TWI609874B - Composition for organic electroluminescent element, organic electroluminescent element, display and lighting - Google Patents
Composition for organic electroluminescent element, organic electroluminescent element, display and lighting Download PDFInfo
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- TWI609874B TWI609874B TW105109148A TW105109148A TWI609874B TW I609874 B TWI609874 B TW I609874B TW 105109148 A TW105109148 A TW 105109148A TW 105109148 A TW105109148 A TW 105109148A TW I609874 B TWI609874 B TW I609874B
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- organic electroluminescence
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- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 150000001875 compounds Chemical class 0.000 claims abstract description 105
- 125000001424 substituent group Chemical group 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000005401 electroluminescence Methods 0.000 claims abstract description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
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- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims 4
- 238000006467 substitution reaction Methods 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 4
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- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本發明提供一種保存穩定性或成膜步驟穩定性較高之有機電致發光元件用組成物、使用該組成物製作之電流效率較高之有機電致發光元件、及使用該有機電致發光元件之顯示裝置及照明裝置。本發明係關於一種有機電致發光元件用組成物，其至少含有：磷光發光材料；電荷輸送性化合物；及酚性化合物，其具有酚性羥基，且將該酚性羥基設為1位時，於2、4、6位中，僅於任意二者具有取代基。 The invention provides a composition for an organic electroluminescence element with higher storage stability or film formation step stability, an organic electroluminescence element with higher current efficiency produced by using the composition, and an organic electroluminescence element using the same. Display device and lighting device. The present invention relates to a composition for an organic electroluminescent device, which contains at least: a phosphorescent light-emitting material; a charge transporting compound; and a phenolic compound having a phenolic hydroxyl group, and when the phenolic hydroxyl group is set to the In the 2, 4, and 6 positions, there are substituents only in any two.
Description
本發明係關於一種有機電致發光元件用組成物，且係關於一種用以提供效率較高之有機電致發光元件之有機電致發光元件用組成物、使用該組成物製造之有機電致發光元件、及含有該有機電致發光元件之顯示裝置及照明裝置。 The present invention relates to a composition for an organic electroluminescence element, and relates to a composition for an organic electroluminescence element for providing an organic electroluminescence element with high efficiency, and an organic electroluminescence manufactured using the composition Element, and display device and lighting device containing the organic electroluminescence element.
近年來，有機電致發光照明(有機EL照明)或有機電致發光顯示器(有機EL顯示器)等利用有機電致發光元件(以下，有時亦稱為「有機EL元件」)之各種電子器件(device)不斷實用化。由於有機EL面板之外加電壓較低而消耗電力較小，為面發光，且亦可三原色發光，因此業界積極研究其於照明或顯示器中之應用。進而，尋求製造成本之降低、或使用大面積之有機EL面板之電子器件之實用化。 In recent years, various types of electronic devices (such as organic electroluminescence) or organic electroluminescence displays (organic EL displays) that use organic electroluminescence elements (hereinafter, sometimes also referred to as "organic EL elements") ( device) continues to be put into practical use. Since the organic EL panel has a lower applied voltage and consumes less power, it is surface-emitting, and it can also emit light in three primary colors. Therefore, the industry actively studies its application in lighting or displays. Furthermore, reduction of manufacturing cost and practical use of electronic devices using a large-area organic EL panel have been sought.
另一方面，針對其實用化，尋求進一步之長壽化、高效率化。有機電致發光元件係藉由自陽極及陰極注入之電荷於發光層上進行再結合，產生激子而發光。因此，作為提高效率之手段，有效的是將所注入之電荷封入發光層內。作為代表性之手法，有防止所產生之激子擴散之方法，可列舉於發光層之陰極側鄰接層設置 防激子擴散層(專利文獻1)。 On the other hand, for its practical use, it is seeking further longevity and high efficiency. Organic electroluminescence elements recombine on the light-emitting layer by the charges injected from the anode and cathode to generate excitons and emit light. Therefore, as a means to improve efficiency, it is effective to encapsulate the injected charges in the light emitting layer. As a representative method, there is a method for preventing the generated exciton from diffusing, and it can be provided on the cathode side adjacent layer of the light emitting layer. Anti-excitation diffusion layer (Patent Document 1).
作為用以於發光層內部實現高效率化而將電荷封入發光層內之手法，考慮到將具有電荷捕捉性之材料用於發光層之手段。作為實現其之一手段，考慮藉由雜原子所具有之孤電子對捕捉電荷而將其封入發光層內之方法。作為含有具孤電子對之雜原子的化合物，例如可列舉具有酚性羥基之化合物。該具有酚性羥基之化合物習知用作抗氧化劑(專利文獻2、專利文獻3)。 As a method for achieving high efficiency inside the light-emitting layer and encapsulating charges in the light-emitting layer, a method of using a material having charge trapping properties for the light-emitting layer is considered. As one of the means to achieve this, a method of encapsulating a heteroatom with a lone electron pair to capture a charge and encapsulating the charge in a light emitting layer is considered. Examples of the compound containing a hetero atom having a lone electron pair include a compound having a phenolic hydroxyl group. This compound having a phenolic hydroxyl group is conventionally used as an antioxidant (Patent Document 2, Patent Document 3).
又，於專利文獻4中，記載有：若酚系抗氧化劑殘留，則外部量子效率等有機EL元件性能下降，因此使用不會殘留之抗氧化劑。於專利文獻5中，記載有：作為具有酚性羥基之化合物之穩定劑因使元件性能大幅度劣化而去除。 Further, Patent Document 4 describes that if a phenol-based antioxidant remains, the performance of an organic EL device such as external quantum efficiency is reduced, and therefore an antioxidant that does not remain is used. Patent Document 5 describes that a stabilizer, which is a compound having a phenolic hydroxyl group, is removed due to a significant deterioration in device performance.
專利文獻1：國際公開第2012/070226號 Patent Document 1: International Publication No. 2012/070226
專利文獻2：日本專利特開平10-255981號公報 Patent Document 2: Japanese Patent Laid-Open No. 10-255981
專利文獻3：日本專利特開2004-088094號公報 Patent Document 3: Japanese Patent Laid-Open No. 2004-088094
專利文獻4：日本專利特開2013-165089號公報 Patent Document 4: Japanese Patent Laid-Open No. 2013-165089
專利文獻5：日本專利特開2013-060396號公報 Patent Document 5: Japanese Patent Laid-Open No. 2013-060396
然而，如專利文獻2、3中所記載，於使具有酚性羥基之化合物與含有磷光發光材料之發光層之材料共存之情形時，考慮到引起特性惡化之可能性。因此，亦如專利文獻4、5中所記載， 為了避免具有酚性羥基之化合物對含有磷光發光材料之發光材料的不良影響，去除該具有酚性羥基之化合物成為前提。 However, as described in Patent Documents 2 and 3, when a compound having a phenolic hydroxyl group and a material of a light-emitting layer containing a phosphorescent light-emitting material coexist, a possibility of causing deterioration in characteristics is considered. Therefore, as described in Patent Documents 4 and 5, In order to avoid the adverse effect of a compound having a phenolic hydroxyl group on a light-emitting material containing a phosphorescent light-emitting material, it is a prerequisite to remove the compound having a phenolic hydroxyl group.
即，對於業者而言，認為較佳為將此種帶來不良影響之化合物去除而使之不殘留。根據上述技術背景，並未實施積極地使用具有酚性羥基之化合物，進而將電荷封入發光層內等手段。 That is, it is considered that it is preferable for the industry to remove such a compound having an adverse effect so that it does not remain. According to the above-mentioned technical background, no means such as actively using a compound having a phenolic hydroxyl group, and further sealing a charge in a light-emitting layer has been implemented.
因此，本發明之課題在於提供一種用於效率較高之有機電致發光元件之組成物。 Therefore, an object of the present invention is to provide a composition for an organic electroluminescent device having high efficiency.
本發明者等人鑒於上述課題進行銳意研究，結果驚人地發現：使用如下組成物製作之有機電致發光元件可獲得不損害電流效率，反而使電流效率提高，進而長壽化之效果，從而完成本發明，其中該組成物至少含有：特定之酚性化合物，其係具有酚性羥基，且將酚性羥基設為1位時，於2、4、6位中，僅於任意二者具有取代基之酚性化合物；磷光發光材料；及電荷輸送性化合物。 The present inventors conducted intensive research in view of the above-mentioned problems, and surprisingly found that the organic electroluminescent element produced by using the following composition can achieve the effect of not impairing the current efficiency, but improving the current efficiency, and further prolonging the life, thereby completing the present invention. The invention, wherein the composition contains at least: a specific phenolic compound having a phenolic hydroxyl group, and when the phenolic hydroxyl group is set to the 1st position, it has substituents only at any of the 2, 4, and 6 positions Phenolic compounds; phosphorescent materials; and charge transporting compounds.
再者，本發明之作用機制係推斷如下。注入至發光層之電荷係藉由於發光層所含之電荷輸送性化合物上進行跳躍傳導而輸送。推斷出由於羥基具有孤電子對，且電子密度較高，因此引起跳躍電洞之輸送抑制而將電洞封入發光層內之效果得以提高。 The mechanism of action of the present invention is inferred as follows. The charge injected into the light-emitting layer is transferred by performing jump conduction on the charge-transporting compound contained in the light-emitting layer. It is inferred that because the hydroxyl group has a lone electron pair and the electron density is high, the effect of enclosing the hole in the light emitting layer due to the inhibition of the transport of the jumping hole is improved.
然而，認為於鄰位之兩者均不存在取代基之情形時，羥基成為未受保護之狀態，對周邊之電荷輸送性化合物或發光材料帶來不良影響。即，就羥基而言，認為鄰位、對位對酚性羥基之影響較大，因此藉由將酚性羥基設為1位時於2、4、6位中僅於任意二者具有取代基，而發揮本發明之效果。 However, when there are no substituents in both ortho positions, it is considered that the hydroxyl group is in an unprotected state, which adversely affects the surrounding charge-transporting compound or the light-emitting material. That is to say, as for the hydroxyl group, the ortho and para positions are considered to have a great influence on the phenolic hydroxyl group. Therefore, when the phenolic hydroxyl group is set to the 1st position, only two of them are substituted at any of the 2, 4, and 6 positions. , And exert the effect of the present invention.
即，本發明之主旨如以下所示。 That is, the gist of the present invention is as follows.
1.一種有機電致發光元件用組成物，其至少含有：磷光發光材料；電荷輸送性化合物；及酚性化合物，且其具有酚性羥基，將該酚性羥基設為1位時，於2、4、6位中，僅於任意二者具有取代基。 A composition for an organic electroluminescence element, comprising at least: a phosphorescent light-emitting material; a charge-transporting compound; and a phenolic compound, which has a phenolic hydroxyl group. Only two of the 4, 4, and 6 positions have a substituent.
2.如上述1中記載之有機電致發光元件用組成物，其中，於上述酚性化合物中酚構造僅有1個。 2. The composition for an organic electroluminescence device according to the above 1, wherein there is only one phenol structure in the phenolic compound.
3.如上述1或2中記載之有機電致發光元件用組成物，其中，上述酚性化合物係在酚性羥基設為1位時，僅於2、4、6位中之任意二者具有取代基，且3位及5位未經取代者。 3. The composition for an organic electroluminescence device according to the above 1 or 2, wherein the phenolic compound has only one of the 2, 4, and 6 positions when the phenolic hydroxyl group is set to the 1 position. Substituents with unsubstituted 3 and 5 positions.
4.如上述1至3中任一項記載之有機電致發光元件用組成物，其中，上述取代基選自碳數1~12之烷基、碳數1~12之烷氧基、使用碳數6~18之芳基之芳氧基、碳數1~24之芳烷基。 4. The composition for an organic electroluminescence device according to any one of the above 1 to 3, wherein the substituent is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon used. An aryloxy group having 6 to 18 aryl groups and an aralkyl group having 1 to 24 carbon numbers.
5.如上述1至4中任一項記載之有機電致發光元件用組成物，其中，上述取代基選自碳數1~12之烷基或碳數1~12之烷氧基。 5. The composition for an organic electroluminescence device according to any one of 1 to 4 above, wherein the substituent is selected from an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
6.如上述1至5中任一項記載之有機電致發光元件用組成物，其中，上述酚性化合物相對於上述組成物中之上述電荷輸送性化合物之總量，為0.01質量%以上且10質量%以下。 6. The composition for an organic electroluminescence device according to any one of the above 1 to 5, wherein the total amount of the phenolic compound with respect to the total amount of the charge transporting compound in the composition is 0.01% by mass or more and 10% by mass or less.
7.如上述1至6中任一項記載之有機電致發光元件用組成物，其中，上述酚性化合物相對於上述組成物中所含之上述電荷輸送性化合物之總量，為0.1質量%以上且1質量%以下。 7. The composition for an organic electroluminescence device according to any one of the above 1 to 6, wherein the phenolic compound is 0.1% by mass relative to the total amount of the charge-transporting compound contained in the composition. It is more than 1 mass%.
8.一種有機電致發光元件，其係具有陽極、陰極、及於上述陽極與上述陰極之間至少1層之發光層者，且上述發光層之至少1層係藉由使用如上述1至7中任一項記載之有機電致發光元件用組成物進行濕式成膜而形成。 8. An organic electroluminescence element comprising an anode, a cathode, and at least one light-emitting layer between the anode and the cathode, and at least one layer of the light-emitting layer is used as described above 1 to 7 The composition for an organic electroluminescence device according to any one of the claims is formed by wet film formation.
9.一種顯示裝置，其具有如上述8中記載之有機電致發光元件。 9. A display device having the organic electroluminescence element as described in 8 above.
10.一種照明裝置，其具有如上述8中記載之有機電致發光元件。 10. A lighting device comprising the organic electroluminescence element as described in 8 above.
根據本發明之有機電致發光元件用組成物，能夠使利用其而獲得之有機電致發光元件表現出高電流效率，實現長壽化，且於酚性羥基之特性上，可期待有機電致發光元件用組成物之保存穩定性或成膜步驟穩定性，係能夠同時實現兩者之技術，作為有機電致發光元件用組成物非常有用。 According to the composition for an organic electroluminescence element of the present invention, the organic electroluminescence element obtained by using the composition can exhibit high current efficiency, achieve longevity, and can be expected to have organic electroluminescence in terms of characteristics of a phenolic hydroxyl group. The storage stability of the composition for the device or the stability of the film formation step are technologies capable of achieving both, and are very useful as a composition for an organic electroluminescence device.
1‧‧‧基板 1‧‧‧ substrate
2‧‧‧陽極 2‧‧‧ anode
3‧‧‧電洞注入層 3‧‧‧ Hole injection layer
4‧‧‧電洞輸送層 4‧‧‧ Hole transporting layer
5‧‧‧發光層 5‧‧‧ luminescent layer
6‧‧‧電洞阻擋層 6‧‧‧ Hole barrier
7‧‧‧電子輸送層 7‧‧‧ electron transport layer
8‧‧‧電子注入層 8‧‧‧ electron injection layer
9‧‧‧陰極 9‧‧‧ cathode
10‧‧‧有機電致發光元件 10‧‧‧Organic electroluminescence element
圖1係示意性地表示本發明之有機電致發光元件之構造之一例的剖面圖。 FIG. 1 is a cross-sectional view schematically showing an example of a structure of an organic electroluminescence element of the present invention.
