阅读说明：本技术 一种丙烯酸类聚合物包覆量子点的制备方法 (A kind of preparation method of acrylic polymer coated quantum dots ) 是由 孙小卫 王恺 杨鸿成 徐冰 刘乙樽 沈健 丁时浩 郑凡凯 于 2019-09-20 设计创作，主要内容包括：本发明提供一种丙烯酸类聚合物包覆量子点的制备方法,所述制备方法为：将量子点分散液与丙烯酸类单体混合、反应,得到所述丙烯酸类聚合物包覆量子点。所述制备方法无需将油相合成的量子点转成水相,也无需加入引发剂或催化剂,避免传统制备方法中配体交换或配体流失对量子点造成缺陷而导致其发光效率和稳定性下降,从根源上解决了量子点后期修饰影响其发光性能的问题,基于本发明所述制备方法得到的丙烯酸类聚合物包覆量子点稳定性高、发光性能好。因此,本发明提供的制备方法操作简单、反应时间短、效率高,可以得到的稳定的高发光性能的产物,同时适合于工业化批量生产,具有广阔的应用前景。(The present invention provides a kind of preparation method of acrylic polymer coated quantum dots, the preparation method is that: quantum dot dispersion liquid is mixed with acrylic monomer, is reacted, the acrylic polymer coated quantum dots are obtained.The preparation method is not necessarily to the quantum dot that oil is combined to changing into water phase, without addition initiator or catalyst, ligand exchange or ligand loss in traditional preparation methods is avoided to cause defect to quantum dot and its luminous efficiency and stability is caused to decline, solve the problems, such as that the modification of quantum dot later period influences its luminescent properties from the root, the acrylic polymer coated quantum dots stability obtained based on preparation method of the present invention is high, good luminous performance.Therefore, preparation method provided by the invention is easy to operate, the reaction time is short, high-efficient, the product of available stable high luminescence energy, while being suitable for industrialized mass production, has broad application prospects.)

1. a kind of preparation method of acrylic polymer coated quantum dots, which is characterized in that the preparation method is that: by quantum Point dispersion liquid is mixed with acrylic monomer, is reacted, and obtains the acrylic polymer coated quantum dots.

2. preparation method according to claim 1, which is characterized in that the quantum dot includes monokaryon quantum dot and/or core Core-shell structure quantum dots, preferably nuclear shell structure quantum point；

Preferably, the monokaryon quantum dot is selected from silicon quantum dot, germanium quantum point, carbon quantum dot, CdSe quantum dot, CdTe quantum Point, CdS quantum dot, PbSe quantum dot, PbTe quantum dot, PbS quantum, ZnSe quantum dot, CuInS₂Quantum dot, InP quantum Any one in point, InAs quantum dot, CuZnSe quantum dot, ZnMnSe quantum dot or perovskite quantum dot or at least two Combination；

Preferably, the nuclear material of the nuclear shell structure quantum point be selected from CdSe, CdTe, CdS, ZnSe, PbSe, PbTe, PbS, CuInS₂、InP、InAs、CuZnSe、ZnMnSe、GaP、CsPbBr₃、CsPbI₃Or CsPbCl₃In any one or at least two The combination of kind, further preferably CdSe；

Preferably, any one of the shell material of the nuclear shell structure quantum point in CdS, ZnS, ZnO, ZnSe or ZnSeS Or at least two combination, further preferably ZnS.

3. preparation method according to claim 1 or 2, which is characterized in that the quantum dot dispersion liquid is quantum dot solution With the mixture of dispersion solvent；

Preferably, the concentration of the quantum dot solution is 30~80mg/mL；

Preferably, the volume ratio of the quantum dot solution and dispersion solvent is 1:(5~20), further preferably 1:10；

Preferably, the solvent of the quantum dot solution be selected from hexamethylene, n-hexane, octadecylene, hexadecylene, tetradecene, laurylene, In toluene or chloroform any one or at least two combination；

Preferably, the dispersion solvent is octadecylene.

