリール基、又は、置換もしくは無置換の環形成原子数5~30のヘテロアリール基を示す。R19~R20としてより好ましくは、それぞれ独立に、置換もしくは無置換の環形成炭素数6~30のアリール基、又は、置換もしくは無置換の件形成原子数5~30のヘテロアリール基を示す。
本発明の一実施態様の有機EL素子用材料は、上記カルバゾール誘導体を含む。本発明の一実施態様の有機EL素子用材料におけるカルバゾール誘導体の含有量は、特に制限されず、例えば、1質量%以上であればよく、10質量%以上であることが好ましく、50質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることが特に好ましい。
本発明の一実施態様のカルバゾール誘導体及び有機EL素子用材料は、有機EL素子における材料として有用であり、例えば、蛍光発光ユニットの発光層におけるホスト材料及びドーパント材料や、燐光発光ユニットの発光層におけるホスト材料として用いることができる。この場合、発光層は本発明の一実施態様のカルバゾール誘導体と蛍光発光材料又は燐光発光材料を含有する。また、蛍光発光ユニット及び燐光発光ユニットのいずれにおいても、有機EL素子の陽極と発光層との間に設けられる陽極側有機薄膜層や、有機EL素子の陰極と発光層との間に設けられる陰極側有機薄膜層の材料、すなわち、正孔輸送層、正孔注入層、電子輸送層、電子注入層、正孔阻止層、電子阻止層等の材料としても有用である。
ここで、「発光ユニット」とは、一層以上の有機層を含み、そのうちの一層が発光層であり、注入された正孔と電子が再結合することにより発光することができる最小単位をいう。
次に、本発明の一実施態様の有機EL素子について説明する。
本発明の一実施態様の有機EL素子は、陰極と陽極の間に発光層を含有する有機薄膜層を有し、この有機薄膜層のうちの少なくとも1層が前述した有機EL素子用材料を含むことを特徴とする。
前述の有機EL素子用材料が含まれる有機薄膜層の例としては、陽極と発光層との間に設けられる陽極側有機薄膜層(正孔輸送層、正孔注入層等)、発光層、陰極と発光層との間に設けられる陰極側有機薄膜層(電子輸送層、電子注入層等)、スペース層、障壁層等が挙げられるが、これらに限定されるものではない。前述の有機EL素子用材料は、上記いずれの層に含まれていてもよく、例えば、蛍光発光ユニットの発光層におけるホスト材料やドーパント材料、燐光発光ユニットの発光層におけるホスト材料、発光ユニットの正孔輸送層、電子輸送層等として用いることができる。
(1)陽極/発光ユニット/陰極
また、上記発光ユニットは、燐光発光層や蛍光発光層を複数有する積層型であってもよく、その場合、各発光層の間に、燐光発光層で生成された励起子が蛍光発光層に拡散することを防ぐ目的で、スペース層を有していてもよい。発光ユニットの代表的な層構成を以下に示す。
(a)正孔輸送層/発光層(/電子輸送層)
(b)正孔輸送層/第一燐光発光層/第二燐光発光層(/電子輸送層)
(c)正孔輸送層/燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(d)正孔輸送層/第一燐光発光層/第二燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(e)正孔輸送層/第一燐光発光層/スペース層/第二燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(f)正孔輸送層/燐光発光層/スペース層/第一蛍光発光層/第二蛍光発光層(/電子輸送層)
(g)正孔輸送層/電子障壁層/発光層(/電子輸送層)
(h)正孔輸送層/発光層/正孔障壁層(/電子輸送層)
(i)正孔輸送層/蛍光発光層/トリプレット障壁層(/電子輸送層)
なお、各発光層と正孔輸送層あるいはスペース層との間には、適宜、電子障壁層を設けてもよい。また、各発光層と電子輸送層との間には、適宜、正孔障壁層を設けてもよい。電子障壁層や正孔障壁層を設けることで、電子又は正孔を発光層内に閉じ込めて、発光層における電荷の再結合確率を高め、発光効率を向上させることができる。
(2)陽極/第一発光ユニット/中間層/第二発光ユニット/陰極
ここで、上記第一発光ユニット及び第二発光ユニットとしては、例えば、それぞれ独立に上述の発光ユニットと同様のものを選択することができる。
上記中間層は、一般的に、中間電極、中間導電層、電荷発生層、電子引抜層、接続層、中間絶縁層とも呼ばれ、第一発光ユニットに電子を、第二発光ユニットに正孔を供給する、公知の材料構成を用いることができる。
