CN103626966B - It is used in the compounds of carrier transportation, the element of application compounds and electronic installation - Google Patents
It is used in the compounds of carrier transportation, the element of application compounds and electronic installation Download PDFInfo
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- CN103626966B CN103626966B CN201210301768.3A CN201210301768A CN103626966B CN 103626966 B CN103626966 B CN 103626966B CN 201210301768 A CN201210301768 A CN 201210301768A CN 103626966 B CN103626966 B CN 103626966B
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- ptc
- thin film
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- carrier transportation
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Abstract
The present invention is to be used in the compounds of carrier transportation, the element of application compounds and electronic installation, it is provided that chemical formula i compoundFormula I wherein, A, B and C be repetitive (repeating unit), A Yu B respectively for formed conjugated polymer the group being optionally substituted, C is crosslinkable groups, and n is the integer equal to or more than 1.The present invention further provides element and the electronic installation using chemical formula i compound, and more specifically, the present invention provides light emitting diode (light emitting diode, the LED) device using chemical formula i compound.
Description
Technical field
The present invention is about the compounds being used in carrier transportation, is specifically about element and the electronics using compounds
Device, is more specifically about the light emitting diode using compounds.
Background technology
Because having low power consuming, light weight, fast reaction and wide viewing angle characteristic, Organic Light Emitting Diode (OLED) and polymer
The development of light emitting diode (PLED) obtains attention deeply.Carrier transportation is the key factor of this kind of device usefulness.For high-effect
LED matrix, it is necessary to the carrier that the exciton (exciton) formed by luminescent layer offsets from negative and positive the two poles of the earth injects and carrier
Transmission.It is said that in general, LED matrix comprises is clipped in two interelectrode three-deckers, including electricity hole injection/transport layer (hole
Injection/transport layer, HITL), electron emission layer (electron-emitting layer, EML) and electron transfer layer
(electron-transporting layer,ETL).Package arrangements makes each layer inject at carrier, carrier transportation is optimized with luminescence.
Develop at present and be used in the polymeric material of electricity hole injections/transport layer (HITL) and mainly can depend on the chemical bond formed in it
Type is divided into two kinds, i.e. ion of bonding valence link type together.
Poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulphonate) shown in Fig. 1
(poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate), hereinafter referred to as PEDOT-PSS) is by ion
A kind of material that bond is formed.PEDOT-PSS has been focused on for having the research of the organic material of high electricity hole injectability,
Because it has suitable ionization potential (Ip=-5.2to-5.3eV), high conductivity (～1-10S/cm) and good electricity
Hole injectability.But, PEDOT-PSS is ionic, acid and is to make via water dispersion (water dispersion)
Standby.For OLED Yu PLED, water has more destructiveness than oxygen.Therefore, PEDOT-PSS is used in light-emitting diodes
In the structure of pipe highly unstable.Because the defect of aforementioned PEDOT-PSS material character, it cannot be employed at present effectively
At extensive coating process.
Furthermore, PEDOT-PSS can be used in known organic transistor element.But, PEDOT has bad orientation in the electrodes
Character and as electrode material, it is impossible to show sufficient carrier transportation characteristic.
Material (being called for short HITM) is injected/transmitted in the covalent cross-linking electricity hole resulting in solvent resistant electricity hole implanted layer by widely
Research.Multiple heat cross-linking material, photochemical crosslinking material and electrochemistry cross-linked material are avoided that solwution method processing procedure (solution
Process) intermixing (interfacial mixing) caused.For example, covalently bonded as shown in Figure 2 is formed
Thermosetting polymer (Adv.Fun.Mater.2002.12 745.；Adv.Mater.2007,19,300.；Adv.Mater.2009,21,
1972.) there is suitable molecular entergy level (highest occupied molecular orbital (highest occupied molecular orbital, HOMO)
And good electric hole injectability Ip=-5.3eV).Therefore, the electronic component using this thermosetting polymer has good effect
Rate.Although the thermosetting polymer that covalently bonded is formed does not has a shortcoming of PEDOT-PSS, but thermosetting polymer
Matter makes it lack machinability.Additionally, it is complex with harsh (example to use this thermosetting polymer to manufacture the processing procedure of electronic component
As: carry out heat cure and require more than the high temperature of 200 DEG C).Because using this thermosetting polymer to manufacture the cost height of electronic component,
This polymer is the most only useful in laboratory small device, does not have the potentiality of high commercial volume production.
Summary of the invention
In order to overcome the shortcomings of current material, active pursuit without ion and hydrophilic group with replace PEDOT-PSS with
The novelty of thermosetting polymer and cost-effective material.We thus a kind of compounds is provided, it is mutual by height
Mend non-covalently bonded and form physics cross-linked structure, and can reach the effect as covalency cross-linked material, without additionally
Processing procedure.
In an aspect, the present invention provides a kind of chemical formula i compound
Wherein A, B and C are repetitive (repeating unit)；A with B is respectively for forming optionally being substituted of conjugated polymer
Group；C is crosslinkable groups；And n is the integer equal to or more than 1.