以下，對本發明之實施形態進行詳細說明，但本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變化而實施。 Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.
本發明之磷光發光材料係指自激發三重態顯示發光之材料。例如具有Ir、Pt、Eu等之金屬錯合物化合物係其代表例，作為材料之構造，較佳為含有金屬錯合物者。 The phosphorescent light-emitting material of the present invention refers to a material that emits light in a self-excited triplet state. For example, a metal complex compound having Ir, Pt, Eu, etc. is a representative example thereof. As a material structure, a metal complex compound is preferably contained.
於金屬錯合物中，作為經由三重態而發光之磷光發光性有機金屬錯合物，可列舉含有選自長週期型週期表(以下，只要無特別附文，則於稱為「週期表」之情形時，指長週期型週期表)第7 ~11族之金屬作為中心金屬之Werner型錯合物或有機金屬錯合物化合物。較佳為可列舉下述式(I)或式(II)所表示之化合物。 Among the metal complexes, examples of the phosphorescent light-emitting organometallic complexes that emit light through the triplet state include those selected from the long-period periodic table (hereinafter, unless otherwise specified, they are referred to as "periodic table" (In the case of a long-period periodic table) Group 11 metals are Werner type complexes or organometallic complex compounds as the central metal. Preferable examples include compounds represented by the following formula (I) or formula (II).
ML(q-j)L'j…(I) ML (qj) L ' j … (I)
(式(I)中，M表示金屬，q表示上述金屬之價數。又，L及L'表示雙牙配位基。j表示0、1或2之數。於有數個L或L'之情形時，數個L或數個L'可分別相同亦可不同) (In formula (I), M represents a metal, and q represents the valence of the above-mentioned metals. In addition, L and L 'represent bidentate ligands. J represents a number of 0, 1, or 2. In the case where there are several L or L' In the case, several L's or several L's may be the same or different respectively)
(式(II)中，M2表示金屬，T表示碳原子或氮原子。R92~R95分別獨立表示取代基。其中，於T為氮原子之情形時，無R94及R95) (In the formula (II), M 2 represents a metal, and T represents a carbon atom or a nitrogen atom. R 92 to R 95 each independently represent a substituent. However, when T is a nitrogen atom, R 94 and R 95 are absent.)
對式(I)所表示之化合物進行說明。式(I)中，M係選自週期表第7~11族之金屬。較佳為可列舉釕、銠、鈀、銀、錸、鋨、銥、鉑、金等。其中更佳為銥或鉑。就穩定性較高之方面及發光效率較高之方面而言，最佳為銥。又，式(I)中，雙牙配位基L表示具有以下之式(III)所表示之部分構造之配位基。 The compound represented by formula (I) will be described. In formula (I), M is a metal selected from Groups 7 to 11 of the periodic table. Preferable examples include ruthenium, rhodium, palladium, silver, osmium, osmium, iridium, platinum, gold, and the like. Among them, iridium or platinum is more preferable. In terms of higher stability and higher luminous efficiency, iridium is preferred. In the formula (I), the bidentate ligand L represents a ligand having a partial structure represented by the following formula (III).
[化2]
於上述式(III)之部分構造中，環A1表示可具有取代基之芳香環基。本發明中之芳香環基可為芳香族烴環基，亦可為芳香族雜環基。又，於上述式(III)之部分構造中，環A2表示可具有取代基之含氮芳香族雜環基。又，式(I)中，雙牙配位基L'表示具有以下之部分構造之配位基。 In the partial structure of the formula (III), the ring A1 represents an aromatic ring group which may have a substituent. The aromatic ring group in the present invention may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. In the partial structure of the formula (III), the ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent. In formula (I), the bidentate ligand L ′ represents a ligand having the following partial structure.
該等之中，作為L'，就錯合物之穩定性之觀點而言，較佳為以下列舉之配位基。 Among these, from the viewpoint of the stability of the complex, L 'is preferably a ligand listed below.
[化4]
作為式(I)所表示之化合物，進而較佳為可列舉下述式(Ia)、(Ib)、(Ic)所表示之化合物。 As the compound represented by the formula (I), a compound represented by the following formulae (Ia), (Ib), and (Ic) is more preferable.
(式(Ia)中，M4表示與M相同之金屬，w表示上述金屬之價數，環A1表示可具有取代基之芳香環基，環A2表示可具有取代基之含氮芳香族雜環基。於w為2以上而具有數個環A1及環A2之情形時，數個環A1或環A2可分別相同亦可不同) (In formula (Ia), M 4 represents the same metal as M, w represents the valence of the above metal, ring A1 represents an aromatic ring group which may have a substituent, and ring A2 represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent. When w is 2 or more and there are several rings A1 and A2, the rings A1 or A2 may be the same or different)
(式(Ib)中，M5表示與M相同之金屬，w-1表示上述金屬之價數，環A1表示可具有取代基之芳香環基，環A2表示可具有取代基之含氮芳香族雜環基。於w為3以上而具有數個環A1及環A2之情形時，數個環A1或環A2可分別相同亦可不同) (In formula (Ib), M 5 represents the same metal as M, w-1 represents the valence of the above metal, ring A1 represents an aromatic ring group which may have a substituent, and ring A2 represents a nitrogen-containing aromatic group which may have a substituent. Heterocyclic group. When w is 3 or more and has several rings A1 and A2, the rings A1 or A2 may be the same or different)
[化7]
(式(Ic)中，M6表示與M相同之金屬，w表示上述金屬之價數，j表示0、1或2，環A1及環A1'分別獨立表示可具有取代基之芳香環基，環A2及環A2'分別獨立表示可具有取代基之含氮芳香族雜環基。於w-j為2以上或j為2以上而具有數個環A1、環A1'、環A2或環A2'之情形時，數個環A1、環A1'、環A2或環A2'可分別相同亦可不同) (In formula (Ic), M 6 represents the same metal as M, w represents the valence of the above metal, j represents 0, 1 or 2, and ring A1 and ring A1 'each independently represent an aromatic ring group which may have a substituent, Ring A2 and ring A2 'each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent. When wj is 2 or more or j is 2 or more, it has several rings A1, A1', A2, or A2 '. In this case, several rings A1, A1 ', A2, or A2' may be the same or different)
於上述式(Ia)~(Ic)、(III)中，環A1及環A1'之芳香環為芳香族烴基或芳香族雜環基。較佳為具有2個游離原子價之苯環、萘環、蒽環、聯三苯環、乙烷合萘環、熒蒽環、茀環、呋喃環、苯并呋喃環、噻吩環、苯并噻吩環。進而較佳為苯環、萘環，最佳為苯環。 In the formulae (Ia) to (Ic) and (III), the aromatic ring of the ring A1 and the ring A1 ′ is an aromatic hydrocarbon group or an aromatic heterocyclic group. A benzene ring, a naphthalene ring, an anthracene ring, a bitriphenyl ring, an ethane naphthalene ring, a fluoranthene ring, a fluorene ring, a furan ring, a benzofuran ring, a thiophene ring, and a benzo ring having two free atomic valences are preferred. Thiophene ring. Furthermore, a benzene ring and a naphthalene ring are preferable, and a benzene ring is the most preferable.
此處，於本說明書中，所謂游離原子價，如有機化學、生物化學命名法(上)(修訂第2版、南江堂、1992年發行)中所記載，係指可與其他游離原子價形成鍵者。即，例如，「具有1個游離原子價之苯環」係指苯基之情況，「具有2個游離原子價之苯環」係指伸苯基之情況。 Here, in this specification, the so-called free atomic valence, as described in the nomenclature of organic chemistry and biochemistry (Part 1) (Revised 2nd Edition, Nanjiangtang, issued in 1992) means that it can form bonds with other free atomic valences. By. That is, for example, "a benzene ring having one free atomic valence" refers to the case of a phenyl group, and "a benzene ring having two free atomic valences" refers to a case of a phenyl group.
於上述式(Ia)~(Ic)、(III)中，作為環A2及環A2'之含氮芳香族雜環基，較佳為吡啶基、嘧啶基、吡
進而較佳為吡啶基、吡
最佳為吡啶基、咪唑基、喹啉基、喹
於上述式(Ia)~(Ic)、(III)中，作為環A1與環A2之組合構造，或環A1'與環A2'之組合構造，最佳為可具有取代基之苯基-吡啶構造、可具有取代基之苯基-喹啉構造、可具有取代基之苯基-喹
作為上述式(Ia)~(Ic)、(III)中之環A1、環A1'、環A2及環A2'可具有之取代基，可列舉：鹵素原子、碳數1~12之烷基、碳數1~12之烯基、碳數1~12之烷氧羰基、碳數1~12之烷氧基、碳數1~24之芳烷基、碳數1~12之芳氧基、碳數1~24之二烷基胺基、碳數8~24之二芳基胺基、五或六員環之單環或2~4縮合環之芳香族烴環基、碳數6~24之芳香族烴基、咔唑基、醯基、鹵烷基、氰基等。 Examples of the substituents which the ring A1, ring A1 ', ring A2, and ring A2' in the formulae (Ia) to (Ic) and (III) may have include a halogen atom, an alkyl group having 1 to 12 carbon atoms, Alkenyl group with 1 to 12 carbons, alkoxycarbonyl group with 1 to 12 carbons, alkoxy group with 1 to 12 carbons, aralkyl group with 1 to 24 carbons, aryloxy group with 1 to 12 carbons, carbon Dialkylamino groups of 1 to 24, diarylamino groups of 8 to 24 carbons, monocyclic five- or six-membered rings or aromatic hydrocarbon ring groups of 2 to 4 condensed rings, 6 to 24 carbons Aromatic hydrocarbon groups, carbazolyl, fluorenyl, haloalkyl, cyano, and the like.
較佳為碳數1~12之烷基、碳數1~12之烷氧基、碳數1~24之芳烷基、碳數8~24之二芳基胺基、五或六員環之單環或2~4縮合環之芳香族烴環基、碳數6~24之芳香族烴基、咔唑基。 Preferred are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, aralkyl having 1 to 24 carbons, diarylamino having 8 to 24 carbons, five or six membered ring Monocyclic or 2 to 4 condensed aromatic hydrocarbon ring groups, aromatic hydrocarbon groups with 6 to 24 carbon atoms, and carbazole groups.
碳數8~24之二芳基胺基、五或六員環之單環或2~4縮合環之芳香族烴環基、碳數6~24之芳香族烴基、咔唑基亦可於構成該基之芳基部位進而具有取代基。作為該取代基，可列舉碳 數1~12之烷基、碳數1~12之烷氧基、碳數1~24之芳烷基、可經碳數1~12之烷基取代之碳數6~24之一價芳香族烴基。作為碳數6~24之一價芳香族烴基，較佳為1至4個苯環連結而成之一價基。 A diarylamino group having 8 to 24 carbon atoms, a monocyclic five- or six-membered ring or an aromatic hydrocarbon ring group having 2 to 4 condensed rings, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a carbazole group can also be used in the composition. The aryl portion of this group further has a substituent. Examples of the substituent include carbon Alkyl groups of 1 to 12, alkoxy groups of 1 to 12 carbons, aralkyl groups of 1 to 24 carbons, monovalent aromatic groups of 6 to 24 carbons that can be substituted by alkyl groups of 1 to 12 carbons Alkyl. The monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms is preferably a monovalent group obtained by linking 1 to 4 benzene rings.
再者，該等取代基亦可相互連結而形成環。作為具體例，亦可藉由環A1具有之取代基與環A2具有之取代基鍵結、或環A1'具有之取代基與環A2'具有之取代基鍵結而形成一個縮合環。 Furthermore, these substituents may be linked to each other to form a ring. As a specific example, a condensed ring may be formed by bonding a substituent having ring A1 and a substituent having ring A2, or a substituent having ring A1 ′ and a substituent having ring A2 ′.
作為此種縮合環，可列舉7,8-苯并喹啉基等。該等取代基相互連結而形成之環亦可進而具有上述取代基。又，上述取代基可具有1個，亦可具有相同或不同之2個以上之取代基。 Examples of such a condensed ring include 7,8-benzoquinolinyl and the like. The ring formed by connecting these substituents to each other may further have the above-mentioned substituent. Moreover, the said substituent may have one, and may have two or more substituents which are the same or different.
又，作為式(Ia)~(Ic)中之M之較佳例，係與式(I)中之M相同。其次，對式(II)所表示之化合物進行說明。式(II)中，M2表示金屬。作為具體例，可列舉作為選自週期表第7~11族之金屬而於上文所述之金屬。其中，較佳為可列舉釕、銠、鈀、銀、錸、鋨、銥、鉑或金，尤佳為可列舉鉑、鈀等二價金屬。 A preferable example of M in the formulae (Ia) to (Ic) is the same as M in the formula (I). Next, the compound represented by formula (II) will be described. In formula (II), M 2 represents a metal. Specific examples include the metals described above as metals selected from Groups 7 to 11 of the periodic table. Among them, preferred examples include ruthenium, rhodium, palladium, silver, osmium, osmium, iridium, platinum, or gold, and particularly preferred examples include divalent metals such as platinum and palladium.
又，於式(II)中，R92及R93分別獨立表示氫原子、鹵素原子、烷基、芳烷基、烯基、氰基、胺基、醯基、烷氧羰基、羧基、烷氧基、烷基胺基、芳烷基胺基、鹵烷基、羥基、芳氧基、芳香族烴基或芳香族雜環基。 In formula (II), R 92 and R 93 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amine group, a fluorenyl group, an alkoxycarbonyl group, a carboxyl group, and an alkoxy group. Group, alkylamino group, aralkylamino group, haloalkyl group, hydroxy group, aryloxy group, aromatic hydrocarbon group or aromatic heterocyclic group.
進而，於T為碳原子之情形時，R94及R95分別獨立表示與R92及R93相同之例示物所表示之取代基。又，於T為氮原子之情形時，不存在直接鍵結於該T之R94或R95。又，R92~R95亦可進而具有取代基。作為取代基，可設為上述取代基。進而，R92~R95中之任意2個以上之基亦可相互連結而形成環。作為磷光發 光性有機金屬錯合物，較佳為式(I)所表示之化合物。 Furthermore, when T is a carbon atom, R 94 and R 95 each independently represent a substituent represented by the same exemplified as R 92 and R 93 . When T is a nitrogen atom, there is no R 94 or R 95 directly bonded to T. R 92 to R 95 may further have a substituent. As a substituent, the said substituent can be mentioned. Furthermore, any two or more of R 92 to R 95 may be connected to each other to form a ring. As the phosphorescent organic organometallic complex, a compound represented by the formula (I) is preferred.
本發明中之酚性化合物只要為具有酚性羥基，且將酚性羥基設為1位時，於2、4、6位中，僅於任意二者具有取代基者，則並無特別限制，3位及/或5位可未經取代亦可具有取代基。 The phenolic compound in the present invention is not particularly limited as long as it has a phenolic hydroxyl group, and when the phenolic hydroxyl group is at the 1-position, and only any of them has a substituent at the 2, 4, and 6, The 3- and / or 5-position may be unsubstituted or may have a substituent.
