JP2005259377A - Organic electroluminescent element - Google Patents
Organic electroluminescent element Download PDFInfo
- Publication number
- JP2005259377A JP2005259377A JP2004065966A JP2004065966A JP2005259377A JP 2005259377 A JP2005259377 A JP 2005259377A JP 2004065966 A JP2004065966 A JP 2004065966A JP 2004065966 A JP2004065966 A JP 2004065966A JP 2005259377 A JP2005259377 A JP 2005259377A
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic
- anion
- electroluminescent element
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 28
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 15
- 239000012044 organic layer Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- -1 phosphino group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000707 boryl group Chemical group B* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-M pyridin-2-olate Chemical compound [O-]C1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-M 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- 239000003446 ligand Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- KXZSVYHFYHTNBI-UHFFFAOYSA-N 1h-quinoline-2-thione Chemical compound C1=CC=CC2=NC(S)=CC=C21 KXZSVYHFYHTNBI-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- 150000005360 2-phenylpyridines Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 0 NP1(*(cccc2)c2-c2ccccc12)N Chemical compound NP1(*(cccc2)c2-c2ccccc12)N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
本発明は、有機エレクトロルミネッセンス素子（有機ＥＬ素子）に関するものである。 The present invention relates to an organic electroluminescence element (organic EL element).
有機ＥＬ素子は、無機ＥＬ素子に比べて、大面積化が容易であり、また発光材料の選択により所望の発色が得られ、低電圧で駆動可能であるため、近年盛んに応用研究がなされている。有機ＥＬ素子に用いられる発光材料としては、高い発光効率が期待できることから、イリジウム錯体などの三重項励起発光材料が注目されている。 Organic EL elements are easy to increase in area as compared with inorganic EL elements, and can produce a desired color by selecting a light emitting material and can be driven at a low voltage. Yes. As a light-emitting material used for an organic EL element, triplet excited light-emitting materials such as iridium complexes have attracted attention because high light emission efficiency can be expected.
三重項励起発光材料は主に重金属を中心金属に用いた金属錯体であるが、この中で平面四配位構造をとるものとして、白金、パラジウム、金などの錯体が知られている。これらの金属錯体は、錯体同士が集積することにより単独のものと異なる特性を示す場合がある。非特許文献１及び２においては、架橋配位子で複数の金属をつなげて一分子内において集積させた２−フェニルピリジナト白金複核錯体について、その光化学的特性及び光触媒能などを検討している。
The triplet excited light-emitting material is a metal complex mainly using a heavy metal as a central metal, and platinum, palladium, gold and the like are known as those having a planar four-coordinate structure. These metal complexes may exhibit characteristics different from those of single substances due to the accumulation of the complexes. In
しかしながら、これらの金属錯体について、有機ＥＬ素子の発光材料としての検討は未だなされていない。特に、２つの架橋配位子が互いに逆の向きで配位子するａｎｔｉ型配位錯体の複核金属錯体については、有機ＥＬ素子の発光材料としての検討はなされていない。
本発明の目的は、ａｎｔｉ型配位形態の複核金属錯体を発光材料として用いた有機ＥＬ素子を提供することにある。 An object of the present invention is to provide an organic EL device using a binuclear metal complex having an anti-coordination form as a light emitting material.
本発明は、一対の電極の間に配置された有機層を備える有機ＥＬ素子であり、有機層が、以下の一般式（１）で表わされる複核金属錯体を含むことを特徴としている。 This invention is an organic EL element provided with the organic layer arrange | positioned between a pair of electrodes, The organic layer contains the binuclear metal complex represented by the following General formula (1), It is characterized by the above-mentioned.
