CN100454603C - 一种有机电致发光器件 - Google Patents
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- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
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- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
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- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
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- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 53
- 238000005401 electroluminescence Methods 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 9
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
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- 230000027756 respiratory electron transport chain Effects 0.000 description 7
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 7
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Abstract
本发明涉及一种有机电致发光器件，提供了一种新的电子注入层材料组成方案，本发明的有机电致发光器件的电子注入层含有式为AxByOz的材料，其中A为碱金属或碱土金属的一种，B为VIII族金属的一种，0＜x≤2，0＜y≤3，0＜z≤6。A选自Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba的一种，B选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的一种。电子注入层可以由铝和AxByOz组成。此种电子注入层的电子注入能力良好，器件的起亮电压低、亮度高、效率高、寿命长。
Description
技术领域
本发明涉及一种有机电致发光器件，尤其涉及有机电致发光器件的电子注入层。
背景技术
在有机电致发光器件中，为降低器件工作电压，平衡电子和空穴的注入。电子的注入能力需要提高。
采用低功函数金属作为阴极可以有效提高电子的注入能力，但低功函数金属过于活泼，易与水氧反应。
提高电子注入能力的另一种方法是在阴极和有机层之间加一层无机化合物组成的电子注入层，实践证明LiF/Al是一种电子注入能力优良的阴极结构，被广泛的应用于OLED产品中。但卤素原子的存在会对发光产生猝灭。
发明内容
本发明的目的是提供一种电子注入能力优良的电子注入层材料。
本发明的技术方案是：一种有机电致发光器件，在阴极和有机层之间有一层电子注入层，其特征在于电子注入层含有式AxByOz的材料，其中A为碱金属或碱土金属的一种，B为VIII族金属的一种，0＜x≤2，0＜y≤3，0＜z≤6。
电子注入层的厚度优选为0.5-20nm。
碱金属或碱土金属可以选自Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba的一种。
第VIII的金属可以选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的一种。
电子注入层材料可以为LiNiO2。
电子注入层材料可以为LiCoO2。
电子注入层材料可以由铝和式为AxByOz的材料组成。
本发明的有益效果是：有机电致发光器件从阴极注入有机层的电子注入效率高，工作电压低、器件亮度和效率高、器件寿命长。
附图说明
图1为OLED的层结构。
图2为实施例1和对比例1的起亮电压对比图。
图3为实施例1和对比例1的亮度-电压对比图。
图4为实施例1和对比例1的效率-电流密度对比图。
图5为实施例1和对比例1的寿命对比图。
具体实施方式
本发明所述的电子注入层是介于阴极和有机层(例如发光层、电子传输层)之间的层。
如图1所示，现将构成图1OLED器件各层的组成和作用说明如下：
基片101用来支撑OLED器件的其它层。
当给器件通电时空穴从阳极102中发出。
空穴注入层103，具有提高将空穴从阳极注入有机层的效率的作用。
空穴传输层104，具有将空穴传输到发光层105的作用。
发光层105提供了电子和空穴复合的场所，复合后发光。
电子传输层106具有将电子传输到有机层的作用。
当给器件通电时电子从阴极108发出。
OLED器件的上述各层的功能、材料及其制备工艺是本领域普通技术人员所熟知的，在此不作赘述。
本发明提出的电子注入层式AxByOz的所代表的材料，0＜x≤2，0＜y≤3，0＜z≤6。
上述材料所构成的电子注入层可以蒸镀在发光层105或电子传输层106之上。其厚度优选为0.5-20nm，厚度若低于0.5nm，不容易形成电子注入层薄膜，厚度若高于20nm，又会降低电子注入效果，但应该理解的是在其它厚度下仍然是可用的。第VIII族元素是一类极为重要的过渡金属元素，其最外层s电子数和内层d电子数之和大于或等于8；由于这种电子排布的特殊性，导致第八族金属元素具备变价的特点，因此也使得第八副族金属元素同碱金属和碱土金属的复合氧化物具备较高的电子注入和导通能力。
本领域的普通技术人员应该理解的是：图1所示的OLED的层结构的实施方案是优选的，不采用空穴注入层103、空穴传输层104和电子传输层106也能够制造出器件。本发明的思想是阴极和有机层之间加一层式AxByOz的所代表的材料的组成的电子注入层。尽管结合优选实施例对本发明进行了说明，但本发明并不局限于上述实施例和附图，例如采用顶部出射的器件结构也是可以的，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。
实施例1：
ITO/CuPc(15nm)/NPB(60nm)/TADN(40nm)/Alq3(10nm)/LiCoO2(0.7nm)/Al(150nm)
(1)预刻有ITO的玻璃基板的清洗：利用热的洗涤剂超声和去离子水超声的方法对透明导电基片ITO玻璃进行清洗，清洗后将其放置在红外灯下烘干，然后对烘干的ITO玻璃进行紫外臭氧清洗和低能氧离子束轰击的预处理，其中导电基片上面的ITO膜作为器件的阳极层，ITO膜的方块电阻为50Ω，膜厚为150nm；
