CN102336644A - Alkyl substituted acetate and application of alkyl substituted acetate in organic electroluminescent device - Google Patents

Alkyl substituted acetate and application of alkyl substituted acetate in organic electroluminescent device Download PDF

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CN102336644A
CN102336644A CN2011102106420A CN201110210642A CN102336644A CN 102336644 A CN102336644 A CN 102336644A CN 2011102106420 A CN2011102106420 A CN 2011102106420A CN 201110210642 A CN201110210642 A CN 201110210642A CN 102336644 A CN102336644 A CN 102336644A
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alkyl substituted
acetic acid
acid salt
substituted acetic
substituted acetate
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王磊
上官荣刚
穆广园
陈长清
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Wuhan Seung Cheng Venture Capital Co., Ltd.
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Huazhong University of Science and Technology
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Abstract

The invention relates to alkyl substituted acetate and application of alkyl substituted acetate in an organic electroluminescent device. According to the invention, alkyl is based on (CH3)nHmCCOO- as a main structure (wherein n is 1,2 or 3, and m is 3-n) and can be combined with an alkali metal ion Li<+1> or Na<+1> or Rb<+1> or Cs<+1> so as to form alkyl substituted acetate. Alkyl substituted acetate provided by the invention has low sublimation temperature and high decomposition temperature, can be used as a functional layer, having electron conduction capacity, of the organic electroluminescent device; and by using alkyl substituted acetate in the invention, the electron injection capacity can be effectively improved, the switch-on voltage and operating voltage of the device are reduced and the efficiency of the device is promoted, as compared with the traditional electron injection material such as LiF, CsF, Li2CO3 or Cs2CO3.

