CN109593309B - Perovskite quantum dot film and structure containing perovskite quantum dot film - Google Patents
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Abstract
The invention discloses a perovskite quantum dot film and a structure containing the same, wherein the quantum dot film comprises: polyvinyl butyral; a plasticizer dispersed in the polyvinyl butyral; perovskite quantum dots which are dispersed in polyvinyl butyral to absorb ultraviolet rays and have the chemical formula ABX3Wherein, A is at least one of amine organic group and inorganic metal, B is at least one of Pb, Sn and Ge, and X is at least one of Cl, Br and I. The perovskite quantum dots in the perovskite quantum dot film have good light absorption performance, can absorb a large amount of ultraviolet rays, are not easy to degrade after absorbing the ultraviolet rays, and cannot be reduced or lose efficacy when absorbing the ultraviolet rays.
Description
Technical Field
The application belongs to the field of quantum dots, and particularly relates to a quantum dot film and a structure containing the quantum dot film.
Background
The excessively strong ultraviolet rays may damage the human body or discolor colored objects. In daily life, ultraviolet rays are prevented by using an ultraviolet absorbing film. In the conventional ultraviolet absorbing film, ultraviolet rays are absorbed by an ultraviolet absorber, thereby preventing ultraviolet rays.
However, these ultraviolet absorbers degrade over time, and thus adversely affect the absorption of ultraviolet rays by the ultraviolet absorbing film.
Disclosure of Invention
In view of the above technical problems, the present application provides a chemically stable ultraviolet absorbing film.
A perovskite quantum dot film comprising: polyvinyl butyral; a plasticizer dispersed in polyvinyl butyral (PVB); amount of perovskiteSub-dots dispersed in the polyvinyl butyral to absorb ultraviolet rays, and the chemical formula of the perovskite quantum dots is ABX3Wherein, A is at least one of amine organic group and inorganic metal, B is at least one of Pb, Sn and Ge, and X is at least one of Cl, Br and I.
The perovskite quantum dots in the perovskite quantum dot film have good light absorption performance, can absorb a large amount of ultraviolet rays, are not easy to degrade after absorbing the ultraviolet rays, and cannot be reduced or lose efficacy when absorbing the ultraviolet rays.
In one embodiment, the perovskite quantum dots have a fluorescence quantum efficiency of 0% to 30%; preferably, the perovskite quantum dot has a fluorescence quantum efficiency of 0% to 10%.
In one embodiment, the perovskite quantum dot is CsPbBr3And (4) quantum dots.
In one embodiment, the perovskite quantum dots are coated with a shell layer, and the shell layer is Cs4PbBr6Or Rb4PbBr6。
In one embodiment, the mass fraction of the perovskite quantum dots in the quantum dot film is 2% to 5%.
In one embodiment, the plasticizer comprises triethylene glycol diisooctanoate (3 GO); the mass ratio of the polyvinyl butyral to the triethylene glycol diisocaprylate is 3.5-2.5: 1.
in one embodiment, the polyvinyl butyral has a number average molecular weight of 10000 to 200000.
A structure containing a perovskite quantum dot film comprises a transparent substrate and the perovskite quantum dot film; the perovskite quantum dot film comprises: polyvinyl butyral; triethylene glycol diisocaprylate dispersed in polyvinyl butyral; perovskite quantum dots which are dispersed in polyvinyl butyral to absorb ultraviolet rays and have the chemical formula ABX3Wherein, A is at least one of amine organic group and inorganic metal, B is at least one of Pb, Sn and Ge, and X is at least one of Cl, Br and I.
In one embodiment, the thickness of the quantum dot film is 0.01-1 mm.
In one embodiment, two transparent substrates are included, and the two transparent substrates are respectively arranged on two sides of the quantum dot film.
Drawings
Fig. 1 is a schematic structural view of a perovskite quantum dot glass according to an embodiment of the present application.
In the drawings like parts are provided with the same reference numerals. The figures show embodiments of the application only schematically.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments.
The present embodiment discloses a quantum dot film including polyvinyl butyral, a plasticizer, and perovskite quantum dots, the plasticizer and the perovskite quantum dots being dispersed in the polyvinyl butyral. The perovskite quantum dots are used for absorbing ultraviolet rays. The chemical formula of the perovskite quantum dot is ABX3Wherein A is an amine organic group (e.g. CH)3NH3) And inorganic metal (such as Cs), B is at least one of Pb, Sn and Ge, and X comprises at least one of Cl, Br and I.
