CN1329654A - 电致发光材料 - Google Patents
电致发光材料 Download PDFInfo
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- H—ELECTRICITY
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Abstract
Tb(TMHD)3OPNP为一种在施加高于12伏特电压下发射白光的电致发光材料,其中TMHD为2,2,6,6-四甲基-3,5-庚二酮根,OPNP为二苯基膦酰亚胺三苯基正膦。
Description
本发明涉及电致发光材料和包含其的器件。
在电流通过其时能够发光的材料是熟知的,且广泛用于各种显示应用。已广泛使用液晶器件和基于无机半导体体系的各种器件,但它们的缺点在于能耗高、生产成本高、量子效率低且不能制造平板显示器、反射比问题,即在明亮条件下的低可见度和窄视角(例如+/-45°)。
已经提出将有机聚合物用于电致发光器件,但不可能得到纯色,它们制造昂贵且效率较低。
已经提出的另一种化合物是喹啉酚铝(aluminiumquino1ate),但这需要使用掺杂剂以得到各种颜色,且效率较低。
在《化学通报》(657-660页,1990)的一篇论文中,Kido等人公开,乙酰丙酮合铽III配合物是绿色电致发光的,另外在《应用物理通报》65(17)(1994年10月24日)的一篇论文中,Kido等人公开,铕III三亚苯基二胺配合物是红色电致发光的,但它们在大气条件下不稳定且难以制膜。
这些论文中公开的配合物光致发光效率低,且仅能够产生绿色或红色光,而不能产生其它颜色。
通过电致发光产生白光难以实现,并且需要使用混合的或在顺序层中的多种不同电致发光材料。另一改变发射光颜色的方法是使用与电致发光材料混合的或在顺序层中的一种或多种荧光染料。
在《应用表面科学》113/114(698-704页,1997)的一篇论文中,Takeo Wakimoto等人公开了电致发光板,其中为改变发射光的颜色将喹啉酚铝用作发射体,将该喹啉酚铝通过喹吖啶衍生物(其为荧光染料)掺杂。
我们现在已发现了一些电致发光化合物,这些化合物发射的光可通过施加电压而改变,并且这些化合物可发射白光。
根据本发明,提供一种其中电致发光化合物为Tb(TMHD)3OPNP的电致发光器件。
其中TMHD为2,2,6,6-四甲基-3,5-庚二酮根,OPNP为二苯基膦酰亚胺三苯基正膦。
光的颜色是主观的,颜色可通过二维图上的纵坐标定义,其中颜色为图上的区域,在本发明中,当观察到白光时,将白光定义为比色图CIE I931中的一个区域。
可将电致发光化合物与可改变发射光颜色的其它过渡金属、镧系或锕系有机配合物混合。
电致发光器件包括用作阳极的导电基材、电致发光材料层和与电致发光层连接的用作阴极的金属接触点。当电流通过电致发光层时,该层发射光。
本发明的电致发光器件优选包括一种透明基材,它是一种用作阳极的导电玻璃或塑料,优选的基材是导电玻璃,如氧化锡铟涂覆的玻璃,但可以使用任何导电的或具有导电层的玻璃。导电聚合物和导电聚合物涂布的玻璃或塑料也可用作基材。Tb(TMHD)3OPNP可从有机溶剂的溶液中通过蒸发直接沉积到基材上。使用的溶剂可为例如醇如乙醇、酮如丙酮和乙酰丙酮酸甲酯及氯代烃如二氯甲烷。
此外,该材料可从固态通过旋涂或通过真空沉积例如通过溅射沉积,或可使用任何其它常规方法。
Tb(TMHD)3OPNP膜优选通过如下方法制备:将Tb(TMHD)3与OPNP混合,将形成的混合物在真空下加热,这样使混合物蒸发并使蒸气凝结于基材上由此在基材上形成有机金属配合物薄膜或层。此外,可将Tb(TMHD)3和OPNP顺序沉积到基材上。
在本发明的一个实施方案中,有一层沉积在透明基材上的空穴传导层,且Tb(TMHD)3OPNP就沉积在该空穴传导层上。该空穴传导层可用于传导空穴和阻塞电子,这样可防止电子移动到电极中而没有与空穴复合。因此,载流子的复合主要发生在发射体层。
空穴传导层被用于聚合物电致发光器件中,且可使用任何已知的膜形式的空穴传导材料。
空穴传导层可由芳族胺配合物,如聚(乙烯基咔唑)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-二苯基-4,4’-二胺(TPD)、聚苯胺等的膜制成。
可非必要地包括发荧光的激光染料、发光激光染料以改进发射光的色谱并增强光致发光和电致发光效果。
在一个实施方案中,将Tb(TMHD)3OPNP与聚合物材料如聚烯烃(例如聚乙烯、聚丙烯等),优选聚苯乙烯混合。活性材料在混合物中的优选量为95至5wt%,更优选25至20wt%。
空穴传导材料可非必要地与Tb(TMHD)3OPNP进行混合,Tb(TMHD)3OPNP与空穴传导化合物的重量比率各自为5-95%和95-5%。