（式中、ＭはＰｔ、Ｐｄ、またはＡｕを示し、Ｙは周期律表１４族、１５族及び１６族の非金属元素の中から選ばれる少なくとも１種の元素を示し、Ｘ1及びＸ2は環状有機基を示し、Ｒ1〜Ｒ16は互いに同一であっても異なっていてもよく、水素、または置換されてもよいアルキル基（炭素数１〜２０）、アルケニル基（炭素数２〜２５）、アルキニル基、アルコキシ基、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アルキルチオ基、ヘテロ環基、アミノ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、ヒドロキシル基、イミノ基、シアノ基、ニトロ基、ハロゲン基、スルホニル基、シリル基、ボリル基、ホスフィノ基の内のいずれかを示し、Ｒ1〜Ｒ8内及びＲ9〜Ｒ16内においては互いに結合して環を形成していてもよい。）
上記一般式（１）において、Ｘ1及びＸ2は、例えば、ピリジン−２−チオールアニオン、キノリン−２−チオールアニオン、キノリン−８−チオールアニオン、２−ピリジノールアニオン、２−キノリノールアニオン及びこれらの誘導体からなる群より選択されるものが挙げられる。
(In the formula, M represents Pt, Pd, or Au, Y represents at least one element selected from Group 14, Group 15, and Group 16 nonmetallic elements, and X 1 and X 2 Represents a cyclic organic group, and R 1 to R 16 may be the same or different from each other, and are hydrogen, an alkyl group (having 1 to 20 carbon atoms), an alkenyl group (having 2 to 2 carbon atoms). 25), alkynyl group, alkoxy group, aryl group, aralkyl group, aryloxy group, arylthio group, alkylthio group, heterocyclic group, amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, hydroxyl group, an imino group, a cyano group, a nitro group, a halogen group, a sulfonyl group, a silyl group, a boryl group, any of a phosphino group, R 1 to R 8 in及Bonded to each other in the R 9 to R 16 may form a ring.)
In the general formula (1), X 1 and X 2 are, for example, pyridine-2-thiol anion, quinoline-2-thiol anion, quinoline-8-thiol anion, 2-pyridinol anion, 2-quinolinol anion and Those selected from the group consisting of these derivatives may be mentioned.
また、Ｙは、周期律表１４族、１５族及び１６族の非金属元素の中から選ばれる少なくとも１種の元素である。周期律表１４族の非金属元素としては、炭素（Ｃ）及びケイ素（Ｓｉ）が挙げられる。また、周期律表１５族の非金属元素としては、窒素（Ｎ）、リン（Ｐ）、及びヒ素（Ａｓ）が挙げられる。また、周期律表１６族の非金属元素としては、酸素（Ｏ）、硫黄（Ｓ）、セレン（Ｓｅ）、及びテルル（Ｔｅ）が挙げられる。 Y is at least one element selected from Group 14, Group 15 and Group 16 non-metallic elements. Examples of the nonmetallic element of Group 14 of the periodic table include carbon (C) and silicon (Si). In addition, examples of the nonmetallic element of Group 15 of the periodic table include nitrogen (N), phosphorus (P), and arsenic (As). In addition, examples of the non-metallic element of Group 16 of the periodic table include oxygen (O), sulfur (S), selenium (Se), and tellurium (Te).
一般式（１）で表わされる複核金属錯体は、平面四配位構造をとる金属錯体であり、平面性が高く、集積することにより分子間の相互作用に基づいて錯体そのものと異なる発光特性を示す。分子間の相互作用としては、錯体の中心金属同士の相互作用（ＭＭ相互作用）が知られており、この相互作用に基づく発光は、三重項3ＭＭＬＣＴ励起状態からのものであるため、量子収率が高い。また、ＭＭ相互作用によって、より長波長側の発光を示す。このため、赤色発光材料として利用することができる。 The binuclear metal complex represented by the general formula (1) is a metal complex having a planar four-coordinate structure, has high planarity, and exhibits luminescence characteristics different from the complex itself based on the interaction between molecules when accumulated. . As the interaction between molecules, the interaction between the central metals of the complex (MM interaction) is known, and the light emission based on this interaction is from the triplet 3 MMLCT excited state. The rate is high. In addition, longer wavelength light is emitted due to the MM interaction. Therefore, it can be used as a red light emitting material.
一般式（１）で表わされる複核金属錯体は、π共役系配位子を有し、かつ架橋配位子によって複数の金属がつながれた構造を有しているので、優先的に上記の三重項3ＭＭＬＣＴ励起状態からの発光を示す。 Since the binuclear metal complex represented by the general formula (1) has a π-conjugated ligand and has a structure in which a plurality of metals are connected by a bridging ligand, the above triplet is preferentially used. 3 Emission from MMLCT excited state is shown.
本発明における複核金属錯体としては、π共役系配位子として２−フェニルピリジンを含み、ピリジンチオラト架橋配位子によって２つの中心金属につながれた構造を有する白金複核金属錯体ａｎｔｉ−〔Ｐｔ（II）2（ｐｐｙ）2（ｐｙｔ）2〕が挙げられる。その構造を以下に示す。 As the binuclear metal complex in the present invention, a platinum binuclear metal complex anti- [Pt () containing 2-phenylpyridine as a π-conjugated ligand and having a structure linked to two central metals by a pyridinethiolato bridging ligand. II) 2 (ppy) 2 (pyt) 2 ]. The structure is shown below.
