CN107946485B - A method of caesium lead bromine quanta point electroluminescent device is prepared with body solid-liquid exchange process by conjugated molecule - Google Patents
A method of caesium lead bromine quanta point electroluminescent device is prepared with body solid-liquid exchange process by conjugated molecule Download PDFInfo
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 73
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 64
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002096 quantum dot Substances 0.000 claims abstract description 67
- 239000003446 ligand Substances 0.000 claims abstract description 57
- 238000004528 spin coating Methods 0.000 claims abstract description 32
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 18
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 18
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims abstract description 10
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 54
- 238000010422 painting Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000005642 Oleic acid Substances 0.000 claims description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 21
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- IRAGENYJMTVCCV-UHFFFAOYSA-N 2-phenylethanamine;hydrobromide Chemical compound [Br-].[NH3+]CCC1=CC=CC=C1 IRAGENYJMTVCCV-UHFFFAOYSA-N 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 10
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- -1 octadecylene Chemical group 0.000 claims description 6
- DHHVAGZRUROJKS-UHFFFAOYSA-N phentermine Chemical compound CC(C)(N)CC1=CC=CC=C1 DHHVAGZRUROJKS-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- AKNWFTSJWORAMI-UHFFFAOYSA-N 3-phenylpropan-1-amine;hydrobromide Chemical compound [Br-].[NH3+]CCCC1=CC=CC=C1 AKNWFTSJWORAMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 3
- 229940025084 amphetamine Drugs 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229960003562 phentermine Drugs 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- REMPQPDQHXJQBU-UHFFFAOYSA-N [Br-].C(CCC)[NH3+].C1=CC=CC=C1 Chemical compound [Br-].C(CCC)[NH3+].C1=CC=CC=C1 REMPQPDQHXJQBU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 2
- RBKVCANILNEQJT-UHFFFAOYSA-N [Br].CCCCCCCC Chemical compound [Br].CCCCCCCC RBKVCANILNEQJT-UHFFFAOYSA-N 0.000 claims 1
- SXMUSCUQMMSSKP-UHFFFAOYSA-N [O].C=1C=CSC=1 Chemical compound [O].C=1C=CSC=1 SXMUSCUQMMSSKP-UHFFFAOYSA-N 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QJFMCHRSDOLMHA-UHFFFAOYSA-N phenylmethanamine;hydrobromide Chemical group Br.NCC1=CC=CC=C1 QJFMCHRSDOLMHA-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QNHKJSKLKSGFJF-UHFFFAOYSA-N [Br].[Ca] Chemical compound [Br].[Ca] QNHKJSKLKSGFJF-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Match the method that body solid-liquid exchange process prepares caesium lead bromine quanta point electroluminescent device by conjugated molecule the invention discloses a kind of, synthesizes caesium lead bromine quantum dot using hot injecting method first, and purify quantum dot with methyl acetate；Then poly- 3 are being covered with, then the caesium lead bromine quantum dot of spin coating after purification on the tin indium oxide of 4- ethylenedioxy thiophene, poly- [bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene and poly- (9- vinyl carbazole) chlorobenzene, and carry out solid-liquid ligand exchange；Then one layer of 1,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene, lithium fluoride and aluminium is deposited on quantum dot layer again.The present invention can be made with high brightness, high efficiency, the caesium lead bromine quanta point electroluminescent diode of low turn-on voltage.
Description
Technical field
Caesium lead bromine quanta point electroluminescent device is prepared with body solid-liquid exchange process by conjugated molecule the present invention relates to a kind of
Method, pi-conjugated small molecule is introduced by solid-liquid ligand exchange method to prepare the caesium lead bromine quanta point electroluminescent device of high property
Part.
Background technique
Full-inorganic caesium lead halogen (CsPbX3, X=Cl, Br, I) perovskite quantum dot have high quantum yield, Gao Faguang face
The characteristics such as the optical band gap of color saturation and size adjustable, so since Kovalenko seminar reports this perovskite for the first time
Since the hot injecting method synthesis of quantum dot, they are just applied to various optics devices as most promising candidate light source material
In part, such as electroluminescent diode, photodetector, in laser and solar battery.