在本发明的另一实施方案中,在阴极和Tb(TMHD)3OPNP层之间有一层电子传导材料,该电子传导材料优选为一种金属配合物,如喹啉酚的金属盐(如,喹啉酚铝),它能够在电流通过其时传导电子。另外,该电子传导材料可与Tb(TMHD)3OPNP混合,然后与其共沉积。
在一个优选结构中,其基材由作为阳极的透明导电材料组成,在该基材上相继沉积有空穴传导层、Tb(TMHD)3OPNP层和连接到阳极上的电子传导层。该阳极可以是任何功函数低的金属,如铝、钙、锂、银/镁合金等,铝是优选的金属。
在低电压(例如低于10伏特)下,发射的光主要为黄绿色,相当于铽III配合物发射光的典型颜色。随着电压升高,发出的光变为接近白色,在超过12伏特时,肉眼看上去为白色。
发出的光的波长可以变化,原因在于配体导致辐射强度增强,该配体随电压升高发射更短波长的光,这样总体效果为来自配合物中各部分和与空穴传导层相互作用的组合。
非常令人吃惊的是,此效果可产生白光。
实施例1
薄膜Tb(TMHD)3OPNP
(i)将50mg Tb(TMHD)3(7×10-5mol)和33.68mg OPNP(7.05×10-5mol)在研钵中用研棒一起研磨,并将一部分(3mg)放在Edwards(E306)真空涂布器中的钼舟上。将该真空涂布器抽真空至10-7torr,并将该样品用电加热器在10至90A和10V下加热至多20秒,得到Tb(TMHD)3OPNP薄膜。
(ii)加工基于Tb(TMHD)3OPNP的电致发光器件
将(i)中制备的3mg Tb(TMHD)3OPNP混合物蒸发到布图的ITO电极上,得到50nm厚的薄膜。该布图的ITO已预先涂布由TPD构成的20nm空穴传导层。然后将喹啉酚铝(Alq3)蒸发到该层上,得到20nm厚的薄膜作为电子传导层。设置一铝顶部接触点(900nm)以形成附图1的结构。
将测量的电压通过该器件并测量发射光的波长。结果在图2a、2b和2c中给出。可以看出,随着电压升高,在除峰外的波长处光强度因Tb而升高,这导致发射光在2c光谱中变白,在比色图CIE I931中图2c发射的光的颜色坐标为x:0.22,y:0.25,其为白光。
Claims (16)
1.一种其中电致发光化合物为Tb(TMHD)3OPNP的电致发光器件,其中TMHD为2,2,6,6-四甲基-3,5-庚二酮根,OPNP为二苯基膦酰亚胺三苯基正膦。
2.如权利要求1的电致发光器件,包括用作阳极的导电基材、Tb(TMHD)3OPNP层和与电致发光层连接的用作阴极的金属接触点。
3.如权利要求2的电致发光器件,其中将Tb(TMHD)3OPNP从有机溶剂的溶液中通过蒸发直接沉积到基材上。
4.如权利要求2的电致发光器件,其中将Tb(TMHD)3OPNP通过旋涂或通过真空沉积从固态沉积到基材上。
5.如权利要求1至4任何一项的电致发光器件,其中Tb(TMHD)3OPNP薄膜通过如下方法制备:将Tb(TMHD)3与OPNP混合,将形成的混合物在真空下加热,这样使混合物蒸发并使蒸气凝结于基材上由此在基材上形成Tb(TMHD)3OPNP薄膜或层。
6.如权利要求1至4任何一项的电致发光器件,其中Tb(TMHD)3OPNP薄膜通过将Tb(TMHD)3和OPNP顺序沉积到基材上制备。
7.如权利要求1至6任何一项的电致发光器件,其中,有一层沉积在透明基材上的空穴传导层,且Tb(TMHD)3OPNP就沉积在该空穴传导层上。
8.如权利要求7的电致发光器件,其中空穴传导层由聚(乙烯基咔唑)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-二苯基-4,4’-二胺(TPD)或聚苯胺的膜制成。
9.如权利要求7或8的电致发光器件,其中将空穴传导材料与Tb(TMHD)3OPNP进行混合,Tb(TMHD)3OPNP与空穴传导化合物的重量比率各为5-95%和95-5%。
10.如权利要求1至9任何一项的电致发光器件,其中加入染料以改善发射光的色谱并提高光致发光和电致发光效率。
11.如权利要求1至10任何一项的电致发光器件,其中将Tb(TMHD)3OPNP与聚烯烃混合,Tb(TMHD)3OPNP在混合物中的量为95至5wt%。
12.如权利要求1至11任何一项的电致发光器件,其中在阴极和Tb(TMHD)3OPNP层之间有一层电子传导材料。
13.如权利要求1至11任何一项的电致发光器件,其中将电子传导材料与Tb(TMHD)3OPNP混合,然后与其共沉积。
14.如权利要求12的电致发光器件,其中电子传导材料为喹啉酚铝。
15.如权利要求12的电致发光器件,包括由作为阳极的透明导电材料组成的基材,在该基材上相继沉积有空穴传导层、Tb(TMHD)3OPNP层和连接到阳极上的电子传导层。
16.一种从电致发光器件发射白光的方法,其中器件为前述权利要求任何一项所述的,施加于该器件的电压为12伏特以上。