Another aspect of the present invention is chemical formula i compound, and wherein A with B is identical or different, and A Yu B is each independently
One of choosing freely following formed group: the triphenylamine (triphenylamine) that is optionally substituted, be optionally substituted
Carbazole (carbazole), the thiophene (thiophene) being optionally substituted, the fluorenes (fluorene) being optionally substituted, regard need
To be substituted to phenylene vinylene (p-phenylene vinylene) and combinations thereof；C is choosing freely following formed group
Group: the group (amide-containing group) of amide-containing, carboxylic group (carboxyl-containing group),
The group (hydroxyl-containing group) of hydroxyl, the group (amino-containing group) containing amino, Halogen
The group (halogen-containing group) of element, the group (base-containing group) containing base and combinations thereof；With
And the substituent group of A or B is independently selected from by following formed group: C1-15Alkyl and C6-10Aryl.
According to the present invention, the example of the group containing base can comprise adenine (adenine), thymus pyrimidine (thymine), born of the same parents
Pyrimidine (cytosine), guanine (guanine), uracil (uracil) and combinations thereof etc..It is preferred that the group containing base
For adenine or uracil.Additionally, the example of C can be A combination thereof etc., and the substituent group of R1 can be C1-15 alkyl and C6-10 aryl.
In a further aspect, the present invention provides chemical formula i compound, and wherein, A is the triphenylamine being optionally substituted,
B is the carbazole being optionally substituted, and the substituent group of A Yu B is butyl.
In another aspect, the present invention provides chemical formula i compound, and only when C is crosslinkable groups, both A and B are not
It is thiophene, fluorenes or to phenylene vinylene simultaneously；When C is crosslinkable groups, A and B is different；As A and B two
When person is the carbazole being optionally substituted simultaneously, C is not guanine；Or when A is that the fluorenes being optionally substituted and B need for regarding
During carbazole to be substituted, C is not guanine.
In a specific embodiment of chemical formula i compound of the present invention, repetitive is: 1-[4-(3-{4-[(4-butyl phenyl) (benzene
Base) amino] phenyl }-9H-carbazole-9-base) butyl]-1,2,3,4-tetrahydropyrimidine-2,4-diketone；
9-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-9H-purine-6-amine；
1-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-5-methyl isophthalic acid, 2,3,4-tetrahydropyrimidine-2,4-
Diketone；
4-amino-1-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-1,2-dihydropyrimidine-2-keto；Or
2-amino-9-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-6,9-dihydro-1H-purine-6-
Ketone.
In another aspect of the present invention, it is provided that comprise the conductive film of aforementioned arbitrary compound.
In another aspect again of the present invention, it is provided that comprise the carrier transportation layer of aforementioned arbitrary compound.It is preferred that carrier passes
Defeated layer can be electricity hole transport layer.
In yet another aspect of the present invention, it is provided that electronic installation, wherein, comprise conductive film and conductive film comprises aforementioned
Arbitrary compound.
One aspect of the present invention provides the electronic installation comprising carrier transportation layer, and carrier transportation layer comprises aforementioned arbitrary compound.
It is preferred that electronic installation can be el light emitting device (electroluminescent device) or transistor (transistor).More
Goodly, el light emitting device can be light-emitting diode assembly.Specifically, light-emitting diode assembly can be Organic Light Emitting Diode
Device.
In another aspect of the present invention, it is provided that solaode, wherein, carrier transportation layer, and carrier transportation layer bag are comprised
Containing aforementioned arbitrary compound.
In another aspect of the present invention, it is provided that optical detector, wherein, comprise carrier transportation layer, and carrier transportation layer comprises
Aforementioned arbitrary compound.
In a further aspect, the present invention provides the method manufacturing electronic component, and electronic component comprises aforementioned arbitraryization of use
The layer that compound is formed.It is preferred that layer is film.
In another aspect of the present invention, it is provided that the method manufacturing electronic installation, wherein, method comprises aforementioned arbitraryization of use
The step of compound.The example of electronic installation can be el light emitting device or transistor.It is preferred that el light emitting device can be to send out
Optical diode device.More preferably, light-emitting diode assembly can be oled device.
Because the compound of the present invention is not the polymer formed by ion bond, it has good environmental stability.This
Bright not only possess electricity hole now and inject/transmit the character of material, also can overcome the defect of many technology at present simultaneously.Additionally, because of
For the character of the present invention, so the processing procedure of the preparation present invention is simple, and promote by the solvent resistant ability of the formed element of the present invention.
Accompanying drawing explanation
Fig. 1 shows the chemical constitution of PEDOT-PSS；
Fig. 2 shows the chemical constitution of thermosetting polymer；
Fig. 3 shows the FTIR spectrum figure (2400～3700cm of PTC, PTC-A, PTC-U-1)；
Fig. 4 shows the FTIR spectrum figure (1400～2000cm of PTC, PTC-A, PTC-U-1)；
Fig. 5 shows the TGA figure of PTC, PTC-A, PTC-U；
Fig. 6 shows the DSC figure of PTC, PTC-A, PTC-U；
Fig. 7 A-7C shows the solvent resistant ability of PTC, PTC-A, PTC-U respectively；
Fig. 8 shows have by the I-V diagram of PTC, PTC-A Yu the structure of the formed thin film of PTC-U；
Fig. 9 shows the energy diagram of different materials；
Figure 10 shows have I-V diagram by PTC, PTC-A Yu the element of the formed thin film of PTC-U respectively；
Figure 11 shows have respectively by the L-V figure of PTC, PTC-A and the element of the formed thin film of PTC-U；
Figure 12 shows the method manufacturing LED matrix；
Figure 13 shows have respectively by the EQE-V figure of PTC, PTC-A and the OLED device of the formed thin film of PTC-U；
Figure 14 shows have respectively by the LE-V figure of PTC, PTC-A and the OLED device of the formed thin film of PTC-U；
Figure 15 shows have respectively by the PE-V figure of PTC, PTC-A and the OLED device of the formed thin film of PTC-U；
And
Figure 16 A-16D show have respectively by the formed thin film of PTC-U/PTC-A of ratio 1:4 and 1:10 element and
The light transmittance efficiency figure of OLED device.