該化合物較佳為具有孤電子對，且不具有電荷輸送性之化合物。更佳為將酚性羥基設為1位時，僅於2、4、6位中之任意二者具有取代基，且3位及5位未經取代之酚性化合物。 The compound is preferably a compound having a lone electron pair and having no charge transportability. More preferably, when the phenolic hydroxyl group is set to the 1-position, the phenolic compound has a substituent only at any of the 2, 4, and 6 positions, and the 3- and 5-positions are unsubstituted phenolic compounds.
取代基無特別限制，只要於本化合物中存在1個以上之酚構造即可，於存在2個以上之酚構造之情形時，只要於任一構造中含有本發明所規定之構造即可。較佳為於酚性化合物中僅存在1個酚構造。 The substituent is not particularly limited, as long as one or more phenol structures are present in the present compound, and when two or more phenol structures are present, any structure may be included in the structure specified in the present invention. It is preferable that only one phenol structure is present in the phenolic compound.
該取代基之中，較佳為烷基、烷氧基、使用芳基之芳氧基、芳烷基。具體而言，更佳為選自碳數1~12之烷基、碳數1~12之烷氧基、使用碳數6~18之芳基之芳氧基、碳數1~24之芳烷基之基。 Among the substituents, an alkyl group, an alkoxy group, an aryloxy group using an aryl group, or an aralkyl group is preferred. Specifically, it is more preferably selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group using an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 1 to 24 carbon atoms. Base of base.
該等之中，較佳為烷基或烷氧基，更佳為碳數1~12之烷基或碳數1~12之烷氧基，尤佳為碳數1~12之烷基。 Among these, an alkyl group or an alkoxy group is preferred, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms is more preferred, and an alkyl group having 1 to 12 carbon atoms is particularly preferred.
認為將酚性羥基設為1位時，於2、4、6位中，僅於任意二者具有擬π共軛效應，且具有減弱孤電子對之效應、即孤電子對穩定化之效應之能力。若孤電子對穩定化，則來自酚性羥基之質子容易脫離，擔憂因脫離之質子而引起之不良影響，藉由減弱孤電子對之穩定化效應，質子不易脫離，從而較佳。 It is considered that when the phenolic hydroxyl group is set to the 1 position, it has the pseudo-π conjugation effect only at any of the 2, 4 and 6 positions, and has the effect of weakening the lone electron pair, that is, the effect of the lone electron pair stabilization ability. If the lone electron pair is stabilized, protons derived from the phenolic hydroxyl group are easily detached, and an adverse effect caused by the detached protons is concerned. By weakening the stabilization effect of the lone electron pair, the protons are not easily detached, which is preferable.
藉由於該等位置具有取代基，酚性化合物之穩定性得以提高。進而，認為於取代基為如烷基或烷氧基般之電子供應性基之情形時，氧原子之孤電子對之電子密度增大，從而提高將電洞封入發光層內之效果。 By having a substituent at these positions, the stability of the phenolic compound is improved. Furthermore, when the substituent is an electron-donating group such as an alkyl group or an alkoxy group, it is considered that the electron density of a lone electron pair of an oxygen atom increases, thereby increasing the effect of encapsulating a hole in a light-emitting layer.
酚構造係藉由共振效應，使負電荷非定域化於氧原子上及將酚性羥基設為1位時之2、4、6位。由於負電荷定域化之位置反應性較高，因此通常常用之作為抗氧化劑之二丁基羥基甲苯(BHT，Butylated Hydroxy Toluene)藉由2、4、6位所具有之烷基亦會提高酚性化合物本身之穩定性。 The phenol structure is a system in which a negative charge is delocalized to an oxygen atom through resonance effects, and the phenolic hydroxyl group is set to the 2, 4, and 6 positions. Due to the high reactivity of the negative charge localization, dibutyl hydroxytoluene (BHT), which is commonly used as an antioxidant, will also increase the phenol by the alkyl groups at the 2, 4, and 6 positions. The stability of the sex compound itself.
然而，本發明者等人驚人地發現：於用於含有磷光發光材料及電荷輸送性化合物之有機電致發光元件之發光層的酚性化合物之情形時，藉由使用於將酚性羥基設為1位時之2、4、6位中，僅於任意二者具有取代基，且未於被認為負電荷密度較高而富有反應性之位置之一具有取代基之化合物，有機電致發光元件之效率得以提高，驅動穩定性得以提高。 However, the present inventors have surprisingly discovered that in the case of a phenolic compound used in a light-emitting layer of an organic electroluminescence element containing a phosphorescent light-emitting material and a charge-transporting compound, the phenolic hydroxyl group is used by A compound having a substituent in any of positions 2, 4, and 6 at the 1-position, and having no substituent in one of the positions considered to have a high negative charge density and being reactive, an organic electroluminescent device The efficiency is improved and the driving stability is improved.
其原因可考慮為，藉由除氧原子以外存在一個負電荷密度較高之位置，將電洞封入發光層內之效果得以提高。因此，將酚性羥基設為1位時之2、4、6位之取代基之數量需為2個而非3個。 The reason for this is considered to be that the existence of a position with a high negative charge density other than the oxygen atom improves the effect of sealing the holes in the light-emitting layer. Therefore, when the phenolic hydroxyl group is set to the 1 position, the number of the substituents at the 2, 4, and 6 positions needs to be 2 instead of 3.
進而較佳為酚性化合物僅於將酚性羥基設為1位時之2、4、6位中之任意二者具有取代基。其原因可考慮為，藉由僅於將酚性羥基設為1位時之2、4、6位中之任意二者具有取代基，不易抑制電荷之跳躍輸送。 It is further preferred that the phenolic compound has a substituent only at any of the 2, 4, and 6 positions when the phenolic hydroxyl group is at the 1-position. The reason for this is considered to be that it is difficult to suppress the jump transfer of charge by having a substituent only at any of the 2, 4, and 6 positions when the phenolic hydroxyl group is set to the 1-position.
進而認為，於僅在將酚性羥基設為1位時之2、4、6 位中之2、6位之二者具有取代基之情形時，羥基之氧原子之孤電子對受到保護，酚性化合物變得最穩定，因此使有機電致發光元件之效率提高，並且驅動穩定性亦提高，從而特佳。 Furthermore, it is considered that only when the phenolic hydroxyl group is set to the 1, 2, 6 When two of the two and six positions have a substituent, the lone electron pair of the oxygen atom of the hydroxyl group is protected, and the phenolic compound becomes the most stable. Therefore, the efficiency of the organic electroluminescent device is improved, and the driving is stable. Sex is also improved, which is particularly good.
又，認為於取代基為烷氧基之情形時，藉由僅於將酚性羥基設為1位時之2、4、6位中之任意二者具有取代基，則酚性羥基之氧原子及烷氧基之氧原子之電子密度適度增大，將電洞封入發光層內之效果提高，並且維持穩定性亦優異之狀態。 In addition, when the substituent is an alkoxy group, it is considered that the oxygen atom of the phenolic hydroxyl group has a substituent only when any two of the 2, 4, and 6 positions when the phenolic hydroxyl group is set to the 1 position. The electron density of the oxygen atom of the alkoxy group is increased moderately, the effect of sealing the hole in the light-emitting layer is improved, and the state of maintaining stability is also excellent.
又，作為具體之構造式，本發明中之酚性化合物亦可以下述式(1)表示。但是，本化合物並不限定於下述構造式。 Moreover, as a specific structural formula, the phenolic compound in this invention can also be represented by following formula (1). However, the present compound is not limited to the following structural formula.
其中，A為具有取代基之酚構造。n為1~5之整數。較佳為L於n=1之情形時不存在，於n=2~5之情形時為連結基。於n為2~5之情形時，A所具有之取代基可相同亦可不同。 Among them, A is a phenol structure having a substituent. n is an integer from 1 to 5. Preferably, L does not exist when n = 1, and is a linking group when n = 2-5. When n is 2 to 5, the substituents of A may be the same or different.
A於n=1之情形時，且於將酚構造之羥基設為1位之情形時，於2、4、6位中，僅於任意2個位置具有取代基，又，亦可於3位或5位具有取代基。 When A is n = 1, and when the hydroxy group of the phenol structure is set to the 1 position, the substituents are only at any 2 positions in the 2, 4, and 6 positions, and may be at the 3 position. Or it has a substituent at the 5-position.
A可具有之取代基為碳數1~12之烷基、碳數1~12之烷氧基、使用碳數6~18之芳基之芳氧基、碳數1~24之芳烷基。 A may have an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, and an aralkyl group having 1 to 24 carbon atoms.
就化合物之穩定性之觀點而言，較佳為將酚構造之羥基設為1位之情形時之2位或6位為烷基。進而，為了避免與發光層形成用組成物中之其他材料相互作用，被取代於2位及6位之烷基較佳為作為具有立體阻礙之二級烷基(異丙基等)或三級烷基(第 三丁基等)之烷基，最佳為立體阻礙性最高之三級烷基。 From the viewpoint of the stability of the compound, when the hydroxy group of the phenol structure is set to the 1-position, the 2- or 6-position is preferably an alkyl group. Furthermore, in order to avoid interaction with other materials in the composition for forming a light-emitting layer, the alkyl group substituted at the 2-position and the 6-position is preferably a secondary alkyl group (isopropyl group, etc.) or tertiary having a steric hindrance. Alkyl (section An alkyl group such as tributyl group is preferably a tertiary alkyl group having the highest steric hindrance.
於n=2~5之情形時，A具有連結基L。L以具有sp3混成軌道之碳或氧對A進行鍵結。L可取代在2~6位之任一位置，於取代在2、4、6位之情形時，符合化合物A之取代基之規定即「於2、4、6位中，僅於任意2個位置具有取代基」。 When n = 2 to 5, A has a linking group L. L bonds A with carbon or oxygen with sp 3 mixed orbitals. L can be substituted at any of the 2 to 6 positions. When it is substituted at the 2, 4, and 6 positions, it complies with the requirements for the substituent of compound A. Has a substituent ".
即，於骨架A之2、4、6位中，僅於任意2個位置，以連結基與其以外之1種取代基進行取代。n並無特別限定，較佳為3以下，進而較佳為2以下，最佳為1。其原因可推斷為：由於發光層形成後均勻地擴展，酚性羥基濃度亦均勻地擴展，故而電荷陷阱均勻地產生，電荷再結合於膜內亦均勻地進行，藉此防止激子之濃度淬滅。 That is, in the 2, 4, and 6 positions of the skeleton A, the linking group is substituted with one substituent other than the substituent at only two arbitrary positions. n is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and most preferably 1. The reason can be inferred that: since the light-emitting layer expands uniformly and the phenolic hydroxyl concentration also expands uniformly, the charge traps are generated uniformly, and the charges are recombined in the film, and the uniformity of the exciton is prevented to prevent Off.
L只要以具有sp3混成軌道之碳或氧進行鍵結，則並無特別限定。較佳為可具有碳數1~12之烷基取代基之伸烷基。於具有共軛鏈之情形時，上述烷基之碳數較佳為2~6。作為原因，係為了於與發光材料共存之情形時，排除可能成為淬滅因子之要素，即防止因共軛鏈之擴大而引起之能量轉移型淬滅。 L is not particularly limited as long as it is bonded with carbon or oxygen having a sp 3 mixed orbital. An alkylene group which may have an alkyl substituent having 1 to 12 carbon atoms is preferred. When having a conjugated chain, the carbon number of the alkyl group is preferably 2 to 6. The reason is to exclude the element that may become the quenching factor when coexisting with the luminescent material, that is, to prevent the energy transfer type quenching caused by the expansion of the conjugated chain.
作為具體之構造，可列舉2,6-第三丁基苯酚、4-甲氧基-2-第三丁基苯酚、4,4'-亞丁基雙(6-第三丁基-3-甲基苯酚)等下述中所記載之化合物。 Specific structures include 2,6-tert-butylphenol, 4-methoxy-2-tert-butylphenol, 4,4'-butylenebis (6-tert-butyl-3-methyl) Phenol) and other compounds described below.
[化9]
作為本發明之組成物可含有之電荷輸送性化合物，可使用習知用作有機電致發光元件用材料者。例如可列舉：吡啶、咔唑、萘、苝、芘、蒽、
本發明之組成物中之電荷輸送性化合物之含量通常為0.01質量%以上，較佳為0.1質量%以上。又，本發明之組成物中之電荷輸送性化合物之含量通常為50質量%以下，較佳為30質量%以下，進而較佳為10質量%以下。 The content of the charge-transporting compound in the composition of the present invention is usually 0.01% by mass or more, and preferably 0.1% by mass or more. The content of the charge-transporting compound in the composition of the present invention is usually 50% by mass or less, preferably 30% by mass or less, and further preferably 10% by mass or less.
本發明之組成物至少含有磷光發光材料、電荷輸送性化合物及上述酚性化合物。又，於油墨等組成物中亦可含有溶劑。本發明之組成物通常用於藉由濕式成膜法形成層或膜，尤其較佳為用於形成有機電致發光元件之發光層。即，本發明之組成物較佳為有機電致發光元件用組成物，尤佳為進而用作有機電致發光元件之發光層形成用組成物。 The composition of the present invention contains at least a phosphorescent material, a charge transporting compound, and the phenolic compound. A solvent may be contained in a composition such as ink. The composition of the present invention is generally used to form a layer or film by a wet film formation method, and is particularly preferably used to form a light-emitting layer of an organic electroluminescence element. That is, the composition of the present invention is preferably a composition for an organic electroluminescence element, and particularly preferably a composition for forming a light-emitting layer of an organic electroluminescence element.
本發明之組成物中之磷光發光材料之含量相對於電荷輸送性化合物之總量，通常為1質量%以上，較佳為5質量%以上，進而較佳為15質量%以上。又，本發明之組成物中之磷光發光材料之含量相對於電荷輸送性化合物之總量，通常為50質量%以下，較佳為40質量%以下。 The content of the phosphorescent light-emitting material in the composition of the present invention is generally 1% by mass or more, preferably 5% by mass or more, and more preferably 15% by mass or more with respect to the total amount of the charge-transporting compound. The content of the phosphorescent light-emitting material in the composition of the present invention is usually 50% by mass or less, and preferably 40% by mass or less with respect to the total amount of the charge-transporting compound.
藉由將組成物中之磷光發光材料之含量設為上述範圍，例如於使用該組成物而形成發光層之情形時，可自鄰接之層(例如電洞輸送層或電洞阻擋層)向發光層高效率地進行電洞或電子之注入，降低驅動電壓。再者，磷光發光材料於組成物中可僅包含1種，亦可組合而包含2種以上。 By setting the content of the phosphorescent light-emitting material in the composition to the above range, for example, when a light-emitting layer is formed using the composition, light can be emitted from an adjacent layer (for example, a hole transporting layer or a hole blocking layer). The layer efficiently injects holes or electrons to reduce the driving voltage. The phosphorescent light-emitting material may be contained in the composition alone or in combination of two or more.
又，發光材料之發光色並無特別限定，但較佳為長波長。具體而言，較佳為該組成物之塗佈膜之發光色(峰值波長)較綠色更長波(500nm以上)，進而較佳為較黃綠色更長波(550nm以上)。 The emission color of the light-emitting material is not particularly limited, but it is preferably a long wavelength. Specifically, the emission color (peak wavelength) of the coating film of the composition is preferably longer than green (500 nm or longer), and more preferably yellower green (longer than 550 nm).
