CN104292261A - Phosphine sulfur group electron transport material, preparation method and application thereof - Google Patents
Phosphine sulfur group electron transport material, preparation method and application thereof Download PDFInfo
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- CN104292261A CN104292261A CN201310305809.0A CN201310305809A CN104292261A CN 104292261 A CN104292261 A CN 104292261A CN 201310305809 A CN201310305809 A CN 201310305809A CN 104292261 A CN104292261 A CN 104292261A
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- electron transport
- transport material
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- sulfenyl
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- PVGOPEUJUVXCGN-UHFFFAOYSA-N CC1(C)OB(c(cc2)ccc2-c2nc(-c3ccccc3)nc(-c3ccccc3)n2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)ccc2-c2nc(-c3ccccc3)nc(-c3ccccc3)n2)OC1(C)C PVGOPEUJUVXCGN-UHFFFAOYSA-N 0.000 description 1
Abstract
Belonging to the field of organic semiconductors, the invention discloses a phosphine sulfur group electron transport material, a preparation method and application thereof. The structural formula of the host material is shown as the specification. In the phosphine sulfur group electron transport material provided by the invention, a tetrahedral structure diphenyl phosphine sulfur group contains electron-withdrawing P=S, and is a good electron transport unit; and triazine also has excellent electron transport performance. Thus, the electron transport material has high electron mobility and good thermal stability, and can be used as an electron transport layer in organic electroluminescent devices to improve the luminous efficiency.
Description
Technical field
The present invention relates to organic semiconductor material field, particularly relate to a kind of phosphine sulfenyl electron transport material and its preparation method and application.
Background technology
Organic electroluminescence device has light, thin, luminous, low consumpting power, does not need light source, without angle limitations, high reaction rate and can be produced on the good characteristics such as flexible base plate, be regarded as the rising star of flat-panel screens and flexible display.The carrier mobility of traditional electron transport material is the thousandth of hole mobile material, and thermostability is not good, therefore, often cause the problems such as the not good or component life of luminous efficiency is long, represent according to pertinent literature, shared by electron transport material, charge consumption ratio reaches 35.9%, is the consumption (39.8%) being only second to luminescent layer, and the electron transport material therefore developing high carrier is now the emphasis of OLED ability developing material now.
Alq
3because of the film-forming properties had, therefore, be the host emitter of electron transport material conventional at present, but have some carrier mobilities and T successively
ghigher than Alq
3material occur, as metal (Be, Al, Zn) complex compound, 1,2, the derivative of 4-phosphine sulphur (TAZ), fluorochemicals and silicon-containing compound etc., but these known material carrier mobilities are still not good, and there is not thermostability good or be used in the problems such as generation current density on device is low, therefore, developing new electron transport material is a very important problem.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is the phosphine sulfenyl electron transport material providing a kind of electronic mobility high.
Technical scheme of the present invention is as follows:
A kind of phosphine sulfenyl electron transport material provided by the invention, its structural formula is as follows:
i.e. 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines;
Another object of the embodiment of the present invention is the preparation method providing a kind of phosphine sulfenyl electron transport material, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
A:
i.e. (4-bromophenyl) diphenylphosphine sulphur;
B:
i.e. 2-(4-tetramethyl ethylene ketone boric acid ester phenyl)-4,6-phenylbenzene-1,3,5-triazines;
Under oxygen-free environment (oxygen-free environment of at least one gas composition in preferred argon gas, nitrogen), be after dissolving during the compd A of 1:2 ~ 2.4 and B are added into containing catalyzer and alkaline solution organic solvent by mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours under 70 ~ 130 ° of C, polyreaction is stopped after cooling, through separating-purifying reaction solution, obtain the described phosphine sulfenyl electron transport material of following structural formula:
Wherein, described catalyzer is described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; Or
Palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture;
The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
Described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and in described alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
In a preferred embodiment, organic solvent is selected from solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
In a preferred embodiment, Suzuki coupling reaction temperature is at 90 ~ 120 DEG C, the reaction times is 24 ~ 36 hours.
In a preferred embodiment, separating-purifying reaction solution comprises step:
After reaction stops, methyl alcohol precipitating is added in reaction solution, methyl alcohol and normal hexane extracting is used successively after being filtered by apparatus,Soxhlet's, then be that solvent extraction is to colourless with chloroform, collect chloroformic solution and be spin-dried for and obtain powder, powder after collection under vacuo after the dry 24h of 50 ° of C, obtains described phosphine sulfenyl electron transport material again.
The present invention also provides the application of a kind of phosphine sulfenyl electron transport material described above in organic electroluminescence device field.
In phosphine sulfenyl electron transport material of the present invention, the diphenyl phosphine methylthio group of tetrahedral structure contains electrophilic P=S, is a good electric transmission unit; Triazine also has excellent electronic transmission performance; Therefore higher, the better heat stability of this material electronics mobility, is used for improving luminous efficiency in device as electron transfer layer.