Detailed description of the invention
The content that illustrative specific embodiment presented below disclosed herein with explanation.These of the present invention with other advantages and
Effect person of ordinary skill in the field read this specification disclose after it will be clearly understood that.
As described herein, term " conjugated polymer (conjugated polymer) " refers to endogenous conducting polymer (intrinsic
Conductive polymer), wherein the main chain of polymer is to be formed with double bond by singly-bound alternately.
As described herein, term " crosslinkable groups (crosslinkable group) " refers to be formed the base of crosslinking by hydrogen bond
Group.Thus the example of the crosslinkable groups that hydrogen bond forms crosslinking can include amide group, carboxylic group, oh group, ammonia
Base group, halogen-containing group, group etc. containing base.
As described herein, term " halogen (halogen) " refers to iodine, bromine, chlorine or fluorine.
As described herein, term " group containing base " refers to any group containing base.The example of base can include that gland is fast
Purine, cytosine, guanine, uracil, thymus pyrimidine etc., and the example of group containing base also can include adenine, born of the same parents
Pyrimidine, guanine, uracil and thymus pyrimidine.
As described herein, " alkyl (alkyl) " refers to hydrocarbon chain, and its typical case has about 1 to 15 carbon atom length.This hydrocarbon
Chain is preferable, but optionally, for saturated, and can be side chain or straight chain, but typical case's straight chain is preferable.Exemplary alkyl can comprise
Methyl (methyl), ethyl (ethyl), propyl group (propyl), butyl (butyl), amyl group (pentyl), 1-methyl butyl
(1-methylbutyl), 1-ethyl propyl (1-ethylpropyl), 3-methyl amyl (3-methylpentyl) etc..
As described herein, " aryl (aryl) " refers to one or more aromatic rings, and it is former that its typical case has about 6 to 10 carbon
Son.Aryl can comprise the multiple aryl rings that can condense, such as naphthyl (naphthyl), and maybe can comprise can multiple virtues of non-condensed
Basic ring, such as xenyl (biphenyl).Aryl rings also can with one or more cyclic hydrocarbons (cyclic hydrocarbon),
Heteroaryl (heteroaryl) or heterocycle (heterocyclic rings) condense or uncondensed.Exemplary aryl can comprise phenyl,
Naphthyl etc..
As described herein, " electricity hole transport layer (HTL) " refers to promote the element of electricity hole transmission.For example, when by electricity hole
Transport layer be placed on tin indium oxide (hereinafter referred to as ITO) and luminescent layer between the two time, significantly decrease electricity hole transmission obstacle to promote
Enter the transmission of electricity hole；It moreover has been found that the gap state (gap state) in HTL band gap improves the electric hole note at interface further
Enter.The usefulness that soluble el light emitting device (espespecially OLED device) display why with HTL of this phenomenon improves.With
Example at the material of electricity hole transport layer can include the double (naphthalene-1-of triphenyl diamine (triphenyl diamine, TPD), N, N-
Base) double (phenyl) benzidine of-N, N-(being called for short NPB (KODAK)), polyvinylcarbazole (polyvinylcarbazole, PVK),
Spiro-TPD (Covion), Spiro-NPB (Covion) etc..
The synthesis of double (4-bromophenyl) aniline (compound 1) of embodiment 1:4-butyl-N, N-
As shown in response diagram 1, the most sequentially by toluene (50 milliliters), butyl-benzene amine (4.23 milliliters, 26.8 mmoles
You), 1-bromo-4-iodobenzene (16.68 grams, 59 mMs), 1,10-phenanthrolene (0.18 gram, 0.97 mM), chlorination
Cuprous (CuCl) (0.1 gram, 0.95 mM), and potassium hydroxide (13.67 grams, 243 mMs) add be furnished with condensation
Device, magnetic stirrer, 250 milliliters of three-necked bottles of import and export of nitrogen.Reactant mixture was heated to reflux temperature in 30 minutes,
And stir 48 hours under reflux.Then mixture is cooled to 75 DEG C, and uses the toluene of 100 milliliters and 100 milliliters
Distilled water extracts.Separation of methylbenzene phase, use anhydrous magnesium sulfate (MgSO4) be dried, filter and vacuum distilling.By crude product
Through silicone tube column chromatography (use toluene is eluant) purification to obtain colorless oil (3.8 grams, 31%).