4. described in any item preparation methods according to claim 1~3, which is characterized in that the acrylic monomer is selected from third It is any in olefin(e) acid, acrylate, methacrylic acid, methacrylate, metering system acid metal salt or acrylate metal salt It is a kind of or at least two combination；

Preferably, the metering system acid metal salt is selected from zinc methacrylate, magnesinm methacrylate, methacrylic acid copper or first In base acrylic acid cadmium any one or at least two combination；

Preferably, the acrylate metal salt in zinc acrylate resin, Magnesium Acrylate Prepared or acrylic acid copper any one or at least Two kinds of combination；

Preferably, the mass ratio (1~5) of the acrylic monomer and quantum dot: 1.

5. preparation method according to any one of claims 1 to 4, which is characterized in that the temperature of the reaction be 180~ 230 DEG C, preferably 200 DEG C.

6. described in any item preparation methods according to claim 1~5, which is characterized in that the time of the reaction is 2~8h, Preferably 4~7h.

7. described in any item preparation methods according to claim 1~6, which is characterized in that further include in the raw material of the reaction Sulphur powder；

Preferably, the mass ratio of the sulphur powder and acrylic monomer is (0.1~1): 1, further preferably (0.3~0.7): 1；

Preferably, the sulphur powder is the sulphur powder being dissolved in tri octyl phosphine.

8. described in any item preparation methods according to claim 1~7, which is characterized in that the preparation method further includes product Post-processing；

Preferably, the post-processing includes separation, washing and drying；

Preferably, the isolated method is centrifuge separation；

Preferably, the cleaning solution of the washing is n-hexane；

Preferably, the preparation method specifically includes the following steps:

By quantum dot solution and octadecylene that concentration is 30~80mg/mL with volume ratio 1:(5~20) mixing, obtain quantum dot point Dispersion liquid；The quantum dot dispersion liquid is reacted into 2~8h with acrylic monomer mixing, 180~230 DEG C, separation washs, is dry, Obtain the acrylic polymer coated quantum dots；Wherein, the mass ratio (1~5) of the acrylic monomer and quantum dot: 1, the acrylic monomer is selected from acrylic acid, acrylate, methacrylic acid, methacrylate, methacrylic acid metal In salt or acrylate metal salt any one or at least two combination.

9. a kind of acrylic polymer coated quantum dots that preparation method as described in any one of claims 1 to 8 obtains.

10. a kind of application of acrylic polymer coated quantum dots as claimed in claim 9 in luminescent material.

Technical field

The invention belongs to technical field of semiconductor, and in particular to a kind of system of acrylic polymer coated quantum dots Preparation Method.

Background technique

Quantum dot is a kind of novel semiconductor material with excellent luminance characteristic, mainly by II-VI group, iii-v, IV The elements such as race composition is closely sized to or is less than Exciton Bohr Radius, and absorption spectrum is wide and continuous, and emission spectrum is narrow and symmetrical, Therefore the property reconciled that optical property can be realized by the composition and partial size of quantum point, in luminescent material, biological diagnosis There is great application prospect with sensor field.Quantum dot can be used as fluorescence transition material for hand in LED illumination field In the backlight display of machine and TV, wherein white light quanta point film needs to mix red green quantum dot, then passes through core Piece blue light is excited and is shone, and obtains white light with the outgoing photoreactivation of chip.However in application process, red green quantum dot is direct Closely resonance energy transfer effect occurs for the spacing that mixing will lead to red green quantum dot very much, i.e. the luminous of green light quantum point can excite Red light quantum point causes the luminous efficiency of green light quantum point to reduce；The conventional process for solving the problems, such as this is to increase green quantum The dosage of point, consequently quantum dot usage amount can be made to increase, production difficulty and cost improve.In order to obtain a kind of saving The resonance energy transfer solution to the problem of son point is needed suitably to increase the distance between quantum dot, be carried out to quantum dot Cladding or surface modification are a kind of very good solution thinkings, and this cladding or surface modification can also improve the steady of quantum dot It is qualitative.

