TWI651302B - Hole-only device based on semiconductor diodes asymmetric organic hole transporting material - Google Patents
Hole-only device based on semiconductor diodes asymmetric organic hole transporting material Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 239000012044 organic layer Substances 0.000 claims abstract description 19
- 230000000903 blocking effect Effects 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 230000005525 hole transport Effects 0.000 claims description 19
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 12
- 238000002474 experimental method Methods 0.000 abstract description 2
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- 239000011799 hole material Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001894 space-charge-limited current method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 carbazole compound Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/20—Organic diodes
-
- H—ELECTRICITY
- 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
- H10K85/60—Organic compounds having low molecular weight
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- H—ELECTRICITY
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本發明涉及一種基於非對稱有機空穴傳輸材料的僅空穴半導體二極體器件,包含陽極,陰極,和有機層,所述有機層為電子阻擋層、空穴傳輸層、空穴注入層中的一層或多層,所述有機層具有式(I)所述的化合物,其中,R1 與R2 分別獨立地選自為氫、具有1~8個碳原子的烷基、具有2~8個碳原子的烯烷基、具有2~8個碳原子的炔烷基、或具有5~20個碳原子的芳香基。實驗表明,本發明的式(I)所述的化合物具有高玻璃化轉變溫度,熱穩定性高,所製備的僅空穴有機半導體二極體器件性能良好且穩定,器件壽命長。 The present invention relates to a hole-only semiconductor diode device based on an asymmetric organic hole transporting material, comprising an anode, a cathode, and an organic layer, the organic layer being an electron blocking layer, a hole transporting layer, and a hole injecting layer One or more layers, the organic layer having the compound of the formula (I), wherein R 1 and R 2 are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 8 carbon atoms, and 2 to 8 An olefinic group of a carbon atom, an alkynyl group having 2 to 8 carbon atoms, or an aromatic group having 5 to 20 carbon atoms. Experiments have shown that the compound of the formula (I) of the present invention has a high glass transition temperature and high thermal stability, and the prepared hole-only organic semiconductor diode device has good and stable performance and long device life.
Description
本發明涉及新型僅空穴半導體二極體器件,特別是涉及一種基於非對稱有機空穴傳輸材料的僅空穴半導體二極體器件。 The present invention relates to novel hole-only semiconductor diode devices, and more particularly to a hole-only semiconductor diode device based on an asymmetric organic hole transport material.
僅空穴有機半導體二極體器件是單載流子器件的一種,作為半導體裝置用於智慧數位功率積體電路的開關或整流器。其中本發明的空穴傳輸材料也可應用於有機電致發光器件(OLED)及場效應電晶體。 The hole-only organic semiconductor diode device is a type of single carrier device used as a switch or rectifier for a smart digital power integrated circuit as a semiconductor device. The hole transporting material of the present invention is also applicable to organic electroluminescent devices (OLEDs) and field effect transistors.
僅空穴有機半導體二極體器件一般採用“夾層式三明治”結構,包含陽極,空穴傳輸層和陰極。也可以在陽極和空穴傳輸層之間加入一層能級匹配的空穴注入層,或者在空穴傳輸層和陰極之間加入電子阻擋層,進一步改善器件性能。當驅動電壓達到開啟電壓(Von)後,陽極產生的空穴經空穴傳輸層傳輸到達陰極,而由於電子阻擋層的存在,電子則不能進入至傳輸層中。僅空穴有機半導體二極體器件中的空穴傳輸材料也可應用到其它半導體器件如有機電致發光器件(OLED)中。有機電致發光器件具有廣闊的市場前景,開發高效穩定的有機空穴傳輸材料對有機電致發光器件的應用和推廣顯得尤為重要,同時也是平面顯示市場的迫切需求。 Hole-only organic semiconductor diode devices generally employ a "sandwich sandwich" structure comprising an anode, a hole transport layer and a cathode. It is also possible to add a level matching hole injection layer between the anode and the hole transport layer, or to add an electron blocking layer between the hole transport layer and the cathode to further improve device performance. When the driving voltage reaches the turn-on voltage ( Von ), holes generated by the anode are transported through the hole transport layer to the cathode, and electrons cannot enter the transport layer due to the presence of the electron blocking layer. The hole transporting material in the hole-only organic semiconductor diode device can also be applied to other semiconductor devices such as organic electroluminescent devices (OLEDs). Organic electroluminescent devices have broad market prospects. It is particularly important to develop efficient and stable organic hole transport materials for the application and promotion of organic electroluminescent devices, and it is also an urgent demand in the flat display market.