1H NMR(300MHz,CDCl3,δ):7.30(dd,4H；Ar H),7.07(d,2H；Ar H),6.96(d,2H；Ar H),
6.90(dd,4H；Ar H),2.56(t,2H；CH2),1.63-1.52(m,2H；CH2),1.41-1.29(m,2H；CH2),0.93(t,
3H；CH3)
13C NMR(300MHz,CDCl3,δ):146.7,144.4,138.8,132.2,129.4,125.0,114.9,35.0,33.6,
22.4,14.0
HRMS (ESI, m/z): C22H21NBr2 [M+H]+value of calculation: 457.0041；Discovery value: 457.0039
The synthesis of double (4,4,5,5-tetramethyl-1,3,2-dioxy boron penta ring-4-the phenyl)-aniline (compound 2) of embodiment 2:4-butyl-N, N-
As shown in response diagram 1, at-78 DEG C, by n-BuLi (n-BuLi, 4.4 milliliters, 11.1 mMs, at hexane
2.5M) add double (4-the bromophenyl)-aniline (2.02 grams, 4.4 mMs) of 4-butyl-N, N-at anhydrous tetrahydro furan
Solution in (tetrahydrofuran, hereinafter referred to as THF, 44 milliliters).Mixture is stirred 45 minutes at-78 DEG C.Hurry up
Speed adds 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxy boron penta ring (dioxaborolane) (2.7 milliliters, 13.2 mMs)
To solution.Mixture is stirred 2 hours at-78 DEG C.Pour the mixture in water and use diethyl ether, by organic extraction
Take thing to combine and wash with saline.Solvent is removed under reduced pressure atmosphere, and colourless to obtain with methanol recrystallization purification of crude product
Crystal (1.36 grams, 56%, mp:204-206 DEG C).
1H NMR(300MHz,CDCl3,δ):7.64(d,4H；Ar H),7.03(m,8H；Ar H),2.56(t,2H；CH2),
1.63-1.53(m,2H；CH2),1.38-1.31(m,26H；CH2and C8H24),0.92(t,3H；CH3)
13C NMR(300MHz,CDCl3,δ):150.5,144.7,139.0,135.9,129.4,126.2,122.7,83.8,35.3,
33.9,24.9,22.5,14.3
HRMS (ESI, m/z): C34H45B2NO4 [M+H]+value of calculation: 553.3534；Discovery value: 553.3539
The synthesis of embodiment 3:4-brombutyl-9 (3,6-dibromo carbazole) (compound 3)
As shown in response diagram 1, following reagent is placed on the reaction bulb being furnished with condenser: product 3,6-bis-bromo-9H-carbazole
(3,6-dibromo-9H-carbazole) (6.5 grams, 0.02 mole), Anhydrous potassium carbonate powder (5.53 grams, 0.04 mole),
Anhydrous acetonitrile (acetonitrile) (80 milliliters) and Isosorbide-5-Nitrae-dibromobutane (Isosorbide-5-Nitrae-dibromobutane) (25 milliliters, 0.2
Mole).Purge reactor with argon, and maintain this pressure in reaction whole process.95 DEG C, in oil bath, under backflow, will reaction
Mixture stirs and heats 36 hours.Finally, filter reactant mixture, evaporate solvent, and with the residual matter of petroleum ether recrystallization with
Obtain crystal (6.9 grams, 75%).
1H NMR(300MHz,CDCl3,δ):8.10(d,2H；Ar H),7.54(dd,2H；Ar H),7.25(d,2H；Ar H),
4.25(t,2H；CH2),3.36(t,2H；CH2),2.04–1.95(m,2H；CH2),1.89–1.80(m,2H；CH2)
13C NMR(300MHz,CDCl3,δ):134.4,124.4,118.9,107.6,105.8,37.8,28.4,25.5,22.9
The synthesis of embodiment 4:4-uracil butyl-9 (3,6-dibromo carbazole) (compound 4, R=uracil)
As shown in response diagram 1, following reactants is placed on the reaction bulb being furnished with condenser: 4-brombutyl-9 (3,6-dibromo carbazole) (1.0
Gram, 2.17 mMs), Anhydrous potassium carbonate powder (0.45 gram, 3.25 moles), dimethyl fumarate (DMF, 20 milliliters)
With uracil (0.3653 gram, 3.26 mMs).Purge reactor with argon, and maintain this pressure in reaction whole process.70 DEG C,
In oil bath, under backflow, reactant mixture is stirred and heats 72 hours.Finally, filter reactant mixture, evaporate solvent, and
Solid several times is washed with water.Solid is collected by filtration and with toluene recrystallization to obtain crystal (0.54 gram, 51%, mp:190 DEG C).