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GB9826407.0 | 1998-12-02 | ||
GBGB9826407.0A GB9826407D0 (en) | 1998-12-02 | 1998-12-02 | Novel electroluminescent materials |
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US (1) | US6565995B1 (zh) |
EP (1) | EP1171544B1 (zh) |
JP (1) | JP2002531630A (zh) |
KR (1) | KR20010080630A (zh) |
CN (1) | CN1329654A (zh) |
AT (1) | ATE250657T1 (zh) |
AU (1) | AU758754B2 (zh) |
BR (1) | BR9916921A (zh) |
CA (1) | CA2352883A1 (zh) |
DE (1) | DE69911658T2 (zh) |
DK (1) | DK1171544T3 (zh) |
ES (1) | ES2203255T3 (zh) |
GB (1) | GB9826407D0 (zh) |
HK (1) | HK1040527B (zh) |
ID (1) | ID30167A (zh) |
MX (1) | MXPA01005539A (zh) |
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JPH06145146A (ja) | 1992-11-06 | 1994-05-24 | Chisso Corp | オキシネイト誘導体 |
US5707745A (en) | 1994-12-13 | 1998-01-13 | The Trustees Of Princeton University | Multicolor organic light emitting devices |
ATE182355T1 (de) | 1995-05-25 | 1999-08-15 | Amersham Int Plc | Fluoreszente verbindungen |
DE19627070A1 (de) | 1996-07-05 | 1998-01-08 | Bayer Ag | Elektrolumineszierende Anordnungen unter Verwendung von Blendsystemen |
US5755999A (en) | 1997-05-16 | 1998-05-26 | Eastman Kodak Company | Blue luminescent materials for organic electroluminescent devices |
GB9711237D0 (en) | 1997-06-02 | 1997-07-23 | Isis Innovation | Organomettallic Complexes |
GB9712483D0 (en) * | 1997-06-17 | 1997-08-20 | Kathirgamanathan Poopathy | Fabrication of light emitting devices from chelates of transition metals, lanthanides and actinides |
GB9826406D0 (en) | 1998-12-02 | 1999-01-27 | South Bank Univ Entpr Ltd | Quinolates |
JP4514841B2 (ja) | 1998-02-17 | 2010-07-28 | 淳二 城戸 | 有機エレクトロルミネッセント素子 |
GB9823761D0 (en) | 1998-11-02 | 1998-12-23 | South Bank Univ Entpr Ltd | Novel electroluminescent materials |
GB9826405D0 (en) | 1998-12-02 | 1999-01-27 | South Bank Univ Entpr Ltd | Method for forming films or layers |
GB9901971D0 (en) | 1999-02-01 | 1999-03-17 | South Bank Univ Entpr Ltd | Electroluminescent material |
-
1998
- 1998-12-02 GB GBGB9826407.0A patent/GB9826407D0/en not_active Ceased