本発明の一実施態様の有機EL素子は、透光性基板上に作製する。透光性基板は有機EL素子を支持する基板であり、400nm~700nmの可視領域の光の透過率が50%以上で平滑な基板が好ましい。具体的には、ガラス板、ポリマー板等が挙げられる。ガラス板としては、特にソーダ石灰ガラス、バリウム・ストロンチウム含有ガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、石英等を原料として用いてなるものを挙げられる。またポリマー板としては、ポリカーボネート、アクリル、ポリエチレンテレフタレート、ポリエーテルサルファイド、ポリサルフォン等を原料として用いてなるものを挙げることができる。
有機EL素子の陽極は、正孔を正孔輸送層又は発光層に注入する役割を担うものであり、4.5eV以上の仕事関数を有するものを用いることが効果的である。陽極材料の具体例としては、酸化インジウム錫合金(ITO)、酸化錫(NESA)、酸化インジウム亜鉛酸化物、金、銀、白金、銅等が挙げられる。陽極はこれらの電極物質を蒸着法やスパッタリング法等の方法で薄膜を形成させることにより作製することができる。発光層からの発光を陽極から取り出す場合、陽極の可視領域の光の透過率を10%より大きくすることが好ましい。また、陽極のシート抵抗は、数百Ω/□以下が好ましい。陽極の膜厚は、材料にもよるが、通常10nm~1μm、好ましくは10nm~200nmの範囲で選択される。
陰極は電子注入層、電子輸送層又は発光層に電子を注入する役割を担うものであり、仕事関数の小さい材料により形成するのが好ましい。陰極材料は特に限定されないが、具体的にはインジウム、アルミニウム、マグネシウム、マグネシウム-インジウム合金、マグネシウム-アルミニウム合金、アルミニウム-リチウム合金、アルミニウム-スカンジウム-リチウム合金、マグネシウム-銀合金等が使用できる。陰極も、陽極と同様に、蒸着法やスパッタリング法等の方法で薄膜を形成させることにより作製することができる。また、必要に応じて、陰極側から発光を取り出してもよい。
発光機能を有する有機層であって、ドーピングシステムを採用する場合、ホスト材料とドーパント材料を含んでいる。このとき、ホスト材料は、主に電子と正孔の再結合を促し、励起子を発光層内に閉じ込める機能を有し、ドーパント材料は、再結合で得られた励起子を効率的に発光させる機能を有する。
燐光素子の場合、ホスト材料は主にドーパントで生成された励起子を発光層内に閉じ込める機能を有する。
また、量子収率の高いドーパント材料を二種類以上入れることによって、それぞれのドーパントが発光するダブルドーパントを採用してもよい。具体的には、ホスト、赤色ドーパント及び緑色ドーパントを共蒸着することによって、発光層を共通化して黄色発光を実現する態様が挙げられる。
発光層への正孔の注入し易さと電子の注入し易さは異なっていてもよく、また、発光層中での正孔と電子の移動度で表される正孔輸送能と電子輸送能が異なっていてもよい。
R0の置換基としは、式(1)の置換基と同様の例が挙げられる。
本発明の一実施態様の有機EL素子用材料とそれ以外の化合物を同一の発光層内の燐光ホスト材料として併用してもよいし、複数の発光層がある場合には、そのうちの一つの発光層の燐光ホスト材料として本発明の一実施態様の有機EL素子用材料を用い、別の一つの発光層の燐光ホスト材料として本発明の一実施態様の有機EL素子用材料以外の化合物を用いてもよい。また、本発明の一実施態様の有機EL素子用材料は発光層以外の有機層にも使用しうるものであり、その場合には発光層の燐光ホストとして、本発明の一実施態様の有機EL素子用材料以外の化合物を用いてもよい。
本発明の一実施態様の有機EL素子は、陰極と発光ユニットとの界面領域に電子供与性ドーパントを有することも好ましい。このような構成によれば、有機EL素子における発光輝度の向上や長寿命化が図られる。ここで、電子供与性ドーパントとは、仕事関数3.8eV以下の金属を含有するものをいい、その具体例としては、アルカリ金属、アルカリ金属錯体、アルカリ金属化合物、アルカリ土類金属、アルカリ土類金属錯体、アルカリ土類金属化合物、希土類金属、希土類金属錯体、及び希土類金属化合物等から選ばれた少なくとも一種類が挙げられる。
本発明の一実施態様の有機EL素子における、主成分と電子供与性ドーパントの割合は、モル比で主成分:電子供与性ドーパント=5:1~1:5であると好ましく、2:1~1:2であるとさらに好ましい。
電子輸送層は、発光層と陰極との間に形成される有機層であって、電子を陰極から発光層へ輸送する機能を有する。電子輸送層が複数層で構成される場合、陰極に近い有機層を電子注入層と定義することがある。電子注入層は、陰極から電子を効率的に有機層ユニットに注入する機能を有する。本発明の一実施態様のカルバゾール誘導体及び有機EL素子用材料は、電子輸送層(第2の電荷輸送層)に含有される電子輸送材料として用いることもできる。
この含窒素環誘導体としては、例えば、下記式(A)で表される含窒素環金属キレート錯体が好ましい。
置換されていてもよいアミノ基の例としては、アルキルアミノ基、アリールアミノ基、アラルキルアミノ基が挙げられる。