In perovskite electroluminescent field, the uniform little crystal grain with higher exciton bonded energy and fewer defects state
Be obtain a high efficiency device prerequisite because this little crystal grain be more advantageous to by injection charge formed exciton to
Increase the probability of radiation recombination, and is easier to obtain fine and close, low roughness a solid film.These are characterized in calcium titanium
The essential attribute of mine quantum dot, but do not allow but to obtain for polycrystalline perovskite bulk film, unless addition is some to be had
Machine object.The preparation of caesium lead bromine perovskite quanta point electroluminescent diode is reported in document for the first time, performance is maximum brightness
For 946 candelas/square metre and external quantum efficiency (EQE) be 0.12%.Then caesium lead bromine quantum is clicked through with ethyl acetate
Repeatedly purification regulates and controls the long-chain Ligand concentration of quantum dot surface to row, can further by the brightness of light emitting diode improve to
15185 candelas/every square metre, external quantum efficiency are also improved to 6.27%.Another document passes through control caesium lead bromine quantum dot table
The atomic component in face come obtain a brightness be 12090 candelas/square metre diode.Recently, manganese and tin element are adulterated
Caesium lead bromine quantum dot is also used to prepare light emitting diode, obtain respectively brightness be 9719 candelas/square metre and EQE be
1.49% and brightness be 12500 candelas/square metre and external quantum efficiency be 4.13% performance.However, with caesium lead bromine polycrystalline
Film or other hybrid inorganic-organic perovskite systems (maximum brightness > 50000 candelas/square metre) compare, caesium lead bromine calcium
Still there is a big difference needs to pursue for titanium ore light emitting diode with quantum dots.Fortunately, above-mentioned several work show caesium lead bromine amount
Son point surface has important influence to the performance of electroluminescent diode, and it is presumed that the long-chain Ligand of quantum dot surface is oily
Amine and oleic acid limit the further promotion of light emitting diode performance, because these long-chain Ligands are insulating materials, they can be limited
The transmission of carrier processed.Because of a kind of effective ligand exchange processes of the invention, the long-chain Ligand of quantum dot surface is substituted for
Short chain ligand is a very necessary job.
Summary of the invention
The present invention is in order to avoid above-mentioned existing deficiencies in the technology, it is desirable to provide one kind is matched by conjugated molecule
The method that body solid-liquid exchange process prepares caesium lead bromine quanta point electroluminescent device introduces conjugated molecule by solid-liquid ligand exchange method
Ligand prepares the caesium lead bromine quanta point electroluminescent device of high brightness and low turn-on voltage.
Ligand exchange processes of the present invention have do not damage caesium lead bromine quantum dot optical property and crystal structure, can be effective
Original long-chain Ligand is substituted for pi-conjugated short chain ligand, is easy to get fine and close and low roughness a quantum solid point
Body thin film significantly improves the advantages that quantum dot film electric conductivity.
The present invention matches the method that body solid-liquid exchange process prepares caesium lead bromine quanta point electroluminescent device, packet by conjugated molecule
Include following steps:
Step 1: the synthesis and purification of caesium lead bromine quantum dot
Step 1a: the preparation of oleic acid caesium precursor
0.5g cesium carbonate, 2mL oleic acid and 50mL octadecylene are added in the three-necked round bottom flask of 100mL first, taken out true
Sky is simultaneously heated to 120 DEG C of heat preservations 30 minutes, then stops vacuumizing and leading to nitrogen 10 minutes, then starts to vacuumize again, recycles
Three times to remove the moisture and oxygen in flask, the final colorless cleared solution that obtains is oleic acid caesium presoma, places it in 70
Nitrogen protection is stirred and led at DEG C, it is spare；
Step 1b: the synthesis of caesium lead bromine quantum dot
0.8g lead bromide and 50mL octadecylene are added in the three-necked round bottom flask of 500ml, are heated with stirring to 120 DEG C,
Then reaction one hour is vacuumized, the oleic acid of 5mL and the oleyl amine of 5ml is then added, reaction 15-30 minutes is vacuumized, until bromine
Change lead to be completely dissolved, then vacuumize and lead to nitrogen protection to three-neck flask stopping and is heated to 170 DEG C, addition 8mL step 1a
Three-neck flask is placed in after reaction 5 seconds and stops reacting in ice-water bath by the oleic acid caesium precursor of preparation；
Step 1c: the purification of caesium lead bromine quantum dot
The methyl acetate of 200mL is added in the reaction solution that step 1b is obtained, is centrifuged 5 minutes under 8000 turns, in removal
Clear liquid is precipitated, and is dissolved sediment with 5mL hexane, is added 5mL methyl acetate, and be centrifuged 2 minutes under 8000 turns, removes
Supernatant is precipitated, and sediment 20mL hexane dissolves, and is centrifuged 5 minutes under 4000 turns, and obtain supernatant, revolving is removed
Solvent is removed, gained quantum dot is dissolved in the caesium lead bromine quantum dot solution for being configured to 20mg/mL in octane；
Step 2: the preparation and purification of benzene alkyl ammonium bromide ligand
1g phenylalkylamine and 15mL ethyl alcohol are added in the three-neck flask of 50mL, is stirred at 0 DEG C, equimolar is then added dropwise
The aqueous solution of hydrogen bromide (48%) of amount stops reaction after stirring 2 hours at 0 DEG C, 45mL ether, filtering are added into reaction solution
Sediment is obtained, dissolves sediment with 5mL ethyl alcohol, adds 20mL ether, filtering obtains sediment, repeats to dissolve precipitation process
Obtain benzene alkyl ammonium bromide ligand 2-3 times；
The phenylalkylamine is benzene first ammonium, phenyl ethylamine, amphetamine or phentermine.