上記構造に示すように、２つの架橋配位子において、ＮとＳの位置が異なっている。このような構造は、ａｎｔｉ構造と呼ばれている。これに対し、ｓｙｎ構造と呼ばれる配位形態が知られている。例えば、π共役系配位子としてビピリジンを含み、ピリジンチオラト架橋配位子によって２つの白金金属がつながれた、以下の構造の白金二核錯体が知られている。 As shown in the above structure, the positions of N and S are different in the two bridging ligands. Such a structure is called an anti structure. On the other hand, a coordination form called a syn structure is known. For example, a platinum binuclear complex having the following structure in which bipyridine is included as a π-conjugated ligand and two platinum metals are connected by a pyridinethiolato bridging ligand is known.
上記のビピリジン錯体は、ビピリジンが電荷的に中性な配位子であるので、カチオン錯体となる。これに対して、本発明の２−フェニルピリジン錯体は、オルトメタル化配位子である２−フェニルピリジンがアニオン配位子であるため、分子全体で電荷を持たない中性錯体となる。このため、昇華性を有しており、真空蒸着法により薄膜を形成することができる。従って、有機ＥＬ素子の発光材料として適したものである。 The bipyridine complex is a cation complex because bipyridine is a charge neutral ligand. In contrast, the 2-phenylpyridine complex of the present invention is a neutral complex having no charge in the whole molecule because 2-phenylpyridine, which is an orthometalated ligand, is an anionic ligand. For this reason, it has sublimation property and a thin film can be formed by a vacuum evaporation method. Therefore, it is suitable as a light emitting material for organic EL elements.
また、２−フェニルピリジン誘導体からなる配位子は、ビピリジンよりも配位子場が強いため、トランス効果が強くなり、２つの架橋配位子が互いに異なる向きで配位するａｎｔｉ型配位形態を優先的にとる。このようなａｎｔｉ型配位形態をとるものは、ｓｙｎ型配位形態をとるものとは異なり、結晶内への溶媒や水分子の挿入による発光特性の変化がない。このことから、この配位形態の錯体を用いた有機ＥＬ素子においては、外気の環境に影響されることなく、安定な発光が得られる。 In addition, a ligand composed of a 2-phenylpyridine derivative has a stronger ligand effect than bipyridine, so that the trans effect is strong, and the anti-coordination form in which two bridging ligands are coordinated in different directions. Take priority. Those having such an anti-coordination form are different from those having a syn-type coordination form, and have no change in light emission characteristics due to the insertion of a solvent or water molecules into the crystal. For this reason, in an organic EL device using this coordination form complex, stable light emission can be obtained without being affected by the environment of the outside air.
本発明における複核金属錯体で発光層を形成する場合、複核金属錯体単独で、上述の真空蒸着法等により発光層を形成することができる。また、複核金属錯体をドーパントとして発光層内に分散させて用いても良好な発光特性を得ることができる。ホスト化合物としては、その発光ピークがドーパントの吸収ピークと重なりを有するものであることが好ましい。上記の白金二核錯体を用いる場合には、以下に示す構造を有するＣＢＰ（４，４′−ビス（カルバゾール−９−イル）−ビフェニル）をホスト材料として用いることが好ましい。発光層におけるドーパントの含有量としては、一般にホスト材料の５〜６重量％程度であることが好ましい。ホスト材料とドーパント材料を、例えば共蒸着させることにより発光層を形成することができる。 When forming a light emitting layer with the binuclear metal complex in this invention, a light emitting layer can be formed by the above-mentioned vacuum evaporation method etc. with a binuclear metal complex alone. Further, even when a binuclear metal complex is used as a dopant dispersed in the light emitting layer, good light emission characteristics can be obtained. The host compound preferably has an emission peak that overlaps with the absorption peak of the dopant. When the above platinum binuclear complex is used, CBP (4,4′-bis (carbazol-9-yl) -biphenyl) having the following structure is preferably used as the host material. In general, the content of the dopant in the light emitting layer is preferably about 5 to 6% by weight of the host material. A light emitting layer can be formed by co-evaporating a host material and a dopant material, for example.
