CN114824146B - 有机电致发光器件、显示器装置、光源装置及电子产品 - Google Patents
有机电致发光器件、显示器装置、光源装置及电子产品 Download PDFInfo
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- CN114824146B CN114824146B CN202210714380.XA CN202210714380A CN114824146B CN 114824146 B CN114824146 B CN 114824146B CN 202210714380 A CN202210714380 A CN 202210714380A CN 114824146 B CN114824146 B CN 114824146B
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- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 abstract description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000010410 layer Substances 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 39
- 238000012360 testing method Methods 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 21
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 15
- 239000012043 crude product Substances 0.000 description 15
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- 239000002904 solvent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
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- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 8
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- 239000000203 mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 125000005562 phenanthrylene group Chemical group 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000005551 pyridylene group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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- C07D277/62—Benzothiazoles
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Abstract
本发明提供了一种有机电致发光器件、显示器装置、光源装置及电子产品。本发明的有机电致发光器件包括:第一电极,第二电极,至少一层有机膜,其设置在所述第一电极与第二电极之间;及所述有机膜包括电子传输层,所述电子传输层材料包括含有苯并咪唑结构单元的材料;至少一层有机覆盖层,在所述第二电极之上;所述有机覆盖层材料包括含有苯并噁唑和/或苯并噻唑结构单元的材料。本发明的有机电致发光器件通过电子传输层材料与有机覆盖层材料的相互配合,有利于提高光取出效果,减少光损失,使得可以提高顶发射有机光电装置的发光效率。
Description
技术领域
本发明属于有机电致发光技术领域,涉及一种有机电致发光器件、显示器装置、光源装置及电子产品。
背景技术
有机电激发光二极管(Organic Light-Emitting Diode,简称为OLED)。该发光器件具有薄型且能在低驱动电压下高亮度发光以及能通过选择发光材料而进行多色发光的特征,因此倍受关注。
该研究自从由柯达公司的C.W.Tang等揭示有机薄膜元件能以高亮度发光以来,大量OLED 行业研究人员对于其应用,做了很多研究和推进。有机薄膜发光器件被广泛应用在各种主显示屏等中,其实用化取得长足的进展。但是,现今还存在很多技术课题,其中,发光的高效利用及减少发光损耗是一个很大的课题。
根据OLED的出光方式,可以分为底发射有机发光器件和顶发射有机发光器件。最初的OLED都是底发射型器件,器件的结构从上至下依次是:不透明的金属阴极/有机功能层/透明阳极,光线从阳极出射, 因而称为底发射。顶发射OLED是指光从器件顶部射出的OLED。其中,顶发射OLED由于不受基板是否透光的影响,可有效提高显示面板的开口率,拓展了基板上TFT电路的设计,丰富了电极材料的选择,有利于器件与TFT电路的集成。如果器件是以底发射形式出光,光经过基板的时候就会被基板上的TF和金属配线阻挡,这样就会影响实际的发光面积。如果光线是从器件上方出射,采用顶发射器件结构,那么基板的线路设计就不会影响器件的出光面积,相同亮度下OLED的工作电压更低,可以获得更长的使用寿命。因此,顶发射器件是小像素、高PPI的小屏如手机等主动显示的首选。
一直采用高折CPL材料改善器件性能,只能一定程度提高光取出效果,但是并不能改善器件内部的光的取出,这是由于器件中EML层发出的光会向阴极和阳极两个方向发射,阳极发射方向的光容易发生损耗。因此,在本领域,寻找能够进一步提高器件发光效率的材料和方法非常有必要。
发明内容