The benzene alkyl ammonium bromide is benzyl ammonium bromide, phenethyl ammonium bromide, phenylpropyl ammonium bromide or benzene butyl bromination
Ammonium.
Step 3: the preparation of ligand solution
0.6mmol benzene alkyl ammonium bromide ligand and 400 μ L oleic acid are dissolved in 32mL methyl acetate, ultrasonic disperse uniformly obtains
Obtain the ligand solution of achromaticity and clarification；
Step 4: the preparation of caesium lead bromine perovskite electroluminescent device
First by tin indium oxide (ITO) piece ozone treatment 15 minutes, then in one strata of surface spin coating of tin indium oxide piece
3,4-ethylene dioxythiophene (4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating is dense in glove box
Poly- [bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds) that degree is 8mg/mL, and moved back in 120 DEG C
Fire processing 20 minutes；Poly- (9- vinyl carbazole) chlorobenzene solution (4000 rotate painting 60 seconds) of following spin coating 1.5mg/mL, and in
170 DEG C make annealing treatment 30 minutes；Being then spin coated onto the caesium lead bromine quantum dot solution of 20mg/mL of step 1c preparation, (2500 rotate painting
60 seconds), it handles 5 minutes at 80 DEG C；The ITO piece that finally will be covered with caesium lead bromine quantum dot immerses the ligand solution that step 3 is prepared
It is middle to be kept for 30 seconds, it is then cleaned with methyl acetate, is heated 4 minutes at 100 DEG C, be subsequently placed in vapor deposition instrument, be in vacuum
1-2×10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene of 40 nanometer thickness, the fluorine of 1 nanometer thickness are successively deposited under Pa
Change the aluminium electrode of lithium and 100 nanometer thickness.
The exchange ligand that the present invention uses is the short chain ligand with pi-conjugated phenyl ring.It is pi-conjugated compared to direct-connected ligand
The coupling between quantum dot can be improved in the conjugated nature of phenyl ring, to improve the transporting of carrier in quantum dot layer；Separately
On the one hand since phenyl ring has bigger volume, so as to avoid cracking in solid-liquid ligand exchange processes.
The solvent of anti-solvent and ligand exchange that the present invention adds in caesium lead bromine quantum dot purification process is methyl acetate.Second
Sour methyl esters is a kind of low polar solvent, will not be damaged to the crystal structure of caesium lead bromine quantum dot, and will not be substantially reduced it
Optical property.Oleic acid is added in ligand solution to provide an acidic environment in the present invention, can be quantum dot surface in this way
Oleyl amine protonation, promotes the progress of ligand exchange.
The present invention introduces hole transport strata (9- vinyl carbazole) on poly- [bis- (4- phenyl) (4- butyl phenyl) amine].Phase
Than in poly- [bis- (4- phenyl) (4- butyl phenyl) amine], poly- (9- vinyl carbazole) has higher minimum vacant orbital energy level
(LUMO) and lower highest occupies orbital energy level (HOMO), is injected into caesium lead so as to be conducive to hole from hole transmission layer
In bromine quantum dot active layer, and be conducive to that electronics is stopped to be injected into hole transmission layer from caesium lead bromine quantum dot active layer, this
Sample can improve the efficiency of electroluminescent device.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, the present invention is a kind of solid-liquid ligand exchange method, easy to operate and easy to accomplish, short processing time.