目前廣泛使用的空穴傳輸材料NPB,見下式,就光電性能而言,基本上能符合有機電致發光面板市場的需求,但其玻璃化轉變溫度(Tg)較低, 僅為98℃。NPB對稱的分子結構使其傾向於有規則地堆疊,易於結晶。空穴傳輸材料一旦結晶,會導致器件中載流子遷移機制發生改變,傳輸不平衡,對器件的穩定性及壽命產生不利的影響。而有機層材料由非晶態轉變為晶態的難易程度,主要與材料的玻璃化轉變溫度(Tg)相關,玻璃化轉變溫度越高,真空蒸鍍時形成的薄膜越均勻,同時穩定性也越好。因此,開發新型具有高玻璃化轉變溫度的空穴傳輸材料具有重要意義。 The hole transport material NPB, which is widely used at present, is as follows. In terms of photoelectric properties, it basically meets the requirements of the organic electroluminescent panel market, but its glass transition temperature (T g ) is low, only 98 ° C. . The NPB symmetrical molecular structure tends to be regularly stacked and easy to crystallize. Once the hole transporting material is crystallized, the carrier migration mechanism in the device is changed, the transmission is unbalanced, and the stability and life of the device are adversely affected. The degree of difficulty in converting the organic layer material from amorphous to crystalline is mainly related to the glass transition temperature (T g ) of the material. The higher the glass transition temperature, the more uniform the film formed during vacuum evaporation and the stability. The better. Therefore, it is important to develop a novel hole transporting material having a high glass transition temperature.
針對上述材料的缺陷,本發明提供一種基於非對稱有機空穴傳輸材料的僅空穴半導體二極體器件,具有高形態穩定性。 In view of the defects of the above materials, the present invention provides a hole-only semiconductor diode device based on an asymmetric organic hole transport material, which has high morphological stability.
一種基於非對稱有機空穴傳輸材料的僅空穴半導體二極體器件,包含陽極,陰極,和有機層,所述有機層為電子阻擋層、空穴傳輸層、空穴注入層中的一層或多層,所述有機層具有式(I)所述的化合物,
其中,R1與R2分別獨立地表示為氫、具有1~8個碳原子的烷基、具有2~8個碳原子的烯烷基、具有2~8個碳原子的炔烷基、或具有5~20個碳原子的芳香基。 Wherein R 1 and R 2 are each independently represented by hydrogen, an alkyl group having 1 to 8 carbon atoms, an olefinic group having 2 to 8 carbon atoms, an alkyne group having 2 to 8 carbon atoms, or An aromatic group having 5 to 20 carbon atoms.
優選:其中,R1與R2分別獨立地表示為氫、具有1~4個碳原子的烷基、具有2~4個碳原子的烯烷基、具有2~4個碳原子的炔烷基、或具有5~10個碳原子的芳香基。 Preferably, wherein R 1 and R 2 are each independently represented by hydrogen, an alkyl group having 1 to 4 carbon atoms, an olefinic group having 2 to 4 carbon atoms, and an acetylene group having 2 to 4 carbon atoms. Or an aromatic group having 5 to 10 carbon atoms.
優選:其中,R1與R2分別獨立地表示為氫、具有1~4個碳原子的烷基,苯基,萘基,具有1~4個碳原子烷基取代的苯基或萘基。 Preferably, R 1 and R 2 are each independently represented by hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, a phenyl group or a naphthyl group having an alkyl group substituted by 1 to 4 carbon atoms.
優選:R1與R2相同。 Preferably, R 1 is the same as R 2 .
優選:其中,R1與R2優選表示為氫、苯基或異丁基。 Preferably, wherein R 1 and R 2 are preferably represented by hydrogen, phenyl or isobutyl.
式(I)所述的化合物為下列結構化合物:
所述有機層為電子阻擋層、空穴傳輸層和空穴注入層,式(I)所述的化合物位於空穴傳輸層。 The organic layer is an electron blocking layer, a hole transporting layer, and a hole injecting layer, and the compound of the formula (I) is located in the hole transporting layer.
本發明中器件有機層的總厚度為1-1000nm,優選1-500nm,更優選10-300nm。 The total thickness of the organic layer of the device in the present invention is from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 10 to 300 nm.
所述有機層可以通過蒸渡或溶液法製備薄膜。 The organic layer can be prepared by a vaporization or solution method.
