CN113054067B - Perovskite light emitting diode and method for smoothly orienting perovskite thin film thereof - Google Patents
Perovskite light emitting diode and method for smoothly orienting perovskite thin film thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011787 zinc oxide Substances 0.000 claims abstract description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000004528 spin coating Methods 0.000 claims abstract description 24
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 19
- 230000005525 hole transport Effects 0.000 claims abstract description 17
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 17
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 62
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 30
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 25
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 16
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- 239000000843 powder Substances 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001771 vacuum deposition Methods 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DMRWWDPLMWRFDV-UHFFFAOYSA-N cesium copper Chemical compound [Cu++][Cs+] DMRWWDPLMWRFDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
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- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims 1
- 210000002858 crystal cell Anatomy 0.000 claims 1
- 239000012296 anti-solvent Substances 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 8
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- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 4
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- AQOUTLFYXBBFQD-UHFFFAOYSA-N [Cs].[Cu].[I] Chemical compound [Cs].[Cu].[I] AQOUTLFYXBBFQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/16—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
- H01L33/18—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous within the light emitting region
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Abstract
The invention discloses a perovskite light-emitting diode, which comprises a glass substrate (1), an ITO anode electrode (2), a zinc oxide electron transport layer (3), a perovskite thin film (4), a molybdenum oxide hole transport layer (5) and an Ag metal electrode layer (6) which are sequentially overlapped from bottom to top; the perovskite thin film (4) has no gaps among unit cells. The invention also discloses a method for smoothly orienting the perovskite thin film of the perovskite light-emitting diode. In the invention, in addition to spin coating of a mixed solution of cuprous iodide and cesium iodide, a toluene anti-solvent needs to be flushed on the film in the spin coating process, compared with the traditional technology, the obtained perovskite film has more uniform distribution and less pinhole structures on the surface of the film, the film forming quality is improved, the density defect is reduced, and the efficiency of preparing a device is obviously improved by flushing the anti-solvent to improve the perovskite light-emitting diode film.
Description
Technical Field
The invention relates to a perovskite light-emitting diode and a method for smoothly orienting a perovskite thin film thereof, belonging to the technical field of perovskite light-emitting diodes.
Background
In recent years, with the vigorous development of the photoelectric field, the organic metal halide perovskite light emitting diode is more and more widely concerned as a photoelectronic material with a wide prospect, the perovskite light emitting diode has excellent performances such as higher external quantum conversion efficiency (PLQY), low-cost manufacturing process and the like, the research of domestic and foreign scholars is attracted, and the external quantum conversion efficiency of the perovskite light emitting diode reaches 21.6%. These excellent results can be attributed to the unique properties of perovskite materials.
For a device using a perovskite thin film as a light emitting layer, the growth condition and surface morphology of the unit cell of the perovskite thin film play a crucial role in a series of parameters of the device using the perovskite thin film as the light emitting layer, including the voltage-current density, the turn-on voltage and the lumen efficiency of the light emitting device, and the open-circuit voltage, the short-circuit current density, the fill factor and the photoelectric conversion efficiency of the perovskite light emitting diode device.
In order to further improve the photoelectric conversion efficiency of the perovskite light-emitting diode thin film, the maximum reduction of charge recombination at the interface of the perovskite thin film and the charge transport layer is required, and the specific method for achieving the aim is to improve the surface film forming quality of the perovskite, increase the crystal size and reduce the defect density, while the perovskite ABX 3 The preparation method of the film has great influence on the structure, the appearance, the charge mobility, the electron service life and the photoelectric conversion performance of the film.
In the prior art, cuprous iodide and cesium iodide are generally selected as components in a precursor solution for preparing a perovskite light-emitting diode, the crystal grain distribution of a perovskite thin film prepared by the precursor solution is not particularly uniform, and the surface of the perovskite thin film has pinhole defects, so that the photoelectric conversion efficiency of a device is influenced; therefore, it is necessary to design a method for inducing the orientation of perovskite crystals in a specific direction to improve the film formation quality of the perovskite surface, so that the crystal grains are more uniformly distributed, the pinhole defects on the surface are reduced, and the energy conversion efficiency of the perovskite light emitting diode device is further improved.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention provides a perovskite light-emitting diode.