Description

Alkyl substituted acetic acid salt and the application in organic electroluminescence device thereof
Technical field
The invention belongs to photovaltaic material applicating technology field, be specifically related to alkyl substituted acetic acid salt and the application in organic electroluminescent device OLED (comprising polymer electroluminescent device, down together) thereof.
Background technology
The organic electroluminescent phenomenon is found in 1963 the earliest; Pu Bai (Pope) professor adds above 100V voltage on the anthracene crystal, observed electro optical phenomenon (J.Chem.Phys., 1963; 38; 2024), the still too high driving voltage and the luminous efficiency of extreme difference and life-span did not cause people's attention at that time far away from inorganic electroluminescence device.1987, Deng Qingyun (C.W.Tang) doctor proposed to prepare with vacuum vapour deposition the OLED device (Appl.Phys.Lett., 1987,52,913) of bilayer film first, and its external quantum efficiency under less than the voltage of 10V has reached 1%; Nineteen ninety, Jackie Burroughs people such as (Burroughes) reported polymer LED (Nature, 1990,347,539), and organic electroluminescent research has got into a brand-new stage since then.Development through two more than ten years; Organic Light Emitting Diode has with it that saturation ratio height, brightness are high, response is fast, WV is low and can realize advantage such as flexible demonstration and be applied to (Journal of the American Chemical Society in the FPD by increasing; 2002; 124,11576; Journal of Display Technology, 2005,1,90; Molecular Electronics and Bioelectronics.2007,18,25).At lighting field, white light OLED development in recent years rapidly, efficient has has met or exceeded inorganic LED (Nature, 2009,459,234), and it is that face is luminous, homogeneity also more and more receives people's attention.
Because the electronic mobility of organic materials is high far away from its hole mobility usually; And high electron hole balance ratio and high recombination rate are to realize high efficiency electroluminescent primary factor; Therefore; The organic materials of exploitation high electron mobility reaches electronics injecting material efficiently, is the important channel of improving carrier balance, realizing high efficiency light-emitting.
The lumo energy of organic electronic transport material between 2.5～3.0eV, realized the good electron injection mostly, and the metal (like alkalies and alkaline earth) that just needs to use low work content is as negative electrode.But the metal pair moisture of so low work content and oxygen divide very responsive, and is very unstable in atmosphere.So metallic aluminium is selected for use the negative electrode as OLED by everybody.But the work content of aluminium has reached 4.2eV, injects to electronics and has caused bigger energy barrier.1997; People's reported first such as Deng Qingyun use negative electrode (Appl.Phys.Lett., 1997,70 of the bilayer structure of Al/LiF as OLED; 152); Compare with single Al negative electrode, the existence of LiF thin layer makes the work content of electrode obtain significantly reducing, and has greatly improved electron injection efficiency.Since then, Al/LiF bilayer electrode becomes the most frequently used electrode structure.
After LiF, many other alkali metal cpds are in the news as the electronics injecting material in succession.CsF (App.Phys.Lett., 1998,73,1185) for example, MgF 2(Synth.Met., 1997,91,125), NaF (Optics Express, 2010,18,102), NaCl (Appl.Phys.Lett., 2005,86,113503), CsCl (Appl.Phys.Lett., 2005,86,213502), Li 3N (J.Phys.Chem.C., 2009,113,13386), CsN 3(Adv.Funct.Mater., 2010,20,1), alkali metal acetate CH 3COOLi, CH 3COONa, CH 3COOK, CH 3COORb, CH 3COOCs (Materials Science and Engineering, 2001, B85,140), Li 2CO 3(Synth.Met., 2010,160,1749), Cs 2CO 3(Appl.Phys.Lett., 2007,90,012119; Adv.Funct.Mater., 2007,17,1966), 8-phenopyridine lithium Liq (Appl.Phys.Lett.; 2010,97,223302), 8-phenopyridine sodium Naq (J.Phys.Chem.C.; 2010,115,2433), 8-phenopyridine caesium Csq (Appl.Phys.Lett.; 2008,93,183302), 8-phenopyridine bait Erq 3(J.Phys.D:Appl.Phys., 2008,41,085108) etc.Yet, because these an alkali metal salt synthetic complicacy, or the unstable under atmospheric environment, never shake the dominant position of LiF as the electronics injecting material.
But the sublimation temperature of LiF too high (717 ℃) needs superpower thermal source ability vapor deposition, injects and the also relatively poor (Appl.Phys.Lett. of transport property with inert material (for example MADN) collocation electronics; 2010; 97,223302), limited selection to electron transport material.
Summary of the invention
The purpose of this invention is to provide a kind of alkyl substituted acetic acid salt, have lower sublimation temperature and higher decomposition temperature, stable under atmospheric environment; The raw material simple cheap is easy to synthesize, and is easy to use; The electronics injectability is good, and is wide to the range of choice of electron transport material.
Another object of the present invention provides such application of alkyl substituted acetic acid salt in organic electroluminescence device; It can effectively promote electronics to inject; Reduce device cut-in voltage and operating voltage, boost device efficient realizes high efficiency organic electroluminescence device.
Realize that technical scheme of the present invention is:
This alkyl substituted acetic acid salt provided by the invention has as shown in the formula structure shown in the I:
Figure BDA0000078506380000021
Wherein, R 1=H or CH 3, R 2=H or CH 3, R 3=Li or Na or K or Rb or Cs.
Technique effect of the present invention is embodied in:
Alkyl substituted acetic acid salt involved in the present invention is white powder, and is stable under atmospheric environment; Have lower sublimation temperature (all between 170～220 ℃, example: the sublimation temperature of compound 15 is 180 ℃) and higher decomposition temperature (all reach 400 ℃ even higher, example: the decomposition temperature of compound 15 is 424 ℃); The raw material simple cheap is easy to synthesize, (low sublimation temperature is also low to the power requirement of thermal source) easy to use; The electronics injectability is good; Wide and some chemically inert materials (for example MADN) cooperation of range of choice to electron transport material also has good electronics and injects and laser propagation effect.Be applied in the organic electroluminescence device, can effectively promote electronics to inject, reduce device cut-in voltage and operating voltage, boost device efficient.Such alkyl substituted acetic acid salt will be expected to become the new electronics injecting material that substitutes LiF.
Description of drawings
Fig. 1. with The compounds of this invention 15 is the structural representation that the electronics injecting material prepares organic electroluminescence fluorescence radiation device;
Fig. 2. with The compounds of this invention 12 is the structural representation that the electronics injecting material prepares organic electro-phosphorescent luminescent device;
Fig. 3. advance electron transport material with The compounds of this invention 2 doping, cause the adulterated electron transfer layer of n type, the structural representation of preparation organic electroluminescence device;
