CN115466615A - Perovskite quantum dot-based luminescent thin film and preparation method and application thereof - Google Patents
Perovskite quantum dot-based luminescent thin film and preparation method and application thereof Download PDFInfo
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a luminescent film based on perovskite quantum dots, and a preparation method and application thereof. The luminescent film based on the perovskite quantum dots comprises composite perovskite and polyimide coating the composite perovskite; wherein, the composite perovskite comprises perovskite and passivating agent. The passivating agent is added to passivate the surface of the quantum dot, so that the further growth of the PQDs is limited, and the aggregation of the PQDs to form larger nanocrystals is avoided. The particle size of PQDs in the quantum dot film is only 5-10 nm, and the small particle size can effectively improve the luminous intensity. In addition, the surface of the existing perovskite quantum dot has a plurality of defects, and the more the defects are, the poorer the luminous intensity of the quantum dot is caused.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a luminescent film based on perovskite quantum dots and a preparation method and application thereof.
Background
All-inorganic perovskite CsPbX 3 The (X = Cl, br, I) quantum dots (PQDs) have wide application prospects in the fields of illumination, display and the like due to excellent photoelectric characteristics (high color purity and efficiency over 90%).
However, csPbX 3 PQDs are sensitive to the environment and are easily affected by light, heat, water, and oxygen, thus being disadvantageous for practical applications. There are many current improvements to CsPbX 3 Solutions to the stability of PQDs, however, also suffer from several deficiencies, such as: selecting and using CsPbX 3 The ligand with stronger binding capacity of the PQDs can effectively protect the quantum dots and improve the stability, but the ligand is easy to fall off from the surfaces of the quantum dots to cause the growth of the particles of the quantum dots so as to reduce the quantum efficiency (PLQY); in CsPbX 3 The stability of PQDs can be improved to some extent by doping them with other ions, but CsPbX is affected 3 Intrinsic emission of PQDs; in addition, organic or inorganic materials are coated on the surface of the PQDs, so that the PQDs can be effectively prevented from being corroded by water oxygen, and strong chemical action can be generated between functional groups in the polymer and the PQDs, so that the influence of environmental factors on the PQDs is weakened due to the combined action of the functional groups and the PQDs, and the PQDs are an effective way for improving the stability of the PQDs, but the synthesis steps are very complicated. In general, quantum dot composites are mostly prepared by synthesizing CsPbX by thermal injection 3 PQDs, and then organic or inorganic coated two-step process. For example: firstly, PQDs is synthesized, and then quantum dots and mesoporous SiO are added 2 Mixed to form CsPbBr 3 @SiO 2 Or crosslinking styrene after preparing quantum dotsThe globule is swelled in good solvent containing PQDs, and then transferred to poor solvent for shrinkage, so as to obtain the nanometer and micrometer scale luminescent globule. Although these methods can improve the stability of quantum dots to some extent, the synthesis steps are cumbersome, which is disadvantageous for industrial production. In addition, the particle size of the conventional perovskite quantum dot is too large, and the luminous intensity is small.
Therefore, a novel perovskite quantum dot and modification method is urgently needed to solve the problems.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a luminescent thin film based on perovskite quantum dots is provided.
The second technical problem to be solved by the invention is:
a preparation method of the luminescent film based on the perovskite quantum dots is provided.
The third technical problem to be solved by the invention is:
application of the luminescent thin film based on perovskite quantum dots.
In order to solve the first technical problem, the technical scheme adopted by the invention is as follows:
a luminescent thin film based on perovskite quantum dots comprises a composite perovskite and polyimide coating the composite perovskite;
wherein the composite perovskite comprises a perovskite and a passivating agent.
According to the embodiment of the invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
1. in the luminescent film based on the perovskite quantum dots, the composite perovskite quantum dots are coated by polyimide, so that the quantum dots have excellent stability.
2. The passivating agent is added to passivate the surface of the quantum dot, so that the further growth of the PQDs is limited, and the aggregation of the PQDs to form larger nanocrystals is avoided. The particle size of PQDs in the quantum dot film is only 5-10 nm, and the small particle size can effectively improve the luminous intensity. In addition, the surface of the existing perovskite quantum dot often has a plurality of defects, and the more the defects are, the poorer the luminous intensity of the quantum dot is, the passivating agent is added in the luminous film of the perovskite quantum dot, so that the defects of the quantum dot can be eliminated, and the luminous intensity is improved.