The perovskite quantum dot has excellent light absorption capacity, and particularly in an ultraviolet band, the perovskite quantum dot can absorb a large amount of ultraviolet rays, so that the quantum dot film has good ultraviolet ray absorption capacity. The quantum dot film fully utilizes the advantage of strong light absorption capacity of the perovskite quantum dots, and the perovskite quantum dots absorb ultraviolet rays, so that the perovskite quantum dots are not easy to degrade, and the ultraviolet absorption capacity of the quantum dot film cannot be obviously reduced and cannot be invalidated.
In the present embodiment, the perovskite quantum dots have a fluorescence quantum efficiency of 0% to 30%, and the light conversion efficiency of these perovskite quantum dots is low, and only a small amount of light is emitted after the perovskite quantum dots absorb light. Furthermore, the fluorescence quantum efficiency of the perovskite quantum dots is 0% -10%, and the perovskite quantum dots can hardly emit light or emit weak light after absorbing light. Therefore, after these perovskite quantum dots absorb ultraviolet rays, the intensity of light no longer undergoes photoconversion or conversion is very weak. That is to say, the quantum dot film after the perovskite quantum dots with the fluorescence quantum efficiency of 0% -30% or 0% -10% are adopted can absorb ultraviolet rays, and the quantum dot film does not emit light or emit light with weak intensity any more, and does not interfere or influence light with other wavelengths in the environment, so that adverse effects on daily life are avoided.
At present, when quantum dots are prepared or used, higher fluorescence quantum efficiency is pursued, and the fluorescence quantum efficiency is further improved. At present, the fluorescence quantum efficiency of some quantum dots can reach more than 95%. The low fluorescence quantum efficiency of quantum dots is considered a disadvantage. On the other hand, the perovskite quantum dots used in the present invention need not only higher fluorescence quantum efficiency but also lower fluorescence quantum efficiency as better. That is, the perovskite quantum dots employed in the present invention are capable of absorbing a large amount of light without converting the absorbed light into light or converting only a small portion of light. The quantum dot film skillfully utilizes the low fluorescence quantum efficiency of the perovskite quantum dots, and when the quantum dots which are considered to have obvious disadvantages are arranged in the quantum dot film, the quantum dot film absorbs ultraviolet rays and has little or no interference on light of other wave bands in the environment, so that the quantum dot film is widely applied to daily life, cannot generate adverse effect on the daily life, and has an advantage, thereby achieving the effect which is unexpected.
Here, the perovskite quantum dots having a high fluorescence quantum efficiency can be placed in an environment at a temperature of 85 ℃ and a relative humidity of 85% to reduce the fluorescence quantum efficiency of the perovskite quantum dots. After 48 hours in the environment, the fluorescence quantum efficiency of the perovskite quantum dots is obviously reduced, and the fluorescence quantum efficiency of the perovskite quantum dots can be reduced to be below 30%.
In this embodiment, the perovskite quantum dot may be CsPbBr3And (4) quantum dots. The inventor finds that CsPbBr is in perovskite quantum dots3The quantum dots have stable structure and excellent light absorption capacity, so that CsPbBr3Quantum dots can absorb much uv light. In other words, the quantum dot film adopts CsPbBr3The quantum dots can use a smaller amount of quantum dots when the same ultraviolet absorption effect is ensured, thereby saving the cost.
The outer layer of the perovskite quantum dot in the embodiment can be further coated with shell layers which are Cs4PbBr6Or Rb4PbBr6Therefore, the perovskite quantum dot has a stable structure and is not easily influenced by the outside.
After being irradiated by light, the perovskite quantum dot film needs to absorb ultraviolet rays and can transmit light in a visible light wave band. However, the wavelength of light cannot be selected ideally in the process of light absorption of perovskite quantum dots, and certain visible light is absorbed at the same time as ultraviolet light is absorbed. The inventor finds that the content of ultraviolet rays is low and the content of visible light is high in the solar spectrum, and when the mass fraction of the perovskite quantum dots in the quantum dot film is 2-5%, most of the ultraviolet rays in sunlight can be absorbed, but the perovskite quantum dot film hardly absorbs visible light (such as blue light) and does not affect the normal use of the perovskite quantum dot film.