1H NMR(300MHz,DMSO,δ):11.2(s,1H；NH),7.63(d,2H；Ar H),7.60-7.54(m,5H；Ar
H),5.49(d,1H；Ar H),4.39(t,2H；CH2),3.63(t,2H；CH2),1.69(m,2H；CH2),1.58(m,2H；
CH2)
13C NMR(300MHz,DMSO,δ):164.3,151.6,146.1,139.6,129.6,124.1,123.4,112.3,112.0,
101.7,47.7,42.9,26.7,26.0
HRMS (ESI, m/z): C20H17Br2N3O2 [M+H]+value of calculation: 491.18；Discovery value: 491；
ELEM.Anal.C20H17Br2N3O2 value of calculation: C, 48.91；H,3.49；N,8.56；Discovery value: C, 49.98；H,
3.91；N,8.56
The synthesis of embodiment 5:4-adenine butyl-9 (3,6-dibromo carbazole) (compound 4, R=adenine)
As shown in response diagram 1, following reactants is placed on the reaction bulb being furnished with condenser: 4-brombutyl-9 (3,6-dibromo carbazole)
(1.0 grams, 2.17 mMs), Anhydrous potassium carbonate powder (0.66 gram, 4.77 moles), anhydrous DMF (20
Milliliter) and adenine (0.44 gram, 3.255 mMs).Purge reactor with argon, and maintain this pressure in reaction whole process.
70 DEG C, in oil bath, under backflow, reactant mixture is stirred and heats 72 hours.Finally, filter reactant mixture, steam
Send out solvent, and wash solid several times with water.Solid is collected by filtration and with toluene recrystallization to obtain crystal (0.59 gram, 53%).
1H NMR (300Hz, DMSO, ppm): 8.43 (s, 2H), 8.11 (s, 1H), 8.04 (s, 1H), 7.55 (s, 2H), 7.21 (d, 4H),
4.36(t,2H),4.12(t,2H),1.78(m,2H),1.69(m,2H)
13C NMR (300Hz, DMSO, ppm): 156.7,153.2,150.3,141.3,139.5,129.4,124.1,123.6,
112.3,112.0,43.1,42.6,27.8,26.7
The synthesis of embodiment 6:4-octyl group-9 (3,6-dibromo carbazole) (compound 5)
As shown in response diagram 1, following reactants is placed on the reaction bulb being furnished with condenser: 3,6-bis-bromo-9H-carbazoles (6.5 grams,
0.02 mole), Anhydrous potassium carbonate powder (5.53 grams, 0.04 mole), anhydrous acetonitrile (80 milliliters) and 1-bromooctane
(1-bromooctane) (0.2 mole).Purge reactor with argon, and maintain this pressure in reaction whole process.At 95 DEG C, oil
In bath, under backflow, reactant mixture is stirred and heats 36 hours.Finally, filter reactant mixture, evaporate solvent, and
With the residual matter of petroleum ether recrystallization to obtain crystal (7 grams, 80%).
1H NMR(300MHz,DMSO,δ):8.07(d,2H；Ar H),7.51(dd,2H；Ar H),7.20(d,2H；Ar H),
4.15(t,2H；CH2),1.77(m,2H；CH2),1.20–1.30(m,10H；CH2),0.85(t,3H；CH3)
13C NMR(300MHz,CDCl3,δ):139.6,129.2,123.6,123.4,112.0,110.7,43.6,31.9,29.5,
29.3,29.0,27.4,22.9,14.3
Embodiment 7:1-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-1,2,3,4-tetrahydrochysene is phonetic
The synthesis of pyridine-2,4-diketone (PTC-U)
As shown in response diagram 2, by THF (6 milliliters), DMF (6 milliliters) and aqueous 2M K2CO3The deoxidation of (8 milliliters)
Mixture adds to 4-uracil butyl-9 (3,6-dibromo carbazole) (0.75 gram, 1.5 mMs), 4-butyl-N, N-double (4,4,5,5-tetra-
Methyl isophthalic acid, 3,2-dioxy boron penta ring-4-phenyl) Pd (the 0) (PPh of-aniline (0.82 gram, 1.5 mMs) and fresh preparation3)4(0.18
Gram) mixture.It is stirred vigorously 48-72 hour at 85-90 DEG C.After solution cools down, whole mixture is fallen lentamente
Enter the cold mixing liquid of methanol/deionized water (volume ratio 10/1).Polymer is collected by filtration and washs with methanol.Then in Soxhlet
Washing with acetone solid is used 24 hours, to remove oligomer (oligomer) and catalysis in instrument (Soxhlet apparatus)
The residual matter of agent.Before being dried under fine vacuum room temperature, by being re-dissolved in DMF and being further purified with ice methanol extraction afterwards
Title compound.
1H NMR(300MHz,DMSO-d6,δ):11.2(br,NH),8.54(br,ArCH),7.67(br,ArCH and CH),
7.06(br,ArCH),5.48(br,CH),4.40(br,CH2),3.63(br,CH2),2.52(br,CH2),1.73(br,CH2),
1.63(br,CH2),1.51(br,CH2),1.26(br,CH2),0.86(br,CH2)
Embodiment 8:9-[4-(3-{4-[(4-butyl phenyl) (phenyl) amino] phenyl }-9H-carbazole-9-base) butyl]-9H-purine-6-amine
(PTC-A) synthesis
As shown in response diagram 2, by THF (10 milliliters), DMF (6 milliliters) and aqueous 2M K2CO3The deoxidation mixing of (10 milliliters)
Thing adds to 4-adenine butyl-9 (3,6-dibromo carbazole) (0.186 gram, 0.36 mM), double (4,4,5, the 5-tetramethyls of 4-butyl-N, N-
-1,3,2-dioxy boron penta ring-4-phenyl)-aniline (0.2 gram, 0.36 mM) and fresh preparation Pd (0) (PPh3) 4 (0.041 gram,
0.036 mM) mixture.It is stirred vigorously mixture 48-72 hour at 85-90 DEG C.After solution cools down, by whole mixing
Thing pours the cold mixing liquid of methanol/deionized water (volume ratio 3/1) lentamente into.Polymer is collected by filtration and washs with methanol.Then
Washing with acetone solid is used 24 hours, to remove oligomer and the residual matter of catalyst in Soxhlet instrument.It is dried under fine vacuum room temperature
Before, it is further purified title compound by after being re-dissolved in DMF with ice methanol extraction.
