CN115287742A - Method for synthesizing red light emitting perovskite single crystal at room temperature and product thereof - Google Patents
Method for synthesizing red light emitting perovskite single crystal at room temperature and product thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000013078 crystal Substances 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 68
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 13
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical group [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 25
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- OAZMQDHYJDWACA-UHFFFAOYSA-N N-[diethoxy(methyl)silyl]propan-1-amine Chemical compound C(CC)N[Si](OCC)(OCC)C OAZMQDHYJDWACA-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 43
- VPTDFJOOPWOZRN-UHFFFAOYSA-N [I].[Pb].[Cs] Chemical compound [I].[Pb].[Cs] VPTDFJOOPWOZRN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 27
- 239000012296 anti-solvent Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005424 photoluminescence Methods 0.000 description 9
- 230000005284 excitation Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IWDXBHSUFKRAQP-UHFFFAOYSA-N [Cs].[Pb] Chemical compound [Cs].[Pb] IWDXBHSUFKRAQP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention discloses a method for synthesizing red light emitting perovskite single crystal at room temperature and a product thereof, wherein the synthesis method comprises the following steps: step 1: uniformly mixing cesium salt, lead salt, a ligand and N, N-dimethylformamide to obtain a precursor I; the cesium salt is selected from cesium iodide, and the lead salt is selected from lead iodide and lead bromide; step 2: uniformly mixing the precursor I with a silane coupling agent to obtain a precursor II; and step 3: and mixing the precursor II with isopropanol, fully hydrolyzing, standing, and taking the lower layer precipitate as the red light emitting perovskite single crystal. The synthesis method has mild reaction conditions, does not need inert gas protection, has simple and controllable process and is suitable for industrial production; the prepared cesium lead iodine perovskite single crystal has high luminous intensity and stable property, and does not change after standing in a bottle and standing at room temperature for one month.
Description
Technical Field
The invention relates to the technical field of perovskite materials, in particular to a method for synthesizing red light emitting perovskite single crystals at room temperature and a product thereof.
Background
The lead-halogen perovskite has more excellent performance in the aspect of optical performance, and has higher luminescent color purity compared with fluorescent powder if the lead-halogen perovskite has narrower half-peak width (12-42 nm) of an emission peak; the emission wavelength is easy to adjust and has wide adjustable range, and the light emission in the whole visible spectrum range (400-700 nm) can be realized by adjusting the proportion of halogen elements in the component; the photoluminescence quantum yield (PLQY) is high, so that the method has wider application prospect in the fields of photoelectric luminescence and display.
At present, the traditional process for preparing the lead-halogen perovskite is a high-temperature thermal injection method, but the method has the defects of complicated synthesis process, high required temperature and inert gas protection in the reaction process, and is not suitable for industrial batch production. The room temperature ligand-assisted reprecipitation method can successfully prepare the lead-halogen perovskite at room temperature, and is expected to solve a series of problems existing in the high temperature thermal injection method.
The room temperature ligand-assisted reprecipitation method needs two solvents, and high-quality perovskite nanocrystalline can be obtained at room temperature by utilizing different solubilities. The polarity of two solvents selected by the method needs to be greatly different, generally, a strong polar solvent is selected to dissolve a medicine, then a weak polar solvent is selected as an anti-solvent, such as toluene or n-hexane, and the nanocrystalline is separated out by utilizing the solubility difference. The existing research finds that if the polarity of the anti-solvent is too large, perovskite nanocrystals are not easy to generate, and fluorescence quenching is easy to cause.
In addition, the prior room-temperature ligand-assisted reprecipitation method mostly adopts CsPbBr 3 For the object of study byPreparation of red light emitting CsPbI by room temperature ligand assisted reprecipitation method 3 It is rarely reported that CsPbI 3 The multiple phases of (2) are reversed with the change of temperature, and exist in delta phase non-perovskite phase at room temperature all the time, so that no luminescence is caused, and CsPbI prepared at room temperature 3 Is unstable.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a method for synthesizing red light emitting perovskite single crystal at room temperature, which realizes the successful preparation of red light emitting cesium lead iodine perovskite single crystal at room temperature, has mild reaction conditions, does not need inert gas protection, has simple and controllable process and is suitable for industrial production; the prepared cesium-lead-iodine perovskite single crystal has high luminous intensity and stable property.