上述有機空穴材料的製備方法,採用如下步驟:(1)氮氣保護下,以咔唑類化合物Cz和溴代螺芴SF-Br為原料,經鈀催化碳氮偶聯反應合成中間體Cz-SF,催化體系為Pd2(dba)3/P(t-Bu)3/t-BuONa,溶劑為甲苯,在90-150℃的條件下反應10-30h;(2)以NBS為溴化劑,合成中間體Cz-SF-Br,在0-50℃的條件下反應10-30h;(3)通過Cz-SF-Br與雙頻哪醇合二硼(B2Pin2)之間的偶聯反應合成中間體Cz-SF-B,催化體系為Pd(dppf)Cl2/CH3COOK,溶劑為二氧六環,在60-120℃的條件下反應10-30h; (4)最後,Cz-SF-B與TPA-Br經Suzuki偶聯反應即可得到目標產物,該步驟所使用催化劑為Pd(PPh3)4,溶劑為四氫呋喃,在80-120℃的條件下反應10-30h。 The preparation method of the above organic hole material adopts the following steps: (1) under the protection of nitrogen, the intermediate Cz- is synthesized by palladium-catalyzed carbon-nitrogen coupling reaction using carbazole compound Cz and brominated spiro sulfonium SF-Br as raw materials. SF, the catalytic system is Pd 2 (dba) 3 /P(t-Bu) 3 /t-BuONa, the solvent is toluene, reacting at 90-150 ° C for 10-30h; (2) using NBS as brominating agent , the synthesis intermediate Cz-SF-Br, reacted at 0-50 ° C for 10-30h; (3) through the coupling between Cz-SF-Br and dipinacol diboron (B 2 Pin 2 ) The synthesis reaction intermediate Cz-SF-B, the catalytic system is Pd(dppf)Cl 2 /CH 3 COOK, the solvent is dioxane, and the reaction is carried out at 60-120 ° C for 10-30 h; (4) Finally, The target product can be obtained by Suzuki coupling reaction of Cz-SF-B with TPA-Br. The catalyst used in this step is Pd(PPh 3 ) 4 , the solvent is tetrahydrofuran, and the reaction is carried out at 80-120 ° C for 10-30 h.
如上面提到的,本發明中式(I)所述的化合物如下,但不限於所列舉的結構:
實驗表明,由於本發明的有機空穴傳輸材料包含三芳胺、咔唑和螺芴等關鍵構築單元,具有高玻璃化轉變溫度,熱穩定性高,因此本發明的僅空穴有機半導體二極體器件性能良好且穩定,器件壽命長。 Experiments have shown that since the organic hole transporting material of the present invention contains key building blocks such as triarylamine, carbazole and snail, has high glass transition temperature and high thermal stability, the hole-only organic semiconductor diode of the present invention The device performs well and is stable with long device life.
10‧‧‧玻璃基板 10‧‧‧ glass substrate
20‧‧‧陽極 20‧‧‧Anode
30‧‧‧空穴注入層 30‧‧‧ hole injection layer
40‧‧‧空穴傳輸層 40‧‧‧ hole transport layer
50‧‧‧電子阻擋層 50‧‧‧Electronic barrier
60‧‧‧陰極 60‧‧‧ cathode
圖1為化合物1的DSC曲線;以及圖2為本發明的器件結構圖,其中10代表為玻璃基板,20代表為陽極,30代表為空穴注入層,40代表為空穴傳輸層,50代表電子阻擋層,60代表為陰極。 1 is a DSC curve of Compound 1; and FIG. 2 is a structural view of the device of the present invention, wherein 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a hole transport layer, and 50 represents a hole transport layer. The electron blocking layer, 60 represents the cathode.
為了更詳細敘述本發明,特舉以下例子,但是不限於此。 In order to describe the present invention in more detail, the following examples are given, but are not limited thereto.