2, the present invention can effectively replace the long-chain Ligand of quantum dot surface, and will not change the crystal of quantum dot
Structure, quantum dot film while photoluminescence quantum yield with higher.
3, the present invention successfully introduces pi-conjugated smaller ligand, the electric conductivity of quantum dot is improved significantly, to mention
The high performance of electroluminescent diode.
4, the present invention is readily available fine and close, uniform and low roughness a quantum dot film.
5, the present invention introduces a strata (9- ethylene click on poly- [bis- (4- phenyl) (4- butyl phenyl) amine] hole transmission layer
Azoles) transport layer, the luminous efficiency of electroluminescent diode can be improved significantly.
Detailed description of the invention
The low resolution for the caesium lead bromine quantum dot that Fig. 1 present invention synthesizes and high-resolution-ration transmission electric-lens picture (a) and quantum dot
Absorption-spectral line of emission (b) of solution volume.Caesium lead bromine quantum dot have good monodispersity and high quantum yield, and cube
Phase crystal structure.
The Fourier transform infrared spectroscopy of caesium lead bromine quantum dot surface absorption ligand before and after Fig. 2 ligand exchange of the present invention
(FTIR, a), x-ray photoelectron spectroscopy line (XPS, b).After ligand exchange, oleyl amine, oleic acid long-chain Ligand are obviously by pi-conjugated benzene
Alkyl bromination ammonium ligand substituting, and the composition of quantum dot surface richness Br will not be changed after ligand exchange.
Caesium lead bromine quanta point electroluminescent diode behavior curve before and after Fig. 3 ligand exchange of the present invention: (a) different voltages
Under current density and brightness curve, (b-c) current efficiency and external quantum efficiency curve, (d) different components maximum brightness is electroluminescent
Luminescence spectrum.After ligand exchange is complete, the electric conductivity of light emitting diode is obviously improved；After phenethyl ammonium bromide (PEABr) exchange,
Brightness highest can achieve 12650 candelas/square metre, current efficiency is up to 5.91 candelas/ampere, external quantum efficiency
It (EQE) is up to 1.79%, cut-in voltage is down to 2.85V.
Caesium lead bromine amount of Fig. 4 present invention on the basis of ligand exchange, after introducing poly- (9- vinyl carbazole) hole transmission layer
Son point electroluminescent diode performance curve: (a) device energy level plan view, (b-d) current density, brightness, current efficiency and outer
Quantum efficiency curve.After introducing poly- (9- vinyl carbazole), the current efficiency of light emitting diode can be promoted to 13.43 candelas/
Ampere, external quantum efficiency up to 4.33%, cut-in voltage drops to 2.66V, but 5435cd/A is down in maximum brightness simultaneously；By into
One step is thinned poly- (9- vinyl carbazole) layer, brightness can be promoted to 9294 candelas/square metre, while have 7.93 candelas/
Ampere current efficiency and 2.47% outer quantum yield.