根據磷光發光層之發光原理推測出：雖發生因孤電子對而引起之三重激發態之淬滅，但長波長發光之激發態相較於短波長發光之激發態，能量更低，三重激發態自身更穩定，因此不易受到因孤電子對而引起之淬滅之影響。 According to the light-emitting principle of the phosphorescent light-emitting layer, it is inferred that although the quenching of the triplet excited state due to the lone electron pair occurs, the excited state of the long-wavelength emission is lower in energy and the triplet excited state than the excited state of the short-wavelength emission It is more stable and therefore less susceptible to quenching caused by lone electron pairs.
本發明之組成物中之酚性化合物相對於溶劑之含量相對於組成物中之電荷輸送性化合物之總量，通常為0.01質量%以上，較佳為0.1質量%以上。又，相對於組成物中之電荷輸送性化合物之總量，通常為10質量%以下，更佳為5質量%以下，進而較佳為1質量%以下。 Content of the phenolic compound with respect to a solvent in the composition of this invention with respect to the total amount of the charge transporting compound in a composition is 0.01 mass% or more normally, Preferably it is 0.1 mass% or more. The total amount of the charge-transporting compound in the composition is usually 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.
其原因在於：若為下限以上，則提高電荷捕捉之效率。又，其原因在於：於含有過剩之情形，使用組成物形成膜時，能夠預測到因超越2、6位之立體阻礙的孤電子對之相互作用之顯現而引起淬滅之可能性。 The reason is that if it is above the lower limit, the efficiency of charge trapping is improved. In addition, the reason is that when the composition is contained in excess, when forming a film using the composition, it is possible to predict the possibility of quenching due to the appearance of the interaction of the lone electron pair that is three-dimensionally hindered beyond the 2nd and 6th positions.
於將本發明之組成物用於例如有機電致發光元件用之情形時，組成物中除了上述磷光發光材料、具有酚性羥基之化合物及電荷輸送性化合物以外，於用於油墨時還可含有溶劑。本發明之組成物中可包含之溶劑，係用於藉由濕式成膜而形成包含金屬錯合物化合物之層、具有揮發性之液體成分。 When the composition of the present invention is used in, for example, an organic electroluminescence device, the composition may contain, in addition to the above phosphorescent light-emitting material, a compound having a phenolic hydroxyl group, and a charge-transporting compound, when used in ink Solvent. The solvent which can be contained in the composition of the present invention is a volatile liquid component for forming a layer containing a metal complex compound by wet film formation.
該溶劑只要為良好地溶解作為溶質之金屬錯合物化 合物、下述電荷輸送性化合物及本發明之酚性化合物之溶劑，則並無特別限定。 As long as the solvent is a metal complex compound that dissolves well as a solute, The solvent of the compound, the charge-transporting compound described below, and the phenolic compound of the present invention is not particularly limited.
作為較佳之溶劑，例如可列舉：正癸烷、環己烷、乙基環己烷、十氫萘、雙環己烷等烷烴類；甲苯、二甲苯、均三甲苯、苯基環己烷、萘滿等芳香族烴類；氯苯、二氯苯、三氯苯等鹵化芳香族烴類；1,2-二甲氧基苯、1,3-二甲氧基苯、大茴香醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基大茴香醚、2,4-二甲基大茴香醚、二苯醚等芳香族醚類；乙酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯類；環己酮、環辛酮、葑酮等脂環式酮類；環己醇、環辛醇等脂環式醇類；甲基乙基酮、二丁基酮等脂肪族酮類；丁醇、己醇等脂肪族醇類；乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚乙酸酯(PGMEA)等脂肪族醚類等。 Examples of preferred solvents include alkanes such as n-decane, cyclohexane, ethylcyclohexane, decahydronaphthalene, and dicyclohexane; toluene, xylene, mesitylene, phenylcyclohexane, and naphthalene Fully aromatic hydrocarbons; Halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenyl ether , 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether, etc. Ethers; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; lipids such as cyclohexanone, cyclooctanone, and fluorenone Cyclic ketones; Alicyclic alcohols such as cyclohexanol, cyclooctanol; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; aliphatic alcohols such as butanol and hexanol; ethylene glycol two Aliphatic ethers such as methyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA).
其中，較佳為烷烴類或芳香族烴類，尤其是苯基環己烷於濕式成膜步驟中具有較佳之黏度與沸點。 Among them, alkanes or aromatic hydrocarbons are preferred, especially phenylcyclohexane has better viscosity and boiling point in the wet film forming step.
該等溶劑可單獨使用1種，又，亦可按照任意之組合及比率使用2種以上。 These solvents may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and ratios.
溶劑之沸點通常為80℃，較佳為90℃以上，更佳為100℃以上，尤佳為110℃以上。又，溶劑之沸點通常為300℃以下，較佳為280℃以下，更佳為250℃以下。若溶劑之沸點低於上述下限，則存在於濕式成膜時，因來自組成物之溶劑蒸發而導致成膜穩定性下降之可能性。 The boiling point of the solvent is usually 80 ° C, preferably 90 ° C or higher, more preferably 100 ° C or higher, and even more preferably 110 ° C or higher. The boiling point of the solvent is usually 300 ° C or lower, preferably 280 ° C or lower, and more preferably 250 ° C or lower. If the boiling point of the solvent is lower than the above-mentioned lower limit, there is a possibility that the stability of the film formation may decrease due to evaporation of the solvent from the composition during wet film formation.
本發明之組成物中之溶劑之含量通常為10質量%以上，較佳為20質量%以上，更佳為50質量%以上，進而較佳為80 質量%以上。又，本發明之組成物中之溶劑之含量通常為99.99質量%以下，較佳為99.95質量%以下，更佳為99.9質量%以下，進而較佳為99.8質量%以下。 The content of the solvent in the composition of the present invention is usually 10% by mass or more, preferably 20% by mass or more, more preferably 50% by mass or more, and still more preferably 80% by mass. Above mass%. The content of the solvent in the composition of the present invention is usually 99.99% by mass or less, preferably 99.95% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.
例如，發光層通常形成為3~200nm左右之厚度，於使用本發明之組成物形成此種厚度之發光層之情形時，若溶劑之含量低於上述下限，則存在組成物之黏性過高，而成膜作業性下降之可能性。另一方面，若超過上述上限，則存在因成膜後去除溶劑所獲得之膜之厚度變得無法獲取，而難以成膜之傾向。 For example, the light-emitting layer is usually formed to a thickness of about 3 to 200 nm. When the light-emitting layer of such a thickness is formed using the composition of the present invention, if the content of the solvent is lower than the above lower limit, the viscosity of the composition is too high , The possibility of film forming workability decline. On the other hand, if the above-mentioned upper limit is exceeded, the thickness of the film obtained by removing the solvent after film formation becomes unobtainable, and it tends to be difficult to form a film.
於本發明之組成物中，除了上述化合物等以外亦可視需要進一步含有其他化合物等。例如，除了上述溶劑以外，亦可含有其他溶劑。作為此種溶劑，例如可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類、二甲基亞碸等。該等可單獨使用1種，又，亦可按照任意之組合、及比率使用2種以上。 The composition of the present invention may further contain other compounds and the like in addition to the above-mentioned compounds and the like as necessary. For example, in addition to the above solvents, other solvents may be contained. Examples of such a solvent include ammoniums such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethylsulfinium. These may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and ratios.
濕式成膜法係指於基板上塗佈含有溶劑之組成物，並乾燥去除溶劑而形成膜之方法。作為塗佈方法，並無特別限定，例如可列舉：旋轉塗佈法、浸漬塗佈法、模嘴塗佈法、棒式塗佈法、刮刀塗佈法、輥式塗佈法、噴塗法、毛細管塗佈法、噴墨法、網版印刷法、凹版印刷法、快乾印刷法等。 The wet film forming method refers to a method of applying a composition containing a solvent on a substrate, and drying and removing the solvent to form a film. The coating method is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a die coating method, a bar coating method, a doctor blade coating method, a roll coating method, a spray coating method, Capillary coating method, inkjet method, screen printing method, gravure printing method, quick-drying printing method, and the like.
作為乾燥去除溶劑之方法，通常進行加熱乾燥。作為加熱步驟中所使用之加熱手段之例，可列舉潔淨烘箱、加熱板、紅外線加熱。作為紅外線加熱，可使用鹵素加熱器或經塗佈陶瓷之鹵素加熱器、陶瓷加熱器等。 As a method of removing the solvent by drying, heat drying is usually performed. Examples of the heating means used in the heating step include a clean oven, a hot plate, and infrared heating. As the infrared heating, a halogen heater, a ceramic-coated halogen heater, a ceramic heater, or the like can be used.
利用紅外線之加熱由於直接將熱量供給至基板或膜，故而相較於使用烘箱或加熱板之加熱，能夠實現短時間內之乾燥。因此，可將加熱環境之氣體(水分或氧氣)之影響、或微小污物之影響抑制至最小限度，生產性提高而較佳。 The heating using infrared rays can directly supply heat to the substrate or film, so compared with the heating using an oven or a heating plate, it can achieve drying in a short time. Therefore, the influence of the gas (moisture or oxygen) in the heating environment, or the influence of fine dirt can be suppressed to a minimum, and productivity is improved, which is preferable.
加熱溫度通常為70℃以上，較佳為75℃以上，更佳為80℃以上。又，加熱溫度通常為150℃以下，較佳為140℃以下，更佳為130℃以下。 The heating temperature is usually 70 ° C or higher, preferably 75 ° C or higher, and more preferably 80 ° C or higher. The heating temperature is usually 150 ° C or lower, preferably 140 ° C or lower, and more preferably 130 ° C or lower.
加熱時間通常為10秒以上，較佳為60秒以上，更佳為90秒以上，通常為120分鐘以下，較佳為60分鐘以下，更佳為30分鐘以下。 The heating time is usually 10 seconds or longer, preferably 60 seconds or longer, more preferably 90 seconds or longer, usually 120 minutes or shorter, preferably 60 minutes or shorter, and more preferably 30 minutes or shorter.
又，於加熱乾燥前進行真空乾燥亦較佳。藉由濕式成膜法將本發明之組成物成膜而成之有機層之膜厚通常為5nm以上，較佳為10nm以上，進而較佳為20nm以上。又，膜厚通常為500nm以下，較佳為300nm以下，進而較佳為200nm以下。 It is also preferable to perform vacuum drying before heating and drying. The film thickness of the organic layer formed by forming the composition of the present invention by a wet film forming method is usually 5 nm or more, preferably 10 nm or more, and further preferably 20 nm or more. The film thickness is usually 500 nm or less, preferably 300 nm or less, and further preferably 200 nm or less.
本發明之有機電致發光元件之特徵在於：其係具有陽極、陰極、及於該等之間之至少1層有機層者，且該有機層中之至少1層係使用本發明之組成物藉由濕式製膜而形成之層。該層較佳為發光層。 The organic electroluminescent device of the present invention is characterized in that it has an anode, a cathode, and at least one organic layer therebetween, and at least one of the organic layers is borrowed using the composition of the present invention. A layer formed by wet film formation. This layer is preferably a light emitting layer.
圖1係表示對本發明之有機電致發光元件而言較佳之構造例的剖面之示意圖，於圖1中，符號1表示基板，符號2表示陽極，符號3表示電洞注入層，符號4表示電洞輸送層，符號5表示發光層，符號6表示電洞阻擋層，符號7表示電子輸送層，符 號8表示電子注入層，符號9表示陰極。 FIG. 1 is a schematic diagram showing a cross-section of a preferred structural example of an organic electroluminescent device according to the present invention. In FIG. 1, reference numeral 1 indicates a substrate, reference numeral 2 indicates an anode, reference numeral 3 indicates a hole injection layer, and reference numeral 4 indicates electrical Hole transport layer, symbol 5 represents the light-emitting layer, symbol 6 represents the hole blocking layer, symbol 7 represents the electron transport layer, and the symbol No. 8 indicates an electron injection layer, and numeral 9 indicates a cathode.
基板1係成為有機電致發光元件之支持體者，可使用石英或玻璃板、金屬板或金屬箔、塑膠薄膜或片材等。尤其較佳為玻璃板、或聚酯、聚甲基丙烯酸酯、聚碳酸酯、聚碸等透明合成樹脂之板。 The substrate 1 is a support for an organic electroluminescence element, and quartz or glass plates, metal plates or metal foils, plastic films or sheets can be used. Particularly preferred are glass plates or plates of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polyfluorene.
於使用合成樹脂基板之情形時，需要留意阻氣性。若基板之阻氣性過小，則存在因通過基板之外部大氣而導致有機電致發光元件劣化之情況，故而不佳。因此，於合成樹脂基板之至少單面設置緻密之氧化矽膜等而確保阻氣性之方法亦為較佳之方法之一。 When a synthetic resin substrate is used, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescence element may be deteriorated due to the external atmosphere passing through the substrate, which is not preferable. Therefore, a method of providing a dense silicon oxide film or the like on at least one side of a synthetic resin substrate to ensure gas barrier properties is also one of the preferred methods.
於基板1上設置陽極2。陽極2係發揮向發光層側之層(電洞注入層3、電洞輸送層4或發光層5等)注入電洞之作用者。 An anode 2 is provided on the substrate 1. The anode 2 plays a role of injecting holes into layers on the light emitting layer side (hole injection layer 3, hole transport layer 4, or light emitting layer 5).
該陽極2通常包含鋁、金、銀、鎳、鈀、鉑等金屬；銦及/或錫之氧化物等金屬氧化物；碘化銅等鹵化金屬；碳黑；或者聚(3-甲基噻吩)、聚吡咯、聚苯胺等導電性高分子等。 The anode 2 usually includes metals such as aluminum, gold, silver, nickel, palladium, and platinum; metal oxides such as indium and / or tin oxides; halogenated metals such as copper iodide; carbon black; or poly (3-methylthiophene) ), Conductive polymers such as polypyrrole and polyaniline.
陽極2之形成通常可藉由濺鍍法、真空蒸鍍法等進行。又，於使用銀等金屬微粒子、碘化銅等微粒子、碳黑、導電性金屬氧化物微粒子、導電性高分子微粉末等形成陽極之情形時，亦可藉由使其分散於適當之黏合劑樹脂溶液中，並塗佈於基板1上而形成陽極2。進而，於導電性高分子之情形時，亦可藉由電解聚合而直接於基板1上形成薄膜，或於基板1上塗佈導電性高分子而形 成陽極2(Appl.Phys.Lett.、60卷、2711頁、1992年)。 The formation of the anode 2 can be generally performed by a sputtering method, a vacuum evaporation method, or the like. When the anode is formed using metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide particles, conductive polymer fine powder, etc., it is also possible to disperse them in an appropriate binder. The resin solution is applied to the substrate 1 to form the anode 2. Furthermore, in the case of a conductive polymer, a thin film may be directly formed on the substrate 1 by electrolytic polymerization, or a conductive polymer may be coated on the substrate 1 to shape it. Anode 2 (Appl. Phys. Lett., Vol. 60, p. 2711, 1992).