本発明の複核金属錯体を用いて有機ＥＬ素子の有機層を形成することにより、高輝度及び高発光効率の有機ＥＬ素子とすることができる。 By forming the organic layer of an organic EL element using the binuclear metal complex of this invention, it can be set as an organic EL element of high brightness | luminance and high luminous efficiency.
以下、本発明を実施例により詳細に説明するが、本発明は以下の実施例に限定されるものではなく、適宜変更して実施することが可能なものである。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, It can change and implement suitably.
（合成例１）
＜白金二核錯体〔Ｐｔ2（ｐｐｙ）2（ｐｙｔ）2〕の合成＞
以下に示す合成スキームに従い、白金二核錯体〔Ｐｔ2（ｐｐｙ）2（ｐｙｔ）2〕を合成した。
(Synthesis Example 1)
<Synthesis of platinum binuclear complex [Pt 2 (ppy) 2 (pyt) 2 ]>
A platinum binuclear complex [Pt 2 (ppy) 2 (pyt) 2 ] was synthesized according to the following synthesis scheme.
２００ｍｌのマイヤーフラスコ内において、（ｎ−Ｂｕ）4Ｎ〔Ｐｔ（ｐｐｙ）Ｃｌ2〕４０．０ｍｇ（０．１５ｍｍｏｌ）をアセトニトリル５０ｍｌに溶解させ、これに２−ピリジンチオール１６．８ｍｇ（０．１５ｍｍｏｌ）、トリ（ｎ−ブチル）アミン２７．８ｍｇ（１．５ｍｍｏｌ）、及びエタノール２５ｍｌを加えて室温で一晩攪拌した。攪拌後、析出した目的物（赤色固体）を濾別した。精製は、再結晶法と昇華精製によって行った。 In a 200 ml Meyer flask, 40.0 mg (0.15 mmol) of (n-Bu) 4 N [Pt (ppy) Cl 2 ] was dissolved in 50 ml of acetonitrile, to which 16.8 mg (0.15 mmol) of 2-pyridinethiol was dissolved. ), 27.8 mg (1.5 mmol) of tri (n-butyl) amine, and 25 ml of ethanol were added and stirred overnight at room temperature. After stirring, the precipitated target product (red solid) was filtered off. Purification was performed by recrystallization and sublimation purification.
なお、後述の実施例３及び実施例４において用いた白金二核錯体についても、原料として、対応のメチル置換体またはフッ素置換体あるいは２−キノリンチオールを用いることにより同様にして合成した。 In addition, the platinum binuclear complex used in Example 3 and Example 4 described later was synthesized in the same manner by using a corresponding methyl-substituted product, fluorine-substituted product, or 2-quinolinethiol as a raw material.
（実施例１）
合成例１において得られた白金二核錯体を発光材料として用い、有機ＥＬ素子を作製した。図１は、作製した有機ＥＬ素子の構造を模式的に示す断面図である。図１を参照して、ガラス基板１の上に、インジウム−スズ酸化物（ＩＴＯ）からなるホール注入電極（陽極）２を形成し、この上にＣｕＰｃ（銅フタロシアニン）からなるホール注入層３（厚み１０ｎｍ）を形成し、さらにこの上にＮＰＢ（Ｎ，Ｎ′−ジ−１−ナフチル−Ｎ，Ｎ′−ジフェニルベンジジン）からなるホール輸送層４（厚み５０ｎｍ）を形成した。このホール輸送層４の上に、上記の白金二核錯体〔Ｐｔ2（ｐｐｙ）2（ｐｙｔ）2〕からなる発光層５（厚み１２ｎｍ）を形成した。発光層５の上に、ＢＣＰ（２，９−ジメチル−４，７−ジフェニル−〔１，１０〕フェナントロリン）からなるホール阻止層６（厚み１０ｎｍ）及びＡｌｑ（トリス−（８−キノリナト）アルミニウム（III））からなる電子輸送層７（厚み４０ｎｍ）を形成した。その上に、フッ化リチウム及びアルミニウムからなる電子注入電極（陰極）８（厚み２００ｎｍ）を形成した。
Example 1
Using the platinum binuclear complex obtained in Synthesis Example 1 as a light-emitting material, an organic EL device was produced. FIG. 1 is a cross-sectional view schematically showing the structure of the produced organic EL element. Referring to FIG. 1, a hole injection electrode (anode) 2 made of indium-tin oxide (ITO) is formed on a glass substrate 1, and a hole injection layer 3 (CuPc (copper phthalocyanine)) is formed thereon. Further, a hole transport layer 4 (thickness: 50 nm) made of NPB (N, N′-di-1-naphthyl-N, N′-diphenylbenzidine) was formed thereon. On the
上記各層の形成は、具体的には、以下のようにして行った。 Specifically, each of the above layers was formed as follows.