According to an embodiment of the invention, the passivating agent comprises at least one of oleic acid, oleylamine, octylamine octanoate, dodecylbenzene sulphonic acid, dodecyldimethyl ammonium bromide and hexadecyltrimethyl ammonium bromide. Oleic acid and oleylamine are both long-chain (18 carbon) macromolecules, can limit the growth of perovskite quantum dots in space, and if the growth is not limited, the grown quantum dots can be agglomerated into nano crystals, so that the luminous intensity can be reduced. Thus, the passivation of oleic acid and oleylamine refers to the "elimination" of quantum dot surface defects and avoidance of CsPbBr 3 The quantum dots grow into large nanocrystals, which are all intended to increase the emission intensity of the quantum dots.
According to one embodiment of the invention, the amount of the passivating agent is 1 to 5mL.
In order to solve the second technical problem, the invention adopts the technical scheme that:
a method of preparing the perovskite quantum dot based luminescent thin film, comprising the steps of:
and mixing the composite perovskite and polyimide, and reacting to obtain the luminescent film based on the perovskite quantum dots.
According to the embodiment of the invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
the method for preparing the luminescent film based on the perovskite quantum dots adopts a one-step method to realize the aim that the CsPbBr is subjected to PI (polyimide) 3 In situ encapsulation of PQDs, thereby avoiding CsPbBr 3 The complicated steps of respectively preparing PQDs and PI and then wrapping are adopted, so that the preparation time of the quantum dot and the polymer film is saved, the production cost is reduced, and the economic benefit is improved.
According to one embodiment of the invention, the raw materials for preparing the composite perovskite comprise the following components: lead halides and cesium halides.
According to one embodiment of the invention, the molar ratio of the lead halide to the cesium halide is from 1 to 3:1 to 3.
According to an embodiment of the present invention, the lead halide includes at least one of lead bromide, lead chloride and lead iodide.
According to one embodiment of the invention, the cesium halide comprises at least one of cesium bromide, cesium chloride and cesium iodide.
According to one embodiment of the invention, the preparation of the composite perovskite comprises the following steps: mixing lead halide, cesium halide and a passivating agent, reacting for 30-90 min at 60-90 ℃, and then reacting for 10-30 min at 110-150 ℃ to obtain the composite perovskite.
According to one embodiment of the present invention, the raw materials for preparing the polyimide comprise the following components: the polyimide precursor reagent is used in an amount of 3 to 9g.
According to an embodiment of the present invention, the method of preparing the perovskite quantum dot based luminescent thin film comprises the following steps:
dissolving 0.4-1.2 mmol of lead halide and 0.4-1.2 mmol of cesium halide in 10-30 ml of solvent, and fully stirring for 15-45 min (500 rpm/min); then, 1-5 ml of passivating agent is added to be continuously stirred for 5-10 min (500 rpm/min) to obtain a first mixed solution; and (2) sufficiently mixing 0.5-1.5 ml of mixed solution with 3-9 g of polyimide precursor solution to obtain a second mixed solution, dripping 0.2-0.6 g of the second mixed solution on a quartz glass sheet, placing the quartz glass sheet in a vacuum drying oven, drying at low temperature (60-90 ℃) for 30-90 min and at high temperature (110-150 ℃) for 10-30 min, and naturally cooling to room temperature to prepare the luminescent film based on the perovskite quantum dots.
According to an embodiment of the present invention, a method of preparing the perovskite quantum dot based light emitting thin film includes the following reaction formula:
(1) The reaction formula for forming perovskite quantum dots: pbBr 2 +CsBr＝CsPbBr 3 。
(2) The monomer is polymerized to form polyimide according to the reaction formula: a polyimide precursor reagent comprising at least two monomers: hexafluoro anhydride and diamine, which are dissolved in N, N-dimethylformamide, react for 30-90 min at 60-90 ℃ and then react for 10-30 min at 110-150 ℃, thus generating polyimide by polymerization.
(3) Reaction formula of the composite film: the first two reactions are carried out simultaneously, and CsPbBr is formed in one step 3 Quantum dot and polyimide composite luminescent film.
In another aspect, the invention also relates to the application of the luminescent thin film of the perovskite quantum dot in illumination. Comprising a perovskite quantum dot based luminescent thin film as described in the embodiment of aspect 1 above. Since the application adopts all the technical schemes of the luminescent thin film based on the perovskite quantum dots, the luminescent thin film has at least all the beneficial effects brought by the technical schemes of the embodiments.
In still another aspect, the invention also relates to the application of the luminescent thin film of the perovskite quantum dot in a display screen. Comprising a perovskite quantum dot based luminescent thin film as described in the embodiment of aspect 1 above. Since the application adopts all the technical schemes of the luminescent thin film based on the perovskite quantum dots, the luminescent thin film has at least all the beneficial effects brought by the technical schemes of the embodiments.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph showing an emission spectrum of a luminescent film prepared in example 1 under ultraviolet light excitation.