The preparation method of above-mentioned phosphine sulfenyl electron transport material, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And obtained polymeric material constructions is novel, solubility property is good, and film forming properties is excellent, is applicable to organic electroluminescence device.This material has higher electroluminescent efficiency.
Accompanying drawing explanation
Fig. 1 is the thermogravimetic analysis (TGA) figure of the phosphine sulfenyl electron transport material that embodiment 1 obtains;
Fig. 2 is the structural representation of the organic electroluminescence device that embodiment 5 obtains.
Embodiment
In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein compd A, compd B commercially obtain.
Embodiment 1:
The phosphine sulfenyl electron transport material of the present embodiment, i.e. 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines, its preparation process is as follows:
Under argon shield, by (4-bromophenyl) diphenylphosphine sulphur (75mg, 0.2mmol), 2-(4-tetramethyl ethylene ketone boric acid ester phenyl)-4,6-phenylbenzene-1,3,5-triazine (87mg, 0.2mmol) adds in the flask filling 10ml toluene solvant, by salt of wormwood (2mL after fully dissolving, 2mol/L) solution joins in flask, vacuumize deoxygenation and be filled with argon gas, then adding bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol); Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 24h.Subsequently, after cooling, stop polyreaction, drip in flask in 50ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain white powder, be pumped through under vacuum pump and obtain product night, productive rate 85%.Mass spectrum: m/z601.2(M
++ 1); Ultimate analysis (%) C
39h
28n
3pS: theoretical value: C77.85, H4.69, N6.98, P5.15, S5.33; Measured value: C77.91, H4.74, N7.02, P5.18, S5.27.
Fig. 1 is the thermogravimetic analysis (TGA) figure of the phosphine sulfenyl electron transport material that embodiment 1 obtains; Wherein, thermogravimetic analysis (TGA) is completed by the measurement of Perkin-Elmer Series7 Thermo System, and all measurements all complete in atmosphere at room temperature.As shown in Figure 1, the thermal weight loss temperature (T of phosphine sulfenyl electron transport material 5%
d) be 382 DEG C.
Embodiment 2:
The phosphine sulfenyl electron transport material of the present embodiment, i.e. 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines, its preparation process is as follows:
Under nitrogen and argon gas gas mixture are protected; by (4-bromophenyl) diphenylphosphine sulphur (112mg; 0.3mmol), 2-(4-tetramethyl ethylene ketone boric acid ester phenyl)-4; 6-phenylbenzene-1; 3; 5-triazine (144mg; 0.33mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution again.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Suzuki coupling reaction 96h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain white solid, after collection, obtain product after 50 DEG C of dry 24h under vacuo.Productive rate is 84%.
Embodiment 3:
The phosphine sulfenyl electron transport material of the present embodiment, i.e. 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines, its preparation process is as follows:
Under nitrogen protection, by (4-bromophenyl) diphenylphosphine sulphur (112mg, 0.3mmol), 2-(4-tetramethyl ethylene ketone boric acid ester phenyl)-4,6-phenylbenzene-1,3,5-triazine (157mg, 0.36mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF filling 12mL, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution, after in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain white powder, after collection under vacuo after 50 DEG C of dry 24h, be P3 product, productive rate 80%.
Embodiment 4:
The phosphine sulfenyl electron transport material of the present embodiment, i.e. 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines, its preparation process is as follows:
Under nitrogen protection; by (4-bromophenyl) diphenylphosphine sulphur (112mg; 0.3mmol), 2-(4-tetramethyl ethylene ketone boric acid ester phenyl)-4; 6-phenylbenzene-1; 3; 5-phosphine sulphur (157mg; 0.36mmol), three or two argon benzyl acetone two palladium (9mg; 0.009mmol) with 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins in the flask of the DMF filling 12mL; sodium bicarbonate (3mL, 2mol/L) solution is added after abundant dissolving.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 36h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain white powder, after collection under vacuo after 50 DEG C of dry 24h, obtain product, productive rate is 82%.
Embodiment 5:
The present embodiment is organic electroluminescence device, and its electron transfer layer adopts embodiment 1 to 4 arbitrary obtained 2-(4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines (TRz).