Meanwhile, the invention provides a method for smoothly orienting the perovskite thin film of the perovskite light-emitting diode, which adopts an anti-solvent to induce the perovskite light-emitting diode thin film to be smoothly oriented and improves the photoelectric conversion efficiency of the perovskite light-emitting diode device by improving the film forming quality of the surface of the perovskite.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a perovskite light-emitting diode comprises a glass substrate, an ITO positive electrode, a zinc oxide electron transport layer, a perovskite film, a molybdenum oxide hole transport layer and an Ag metal electrode layer which are sequentially stacked from bottom to top; the perovskite thin film has no gaps among unit cells.
The perovskite film is a cesium copper iodoperovskite film luminescent layer.
A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode,
the method comprises the following steps: etching an ITO positive electrode on the surface of the glass substrate to obtain an ITO substrate;
step two: preparing a zinc oxide electron transport layer;
step three: preparing a perovskite precursor solution: mixing a mixture of 3: 2, dissolving cuprous iodide, CuI, and cesium iodide, CsI, in DMSO to DMF at a volume ratio of 6:4, magnetically stirring for 11.5-12 hours at the temperature of 60-70 ℃ to obtain a precursor liquid of the perovskite film, namely the perovskite precursor liquid, wherein the final concentration of the perovskite precursor liquid is 0.2-0.3 mol/L;
step four: preparing a perovskite thin film: and (2) dropwise adding 65-75 mu L of the perovskite precursor solution on the zinc oxide electron transport layer, starting spin coating at a rotating speed of 3500-4000 rmp, immediately washing for 1-3 s with 180-200 mu L of toluene solution when the coating process is carried out for 12-15 s, carrying out spin coating and washing simultaneously, and after the spin coating is finished for 50-60 s, annealing on a hot bench at 100-120 ℃ for 1-1.5 h, wherein the thickness of the perovskite thin film is 70-90 nm.
The preparation method of the ITO substrate comprises the following steps: and (3) sequentially carrying out ultrasonic cleaning on the glass substrate etched with the ITO positive electrode in deionized water, acetone and ethanol for more than 20min, completely cleaning, and then putting the glass substrate into an ozone plasma processor to clean the surface for 4-5 min to obtain the ITO substrate.
The preparation method of the zinc oxide electron transport layer comprises the following steps: and (3) coating the ZnO solution on the ITO substrate in a rotating speed of 2500-3000 rpm in a rotating mode, and then annealing for 10-15 min at 70-80 ℃ to obtain the zinc oxide electron transmission layer, wherein the thickness of the zinc oxide electron transmission layer is 30-40 nm.
A method for smoothly orienting a perovskite thin film of a perovskite light emitting diode, further comprising the steps of:
step five: preparing a molybdenum oxide hole transport layer: in the cavity of the vacuum coating machine, perovskite filmSurface vapor deposition of MoO 3 The thickness of the molybdenum oxide hole transport layer is 10-11 nm;
step six: preparing an Ag metal electrode layer: and in a vacuum coating machine cavity, evaporating an Ag metal electrode on the surface of the molybdenum oxide hole transport layer, wherein the thickness of the Ag metal electrode layer is 90-110 nm.
The preparation method of the ZnO solution comprises the following steps:
firstly, material preparation: weighing 4-4.5 g of anhydrous zinc acetate powder, placing the anhydrous zinc acetate powder in a three-neck flask, adding 150-160 mL of ethanol, heating to 85-90 ℃ under the nitrogen atmosphere, and stirring and dissolving by using a magnetic rotor until the anhydrous zinc acetate powder is in a clear and transparent state;
weighing 2-2.5 g of potassium hydroxide, placing the potassium hydroxide in a beaker, adding 20-25 mL of ethanol solution, sealing, and carrying out ultrasonic treatment for 20-25 min to fully dissolve the potassium hydroxide until the potassium hydroxide is colorless and clear;
secondly, reaction process: when the anhydrous zinc acetate solution is fully dissolved and begins to boil stably, controlling a separating funnel to dropwise add the ultrasonically dissolved potassium hydroxide solution into the anhydrous zinc acetate solution at a constant speed of 10-12 drops/min; after the dripping is finished, the two react for more than 30min at constant room temperature, wherein the constant room temperature is 20-25 ℃, until the solution is changed into turbid white from clear;
thirdly, purifying the product: stopping heating, naturally cooling the reactant to room temperature, pouring the solution in the three-neck flask into a beaker, and adding 150-200 mL of normal hexane while stirring; then sealing the beaker, putting the beaker into a refrigerator at 0-10 ℃ for sedimentation for 2-2.5 hours, taking out the beaker after the first sedimentation is finished, and then generating a large amount of milky white sediment at the bottom of the beaker; removing the supernatant, adding 150-180 mL of ethanol while stirring to fully disperse the precipitate, then sealing the beaker again, and putting the beaker into a refrigerator to settle for 2-2.5 hours;
fourthly, generating a solution: after the second sedimentation is finished, removing supernatant in the beaker, taking turbid liquid at the bottom of the beaker into a centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 4-5 minutes under the condition of 4500-5000 r/min; then, adding the precipitate into high-purity ethanol and an ethanolamine dispersant respectively for ultrasonic dissolution; and after the solution is fully dissolved, the solution is subjected to the centrifugal operation, and finally the supernatant is taken, namely the product ZnO solution.