アルキルアミノ基及びアラルキルアミノ基は-NQ1Q2と表される。Q1及びQ2は、それぞれ独立に、炭素数1~20のアルキル基又は炭素数1~20のアラルキル基を表す。Q1及びQ2の一方は水素原子又は重水素原子であってもよい。
アリールアミノ基は-NAr1’Ar2’と表され、Ar1’及びAr2’は、それぞれ独立に、炭素数6~50の非縮合芳香族炭化水素基又は縮合芳香族炭化水素基を表す。Ar1及びAr2の一方は水素原子又は重水素原子であってもよい。
アルコキシカルボニル基は-COOY’と表され、Y’は炭素数1~20のアルキル基を表す。
Mは、アルミニウム(Al)、ガリウム(Ga)又はインジウム(In)であり、Inであると好ましい。
L100は、下記式(A’)又は(A”)で表される基である。
HAr-L101-Ar101-Ar102 (D1)
前記式(D1)中、HArは、置換もしくは無置換の炭素数3~40の含窒素複素環基であり、L101は単結合、置換もしくは無置換の炭素数6~40の芳香族炭化水素基又は縮合芳香族炭化水素基又は置換もしくは無置換の炭素数3~40の芳香族複素環基又は縮合芳香族複素環基であり、Ar101は置換もしくは無置換の炭素数6~40の2価の芳香族炭化水素基であり、Ar102は置換もしくは無置換の炭素数6~40の芳香族炭化水素基又は縮合芳香族炭化水素基又は置換もしくは無置換の炭素数3~40の芳香族複素環基又は縮合芳香族複素環基である。
R301及びR302は、それぞれ独立に、置換もしくは無置換の環形成炭素数6~50のアリール基、置換もしくは無置換の環形成原子数5~50のヘテロアリール基、置換もしくは無置換の炭素数1~20のアルキル基、置換もしくは無置換の炭素数1~20のハロアルキル基又は置換もしくは無置換の炭素数1~20のアルコキシ基である。
vは、0~5の整数であり、vが2以上の整数であるとき、複数のR301は互いに同一でも異なっていてもよい。また、隣接する2つのR301同士が互いに結合して、置換もしくは無置換の炭化水素環を形成していてもよい。
Ar201は、置換もしくは無置換の環形成炭素数6~50のアリール基又は置換もしくは無置換の環形成原子数5~50のヘテロアリール基である。
Ar202は、水素原子、置換もしくは無置換の炭素数1~20のアルキル基、置換もしくは無置換の炭素数1~20のハロアルキル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~50のアリール基又は置換もしくは無置換の環形成原子数5~50のヘテロアリール基である。
但し、Ar201、Ar202のいずれか一方は、置換もしくは無置換の環形成炭素数10~50の縮合芳香族炭化水素環基又は置換もしくは無置換の環形成原子数9~50の縮合芳香族複素環基である。
Ar203は、置換もしくは無置換の環形成炭素数6~50のアリーレン基又は置換もしくは無置換の環形成原子数5~50のヘテロアリーレン基である。
L201、L202及びL203は、それぞれ独立に、単結合、置換もしくは無置換の環形成炭素数6~50のアリーレン基、又は置換もしくは無置換の環形成原子数9~50の2価の縮合芳香族複素環基である。)
環形成原子数5~50のヘテロアリール基としては、ピローリル基、フリル基、チエニル基、シローリル基、ピリジル基、キノリル基、イソキノリル基、べンゾフリル基、イミダゾリル基、ピリミジル基、カルバゾリル基、セレノフェニル基、オキサジアゾリル基、トリアゾーリル基、ピラジニル基、ピリダジニル基、トリアジニル基、キノキサリニル基、アクリジニル基、イミダゾ[1,2-a]ピリジニル基、イミダゾ[1,2-a]ピリミジニル基などが挙げられる。
炭素数1~20のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基などが挙げられる。
炭素数1~20のハロアルキル基としては、前記アルキル基の1又は2以上の水素原子をフッ素、塩素、ヨウ素及び臭素から選ばれる少なくとも1のハロゲン原子で置換して得られる基が挙げられる。
炭素数1~20のアルコキシ基としては、前記アルキル基をアルキル部位としては有する基が挙げられる。
環形成炭素数6~50のアリーレン基としては、前記アリール基から水素原子1個を除去して得られる基が挙げられる。
環形成原子数9~50の2価の縮合芳香族複素環基としては、前記ヘテロアリール基として記載した縮合芳香族複素環基から水素原子1個を除去して得られる基が挙げられる。
また、電子輸送層に隣接して設けることができる電子注入層の構成成分として、含窒素環誘導体の他に無機化合物として、絶縁体又は半導体を使用することが好ましい。電子注入層が絶縁体や半導体で構成されていれば、電流のリークを有効に防止して、電子注入性を向上させることができる。