The polyvinyl butyral has excellent optical property and chemical stability, so that the quantum dot film has excellent optical property and chemical stability. The quantum dot film has excellent transmittance for light of other wavelength bands while absorbing ultraviolet rays. After the plasticizer is added into the polyvinyl butyral, the perovskite quantum dots can have good dispersibility in the polyvinyl butyral. The plasticizer can be aliphatic dibasic acid esters, phthalic acid esters (including phthalic acid esters and terephthalic acid esters), benzene polyacid esters, benzoic acid esters, polyol esters, chlorinated hydrocarbons, epoxy compounds, citric acid esters, polyesters and the like. The inventors have found that perovskite quantum dots have very good dispersibility in polyvinyl butyral when the plasticizer is triethylene glycol diisooctanoate. In other words, under the action of triethylene glycol diisocaprylate, the perovskite quantum dots are not easy to agglomerate in polyvinyl butyral, and the light absorption capacity and the like of the perovskite quantum dots are not adversely affected. The perovskite quantum dots have excellent dispersion performance in the whole quantum dot film, obvious agglomeration phenomenon does not occur among the quantum dots, the ultraviolet absorption capacity is not greatly reduced, and the ultraviolet absorption is uniform on the whole. When the mass ratio of the polyvinyl butyral to the triethylene glycol diisocaprylate is 3.5-2.5: 1, the perovskite quantum dots have good dispersibility in the quantum dot film.
The inventor finds that when the number average molecular weight of the polyvinyl butyral is 10000-200000, the perovskite quantum dot film can have better stability and optical properties. Thereby improving the service life and the effect of the quantum dot film.
Referring now to fig. 1, this embodiment also discloses a structure 1 containing a perovskite quantum dot film, the structure 1 comprising a first transparent substrate 11 and the perovskite quantum dot film 12 described above. The perovskite quantum dot film 12 comprises polyvinyl butyral, triethylene glycol diisocaprylate and perovskite quantum dots, the perovskite quantum dots and the triethylene glycol diisocaprylate are dispersed in the polyvinyl butyral, and the perovskite quantum dots can absorb ultraviolet rays. The structure 1 can thus absorb ultraviolet rays, thereby reducing the adverse effects of ultraviolet rays on the human body and the like.
The thickness of the perovskite quantum dot film 12 is 0.01-1 mm, and the film has good ultraviolet absorption and good light transmittance.
Of course, the other side of the perovskite quantum dot film 12 may be provided with a second transparent substrate 13, thereby forming a sandwich structure in which the quantum dot film 12 is located between the first transparent substrate 11 and the second transparent substrate 13.
The specific structure of the perovskite quantum dot-containing film in the present invention will be described below with reference to several specific examples.
Example 1:
glass substrates are arranged on two sides of the quantum dot film. The thickness of the quantum dot film was 0.38 mm. The quantum dot film comprises CsPbBr3Quantum dots, triethylene glycol diisocaprylate and polyvinyl butyral, wherein the mass ratio of the quantum dots to the triethylene glycol diisocaprylate to the polyvinyl butyral is 1: 10: 30. the number average molecular weight of the polyvinyl butyral is 100000. CsPbBr3The fluorescence quantum efficiency of the quantum dots is 2.0%.
Example 2:
both sides of the quantum dot film are provided with PET substrates. The thickness of the quantum dot film was 0.76 mm. The quantum dot film comprises CsPbBr3Quantum dots, triethylene glycol diisocaprylate and polyvinyl butyral, wherein the mass ratio of the quantum dots to the triethylene glycol diisocaprylate to the polyvinyl butyral is 1: 5.5: 14. the polyvinyl butyral has a number average molecular weight of 12000. CsPbBr3The fluorescence quantum efficiency of the quantum dots is 4.2%.
Example 3:
one side of the quantum dot film is provided with a glass substrate, and the other side of the quantum dot film is provided with a barrier film. The thickness of the quantum dot film was 0.05 mm. The quantum dot film comprises CH3NH3PbBr3Quantum dots, triethylene glycol diisocaprylate and polyvinyl butyral, wherein the mass ratio of the quantum dots to the triethylene glycol diisocaprylate to the polyvinyl butyral is 1: 7: 21. the number average molecular weight of the polyvinyl butyral was 150000. CH (CH)3NH3PbBr3The fluorescence quantum efficiency of the quantum dots is 5.8%.