The specific technical scheme is as follows:
a method for synthesizing red light emitting perovskite single crystal at room temperature comprises the following steps:
step 1: uniformly mixing cesium salt, lead salt, a ligand and N, N-dimethylformamide to obtain a precursor I;
the cesium salt is selected from cesium iodide and the lead salt is selected from lead iodide and lead bromide;
step 2: uniformly mixing the precursor I with a silane coupling agent to obtain a precursor II;
and step 3: and mixing the precursor II with isopropanol, fully hydrolyzing, standing, and taking the lower layer precipitate as the red light emitting perovskite single crystal.
The invention discloses a method for successfully preparing cesium lead perovskite single crystal emitting red light by a room-temperature ligand-assisted reprecipitation method for the first time, which has three key points: firstly, screening special solvent combination of N, N-dimethyl formamide and isopropanol, and finding that the solvent combination is not enough by tests, if any replacement is carried out, the cesium lead iodoperovskite single crystal emitting red light cannot be successfully prepared at room temperature; secondly, adding a silane coupling agent at a specific time, namely adding the silane coupling agent firstly and then mixing the silane coupling agent with isopropanol as an anti-solvent, and experiments show that if the adding sequence is changed, phase change can be caused, red light cannot be emitted, and fluorescence quenching can be caused; thirdly, doping a certain proportion of element bromine, and experiments show that if the element bromine is not doped or the doping proportion is not proper, the cesium-lead-iodine-perovskite single crystal emitting red light cannot be successfully prepared.
In the step 1:
the molar ratio of cesium salt to lead salt is 1:1;
the molar ratio of the lead iodide to the lead bromide is 0.8-1.8: 1;
the ligand is selected from oleic acid and oleylamine;
the volume ratio of the ligand to the N, N-dimethylformyl is 1-5: 10;
preferably, the oleic acid and oleylamine are mixed in equal volumes; the volume ratio of the ligand to the N, N-dimethylformyl is 1:5.
the concentration of cesium salt in the precursor I is 0.05-0.25 mol/L; preferably 0.08mol/L.
Preferably, the molar ratio of lead iodide to lead bromide is 1.0 to 1.8:1; further preferably, the molar ratio of lead iodide to lead bromide is 1:1.
tests show that the luminous intensity of the prepared perovskite single crystal is continuously improved along with the continuous optimization of the proportion.
In the step 2:
the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane and 3-propylamino (diethoxy) methylsilane;
the volume ratio of the precursor I to the silane coupling agent is 100:0.5 to 4.
Preferably, the volume ratio of the precursor I to the silane coupling agent is 100:1 to 4; further preferably, the volume ratio of the precursor I to the silane coupling agent is 100:2.
tests show that the luminous intensity of the prepared perovskite single crystal is continuously improved along with the continuous optimization of the proportion.
In the step 3:
the volume ratio of the precursor II to the isopropanol is 1:5 to 10; preferably 1:10.
the hydrolysis is carried out at room temperature in an air environment, and the hydrolysis time is long enough to ensure that the silane coupling agent is fully hydrolyzed.
And standing for layering for at least 6h to ensure that more target products are prepared.
The invention also discloses the red light-emitting perovskite single crystal prepared by the method, and the structural general formula is CsPbI 3- x Br x And x is selected from 0.7 to 1.1.
The product prepared by the invention can emit red light, has stable property, and is still placed in a bottle and does not change after being placed for one month at room temperature.
Preferably, x =1.0; the prepared product is CsPbI 2 Br, which is bright red light emitting with high luminous intensity.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for synthesizing red light emitting perovskite single crystal at room temperature, which realizes the successful preparation of cesium lead iodine perovskite single crystal emitting red light at room temperature by screening a solvent system with special composition, adding a silane coupling agent at a specific time and doping element bromine with proper content, has mild reaction conditions, does not need inert gas protection, has simple and controllable process and is suitable for industrial production; the prepared cesium lead iodine perovskite single crystal has high luminous intensity and stable property, and does not change after standing in a bottle and standing at room temperature for one month.
Drawings
FIG. 1 is a Photoluminescence (PL) spectrum of products prepared in examples 1 to 3, respectively;
FIG. 2 is a Photoluminescence (PL) spectrum of each of the products prepared in examples 1 and 4 to 5.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description is given for the purpose of illustrating the invention by way of example, without thereby limiting the scope of the invention.
Example 1
(1) Mixing 1.0mmol CsI and 0.5mmol PbI 2 、0.5mmolPbBr 2 And 1mL of oilDissolving acid (OA) and 1mL Oleylamine (OLA) in 10mL of DMF, and stirring at room temperature until the materials are fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 40 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer at room temperature to fuse the precursor I and obtain a precursor II;
(3) Taking 0.5mL of the precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the light is excited by an ultraviolet lamp with the wavelength of 365nm and is emitted in bright red light;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the CsPbI coated by silane 2 A Br perovskite single crystal.