The purity ranges of the high-purity ethanol and the ethanolamine are 99.5-99.9%.
The dosage of the high-purity ethanol and the dosage of the ethanolamine are 150-200 mL respectively.
The invention has the beneficial effects that: compared with the prior art, the perovskite thin film obtained by the method has the advantages that the distribution is more uniform, the pinhole structures on the surface of the thin film are fewer, the film forming quality is improved, the density defect is reduced, and the efficiency of the perovskite light-emitting diode thin film for preparing a device is obviously improved by flushing the anti-solvent.
According to the invention, the anti-solvent is used for inducing the perovskite light-emitting diode thin film to be oriented smoothly, the anti-solvent liquid is toluene, the perovskite light-emitting diode thin film device with good film forming quality is obtained, and the brightness and the photoelectric conversion efficiency of the perovskite light-emitting diode are effectively improved.
Drawings
FIG. 1 is a schematic diagram of the structure of a perovskite light emitting diode of the present invention;
FIG. 2 is a graph comparing J-V curves of perovskite light emitting diodes prepared according to example 1 of the present invention and a comparative example;
FIG. 3 is a SEM representation of perovskite thin films obtained in example 1 of the present invention ((b) toluene used as an anti-solvent) and in comparative example ((a) toluene used without an anti-solvent);
FIG. 4 is a diagram of perovskite thin film devices obtained in example 1 of the present invention (right panel) using anti-solvent toluene and comparative example (left panel) without anti-solvent toluene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Comparative example:
as shown in fig. 1, the perovskite light emitting diode comprises a glass substrate 1, an ITO anode electrode 2, a zinc oxide electron transport layer 3, a perovskite thin film 4, a molybdenum oxide hole transport layer 5 and an Ag metal electrode layer 6 which are sequentially stacked from bottom to top.
The perovskite thin film 4 is a cesium copper iodoperovskite thin film luminescent layer.
A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode is characterized in that a perovskite thin film is prepared by using a mixed solution of cuprous iodide (CuI) and cesium iodide (CsI) in an inducing manner.
Step 1: and sequentially carrying out ultrasonic cleaning on the glass substrate 1 etched with the ITO anode electrode 2 in deionized water, acetone and ethanol for 20min respectively, and putting the glass substrate into an ozone plasma processor to clean the surface for 4min after complete cleaning to obtain the ITO substrate.
Step 2: preparation of zinc oxide electron transport layer 3: the prepared ZnO solution is coated on an ITO substrate in a rotating speed of 3000rpm, and then annealing is carried out for 10min at 80 ℃.
And step 3: preparing a perovskite precursor solution: copper iodide (CuI) and cesium iodide (CsI) were mixed at a molar ratio of 3: 2 in a mixed solvent of dimethyl sulfoxide (DMSO) and dimethyl amide (DMF) in a volume ratio of 6:4, the final molar concentration of the precursor solution is 0.2mol/L, and the solution is stirred at 60 ℃ for 12 h.
And 4, step 4: and spin-coating the perovskite precursor solution on the zinc oxide electron transport layer 3 at the rotating speed of 4000rpm to prepare a perovskite thin film 4, placing the substrate on a hot table after spin-coating, and heating for 1h at the temperature of 100 ℃.
And 5: in the cavity of a vacuum coating machine, MoO is evaporated and coated under the condition of high vacuum 3 With a thickness of 10nm, a molybdenum oxide hole transport layer 5 was obtained.