Fig. 2 is a TEM (transmission electron microscope) test chart of the luminescent thin film prepared in example 4.
FIG. 3 is an X-ray photoelectron spectrum of the luminescent thin film prepared in example 5.
Fig. 4 is a TEM test image of the luminescent thin film prepared in the comparative example.
Fig. 5 is an emission spectrum test chart of the luminescent thin film prepared in the comparative example and the perovskite quantum dot-based luminescent thin film prepared in example 1.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention and are not to be construed as limiting the present invention.
In the description of the present invention, if there are first, second, etc. described, it is only for the purpose of distinguishing technical features, and it is not understood that relative importance is indicated or implied or that the number of indicated technical features is implicitly indicated or that the precedence of the indicated technical features is implicitly indicated.
In the description of the present invention, it should be understood that the orientation or positional relationship referred to, for example, the upper, lower, etc., is indicated based on the orientation or positional relationship shown in the drawings, and is only for convenience of description and simplification of description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that unless otherwise explicitly defined, terms such as arrangement, installation, connection and the like should be broadly understood, and those skilled in the art can reasonably determine the specific meanings of the above terms in the present invention in combination with the specific contents of the technical solutions.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
In examples and comparative examples, polyimide precursor reagents were purchased from New materials, inc. available in Dongguan; the product model is as follows: a transparent polyimide resin; the goods number is: DNSI-6CF20.
Example 1
The method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are weighed out and placed in a 20ml glass bottle.
(2) 0.4mmol of PbBr was weighed separately 2 0.4mmol CsBr was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 0.5ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixed solution was weighed and placed in a 5ml beaker, and thoroughly mixed with 3g of the polyimide precursor solution, stirred with a glass rod for 2min, and then allowed to stand for 20min.
(5) 0.2g of the above mixed solution was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) And setting the condition as 70 ℃ for 30min, continuously heating to 120 ℃ for 10min, naturally cooling to room temperature after the program is finished, and taking out.
Example 2
Example 2 differs from example 1 in that: example 2 PbBr 2 The amounts used with CsBr were 0.6mmol. Specifically, the method comprises the following steps:
the method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are weighed out and placed in a 20ml glass bottle.
(2) 0.6mmol of PbBr was weighed separately 2 0.6mmol CsBr was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 0.5ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixture was weighed and placed in a 5ml beaker, and mixed thoroughly with 3g of the polyimide precursor solution, stirred with a glass rod for 2min and then allowed to stand for 20min.
(5) 0.2g of the above mixed solution was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) Setting the conditions as 70 ℃ for 30min, continuously heating to 120 ℃ for 10min, naturally cooling to room temperature after the program is finished, and taking out.
Example 3
Example 3 differs from example 1 in that: the amounts of oleic acid and oleylamine used in example 3 were 1ml each. Specifically, the method comprises the following steps:
the method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are weighed out and placed in a 20ml glass bottle.
(2) 0.4mmol of PbBr was weighed separately 2 0.4mmol CsBr was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 1ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixture was weighed and placed in a 5ml beaker, and mixed thoroughly with 3g of the polyimide precursor solution, stirred with a glass rod for 2min and then allowed to stand for 20min.
(5) 0.2g of the above mixture was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) Setting the conditions as 70 ℃ for 30min, continuously heating to 120 ℃ for 10min, naturally cooling to room temperature after the program is finished, and taking out.
Example 4
Example 4 differs from example 1 in that: the polyimide precursor solution in example 4 was 6g. Specifically, the method comprises the following steps:
the method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are weighed out and placed in a 20ml glass bottle.
(2) 0.4mmol of PbBr was weighed separately 2 0.4mmol CsBr was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 0.5ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixed solution was weighed out and placed in a 5ml beaker, and mixed thoroughly with 6g of the polyimide precursor solution, stirred with a glass rod for 2min, and then left to stand for 20min.
(5) 0.2g of the above mixture was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) And setting the condition as 70 ℃ for 30min, continuously heating to 120 ℃ for 10min, naturally cooling to room temperature after the program is finished, and taking out.
Example 5
Example 5 differs from example 1 in that: in the step (6), the time for 10min is changed to 30min. Specifically, the method comprises the following steps:
the method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are weighed out and placed in a 20ml glass bottle.