The product prepared in this example still showed bright red light emission upon excitation with an ultraviolet lamp having a wavelength of 365 nm. The product prepared in this example was tested to stand in a bottle and was unchanged for one month at room temperature.
Comparative example 1
(1) Mixing 1.0mmol CsI and 0.5mmol PbI 2 、0.5mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of the mixed solution of sulfuric acid and sulfuric acid, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) Injecting 0.5mL of the precursor I into 5mL of anti-solvent isopropanol, and mixing and stirring for 10min at room temperature at the rotating speed of 600r/min under a magnetic stirrer to obtain a reaction solution;
(3) Mixing 2mL of reaction liquid with 40 mu L of APTES, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the light is excited by an ultraviolet lamp with the wavelength of 365nm and is emitted by yellow orange light;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the product.
The product prepared in this comparative example exhibited fluorescence quenching upon excitation with an ultraviolet lamp having a wavelength of 365 nm.
Comparing example 1 with comparative example 1, it can be seen that the red light emitting perovskite single crystal cannot be successfully prepared by exchanging the preparation steps; in the experiment, the fact that the APTES added later in the comparative example causes phase change in the hydrolysis process to emit yellow orange light is further found, and fluorescence quenching is further caused by the phase change after standing and layering.
Comparative example 2
The preparation process was substantially the same as in example 1 except that DMF added in step (1) was replaced with an equal volume of DMSO.
After testing: in the uncapping hydrolysis process, the product is excited by an ultraviolet lamp with the wavelength of 365nm for the first 30min to emit dark color or even no light; after 3h hydrolysis had taken place, complete quenching was achieved.
Comparative example 3
The preparation process was substantially the same as in example 1 except that the anti-solvent added in step (3) was replaced with an equal volume of a weakly polar solvent, n-hexane.
The test shows that no product is obtained, and no luminescence phenomenon is generated after the product is excited by an ultraviolet lamp with the wavelength of 365 nm.
Comparative example 4
The preparation process was substantially the same as in example 1 except that the anti-solvent added in step (3) was replaced with an equal volume of ethanol.
Through the test: in the uncapping hydrolysis process, the light is emitted into dark color or even does not emit light after being excited by an ultraviolet lamp with the wavelength of 365nm for the first 30 min; after 1h hydrolysis had proceeded, it was completely quenched.
Comparative example 5
(1) Mixing 1.0mmol CsI and 1.0mmol PbI 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of DMF, and stirring at room temperature until the oleic acid and the oleylamine are fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 40 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer at room temperature to fuse the precursor I and obtain a precursor II;
(3) Taking 0.5mL of the precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the LED lamp is excited by an ultraviolet lamp with the wavelength of 365nm and does not emit light;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the product.
At this time, the prepared product is dark purple under natural light, and still does not emit light after being excited by an ultraviolet lamp with the wavelength of 365 nm.
Comparative example 6
(1) Mixing 1.0mmol CsI and 0.5mmol PbI 2 、0.5mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of the mixed solution of sulfuric acid and sulfuric acid, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) 0.5mL of the precursor I is injected into 5mL of anti-solvent isopropanol, and stirred for 6h at the room temperature at the rotating speed of 600r/min under a magnetic stirrer;
in the stirring process, in the first 30min, red light emission is obtained by excitation of an ultraviolet lamp with the wavelength of 365 nm; after stirring for 3h, a clear decrease in brightness occurred, and after 6h, quenching was complete.
(3) Standing and layering the stirred product for 6h, and pouring out the upper solution to obtain the product.
The product is observed to be milky flocculent precipitate under natural light, and does not emit light after being excited by an ultraviolet lamp with the wavelength of 365 nm.
Comparative example 7
(1) Mixing 1.0mmol CsI and 0.375mmol PbI 2 、0.625mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of DMF, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 40 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer at room temperature to fuse the precursor I and obtain a precursor II;
(3) Taking 0.5mL of precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at room temperature at the rotating speed of 600r/min under a magnetic stirrer, uncovering the cover, and hydrolyzing for 6 hours;
at the moment, the light is excited by an ultraviolet lamp with the wavelength of 365nm and is emitted in yellow orange light;
(4) Standing for layering for 6h, and pouring out the upper solution to obtain the product.
Excited by an ultraviolet lamp with the wavelength of 365nm, and still emits yellow orange light.
