CN1108730C - 改进阴极的有机光发射器件 - Google Patents
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Abstract
本发明提供一种有机光发射器件，其中阴极(4，5)包含第一导电材料层(5)和功函数最大为3.7eV的第二导电材料层(4)，第二层比第一层薄得多，厚度最多为5mm。
Description
发明领域
本发明涉及带高效率电子注入电极的有机光发射器件。
背景技术
有机光发射器件(OLED)在各种显示应用中具有巨大的应用前景，这类器件可参见已经转让给剑桥显示技术有限公司的早期美国专利No.5,247,190或者VanSlyke等人的美国专利No.4,539,507，这些发明的内容作为参考文献和例子已经包含在本发明中。从原理上讲，OLED由注入正电荷载流子的阳极、注入负电荷载流子的阴极以及夹在两电极之间的至少一层有机场致发光层组成。OLED技术其中一个关键优势是，如果采用合适的场致发光有机层和正负电荷载流子注入效率高的电极，则器件可以工作在较低的驱动电压下。阳极一般情况下(但非一定)是氧化铟锡(ITO)薄膜，这是一种淀积在玻璃或塑料衬底上的半透明导电氧化物，有现成的商品可购。有机层通常通过蒸发或旋转涂覆、刮刀涂覆、浸渍涂覆和半月板涂覆方法中的一种淀积在ITO覆盖层衬底上。最后将阴极层淀积在有机层上面的步骤一般利用热蒸发或溅射合适的阴极金属完成。Al、Ca层或者Mg∶Ag或Mg∶In或Al合金层通常用作阴极材料。为了获得性能优良的OLED，对各层(阳极、阴极和有机层)以及层之间界面进行优化是非常重要的。
研究人员经常发现阴极的电子注入性质对于器件高效率操作的实现特别重要。由于大多数有机场致发光材料的电子结构，经常需要采用功函数较低的阴极材料来实现高效的电子注入和较低的工作电压。用于OLED的这类阴极典型的有碱金属Li、Na、K、Rb、或Cs、碱土金属Mg、Ca、Sr或Ba或镧系元素Sm、Eu、Tb或Yb。这些材料非常容易氧化和受潮，因此处理起来和/或在淀积至OLED之上期间或之后都需要特别小心。这些低功函数的材料通常以合金的形式作为阴极层淀积在OLED上，合金中的其它成份起稳定阴极层的作用；典型的合金有Mg∶Al、Mg∶In或Mg∶Ag或Al∶Li。当这些低功函数元素中的一部分(例如Ca、K、Li或Sm)以纯金属或合金的形式构成OLED阴极层时，它们可能会扩散入有机层并随后掺杂在有机层内，导致电学短路或者光荧光猝灭，并影响器件性能。
发明内容
因此本发明的一个目标是提供一种有机光发射器件结构及其制造方法，该器件采用低功函数元素作为阴极以实现高效的负电荷载流子注入和低工作电压，但是又最大限度地解决了上述问题。
按照本发明的第一方面，提供了一种有机光发射器件，它包含排列在器件阴极与阳极之间的至少一层光发射有机材料，其中阴极包含作为高电导率不透明金属层的第一导电材料层和位于至少一层有机材料与第一导电材料之间的低功函数第二导电材料层，第二导电材料层比第一导电材料层薄得多，厚度为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV。
这样，阴极由元素金属、合金或金属间化合物薄层组成，功函数最大为3.7eV，但是比较好的是小于3.2eV。阴极层的厚度最多为5nm，但是比较好的是介于0.5～2nm之间。低功函数的薄阴极层比较好的是覆盖一层典型厚度为100-500nm的另一导电层，它保证了其下面薄薄的低功函数层具有较高的电导率，并使该层的环境稳定。按照本发明第一方面的这种双层电极结构OLED的高效率电子注入的阴极层，在该OLED中，至少有一层场致发光有机层介于所述阴极层与注入正电荷载流子的阳极层之间。
这种结构防止了过度的掺杂，并对该结构的短路和对至少一层有机材料的电荧光猝灭的危险降至最低限度。
本发明的第一方面还提供了有机光发射器件的制造方法，它包含：在衬底上形成器件阴极的步骤，该步骤包含在衬底上形成第一导电材料层并在第一导电材料层上形成低功函数的第二导电材料层的步骤，其中第一导电材料层为不透明金属层而第二导电材料层比第一导电材料层薄得多，厚度为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV；在阴极上形成至少一层光发射有机材料的步骤；以及在至少一层有机材料层上形成器件阳极的步骤。