まず、ＩＴＯが形成されたガラス基板をイソプロピルアルコールで５分間超音波洗浄を２回行った後、オゾンクリーナーにて基板表面の洗浄を行った。この後、上記ＩＴＯからなる陽極上にホール注入層３、ホール輸送層４、発光層５、ホール阻止層６、電子輸送層７、及び電子注入電極８を順次真空蒸着法にて形成し積層した。これらの蒸着は、いずれも真空度１×１０-6Ｔｏｒｒ、基板温度制御なしの条件で行った。
First, the glass substrate on which ITO was formed was subjected to ultrasonic cleaning twice with isopropyl alcohol for 5 minutes, and then the substrate surface was cleaned with an ozone cleaner. Thereafter, a
ＣｕＰｃの構造を以下に示す。 The structure of CuPc is shown below.
ＮＰＢの構造を以下に示す。 The structure of NPB is shown below.
ＢＣＰの構造を以下に示す。 The structure of BCP is shown below.
Ａｌｑの構造を以下に示す。 The structure of Alq is shown below.
得られた素子のホール注入電極をプラス、電子注入電極をマイナスにバイアスして電圧を印加したところ、発光の外部量子収率１．４％、発光極大波長６７０ｎｍ、色度ＣＩＥ座標（０．６５，０．３５）、最高輝度３５６ｃｄ／ｍ2の赤色発光を得た。この素子の発光スペクトルを図２に示す。図２から明らかなように、赤色発光が得られている。なお、発光スペクトル及び色度は、印加電圧に依存せず、一定であった。 When a voltage was applied with the hole injection electrode of the obtained device positively biased and the electron injection electrode negatively biased, the external quantum yield of light emission was 1.4%, the light emission maximum wavelength was 670 nm, and the chromaticity CIE coordinates (0.65). , 0.35) and a red emission with a maximum luminance of 356 cd / m 2 was obtained. The emission spectrum of this device is shown in FIG. As is clear from FIG. 2, red light emission is obtained. The emission spectrum and chromaticity were constant without depending on the applied voltage.
（実施例２）
実施例１において、ＢＣＰに代えて、ＢＡｌｑ（ビス（２−メチル−８−キノリノラト）−４−フェニルフェノラトアルミニウム（III））を用いてホール阻止層を形成する以外は、実施例１と同様にして素子を作製した。
(Example 2)
In Example 1, it replaces with BCP and is the same as Example 1 except forming a hole blocking layer using BAlq (bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III)). Thus, an element was produced.
得られた素子に電圧を印加したところ、発光の外部量子収率２．６％、発光極大波長６７０ｎｍ、色度ＣＩＥ座標（０．６５，０．３５）、及び最高輝度５８４ｃｄ／ｍ2の赤色発光が得られた。この素子において、発光スペクトル及び色度は、印加電圧に依存せず、一定であった。 When a voltage was applied to the resulting device, the external quantum yield of light emission was 2.6%, the light emission maximum wavelength was 670 nm, the chromaticity CIE coordinates (0.65, 0.35), and the maximum luminance of 584 cd / m 2 red. Luminescence was obtained. In this device, the emission spectrum and chromaticity were constant without depending on the applied voltage.
ＢＡｌｑの構造を以下に示す。 The structure of BAlq is shown below.
（実施例３）
実施例１において、実施例２と同様に、ＢＣＰに代えて、ＢＡｌｑを用いてホール阻止層を形成し、さらに白金二核錯体〔Ｐｔ2（ｐｐｙ）2（ｐｙｔ）2〕に代えて、以下に示す構造を有する白金二核錯体〔Ｐｔ2（ｐｔｐｙ）2（ｐｙｔ）2〕を用いて発光層を形成する以外は、実施例１と同様にして発光素子を作製した。
(Example 3)
In Example 1, as in Example 2, a hole blocking layer was formed using BAlq instead of BCP, and further replaced with platinum binuclear complex [Pt 2 (ppy) 2 (pyt) 2 ]. A light emitting device was produced in the same manner as in Example 1 except that a light emitting layer was formed using a platinum binuclear complex [Pt 2 (ptpy) 2 (pyt) 2 ] having the structure shown in FIG.