Specific embodiment
Embodiment 1: the synthesis and purification of caesium lead bromine quantum dot
The preparation of 1a, oleic acid caesium precursor
0.5g cesium carbonate, 2mL oleic acid and 50mL octadecylene are added in the three-necked round bottom flask of 100mL first, taken out true
Sky is simultaneously heated to 120 DEG C of heat preservations 30 minutes, then stops vacuumizing and leading to nitrogen 10 minutes, then starts to vacuumize again, recycles
Three times to remove the moisture and oxygen in flask, the final colorless cleared solution that obtains is oleic acid caesium presoma, places it in 70
Nitrogen protection is stirred and led at DEG C, it is spare；
The synthesis of 1b, caesium lead bromine quantum dot
0.8g lead bromide and 50mL octadecylene are added in the three-necked round bottom flask of 500ml, are heated with stirring to 120 DEG C,
Then reaction one hour is vacuumized, the oleic acid of 5mL and the oleyl amine of 5ml is then added, reaction 15-30 minutes is vacuumized, until bromine
Change lead to be completely dissolved, then vacuumize and lead to nitrogen protection to three-neck flask stopping and is heated to 170 DEG C, addition 8mL step 1a
Three-neck flask is placed in after reaction 5 seconds and stops reacting in ice-water bath by the oleic acid caesium precursor of preparation；
The purification of 1c, caesium lead bromine quantum dot
The methyl acetate of 200mL is added in the reaction solution that step 1b is obtained, is centrifuged 5 minutes under 8000 turns, in removal
Clear liquid is precipitated, and is dissolved sediment with 5mL hexane, is added 5mL methyl acetate, and be centrifuged 2 minutes under 8000 turns, removes
Supernatant is precipitated, and sediment 20mL hexane dissolves, and is centrifuged 5 minutes under 4000 turns, and obtain supernatant, revolving is removed
Solvent is removed, gained quantum dot is dissolved in the caesium lead bromine quantum dot solution for being configured to 20mg/mL in octane；
Embodiment 2: the preparation of benzene alkyl ammonium bromide ligand solution
1g phenylalkylamine and 15mL ethyl alcohol are added in the three-neck flask of 50mL, is stirred at 0 DEG C, equimolar is then added dropwise
The aqueous solution of hydrogen bromide (48%) of amount stops reaction after stirring 2 hours at 0 DEG C, 45mL ether, filtering are added into reaction solution
Sediment is obtained, dissolves sediment with 5mL ethyl alcohol, adds 20mL ether, filtering obtains sediment, repeats to dissolve precipitation process
Obtain benzene alkyl ammonium bromide ligand 2-3 times；0.6mmol benzene alkyl ammonium bromide ligand and 400 μ L oleic acid are dissolved in 32mL acetic acid first
In ester, ultrasonic disperse uniformly obtains the ligand solution of achromaticity and clarification；
The phenylalkylamine is benzene first ammonium, phenyl ethylamine, amphetamine or phentermine.
The benzene alkyl ammonium bromide is benzyl ammonium bromide, phenethyl ammonium bromide, phenylpropyl ammonium bromide or benzene butyl bromination
Ammonium.
Embodiment 3:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；So
The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) for the 20mg/mL that spin coating embodiment 1 is prepared afterwards is handled 5 minutes at 80 DEG C；
Then piece is put into vapor deposition instrument, is 1-2 × 10 in vacuum-6(the 1- phenyl-of 1,3,5- tri- of 40 nanometer thickness is successively deposited under Pa
1H benzimidazolyl-2 radicals-yl) benzene, the lithium fluoride of 1 nanometer thickness and 100 nanometer thickness aluminium electrode.
Embodiment 4:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；So
The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) for the 20mg/mL that spin coating embodiment 1 is prepared afterwards is handled 5 minutes at 80 DEG C；
Then the ITO piece for covering caesium lead bromine quantum dot is immersed in prepared benzyl ammonium bromide (PMABr) ligand solution and keeps 30
Second, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument, in vacuum
For 1-2 × 10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene of 40 nanometer thickness, 1 nanometer thickness are successively deposited under Pa
The aluminium electrode of lithium fluoride and 100 nanometer thickness.
Embodiment 5:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；So
The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) for the 20mg/mL that spin coating embodiment 1 is prepared afterwards is handled 5 minutes at 80 DEG C；
Then the ITO piece for covering caesium lead bromine quantum dot is immersed in prepared phenethyl ammonium bromide (PEABr) ligand solution and keeps 30
Second, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument, in vacuum
For 1-2 × 10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene of 40 nanometer thickness, 1 nanometer thickness are successively deposited under Pa
The aluminium electrode of lithium fluoride and 100 nanometer thickness.
Embodiment 6:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；So
The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) for the 20mg/mL that spin coating embodiment 1 is prepared afterwards is handled 5 minutes at 80 DEG C；
Then the ITO piece for covering caesium lead bromine quantum dot is immersed in prepared phenylpropyl ammonium bromide (PPABr) ligand solution and keeps 30
Second, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument, in vacuum
For 1-2 × 10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene of 40 nanometer thickness, 1 nanometer thickness are successively deposited under Pa
The aluminium electrode of lithium fluoride and 100 nanometer thickness.
Embodiment 7:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；So
The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) for the 20mg/mL that spin coating embodiment 1 is prepared afterwards is handled 5 minutes at 80 DEG C；
Then the ITO piece for covering caesium lead bromine quantum dot is immersed in prepared benzene butylammonium bromide (PBABr) ligand solution and keeps 30
Second, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument, in vacuum
For 1-2 × 10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene of 40 nanometer thickness, 1 nanometer thickness are successively deposited under Pa
The aluminium electrode of lithium fluoride and 100 nanometer thickness.