本发明的第一方面进一步提供了有机光发射器件的制造方法，它包含在衬底上形成器件阳极、在阳极上形成至少一层光发射有机材料和在至少一层有机材料上形成阴极的步骤，该步骤包含在至少一层有机材料上形成低功函数的第二导电材料层并在第二导电材料层上形成高电导率的第一导电材料层的步骤，其中第一导电材料层为不透明金属层而第二导电材料层比第一导电材料层薄得多，厚度为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV。
本发明还提供了一种带高效率电子注入电极的OLED制造方法，其中至少一层场致发光有机层淀积在预先涂覆阳极的支承衬底上，比较好的有机层是聚合物或分子。在一个实施例内，利用真空蒸发的方法在有机层上涂覆一层导电的低功函数材料薄层。该层最多为5nm，比较好的是介于0.5-2nm之间，更好的是0.5nm左右。该薄层一般(但不一定)是碱金属、碱土金属、镧系元素或者包含一种或多种所述碱金属、碱土金属或镧系元素的金属间化合物。低功函数薄层比较好的是覆盖一层典型厚度为100-500nm的另一厚导电层，它保证了其下面薄薄的低功函数层具有较高的电导率，并使该层的环境稳定，而且比较好的是采用真空蒸发或溅射淀积方法涂覆。
按照本发明的第二方面，提供了一种有机光发射器件，它包含排列在器件阴极与阳极之间的至少一层光发射有机材料，其中阴极包含作为高电导率直流磁控溅射金属层的第一导电材料层和位于至少一层有机材料与第一导电材料之间的低功函数第二导电材料层，第二导电材料层比第一导电材料层薄得多。
这种结构提供了与本发明第一方面所述类似的优点。
附图的简要说明
以下结合附图对本发明进行描述，其中：
图1示出了按照本发明的OLED的结构。
实施发明的较佳方式
按照本发明示出的实施例，首先通过在透明支承衬底上形成半透明阳极形成OLED。衬底例如是玻璃或塑料片，例如聚酯、聚碳酸酯、聚酰亚胺、聚醚亚胺等。参见图1，玻璃衬底1上覆盖一层半透明导电氧化铟锡(ITO)层2，一般是150nm厚，面电阻≤30欧姆/平方。虽然图1所示半透明阳极是氧化铟锡之类的导电氧化薄层，但是它也可以是掺杂的氧化锡或氧化锌。
在阳极/衬底上淀积的有机层比较好的(但不一定)是一层或多层场致发光共轭聚合物，例如参见已转让给剑桥显示技术有限公司的早期美国专利No.5,247,190。这种有机层的厚度一般在100nm量级。有机层也可以是小分子量化合物(例如参见美国专利No.4,539,507)或者共轭聚合物层与小分子量化合物层的组合。在图1中，ITO层上覆盖约100nm厚的场致发光聚(对-亚苯基亚乙烯基)PPV层3，例如参见美国专利No.5,247,190。
阴极为碱金属、碱土金属、镧系元素或者包含一种或多种所述碱金属、碱土金属或镧系元素的金属间化合物的薄层。阴极层最多为5nm，但是比较好的是介于0.5-2nm之间，材料可以采用Li、K、Sm、Ca或Al∶Li合金。在图1实例中，PPV层3比较好的是覆盖一层0.5nm厚的Li层4，该层通过真空升华商用Al∶Li合金淀积而成。
阴极薄层可以溅射淀积，比较好的是利用直流磁控溅射淀积或射频溅射淀积。阴极薄层也可以蒸发淀积，比较好的是电阻蒸发或者电子束热蒸发。
作为导电材料的阴极薄层包含元素金属、合金或金属间化合物，其功函数最大为3.7eV，并且比较好的是最大为3.2eV。
薄层上比较好的是覆盖例如厚度介于100-500nm之间铝或铝合金的导电层，并且比较好的是100nm左右。在图1中，薄层4上比较好的是不破坏真空地覆盖150nm厚通过真空蒸发方法淀积的铝层5。
厚导电层可以溅射淀积，比较好的是利用直流磁控溅射淀积或射频溅射淀积。厚导电层也可以蒸发淀积，比较好的是电阻蒸发或者电子束热蒸发。
厚导电层与薄导电层的厚度之比比较好的是20∶1。
层厚由标准石英晶体厚度监视仪结合挡板一起控制。
在另一种结构中，在衬底上形成图1所示的双层阴极，在阴极上至少形成一层光发射有机材料，并在至少一层光发射有机材料上形成阳极。
Li的薄层具有出色的电子注入效率和较低的开启和工作电压，虽然Li从层4扩散入PPV层3引起掺杂和PPV内场致发光的猝灭，但是一定厚度和数量的层4材料能够避免过量掺杂和场致发光猝灭。
在上面描述的器件结构及其制造方法中，OLED采用高效率低功函数电子注入阴极并最大限度抑制了有机层过量掺杂带来的不利影响，因此也最大限度地解决了器件结构短路和场致发光猝灭的问题。
Claims (14)
1.一种有机发光器件，其特征在于，它包含排列在器件阳极(2)与阴极(4，5)之间的至少一层有机发光材料(3)，其中，所述阴极包含作为高导电率不透明金属层的第一导电材料层(5)，和位于至少一层有机材料(3)与第一导电材料(5)之间的低功函数第二导电材料层(4)，所述第二导电材料层(4)比第一导电材料层(5)薄得多，厚度最大为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV。
