Method for synthesizing perovskite quantum dot film
11193060 · 2021-12-07
Assignee
- National Taiwan University Of Science And Technology (Taipei, TW)
- National Taiwan Normal University (Taipei, TW)
- National Taiwan University (Taipei, TW)
Inventors
- Chih-Hao Chiang (Taipei, TW)
- Ting-You Li (Taipei, TW)
- Meng-Lin Tsai (Taipei, TW)
- Ya-Ju Lee (Taipei, TW)
- Hsiang-Chieh Lee (Taipei, TW)
Cpc classification
C09K11/025
CHEMISTRY; METALLURGY
International classification
Abstract
Provided is a method for synthesizing a perovskite quantum dot film, including: preparing a cellulose nanocrystal (CNC) solution, wherein the CNC solution includes a plurality of CNCs with sulfate groups; preparing a precursor solution; mixing the CNC solution and the precursor solution to form a mixed solution; and filtering and drying the mixed solution to form a perovskite quantum dot film.
Claims
1. A method for synthesizing a perovskite quantum dot film, comprising: preparing a cellulose nanocrystal (CNC) solution, wherein the CNC solution comprises a plurality of CNCs with sulfate groups; preparing a precursor solution; mixing the CNC solution and the precursor solution to form a mixed solution; and filtering and drying the mixed solution to form a perovskite quantum dot film, wherein the perovskite quantum dot film comprises a plurality of perovskite quantum dots uniformly distributed among the CNCs, and the perovskite quantum dots are represented by the following formula (1):
ABX.sub.3 (1), wherein A comprises an inorganic cation or an organic amine, the inorganic cation comprises Li, Na, K, Rb, Cs or a combination thereof, and the organic amine comprises ammonia, methylamine, formamidine acetate, formamidine amine, formamidine, ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine, isopropyl amine, trimethylenediamine, ethylamine, butylamine, isobutylamine, tert-butyl amine, diethylamine, 5-aminovaleric acid, 2-thiophene methylamine, hexylamine, aniline, benzylamine, phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosamine or a hereof; B comprises Cd, Co Cr Cu Fe, Ge, Pb Sn or a combination thereof; and X comprises halogen.
2. The method for synthesizing the perovskite quantum dot film according to claim 1, wherein preparing the CNC solution comprises: dissolving CNC powder in water to form a first solution; and dissolving the first solution in an organic solvent to form the CNC solution.
3. The method for synthesizing the perovskite quantum dot film according to claim 2, wherein flexibility and a tensile property of the perovskite quantum dot film increase with an increase of a water content of the first solution.
4. The method for synthesizing the perovskite quantum dot film according to claim 1, wherein the sulfate groups of the CNCs are connected with the perovskite quantum dots to improve stability of the perovskite quantum dot film.
5. The method for synthesizing the perovskite quantum dot film according to claim 1, wherein preparing the precursor solution comprises: providing a first precursor comprising A and X; providing a second precursor comprising B and X; and adding the first precursor and the second precursor into an organic solvent and uniformly mixing the first precursor, the second precursor and the organic solvent.
6. The method for synthesizing the perovskite quantum dot film according to claim 5, wherein a wavelength of light emitted by the perovskite quantum dots increases with an increase of a concentration of the precursor solution.
7. The method for synthesizing the perovskite quantum dot film according to claim 1, wherein each CNC has a length of 100 nm to 300 nm and a width of 3 nm to 20 nm.
8. The method for synthesizing the perovskite quantum dot film according to claim 1, wherein a molecular weight of the CNC is 14700 to 27850.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
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DESCRIPTION OF THE EMBODIMENTS
(9) The present invention will be fully explained with reference to the drawings of the embodiments. However, the present invention may also be embodied in various different forms and should not be limited to the embodiments described in the specification. Thicknesses of layers or regions may be enlarged for clarity. Same or like reference numerals are used to indicate same or like elements. Details may be omitted in the description of the following sections.
(10) In this specification, a range represented by “from a numerical value to another numerical value” is a summary representation that avoids enumerating all numerical values in this range one by one. Therefore, recording a specific numerical range is equivalent to disclosing any numerical value within this numerical range and a smaller numerical range defined by another numerical value within this numerical range, as if the numerical value and the smaller numerical range are explicitly written in the specification. For example, recording a range of “particle diameter ranging from 5 nm to 15 nm” is equivalent to disclosing a range of “particle diameter ranging from 10 nm to 13 nm”, regardless of whether other numerical values are listed in the specification.
(11)
(12) Referring to
(13) It is worth noting that, in the present embodiment, the CNC solution includes a plurality of CNCs with sulfate groups. For example, the CNC may be represented by the following structure:
(14) ##STR00001##
(15) In this case, as illustrated in
(16) Next, step S104 of preparing a precursor solution is performed. Specifically, preparing the precursor solution may include the following steps: providing a first precursor with a first inorganic halide; providing a second precursor with a second inorganic halide; and adding the first precursor and the second precursor to an organic solvent and uniformly mixing the first precursor, the second precursor and the organic solvent.