Fig. 4. separately as one deck intermediate connecting layer, prepare the structural representation of tandem organic electroluminescence device with The compounds of this invention 8;
Fig. 5. advance other material with The compounds of this invention 4 doping, as intermediate connecting layer, the structural representation of preparation tandem organic electroluminescence device;
Fig. 6. the current density of device-efficiency characteristic graphic representation and voltage-to-current density-luminosity response figure among the embodiment 1.
Embodiment
Alkyl substituted acetic acid salt involved in the present invention comprises referring to the said compound of table 1:
Structural formula of compound, molecular formula, English name and Chinese name that table 1 is involved in the present invention
Figure BDA0000078506380000041
Figure BDA0000078506380000051
Compound provided by the invention is made by the acid-base neutralisation reaction, and concrete grammar is following:
With propionic acid (CH 3CH 2COOH), isopropylformic acid ((CH 3) 2CHCOOH), trimethylacetic acid ((CH 3) 3CCOOH) respectively with Lithium Hydroxide MonoHydrate (LiOH), sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH) stirring at room 3～5 hours in the aqueous solution, the aqueous solution is removed in decompression, can obtain above-claimed cpd.
Alkyl substituted acetic acid salt involved in the present invention can be used as following functional layer, is applied among the organic electroluminescence device:
One of which: be used between negative electrode and the electron transfer layer, as electron injecting layer;
Its two: as n type doping agent, mix within the electron transport material, cause the adulterated electron transfer layer of n;
Its three: the intermediate connecting layer that is used as the tandem organic electroluminescence device separately;
Its four: mix in other organic materialss, as the intermediate connecting layer of tandem organic electroluminescence device.
For better explanation the present invention, provide 5 embodiment below.
Embodiment 1 provides (CH 3) 3CCOOCs (compound 15) is used between negative electrode and the electron transfer layer, as the fluorescent device structure of electron injecting layer.Wherein, electron transfer layer has used the stronger Alq of chemically reactive respectively 3With chemically inert MADN material.
Embodiment 2 provides (CH 3) 3CCOORb (compound 12) is used between negative electrode and the electron transfer layer, as the phosphorescence device architecture of electron injecting layer.
Embodiment 3 provides (CH 3) 2Bphen is advanced in CHCOOLi (compound 2) doping, causes the device architecture of the adulterated electron transfer layer of n type.
Embodiment 4 provides (CH 3) 2CHCOOK (compound 8) is separately as one deck, with NPB doping WO 3Together, as the device architecture of the intermediate connecting layer of middle tandem OLED.
Embodiment 5 provides CH 3CH 2BCP is advanced in COONa (compound 4) doping, with NPB doping MoO 3Together, as the device architecture of the intermediate connecting layer of middle tandem OLED.
Embodiment specifies as follows:
Embodiment 1: with (CH 3) 3CCOOCs prepares fluorescence OLED device as electron injecting layer.
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then in baking oven 120 ℃ dry 2 hours down.Again ito glass is put into the uv ozone plasma treatment that plasma cleaner carried out 5 minutes, be sent to afterwards in the vacuum chamber, 2～5 * 10 -4Under the vacuum tightness of Pa, the method through vacuum evaporation is with (CH 3) 3Material prepn becomes device (referring to Fig. 1) to CCOOCs as electron injecting layer.
Embodiment 2: with (CH 3) 3CCOORb prepares phosphorescent OLED device as electron injecting layer.
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then in baking oven 120 ℃ dry 2 hours down.Again ito glass is put into the uv ozone plasma treatment that plasma cleaner carried out 5 minutes, be sent to afterwards in the vacuum chamber, 2～5 * 10 -4Under the vacuum tightness of Pa, the method through vacuum evaporation is with (CH 3) 3Material prepn becomes device (referring to Fig. 2) to CCOORb as electron injecting layer.
Embodiment 3: with (CH 3) 2The CHCOOLi into Bphen that mixes causes the adulterated electron transfer layer of n type, makes the OLED device.
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then in baking oven 120 ℃ dry 2 hours down.Again ito glass is put into the uv ozone plasma treatment that plasma cleaner carried out 5 minutes, be sent to afterwards in the vacuum chamber, 2～5 * 10 -4Under the vacuum tightness of Pa, the method through vacuum evaporation is with (CH 3) 3CCOOCs and Bphen be vapor deposition altogether, causes the adulterated electron transfer layer of n type, preparation p-i-n type OLED device (referring to Fig. 3).
Embodiment 4: with (CH 3) 2CHCOOK makes tandem OLED device separately as one deck intermediate connecting layer.
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then in baking oven 120 ℃ dry 2 hours down.Again ito glass is put into the uv ozone plasma treatment that plasma cleaner carried out 5 minutes, be sent to afterwards in the vacuum chamber, 2～5 * 10 -4Under the vacuum tightness of Pa, the method through vacuum evaporation is with (CH 3) 2CHCOOK is prepared into tandem device (referring to Fig. 4) as one deck intermediate connecting layer.
Embodiment 5: with CH 3CH 2COONa mixes into, and BCP makes tandem OLED device as intermediate connecting layer.
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then in baking oven 120 ℃ dry 2 hours down.Again ito glass is put into the uv ozone plasma treatment that plasma cleaner carried out 5 minutes, be sent to afterwards in the vacuum chamber, 2～5 * 10 -4Under the vacuum tightness of Pa, the method through vacuum evaporation is with (CH 3) 3CCOONa and BCP be vapor deposition altogether, as one of intermediate connecting layer, is prepared into tandem device (referring to Fig. 5).
The device architecture of embodiment 1-5 is seen table 2, and wherein, device 1,3 is a comparative device.
Table 2 is applied among the OLED with compound provided by the invention, the device architecture (unit: nm) of preparation
Figure BDA0000078506380000071
The device performance parameter is seen Fig. 6 and table 3 among the embodiment 1.
The device of table 3 embodiment 1 is at 20mA/cm 2Performance data under the current density
Device Operating voltage (V) Cut-in voltage (V) Brightness (cd/m 2) Chromaticity coordinates Current efficiency (cd/A) Power efficiency (lm/W)
1 ?8.62 ?2.55 3717 (0.32，0.64) 18.54 6.75
2 ?7.71 ?2.55 3845 (0.29，0.65) 19.25 7.84
3 ?9.20 ?2.70 3252 (0.30，0.65) 16.21 5.53
4 ?8.27 ?2.52 3676 (0.29，0.66) 18.38 6.98
Visible from Fig. 6 and table 3, use Alq no matter be 3Or as electron transfer layer, use compound 15 ((CH involved in the present invention with MADN 3) 3CCOOCs) as electron injecting layer, to compare as electron injecting layer with using traditional LiF, device efficiency is improved, and when particularly using MADN as electron transfer layer, device efficiency promotes significantly.Simultaneously, use (CH 3) 3CCOOCs compares as electron injecting layer with using traditional LiF as electron injecting layer, and the cut-in voltage of device and the operating voltage under the same current density have all had reduction.This benefits for boost device stability, increase device lifetime.