陽極2通常為單層構造，但亦可根據需要製成包含數種材料之積層構造。陽極2之厚度係根據所需之透明性而不同。於需要透明性之情形時，將可見光之透過率通常設為60%以上，較佳為設為80%以上。於該情形時，陽極之厚度通常為5nm以上，較佳為10nm以上。又，於該情形時，陽極之厚度通常為1000nm以下，較佳為500nm以下左右。於可不透明之情形時，陽極2之厚度為任意，陽極2亦可與基板1相同。又，亦可進而於上述陽極2上積層不同之導電材料。為了去除附著於陽極之雜質，調整游離電位使電洞注入性提高，較佳為對陽極表面進行紫外線(UV)/臭氧處理、或進行氧電漿處理或氬電漿處理。 The anode 2 usually has a single-layer structure, but a multilayer structure including a plurality of materials can also be produced as required. The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the transmittance of visible light is usually set to 60% or more, preferably 80% or more. In this case, the thickness of the anode is usually 5 nm or more, and preferably 10 nm or more. In this case, the thickness of the anode is usually 1000 nm or less, and preferably about 500 nm or less. When it can be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Further, different conductive materials may be further laminated on the anode 2. In order to remove impurities adhering to the anode and adjust the free potential to improve hole injectivity, it is preferable to perform ultraviolet (UV) / ozone treatment, or oxygen plasma treatment or argon plasma treatment on the anode surface.
電洞注入層3係自陽極2向發光層5輸送電洞之層，通常可形成於陽極2上。本發明之電洞注入層3之形成方法可為真空蒸鍍法，亦可為濕式成膜法，並無特別限制，但就降低暗點之觀點而言，較佳為利用濕式成膜法形成電洞注入層3。電洞注入層3之膜厚通常為5nm以上，較佳為10nm以上。又，電洞注入層3之膜厚通常為1000nm以下，較佳為500nm以下之範圍。 The hole injection layer 3 is a layer that transports holes from the anode 2 to the light-emitting layer 5, and can usually be formed on the anode 2. The method for forming the hole injection layer 3 of the present invention may be a vacuum evaporation method or a wet film formation method, which is not particularly limited, but from the viewpoint of reducing dark spots, it is preferable to use the wet film formation. Method to form an electric hole injection layer 3. The film thickness of the hole injection layer 3 is usually 5 nm or more, and preferably 10 nm or more. The film thickness of the hole injection layer 3 is usually 1000 nm or less, and preferably in a range of 500 nm or less.
於利用濕式成膜形成電洞注入層3之情形時，通常使構成電洞注入層3之材料與適當之溶劑(電洞注入層用溶劑)進行混合而製備塗佈用之組成物(電洞注入層形成用組成物)，藉由適當之手法將該 電洞注入層形成用組成物塗佈於相當於電洞注入層3之下層之層(通常為陽極)上，並進行乾燥，藉此形成電洞注入層3。 When the hole injection layer 3 is formed by wet film formation, the material constituting the hole injection layer 3 is usually mixed with an appropriate solvent (solvent for the hole injection layer) to prepare a coating composition (electricity). Composition for hole injection layer formation), The hole injection layer forming composition is coated on a layer (usually an anode) corresponding to the lower layer of the hole injection layer 3 and dried to form the hole injection layer 3.
電洞注入層形成用組成物通常含有電洞輸送性化合物及溶劑作為電洞注入層之構成材料。電洞輸送性化合物只要為通常用於有機電致發光元件之電洞注入層之具有電洞輸送性之化合物，其可為聚合體等高分子化合物，亦可為單體等低分子化合物，但較佳為高分子化合物。 The hole injection layer forming composition usually contains a hole transporting compound and a solvent as constituent materials of the hole injection layer. The hole-transporting compound may be a high-molecular compound such as a polymer or a low-molecular compound such as a monomer as long as it is a compound having hole-transporting properties which is generally used in a hole injection layer of an organic electroluminescent device. A polymer compound is preferred.
作為電洞輸送性化合物，就自陽極2向電洞注入層3之電荷注入障壁之觀點而言，較佳為具有4.5eV~6.0eV之游離電位之化合物。 The hole transporting compound is preferably a compound having a free potential of 4.5 eV to 6.0 eV from the viewpoint of the charge injection barrier from the anode 2 to the hole injection layer 3.
作為電洞輸送性化合物之例，可列舉：芳香族胺衍生物、酞菁衍生物、卟啉衍生物、寡聚噻吩衍生物、聚噻吩衍生物、苄基苯基衍生物、以茀基連結三級胺而成之化合物、腙衍生物、矽氮烷衍生物、矽烷胺衍生物、磷胺衍生物、喹吖酮衍生物、聚苯胺衍生物、聚吡咯衍生物、聚苯乙炔衍生物、聚噻吩乙炔衍生物、聚喹啉衍生物、聚喹
再者，於本說明書中，所謂衍生物，例如若以芳香族胺衍生物為例，則係指包含芳香族胺本身及以芳香族胺為主骨架之化合物者，可為聚合體，亦可為單體。 In addition, in the present specification, the term "derivative" refers to, for example, an aromatic amine derivative, which refers to a compound containing an aromatic amine itself and a compound having an aromatic amine as a main skeleton, which may be a polymer or a polymer. As a monomer.
上述例示中，就非晶質性、可見光之透過率之方面而言，較佳為芳香族胺化合物，尤佳為芳香族三級胺化合物。此處，芳香族三級胺化合物係具有芳香族三級胺構造之化合物，且亦包括 具有來自芳香族三級胺之基之化合物。 Among the above examples, in terms of amorphousness and transmittance of visible light, an aromatic amine compound is preferred, and an aromatic tertiary amine compound is particularly preferred. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and also includes A compound having a group derived from an aromatic tertiary amine.
芳香族三級胺化合物之種類並無特別限制，就利用表面平滑化效果而獲得之均勻發光之方面而言，進而較佳為重量平均分子量為1000以上且1000000以下之高分子化合物(重複單位相連之聚合型化合物)。 The type of the aromatic tertiary amine compound is not particularly limited. In terms of uniform light emission obtained by using a surface smoothing effect, a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (repeated units are connected) Polymerizable compounds).
作為此種高分子化合物之材料，可使用習知用作電洞注入層用化合物之化合物，例如可使用日本專利特開2009-212510號公報、國際公開第2012/096352號、國際公開第2013/191137號等所揭示之化合物。 As a material of such a polymer compound, a compound conventionally used as a compound for hole injection layers can be used, and for example, Japanese Patent Laid-Open No. 2009-212510, International Publication No. 2012/096352, and International Publication No. 2013 / Compound disclosed in No. 191137 and the like.
又，作為電洞輸送性化合物，亦較佳為使作為聚噻吩之衍生物之3,4-乙二氧基噻吩(3,4-ethylenedioxythiophene)於高分子量聚苯乙烯磺酸中聚合而成之導電性聚合物(PEDOT/PSS)。又，亦可為以甲基丙烯酸酯等將該聚合物之末端封住而成者。 The hole transporting compound is also preferably one obtained by polymerizing 3,4-ethylenedioxythiophene, which is a derivative of polythiophene, in a high molecular weight polystyrene sulfonic acid. Conductive polymer (PEDOT / PSS). It is also possible to seal the end of the polymer with a methacrylate or the like.
電洞注入層形成用組成物中之電洞輸送性化合物之濃度只要不明顯損害本發明之效果則為任意，但於膜厚之均勻性之方面而言，通常為0.01質量%以上，較佳為0.1質量%以上，進而較佳為0.5質量%以上。又，電洞注入層形成用組成物中之電洞輸送性化合物之濃度通常為70質量%以下，較佳為60質量%以下，進而較佳為50質量%以下。若該濃度過高，則存在膜厚產生不均之可能性，又，若過低，則存在於所成膜之電洞注入層產生缺陷之可能性。 The concentration of the hole-transporting compound in the hole-injection layer-forming composition is arbitrary as long as the effect of the present invention is not significantly impaired, but in terms of uniformity of the film thickness, it is usually 0.01% by mass or more, preferably It is 0.1% by mass or more, and more preferably 0.5% by mass or more. The concentration of the hole-transporting compound in the hole-injection-layer-forming composition is usually 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less. If the concentration is too high, there is a possibility that the film thickness may be uneven, and if it is too low, there may be a defect in the hole injection layer of the formed film.
電洞注入層形成用組成物較佳為含有電子接受性之化合物作 為電洞注入層之構成材料。電子接受性化合物較佳為具有氧化能力，且具有自上述電洞輸送性化合物接受一電子之能力之化合物，具體而言，較佳為電子親和力為4eV以上之化合物，進而較佳為5eV以上之化合物。 The composition for forming the hole injection layer is preferably a compound containing an electron acceptor. Material for hole injection layer. The electron-accepting compound is preferably a compound having an oxidizing ability and an ability to accept an electron from the hole-transporting compound, and specifically, a compound having an electron affinity of 4eV or more, and more preferably 5eV or more Compound.
作為此種電子接受性化合物，例如可列舉選自由三芳基硼化合物、鹵化金屬、路易斯酸、有機酸、鎓鹽、芳基胺與鹵化金屬之鹽、芳基胺與路易斯酸之鹽所組成之群組中之1種或2種以上之化合物等。 Examples of such an electron-accepting compound include compounds selected from the group consisting of a triarylboron compound, a metal halide, a Lewis acid, an organic acid, an onium salt, an arylamine and a metal halide salt, and an arylamine and a Lewis acid salt. One or more compounds in the group.
更具體而言，可列舉：氯化鐵(III)(日本專利特開平11-251067號公報)、過氧二硫酸銨等高原子價之無機化合物；四氰乙烯等氰基化合物；三(五氟苯基)硼烷(日本專利特開2003-31365號公報)等芳香族硼化合物；經有機基取代之鎓鹽(國際公開第2005/089024號)；富勒烯衍生物；碘；聚苯乙烯磺酸根離子、烷基苯磺酸根離子、樟腦磺酸根離子等磺酸根離子等。 More specifically, high-valent inorganic compounds such as iron (III) chloride (Japanese Patent Laid-Open No. 11-251067) and ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; and three (five) Fluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365) and other aromatic boron compounds; onium salts substituted with organic groups (International Publication No. 2005/089024); fullerene derivatives; iodine; polybenzene Sulfonate ions such as ethylene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, etc.
該等電子接受性化合物可藉由將電洞輸送性化合物氧化而提高電洞注入層之導電率。電洞注入層或電洞注入層形成用組成物中之電子接受性化合物之相對於電洞輸送性化合物之含量通常為0.1莫耳%以上，較佳為1莫耳%以上。但，通常為100莫耳%以下，較佳為40莫耳%以下。 These electron-accepting compounds can increase the conductivity of the hole injection layer by oxidizing the hole-transporting compound. The content of the electron-accepting compound in the hole injection layer or the composition for forming the hole injection layer with respect to the hole transporting compound is usually 0.1 mol% or more, and preferably 1 mol% or more. However, it is usually 100 mol% or less, and preferably 40 mol% or less.
用於濕式成膜法之電洞注入層形成用組成物之溶劑中之至少1種，係較佳為可溶解上述電洞注入層之構成材料之化合物。又，該溶劑之沸點通常為80℃以上，較佳為100℃以上，進而較佳為110 ℃以上。溶劑之沸點通常為300℃以下，較佳為280℃以下。 At least one of the solvents used in the composition for forming the hole injection layer for the wet film formation method is preferably a compound that can dissolve the constituent materials of the hole injection layer. The boiling point of the solvent is usually 80 ° C or higher, preferably 100 ° C or higher, and more preferably 110. Above ℃. The boiling point of the solvent is usually 300 ° C or lower, preferably 280 ° C or lower.
若溶劑之沸點過低，則存在乾燥速度過快，導致膜質惡化之可能性。又，若溶劑之沸點過高，則存在需要提高乾燥步驟之溫度，而對其他層或基板帶來不良影響之可能性。 If the boiling point of the solvent is too low, there is a possibility that the drying speed is too fast and the film quality may deteriorate. In addition, if the boiling point of the solvent is too high, the temperature of the drying step needs to be increased, which may adversely affect other layers or the substrate.
作為溶劑，例如可列舉醚系溶劑、酯系溶劑、芳香族烴系溶劑、醯胺系溶劑等。 Examples of the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amidine-based solvents.
作為醚系溶劑，例如可列舉：乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚乙酸酯(PGMEA)等脂肪族醚；1,2-二甲氧基苯、1,3-二甲氧基苯、大茴香醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基大茴香醚、2,4-二甲基大茴香醚等芳香族醚等。 Examples of the ether-based solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2 Aromatic ethers such as 4-dimethylanisole.
作為酯系溶劑，例如可列舉：乙酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯等。 Examples of the ester-based solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
作為芳香族烴系溶劑，例如可列舉：甲苯、二甲苯、環己基苯、3-異丙基聯苯、1,2,3,4-四甲基苯、1,4-二異丙基苯、甲基萘等。 Examples of the aromatic hydrocarbon-based solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, and 1,4-diisopropylbenzene. , Methylnaphthalene and so on.
作為醯胺系溶劑，例如可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等。除此以外，亦可使用二甲基亞碸等。該等溶劑可僅使用1種，亦可按照任意之組合、及比率使用2種以上。 Examples of the amidine-based solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and the like. In addition, dimethylsulfinium and the like can also be used. These solvents may be used alone, or two or more solvents may be used in any combination and ratio.
於製備電洞注入層形成用組成物後，藉由濕式成膜將該組成物塗佈於相當於電洞注入層3之下層之層(通常為陽極2)上，並進行 乾燥，藉此形成電洞注入層3。為了防止因組成物中產生結晶而導致膜之缺陷，塗佈步驟中之溫度較佳為10℃以上，且較佳為50℃以下。 After the composition for forming the hole injection layer is prepared, the composition is applied to a layer (usually the anode 2) corresponding to the lower layer of the hole injection layer 3 by wet film formation, and is carried out. By drying, the hole injection layer 3 is formed. In order to prevent defects in the film caused by crystallization in the composition, the temperature in the coating step is preferably 10 ° C or higher, and preferably 50 ° C or lower.
塗佈步驟中之相對濕度只要不明顯損害本發明之效果則並無限定，通常為0.01ppm以上，且通常為80%以下。塗佈後，視需要藉由真空乾燥等粗略地去除溶劑，其後藉由加熱對電洞注入層形成用組成物之膜進行乾燥。若列舉加熱步驟中所使用之加熱手段之例，則可列舉潔淨烘箱、加熱板、紅外線加熱器(鹵素加熱器)等。 The relative humidity in the coating step is not limited as long as the effect of the present invention is not significantly impaired, but it is usually 0.01 ppm or more and usually 80% or less. After coating, if necessary, the solvent is roughly removed by vacuum drying or the like, and then the film of the composition for forming the hole injection layer is dried by heating. Examples of the heating means used in the heating step include clean ovens, hot plates, infrared heaters (halogen heaters), and the like.