Example 2
(1) Mixing 1.0mmol CsI and 0.5mmol PbI 2 、0.5mmolPbBr 2 And dissolving 1mL Oleic Acid (OA) and 1mL Oleylamine (OLA) in 10mL DMF, stirring at room temperature until the materials are fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 20 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer to fuse the precursor I and the APTES to obtain a precursor II;
(3) Taking 0.5mL of the precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the red light is emitted under the excitation of an ultraviolet lamp with the wavelength of 365 nm;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the CsPbI coated by silane 2 A Br perovskite single crystal.
The product prepared in this example still showed red emission upon excitation with an ultraviolet lamp having a wavelength of 365nm, but the emission intensity was weaker than that of the product prepared in example 1. The product prepared in this example was tested to stand in a bottle and was unchanged by one month at room temperature.
Example 3
(1) Mixing 1.0mmol CsI and 0.5mmol PbI 2 、0.5mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of the mixed solution of sulfuric acid and sulfuric acid, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 80 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer to fuse the precursor I and the APTES to obtain a precursor II;
(3) Taking 0.5mL of precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at room temperature at the rotating speed of 600r/min under a magnetic stirrer, uncovering the cover, and hydrolyzing for 6 hours;
at the moment, the light is excited by an ultraviolet lamp with the wavelength of 365nm and emits red light;
(4) The hydrolysate is thenStanding for layering for 6h, and pouring out the upper solution to obtain the silane-coated CsPbI 2 A Br perovskite single crystal.
The product prepared in this example still showed red light emission upon excitation with an ultraviolet lamp having a wavelength of 365nm, but the intensity of the emitted light was weaker than that of the product prepared in example 1. The product prepared in this example was tested to stand in a bottle and stored at room temperature for one month without change.
FIG. 1 is a Photoluminescence (PL) spectrum of products prepared from example 1 (designated 40 APTES), 2 (designated 20 APTES) and 3 (designated 80 APTES), respectively.
A sample preparation process: the product was drop coated onto a glass slide and annealed at 120 ℃ for 5min.
As can be seen from the observation of the curves in FIG. 1, the products prepared in examples 1 to 3 respectively all emit red light, but the product prepared in example 1 has the highest luminous intensity and emits bright red light; the product prepared in example 3 had a lower luminous intensity than that of example 1, and the product prepared in example 2 had the weakest luminous intensity.
Example 4
(1) Mixing 1.0mmol CsI and 0.45mmol PbI 2 、0.55mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of DMF, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 40 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer to fuse the precursor I and the APTES to obtain a precursor II;
(3) Taking 0.5mL of the precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the red light is emitted under the excitation of an ultraviolet lamp with the wavelength of 365 nm;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the CsPbI coated by silane 1.9 Br 1.1 A perovskite single crystal.
The product prepared in this example still showed red light emission upon excitation with an ultraviolet lamp having a wavelength of 365nm, but the intensity of the emitted light was weaker than that of the product prepared in example 1. The product prepared in this example was tested to stand in a bottle and was unchanged by one month at room temperature.
Example 5
(1) Mixing 1.0mmol CsI and 0.64mmol PbI 2 、0.36mmolPbBr 2 And dissolving 1mL of Oleic Acid (OA) and 1mL of Oleylamine (OLA) in 10mL of DMF, and stirring at room temperature until the mixture is fully dissolved to obtain a precursor I;
(2) Adding 2mL of the precursor I into 40 mu L of Aminopropyltriethoxysilane (APTES), and mixing and stirring at the rotating speed of 600r/min for 30min under a magnetic stirrer to fuse the precursor I and the APTES to obtain a precursor II;
(3) Taking 0.5mL of the precursor II, injecting the precursor II into 5mL of anti-solvent isopropanol, uniformly stirring at the room temperature at the rotating speed of 600r/min under a magnetic stirrer, and then uncovering the cover to hydrolyze for 6 hours;
at the moment, the light is excited by an ultraviolet lamp with the wavelength of 365nm and emits deep red light;
(4) Standing and layering the hydrolysate for 6h, and pouring out the upper solution to obtain the CsPbI coated by silane 2.3 Br 0.7 A perovskite single crystal.
The product prepared in this example still emits deep red light when excited by an ultraviolet lamp with a wavelength of 365nm, but the luminous intensity is weaker than that of the product prepared in example 1. The product prepared in this example was tested to stand in a bottle and was unchanged for one month at room temperature.
FIG. 2 shows example 1 (denoted as PbI) 2 ：PbBr 2 = 1), 4 (note as PbI) 2 ：PbBr 2 = 0.8) and 5 (noted PbI) 2 ：PbBr 2 = 1.8) Photoluminescence (PL) spectrum of the product prepared separately, sample preparation procedure as above.