発光層と陽極との間に形成される有機層であって、正孔を陽極から発光層へ輸送する機能を有する。正孔輸送層が複数層で構成される場合、陽極に近い有機層を正孔注入層と定義することがある。正孔注入層は、陽極から正孔を効率的に有機層ユニットに注入する機能を有する。本発明の一実施態様のカルバゾール誘導体及び有機EL素子用材料は、正孔輸送層(第1の電荷輸送層)に含有される正孔輸送材料として用いることもできる。
正孔輸送層を形成する他の材料としては、芳香族アミン化合物、例えば、下記式(H)で表される芳香族アミン誘導体が好適に用いられる。
また、前記式(H)において、L211は置換もしくは無置換の環形成炭素数6~50の芳香族炭化水素基又は縮合芳香族炭化水素基、又は置換もしくは無置換の環形成原子数5~50の芳香族複素環基又は縮合芳香族複素環基を表す。
正孔輸送層の膜厚は特に限定されないが、10~200nmであるのが好ましい。
前記アクセプター材料としては下記式(K)で表される化合物が好ましい。
R317としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
アクセプター材料を含有する層の膜厚は特に限定されないが、5~20nmであるのが好ましい。
前記アクセプタ―材料として下記の材料を用いてもよい。
上述の正孔輸送層や電子輸送層においては、特許第3695714号明細書に記載されているように、ドナー性材料のドーピング(n)やアクセプター性材料のドーピング(p)により、キャリア注入能を調整することができる。
nドーピングの代表例としては、電子輸送材料にLiやCs等の金属をドーピングする方法が挙げられ、pドーピングの代表例としては、正孔輸送材料にF4TCNQ(2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane)等のアクセプター材料をドーピングする方法が挙げられる。
上記スペース層とは、例えば、蛍光発光層と燐光発光層とを積層する場合に、燐光発光層で生成する励起子を蛍光発光層に拡散させない、あるいは、キャリアバランスを調整する目的で、蛍光発光層と燐光発光層との間に設けられる層である。また、スペース層は、複数の燐光発光層の間に設けることもできる。
スペース層は発光層間に設けられるため、電子輸送性と正孔輸送性を兼ね備える材料であることが好ましい。また、隣接する燐光発光層内の三重項エネルギーの拡散を防ぐため、三重項エネルギーが2.6eV以上であることが好ましい。スペース層に用いられる材料としては、上述の正孔輸送層に用いられるものと同様のものが挙げられる。スペース層用の材料として、本発明の一実施態様の有機EL素子用材料を用いることもできる。
本発明の一実施態様の有機EL素子は、発光層に隣接する部分に、電子障壁層、正孔障壁層、トリプレット障壁層といった障壁層を有することが好ましい。ここで、電子障壁層とは、発光層から正孔輸送層へ電子が漏れることを防ぐ層であり、正孔障壁層とは、発光層から電子輸送層へ正孔が漏れることを防ぐ層である。正孔障壁層用の材料として、本発明の一実施態様の有機EL素子用材料を用いることもできる。
トリプレット障壁層は、発光層で生成する三重項励起子が、周辺の層へ拡散することを防止し、三重項励起子を発光層内に閉じ込めることによって三重項励起子の発光ドーパント以外の電子輸送層の分子上でのエネルギー失活を抑制する機能を有する。
トリプレット障壁層を設ける場合、燐光素子においては、発光層中の燐光発光性ドーパントの三重項エネルギーをET d、トリプレット障壁層として用いる化合物の三重項エネルギーをET TBとすると、ET d<ET TBのエネルギー大小関係であれば、エネルギー関係上、燐光発光性ドーパントの三重項励起子が閉じ込められ(他分子へ移動できなくなり)、該ドーパント上で発光する以外のエネルギー失活経路が断たれ、高効率に発光することができると推測される。ただし、ET d<ET TBの関係が成り立つ場合であってもこのエネルギー差ΔET=ET TB-ET dが小さい場合には、実際の素子駆動環境である室温程度の環境下では、周辺の熱エネルギーにより吸熱的にこのエネルギー差ΔETを乗り越えて三重項励起子が他分子へ移動することが可能であると考えられる。特に燐光発光の場合は蛍光発光に比べて励起子寿命が長いため、相対的に吸熱的励起子移動過程の影響が現れやすくなる。室温の熱エネルギーに対してこのエネルギー差ΔETは大きい程好ましく、0.1eV以上であるとさらに好ましく、0.2eV以上であると特に好ましい。一方、蛍光素子においては、国際公開WO2010/134350A1に記載するTTF素子構成のトリプレット障壁層用の材料として、本発明の一実施態様の有機EL素子用材料を用いることもできる。
電子注入層は、電界強度0.04~0.5MV/cmの範囲において、10-6cm2/Vs以上であることが望ましい。これにより陰極からの電子輸送層への電子注入が促進され、ひいては隣接する障壁層、発光層への電子注入も促進し、より低電圧での駆動を可能にするためである。