關於加熱步驟中之加熱溫度，只要不明顯損害本發明之效果，則較佳為以電洞注入層形成用組成物所使用之溶劑之沸點以上之溫度進行加熱。又，於電洞注入層所使用之溶劑為包含2種以上之混合溶劑之情形時，較佳為對至少1種以該溶劑之沸點以上之溫度進行加熱。若考慮溶劑之沸點上升，則較佳為於加熱步驟中，以120℃以上且300℃以下之溫度進行加熱。 Regarding the heating temperature in the heating step, as long as the effect of the present invention is not significantly impaired, the heating is preferably performed at a temperature higher than the boiling point of the solvent used for the composition for forming the hole injection layer. When the solvent used in the hole injection layer is a mixed solvent containing two or more kinds, it is preferable to heat at least one kind at a temperature equal to or higher than the boiling point of the solvent. In consideration of the increase in the boiling point of the solvent, it is preferable to perform heating at a temperature of 120 ° C or higher and 300 ° C or lower in the heating step.
於加熱步驟中，只要加熱溫度為電洞注入層形成用組成物之溶劑之沸點以上，且不引起膜之充分之不溶化，則加熱時間並無限定，較佳為10秒以上，通常為180分鐘以下。若加熱時間過長，則存在其他層之成分發生擴散之傾向，若過短，則存在電洞注入層變得不均質之傾向。加熱亦可分為2次進行。 In the heating step, the heating time is not limited as long as the heating temperature is above the boiling point of the solvent of the composition for forming the hole injection layer and does not cause sufficient insolubilization of the film, preferably 10 seconds or more, usually 180 minutes. the following. If the heating time is too long, the components of other layers tend to diffuse, and if it is too short, the hole injection layer tends to become heterogeneous. Heating may be performed in two steps.
於利用真空蒸鍍形成電洞注入層3之情形時，首先，將電洞注入層3之構成材料(上述電洞輸送性化合物、電子接受性化合物等) 之1種或2種以上放入至設置於真空容器內之坩鍋(於使用2種以上之材料之情形時，放入至各自之坩堝)。 In the case where the hole injection layer 3 is formed by vacuum evaporation, first, the constituent materials of the hole injection layer 3 (the above-mentioned hole transporting compound, electron accepting compound, etc.) One or two or more kinds are placed in a crucible set in a vacuum container (in the case of using two or more kinds of materials, they are placed in respective crucibles).
繼而，於藉由適當之真空泵對真空容器內進行排氣至10-4Pa左右後，加熱坩堝(於使用2種以上之材料之情形時，加熱各自之坩堝)，控制蒸發量使電洞注入層3之構成材料蒸發(於使用2種以上之材料之情形時，分別獨立控制蒸發量使其蒸發)，於與坩堝對向放置之基板之陽極2上形成電洞注入層3。 Then, after the inside of the vacuum container is evacuated to about 10 -4 Pa by a suitable vacuum pump, the crucible is heated (in the case of using two or more materials, the respective crucibles are heated), and the evaporation amount is controlled to inject holes. The constituent material of the layer 3 is evaporated (in the case of using two or more materials, the evaporation amount is independently controlled to be evaporated separately), and the hole injection layer 3 is formed on the anode 2 of the substrate placed opposite the crucible.
再者，於使用2種以上之材料之情形時，亦可將該等之混合物放入坩堝，進行加熱使其蒸發而形成電洞注入層3。 When two or more materials are used, the mixture may be placed in a crucible and heated to evaporate to form the hole injection layer 3.
蒸鍍時之真空度只要不明顯損害本發明之效果則並無限定，通常為0.1×10-7Torr(1.3×10-6Pa)以上，且通常為9.0×10-6Torr(12.0×10-4Pa)以下。蒸鍍速度只要不明顯損害本發明之效果則並無限定，通常為0.1Å/秒以上，且通常為5.0Å/秒以下。 The degree of vacuum during vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, and is usually 0.1 × 10 -7 Torr (1.3 × 10 -6 Pa) or more, and usually 9.0 × 10 -6 Torr (12.0 × 10 -4 Pa) or less. The vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but it is usually 0.1 Å / sec or more and usually 5.0 Å / sec or less.
電洞輸送層4於有電洞注入層3之情形時可形成於電洞注入層3上，於無電洞注入層3之情形時可形成於陽極2上。又，本發明之有機電致發光元件亦可為省去電洞輸送層之構成。 The hole transporting layer 4 may be formed on the hole injection layer 3 when the hole injection layer 3 is present, and may be formed on the anode 2 when the hole injection layer 3 is not present. In addition, the organic electroluminescence element of the present invention may have a configuration in which an hole transporting layer is omitted.
電洞輸送層4之形成方法可為真空蒸鍍法，亦可為濕式成膜法，並無特別限制，但就降低暗點之觀點而言，較佳為藉由濕式成膜法形成電洞輸送層4。 The formation method of the hole transporting layer 4 may be a vacuum evaporation method or a wet film formation method, which is not particularly limited, but from the viewpoint of reducing dark spots, it is preferably formed by a wet film formation method电 孔 输 层 4。 Hole transport layer 4.
作為形成電洞輸送層4之材料，較佳為電洞輸送性較高，且可高效率地輸送被注入之電洞之材料。因此，較佳為游離電位較小，對可見光之光透明性較高，電洞移動度較大，穩定性優異， 於製造時或使用時不易產生成為陷阱之雜質。又，於大多情形時，由於相連接於發光層5，故而較佳為不會淬滅來自發光層5之發光、或於與發光層5之間形成激發複合體而使效率下降。 As a material for forming the hole transporting layer 4, a material having high hole transportability and capable of efficiently transporting the injected hole is preferred. Therefore, it is preferable that the free potential is small, the transparency to visible light is high, the hole mobility is large, and the stability is excellent. It is difficult to produce impurities that become traps during manufacture or use. In most cases, since the light-emitting layer 5 is connected to each other, it is preferable not to quench the light emission from the light-emitting layer 5 or form an excitation complex with the light-emitting layer 5 to reduce the efficiency.
作為此種電洞輸送層4之材料，可使用習知用作電洞輸送層用材之材料，例如可使用日本專利特開2009-212510號公報、國際公開2012/096352號、國際公開第2013/191137號等所揭示之化合物。於藉由濕式成膜法形成電洞輸送層4之情形時，與上述電洞注入層3之形成同樣地於製備電洞輸送層形成用組成物後進行塗佈，並加熱乾燥。 As the material of the hole transporting layer 4, a material conventionally used as a material for the hole transporting layer can be used. For example, Japanese Patent Laid-Open No. 2009-212510, International Publication No. 2012/096352, and International Publication No. 2013 / Compound disclosed in No. 191137 and the like. When the hole transporting layer 4 is formed by a wet film formation method, the hole transporting layer forming composition is prepared and coated, and then heated and dried in the same manner as the formation of the hole injection layer 3.
於電洞輸送層形成用組成物中，除了上述電洞輸送性化合物以外，亦含有溶劑。所使用之溶劑與上述電洞注入層形成用組成物所使用者相同。又，塗佈條件、加熱乾燥條件等亦與電洞注入層3之形成之情形相同。又，於藉由真空蒸鍍法形成電洞輸送層之情形時，其成膜條件等亦與上述電洞注入層3之形成之情形相同。如此方式形成之電洞輸送層4之膜厚通常為5nm以上，較佳為10nm以上，又，通常為1000nm以下，較佳為500nm以下。 The hole transporting layer forming composition contains a solvent in addition to the hole transporting compound. The solvent used is the same as that used by the aforementioned hole injection layer forming composition. The coating conditions, heating and drying conditions, and the like are also the same as in the case of forming the hole injection layer 3. In the case where the hole transporting layer is formed by the vacuum evaporation method, the film formation conditions and the like are also the same as those in the case where the hole injection layer 3 is formed. The film thickness of the hole transporting layer 4 formed in this way is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, and preferably 500 nm or less.
於電洞輸送層4上通常設置發光層5。發光層5係於提供有電場之電極間藉由自陽極2經由電洞注入層3注入之電洞與自陰極9經由電子輸送層7注入之電子之再結合而被激發的成為主要發光源之層。 A light emitting layer 5 is usually provided on the hole transporting layer 4. The light emitting layer 5 is excited by the recombination of the holes injected from the anode 2 through the hole injection layer 3 and the electrons injected from the cathode 9 through the electron transport layer 7 between the electrodes provided with an electric field to become the main light source. Floor.
發光層5較佳為含有發光材料(摻雜劑)與1種或2種以上之主體材料。發光材料較佳為本發明之金屬錯合物化合物，主 體材料較佳為本發明之電荷輸送性化合物。發光層5較佳為對本發明之組成物進行濕式成膜而形成之層。發光層5亦可進而具有藉由真空蒸鍍法而形成之層。 The light emitting layer 5 preferably contains a light emitting material (dopant) and one or more host materials. The luminescent material is preferably the metal complex compound of the present invention. The bulk material is preferably a charge-transporting compound of the present invention. The light emitting layer 5 is preferably a layer formed by wet-forming a composition of the present invention. The light emitting layer 5 may further include a layer formed by a vacuum evaporation method.
再者，發光層5亦可於不損害本發明之性能之範圍內含有除了發光材料(摻雜劑)與主體材料以外之其他材料、成分。 In addition, the light emitting layer 5 may contain other materials and components other than the light emitting material (dopant) and the host material within a range that does not impair the performance of the present invention.
有機電致發光元件中，發光層亦可為2層以上。於設置2層以上之發光層之情形時，只要任一發光層滿足本發明之規定即可。於發光層為2層以上之情形時，各發光層可直接相接，亦可於之間介隔其他層。作為於之間介隔之其他層，可列舉電荷輸送層、阻擋層、電荷產生層等。 In the organic electroluminescent device, the light emitting layer may be two or more layers. In the case where two or more light emitting layers are provided, any one of the light emitting layers may satisfy the requirements of the present invention. When the light-emitting layer is two or more layers, the light-emitting layers may be directly connected, or other layers may be interposed therebetween. Examples of other layers interposed therebetween include a charge transport layer, a barrier layer, and a charge generation layer.
於發光層為2層以上之情形時，較佳為於對本發明之組成物進行濕式成膜而形成之層上具有藉由蒸鍍方法而形成之發光層的構成。進而較佳為於對本發明之組成物進行濕式成膜而形成之層上具有藉由蒸鍍方法而形成之螢光發光層的構成。 When the light-emitting layer is two or more layers, it is preferable that the layer formed by wet-forming the composition of the present invention has a light-emitting layer formed by a vapor deposition method. Furthermore, it is preferable that the layer formed by wet-forming the composition of the present invention has a structure of a fluorescent light-emitting layer formed by a vapor deposition method.
藉由於對本發明之組成物進行濕式成膜而形成之層上利用蒸鍍方法形成發光層，可均勻地積層發光層，而較佳。進而，若於對本發明之組成物進行濕式成膜而形成之層上藉由蒸鍍方法形成之發光層為螢光發光層，則螢光發光材料通常不含重原子，可以用相對較低之溫度進行蒸鍍，因此螢光發光材料於下層，即對本發明之組成物進行濕式成膜而形成之層，附著時之能量較低，不存在對下層之損壞，而較佳。 By forming the light-emitting layer by a vapor deposition method on a layer formed by wet-forming the composition of the present invention, the light-emitting layer can be laminated uniformly, which is preferable. Furthermore, if the light-emitting layer formed by the evaporation method on the layer formed by wet-forming the composition of the present invention is a fluorescent light-emitting layer, the fluorescent light-emitting material generally does not contain heavy atoms, and can be used at a relatively low level. The evaporation is performed at the temperature, so that the fluorescent material is on the lower layer, that is, the layer formed by wet-forming the composition of the present invention. The energy at the time of adhesion is low, and there is no damage to the lower layer, which is preferable.
電洞阻擋層6可以相連接於發光層5之陰極側之界面之方式積 層形成於發光層5上。尤其是於使用磷光發光材料、或使用藍色發光材料作為發光層5之發光材料之情形時，設置電洞阻擋層6較為有效。 The hole blocking layer 6 may be connected to the cathode-side interface of the light-emitting layer 5. A layer is formed on the light emitting layer 5. In particular, when a phosphorescent light emitting material or a blue light emitting material is used as the light emitting material of the light emitting layer 5, it is effective to provide the hole blocking layer 6.
電洞阻擋層6具有將電洞與電子封入發光層5內而提高發光效率之功能。即，電洞阻擋層6具有如下作用：藉由阻止自發光層5移動而來之電洞到達電子輸送層7，而增加於發光層5內與電子再結合之機率，將所生成之激子封入發光層5內；及將自電子輸送層7注入之電子高效率地向發光層5之方向輸送。 The hole blocking layer 6 has a function of encapsulating holes and electrons in the light emitting layer 5 to improve light emitting efficiency. That is, the hole blocking layer 6 has the function of increasing the probability of recombination with electrons in the light-emitting layer 5 by preventing holes that have moved from the light-emitting layer 5 from reaching the electron-transporting layer 7, and generating excitons. Encapsulated in the light-emitting layer 5; and electrons injected from the electron-transporting layer 7 are efficiently transported toward the light-emitting layer 5.
作為對構成電洞阻擋層6之材料要求之物性，可列舉電子移動度較高且電洞移動度較低，能隙(HOMO、LUMO之差)較大，激發三重態能階(T1)較高。 As the physical properties required for the material constituting the hole blocking layer 6, the higher the electron mobility and the lower the hole mobility, the larger the energy gap (the difference between HOMO and LUMO), and the excited triplet energy level (T1) are higher. high.
作為滿足此種條件之電洞阻擋層材料，例如可列舉：雙(2-甲基-8-羥基喹啉)(苯酚)鋁、雙(2-甲基-8-羥基喹啉)(三苯基矽烷醇)鋁等混合配位基錯合物；雙(2-甲基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-8-羥基喹啉)鋁二核金屬錯合物等金屬錯合物；二苯乙烯基聯苯衍生物等苯乙烯基化合物(日本專利特開平11-242996號公報)；3-(4-聯苯基)-4-苯基-5-(4-第三丁基苯基)-1,2,4-***等***衍生物(日本專利特開平7-41759號公報)；2,9-二甲基-4,7-聯苯-1,10-啡啉等啡啉衍生物(日本專利特開平10-79297號公報)。進而，國際公開第2005/022962號中記載之具有至少1個2、4、6位經取代之吡啶環之化合物作為電洞阻擋材料亦較佳。 Examples of the hole blocking layer material satisfying such conditions include bis (2-methyl-8-hydroxyquinoline) (phenol) aluminum, bis (2-methyl-8-hydroxyquinoline) (triphenyl) Silyl alcohol) aluminum and other complex coordination complexes; bis (2-methyl-8-hydroxyquinoline) aluminum-μ-sideoxy-bis (2-methyl-8-hydroxyquinoline) aluminum Metal complexes such as nuclear metal complexes; Styryl compounds such as distyryl biphenyl derivatives (Japanese Patent Laid-Open No. 11-242996); 3- (4-biphenyl) -4-phenyl Triazole derivatives such as -5- (4-third butylphenyl) -1,2,4-triazole (Japanese Patent Laid-Open No. 7-41759); 2,9-dimethyl-4,7 -A phenanthroline derivative such as biphenyl-1,10-morpholine (Japanese Patent Laid-Open No. 10-79297). Furthermore, a compound having at least one substituted pyridine ring at positions 2, 4, and 6 described in International Publication No. 2005/022962 is also preferred as a hole blocking material.