Step 6: and (3) evaporating an Ag metal electrode layer 6 in a vacuum coating machine cavity under a high vacuum condition to obtain the perovskite light-emitting diode device.
Example 1:
as shown in fig. 1, a perovskite light emitting diode comprises a glass substrate 1, an ITO anode electrode 2, a zinc oxide electron transport layer 3, a perovskite thin film 4, a molybdenum oxide hole transport layer 5 and an Ag metal electrode layer 6 which are sequentially stacked from bottom to top; the perovskite thin film 4 has no voids between unit cells.
The perovskite thin film 4 is a cesium copper iodoperovskite thin film luminescent layer.
A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode is characterized in that a perovskite thin film is prepared by using a mixed solution of cuprous iodide (CuI) and cesium iodide (CsI) in an inducing manner.
Step 1: and sequentially carrying out ultrasonic cleaning on the glass substrate 1 etched with the ITO anode electrode 2 in deionized water, acetone and ethanol for 20min respectively, and putting the glass substrate into an ozone plasma processor to clean the surface for 4min after complete cleaning to obtain the ITO substrate.
Step 2: preparation of zinc oxide electron transport layer 3: coating the prepared ZnO solution on an ITO substrate in a rotating speed of 3000rpm, and then annealing for 10min at 80 ℃, wherein the ZnO solution is prepared by self, and the thickness of the zinc oxide electron transmission layer 3 is 30 nm;
the preparation method of the ZnO solution comprises the following steps:
firstly, material preparation: weighing 4g of anhydrous zinc acetate powder, placing the anhydrous zinc acetate powder into a three-neck flask, then adding 150mL of ethanol, heating to 85 ℃ under the nitrogen atmosphere, and stirring and dissolving by using a magnetic rotor until the anhydrous zinc acetate powder is in a clear and transparent state;
weighing 2g of potassium hydroxide, placing the potassium hydroxide in a beaker, adding 20mL of ethanol solution, sealing, and carrying out ultrasonic treatment for 20min to fully dissolve the potassium hydroxide until the potassium hydroxide is colorless and clear;
secondly, reaction process: when the anhydrous zinc acetate solution is fully dissolved and begins to boil stably, controlling a separating funnel to dropwise add the potassium hydroxide solution dissolved by ultrasonic waves into the anhydrous zinc acetate solution at a constant speed of 10 drops/min; after the dropwise addition, the two react at constant room temperature of 20 ℃ for 30min until the solution turns from clear to turbid white;
thirdly, purifying the product: after stopping heating, the reaction product was allowed to cool naturally to room temperature, at which time the solution in the three-necked flask was poured into a beaker, and then 150mL of n-hexane was added while stirring; then placing the beaker into a refrigerator at 0 ℃ for sedimentation for 2 hours, taking out the beaker after the first sedimentation is finished, and generating a large amount of milky white sediment at the bottom of the beaker; after removing the supernatant, adding 150mL of ethanol while stirring to fully disperse the precipitate, then sealing the beaker again and putting the beaker into a refrigerator for settling for 2 hours;
fourthly, generating a solution: after the second sedimentation is finished, removing supernatant in the beaker, taking suspension at the bottom of the beaker into a centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 5 minutes under the condition of 5000 r/min; then, adding the precipitate into high-purity ethanol and an ethanolamine dispersant respectively for ultrasonic dissolution; after the solution is fully dissolved, the solution is subjected to the centrifugal operation, and finally supernatant is taken, namely the product ZnO solution;
the purity ranges of the high-purity ethanol and the ethanolamine are 99.5-99.9%;
the dosage of the high-purity ethanol and the ethanolamine is 150mL respectively;
and step 3: preparing a perovskite precursor solution: copper iodide (CuI) and cesium iodide (CsI) were mixed at a molar ratio of 3: 2 is dissolved in a mixed solvent of dimethyl sulfoxide (DMSO) and dimethyl amide (DMF) with a volume ratio of 6:4, the final molar concentration of the precursor solution is 0.2mol/L, and the mixture is stirred at 60 ℃ for 12 hours.