(17) In some embodiments, the first inorganic halide may be any one or a combination of halides of metals Li, Na, K, Rb and Cs. The second inorganic halide may be any one or a combination of halides of metals Cd, Co, Cr, Cu, Fe, Ge, Pb and Sn. The organic solvent may be dimethylformamide (DMF), dimethylsulfoxide (DMSO), trimethyl phosphate (TMP), triethyl phosphate (TEP), N-methylpyrrolidone (NMP), dimethylacetamide (DMAC) or a combination thereof. In some embodiments, a Moore concentration of the first inorganic halide in the precursor solution is 0.01 M to 0.08 M, and is about 0.04 M. A Moore concentration of the second inorganic halide in the precursor solution is 0.01 M to 0.08 M, and is about 0.04 M. In the present embodiment, the first inorganic halide is different from the second inorganic halide. For example, the first precursor may be CsBr, the second precursor may be PbBr.sub.2, and the organic solvent may be DMF. In this case, as illustrated in
(18) In one alternative embodiment, the first precursor may include an organic amine halide, which may be any one or a combination of halides of ammonia, methylamine, formamidine acetate, formamidine amine, formamidine, ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine, isopropylamine, trimethylenediamine, ethylamine, butylamine, isobutylamine, tert-butylamine, diethylamine, 5-aminovaleric acid, 2-thiophene methylamine, hexylamine, aniline, benzylamine, phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosamine. For example, the first precursor may be methanaminium bromide (MABr).
(19) Next, step S106 of mixing the CNC solution and the precursor solution to form a mixed solution is performed. In some embodiments, as illustrated in
(20) Finally, step S108 of filtering and drying the mixed solution to form a perovskite quantum dot film is performed. Specifically, as illustrated in
(21)
ABX.sub.3 (1),
where A includes an inorganic cation or an organic amine, the inorganic cation includes Li, Na, K, Rb, Cs or a combination thereof, and the organic amine includes ammonia, methylamine, formamidine acetate, formamidine amine, formamidine, ethylenediamine, dimethylamine, imidazole, acetamidine, propylamine, isopropylamine, trimethylenediamine, ethylamine, butylamine, isobutylamine, tert-butylamine, diethylamine, 5-aminovaleric acid, 2-thiophene methylamine, hexylamine, aniline, benzylamine, phenylethylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosamine or a combination thereof; B includes Cd, Co, Cr, Cu, Fe, Ge, Pb, Sn or a combination thereof; and X includes halogen, such as F, Cl, Br or I.
(22) As illustrated in an enlarged part of
(23) In order to prove the realizability of the invention, several examples are listed below to further describe the perovskite quantum dots of the invention. Although the following experiments are described, without going beyond the scope of the invention, the materials used, the amount and theratio thereof, the treatment details, the treatment flow and the like may be appropriately changed. Therefore, the invention should not be restrictively explained based on the experiments described below.
Experimental Example 1
(24) CNC powder (purchased from Celluforce) was dissolved in deionized water to form a first solution with a concentration of 5 wt %. Next, a first solution was dropped into DMF (purchased from Aencore, with a purity of 99.5%) to form a CNC solution with a concentration of 1 wt %. Then, 0.4 mmol of CsBr (purchased from Alfa Aesar, with a purity of 99%) and 0.4 mmol of PbBr.sub.2 (purchased from FMPV, with a purity of 98%) were put into a flask, 20 ml of DMF (purchased from Aencore, with a purity of 99.5%) were added, and the mixture was mixed uniformly to form a CsPbBr.sub.3 precursor solution. Next, 20 ml of CsPbBr.sub.3 precursor solution was mixed with 10 ml of the CNC solution and stirred at room temperature (about 25° C.) for at least 30 min to form a mixed solution. Then, the mixed solution was poured into a Buchner funnel for vacuum filtration and drying to form a CsPbBr.sub.3 inorganic perovskite quantum dot film (hereinafter referred to as IPQD of Experimental Example 1). Then, the IPQD of Experimental Example 1 was subjected to PL emission spectrum, UV-vis absorption spectrum and XRD analysis. The results are as illustrated in
(25) Referring to
(26) In addition,
Comparative Example 1
(27) 0.05 M of a CsPbBr.sub.3 solution was prepared in 5 ml of DMF (purchased from Aencore, with a purity of 99.5%) and mixed with 200 μl of oleic acid (purchased from Showa, with a purity of 99%) and 50 μl of oleylamine (purchased from ACROS Organics, with a purity of 90%) to form a precursor solution. Then, 0.5 ml of the precursor solution was dropped into 10 ml of toluene (purchased from Alfa Aesar, with a purity of 99.5%) to form a bright yellow green CsPbBr.sub.3 perovskite quantum dot colloid solution. Then, the colloid solution was washed with methyl acetate with a volume ratio of 1:1 and centrifuged at 7000 rpm for 10 min to remove supernatant (including excess oleic acid and oleylamine). Then, toluene was used to redistribute precipitate, and the cleaned CsPbBr.sub.3 inorganic perovskite quantum dot colloid solution (hereinafter referred to as IPQD of Comparative Example 1) was dropped onto a glass substrate for XRD, TEM, HRTEM and FFT analysis. The results are as illustrated in