1H NMR(300Hz,DMSO,ppm):8.56(br,ArCH),8.17(br,ArCH),7.73(br,ArCH),7.18(br,
ArCH&NH2),4.43(br,CH2),4.19(br,CH2),3.63(br,CH2),1.91(br,CH2),1.81(br,CH2),1.54
(br,CH2),1.29(br,CH2),0.89(br,CH3)
The synthesis of comparative example 1:N-(4-butyl phenyl)-4-(9-octyl group-9H-carbazole-3-base)-N-phenylaniline (PTC)
As shown in response diagram 2, by THF (10 milliliters), DMF (10 milliliters) with aqueous 2M K2CO3's (10 milliliters)
Oxygen-scavenging mixture adds to 4-octyl group-9 (3,6-dibromo carbazole) (0.753 gram, 1.5 mMs), 4-butyl-N, N-double (4,4,5,5-tetra-
Methyl isophthalic acid, 3,2-dioxy boron penta ring-4-phenyl) Pd (0) (PPh3) 4 of-aniline (0.82 gram, 1.5 mMs) and fresh preparation
The mixture of (0.041g, 0.036 mM).It is stirred vigorously mixture 48-72 hour at 85-90 DEG C.Treat that solution cools down
After, whole mixture is poured into lentamente the cold mixing liquid of methanol/deionized water (volume ratio 3/1).Be collected by filtration polymer and
Wash with methanol.Then in Soxhlet instrument, washing with acetone solid is used 24 hours, to remove oligomer and the residual matter of catalyst.
Before being dried under fine vacuum room temperature, it is further purified title compound by after being re-dissolved in DMF with ice methanol extraction.
1H NMR(300Hz,CDCl3,ppm):8.32(br,NH),7.68-7.11(br,ArCH),4.31(br,CH),2.55(br,
CH2),1.88(br,CH2),1.56(br,CH2),1.30(br,CH2),0.89(br,CH2)
Embodiment 9: gel permeation chromatography art (GPC) is measured
In order to compare the character of PTC, PTC-U and tri-kinds of different materials of PTC-A, first put down by by the quantity of three kinds of materials
Average molecular weight (number-average molecular weight, hereinafter referred to as Mn) controls between 5000 to 6500, with row
Except the impact caused because of its molecular weight, and then in following experiment, observe the impact that side chain is caused.By gpc measurement, obtain
Obtain the molecular weight (being relative to standard substance (polystyrene)) of PTC, PTC-U and tri-kinds of materials of PTC-A.Used herein
Eluant is THF or DMF.Result is as shown in table 1 below.
Following embodiment 10 is with embodiment 11, and PTC representative has PTC, PTC-U representative of 11 repetitives and has
PTC-U and PTC-A of 8 repetitives represents the PTC-A with 8 repetitives.
Embodiment 10: Fourier transform infrared spectroscopy art
In order to verify that three kinds of materials PTC, PTC-U are formed with the hydrogen bond of PTC-A, it is dissolved in respectively in DMF, casts
It is vacuum dried on KBr dish and at 70 DEG C.Use Varian UNITY INOVA500MHz and Varian UNITY
300MHz spectrogrph record 1H spectrum and 13C spectrum.The FTIR spectrum of three kinds of materials is as shown in Figure 3.PTC is 3100
In the range of 3700cm-1, do not show any peak value, represent that PTC does not have any N-H key.But, for PTC-U,
The free N-H stretching vibration (stretch vibration) of the peak value display uracil near 3400cm-1, and 3200
The bond N-H stretching vibration of the peak value display uracil near cm-1, represents that hydrogen bond is implicitly present in PTC-U.Equally
Ground, for PTC-A, the peak value near 3600cm-1 shows the free N-H stretching vibration of adenine, and 3180
To the bond N-H stretching vibration of the peak value display adenine between 3450cm-1, represent that hydrogen bond is implicitly present in PTC-A.
As shown in Figure 4, for PTC-U, the C=O stretching vibration of the peak value display uracil near 1750cm-1.
FTIR spectrum shows the difference between PTC, PTC-A and PTC-U together with NMR spectra, and confirms that product closes as expected
Become.
Embodiment 11: thermal property
In the application of OLED, element must have good thermal property and heat stability.Therefore, pyrolytic decomposition temperature (thermal
Decompose temperature, Td) and high glass transformation temperature (glass transition temperature, Tg) to good
It is required character for material.
In the present embodiment, use thermogravimetry device (Thermal Gravimetric Analyzer, TGA) and differential scanning calorimetry
Meter (Differential Scanning Calorimeter, DSC) obtains the thermal property of PTC, PTC-A and PTC-U.