And 4, step 4: after 65 mu L of the perovskite precursor liquid is dripped on the zinc oxide electronic transmission layer 3, spin coating is started at the rotating speed of 4000rmp, 200 mu L of toluene solution is used for rinsing for 3s immediately in the 15 th s of the spin coating process, the spin coating and the rinsing are carried out simultaneously, after the spin coating is finished for 50s, the perovskite thin film 4 is placed on a hot table at 100 ℃ for annealing for 1h, and the thickness of the perovskite thin film 4 is 70 nm;
and 5: in the cavity of a vacuum coating machine, MoO is evaporated and coated under the condition of high vacuum 3 The thickness is 10nm, and a molybdenum oxide hole transport layer 5 is obtained;
step 6: and (3) evaporating an Ag metal electrode layer 6 in a vacuum coating machine cavity under a high vacuum condition, wherein the thickness of the Ag metal electrode layer 6 is 90nm, and finally obtaining the perovskite light-emitting diode device.
Fig. 2 is a graph comparing J-V curves of perovskite light emitting diodes prepared in example 1 of the present invention and a comparative example, and it can be seen from fig. 2 that the photoelectric conversion efficiency of example 1 of the present invention is significantly superior to that of the comparative example.
The SEM characterization comparison results of the perovskite thin film prepared in example 1 are shown in fig. 3, and it can be seen from fig. 3 that the perovskite thin film prepared by CuI and CsI without using anti-solvent (a) has disordered crystals on the surface, more void defects between unit cells, and poor film quality, compared to the perovskite thin film prepared by CuI and CsI using anti-solvent in example 1 of the present invention, which has uniform and ordered crystals, tightly bound unit cells, no void defects between unit cells, and high film quality.
Fig. 4 is device diagrams before and after toluene flushing, the left diagram is a device without toluene flushing, and the right diagram is a device with toluene flushing, and it is obvious that the device flushed with anti-solvent toluene is easy to form a film, has high film forming quality, and plays an important role in improving the photoelectric efficiency of the device.
Example 2:
as shown in fig. 1, a perovskite light emitting diode comprises a glass substrate 1, an ITO anode electrode 2, a zinc oxide electron transport layer 3, a perovskite thin film 4, a molybdenum oxide hole transport layer 5 and an Ag metal electrode layer 6 which are sequentially stacked from bottom to top; the perovskite thin film 4 has no gap between unit cells.
The perovskite thin film 4 is a cesium copper iodoperovskite thin film luminescent layer.
A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode is characterized in that a perovskite thin film is prepared by using a mixed solution of cuprous iodide (CuI) and cesium iodide (CsI) in an inducing manner.
Step 1: and sequentially carrying out ultrasonic cleaning on the glass substrate 1 etched with the ITO anode electrode 2 in deionized water, acetone and ethanol for 30min respectively, completely cleaning, and then putting the glass substrate into an ozone plasma processor to clean the surface for 5min to obtain the ITO substrate.
Step 2: preparation of zinc oxide electron transport layer 3: spin-coating the prepared ZnO solution on an ITO substrate at the rotating speed of 2500rpm, and then annealing at 70 ℃ for 15min, wherein the ZnO solution is prepared by itself, and the thickness of the zinc oxide electron transmission layer 3 is 40 nm;
the preparation method of the ZnO solution comprises the following steps:
firstly, material preparation: weighing 4.5g of anhydrous zinc acetate powder, placing the anhydrous zinc acetate powder into a three-neck flask, then adding 160mL of ethanol, heating to 90 ℃ under the nitrogen atmosphere, and stirring and dissolving by using a magnetic rotor until the anhydrous zinc acetate powder is in a clear and transparent state;
weighing 2.5g of potassium hydroxide, placing in a beaker, adding 25mL of ethanol solution, sealing, and carrying out ultrasonic treatment for 25min to fully dissolve the potassium hydroxide until the potassium hydroxide is colorless and clear;