Quantum dot cladding can be divided into inorganic matter cladding according to clad raw material and Coated with Organic Matter, inorganic matter are coated with metal Based on oxide, silica etc., such as CN107541203A discloses a kind of metal oxide/coated with silica or package Quantum dot and preparation method thereof, the metal oxide includes aluminum oxide, zirconium dioxide and titanium dioxide, the metal The quantum dot of oxide/silicon dioxide cladding or package can be prepared by sol-gel method or pyrolytic reaction method, metal The double shielding layer of oxide and silica can effectively stop the erosion of aqueous vapor, oxygen to quantum dot, improve quantum dot Photostability.But inorganic matter coated quantum dots generally pass through hydrolysis presoma at room temperature and are coated, hydrolysis rate is slow (logical Often greater than for 24 hours), it is unfavorable for industrialized mass production；In addition, hydrolysis presoma needs to carry out under basic or acidic conditions, meeting The ligand or shell of quantum dot surface are eroded, the fluorescence efficiency of quantum dot is caused to decline.

In quantum dot Coated with Organic Matter, due to polymer material do not generate in optical property of the visible region to quantum dot it is bright Development is rung, therefore is a kind of ideal covering material.CN103911142A disclose a kind of blue quantum dot composite particle, There is polymer shell to coat amount of blue for preparation method, photoelectric cell and optoelectronic device, the blue quantum dot composite particle The core-shell structure of son point kernel, and the surface of shell is modified with gold nanoparticle by chemical method；The core-shell structure passes through kind Sub- emulsion polymerization obtains, and instills quantum dot solution after acrylic ester monomer, emulsifier and peroxide initiator are mixed In, monomer occurs polymerization reaction under initiator effect and obtains the quantum dot of polymer overmold.Compound of the quantum dot of blue The fluorescence efficiency of grain is high, and preparation method is simple, controllable.CN109306265A discloses a kind of perovskite amount of polymer overmold Son point and preparation method thereof, the preparation method comprises the following steps: surface is contained to the perovskite quantum of thionothiolic acid class ligand Point dispersion in a solvent formed perovskite quantum dot solution, then into the perovskite quantum dot solution be added polymer monomer and Photoinitiator, reaction generates the perovskite quantum of polymer overmold under the conditions of water vapour content is lower than 30% ultraviolet irradiation Point；Wherein polymer monomer is the unsaturated polymer monomer containing amino.

However polymer overmold quantum dot in the prior art, needing to be added initiator or catalyst makes polymerized monomer exist Quantum dot surface polymerize, and wherein initiator is mostly azo compound or the organic peroxide with strong oxidizing property, Catalyst is Metal and metal complex, and the introducing of initiator or catalyst inevitably corrodes quantum dot surface, causes quantum The fault of construction on point surface, to influence the fluorescence quantum yield and luminescent properties of quantum dot.

Therefore, a kind of polymer overmold quantum dot that is easily operated, high-efficient and not influencing quantum dot optical property is developed Preparation method, be this field urgent problem to be solved.

Summary of the invention

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of acrylic polymer coated quantum dots Preparation method, in the preparation method will quantum dot dispersion liquid and acrylic monomer mix after directly react, draw without being added Send out agent or catalyst, avoid the influence to quantum dot surface structure of initiator or catalyst and caused by quantum dot light emitting performance Loss.

In order to achieve that object of the invention, the invention adopts the following technical scheme:

In a first aspect, the present invention provides a kind of preparation method of acrylic polymer coated quantum dots, the preparation side Method are as follows: quantum dot dispersion liquid is mixed with acrylic monomer, is reacted, the acrylic polymer coated quantum dots are obtained.

In preparation method provided by the invention, quantum dot dispersion liquid and acrylic monomer can directly react, and third Alkene acrylic monomer carries out home position polymerization reaction in quantum dot surface, and obtained acrylic polymer is evenly coated at quantum dot table Face makes to form polymer protective layer outside quantum dot.On the one hand the polymer protective layer can stop aqueous vapor, oxygen to quantum dot Erosion, improve the stability of quantum dot, spacing when on the other hand increasing quantum dot for LED fluorescence transition material is kept away Exempt from resonance energy transfer effect and causes the reduction of green light quantum point luminous efficiency.Therefore, it is based on preparation side of the present invention The acrylic polymer coated quantum dots stability that method obtains is high, good luminous performance.