(28)
Experimental Example 2
(29) A 1 wt % CNC solution was prepared through the steps in Experimental Example 1. Then, CsBr and PbBr.sub.2 were mixed by using chlorine (Cl) with a Cl:Br ratio of 1:1 to form a CsPb(Br/Cl).sub.3 precursor solution. Next, 20 ml of the CsPb(Br/Cl).sub.3 precursor solution was mixed with 10 ml of the CNC solution and stirred at room temperature (about 25° C.) for at least 30 min to form a mixed solution. Then, the mixed solution was poured into a Buchner funnel for vacuum filtration and drying to form a CsPb(Br/Cl).sub.3 inorganic perovskite quantum dot film (hereinafter referred to as IPQD of Experimental Example 2). Then, the IPQD of Experimental Example 2 was subjected to PL emission spectrum analysis. The results are as illustrated in
Experimental Example 3
(30) A 1 wt % CNC solution was prepared through the steps in Experimental Example 1. Then, CsBr and PbBr.sub.2 were mixed by using iodine (I) with an I:Br ratio of 1:1 to form a CsPb(Br/I).sub.3 precursor solution. Next, 20 ml of the CsPb(Br/I).sub.3 precursor solution was mixed with 10 ml of the CNC solution and stirred at room temperature (about 25° C.) for at least 30 min to form a mixed solution. Then, the mixed solution was poured into a Buchner funnel for vacuum filtration and drying to form a CsPb(Br/I).sub.3 inorganic perovskite quantum dot film (hereinafter referred to as IPQD of Experimental Example 3). Then, the IPQD of Experimental Example 3 was subjected to PL emission spectrum analysis. The results are as illustrated in
(31) Referring to
Experimental Example 4
(32) A 1 wt % CNC solution was prepared through the steps in Experimental Example 1. Then, an MAPbBr.sub.3 precursor solution with different volumes (for example, 0.4 ml, 0.6 ml, 0.8 ml and 1.0 ml) was mixed with 20 ml of the CNC solution and stirred at room temperature (about 25° C.) for at least 30 min to form a mixed solution. Then, the mixed solution was poured into a Buchner funnel for vacuum filtration and drying to form an MAPbBr.sub.3 inorganic perovskite quantum dot film with a different concentration of the precursor (hereinafter referred to as IPQD of Experimental Example 4). Then, the IPQD of Experimental Example 4 was subjected to PL emission spectrum analysis. The results are as illustrated in
(33) Referring to
Experimental Example 5
(34) CNC powder (purchased from Celluforce) was dissolved in deionized water to form a 5 wt % first solution. Then, the first solution was dropped into DMF (purchased from Aencore, with a purity of 99.5%) to form a 0.5 wt % CNC solution. Then, 3.5 mmol of MABr (purchased from FMPV, with a purity of 98%) and 3.5 mmol of PbBr.sub.2 (purchased from FMPV, with a purity of 98%) were added into a flask containing 7 ml of DMF (purchased from Aencore, with a purity of 99.5%) and stirred uniformly to form a MAPbBr.sub.3 precursor solution. Next, 1 ml of MAPbBr.sub.3 precursor solution was mixed with 20 ml of CNC solution and stirred at room temperature (about 25° C.) for at least 30 min to form a mixed solution. Then, the mixed solution was poured into a Buchner funnel for vacuum filtration for 24 h to form a dry MAPbBr.sub.3 hybrid perovskite quantum dot film (hereinafter referred to as HPQD of Experimental Example 5). Then, the HPQD of Experimental Example 5 was subjected to stability test. The results are as illustrated in
Comparative Example 2
(35) 0.08 M of an MAPbBr.sub.3 solution was prepared in 5 ml of DMF (purchased from Aencore, with a purity of 99.5%) and mixed with 200 μl of oleic acid (purchased from Showa, with a purity of 99%) and 50 μl of oleylamine (purchased from ACROS Organics, with a purity of 90%) to form a precursor solution. Then, 0.5 ml of the precursor solution was dropped into 10 ml of toluene (purchased from Alfa Aesar, with a purity of 99.5%) and centrifuged at 7000 rpm for 10 min for purification, thus forming an MAPbBr.sub.3 hybrid perovskite quantum dot film (hereinafter referred to as HPQD of Comparative Example 2). Then, the HPQD of Comparative Example 2 was subjected to stability test. The results are as illustrated in
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(37) To sum up, the present embodiment provides a method for synthesizing a perovskite quantum dot film, in which the sulfate groups of a plurality of CNCs are connected with a plurality of perovskite quantum dots, such that the plurality of perovskite quantum dots is uniformly distributed among the plurality of CNCs, thereby improving the stability of the perovskite quantum dot film.
(38) In addition, the synthesis method provided by the present embodiment can improve the flexibility and tensile property of the perovskite quantum dot film by adjusting the water content of the CNC solution. Besides, the synthesis method provided by the present embodiment can also adjust the wavelength of the light emitted by the perovskite quantum dots by adjusting the concentration of the precursor solution.