-
1999
- 1999-12-01 KR KR1020017006744A patent/KR20010080630A/ko active IP Right Grant
- 1999-12-01 EP EP99973058A patent/EP1171544B1/en not_active Expired - Lifetime
- 1999-12-01 DE DE69911658T patent/DE69911658T2/de not_active Expired - Lifetime
- 1999-12-01 BR BR9916921-5A patent/BR9916921A/pt not_active Application Discontinuation
- 1999-12-01 DK DK99973058T patent/DK1171544T3/da active
- 1999-12-01 CN CN99813983A patent/CN1329654A/zh active Pending
- 1999-12-01 AU AU14008/00A patent/AU758754B2/en not_active Ceased
- 1999-12-01 ES ES99973058T patent/ES2203255T3/es not_active Expired - Lifetime
- 1999-12-01 JP JP2000585349A patent/JP2002531630A/ja active Pending
- 1999-12-01 ID IDW00200101441A patent/ID30167A/id unknown
- 1999-12-01 AT AT99973058T patent/ATE250657T1/de not_active IP Right Cessation
- 1999-12-01 MX MXPA01005539A patent/MXPA01005539A/es not_active Application Discontinuation
- 1999-12-01 PT PT99973058T patent/PT1171544E/pt unknown
- 1999-12-01 US US09/857,286 patent/US6565995B1/en not_active Expired - Fee Related
- 1999-12-01 WO PCT/GB1999/004028 patent/WO2000032718A1/en active IP Right Grant
- 1999-12-01 CA CA002352883A patent/CA2352883A1/en not_active Abandoned
-
2002
- 2002-03-15 HK HK02102039.7A patent/HK1040527B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
US6565995B1 (en) | 2003-05-20 |
EP1171544A1 (en) | 2002-01-16 |
EP1171544B1 (en) | 2003-09-24 |
DE69911658T2 (de) | 2004-04-29 |
WO2000032718A1 (en) | 2000-06-08 |
ATE250657T1 (de) | 2003-10-15 |
MXPA01005539A (es) | 2003-07-14 |
HK1040527A1 (en) | 2002-06-14 |
ES2203255T3 (es) | 2004-04-01 |
KR20010080630A (ko) | 2001-08-22 |
GB9826407D0 (en) | 1999-01-27 |
DK1171544T3 (da) | 2004-01-26 |
PT1171544E (pt) | 2004-02-27 |
AU758754B2 (en) | 2003-03-27 |
BR9916921A (pt) | 2001-11-06 |
HK1040527B (zh) | 2004-03-05 |
AU1400800A (en) | 2000-06-19 |
CA2352883A1 (en) | 2000-06-08 |
JP2002531630A (ja) | 2002-09-24 |
ID30167A (id) | 2001-11-08 |
DE69911658D1 (de) | 2003-10-30 |
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