得られた発光素子に電圧を印加したところ、発光の外部量子収率２．５％、発光極大波長６７０ｎｍ、色度ＣＩＥ座標（０．６５，０．３５）、及び最高輝度９９０ｃｄ／ｍ2の赤色発光が得られた。この素子において、発光スペクトル及び色度は、印加電圧に依存せず、一定であった。 When voltage was applied to the obtained light emitting device, the external quantum yield of light emission was 2.5%, the light emission maximum wavelength was 670 nm, the chromaticity CIE coordinates (0.65, 0.35), and the maximum luminance of 990 cd / m 2 . Red emission was obtained. In this device, the emission spectrum and chromaticity were constant without depending on the applied voltage.
（実施例４）
以下に示す構造を有する白金二核錯体を合成した。
Example 4
A platinum binuclear complex having the structure shown below was synthesized.
合成したこれらの錯体の固体状態・室温でのフォトルミネッセンス（ＰＬ）スペクトルの極大波長λPLｍａｘと、励起スペクトルから求めたその発光に対応する励起エネルギーの波長を測定し、以下の表１に示した。また、表１には、実施例１及び２で用いた錯体及び実施例３において用いた錯体についてのＰＬスペクトルの極大波長と励起エネルギー波長とを併せて示している。 The maximum wavelength λ PL max of the photoluminescence (PL) spectrum of these synthesized complexes at room temperature and the wavelength of the excitation energy corresponding to the emission obtained from the excitation spectrum were measured and shown in Table 1 below. It was. Table 1 also shows the maximum wavelength and excitation energy wavelength of the PL spectrum for the complexes used in Examples 1 and 2 and the complex used in Example 3.
表１に示す結果から明らかなように、上記の白金二核錯体は５５０〜６００ｎｍの範囲に励起エネルギー波長を有している。単核錯体の場合、励起エネルギー波長は４００〜４５０ｎｍ程度であるので三重項3ＭＭＬＣＴ遷移に基づいて長波長シフトしているものと思われる。本実施例において合成した表１のＮｏ．３〜７の白金二核錯体は、実施例１及び２で用いたＮｏ．１の白金二核錯体及び実施例３で用いたＮｏ．２の白金二核錯体と近似した波長範囲に吸収ピーク波長及びＰＬスペクトルの極大波長を有している。従って、これらの白金二核錯体も、有機ＥＬ素子の赤色発光材料として用いることができるものであると考えられる。このように配位子に各種置換基を置換しても、有機ＥＬ素子の発光材料として用いることができると考えられるので、電子吸引性及び電子供与性などの置換基の電子的性質を選択することにより、発光材料自体のキャリア輸送性などの特性を調整することが可能であると考えられる。 As is clear from the results shown in Table 1, the platinum binuclear complex has an excitation energy wavelength in the range of 550 to 600 nm. In the case of a mononuclear complex, since the excitation energy wavelength is about 400 to 450 nm, it seems that the wavelength shift is long based on the triplet 3 MMLCT transition. No. 1 of Table 1 synthesized in this example. The platinum binuclear complexes of 3 to 7 are the same as those used in Examples 1 and 2. No. 1 used in the platinum binuclear complex of Example 1 and Example 3. 2 has an absorption peak wavelength and a maximum wavelength of the PL spectrum in a wavelength range approximate to that of the platinum binuclear complex. Therefore, it is considered that these platinum binuclear complexes can also be used as red light emitting materials for organic EL elements. Thus, even if various substituents are substituted on the ligand, it is considered that the ligand can be used as a light-emitting material of the organic EL device. Therefore, the electronic properties of the substituent such as electron withdrawing property and electron donating property are selected. Thus, it is considered that characteristics such as carrier transportability of the light emitting material itself can be adjusted.
１…ガラス基板
２…ホール注入電極（陽極）
３…ホール注入層
４…ホール輸送層
５…発光層
６…ホール阻止層
７…電子輸送層
８…電子注入電極（陰極）
1 ...
DESCRIPTION OF
Claims (4)
前記有機層が、以下の一般式（１）で表わされる複核金属錯体を含むことを特徴とする有機エレクトロルミネッセンス素子。
The said organic layer contains the binuclear metal complex represented by the following general formula (1), The organic electroluminescent element characterized by the above-mentioned.