Embodiment 8:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；It connects
Get off poly- (9- vinyl carbazole) chlorobenzene solution (2000 rotate painting 60 seconds) of spin coating 1.5mg/mL, and makes annealing treatment 30 in 170 DEG C
Minute；The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) of the 20mg/mL of the preparation of embodiment 1 is then spin coated onto, at 80 DEG C
Reason 5 minutes；Then the ITO piece for covering caesium lead bromine quantum dot is immersed into prepared phenethyl ammonium bromide (PEABr) ligand solution
It is middle to be kept for 30 seconds, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument
In, it is 1-2 × 10 in vacuum-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene, 1 of 40 nanometer thickness is successively deposited under Pa
The aluminium electrode of the lithium fluoride of nanometer thickness and 100 nanometer thickness.
Embodiment 9:
First by ITO piece ozone treatment 15 minutes, then in one strata 3,4-ethylene dioxythiophene of the surface spin coating of ITO piece
(4000 rotate painting 40 seconds), and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is the poly- of 8mg/mL in glove box
[bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution (4000 rotate painting 60 seconds), and made annealing treatment 20 minutes in 120 DEG C；It connects
Get off poly- (9- vinyl carbazole) chlorobenzene solution (4000 rotate painting 60 seconds) of spin coating 1.5mg/mL, and makes annealing treatment 30 in 170 DEG C
Minute；The caesium lead bromine quantum dot solution (2500 rotate painting 60 seconds) of the 20mg/mL of the preparation of embodiment 1 is then spin coated onto, at 80 DEG C
Reason 5 minutes；Then the ITO piece for covering caesium lead bromine quantum dot is immersed into prepared phenethyl ammonium bromide (PEABr) ligand solution
It is middle to be kept for 30 seconds, it is then cleaned with methyl acetate, and heated 4 minutes at 100 DEG C；Then piece is put into vapor deposition instrument
In, it is 1-2 × 10 in vacuum-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene, 1 of 40 nanometer thickness is successively deposited under Pa
The aluminium electrode of the lithium fluoride of nanometer thickness and 100 nanometer thickness.
The Fundamental Physical Properties that material is made in above-described embodiment 3-9 see the table below 1:
1 caesium lead bromine quanta point electroluminescent diode component performance of table
From table 1 it follows that caesium lead bromine quantum dot is after ligand exchange is handled, the electroluminescent device of preparation is opened
Voltage is opened to be decreased obviously.This is because the coupling between quantum dot enhances, and electric conductivity improves caused after ligand exchange
's.And after ligand exchange, the brightness of device is also mutually due for promotion, most bright to can achieve 12650 every square metre of candelas.
After introducing poly- (9- vinyl carbazole) transport layer, the efficiency of device is mutually due for promotion, and current efficiency and power efficiency can reach
13.43 every ampere of candelas, 12.05 every watt of lumens, external quantum efficiency can achieve 4.33%.