成膜後は、真空下に加熱(上限250℃)乾燥して、溶媒を除去すればよく、光や250℃を超える高温加熱による重合反応は不要である。従って、光や250℃を超える高温加熱による素子の性能劣化の抑制が可能である。
成膜用溶液は、粘度及び/又は表面張力を調節するための添加剤、例えば、増粘剤(高分子量化合物等)、粘度降下剤(低分子量化合物等)、界面活性剤等を含有していてもよい。また、保存安定性を改善するために、フェノール系酸化防止剤、リン系酸化防止剤等、有機EL素子の性能に影響しない酸化防止剤を含有していてもよい。
上記成膜用溶液中の本発明の化合物の含有量は、成膜用溶液全体に対して0.1~15質量%が好ましく、0.5~10質量%がより好ましい。
氷水に反応液を入れ、塩化メチレンを加えて抽出し、有機層を分離して、炭酸水素ナトリウム水溶液、飽和食塩水にて有機層を洗浄し、硫酸ナトリウムを用いて乾燥し、有機溶媒を減圧留去して、中間体1(20.3g、85mmol(収率97%))を得た。FD-MS(フィールドディソープションマススペクトル)の分析により、中間体1と同定した。
室温まで反応液を冷却した後、有機層を分離し、有機溶媒を減圧留去した。得られた残渣をシリカゲルクロマトグラフィーにて精製し、中間体2(11.6g、49mmol(収率98%))を得た。FD-MSの分析により、中間体2と同定した。
室温まで反応液を冷却した後、上水、塩化メチレンを加え、有機層を分離し、有機溶媒を減圧留去した。得られた残渣をシリカゲルクロマトグラフィーにて精製し、中間体3(8.9g、17mmol(収率40%))を得た。FD-MSの分析により、中間体3と同定した。
室温まで反応液を冷却した後、シリカゲルクロマトグラフィーにて精製し、中間体4(5.7g、11.5mmol(収率67%))を得た。FD-MSの分析により、中間体4と同定した。
室温まで反応液を冷却した後、有機層を分離し、有機溶媒を減圧留去した。得られた残渣をシリカゲルクロマトグラフィーにて精製し、化合物1(1.9g、2.4mmol(収率67%))を得た。FD-MSの分析により、化合物1と同定した。
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C57H36N6、found m/z=804(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C51H32N6、found m/z=728(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C57H36N6、found m/z=804(M+)
室温まで反応液を冷却した後、有機層を分離し、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、中間体10(1.75g、収率80%)を得た。FD-MSの分析により、中間体10と同定した。
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C94H58N8、found m/z=1298(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C42H27N3、found m/z=573(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C56H35N5、found m/z=777(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C50H31N5、found m/z=701(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C58H35N3、found m/z=773(M+)
得られた化合物について、FD-MSを以下に示す。
FDMS、calcd for C52H33N5、found m/z=727(M+)
25mm×75mm×厚さ1.1mmのITO透明電極付きガラス基板(ジオマティック株式会社製)をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間行った。ITO透明電極の厚さは100nmであった。
洗浄後のITO透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まずITO透明電極ラインが形成されている側の面上に前記透明電極を覆うようにして下記化合物(HA1)を蒸着して膜厚10nmのHA1膜を成膜し、正孔注入層を形成した。
次に、この正孔注入層上に前記透明電極を覆うようにして第1正孔輸送材料として下記化合物HT1を蒸着し、膜厚40nmの第1正孔輸送層を成膜した。第1正孔輸送層の成膜に続けて、第2正孔輸送材料として下記化合物HT2を蒸着し、膜厚10nmの第2正孔輸送層を成膜した。