再者，電洞阻擋層6之材料可僅使用1種，亦可按照任意之組合及比率併用2種以上。電洞阻擋層6之膜厚通常為0.3nm以上，較佳為0.5nm以上。電洞阻擋層6之膜厚通常為100nm 以下，較佳為50nm以下。電洞阻擋層6可藉由與電洞注入層3相同之方法形成，但通常使用真空蒸鍍法。 In addition, only one kind of material of the hole blocking layer 6 may be used, and two or more kinds may be used in combination in any combination and ratio. The film thickness of the hole blocking layer 6 is usually 0.3 nm or more, and preferably 0.5 nm or more. The film thickness of the hole blocking layer 6 is usually 100 nm Hereinafter, it is preferably 50 nm or less. The hole blocking layer 6 can be formed by the same method as the hole injection layer 3, but a vacuum evaporation method is generally used.
電子輸送層7可設置於電洞阻擋層6與下述電子注入層8之間以進一步提高元件之發光效率。電子輸送層7係由可於提供有電場之電極間將自陰極9注入之電子高效率地向發光層5之方向輸送之化合物而形成。 The electron transporting layer 7 can be disposed between the hole blocking layer 6 and the electron injection layer 8 described below to further improve the luminous efficiency of the device. The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 9 to the direction of the light emitting layer 5 between electrodes provided with an electric field.
作為電子輸送層7所使用之電子輸送性化合物，必須為來自陰極9或電子注入層8之電子注入效率較高、且具有較高之電子移動度而可高效率地輸送所注入之電子之化合物。 The electron-transporting compound used in the electron-transporting layer 7 must be a compound that has a high electron injection efficiency from the cathode 9 or the electron-injection layer 8 and has a high electron mobility and can efficiently transport the injected electrons. .
作為滿足此種條件之材料，可列舉：8-羥基喹啉之鋁錯合物等金屬錯合物(日本專利特開昭59-194393號公報)、10-羥基苯并[h]喹啉之金屬錯合物、
關於電子輸送層7之膜厚，下限通常為1nm，較佳為5nm左右，上限通常為300nm，較佳為100nm左右。電子輸送層7係與電洞注入層3同樣地藉由濕式成膜法、或真空蒸鍍法而形成，但通常使用真空蒸鍍法。 Regarding the film thickness of the electron transporting layer 7, the lower limit is usually 1 nm, preferably about 5 nm, and the upper limit is usually 300 nm, preferably about 100 nm. The electron transport layer 7 is formed by a wet film formation method or a vacuum deposition method in the same manner as the hole injection layer 3, but a vacuum deposition method is generally used.
電子注入層8發揮將自陰極9注入之電子高效率地向發光層5注入之作用。為了高效率地進行電子注入，形成電子注入層8之材料較佳為工作函數較低之金屬，可使用鈉或銫等鹼金屬、鋇或鈣等鹼土類金屬。 The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the light emitting layer 5. In order to perform electron injection with high efficiency, the material forming the electron injection layer 8 is preferably a metal with a lower work function, and alkali metals such as sodium or cesium, and alkaline earth metals such as barium or calcium can be used.
電子注入層8之膜厚較佳為0.1~5nm。又，於陰極9與電子輸送層7之界面***LiF、MgF2、Li2O、Cs2CO3等極薄絕緣膜(膜厚0.1~5nm左右)作為電子注入層8亦為提高元件之效率之有效方法(Appl.Phys.Lett.、70卷、152頁、1997年；日本專利特開平10-74586號公報；IEEETrans.Electron.Devices、44卷、1245頁、1997年；SID 04 Digest、154頁)。 The film thickness of the electron injection layer 8 is preferably 0.1 to 5 nm. In addition, inserting an extremely thin insulating film (film thickness of about 0.1 to 5 nm) such as LiF, MgF 2 , Li 2 O, and Cs 2 CO 3 at the interface between the cathode 9 and the electron transport layer 7 is also used to improve the efficiency of the device. Effective methods (Appl. Phys. Lett., Vol. 70, 152 pages, 1997; Japanese Patent Laid-Open No. 10-74586; IEEE Trans.Electron. Devices, Vol. 44, pages 1245, 1997; SID 04 Digest, 154 page).
進而，藉由於4,7-二苯基-1,10-啡啉等含氮雜環化合物或8-羥基喹啉之鋁錯合物等金屬錯合物所代表之有機電子輸送材料中摻雜鈉、鉀、銫、鋰、銣等鹼金屬(於日本專利特開平10-270171號公報、日本專利特開2002-100478號公報、日本專利特開2002-100482號公報等中記載)，電子注入輸送性提高，且能夠兼具優異之膜質，故而較佳。 Furthermore, the organic electron transport materials represented by nitrogen-containing heterocyclic compounds such as 4,7-diphenyl-1,10-morpholine and metal complexes such as aluminum complexes of 8-hydroxyquinoline are doped. Sodium, potassium, cesium, lithium, rubidium and other alkali metals (described in Japanese Patent Laid-Open No. 10-270171, Japanese Patent Laid-Open No. 2002-100478, Japanese Patent Laid-Open No. 2002-100482, etc.), electron injection The transportability is improved, and it can also have excellent film quality, so it is preferable.
於該情形時之電子注入層8之膜厚通常為5nm以上，較佳為10nm以上。電子注入層8之膜厚通常為200nm以下，較佳為100nm以下。 The film thickness of the electron injection layer 8 in this case is usually 5 nm or more, and preferably 10 nm or more. The film thickness of the electron injection layer 8 is usually 200 nm or less, and preferably 100 nm or less.
電子注入層8係與發光層5同樣地藉由濕式成膜法、或真空蒸鍍法而形成。於真空蒸鍍法之情形時，將蒸鍍源放入至設置於真空容器內之坩堝或金屬晶舟中，藉由適當之真空泵對真空容 器內進行排氣至10-4Pa左右後，加熱坩堝或金屬晶舟使蒸鍍源蒸發，於與坩堝或金屬晶舟對向放置之基板上形成電子注入層8。 The electron injection layer 8 is formed by a wet film formation method or a vacuum deposition method in the same manner as the light emitting layer 5. In the case of the vacuum evaporation method, the evaporation source is placed in a crucible or a metal crystal boat set in a vacuum container, and the inside of the vacuum container is evacuated to about 10 -4 Pa by an appropriate vacuum pump, and then heated. The crucible or metal boat makes the evaporation source evaporate, and an electron injection layer 8 is formed on the substrate placed opposite to the crucible or metal boat.
鹼金屬之蒸鍍係使用將鉻酸鹼金屬與還原劑填充於鎳鉻合金之鹼金屬點膠機而進行。於真空容器內加熱該點膠機，藉此鉻酸鹼金屬被還原，鹼金屬蒸發。 Alkali metal vapor deposition is performed using an alkali metal dispenser in which an alkali metal chromate and a reducing agent are filled in a nickel-chromium alloy. The dispenser is heated in a vacuum container, whereby the alkali metal chromate is reduced and the alkali metal is evaporated.
於對有機電子輸送材料與鹼金屬進行共蒸鍍之情形時，將有機電子輸送材料放入設置於真空容器內之坩堝，藉由適當之真空泵對真空容器內進行排氣至10-4Pa左右後，同時加熱坩堝及點膠機之各者使有機電子輸送材料與鹼金屬蒸發，於與坩堝及點膠機對向放置之基板上形成電子注入層8。此時，於電子注入層8之膜厚方向上被均勻地共蒸鍍，但即便於膜厚方向上有濃度分佈亦無礙。 In the case of co-evaporation of an organic electron transport material and an alkali metal, the organic electron transport material is placed in a crucible set in a vacuum container, and the inside of the vacuum container is evacuated to about 10 -4 Pa by a suitable vacuum pump. Then, each of the crucible and the dispenser is heated at the same time to vaporize the organic electron transport material and the alkali metal, and an electron injection layer 8 is formed on the substrate placed opposite the crucible and the dispenser. At this time, the electron injection layer 8 is uniformly vapor-deposited in the film thickness direction, but even if there is a concentration distribution in the film thickness direction, it does not matter.
陰極9發揮將電子注入至發光層5側之層(電子注入層8或發光層5等)之作用。用作陰極9之材料亦可使用上述陽極2所使用之材料，但為了高效率地進行電子注入，較佳為工作函數較低之金屬。例如可使用錫、鎂、銦、鈣、鋁、銀等適當之金屬或該等之合金。作為具體例，可列舉鎂-銀合金、鎂-銦合金、鋁-鋰合金等低工作函數合金電極。 The cathode 9 functions as a layer (the electron injection layer 8 or the light emitting layer 5) that injects electrons to the light emitting layer 5 side. The material used for the cathode 9 may also be the same as that used for the anode 2. However, in order to efficiently perform electron injection, a metal having a lower work function is preferred. For example, appropriate metals such as tin, magnesium, indium, calcium, aluminum, and silver, or alloys thereof can be used. Specific examples include low-work-function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
陰極9之膜厚通常與陽極2相同。以保護包含低工作函數金屬之陰極之目的而於其上進一步積層工作函數較高且對於大氣穩定之金屬層會增加元件之穩定性。為了該目的，可使用鋁、銀、銅、鎳、鉻、金、鉑等金屬。 The film thickness of the cathode 9 is generally the same as that of the anode 2. For the purpose of protecting a cathode containing a metal with a low work function, further layering a metal layer with a higher work function and stable to the atmosphere will increase the stability of the element. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum can be used.
以上，以圖1所示之層構成之元件為中心進行了說明，但於本發明之有機電致發光元件中之陽極2及陰極9與發光層5之間，只要不損害其性能，則除了上述說明中之層以外，還可具有任意層，又，亦可省略發光層5以外之任意層。 In the above, the description has been given focusing on the element composed of the layer shown in FIG. 1, but between the anode 2 and the cathode 9 and the light-emitting layer 5 in the organic electroluminescent element of the present invention, as long as the performance is not impaired, Any layer other than the layers described above may be used, and any layer other than the light emitting layer 5 may be omitted.
例如，亦有效的是以與電洞阻擋層6相同之目的，於電洞輸送層4與發光層5之間設置電子阻擋層。電子阻擋層具有如下作用：藉由阻止自發光層5移動而來之電子到達電洞輸送層4，而增加於發光層5內與電洞再結合之機率，將所生成之激子封入發光層5內；及將自電洞輸送層4注入之電洞高效率地向發光層5之方向輸送。 For example, it is also effective to provide an electron blocking layer between the hole transporting layer 4 and the light emitting layer 5 for the same purpose as the hole blocking layer 6. The electron blocking layer has the following function: by preventing electrons from the light-emitting layer 5 from reaching the hole transporting layer 4, the probability of recombination with the holes in the light-emitting layer 5 is increased, and the generated exciton is enclosed in the light-emitting layer 5; and the holes injected from the hole transporting layer 4 are efficiently transported toward the light emitting layer 5.
作為對電子阻擋層要求之特性，可列舉電洞輸送性較高且能隙(HOMO、LUMO之差)較大，激發三重態能階(T1)較高。又，於藉由濕式成膜法形成發光層5之情形時，為了使元件製造變得容易，較佳為電子阻擋層亦藉由濕式成膜法形成。 Examples of characteristics required for the electron blocking layer include high hole transportability, large energy gap (difference between HOMO and LUMO), and high excited triplet energy level (T1). In the case where the light-emitting layer 5 is formed by a wet film formation method, it is preferable that the electron blocking layer is also formed by a wet film formation method in order to facilitate the manufacture of the device.
因此，較佳為電子阻擋層亦具有濕式成膜適合性，作為此種電子阻擋層所使用之材料，可列舉F8-TFB所代表之二辛基茀與三苯胺之共聚合體(國際公開第2004/084260號)等。 Therefore, it is preferable that the electron blocking layer also has wet film formation suitability. As a material used for such an electron blocking layer, a copolymer of dioctylfluorene and triphenylamine represented by F8-TFB (International Publication No. 2004/084260), etc.
再者，亦可為與圖1相反之構造，即於基板1上依序積層陰極9、電子注入層8、電子輸送層7、電洞阻擋層6、發光層5、電洞輸送層4、電洞注入層3、陽極2，亦可於至少一者透明性較高之2片基板之間設置本發明之有機電致發光元件。 Furthermore, it can also have a structure opposite to FIG. 1, that is, a cathode 9, an electron injection layer 8, an electron transport layer 7, a hole blocking layer 6, a light emitting layer 5, and a hole transport layer 4 are sequentially laminated on the substrate 1. The hole injection layer 3 and the anode 2 may also include the organic electroluminescent device of the present invention between at least one of the two substrates having high transparency.
進而，亦可將圖1所示之層構成設為重疊數段而成之 構造(積層數個發光單元而成之構造)。此時，若使用例如V2O5等作為電荷產生層代替階段間(發光單元間)之界面層(於陽極為ITO、陰極為Al之情形時為該2層)，則階段間之障壁變少，就發光效率、驅動電壓之觀點而言更佳。 Furthermore, the layer structure shown in FIG. 1 may be a structure in which several layers are overlapped (a structure in which a plurality of light-emitting units are stacked). At this time, if, for example, V 2 O 5 is used as a charge generating layer instead of the interface layer between the stages (inter-light emitting units) (these two layers when the anode is ITO and the cathode is Al), the barrier between the stages changes. It is less in terms of luminous efficiency and driving voltage, and is more preferable.
本發明之有機電致發光元件可應用於單一之元件、包含配置為陣列狀之構造之元件、陽極與陰極配置為X-Y矩陣狀之構造之任一者中。 The organic electroluminescence element of the present invention can be applied to any one of a single element, an element including an array structure, and an anode and cathode structure having an X-Y matrix structure.
本發明之顯示裝置及照明裝置係使用如上所述之本發明之有機電致發光元件者。本發明之顯示裝置及照明裝置之形式或構造並無特別限定，可使用本發明之有機電致發光元件按照常規方法進行組裝。 The display device and lighting device of the present invention are those using the organic electroluminescence element of the present invention as described above. The form or structure of the display device and the lighting device of the present invention is not particularly limited, and the organic electroluminescence element of the present invention can be assembled by a conventional method.
例如可藉由如「有機EL顯示器」(Ohmsha，2004年8月20日發行，時任靜士、安達千波矢、村田英幸著)中所記載之方法形成本發明之顯示裝置及照明裝置。 For example, the display device and the lighting device of the present invention can be formed by a method described in "Organic EL Display" (Ohmsha, issued on August 20, 2004, by Ren Jingshi, Anda Chihaya, and Hideyuki Murata).
以下，藉由實施例對本發明進行更詳細之說明，但本發明只要不超出其主旨則並不限定於以下之實施例。 Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited to the following examples as long as the present invention is not exceeded.