本发明提供了一种有机电致发光器件、显示器装置、光源装置及电子产品。本发明的有机电致发光器件通过电子传输层材料与有机覆盖层材料的相互配合,有利于提高光取出效果,减少光损失,使得可以提高顶发射有机光电装置的发光效率。
为了实现本发明的目的,本发明的技术方案如下:
本发明提供了一种有机电致发光器件,其包括:
第一电极,
第二电极,
至少一层有机膜,其设置在所述第一电极与第二电极之间;及
所述有机膜包括电子传输层,所述电子传输层材料包括含有苯并咪唑结构单元的材料;
至少一层有机覆盖层,在所述第二电极之上;
所述有机覆盖层材料包括含有苯并噁唑和/或苯并噻唑结构单元的材料。
优选地,
在460nm波长下,所述有机覆盖层材料的折射率n值大于等于2.10且所述电子传输层材料的折射率n值小于等于1.90;
在530nm波长下,所述有机覆盖层材料的折射率n值大于等于1.95且所述电子传输层材料的折射率n值小于等于1.85;
在620nm波长下,所述有机覆盖层材料的折射率n值大于等于1.85且所述电子传输层材料的折射率n值小于等于1.82。
优选地,所述有机覆盖层材料的结构如下式I所示:
式I
其中,X选自O原子、S原子或NR1;
L1-L3各自独立地选自取代或未取代的C6-C30芳基、或取代或未取代的C5-C30的杂芳基;Ar1 和Ar2各自独立地选自取代或未取代的C6-C30芳基、或取代或未取代的C5-C30的杂芳基;
R1选自取代或未取代的C6-C30芳基、或取代或未取代的C5-C30的杂芳基。
更优选地,所述L1-L3各自独立地选自亚苯基、亚萘基、亚菲基、亚联苯基或者亚吡啶基。
更优选地,所述取代或未取代的C6-C30芳基、取代或未取代的C5-C30的杂芳基含有取代基时,所述取代基选自氘、卤素、氰基、未取代或卤代的C1~C15直链或支链烷基、未取代或卤代的C1~C15烷氧基、C1~C15烷硫基、C6~C24芳基、C2~C24杂芳基、或C6~C18芳胺基。
更优选地,所述有机覆盖层材料选自如下结构中的一者或多者:
优选地,所述电子传输层材料的结构如下式II或式III所示:
其中,L4-L5各自独立地选自取代或未取代的C6-C30芳基、取代或未取代的C5-C30的杂芳基;Ar3独立地选自取代或未取代的C6-C30芳基、取代或未取代的C5-C30的杂芳基;
R2和R3各自选自未取代或卤代的C1~C15直链或支链烷基、取代或未取代的C6-C30芳基、取代或未取代的C5-C30的杂芳基。
更优选地,L4-L5各自独立地选自亚苯基、亚萘基、亚菲基、亚联苯基、亚蒽基、亚䓛基、亚吡啶基、亚喹啉基或亚异喹啉基。
更优选地,所述取代或未取代的C6-C30芳基、取代或未取代的C5-C30的杂芳基含有取代基时,所述取代基选自氘、卤素、氰基、
未取代或卤代的C1~C15直链或支链烷基、未取代或卤代的C1~C15烷氧基、C1~C15烷硫基、C6~C24芳基、C2~C24杂芳基或C6~C18芳胺基。
优选地,所述电子传输层材料选自如下结构中的一者或多者:
优选地,所述有机膜还包括发光层、空穴注入层、空穴传输层、电子阻挡层、空穴阻挡层或电子注入层中的至少一种。
本发明又提供了一种显示器装置,包括上述有机电致发光器件。
本发明又提供了一种光源装置,包括上述有机电致发光器件。
本发明进一步提供了一种电子产品,包括上述显示器装置。
具体实施方式
本发明的目的是提供一种有机电致发光器件,其包括:
第一电极,
第二电极,及
至少一层有机膜,其设置在所述第一电极与第二电极之间;
所述有机膜包括电子传输层,所述电子传输层材料包括含有苯并咪唑结构单元的材料;
至少一层有机膜,在所述第二电极之上;
所述有机膜包括有机覆盖层,所述有机覆盖层材料包括含有苯并噁唑和/或苯并噻唑结构单元的材料。
所述有机覆盖层材料的放气流量(out gassing)小于等于80ml/s。
实施例:
实施例1
(1)将P1(6 mmol)、P2(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物A-8-1。
测试目标产物A-8-1的结构:通过液相色谱-质谱联用分 析得到LC-MS (m/z)(Μ+):理论值为210.08,测试值为210.31。
(2) 向反应瓶中加入A-8-1 (10 mmol)、P3(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应;温到30-40℃加入水200ml,分层;洗两次后,浓缩甲苯后加入正庚烷100ml,打浆;到目标产物A-8。
测试目标产物A-8的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为714.27,测试值为714.65。
应用实施例2
(1)将P4(6 mmol)、P2(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物A-14-1。
测试目标产物A-14-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为226.06,测试值为226.28。
(2) 向反应瓶中加入A-14-1 (10 mmol)、P5(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物A-14。
测试目标产物A-14的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为730.24,测试值为730.78。
应用实施例3
(1) 将P1(6 mmol)、P2(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物A-20-1。
测试目标产物A-20-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为210.08,测试值为210.31。
(2) 将A-20-1 (6 mmol)、P6(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物A-20-2。