secondly, reaction process: when the anhydrous zinc acetate solution is fully dissolved and begins to boil stably, controlling a separating funnel to dropwise add the potassium hydroxide solution dissolved by ultrasonic waves into the anhydrous zinc acetate solution at a constant speed of 12 drops/min; after the dropwise addition, the two react at constant room temperature of 25 ℃ for 40min until the solution turns from clear to turbid white;
thirdly, purifying the product: after stopping heating, the reaction product was allowed to cool naturally to room temperature, at which time the solution in the three-necked flask was poured into a beaker, and then 200mL of n-hexane was added while stirring; then placing the beaker seal into a refrigerator with the temperature of 10 ℃ for sedimentation for 2.5 hours, taking out the beaker after the first sedimentation is finished, and then generating a large amount of milky white precipitate at the bottom of the beaker; removing the supernatant, adding 180mL of ethanol while stirring to fully disperse the precipitate, sealing the beaker again, and putting the beaker into a refrigerator for sedimentation for 2.5 hours;
fourthly, generating a solution: after the second sedimentation is finished, removing supernatant in the beaker, taking suspension at the bottom of the beaker into a centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 4 minutes at 4500 r/min; then, adding the precipitate into high-purity ethanol and an ethanolamine dispersant respectively for ultrasonic dissolution; after the solution is fully dissolved, the solution is subjected to the centrifugal operation, and finally the supernatant is taken, namely the product ZnO solution;
the purity ranges of the high-purity ethanol and the ethanolamine are 99.5-99.9%;
the dosage of the high-purity ethanol and the ethanolamine is 200mL respectively;
and step 3: preparing a perovskite precursor solution: copper iodide (CuI) and cesium iodide (CsI) were mixed at a molar ratio of 3: 2 in a mixed solvent of dimethyl sulfoxide (DMSO) and dimethyl amide (DMF) in a volume ratio of 6:4, the final molar concentration of the precursor solution is 0.3mol/L, and the solution is stirred at 70 ℃ for 11.5 h.
And 4, step 4: after 75 mu L of the perovskite precursor liquid is dripped on the zinc oxide electron transport layer 3, spin coating is started at the rotating speed of 3500rmp, 180 mu L of toluene solution is used for washing for 1s immediately in 12s in the spin coating process, the washing is carried out while the spin coating is carried out, after the spin coating is finished for 60s, the perovskite thin film 4 is placed on a 120 ℃ hot bench for annealing for 1.5h, and the thickness of the perovskite thin film 4 is 90 nm;
and 5: in a vacuum coating machine cavity, MoO is evaporated under the high vacuum condition 3 The thickness is 11nm, and a molybdenum oxide hole transport layer 5 is obtained;
and 6: and (3) evaporating an Ag metal electrode layer 6 in a vacuum coating machine cavity under a high vacuum condition, wherein the thickness of the Ag metal electrode layer 6 is 110nm, and finally obtaining the perovskite light-emitting diode device.
Example 3:
as shown in fig. 1, a perovskite light emitting diode comprises a glass substrate 1, an ITO anode electrode 2, a zinc oxide electron transport layer 3, a perovskite thin film 4, a molybdenum oxide hole transport layer 5 and an Ag metal electrode layer 6 which are sequentially stacked from bottom to top; the perovskite thin film 4 has no gap between unit cells.
The perovskite thin film 4 is a cesium copper iodine perovskite thin film light-emitting layer.
A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode is characterized in that a perovskite thin film is prepared by using a mixed solution of cuprous iodide (CuI) and cesium iodide (CsI) in an induction manner.
Step 1: and sequentially carrying out ultrasonic cleaning on the glass substrate 1 etched with the ITO anode electrode 2 in deionized water, acetone and ethanol for 40min respectively, and putting the glass substrate into an ozone plasma processor to clean the surface for 4.5min after complete cleaning to obtain the ITO substrate.