(2)有机发光层的制备：将上述清洗烘干并经过预处理的ITO玻璃置于真空腔内，抽真空至1×10-3Pa，蒸镀15nm的CuPc薄膜，蒸镀速率为0.05nm/s，然后在上述CuPc膜上蒸镀一层空穴传输材料NPB，材料薄膜的蒸镀速率为0.3nm/s，膜厚为60nm；在空穴传输层之上，蒸镀40nm厚的TADN做发光层，10nmAlq3做电子传输层。
(3)电子注入层的制备：
在电子传输层后蒸镀0.7nm厚的LiCoO2作为器件的电子注入层，该层蒸镀速率为0.04nm/s。
(4)阴极的制备：
在本发光器件中阴极由150nm厚的Al薄膜组成，Al层蒸镀速率为0.2nm/s。
(5)用玻璃封装片封装。
对比例1：
ITO/CuPc(15nm)/NPB(60nm)/TADN(40nm)/Alq3(10nm)/LiF(0.7nm)/Al(150nm)
制备步骤如同实施例1，只是在电子传输层后蒸镀0.7nm的LiF。
实施例2：
ITO/CuPc(15nm)/NPB(60nm)/Alq3(30nm)：C545T[1％]/Alq3(20nm)/LiNiO2(0.5nm)/Al(150nm)
制备过程参照实施例1。
对比例2：
ITO/CuPc(15nm)/NPB(60nm)/Alq3(30nm)：C545T[1％]/Alq3(20nm)/LiF(0.5nm)/Al(150nm)
制备过程参照实施例1。
实施例3：
ITO/CuPc(15nm)/NPB(60nm)/Alq3(40nm)/Al(20nm)：LiCoO2[10％]/Al(120nm)
Al(20nm)：LiCoO2[10％]的制备：
使用双源共蒸的方法，制备厚度为20nm的Al、LiCoO2混合电子注入层，该层蒸镀速率为0.1nm/s，LiCoO2掺杂浓度控制为10％。
其它制备步骤参照实施例1。
从图2可以看到对比例1的LiF器件和实施例1的LiCoO2器件在亮度为1cd/m2时电压分别为3.67v和3.55v。
从图3可以看到在相同电压下，实施例1的LiCoO2器件的亮度高于对比例1的LiF器件的亮度。
从图4可以看到实施例1的LiCoO2器件的效率高于对比例1的LiF器件的亮度。
从图5可以看到实施例1的LiCoO2器件的寿命高于对比例1的LiF器件的亮度。
| 器件 | 发光波长 | 效率(5mA/cm<sup>2</sup>) | 寿命(1000nit) |
| 实施例2 | 520nm | 11.5cd/A | 4500小时 |
| 实施例3 | 520nm | 12.1cd/A | 5000小时 |
| 对比例2 | 520nm | 11.5cd/A | 4000小时 |
从上表中可知，看到实施例3的LiCoO2：Al器件的效率、寿命优于实施例2LiNiO2器件的效率、寿命，而实施例2的LiNiO2器件的效率、寿命优于对比例2LiF器件的效率、寿命。
Claims (8)
1、一种有机电致发光器件，在阴极和有机层之间有一层电子注入层，其特征在于电子注入层由铝和式为AxByOz的材料组成，其中A为碱金属或碱土金属的一种，B为VIII族金属的一种，0＜x≤2，0＜y≤3，0＜z≤6。
2、如权利要求1所述的有机电致发光器件，其特征在于所述的电子注入层的厚度为0.5-20nm。
3、如权利要求1所述的有机电致发光器件，其特征在于所述的A选自Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba的一种。
4、如权利要求1所述的有机电致发光器件，其特征在于所述的B选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的一种。
5、如权利要求1所述的有机电致发光器件，其特征在于所述的AxByOz为：LiNiO2。
6、如权利要求1所述的有机电致发光器件，其特征在于所述的AxByOz为LiCoO2。
7、一种有机电致发光器件，在阴极和有机层之间有一层电子注入层，其特征在于电子注入层含有LiNiO2。
8、如权利要求7所述的有机电致发光器件，其特征在于所述的电子注入层的厚度为0.5-20nm。
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| CN102324463B (zh) * | 2011-09-09 | 2013-07-10 | 昆山维信诺显示技术有限公司 | 有机电致发光器件的制备方法 |
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| CN105895817B (zh) * | 2016-04-11 | 2017-09-01 | 郑州大学 | 以Ni(Mg)O作为空穴提供层的钙钛矿绿光LED及制备方法 |
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| CN1261249A (zh) * | 1999-01-21 | 2000-07-26 | Tdk株式会社 | 有机的场致发光器件 |
| US6635365B2 (en) * | 1999-02-15 | 2003-10-21 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent device and method of manufacture thereof |
| CN1505449A (zh) * | 2002-10-28 | 2004-06-16 | �����ձ������ƶ���ʾ��ʽ���� | 有机电致发光器件 |
| CN1725915A (zh) * | 2004-11-23 | 2006-01-25 | 友达光电股份有限公司 | 有机光电组件、用于其的电极结构及提高其操作效率方法 |
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| JP4474721B2 (ja) * | 2000-03-15 | 2010-06-09 | ソニー株式会社 | 有機又は無機発光素子 |
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| CN1261249A (zh) * | 1999-01-21 | 2000-07-26 | Tdk株式会社 | 有机的场致发光器件 |
| US6635365B2 (en) * | 1999-02-15 | 2003-10-21 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent device and method of manufacture thereof |
| CN1505449A (zh) * | 2002-10-28 | 2004-06-16 | �����ձ������ƶ���ʾ��ʽ���� | 有机电致发光器件 |
| CN1725915A (zh) * | 2004-11-23 | 2006-01-25 | 友达光电股份有限公司 | 有机光电组件、用于其的电极结构及提高其操作效率方法 |
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