さらに、この第2正孔輸送層上に、ホスト材料として前記化合物1と、燐光発光材料として下記化合物YD1とを共蒸着し、膜厚20nmの燐光発光層を成膜した。発光層内におけるYD1の濃度は12質量%であった。この共蒸着膜は発光層として機能する。
そして、この発光層成膜に続けて下記化合物ET1を膜厚45nmで成膜した。この化合物ET1膜は第1電子輸送層として機能する。
次に、LiFを電子注入性電極(陰極)として成膜速度0.1Å/secで成膜し、膜厚を1nmとした。このLiF膜上に金属Alを蒸着させ、金属陰極を膜厚80nmで形成し有機EL素子を作製した。
以下に、実施例及び比較例で使用した化合物を示す。
初期輝度10000cd/m2における80%寿命(低電流駆動で、輝度が初期輝度の80%まで低下するまでの時間)を求めた。
実施例1において、燐光発光層のホスト材料として、化合物1の代わりに上記化合物2、化合物3を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
比較例1
実施例1において、燐光発光層のホスト材料として、化合物1の代わりに下記比較化合物1を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
実施例1において、発光層を形成する際、ホスト材料として上記化合物1と下記PG1を用い、燐光発光材料として下記化合物YD1とを共蒸着し、膜厚20nmの燐光発光層を成膜した以外は同様にして有機EL素子を作製した。実施例1と同様に、評価した結果を表1に示す。
発光層内におけるPG1の濃度は44質量%、YD1の濃度は12質量%であった。
実施例4において、燐光発光層のホスト材料として、上記化合物1の代わりに上記化合物2を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
比較例2
実施例4において、燐光発光層のホスト材料として、化合物1の代わりに上記比較化合物1を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
実施例1において、第1正孔輸送層を形成する際、膜厚が20nmとなるように成膜し、発光層を形成する際、ホスト材料として上記化合物6を用い、燐光発光材料として下記化合物RD1とを共蒸着して膜厚が40nmとなるように燐光発光層を成膜し(発光層内におけるRD1の濃度は5質量%)、第1電子輸送層を形成する際、膜厚が40nmとなるように成膜した以外は同様にして有機EL素子を製造した。実施例1と同様に評価した結果を表1に示す。
実施例6において、燐光発光層のホスト材料として、上記化合物6の代わりに上記化合物7を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
実施例6において、燐光発光層のホスト材料として、上記化合物8を用い、燐光発光材料として、上記化合物RD2を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
実施例6において、燐光発光層のホスト材料として、上記化合物6の代わりに上記比較化合物1を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
実施例8において、燐光発光層のホスト材料として、上記化合物8の代わりに上記比較化合物1を用いた以外は同様にして有機EL素子を製造した。実施例1と同様に、評価した結果を表1に示す。
2 基板
3 陽極
4 陰極
5 発光層
6 陽極側有機薄膜層
7 陰極側有機薄膜層
10 発光ユニット
Claims (28)
- 下記式(1)で表されるカルバゾール誘導体。
X1は、N又はCH、X2~X4は、それぞれN又はCRを示す。
R及びB1~B3は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。Rが複数ある場合、それぞれは同一であっても異なっていてもよい。
B1~B3の少なくとも2つは、下記式(2)で表される。
nは0~4の整数。Lは、置換もしくは無置換の環形成炭素数6~60のアリーレン基、置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基、置換もしくは無置換の炭素数1~50のアルキレン基を示す。
Yは、NZ、O、S、CR’R''を示す。
R1~R8、Z、R’及びR''は、それぞれ独立に、単結合、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
ただし、YがNZのとき、R1とR8は水素原子である。