Step 2: preparation of zinc oxide electron transport layer 3: coating the prepared ZnO solution on an ITO substrate in a rotating speed of 2800rpm, and then annealing at 75 ℃ for 12min, wherein the ZnO solution is prepared by itself, and the thickness of the zinc oxide electron transmission layer 3 is 35 nm;
the preparation method of the ZnO solution comprises the following steps:
firstly, material preparation: weighing 4.2g of anhydrous zinc acetate powder, placing the anhydrous zinc acetate powder in a three-neck flask, then adding 155mL of ethanol, heating to 88 ℃ under the nitrogen atmosphere, and stirring and dissolving by using a magnetic rotor until the anhydrous zinc acetate powder is in a clear and transparent state;
weighing 2.1g of potassium hydroxide, placing the potassium hydroxide in a beaker, adding 23mL of ethanol solution, sealing, and carrying out ultrasonic treatment for 22min to fully dissolve the potassium hydroxide until the potassium hydroxide is colorless and clear;
II, reaction process: when the anhydrous zinc acetate solution is fully dissolved and begins to boil stably, controlling a separating funnel to dropwise add the potassium hydroxide solution dissolved by ultrasonic waves into the anhydrous zinc acetate solution at a constant speed of 11 drops/min; after the dropwise addition, the two react at constant room temperature of 23 ℃ for 50min until the solution turns from clear to turbid white;
thirdly, purifying the product: after stopping heating, the reaction product was allowed to cool naturally to room temperature, at which time the solution in the three-necked flask was poured into a beaker, and then 200mL of n-hexane was added while stirring; then placing the beaker seal into a refrigerator with the temperature of 5 ℃ for sedimentation for 2.2 hours, taking out the beaker after the first sedimentation is finished, and then generating a large amount of milky white precipitate at the bottom of the beaker; removing the supernatant, adding 160mL of ethanol while stirring to fully disperse the precipitate, sealing the beaker again, and putting the beaker into a refrigerator for settling for 2.3 hours;
fourthly, generating a solution: after the second sedimentation is finished, removing supernatant in the beaker, taking suspension at the bottom of the beaker into a centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 4.5 minutes under the condition of 4800 r/min; then, adding the precipitate into high-purity ethanol and an ethanolamine dispersant respectively for ultrasonic dissolution; after the solution is fully dissolved, the solution is subjected to the centrifugal operation, and finally supernatant is taken, namely the product ZnO solution;
the purity ranges of the high-purity ethanol and the ethanolamine are 99.5-99.9%;
the dosage of the high-purity ethanol and the ethanolamine is 180mL respectively;
and step 3: preparing a perovskite precursor solution: copper iodide (CuI) and cesium iodide (CsI) were mixed at a molar ratio of 3: 2 in a mixed solvent of dimethyl sulfoxide (DMSO) and dimethyl amide (DMF) in a volume ratio of 6:4, the final molar concentration of the precursor solution is 0.25mol/L, and the solution is stirred at 65 ℃ for 11.7 h.
And 4, step 4: after 70 mu L of the perovskite precursor liquid is dripped on the zinc oxide electron transport layer 3, spin coating is started at the rotating speed of 3750rmp, 190 mu L of toluene solution is used for washing for 2s immediately during the 14 th s of the spin coating process, the spin coating and the washing are carried out simultaneously, after the spin coating is finished for 55s, the perovskite thin film 4 is placed on a heating table at 110 ℃ for annealing for 1.2h, and the thickness of the perovskite thin film 4 is 80 nm;
and 5: in the cavity of a vacuum coating machine, MoO is evaporated and coated under the condition of high vacuum 3 The thickness is 10.5nm, and a molybdenum oxide hole transport layer 5 is obtained;
and 6: and (3) evaporating an Ag metal electrode layer 6 in a vacuum coating machine cavity under a high vacuum condition, wherein the thickness of the Ag metal electrode layer 6 is 100nm, and finally obtaining the perovskite light-emitting diode device.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode is characterized by comprising the following steps: the perovskite light-emitting diode comprises a glass substrate (1), an ITO anode electrode (2), a zinc oxide electron transport layer (3), a perovskite thin film (4), a molybdenum oxide hole transport layer (5) and an Ag metal electrode layer (6) which are sequentially overlapped from bottom to top; the crystal cells of the perovskite thin film (4) have no gaps;
the method for smoothly orienting the perovskite thin film comprises the following steps:
the method comprises the following steps: etching an ITO anode electrode (2) on the surface of a glass substrate (1) to obtain an ITO substrate;
step two: preparing a zinc oxide electron transport layer (3);
step three: preparing a perovskite precursor solution: mixing a mixture of 3: 2, dissolving cuprous iodide, CuI, and cesium iodide, CsI, in DMSO to DMF at a volume ratio of 6:4, magnetically stirring the mixture for 11.5 to 12 hours at the temperature of between 60 and 70 ℃ to obtain a precursor solution of the perovskite thin film (4), namely a perovskite precursor solution, wherein the final concentration of the perovskite precursor solution is 0.2 to 0.3 mol/L;
step four: preparation of the perovskite thin film (4): after 65-75 mu L of perovskite precursor liquid is dripped on the zinc oxide electronic transmission layer (3), spin coating is started at a rotating speed of 3500-4000 rmp, 180-200 mu L of toluene solution is immediately used for washing for 1-3 s when the coating is carried out for 12-15 s in the spin coating process, the coating is carried out while washing, after 50-60 s of spin coating is finished, the coating is placed on a 100-120 ℃ hot table for annealing for 1-1.5 h, and the thickness of the perovskite thin film (4) is 70-90 nm.