Claims (6)
1. a kind of match the method that body solid-liquid exchange process prepares caesium lead bromine quanta point electroluminescent device, feature by conjugated molecule
It is to include the following steps:
Step 1: the synthesis and purification of caesium lead bromine quantum dot
Step 1a: the preparation of oleic acid caesium precursor
0.5g cesium carbonate, 2mL oleic acid and 50mL octadecylene are added in reactor first, vacuumize and are heated to 120 DEG C of guarantors
Temperature 30 minutes then stops vacuumizing and leading to nitrogen 10 minutes, then starts to vacuumize again, recycles three times to remove in flask
Moisture and oxygen, the final colorless cleared solution that obtains is oleic acid caesium presoma, places it at 70 DEG C and stirs and lead to nitrogen guarantor
Shield, it is spare；
Step 1b: the synthesis of caesium lead bromine quantum dot
0.8g lead bromide and 50mL octadecylene are added in reactor, are heated with stirring to 120 DEG C, it is small then to vacuumize reaction one
When, the oleic acid of 5mL and the oleyl amine of 5ml is then added, vacuumizes reaction 15-30 minutes, it is then right until lead bromide is completely dissolved
Three-neck flask stopping vacuumizes and leads to nitrogen protection and is heated to 170 DEG C, and the oleic acid caesium presoma of 8mL step 1a preparation is added,
Three-neck flask is placed in after reaction 5 seconds and stops reacting in ice-water bath；
Step 1c: the purification of caesium lead bromine quantum dot
The methyl acetate of 200mL is added in the reaction solution that step 1b is obtained, centrifugation is moved back except supernatant is precipitated, and uses 5mL
Hexane dissolves sediment, adds 5mL methyl acetate, and centrifugation is moved back except supernatant is precipitated, and sediment is molten with 20mL hexane
Solution, then it is centrifuged and obtains supernatant, revolving removes solvent, and gained quantum dot is dissolved in the caesium lead that 20mg/mL is configured in octane
Bromine quantum dot solution；
Step 2: the preparation and purification of benzene alkyl ammonium bromide ligand
1g phenylalkylamine and 15mL ethyl alcohol are added in the three-neck flask of 50mL, stirred at 0 DEG C, equimolar amounts is then added dropwise
Aqueous solution of hydrogen bromide stops reaction after stirring 2 hours at 0 DEG C, 45mL ether is added into reaction solution, and filtering is precipitated
Object dissolves sediment with 5mL ethyl alcohol, adds 20mL ether, and filtering obtains sediment, repeats dissolution precipitation process 2-3 times
To benzene alkyl ammonium bromide ligand；
The phenylalkylamine is benzene first ammonium, phenyl ethylamine, amphetamine or phentermine；The benzene alkyl ammonium bromide is benzyl bromination
Ammonium, phenethyl ammonium bromide, phenylpropyl ammonium bromide or benzene butylammonium bromide；
Step 3: the preparation of ligand solution
0.6mmol benzene alkyl ammonium bromide ligand and 400 μ L oleic acid are dissolved in 32mL methyl acetate, ultrasonic disperse uniformly obtains nothing
The clear ligand solution of color；
Step 4: the preparation of caesium lead bromine perovskite electroluminescent device
First by tin indium oxide piece ozone treatment 15 minutes, then in one strata 3 of the surface spin coating of tin indium oxide piece, 4- ethylene two
Oxygen thiophene, and made annealing treatment 10 minutes in 140 DEG C；Then spin coating concentration is 8mg/mL in glove box poly- [bis- (4- phenyl)
(4- butyl phenyl) amine] chlorobenzene solution, and made annealing treatment 20 minutes in 120 DEG C；Poly- (the 9- ethylene of following spin coating 1.5mg/mL
Carbazole) chlorobenzene solution, and made annealing treatment 30 minutes in 170 DEG C；It is then spin coated onto the caesium lead bromine quantum of the 20mg/mL of step 1c preparation
Solution is put, is handled 5 minutes at 80 DEG C；The ITO piece that finally will be covered with caesium lead bromine quantum dot immerses the ligand solution that step 3 is prepared
It is middle to be kept for 30 seconds, it is then cleaned with methyl acetate, is heated 4 minutes at 100 DEG C, be subsequently placed in vapor deposition instrument, be in vacuum
1-2×10-61,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene, lithium fluoride and aluminium electrode is successively deposited under Pa.
2. preparation method according to claim 1, it is characterised in that:
In step 4, the spin coating parameters of poly- 3,4-ethylene dioxythiophene rotate painting 40 seconds for 4000.
3. preparation method according to claim 1, it is characterised in that:
In step 4, the spin coating parameters of poly- [bis- (4- phenyl) (4- butyl phenyl) amine] chlorobenzene solution rotate painting 60 seconds for 4000.
4. preparation method according to claim 1, it is characterised in that:
In step 4, the spin coating parameters of poly- (9- vinyl carbazole) chlorobenzene solution rotate painting 60 seconds for 4000.
5. preparation method according to claim 1, it is characterised in that:
In step 4, the spin coating parameters of caesium lead bromine quantum dot solution rotate painting 60 seconds for 2500.
6. preparation method according to claim 1, it is characterised in that:
In step 4, when vapor deposition, control 1,3,5- tri- (1- phenyl -1H benzimidazolyl-2 radicals-yl) benzene with a thickness of 40 nanometers, fluorination
Lithium with a thickness of 1 nanometer, aluminium electrode with a thickness of 100 nanometers.
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