また、R1~R8、Z、R’及びR''のうちいずれか1つはLと結合する単結合を表し、nが0の場合は、式(1)と式(2)との結合が単結合であることを表す。nが2以上の場合は、複数のLは同一であっても異なっていてもよく、L同士で互いに結合して飽和又は不飽和の環構造を形成してもよい。)] - 前記式(1)において、B1~B3の2つが、前記式(2)で表されることを特徴とする請求項1記載のカルバゾール誘導体。
- 前記式(1)において、B1及びB2が、前記式(2)で表されることを特徴とする請求項1記載のカルバゾール誘導体。
- 前記R、B1~B3、R1~R8、Z、R’及びR''が置換基である場合、該置換基が、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換の環形成炭素数3~50のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60のアリール基、置換もしくは無置換の炭素数7~61のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の環形成炭素数6~60のアリールオキシ基、置換もしくは無置換の炭素数1~50のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60のアリールチオ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60のヘテロアリール基、置換もしくは無置換の炭素数1~50のハロアルキル基、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するスルフォニル基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するジ置換ホスフォリル基、アルキルスルホニルオキシ基、アリールスルホニルオキシ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、ホウ素含有基、亜鉛含有基、スズ含有基、ケイ素含有基、マグネシウム含有基、リチウム含有基、ヒドロキシ基、アルキル置換又はアリール置換カルボニル基、カルボキシル基、ビニル基、(メタ)アクリロイル基、エポキシ基、及びオキセタニル基からなる群から選ばれる基である、請求項1~3のいずれかに記載のカルバゾール誘導体。
- 前記R、B1~B3、R1~R8、Z、R’及びR''が置換基である場合、該置換基が、置換もしくは無置換のフェニル基、置換もしくは無置換のビフェニリル基、置換もしくは無置換のターフェニリル基、置換もしくは無置換のナフチル基、置換もしくは無置換のフェナントリル基、置換もしくは無置換のフルオレニル基、置換もしくは無置換の9,9’-スピロビフルオレニル基、置換もしくは無置換のクリセニル基、置換もしくは無置換のトリフェニレニル基、置換もしくは無置換の9,9-ジメチルフルオレニル基、置換もしくは無置換の9,9-ジフェニルフルオレニル基、置換もしくは無置換のピリジル基、置換もしくは無置換のピリミジニル基、置換もしくは無置換のトリアジニル基、置換もしくは無置換のベンゾフラニル基、置換もしくは無置換のイソベンゾフラニル基、置換もしくは無置換のキノリル基、置換もしくは無置換のイソキノリル基、置換もしくは無置換のキナゾリニル基、置換もしくは無置換のベンゾチオフェニル基、置換もしくは無置換のイソベンゾチオフェニル基、置換もしくは無置換のインドリジニル基、置換もしくは無置換のジベンゾフラニル基、置換もしくは無置換のジベンゾチオフェニル基、置換もしくは無置換のカルバゾリル基、置換もしくは無置換のアザトリフェニレニル基、置換もしくは無置換のジアザトリフェニレニル基、置換もしくは無置換のキサンテニル基、置換もしくは無置換のアザカルバゾリル基、置換もしくは無置換のアザジベンゾフラニル基、及び置換もしくは無置換のアザジベンゾチオフェニル基からなる群から選ばれる基である、請求項1~3のいずれかに記載のカルバゾール誘導体。
- 請求項1~11のいずれかに記載のカルバゾール誘導体を含有する有機エレクトロルミネッセンス素子用材料。
- 陰極と陽極間に少なくとも発光層を含む一層又は複数層からなる有機薄膜層が挟持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも1層が、請求項1~11のいずれかに記載のカルバゾール誘導体を含有する有機エレクトロルミネッセンス素子。
- 前記発光層が前記カルバゾール誘導体を含有する請求項13に記載の有機エレクトロルミネッセンス素子。
- 前記陽極と前記発光層との間に、さらに第1の電荷輸送層を有し、該第1の電荷輸送層が前記カルバゾール誘導体を含有する請求項13又は14に記載の有機エレクトロルミネッセンス素子。
- 前記陰極と前記発光層との間に、さらに第2の電荷輸送層を有し、該第2の電荷輸送層が前記カルバゾール誘導体を含有する請求項13~15のいずれかに記載の有機エレクトロルミネッセンス素子。