實施例1 Example 1
氮氣保護下,將咔唑(15.0g,89.7mmol),2-溴螺芴(32g,81.0mmol),Pd2(dba)3(2.2g,2.4mmol)和叔丁醇鈉(10.4g,108.0mmol)加入三口瓶中。抽真空,通入氮氣,反復進行三次。隨後,將三叔丁基膦的甲苯溶液(2.16g,50w%)和無水甲苯(100mL)加入上述反應瓶中。升溫至回流110℃,反應12h。冷至室溫後,減壓蒸除甲苯,剩餘物經乙醇重結晶得白色固體39.0g,收率為90%。1H NMR(400MHz,CDCl3)δ 8.05-8.02(m,3H),7.90(d,J=7.6Hz,1H),7.78(d,J=7.6Hz,2H),7.56(dd,J=8.0,2.0Hz,1H),7.41(t,J=7.6Hz,1H),7.34(t,J=7.6Hz,2H),7.29-7.12(m,9H),6.90(d,J=1.6Hz,1H),6.85(d,J=7.6Hz,2H),6.79(d,J=7.6Hz,1H). Under nitrogen, carbazole (15.0 g, 89.7 mmol), 2-bromospiropurine (32 g, 81.0 mmol), Pd 2 (dba) 3 (2.2 g, 2.4 mmol) and sodium t-butoxide (10.4 g, 108.0) Mm) added to the three-neck bottle. Vacuum was applied and nitrogen gas was introduced and it was repeated three times. Subsequently, a toluene solution of tri-tert-butylphosphine (2.16 g, 50 w%) and anhydrous toluene (100 mL) were added to the above reaction flask. The temperature was raised to reflux at 110 ° C and the reaction was carried out for 12 h. After cooling to room temperature, toluene was evaporated under reduced pressure, and the residue was crystallized from ethanol to yield 39.0 g of white solid. 1 H NMR (400MHz, CDCl 3 ) δ 8.05-8.02 (m, 3H), 7.90 (d, J = 7.6Hz, 1H), 7.78 (d, J = 7.6Hz, 2H), 7.56 (dd, J = 8.0 , 2.0 Hz, 1H), 7.41 (t, J = 7.6 Hz, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.29-7.12 (m, 9H), 6.90 (d, J = 1.6 Hz, 1H) ), 6.85 (d, J = 7.6 Hz, 2H), 6.79 (d, J = 7.6 Hz, 1H).
氮氣保護下,將化合物c(15.0g,31.1mmol)溶於二氯甲烷(100mL)。向上述溶液分批加入NBS(5.5g,30.9mmol),室溫(20℃)反應12h。將反應液傾入水中,分液,有機相經硫酸鈉乾燥。減壓蒸除溶劑後,剩餘物經乙醇重結晶得白色固體15.6g,收率為89%。1H NMR(400MHz,CDCl3)δ 8.14(d,J=1.6Hz,1H),8.04(d,J=7.6Hz,1H),7.99(d,J=7.6Hz,1H),7.92(d,J=7.6Hz,1H),7.80(d,J=7.6Hz,2H),7.53(dd,J=8.0,1.6Hz,1H),7.44(t,J=7.2Hz,1H),7.39-7.34(m,3H),7.30(d,J=8.4Hz,1H),7.23-7.14(m,5H),7.04(d,J=8.8Hz,1H),6.86-6.80(m,4H). Compound c (15.0 g, 31.1 mmol) was dissolved in dichloromethane (100 mL). NBS (5.5 g, 30.9 mmol) was added portionwise to the above solution and allowed to react at room temperature (20 ° C) for 12 h. The reaction solution was poured into water, and the organic layer was dried over sodium sulfate. After distilling off the solvent under reduced pressure, the residue was crystallised from ethanol to yield 15.6 g of white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.14 (d, J = 1.6 Hz, 1H), 8.04 (d, J = 7.6 Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H), 7.92 (d, J = 7.6 Hz, 1H), 7.80 (d, J = 7.6 Hz, 2H), 7.53 (dd, J = 8.0, 1.6 Hz, 1H), 7.44 (t, J = 7.2 Hz, 1H), 7.39-7.34 ( m, 3H), 7.30 (d, J = 8.4 Hz, 1H), 7.23 - 7.14 (m, 5H), 7.04 (d, J = 8.8 Hz, 1H), 6.86-6.80 (m, 4H).