Example 4:
and PVC substrates are arranged on two sides of the quantum dot film. The thickness of the quantum dot film was 0.50 mm. The quantum dot film comprises CsPbI3Quantum dots, triethylene glycol diisocaprylate and polyvinyl butyral, wherein the mass ratio of the quantum dots to the triethylene glycol diisocaprylate to the polyvinyl butyral is 1: 4.8: 14.5. the number average molecular weight of the polyvinyl butyral is 100000. CsPbI3The fluorescence quantum efficiency of the quantum dots was 11.3%.
The quantum dot films of examples 1 to 4 were exposed to ultraviolet light for a long period of time, and the ultraviolet absorptance of the structures containing perovskite quantum dot films in the initial state and after the lapse of 800 hours of ultraviolet light irradiation were measured, and the specific values are shown in the following table. The ultraviolet absorptivity of the structure in the embodiment is obtained by irradiating the structure with light of 380 nm. It was found through measurement that the quantum dot films of examples 1 to 4 have no significant attenuation of the uv absorption rate after a long period of uv irradiation, so it can be seen that the quantum dot films of these examples have stable chemical properties, and the quantum dots are not easily degraded after absorbing uv.
| Initial state absorption rate | Absorption after 800 hours | |
| Example 1 | 98.6％ | 98.4％ |
| Example 2 | 99.3％ | 99.2％ |
| Example 3 | 98.1％ | 97.3％ |
| Example 4 | 99.5％ | 99.5％ |
As can be seen from the above examples, the uv absorption capacity of these structures containing perovskite quantum dot films is not significantly reduced over time. Since the quantum dot films are not greatly changed after long-term ultraviolet irradiation, the quantum dot films and the structures with the quantum dot films disclosed by the invention have better stability.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.
Claims (10)
1. A perovskite quantum dot film comprising: polyvinyl butyral;
a plasticizer dispersed in the polyvinyl butyral;
perovskite quantum dots dispersed in the polyvinyl butyral to absorb ultraviolet rays, the perovskite quantum dots having a chemical formula of ABX3Wherein A is at least one of amine organic group and inorganic metal, B is at least one of Pb, Sn and Ge, and X is at least one of Cl, Br and I;
wherein the fluorescence quantum efficiency of the perovskite quantum dots is 0-30%.
2. The perovskite quantum dot film of claim 1, wherein the perovskite quantum dots have a fluorescence quantum efficiency of 0% to 10%.
3. The perovskite quantum dot film of claim 1, wherein the perovskite quantum dots are CsPbBr3And (4) quantum dots.
4. The perovskite quantum dot film of claim 1, wherein the perovskite quantum dots are coated with a shell layer of Cs4PbBr6Or Rb4PbBr6。
5. The perovskite quantum dot film of claim 1, wherein the mass fraction of the perovskite quantum dots in the quantum dot film is between 2% and 5%.
6. The perovskite quantum dot film of claim 5, wherein the plasticizer comprises triethylene glycol diisooctanoate;
the mass ratio of the polyvinyl butyral to the triethylene glycol diisocaprylate is (3.5-2.5): 1.
7. the perovskite quantum dot film according to claim 1, wherein the polyvinyl butyral has a number average molecular weight of 10000 to 200000.
8. A structure containing a perovskite quantum dot film comprises a transparent substrate and the perovskite quantum dot film;
the perovskite quantum dot film comprises: polyvinyl butyral;
triethylene glycol diisooctanoate dispersed in the polyvinyl butyral;
perovskite quantum dots dispersed in the polyvinyl butyral to absorb ultraviolet rays, the perovskite quantum dots having a chemical formula of ABX3Wherein A is at least one of amine organic group and inorganic metal, B is at least one of Pb, Sn and Ge, and X is at least one of Cl, Br and I;
wherein the fluorescence quantum efficiency of the perovskite quantum dots is 0-30%.
9. The perovskite quantum dot film-containing structure of claim 8, wherein the quantum dot film has a thickness of 0.01 to 1 mm.
10. The perovskite quantum dot film-containing structure of claim 9, comprising two transparent substrates disposed on either side of the quantum dot film.
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