测试目标产物A-20-2的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为412.16,测试值为412.43。
(3) 向反应瓶中加入A-20-2(10 mmol)、P7(12 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物A-20。
测试目标产物A-20的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为714.27,测试值为714.85。
应用实施例4
(1)将P8(8 mmol)、P9(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物B-6-1。
测试目标产物B-6-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为269.12,测试值为269.34。
(2) 向反应瓶中加入B-6-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物B-6。
测试目标产物B-6的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为655.23,测试值为655.67。
应用实施例5
(1)将P11(6 mmol)、P12(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物B-8-1。
测试目标产物B-8-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为319.14,测试值为319.40。
(2) 向反应瓶中加入B-8-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物B-8。
测试目标产物B-8的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为705.24,测试值为705.80。
应用实施例6
(1)将P8(8 mmol)、P13(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物B-9-1。
测试目标产物B-9-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为319.14,测试值为319.40。
(2) 向反应瓶中加入B-9-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物B-9。
测试目标产物B-9的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为705.24,测试值为705.80。
应用实施例7
(1)将P14(8 mmol)、P9(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物B-28-1。
测试目标产物B-28-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为275.08,测试值为275.37。
(2) 向反应瓶中加入B-28-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物B-28。
测试目标产物B-28的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为661.18,测试值为661.67。
应用实施例8
(1)将P15(6 mmol)、P2(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物C-5-1。
测试目标产物C-5-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为332.13,测试值为332.40。
(2) 向反应瓶中加入C-5-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物C-5。
测试目标产物C-5的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为718.24,测试值为718.80。
应用实施例9
(1)将P1(6 mmol)、P2(8 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物C-7-1。
测试目标产物C-7-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为210.08,测试值为210.31。
(2) 向反应瓶中加入C-7-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物C-7。
测试目标产物C-7的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为596.18,测试值为596.63。
应用实施例10
(1)将P12(8 mmol)、P16(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物D-4-1。
测试目标产物D-4-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为220.10,测试值为220.27。
(2) 向反应瓶中加入D-4-1 (10 mmol)、P10(25 mmol)、叔丁醇钠 (10 mmol)、甲苯200ml,氮气置换后,加入pd2(dba)3(0.05mmol)、Sphos(0.05mmol),升温至100-120℃,回流反应6小时,停止反应。降温到30-40℃加入水200ml,分层。水洗两次后,浓缩甲苯后加入正庚烷100ml,打浆。得到目标产物D-4。
测试目标产物D-4的结构:通过液相色谱-质谱联用分析得到ESI-MS (m/z)(Μ+):理论值为606.21,测试值为606.67。