(2) 0.4mmol of PbBr was weighed separately 2 0.4mmol CsBr was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 0.5ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixture was weighed and placed in a 5ml beaker, and mixed thoroughly with 3g of the polyimide precursor solution, stirred with a glass rod for 2min and then allowed to stand for 20min.
(5) 0.2g of the above mixture was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) Setting the conditions as 70 ℃ for 30min, continuously heating to 120 ℃ for 30min, naturally cooling to room temperature after the program is finished, and taking out.
Example 6
Example 6 differs from example 1 in that: in step (2), pbBr of example 1 was added 2 And CsBr, in turn substituted by PbI 2 And CsI. Specifically, the method comprises the following steps:
the method for preparing the luminescent film based on the perovskite quantum dots comprises the following steps:
(1) 10ml of DMF (N, N-dimethylformamide) solution are taken in a 20ml glass bottle.
(2) 0.4mmol of PbI was weighed separately 2 0.4mmol of CsI was poured into the above DMF containing glass bottle and placed on a magnetic stirrer and stirred at 500rpm/min for 20min to dissolve it sufficiently.
(3) 1ml of oleic acid and 0.5ml of oleylamine were added to the above solution respectively and stirring was continued for 5min.
(4) 1ml of the mixture was weighed and placed in a 5ml beaker, and mixed thoroughly with 3g of the polyimide precursor solution, stirred with a glass rod for 2min and then allowed to stand for 20min.
(5) 0.2g of the above mixture was poured onto a smooth quartz glass plate and then placed in a vacuum drying oven.
(6) Setting the conditions as 70 ℃ for 30min, continuously heating to 120 ℃ for 10min, naturally cooling to room temperature after the program is finished, and taking out.
Comparative example
A method of making a luminescent film comprising the steps of:
(1) 0.2mmol of PbBr 2 And 0.2mmol CsBr in 5ml DMF to form a colorless transparent solution.
(2) The solution was added to a beaker, 15g of the polyimide precursor was added and sufficiently stirred. Subsequently, 0.2g of the mixture was taken out on a quartz glass plate, and was put into a vacuum drying oven to be dried at 85 ℃ for 30min and then at 120 ℃ for 30min.
(3) Cooling to room temperature and taking out.
Wherein no passivating agent was added in the comparative examples.
And (4) performance testing:
an emission spectrum test is performed on the luminescent film prepared in example 1, and as shown in fig. 1, fig. 1 is a graph of an emission spectrum of the luminescent film prepared in example 1 under ultraviolet light excitation. From FIG. 1, it can be seen that the main peak of the emission peak of the sample is 521nm. The composite film can be seen in the inset of fig. 1 to emit green light under ultraviolet excitation.
The luminescent film prepared in example 1 was wiped with a piece of dust-free paper stained with ethanol, and the luminescence intensity of the wiped area was not significantly attenuated. As can be seen from this phenomenon, the quantum dot prepared in example 1 is "encapsulated" inside the polyimide because if the quantum dot is attached to the surface of the light emitting film, it can be completely erased by the dust-free paper impregnated with ethanol.
The luminescent film prepared in example 4 was subjected to TEM test. The test results are shown in fig. 2. From (a) in FIG. 2, csPbBr is clearly monodispersed 3 PQDs, no significant agglomeration occurs; from (b) in FIG. 2, csPbBr with clear lattice fringes can be seen 3 PQDs, in general, have a size of 5 to 10nm. The results show that the method can successfully prepare CsPbBr by one step 3 The size of the prepared quantum dot is smaller than that of the existing CsPbBr without ligand 3 @PI。
FIG. 3 is the X-ray photoelectron spectrum of the luminescent film prepared in example 5, and it can be seen from FIG. 3 that Cs, pb and Br in the composite luminescent film are +1, +2 and-1, respectively, and CsPbBr 3 Consistently, indirectly demonstrated that CsPbBr was formed in the synthesis of the composite film 3 PQDs。
The light emitting film prepared in the comparative example was subjected to TEM test, and the test results are shown in fig. 4. As can be seen from fig. 4, since the passivation agent was not included in the raw material of the comparative example, significant agglomeration of the quantum dots occurred.
The emission spectrum test was performed on the luminescent thin film prepared in the comparative example and the luminescent thin film based on perovskite quantum dots prepared in example 1, and the test results are shown in fig. 5. As can be seen from the figure, since the passivating agent is added to the light-emitting film of example 1: oleic acid and oleylamine, the emission spectrum intensity of the quantum dots is obviously enhanced, and the passivation effect of the oleic acid oleylamine can be fully demonstrated to promote the spectrum intensity. In addition, the emission peak position and the size of the quantum dot have a direct relation, and the smaller the size is, the shorter the position of the emission peak is shifted. After the oleic acid oleylamine is added, the emission peak position moves towards the short wave direction (moves towards the left) because the oleic acid oleylamine limits the growth of the quantum dots, and the size of the quantum dots is smaller.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or the related technical fields, which are directly or indirectly applied, are included in the scope of the present invention.