Claims (6)

1. alkyl substituted acetic acid salt, its structural formula does
Figure 584648DEST_PATH_IMAGE001
Wherein, R 1=H or CH 3, R 2=H or CH 3, R 3=Li or Na or K or Rb or Cs.
2. the application of the described alkyl substituted acetic acid of claim 1 salt in organic electroluminescence device is characterized in that, alkyl substituted acetic acid salt is used to prepare the functional layer with electronic conduction ability of organic electroluminescence device.
3. alkyl substituted acetic acid salt according to claim 2 is characterized in that, alkyl substituted acetic acid salt is applied between negative electrode and the electron transfer layer as electron injecting layer.
4. alkyl substituted acetic acid salt according to claim 2 is characterized in that, alkyl substituted acetic acid salt is mixed as n type doping agent into prepares the adulterated electron transfer layer of n within the electron transport material.
5. alkyl substituted acetic acid salt according to claim 2 is characterized in that, with the intermediate connecting layer of alkyl substituted acetic acid salt as the tandem organic electroluminescence device.
6. alkyl substituted acetic acid salt according to claim 5 is characterized in that, alkyl substituted acetic acid salt dopping is advanced behind other organic materialss the intermediate connecting layer as the tandem organic electroluminescence device again.
CN2011102106420A 2011-07-26 2011-07-26 Alkyl substituted acetate and application of alkyl substituted acetate in organic electroluminescent device Pending CN102336644A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104218185A (en) * 2013-05-30 2014-12-17 海洋王照明科技股份有限公司 Organic light-emitting device and preparation method thereof
CN108368058A (en) * 2015-12-18 2018-08-03 剑桥显示技术有限公司 Dopant, charge transfer salt and organic electronic device
CN110875436A (en) * 2018-09-04 2020-03-10 湖北尚赛光电材料有限公司 Flexible OLED display device and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1824735A (en) * 2006-04-05 2006-08-30 贵州大学 Preparation of curcas biological diesel oil by solid phase catalytic method
CN101070369A (en) * 2006-05-04 2007-11-14 气体产品与化学公司 New trimer catalyst additives for improving foam processability
CN101481383A (en) * 2008-12-31 2009-07-15 浙江奥默生物医药有限公司 Cefdinir acid type double salt compound and preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1824735A (en) * 2006-04-05 2006-08-30 贵州大学 Preparation of curcas biological diesel oil by solid phase catalytic method
CN101070369A (en) * 2006-05-04 2007-11-14 气体产品与化学公司 New trimer catalyst additives for improving foam processability
CN101481383A (en) * 2008-12-31 2009-07-15 浙江奥默生物医药有限公司 Cefdinir acid type double salt compound and preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.GANZORIG ET AL.: "Alkali metal acetates as effective electron injection layers for organic electroluminescent devices", 《MATERIALS SCIENCE AND ENGINEERING B》, vol. 85, no. 23, 22 August 2001 (2001-08-22), pages 140 - 143, XP004255449, DOI: doi:10.1016/S0921-5107(01)00547-5 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104218185A (en) * 2013-05-30 2014-12-17 海洋王照明科技股份有限公司 Organic light-emitting device and preparation method thereof
CN108368058A (en) * 2015-12-18 2018-08-03 剑桥显示技术有限公司 Dopant, charge transfer salt and organic electronic device
CN108368058B (en) * 2015-12-18 2022-05-10 剑桥显示技术有限公司 Dopant, charge transfer salt and organic electronic device
CN110875436A (en) * 2018-09-04 2020-03-10 湖北尚赛光电材料有限公司 Flexible OLED display device and preparation method thereof

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