2.如权利要求1所述的有机发光器件，其特征在于，所述第二导电材料层(4)的厚度介于0.5-2nm之间，最好约为0.5nm。
3.如权利要求1或2所述的有机发光器件，其特征在于，所述第二导电材料层(4)包含一种元素金属、合金或金属间化合物，其功函数最大为3.2eV。
4.如权利要求1或2所述的有机发光器件，其特征在于，所述第二导电材料层(4)包含一种碱金属、碱土金属或镧系元素或合金或它们的金属间化合物中的一种。
5.如权利要求4所述的有机发光器件，其特征在于，所述第二导电材料层(4)包含Ca、K、Li、Sm或Al-Li合金的其中一种。
6.如权利要求1或2所述的有机发光器件，其特征在于，所述第一导电材料层(5)与所述第二导电材料层(4)的厚度之比至少为20∶1。
7.一种有机发光器件的制造方法，其特征在于，它包含以下步骤：
在衬底上形成器件阴极，该步骤包含在衬底上形成高导电率的第一导电材料层，并在第一导电材料层上形成低功函数的第二导电材料层，其中，所述第一导电材料层为不透明金属层，而所述第二导电材料层比所述第一导电材料层薄得多，厚度最大为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV；
在所述阴极上形成至少一层有机发光材料；以及
在至少一层有机材料层上形成器件阳极。
8.一种有机发光器件的制造方法，其特征在于，它包含下述步骤：
在衬底(1)上形成器件的阳极(2)；
在所述阳极(2)上形成至少一层有机发光材料(3)；以及
在至少一层有机材料(3)上形成器件的阴极(4，5)，该步骤包含在至少一层有机材料(3)上形成低功函数的第二导电材料层(4)，并在所述第二导电材料层(4)上形成高导电率的第一导电材料层(5)，其中，所述第一导电材料层(5)为不透明金属层，而所述第二导电材料层(4)比所述第一导电材料层(5)薄得多，厚度最大为5nm，并包含元素金属、合金或金属间化合物，其功函数最大为3.7eV。
9.如权利要求7或8所述的有机发光器件的制造方法，其特征在于，所述第二导电材料层(4)的厚度介于0.5-2nm之间，最好是约0.5nm。
10.如权利要求7或8所述的有机发光器件的制造方法，其特征在于，所述第二导电材料层(4)包含一种元素金属、合金或金属间化合物，其功函数最大为3.2eV。
11.如权利要求7或8所述的有机发光器件的制造方法，其特征在于，所述第二导电材料层(4)包含一种碱金属、碱土金属或镧系元素或合金或它们的金属间化合物中的一种。
12.如权利要求11所述的有机发光器件的制造方法，其特征在于，所述第二导电材料层(4)包含Ca、K、Li、Sm或Al-Li合金的其中一种。
13.如权利要求7或8所述的有机发光器件的制造方法，其特征在于，所述第一导电材料层(5)与所述第二导电材料层(4)的厚度之比至少为20∶1。
14.如权利要求7或8所述的有机发光器件的制造方法，其特征在于，所述第一导电材料层(5)是通过直流磁控溅射淀积形成的。
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| EP (1) | EP0925709B1 (zh) |
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| CN (1) | CN1108730C (zh) |
| AT (1) | ATE247372T1 (zh) |
| DE (1) | DE69724129T2 (zh) |
| WO (1) | WO1998010621A1 (zh) |
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| WO1994003032A1 (en) | 1992-07-23 | 1994-02-03 | Idemitsu Kosan Co., Ltd. | Organic el device |
| GB9215929D0 (en) | 1992-07-27 | 1992-09-09 | Cambridge Display Tech Ltd | Electroluminescent devices |
| JP2848207B2 (ja) | 1993-09-17 | 1999-01-20 | 凸版印刷株式会社 | 有機薄膜ｅｌ素子 |
| JPH07150137A (ja) | 1993-11-30 | 1995-06-13 | Idemitsu Kosan Co Ltd | 有機電界発光素子 |