The organic electroluminescent element according to claim 1, wherein the organic layer is a light emitting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004065966A JP4425028B2 (en) | 2004-03-09 | 2004-03-09 | Organic electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004065966A JP4425028B2 (en) | 2004-03-09 | 2004-03-09 | Organic electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005259377A true JP2005259377A (en) | 2005-09-22 |
| JP4425028B2 JP4425028B2 (en) | 2010-03-03 |
Family
ID=35084913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004065966A Expired - Lifetime JP4425028B2 (en) | 2004-03-09 | 2004-03-09 | Organic electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4425028B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012039347A1 (en) * | 2010-09-21 | 2012-03-29 | 国立大学法人 長崎大学 | Metal complex, light emitting element, and display device |
| CN107923038A (en) * | 2015-08-25 | 2018-04-17 | 田中贵金属工业株式会社 | The chemical vapor deposition raw material being made of binuclear ruthenium and the chemical vapor deposition using the chemical vapor deposition raw material |
| US20190123288A1 (en) * | 2017-09-21 | 2019-04-25 | Universal Display Corporation | Organic electroluminescent materials and devices |
-
2004
- 2004-03-09 JP JP2004065966A patent/JP4425028B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012039347A1 (en) * | 2010-09-21 | 2012-03-29 | 国立大学法人 長崎大学 | Metal complex, light emitting element, and display device |
| US8765952B2 (en) | 2010-09-21 | 2014-07-01 | Nagasaki University | Metal complex, light emitting element, and display device |
| JP5924691B2 (en) * | 2010-09-21 | 2016-05-25 | 国立大学法人 長崎大学 | Metal complex, light emitting element, display device |
| CN107923038A (en) * | 2015-08-25 | 2018-04-17 | 田中贵金属工业株式会社 | The chemical vapor deposition raw material being made of binuclear ruthenium and the chemical vapor deposition using the chemical vapor deposition raw material |
| CN107923038B (en) * | 2015-08-25 | 2020-01-07 | 田中贵金属工业株式会社 | Raw material for chemical vapor deposition comprising binuclear ruthenium complex and chemical vapor deposition method using same |
| US20190123288A1 (en) * | 2017-09-21 | 2019-04-25 | Universal Display Corporation | Organic electroluminescent materials and devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4425028B2 (en) | 2010-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6426676B2 (en) | Novel organic light emitting material | |
| JP5973009B2 (en) | Compound | |
| US8247086B2 (en) | Organometallic complex and light-emitting element, light-emitting device and electronic device using the same | |
| JP5149000B2 (en) | Organic light emitting device | |
| US7759490B2 (en) | Phosphorescent Osmium (II) complexes and uses thereof | |
| JP4662854B2 (en) | Organometallic compound in which compound for host and compound for dopant are connected, organic electroluminescent device using the same, and method for producing the same | |
| US20110017984A1 (en) | Metal complex compound and organic electroluminescent device using same | |
| JP5266203B2 (en) | Luminescent substance | |
| JP2003081989A (en) | Metal coordination compound, light emitting element and display | |
| JP2015005765A (en) | Light-emitting element, light-emitting device, electronic device, luminaire | |
| KR20130018550A (en) | Heteroleptic iridium complexes as dopants | |
| JP2003081988A (en) | Light emitting element, display and metal coordination compound for the light emitting element | |
| KR20100085845A (en) | Organometallic complex, and light-emitting element, light-emitting device, electronic device, and lighting device using the organometallic complex | |
| JP6473437B2 (en) | High efficiency phosphorescent material | |
| JP5416098B2 (en) | Bipyridine metal complexes used as luminescent materials | |
| KR101057175B1 (en) | Novel Iridium (III) Complexes and Organic Electroluminescent Devices Comprising the Same | |
| JP4425028B2 (en) | Organic electroluminescence device | |
| JP2013142088A (en) | Highly efficient phosphorescent material | |
| JP2004220965A (en) | Luminescent element using metal coordination compound | |
| CA2487118A1 (en) | Phosphorescent osmium and ruthenium complexes and uses thereof | |
| JP2012188357A (en) | Metal complex, light-emitting device, and display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060725 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090519 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090721 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090818 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091009 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091110 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091208 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4425028 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121218 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131218 Year of fee payment: 4 |
|
| EXPY | Cancellation because of completion of term |