氮氣保護下,將化合物d(15.0g,26.8mmol),雙頻哪醇合二硼(7.5g,29.5mmol),Pd2(dppf)Cl2(2.2g,3.0mmol)和CH3COOK(5.2g,53.0mmol)加入三口瓶中。抽真空,通入氮氣,反復進行三次。隨後,將二氧六環(100mL)加入上述反應瓶中,升溫至80℃,反應12h。冷至室溫後,減壓蒸除溶劑,剩餘物經柱層析分離得白色固體8.2g,收率為50%。1H NMR(400MHz,CDCl3)δ 8.54(s,1H),8.07(d,J=7.6Hz,1H),8.04(d,J=8.0Hz,1H),7.91(d,J=7.6Hz,1H),7.78(d,J=7.6Hz,2H),7.72(d,J=8.4Hz,1H),7.56(dd,J=8.0,1.6Hz,1H),7.42(t,J=7.6Hz,1H),7.35(t,J=7.6Hz,2H),7.31-7.12(m,7H),6.88(d,J=1.6Hz,1H),6.85(d,J=7.6Hz,2H),6.80(d,J=7.6Hz,1H),1.37(s,12H). Compound d (15.0 g, 26.8 mmol), dipinacol diboron (7.5 g, 29.5 mmol), Pd 2 (dppf) Cl 2 (2.2 g, 3.0 mmol) and CH 3 COOK (5.2) g, 53.0 mmol) was added to a three-neck bottle. Vacuum was applied and nitrogen gas was introduced and it was repeated three times. Subsequently, dioxane (100 mL) was added to the above reaction flask, and the mixture was heated to 80 ° C for 12 h. After cooling to room temperature, the solvent was evaporated under reduced pressure. 1 H NMR (400MHz, CDCl 3 ) δ 8.54 (s, 1H), 8.07 (d, J = 7.6Hz, 1H), 8.04 (d, J = 8.0Hz, 1H), 7.91 (d, J = 7.6Hz, 1H), 7.78 (d, J = 7.6 Hz, 2H), 7.72 (d, J = 8.4 Hz, 1H), 7.56 (dd, J = 8.0, 1.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 7.31 - 7.12 (m, 7H), 6.88 (d, J = 1.6 Hz, 1H), 6.85 (d, J = 7.6 Hz, 2H), 6.80 ( d, J = 7.6 Hz, 1H), 1.37 (s, 12H).
氮氣保護下,將化合物e(1.6g,2.7mmol),化合物f(1.5g,2.7mmol)(化合物f參考US 20130112948合成)和Pd(PPh)4(150mg,0.13mmol)加入三口瓶中。抽真空,通入氮氣,反復進行三次。隨後,將四氫呋喃(30mL)和碳酸鉀水溶液(2M,5mL)加入上述反應瓶中。升溫至回流,反應15h。冷至室溫後,將反應液加入水中,混合物用二氯甲烷萃取,合併有機相。減壓蒸除溶劑後,剩餘物經柱層析分離得白色固體1.6g,收率為62%。1H NMR(400MHz,CDCl3)δ 8.15(s,1H),8.07-8.04(m,2H),7.92(d,J=7.6Hz,1H),7.80(d,J=7.6Hz,2H),7.76-7.74(m,3H),7.70(d,J=8.0Hz,1H),7.58(dd,J=8.0,2.0Hz,1H),7.45-7.28(m,10H),7.23-7.11(m,10H),7.06-6.98(m,6H),6.92-6.80(m,7H),6.67(d,J=7.6Hz,1H),6.61(s,1H).MS(m/z):962(M+).玻璃化轉變溫度:193℃。 Compound e (1.6 g, 2.7 mmol), compound f (1.5 g, 2.7 mmol) (compound f with reference to US 20130112948) and Pd(PPh) 4 (150 mg, 0.13 mmol) were added to a three-necked flask under nitrogen. Vacuum was applied and nitrogen gas was introduced and it was repeated three times. Subsequently, tetrahydrofuran (30 mL) and an aqueous potassium carbonate solution (2M, 5 mL) were placed in the above-mentioned reaction flask. The temperature was raised to reflux and the reaction was carried out for 15 h. After cooling to room temperature, the reaction solution was added to water, and the mixture was extracted with dichloromethane, and the organic phase was combined. After distilling off the solvent under reduced pressure, the residue was purified by column chromatography to yield white crystals (yield: 62%). 1 H NMR (400MHz, CDCl 3 ) δ 8.15 (s, 1H), 8.07-8.04 (m, 2H), 7.92 (d, J = 7.6Hz, 1H), 7.80 (d, J = 7.6Hz, 2H), 7.76-7.74 (m, 3H), 7.70 (d, J = 8.0 Hz, 1H), 7.58 (dd, J = 8.0, 2.0 Hz, 1H), 7.45-7.28 (m, 10H), 7.23 - 7.11 (m, 10H), 7.06-6.98 (m, 6H), 6.92-6.80 (m, 7H), 6.67 (d, J = 7.6 Hz, 1H), 6.61 (s, 1H). MS (m/z): 962 (M + ). Glass transition temperature: 193 °C.