As shown in Fig. 5 and table 1, it is seen that PTC, PTC-A and PTC-U all have the Tg higher than 350 DEG C, represent that it can
The most high temperature resistant without decomposing.
As shown in Fig. 6 and table 1, it is seen that because the physical crosslinking that hydrogen bond is caused, the Tg of PTC-U is higher than the Tg of PTC
20 DEG C, and because higher hydrogen bond, the Tg of PTC-A is higher than the Tg of PTC 40 DEG C, represents PTC-U Yu PTC-A tool
There is preferably heat stability.
Embodiment 12: solvent resistant ability
Carry out with polymers manufacturing element processing procedure the most in a wet process.Therefore, for being generally used for manufacturing the polymer of sandwich type element
For, solvent resistant ability is extremely important.The present embodiment confirms the solvent resistant ability of the present invention.
Respectively PTC, PTC-U and PTC-A are applied on quartz glass substrate with rotary coating (spin coating)
Form thin film.Before and after the surface using those thin film of toluene rinse, with UV-visible spectrophotometer (UV-vis
Spectrophotometer) those thin film are measured.As shown in Figure 7 A, PTC the thin film formed processes through toluene at thin film
After, light absorption value significantly reduces, and represents that part PTC is dissolved in toluene in flushing process and departs from substrate.The concentration of PTC reduces,
The absorbance causing its thin film also declines.But, as shown in Fig. 7 B and Fig. 7 C, respectively by PTC-A Yu PTC-U institute shape
The thin film become is before and after toluene processes, and light absorption value almost remains unchanged, and represents that the physical crosslinking caused by hydrogen bond makes polymerization
Thing is difficult to be dissolved in common organic solvents.Therefore, the thin film that PTC-U with PTC-A is formed will not be molten in wet method processing procedure
Agent is corroded.This kind of material makes wet process more efficiently and can extend the life-span of the element using this kind of material.
Embodiment 13: electricity hole transmission
Measure by cyclic voltammetry (cyclic voltammetry, CV) and to be formed by PTC, PTC-U and PTC-A respectively
Thin film, in the hope of its HOMO and lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, with
Lower abbreviation LUMO), as shown in table 2.
aEg (energy gap): obtain (measuring in film shape) with UV-vis spectrum
bEox, onset: using ferrocene is that standard substance obtain with cyclic voltammetry
cHOMO=-Eox, onset-4.8eV
dLUMO=HOMO+Eg
eExcitation wavelength (λ excites=335nm)
In order to compare electric hole transmittability, the structure of construction three kinds only electricity hole transmission (hole transport only): ITO/PTC
The thin film that the thin film formed/NPB/ aluminum (hereinafter referred to as Al), ITO/PTC-U are formed/NPB/Al, ITO/PTC-A institute shape
Thin film/the NPB/Al become, and measure its voltage-current curve.The work function of aluminum is-4.28eV, and the LUMO of NPB is-2.6
EV, causes the energy level difference having 1.68eV between the two.Because energy barrier is the biggest, it is sufficient to stop electric transmission, electronics cannot be from
The thin film that negative pole is formed via PTC, PTC-U or PTC-A transmits to positive pole.May determine that measured by the present embodiment
Electric current is from the transmission of electricity hole.
As shown in Figure 8, under identical voltage, the electric current density of the structure with the formed thin film of PTC-A or PTC-U is high,
Representing thin film formed compared to PTC, those thin film have preferably electricity hole and inject and transmittability.This is because adenine-
The hydrogen bond formed between adenine and between uracil-uracil makes electricity hole effectively from main chain transmission extremely another main chain neighbouring.
Therefore, the electric hole transmittability of the thin film that PTC-U and PTC-A is formed respectively is improved.By PTC-U or PTC-A institute shape
The thin film become, electricity hole can be efficiently transmitted to luminescent layer, and make device luminous, rather than dissipate in the form of heat.
Embodiment 14: electricity hole is injected
According to HOMO value, it is thus achieved that the energy diagram of Fig. 9.As shown in Figure 9, it is known that respectively by PTC-A Yu PTC-U institute shape
The HOMO value of thin film become is close with the work function of ito glass, and the thin film that formed compared to PTC and ito glass
Energy level difference be the energy level difference between the thin film that formed of 0.3eV, PTC-A and ito glass, and the thin film that PTC-U is formed
And the energy level difference between ito glass is only respectively 0.23eV and 0.26eV, represent that PTC-A and PTC-U helps electricity hole and inject.
Embodiment 15: element efficiency
Construction mensuration have thin film/NPB/ ginseng-(8-hydroxyquinoline) aluminum that three kinds of element: ITO/PTC of following structure are formed
(tris-(8-hydroxyquinoline) aluminum, hereinafter referred to as Alq3)/lithium fluoride (hereinafter referred to as LiF)/Al, ITO/PTC-A
Thin film/NPB/Alq3/LiF/Al that thin film/NPB/Alq3/LiF/Al and ITO/PTC-U formed is formed is the thinnest
Film be rotary coating on the surface of ito glass, other layers are then with evaporation-sedimentation (evaporation deposition) shape
Become.