2. The method for smoothly orienting a perovskite thin film of a perovskite light-emitting diode according to claim 1, wherein: the perovskite thin film (4) is a cesium copper iodoperovskite thin film luminescent layer.
3. The method of claim 1, wherein: the preparation method of the ITO substrate comprises the following steps: and (3) sequentially carrying out ultrasonic cleaning on the glass substrate (1) etched with the ITO anode electrode (2) in deionized water, acetone and ethanol for more than 20min, completely cleaning, and then putting the glass substrate into an ozone plasma processor to clean the surface for 4-5 min to obtain the ITO substrate.
4. The method of claim 1, wherein: the preparation method of the zinc oxide electron transport layer (3) comprises the following steps: spin-coating a ZnO solution on an ITO substrate at the rotating speed of 2500-3000 rpm, and then annealing at 70-80 ℃ for 10-15 min to obtain a zinc oxide electron transport layer (3), wherein the thickness of the zinc oxide electron transport layer (3) is 30-40 nm.
5. The method of claim 1, wherein: further comprising the steps of:
step five: preparation of molybdenum oxide hole transport layer (5): in the cavity of the vacuum coating machine, MoO is evaporated on the surface of the perovskite film (4) 3 The thickness of the molybdenum oxide hole transport layer (5) is 10-11 nm;
step six: preparation of Ag metal electrode layer (6): and in a vacuum coating machine cavity, an Ag metal electrode is evaporated on the surface of the molybdenum oxide hole transport layer (5), and the thickness of the Ag metal electrode layer (6) is 90-110 nm.
6. The method of claim 4, wherein: the preparation method of the ZnO solution comprises the following steps:
firstly, material preparation: weighing 4-4.5 g of anhydrous zinc acetate powder, placing the anhydrous zinc acetate powder in a three-neck flask, adding 150-160 mL of ethanol, heating to 85-90 ℃ under the nitrogen atmosphere, and stirring and dissolving by using a magnetic rotor until the anhydrous zinc acetate powder is in a clear and transparent state;
weighing 2-2.5 g of potassium hydroxide, placing the potassium hydroxide in a beaker, adding 20-25 mL of ethanol solution, sealing, and carrying out ultrasonic treatment for 20-25 min to fully dissolve the potassium hydroxide until the potassium hydroxide is colorless and clear;
secondly, reaction process: when the anhydrous zinc acetate solution is fully dissolved and begins to boil stably, controlling a separating funnel to dropwise add the ultrasonically dissolved potassium hydroxide solution into the anhydrous zinc acetate solution at a constant speed of 10-12 drops/min; after the dropwise addition, reacting the two solutions at constant room temperature of 20-25 ℃ for more than 30min until the solution turns from clear to turbid white;
thirdly, purifying the product: stopping heating, naturally cooling the reactant to room temperature, pouring the solution in the three-neck flask into a beaker, and adding 150-200 mL of normal hexane while stirring; then placing the beaker into a refrigerator at 0-10 ℃ for sedimentation for 2-2.5 hours, taking out the beaker after the first sedimentation is finished, and then generating a large amount of milky white precipitate at the bottom of the beaker; removing the supernatant, adding 150-180 mL of ethanol while stirring to fully disperse the precipitate, then sealing the beaker again, and putting the beaker into a refrigerator to settle for 2-2.5 hours;
fourthly, generating a solution: after the second sedimentation is finished, removing supernatant in the beaker, taking turbid liquid at the bottom of the beaker into a centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 4-5 minutes under the condition of 4500-5000 r/min; then, adding the precipitate into high-purity ethanol and an ethanolamine dispersant respectively for ultrasonic dissolution; and after the solution is fully dissolved, the solution is subjected to the centrifugal operation, and finally the supernatant is taken, namely the product ZnO solution.
7. The method of claim 6, wherein: the purity ranges of the high-purity ethanol and the ethanolamine are 99.5-99.9%.
8. The method of claim 6, wherein: the dosage of the high-purity ethanol and the dosage of the ethanolamine are 150-200 mL respectively.
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