| US5723873A (en) | 1994-03-03 | 1998-03-03 | Yang; Yang | Bilayer composite electrodes for diodes |
| JP2701738B2 (ja) * | 1994-05-17 | 1998-01-21 | 日本電気株式会社 | 有機薄膜ｅｌ素子 |
| JPH08264278A (ja) | 1995-03-28 | 1996-10-11 | Japan Radio Co Ltd | 有機ｅｌ素子 |
| JPH0935871A (ja) | 1995-07-24 | 1997-02-07 | Sumitomo Chem Co Ltd | 有機エレクトロルミネッセンス素子 |
| US5776622A (en) | 1996-07-29 | 1998-07-07 | Eastman Kodak Company | Bilayer eletron-injeting electrode for use in an electroluminescent device |
-
1997
- 1997-09-04 DE DE69724129T patent/DE69724129T2/de not_active Expired - Lifetime
- 1997-09-04 AT AT97939034T patent/ATE247372T1/de not_active IP Right Cessation
- 1997-09-04 WO PCT/GB1997/002380 patent/WO1998010621A1/en active IP Right Grant
- 1997-09-04 US US09/254,294 patent/US6255774B1/en not_active Expired - Lifetime
- 1997-09-04 EP EP97939034A patent/EP0925709B1/en not_active Expired - Lifetime
- 1997-09-04 CN CN97197569A patent/CN1108730C/zh not_active Expired - Lifetime
- 1997-09-04 JP JP51235798A patent/JP3786969B2/ja not_active Expired - Lifetime
-
2005
- 2005-03-16 JP JP2005076054A patent/JP4213130B2/ja not_active Expired - Lifetime
-
2008
- 2008-03-05 JP JP2008054944A patent/JP4315996B2/ja not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101379885B (zh) * | 2006-02-03 | 2011-01-26 | Lg化学株式会社 | 有机发光器件的制备方法及由该方法制备的有机发光器件 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69724129T2 (de) | 2004-02-26 |
| US6255774B1 (en) | 2001-07-03 |
| EP0925709B1 (en) | 2003-08-13 |
| DE69724129D1 (de) | 2003-09-18 |
| EP0925709A1 (en) | 1999-06-30 |
| JP3786969B2 (ja) | 2006-06-21 |
| WO1998010621A1 (en) | 1998-03-12 |
| ATE247372T1 (de) | 2003-08-15 |
| JP4315996B2 (ja) | 2009-08-19 |
| JP4213130B2 (ja) | 2009-01-21 |
| CN1228911A (zh) | 1999-09-15 |
| JP2000517468A (ja) | 2000-12-26 |
| JP2005183406A (ja) | 2005-07-07 |
| JP2008135406A (ja) | 2008-06-12 |
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