As shown in Figure 2, this organic electroluminescence device comprises the structure stacked gradually: conductive substrate layer 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, cathode layer 7; Wherein, the material of each functional layer and thickness as follows:
Conductive substrate layer 1 comprises substrate, and is deposited on the anode layer of substrate surface; In the present embodiment, the material of substrate is preferably glass, and the material of anode layer is indium tin oxide (ITO), and itself and glass combine, and is called for short ito glass, and conventional ITO replaces; The thickness of ITO is 150nm;
The material of hole injection layer 2 is CuPc (CuPc); The thickness of hole injection layer 2 is 30nm;
The material of hole transmission layer 3 is 4,4 '-bis-[N-(naphthyl)-N-phenyl-amino] biphenyl (NPB); After hole transmission layer 3 is 40nm;
The material of luminescent layer 4 is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic close iridium (III) (FIrpic) according to 15% mass percent be doped to the dopant mixture of composition in 9,9'-(1,3-phenyl) two-9H-carbazole (mCP); Be expressed as mCP:FIrpic; The thickness of luminescent layer 4 is 20nm;
The material of electron transfer layer 5 is the arbitrary obtained 2-of embodiment 1 to 4 (4'-(diphenylphosphine sulfenyl) xenyl-4-base)-4,6-phenylbenzene-1,3,5-triazines (TRz); The thickness of electron transfer layer 5 is 30nm;
The material of electron injecting layer 6 is LiF, and the thickness of electron injecting layer 6 is 1nm;
The material of cathode layer 7 is aluminium, and the thickness of cathode layer 7 is 100nm.
The structure of this organic electroluminescence device can be expressed as:
Ito glass/CuPc/NPB/mCP:FIrpic/TRz/LiF/Al; Wherein, brace "/" represents laminate structure.
The concrete grammar that this organic electroluminescence device makes is:
Evaporation CuPc successively on conductive glass (ITO) substrate through cleaning, NPB, mCP:FIrpic, TRz, LiF, Al, obtained organic electroluminescence device.
In room temperature, air, adopt Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correcting silicon photoelectric diode, electroluminescent spectrum, by French JY company SPEX CCD3000 spectrometer measurement, carries out current versus brightness-voltage characteristic to the organic electroluminescence device of preparation and measures; Test result shows, and this organic electroluminescence device is 3.6V at trigger voltage, at 1000cd/m
2brightness under, luminous efficiency is 8.1lm/W.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a phosphine sulfenyl electron transport material, is characterized in that, its structural formula is as follows:
2. a preparation method for phosphine sulfenyl electron transport material, is characterized in that, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
A：
B：
Under oxygen-free environment, be dissolve mol ratio during the compd A of 1:2 ~ 2.4 and B are added into containing catalyzer and alkaline solution organic solvent, Suzuki coupling reaction is carried out 12 ~ 96 hours under 70 ~ 130 ° of C, polyreaction is stopped after cooling, separating-purifying reaction solution, obtains the described phosphine sulfenyl electron transport material of following structural formula:
3. the preparation method of phosphine sulfenyl electron transport material according to claim 2, is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
4. the preparation method of phosphine sulfenyl electron transport material according to claim 2, it is characterized in that, palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
5. the preparation method of phosphine sulfenyl electron transport material according to claim 2, is characterized in that, described alkaline solution is at least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution; In described alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
6. the preparation method of phosphine sulfenyl electron transport material according to claim 2, it is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
7. the preparation method of phosphine sulfenyl electron transport material according to claim 2, is characterized in that, Suzuki coupling reaction temperature is at 90 ~ 120 DEG C, the reaction times is 24 ~ 36 hours.
8. the preparation method of phosphine sulfenyl electron transport material according to claim 2, it is characterized in that, separating-purifying reaction solution comprises step:
After reaction stops, methyl alcohol precipitating is added in reaction solution, methyl alcohol and normal hexane extracting is used successively after being filtered by apparatus,Soxhlet's, then be that solvent extraction is to colourless with chloroform, collect chloroformic solution and be spin-dried for and obtain powder, powder after collection under vacuo after the dry 24h of 50 ° of C, obtains described phosphine sulfenyl electron transport material again.
9. the application of a phosphine sulfenyl electron transport material as claimed in claim 1 in organic electroluminescence device field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018529651A (en) * | 2015-09-15 | 2018-10-11 | エルジー・ケム・リミテッド | Heterocyclic compound and organic light emitting device including the same |
| USRE47654E1 (en) | 2010-01-15 | 2019-10-22 | Idemitsu Koasn Co., Ltd. | Organic electroluminescence device |
| CN111793087A (en) * | 2020-05-15 | 2020-10-20 | 浙江虹舞科技有限公司 | Luminescent material, delayed phosphor and organic light-emitting element |
-
2013
- 2013-07-19 CN CN201310305809.0A patent/CN104292261A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE47654E1 (en) | 2010-01-15 | 2019-10-22 | Idemitsu Koasn Co., Ltd. | Organic electroluminescence device |
| JP2018529651A (en) * | 2015-09-15 | 2018-10-11 | エルジー・ケム・リミテッド | Heterocyclic compound and organic light emitting device including the same |
| CN111793087A (en) * | 2020-05-15 | 2020-10-20 | 浙江虹舞科技有限公司 | Luminescent material, delayed phosphor and organic light-emitting element |
| CN111793087B (en) * | 2020-05-15 | 2023-06-09 | 浙江虹舞科技有限公司 | Luminescent material, delayed phosphor and organic light-emitting element |
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Application publication date: 20150121 |