製作圖1所示之有機電致發光元件。首先，於玻璃基板1上將氧化銦錫(ITO，Indium Tin Oxide)透明導電膜堆積為150nm之厚度，並圖案化為2mm寬之條紋，而形成ITO之陽極2，針對該形 成有ITO之陽極2之基板(三容真空公司製造，濺鍍成膜品)，按照利用界面活性劑水溶液之超音波洗淨、利用超純水之水洗、利用超純水之超音波洗淨、利用超純水之水洗之順序進行洗淨後，藉由壓縮空氣使其乾燥，並實施紫外線臭氧洗淨。 An organic electroluminescence device shown in FIG. 1 was fabricated. First, an indium tin oxide (ITO) transparent conductive film is deposited on the glass substrate 1 to a thickness of 150 nm, and patterned into stripes with a width of 2 mm to form an anode 2 of ITO. The substrate with anode 2 formed by ITO (manufactured by Sanrong Vacuum Co., Ltd., sputtered into a film) is washed by ultrasonic waves using an aqueous surfactant solution, washed with ultrapure water, and washed with ultrapure water. 7. After washing in the order of washing with ultrapure water, it is dried by compressed air, and ultraviolet ozone washing is performed.
其次，製備含有具有下述(P1)所表示之重複構造之電洞輸送性高分子化合物2.0質量%、及下述(A1)所表示之4-異丙基-4'-甲基聯苯錪四(五氟苯基)硼酸鹽0.8質量%之苯甲酸乙酯溶液(電洞注入層形成用組成物)。 Next, 2.0 mass% of a hole-transporting polymer compound having a repeating structure represented by the following (P1) and 4-isopropyl-4'-methylbiphenylfluorene represented by the following (A1) were prepared. Tetrakis (pentafluorophenyl) borate 0.8% by mass ethyl benzoate solution (composition for forming hole injection layer).
以下述所示之條件藉由旋轉塗佈法將該電洞注入層形成用組成物塗佈於上述ITO基板上，進而以下述所示之烘烤條件進行烘烤，藉此獲得膜厚40nm之電洞注入層3。 The composition for forming the hole injection layer was coated on the ITO substrate by a spin coating method under the conditions shown below, and then baked under the baking conditions shown below to obtain a film thickness of 40 nm. Electric hole injection layer 3.
旋轉塗佈環境 大氣環境下 Spin coating environment Atmospheric environment
烘烤條件 大氣環境下、230℃、1小時 Baking conditions: 230 ℃ for 1 hour in the atmosphere
其後，製備下述(H1)所表示之電洞輸送性高分子化合物之1質量%環己基苯溶液(電洞輸送層形成用組成物)，以下述所示之條件藉由旋轉塗佈法將其塗佈於電洞注入層3上，並進行利用烘烤之交聯處理，藉此獲得膜厚10nm之電洞輸送層4。 Thereafter, a 1% by mass cyclohexylbenzene solution (composition for forming a hole transporting layer) of a hole transporting polymer compound represented by the following (H1) was prepared, and a spin coating method was used under the conditions shown below. This was coated on the hole injection layer 3 and subjected to a cross-linking treatment by baking, thereby obtaining a hole transport layer 4 having a film thickness of 10 nm.
其次，於形成發光層5時，使用以下所示之發光材料(D-1)、電荷輸送性化合物(h-1~h-3)、及作為酚性化合物之丁基羥基大茴香醚(3-BHA)，製備下述所示之組成之發光層形成用組成物。 Next, in forming the light-emitting layer 5, the light-emitting material (D-1) shown below, a charge-transporting compound (h-1 to h-3), and butylhydroxyanisole (3 -BHA) to prepare a light-emitting layer-forming composition having the composition shown below.
[化13]
於製備該發光層形成用組成物之當天，使用該溶液，按照以下所示之條件藉由旋轉塗佈法塗佈於電洞輸送層4上，並以下述所示之烘烤條件進行烘烤處理，藉此獲得膜厚50nm之發光層5。 On the day of preparing the composition for forming a light-emitting layer, the solution was applied to the hole transporting layer 4 by a spin coating method under the conditions shown below, and the baking was performed under the baking conditions shown below. By processing, a light-emitting layer 5 having a film thickness of 50 nm was obtained.
其次，將濕式成膜有電洞注入層3、電洞輸送層4及發光層5之基板搬入至真空蒸鍍裝置內，進行粗排氣後，使用低溫泵進行排氣直至裝置內之真空度變為3.0×10-4Pa以下。於將真空度保持為2.2×10-4Pa以下之狀態下，以蒸鍍速度0.6~1.2Å/秒，於發光層5上積層至膜厚為10nm之作為電洞阻擋材料之HB1，藉此形成電洞阻擋層6。 Next, the wet-formed substrate with the hole injection layer 3, the hole transport layer 4 and the light emitting layer 5 is carried into a vacuum evaporation device, and after rough exhaust, the exhaust is performed using a cryopump until the vacuum inside the device The degree becomes 3.0 × 10 -4 Pa or less. With the vacuum degree kept at 2.2 × 10 -4 Pa or less, the light-emitting layer 5 was laminated on the light-emitting layer 5 to HB1 as a hole blocking material at a deposition rate of 0.6 to 1.2 Å / sec. Forming an electric hole barrier layer 6.
繼而，於將真空度保持為2.2×10-4Pa以下之狀態下，將三(8-羥基喹啉)鋁(Alq3)進行加熱，以蒸鍍速度0.7~1.3Å/秒，於電洞阻擋層6上積層至膜厚為20nm，藉此形成電子輸送層7。 此處，將進行了至電子輸送層7為止之蒸鍍元件自有機層蒸鍍用腔室向金屬蒸鍍用腔室內搬送。使2mm寬之條紋狀蔽蔭遮罩以與陽極2之ITO條紋正交之方式密接而設置於元件上，作為陰極蒸鍍用之遮罩。與有機層蒸鍍時同樣地對裝置內進行排氣直至真空度變為1.1×10-4Pa以下。 Next, while maintaining the degree of vacuum at 2.2 × 10 -4 Pa or less, the tris (8-hydroxyquinoline) aluminum (Alq3) was heated, and the evaporation rate was 0.7 to 1.3 Å / sec. The layer 6 is laminated to a film thickness of 20 nm, thereby forming an electron transport layer 7. Here, the vapor deposition element that has been subjected to the electron transport layer 7 is transferred from the organic layer vapor deposition chamber into the metal vapor deposition chamber. A stripe-shaped shadow mask having a width of 2 mm was tightly attached to the element so as to be orthogonal to the ITO stripe of the anode 2 and provided on the element as a mask for cathode evaporation. As in the case of the organic layer vapor deposition, the inside of the device was evacuated until the degree of vacuum became 1.1 × 10 -4 Pa or less.
其後，於將真空度保持為1.0×10-4Pa以下之狀態下，藉由使用鉬晶舟進行加熱而以蒸鍍速度0.07~0.15Å/秒於電子輸送層7上積層至膜厚為0.5nm之氟化鋰(LiF)，藉此形成電子注入層8。其次，同樣地於將真空度保持為2.0×10-4Pa之狀態下，藉由使用鉬晶舟進行加熱而以蒸鍍速度0.6~10.0Å/秒將鋁蒸鍍至膜厚為80nm，藉此形成陰極9。以上之電子注入層8及陰極9於蒸鍍時之基板溫度保持為室溫。 Thereafter, while maintaining the degree of vacuum at 1.0 × 10 -4 Pa or less, the electron transport layer 7 was laminated on the electron transport layer 7 by heating using a molybdenum crystal boat at a deposition rate of 0.07 to 0.15 Å / s to a film thickness of 0.5 nm of lithium fluoride (LiF), thereby forming an electron injection layer 8. Next, similarly, while maintaining the degree of vacuum at 2.0 × 10 -4 Pa, aluminum was vapor-deposited to a film thickness of 80 nm by heating using a molybdenum crystal boat at a vapor deposition rate of 0.6 to 10.0 Å / sec. This forms the cathode 9. The substrate temperature of the above electron injection layer 8 and the cathode 9 during the evaporation is kept at room temperature.
繼而，為了防止元件於保管中因大氣中之水分等發生劣化，而藉由以下記載之方法進行密封處理。於氮氣手套箱中，將光硬化性樹脂30Y-437(三鍵化工公司製造)以1mm之寬度塗佈於23mm×23mm尺寸之玻璃板之外周部，並於中央部設置水分吸收片材(Dynic公司製造)。將陰極之形成結束之基板搬入至其上，以經蒸鍍之面與乾燥劑片材對向之方式貼合。其後，僅對塗佈有光硬化性樹脂之區域照射紫外光，使樹脂硬化。 Then, in order to prevent the components from being deteriorated due to moisture in the atmosphere during storage, the sealing process was performed by the method described below. In a nitrogen glove box, a light-curable resin 30Y-437 (manufactured by Sanjian Chemical Co., Ltd.) was coated with a width of 1 mm on the outer periphery of a glass plate having a size of 23 mm × 23 mm. Made by the company). The substrate on which the formation of the cathode was completed was carried onto it, and the vapor-deposited surface and the desiccant sheet were opposed to each other. Thereafter, only the area where the photocurable resin is applied is irradiated with ultraviolet light to harden the resin.
如以上般，獲得具有2mm×2mm尺寸之發光面積部分，且以峰值波長560nm發光之有機電致發光元件。 As described above, an organic electroluminescence element having a light emitting area portion having a size of 2 mm × 2 mm and emitting light at a peak wavelength of 560 nm was obtained.
除了使用4,4'-亞丁基雙(6-第三丁基-3-甲基苯酚)代替3-BHA 作為酚性化合物以外，與實施例1同樣地操作，藉此獲得實施例2之有機電致發光元件。 Except using 4,4'-butylene bis (6-third butyl-3-methylphenol) instead of 3-BHA An organic electroluminescence device of Example 2 was obtained in the same manner as in Example 1 except for the phenolic compound.
除了使用2,6-二-第三丁基苯酚(BHB)代替3-BHA作為酚性化合物以外，與實施例1同樣地操作，藉此獲得實施例3之有機電致發光元件。 An organic electroluminescence device of Example 3 was obtained in the same manner as in Example 1 except that 2,6-di-third-butylphenol (BHB) was used instead of 3-BHA as the phenolic compound.
除了不使用酚性化合物以外，進行與實施例1相同之操作，藉此獲得比較例1之有機電致發光元件。 An organic electroluminescence device of Comparative Example 1 was obtained by performing the same operation as in Example 1 except that no phenolic compound was used.
除了使用2,6-二-第三丁基-4-甲基苯酚(BHT)代替3-BHA作為酚性化合物以外，與實施例1同樣地操作，藉此獲得比較例2之有 機電致發光元件。 Comparative Example 2 was obtained in the same manner as in Example 1 except that 2,6-di-tert-butyl-4-methylphenol (BHT) was used instead of 3-BHA as the phenolic compound. Electroluminescent element.
除了使用Irganox 1330代替3-BHA作為酚性化合物以外，與實施例1同樣地操作，藉此獲得比較例3之有機電致發光元件。 An organic electroluminescent device of Comparative Example 3 was obtained in the same manner as in Example 1 except that Irganox 1330 was used instead of 3-BHA as the phenolic compound.
除了使用4-第三辛基苯酚代替3-BHA作為酚性化合物以外，與實施例1同樣地操作，藉此獲得比較例4之有機電致發光元件。 An organic electroluminescence device of Comparative Example 4 was obtained in the same manner as in Example 1 except that 4-third octylphenol was used instead of 3-BHA as the phenolic compound.
[化22]
針對實施例1~3、比較例1~4，分別對流通10mA/cm2之電流時的光強度電流效率及使用初期光強度5000cd/m2時之電流值的直流電流驅動下於50小時後之相對光強度進行測定。將以比較例1作為基準時之各變化率(相對值)及50小時後之相對光強度率之差彙總於表1。於實施例1~3中，光強度電流效率急劇上升，於在全部之鄰位及對位經烷基取代之比較例2、3中，僅限於效率稍微上升。又，可確認若使用僅於對位經烷基取代之酚性化合物，則會引起光強度電流效率之下降。 For Examples 1 to 3 and Comparative Examples 1 to 4, the light intensity current efficiency at a current of 10 mA / cm 2 and the current value at an initial light intensity of 5000 cd / m 2 were used to drive the DC current after 50 hours. The relative light intensity was measured. The difference between each change rate (relative value) when using Comparative Example 1 as a reference and the relative light intensity rate after 50 hours is summarized in Table 1. In Examples 1 to 3, the light intensity current efficiency sharply increased, and in Comparative Examples 2 and 3 in which all the ortho and para positions were substituted with alkyl groups, the efficiency was only slightly increased. In addition, it was confirmed that the use of a phenolic compound substituted with an alkyl group only at the para position would cause a decrease in light intensity current efficiency.
光強度電流效率之變化率(相對值)：於將作為對象之實施例或比較例之電流效率設為ηE(cd/A)、將比較例1之電流效率設為ηR(cd/A)之情形時，光強度電流效率之變化率(相對值)=(ηE/ηR-1)×100(%)50小時後之相對光強度率之差：於將50小時後之光強度設為L50(cd/m2)之情形時，初期光強度為5000(cd/m2)，因此50小時後之相對光強度率=L50/5000×100(%)。 Change rate (relative value) of light intensity current efficiency: The current efficiency of the target embodiment or comparative example is set to ηE (cd / A), and the current efficiency of Comparative Example 1 is set to ηR (cd / A). In this case, the change rate (relative value) of the light intensity current efficiency = (ηE / ηR-1) × 100 (%) The difference of the relative light intensity ratio after 50 hours: The light intensity after 50 hours is set to L50 ( In the case of cd / m 2 ), the initial light intensity is 5000 (cd / m 2 ), so the relative light intensity ratio after 50 hours = L50 / 5000 × 100 (%).
於將作為對象之實施例或比較例之50小時後之相對光強度率設為τE(%)、將比較例1之50小時後之相對光強度率設為τR(%)之情形時， 50小時後之相對光強度率之差=(τE-τR)(%) In a case where the relative light intensity ratio of the target example or comparative example after 50 hours is τE (%), and the relative light intensity ratio of 50 hours after Comparative Example 1 is τR (%), Difference of relative light intensity ratio after 50 hours = (τE-τR) (%)
以上使用特定之樣態對本發明進行了詳細說明，但從業者應明瞭：可於不脫離本發明之意圖與範圍而進行各種變更及變化。再者，本申請案係基於2015年3月24日提出申請之日本專利申請案(日本專利特願2015-061261)及2015年10月16日提出申請之日本專利申請案(日本專利特願2015-204901)，並藉由引用而援引其全部內容。 The present invention has been described in detail using specific aspects, but practitioners should be aware that various changes and modifications can be made without departing from the intent and scope of the present invention. Furthermore, this application is based on a Japanese patent application filed on March 24, 2015 (Japanese Patent Application No. 2015-061261) and a Japanese patent application filed on October 16, 2015 (Japanese Patent Application No. 2015) -204901), and the entire contents of which are incorporated by reference.
1‧‧‧基板 1‧‧‧ substrate
2‧‧‧陽極 2‧‧‧ anode
3‧‧‧電洞注入層 3‧‧‧ Hole injection layer
4‧‧‧電洞輸送層 4‧‧‧ Hole transporting layer
5‧‧‧發光層 5‧‧‧ luminescent layer
6‧‧‧電洞阻擋層 6‧‧‧ Hole barrier
7‧‧‧電子輸送層 7‧‧‧ electron transport layer
8‧‧‧電子注入層 8‧‧‧ electron injection layer
9‧‧‧陰極 9‧‧‧ cathode
10‧‧‧有機電致發光元件 10‧‧‧Organic electroluminescence element
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