- 前記発光層が燐光発光材料を含有する請求項13~16のいずれかに記載の有機エレクトロルミネッセンス素子。
- 前記発光層が蛍光発光材料を含有する請求項13~16のいずれかに記載の有機エレクトロルミネッセンス素子。
- 前記燐光発光材料が、イリジウム(Ir)、オスミウム(Os)、白金(Pt)から選択される金属原子のオルトメタル化錯体である請求項17に記載の有機エレクトロルミネッセンス素子。
- 請求項13~20のいずれかに記載の有機エレクトロルミネッセンス素子を備える電子機器。
- 下記式(10)で表されるカルバゾール誘導体。
X1及びX5は、それぞれN又はCH、X2~X4及びX6~X8は、それぞれN又はCRを示す。
R及びB1~B6は、それぞれ独立に、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。Rが複数ある場合、それぞれは同一であっても異なっていてもよい。
B1~B3の少なくとも2つは下記式(2)で表される。
nは0~4の整数。Lは、置換もしくは無置換の環形成炭素数6~60のアリーレン基、置換もしくは無置換の環形成原子数5~60のヘテロアリーレン基、置換もしくは無置換の炭素数1~50のアルキレン基を示す。
Yは、NZ、O、S、CR’R''を示す。
R1~R8、Z、R’及びR''は、それぞれ独立に、単結合、水素原子又は置換基を示し、隣接する置換基同士は、互いに結合して飽和又は不飽和の環構造を形成してもよい。
ただし、YがNZのとき、R1とR8は水素原子である。
また、R1~R8、Z、R’及びR''のうちいずれか1つはLと結合する単結合を表し、nが0の場合は、式(10)と式(2)との結合が単結合であることを表す。nが2以上の場合は、複数のLは同一であっても異なっていてもよく、L同士で互いに結合して飽和又は不飽和の環構造を形成してもよい。)] - 前記式(10)において、B1~B3の2つが、前記式(2)で表されることを特徴とする請求項22記載のカルバゾール誘導体。
- 前記式(10)において、B1及びB2が、前記式(2)で表されることを特徴とする請求項22記載のカルバゾール誘導体。
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US10217954B2 (en) | 2013-11-13 | 2019-02-26 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device |
WO2016163372A1 (ja) * | 2015-04-08 | 2016-10-13 | 出光興産株式会社 | 化合物、これを用いた有機エレクトロルミネッセンス素子用材料、及びこれを用いた有機エレクトロルミネッセンス素子並びに電子機器 |
US10629821B2 (en) | 2015-04-08 | 2020-04-21 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent elements using same, and organic electroluminescent element and electronic device each using same |
JP2017210464A (ja) * | 2016-05-26 | 2017-11-30 | 三星ディスプレイ株式會社Samsung Display Co.,Ltd. | 含窒素化合物及び含窒素化合物を含む有機電界発光素子 |
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US10971687B2 (en) | 2017-12-14 | 2021-04-06 | Universal Display Corporation | Organic electroluminescent materials and devices |
Also Published As
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US9963429B2 (en) | 2018-05-08 |
US20160204361A1 (en) | 2016-07-14 |
JP6370791B2 (ja) | 2018-08-08 |
KR102282551B1 (ko) | 2021-07-27 |
CN105408310A (zh) | 2016-03-16 |
KR20160044458A (ko) | 2016-04-25 |
JPWO2015033894A1 (ja) | 2017-03-02 |
CN105408310B (zh) | 2019-11-19 |
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