As shown in Figure 10, under identical voltage, compared to having the element of the thin film that PTC is formed, it is respectively provided with PTC-A
The element of the thin film that the thin film formed and PTC-U are formed has higher electric current density, represents PTC-A and PTC-U
There is preferably electricity hole inject and electricity hole transmittability.
As shown in figure 11, the luminous effect of the element of the thin film that the thin film that PTC-A formed is formed it is respectively provided with PTC-U
The luminous efficacy of the element can relatively with the formed thin film of PTC is preferred.This is because the electric hole of PTC-A Yu PTC-U is injected
Excellent with electricity hole transmittability to have more electricity hole to be combined with electronics, so that sending more light.
Embodiment 16:OLED device usefulness
The present invention can be used in OLED device, therefore according to the processing procedure shown in Figure 12, according to ITO/ thin film (such as table 3 institute
Show) three kinds of devices of structure construction of/NPB/Alq3/LiF/Al.By external quantum efficiency (EQE, the transmitting photon of apparatus surface
The ratio of number is injected in number and electricity hole), luminous efficiency (LE) and power efficiency (PE) assess three kinds of OLED device, use
Solve the luminous efficacy of those OLED device.As illustrated in figs. 13-15, it is known that be respectively provided with PTC-A with PTC-U and formed thin
EQE, LE of the OLED device of film and PE is all better than EQE, the LE with the OLED device of the formed thin film of PTC
With PE, this is because the electric hole being respectively provided with the OLED device of the formed thin film of PTC-A and the formed thin film of PTC-U is noted
Enter and improve with electricity hole transmittability.
The electroluminescent usefulness of table 3:OLED device
Embodiment 17: there is the element efficiency of the thin film that PTC-U/PTC-A is formed
Manufacture the element with the thin film (respectively with the ratio of 1:4 and 1:10) that PTC-U/PTC-A is formed, go forward side by side
One step construction has the OLED device of said elements.As shown in Figure 16 A-16D, it is known that compared to having only by PTC-A institute
Form the element of thin film, there is the element of the formed thin film of PTC-U/PTC-A (respectively with the ratio of 1:4 and 1:10)
Efficiency of element further improve.
The present invention is described by exemplary preferred embodiment.But, it should be understood that the scope of the present invention is not limited in disclosing
Specific embodiment.On the contrary, the scope of the present invention is intended to include various modification and similar configuration.Therefore, apply for a patent
The category of scope should give the most extensively to explain, with comprise different this type of modification and similar configuration.
Claims (10)
1. a chemical formula i compound,
Wherein, A, B and C are repetitive；
A is the triphenylamine being optionally substituted, and B is the carbazole being optionally substituted, and the substituent group of A Yu B is butyl；
C is adenine；And
N is the integer equal to or more than 1.
2. a conducting film, comprises chemical formula i compound described in claim 1.
3. a carrier transportation layer, comprises the chemical formula i compound described in claim 1.
Carrier transportation layer the most according to claim 3, wherein, described carrier transportation layer is electricity hole transport layer.
5. an electronic installation, comprises the conducting film described in claim 2.
6. an electronic installation, comprises the carrier transportation layer described in claim 3.
Electronic installation the most according to claim 6, wherein, described electronic installation is el light emitting device or transistor.
Electronic installation the most according to claim 7, wherein, described el light emitting device is light emitting diode.
9. a solaode, comprises carrier transportation layer as claimed in claim 3.
10. an optical detector, comprises carrier transportation layer as claimed in claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210301768.3A CN103626966B (en) | 2012-08-23 | It is used in the compounds of carrier transportation, the element of application compounds and electronic installation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210301768.3A CN103626966B (en) | 2012-08-23 | It is used in the compounds of carrier transportation, the element of application compounds and electronic installation |
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| Publication Number | Publication Date |
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| CN103626966B true CN103626966B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376655B1 (en) * | 1995-06-02 | 2002-04-23 | Riso National Laboratory | Physically functional materials |
| CN100414734C (en) * | 2001-11-22 | 2008-08-27 | 夏普株式会社 | Polymer material having carrier transport property, and organic thin film element, electronic device, and conductor line which use same |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376655B1 (en) * | 1995-06-02 | 2002-04-23 | Riso National Laboratory | Physically functional materials |
| CN100414734C (en) * | 2001-11-22 | 2008-08-27 | 夏普株式会社 | Polymer material having carrier transport property, and organic thin film element, electronic device, and conductor line which use same |
Non-Patent Citations (3)
| Title |
|---|
| "A New Supramolecular Hole Injection/Transport Material on Conducting Polymer for Application in Light-Emitting Diodes";YuLin Chu等;《Advanced Materials》;20120410;第24卷(第14期);第1894-1898页 * |
| "Biocomplementary Interaction Behavior in DNA-Like and RNA-Like Polymers";CHIH-CHIA CHENG等;《Journal of Polymer Science：Part A：Polymer Chemistry》;20091022;第47卷(第23期);第6388-6395页 * |
| "Hierarchical structures formed from self-complementary sextuple hydrogen-bonding arrays";Chih-Chia Cheng等;《RSC Advances》;20110929;第1卷;第1190-1194页 * |
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