實施例2 Example 2
玻璃化轉變溫度測試: 氮氣保護下,以20℃/min的加熱和冷卻速率用示差掃描量熱法(DSC)測試化合物1的玻璃化轉變溫度。測得化合物1的玻璃化轉變溫度Tg為193℃(圖1)。而文獻所報導的NPB的玻璃化轉變溫度僅為98℃。 Glass transition temperature test: The glass transition temperature of Compound 1 was tested by differential scanning calorimetry (DSC) at a heating and cooling rate of 20 ° C/min under nitrogen atmosphere. The glass transition temperature T g of Compound 1 was measured to be 193 ° C ( FIG. 1 ). The glass transition temperature of NPB reported in the literature is only 98 °C.
可見,本發明中的化合物比常用空穴傳輸材料NPB具有更高的玻璃化轉變溫度,本發明顯著提高了空穴傳輸材料的熱穩定性。 It can be seen that the compound of the present invention has a higher glass transition temperature than the conventional hole transporting material NPB, and the present invention remarkably improves the thermal stability of the hole transporting material.
實施例3 Example 3
僅穴阻有機半導體二極體器件1的製備 Preparation of only hole-blocking organic semiconductor diode device 1
器件結構如圖2,器件製備方式描述如下: 首先,將透明導電ITO玻璃基板(包含10和20)按照以下步驟處理:預先用洗滌劑溶液、去離子水,乙醇,丙酮,去離子水洗淨,再經氧等離子處理30秒。 The device structure is shown in Figure 2. The device preparation method is described as follows: First, the transparent conductive ITO glass substrate (including 10 and 20) was treated as follows: previously washed with a detergent solution, deionized water, ethanol, acetone, deionized water, and then subjected to oxygen plasma treatment for 30 seconds.
然後,在ITO上蒸渡10nm厚的MoO3作為空穴注入層30。 Then, 10 nm thick MoO 3 was vapor-deposited on the ITO as the hole injection layer 30.
然後,在空穴注入層上蒸渡120nm厚的化合物1作為空穴傳輸層40。 Then, a compound 1 having a thickness of 120 nm was vapor-deposited on the hole injection layer as the hole transport layer 40.
然後,在空穴傳輸層上蒸渡10nm厚的MoO3作為電子阻擋層50。 Then, 10 nm thick MoO 3 was vapor-deposited on the hole transport layer as the electron blocking layer 50.
最後,在電子阻擋層上蒸渡100nm厚的鋁作為器件陰極60。 Finally, 100 nm thick aluminum was vaporized on the electron blocking layer as the device cathode 60.
利用空間限制電流法測試材料的空穴遷移率(space charge limited current,SCLC)電流密度與電場強度的關係如式(1):
其中,J為電流密度(mA cm-2),ε為相對介電常數(有機材料通常取值為3),ε0為真空介電常數(8.85×10-14 C V-1 cm-1),E為電場強度(V cm-1),L為器件中樣本的厚度(cm),μ0為零電場下的電荷遷移率(cm2 V-1 s-1),β為Poole-Frenkel因數,表示遷移率隨電場強度變化的快慢程度。 Where J is the current density (mA cm -2 ), ε is the relative dielectric constant (organic material usually takes 3), and ε 0 is the vacuum dielectric constant (8.85 × 10 -14 CV -1 cm -1 ), E is the electric field strength (V cm -1 ), L is the thickness (cm) of the sample in the device, μ 0 is the charge mobility under the electric field (cm 2 V -1 s -1 ), and β is the Poole-Frenkel factor. Indicates how quickly the mobility changes with the strength of the electric field.
比較例 Comparative example
僅空穴有機半導體二極體器件2的製備 Preparation of only hole organic semiconductor diode device 2
方法同實施例3,但使用常用市售化合物NPB作為空穴傳輸層40,製作對比用僅空穴有機半導體二極體器件。 The method was the same as in Example 3 except that the commonly used commercially available compound NPB was used as the hole transport layer 40, and a hole-only organic semiconductor diode device for comparison was produced.
所製備的器件空穴遷移率(cm2 V-1 s-1) The device has a hole mobility (cm 2 V -1 s -1 )
因此,本發明的材料體現了與NPB相近的空穴遷移率,但其熱穩定性更好,更符合高性能有機半導體器件對空穴傳輸材料的要求。 Therefore, the material of the present invention exhibits a hole mobility similar to that of NPB, but its thermal stability is better, and it is more in line with the requirements of a high-performance organic semiconductor device for a hole transporting material.
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