Claims (10)
1. A luminescent thin film based on perovskite quantum dots is characterized in that:
the composite perovskite-coated polyimide ceramic material comprises a composite perovskite and polyimide coating the composite perovskite;
wherein the composite perovskite comprises a perovskite and a passivating agent.
2. A luminescent thin film based on perovskite quantum dots as claimed in claim 1, wherein: the passivating agent comprises at least one of oleic acid, oleylamine, octylamine octanoate, dodecylbenzene sulfonic acid, dodecyl dimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
3. A luminescent thin film based on perovskite quantum dots as claimed in claim 1, wherein: the dosage of the passivator is 1-5 mL.
4. A method of preparing a perovskite quantum dot based luminescent thin film as claimed in any one of claims 1 to 3, wherein: the method comprises the following steps:
and mixing the composite perovskite and polyimide, and reacting to obtain the luminescent film based on the perovskite quantum dots.
5. The method of claim 4, wherein: the raw materials for preparing the composite perovskite comprise the following components: lead halides and cesium halides.
6. The method of claim 4, wherein: preparing the composite perovskite, comprising the following steps: mixing lead halide, cesium halide and a passivating agent, reacting for 30-90 min at 60-90 ℃, and then reacting for 10-30 min at 110-150 ℃ to obtain the composite perovskite.
7. The method of claim 6, wherein: the lead halide includes at least one of lead bromide, lead chloride and lead iodide.
8. The method of claim 6, wherein: the cesium halide includes at least one of cesium bromide, cesium chloride, and cesium iodide.
9. The method of claim 4, wherein: the raw materials for preparing the polyimide comprise the following components: the polyimide precursor reagent is used in an amount of 3 to 9g.
10. Use of a luminescent thin film based on perovskite quantum dots as claimed in any one of claims 1 to 3 in lighting or display screens.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116004230A (en) * | 2023-02-09 | 2023-04-25 | 温州锌芯钛晶科技有限公司 | CsPbI with controllable crystal growth 3 Perovskite quantum dot and preparation method thereof |
| CN116410747A (en) * | 2023-03-20 | 2023-07-11 | 中国科学院长春光学精密机械与物理研究所 | Ultra-small-size CsPbBr with high luminous performance 3 Preparation method of perovskite quantum dot |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016180364A1 (en) * | 2015-05-14 | 2016-11-17 | 北京理工大学 | Perovskite/polymer composite luminescent material, preparation method and application |
| CN107949925A (en) * | 2015-06-30 | 2018-04-20 | 剑桥企业有限公司 | Light-emitting device |
| CN113501993A (en) * | 2021-07-14 | 2021-10-15 | 上海应用技术大学 | Mn (manganese)2+Cesium-lead-halogen-doped perovskite quantum dot film and preparation method thereof |
-
2022
- 2022-09-29 CN CN202211201473.9A patent/CN115466615A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016180364A1 (en) * | 2015-05-14 | 2016-11-17 | 北京理工大学 | Perovskite/polymer composite luminescent material, preparation method and application |
| CN107949925A (en) * | 2015-06-30 | 2018-04-20 | 剑桥企业有限公司 | Light-emitting device |
| CN113501993A (en) * | 2021-07-14 | 2021-10-15 | 上海应用技术大学 | Mn (manganese)2+Cesium-lead-halogen-doped perovskite quantum dot film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| DONG WANG ET AL.: "in Situ Green Preparation of Highly Stable CsPbBr3–Polyimide Films for Flexible Liquid Crystal Displays", ADVANCED OPTICAL MATERIALS, 28 June 2022 (2022-06-28), pages 2200772 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116004230A (en) * | 2023-02-09 | 2023-04-25 | 温州锌芯钛晶科技有限公司 | CsPbI with controllable crystal growth 3 Perovskite quantum dot and preparation method thereof |
| CN116004230B (en) * | 2023-02-09 | 2023-09-26 | 温州锌芯钛晶科技有限公司 | CsPbI with controllable crystal growth 3 Perovskite quantum dot and preparation method thereof |
| CN116410747A (en) * | 2023-03-20 | 2023-07-11 | 中国科学院长春光学精密机械与物理研究所 | Ultra-small-size CsPbBr with high luminous performance 3 Preparation method of perovskite quantum dot |
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