应用实施例11
(1)将P17(8 mmol)、P18(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物E-10-1。
测试目标产物E-10-1的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为600.12,测试值为600.78。
(2)将E-10-1 (8 mmol)、P19(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物E-10。
测试目标产物E-10的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为648.26,测试值为648.79。
应用实施例12
(1)将P20(8 mmol)、P21(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物F-3。
测试目标产物F-3的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为550.24,测试值为550.69。
应用实施例13
(1)将P22(8 mmol)、P21(6 mmol)、Pd(dppf)Cl2 (0.05mmol) 、K2CO3 (9 mmol)加入二氧六环:水(4:1)10mL溶液中混合,放入50mL的烧瓶中,回流反应24小时。冷却至室温,然后向溶液中缓慢加入饱和MgSO4水溶液和乙酸乙酯萃取三次,然后将有机层通过旋转蒸发仪去除溶剂,通过柱层析,得到粗产物F-5。
测试目标产物F-5的结构:通过液相色谱-质谱联用分析得到LC-MS (m/z)(Μ+):理论值为600.26,测试值为600.75。
性能测试一材料折射率表征:
通过椭偏仪测试化合物P1-P12在460nm、528nm和620nm波长处的折射率。如表1所示:
表1
通过表1可看出,相比于对比化合物1,本发明的有机覆盖层材料化合物A-8、A-14、A-20、B-6、B-8、B-9、B-28、C-5、C-7和D4在460nm/530nm/620nm处具有更高的折射率,更高折射率的有机覆盖层对器件出光效率是有利的;相比于对比化合物2,本发明的电子传输层材料化合物E-10、F-3和F-5在460nm/530nm/620nm处具有更低的折射率,更低折射率的电子传输层材料对器件发光效率是有利的。
以下列举几种本发明所述有机化合物应用于OLED器件中的应用例:
上述OLED器件的具体制备步骤如下:
应用例1
首先用超声波清洗仪,使用异丙醇洗涤无碱玻璃基板15分钟,然后在空气中进行30分钟UV臭氧洗涤处理。处理好的基板利用真空蒸镀法,首先蒸镀ITO/Ag/ITO 100nm作为阳极,然后在阳极上蒸镀空穴注入层(HATCN,50nm),空穴传输层(NPB,30nm),蓝色发光层(主体ADN和掺杂BD(重量比95∶5,30nm),电子传输层(化合物F-3: Liq=1:1,30nm),电子注入层(LiF,0.5nm)依次层叠蒸镀后,共蒸镀Mg和Ag(重量比10∶1,15nm)作成半透明阴极。然后蒸镀化合物A-8(65nm)作为有机覆盖层。最后在氮气氛围下利用环氧树脂粘合剂封装发光器件。
对比化合物1和对比化合物2结构如下:
应用例2-10,与应用例1的区别是仅在于:将有机覆盖层化合物A-8替换为化合物A-14、A-20、B-6、B-8、B-9、B-28、C-5、C-7和D4,其他制备步骤均相同。
应用例11-20,与应用例1的区别是仅在于:将电子传输层化合物F-3都替换为化合物F-5,将有机覆盖层化合物A-8替换为化合物A-14、A-20、B-6、B-8、B-9、B-28、C-5、C-7和D4,其他制备步骤均相同。
应用例21-22,与应用例1的区别是仅在于:将电子传输层化合物F-3替换为化合物E-10,将有机覆盖层化合物A-8替换为化合物B-8和C-7,其他制备步骤均相同。
对比例1,与应用例1的区别是仅在于:将电子传输层化合物F-3都替换为对比化合物2,将有机覆盖层化合物A-8替换为化合物C-7,其他制备步骤均相同。
对比例2,与应用例1的区别是仅在于:将电子传输层化合物F-3都替换为化合物F-5,将有机覆盖层化合物A-8替换为对比化合物1,其他制备步骤均相同。
对比例3,与应用例1的区别是仅在于:将电子传输层化合物F-3都替换为对比化合物2,将有机覆盖层化合物A-8替换为对比化合物1,其他制备步骤均相同。
OLED器件的性能评价:
用Keithley 2365Α数字纳伏表测试OLED器件在不同电压下的电流,然后用电流除以发光面积得到OLED器件在不同电压下的电流密度;用Konicaminolta CS-2000分光辐射亮度计测试OLED器件在不同电压下的亮度和辐射能流密度;根据OLED器件在不同电压下的电流密度和亮度,得到在相同电流密度下(10mA/cm2)的工作电压Volt和电流效率(cd/A),BI=E/CIEy是指蓝光中的Blue Index,也是衡量蓝光发光效率的参数,E指电流效率,CIEy指根据器件发光半峰宽波长带入CIE1930软件中得到的纵坐标色点。测试数据如表2所示。
表2
从表2测试数据可以看出,由于电子传输层材料更大程度的影响器件电压,高折射率的有机覆盖层材料和低折射率的电子传输层材料两者共同影响器件出光效率,只是电子传输材料的折射率高低对器件出光效率影响不是决定性的。因此,相比于对比例1、对比例2和对比例3,本发明的应用例1至应用例22,具有更低的器件工作电压、更高的BI发光效率。
Claims (5)
2.根据权利要求1所述的有机电致发光器件,其特征在于,所述有机膜还包括发光层、空穴注入层、空穴传输层、电子阻挡层、空穴阻挡层或电子注入层中的至少一种。
3.一种显示器装置,其特征在于,包括权利要求1所述的有机电致发光器件。
4.一种光源装置,其特征在于,包括权利要求1所述的有机电致发光器件。
5.一种电子产品,其特征在于,包括权利要求3所述的显示器装置。
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