As can be seen from the observation of the curves in FIG. 2, the products prepared in examples 1, 4-5 respectively all showed red light emission, but the product prepared in example 1 showed the highest luminous intensity and showed bright red light emission; the spectrum of the product prepared in example 4 appears blue-shifted and emits red light with a lower luminous intensity than that of example 1; the spectrum of example 5 was red-shifted and emitted in a deep red light, and the intensity of the emitted light was also weaker than that of example 1.
The above examples are intended to aid in the understanding of the method and key points of the invention. This summary should not be construed to limit the present invention.
Claims (10)
1. A method for synthesizing red light emitting perovskite single crystal at room temperature is characterized by comprising the following steps:
step 1: uniformly mixing cesium salt, lead salt, a ligand and N, N-dimethylformamide to obtain a precursor I;
the cesium salt is selected from cesium iodide and the lead salt is selected from lead iodide and lead bromide;
step 2: uniformly mixing the precursor I with a silane coupling agent to obtain a precursor II;
and 3, step 3: and mixing the precursor II with isopropanol, fully hydrolyzing, standing, and taking the precipitate as a lower layer to obtain the red light-emitting perovskite single crystal.
2. The method for room temperature synthesis of a red-emitting perovskite single crystal according to claim 1, wherein in step 1:
the molar ratio of cesium salt to lead salt is 1:1;
the molar ratio of the lead iodide to the lead bromide is 0.8-1.8: 1;
the ligand is selected from oleic acid and oleylamine;
the volume ratio of the ligand to the N, N-dimethylformyl is 1-5: 10;
the concentration of cesium salt in the precursor I is 0.05-0.25 mol/L.
3. The method for room-temperature synthesis of a red-emitting perovskite single crystal according to claim 2, wherein the molar ratio of lead iodide to lead bromide is 1.0 to 1.8:1.
4. the method for room temperature synthesis of a red-emitting perovskite single crystal according to claim 3, characterized in that the molar ratio of lead iodide to lead bromide is 1:1.
5. the method for room temperature synthesis of a red-emitting perovskite single crystal according to claim 1, wherein in step 2:
the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane and 3-propylamino (diethoxy) methylsilane;
the volume ratio of the precursor I to the silane coupling agent is 100:0.5 to 4.
6. The method for room-temperature synthesis of a red-emitting perovskite single crystal as claimed in claim 5, wherein the volume ratio of the precursor I to the silane coupling agent is 100:1 to 4.
7. The method for room-temperature synthesis of a red-emitting perovskite single crystal according to claim 6, wherein the volume ratio of the precursor I to the silane coupling agent is 100:2.
8. the method for room temperature synthesis of a red-emitting perovskite single crystal according to claim 1, wherein in step 3:
the volume ratio of the precursor II to the isopropanol is 1:5 to 10.
9. A red light emitting perovskite single crystal prepared according to the method of any one of claims 1 to 8, characterized in that the general structural formula is CsPbI 3-x Br x And x is selected from 0.7 to 1.1.
10. The red-emitting perovskite single crystal prepared according to the method of claim 9, wherein x =1.0.
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| US20190062175A1 (en) * | 2017-08-30 | 2019-02-28 | Florida State University Research Foundation, Inc. | Bandgap-tunable perovskite materials and methods of making the same |
| CN111286779A (en) * | 2020-03-16 | 2020-06-16 | 山东科技大学 | Method for growing large-size perovskite single crystal by using ternary mixed solvent |
| CN111792851A (en) * | 2020-07-24 | 2020-10-20 | 西安电子科技大学 | High-stability all-inorganic CsPbI2Br perovskite film and preparation method thereof |
| 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 |
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| US20190062175A1 (en) * | 2017-08-30 | 2019-02-28 | Florida State University Research Foundation, Inc. | Bandgap-tunable perovskite materials and methods of making the same |
| CN111286779A (en) * | 2020-03-16 | 2020-06-16 | 山东科技大学 | Method for growing large-size perovskite single crystal by using ternary mixed solvent |
| CN111792851A (en) * | 2020-07-24 | 2020-10-20 | 西安电子科技大学 | High-stability all-inorganic CsPbI2Br perovskite film and preparation method thereof |
| 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 |
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| CN116285990A (en) * | 2023-03-10 | 2023-06-23 | 合肥工业大学 | Method for preparing antimony doped cesium yttrium chloride lead-free perovskite luminescent material by room temperature anti-solvent precipitation method |
| CN116285990B (en) * | 2023-03-10 | 2024-01-30 | 合肥工业大学 | Method for preparing antimony doped cesium yttrium chloride lead-free perovskite luminescent material by room temperature anti-solvent precipitation method |
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