It is different from the method that initiator or catalyst polymerize monomer in quantum dot surface is added in the prior art, the present invention In the preparation method, in quantum dot surface home position polymerization reaction occurs for acrylic monomer at the reaction temperatures, without being added Azo or organic peroxide initiator, Metal and metal complex class catalyst, effectively prevent initiator or catalyst Caused by quantum dot surface ligand be lost and to quantum dot surface structural damage；And preparation method of the present invention exists It is directly carried out in organic phase, the quantum dot it is not necessary that oil to be combined to changes into water phase, and ligand exchange is avoided to cause defect to quantum dot And its luminous efficiency and stability is caused to decline, solving the modification of quantum dot later period from the root influences asking for its luminescent properties Topic.To sum up, preparation method provided by the invention is easy to operate, the reaction time is short, high-efficient, obtained acrylic polymer packet Cover that quantum dot is with good stability and fluorescence quantum efficiency.

Preferably, the quantum dot includes monokaryon quantum dot and/or nuclear shell structure quantum point, preferably core-shell structure quantum Point.

Preferably, the monokaryon quantum dot is selected from silicon quantum dot, germanium quantum point, carbon quantum dot, CdSe quantum dot, CdTe amount Sub- point, CdS quantum dot, PbSe quantum dot, PbTe quantum dot, PbS quantum, ZnSe quantum dot, CuInS₂Quantum dot, InP amount Any one in sub- point, InAs quantum dot, CuZnSe quantum dot, ZnMnSe quantum dot or perovskite quantum dot or at least two Combination.

Preferably, the nuclear material of the nuclear shell structure quantum point be selected from CdSe, CdTe, CdS, ZnSe, PbSe, PbTe, PbS、CuInS₂、InP、InAs、CuZnSe、ZnMnSe、GaP、CsPbBr₃、CsPbI₃Or CsPbCl₃In any one or extremely Few two kinds of combination, further preferably CdSe.

Preferably, the shell material of the nuclear shell structure quantum point is any in CdS, ZnS, ZnO, ZnSe or ZnSeS It is a kind of or at least two combination, further preferably ZnS.

Preferably, the quantum dot dispersion liquid is the mixture of quantum dot solution and dispersion solvent.

Preferably, the concentration of the quantum dot solution be 30~80mg/mL, such as 32mg/mL, 34mg/mL, 36mg/mL, 38mg/mL、40mg/mL、43mg/mL、45mg/mL、48mg/mL、50mg/mL、53mg/mL、55mg/mL、58mg/mL、60mg/ Between mL, 63mg/mL, 65mg/mL, 68mg/mL, 70mg/mL, 73mg/mL, 75mg/mL or 78mg/mL and above-mentioned point value Specific point value, as space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.

Preferably, the volume ratio of the quantum dot solution and dispersion solvent is 1:(5~20), such as 1:6,1:7,1:8,1: 9,1:10,1:11,1:12,1:13,1:14,1:15,1:16,1:17,1:18 or 1:19 etc., further preferably 1:10.

Preferably, the solvent of the quantum dot solution is selected from hexamethylene, n-hexane, octadecylene, hexadecylene, tetradecene, ten In diene, toluene or chloroform any one or at least two combination.

Preferably, the dispersion solvent is octadecylene.

Preferably, the acrylic monomer is selected from acrylic acid, acrylate, methacrylic acid, methacrylate, first In base acrylate metal salt or acrylate metal salt any one or at least two combination.

Preferably, the metering system acid metal salt is selected from zinc methacrylate, magnesinm methacrylate, methacrylic acid copper In methacrylic acid cadmium any one or at least two combination.

Preferably, the acrylate metal salt in zinc acrylate resin, Magnesium Acrylate Prepared or acrylic acid copper any one or At least two combination.

Preferably, the mass ratio (1~5) of the acrylic monomer and quantum dot: 1, such as 1.2:1,1.5:1,1.8: 1,2:1,2.2:1,2.5:1,2.8:1,3:1,3.2:1,3.5:1,3.8:1,4:1,4.2:1,4.5:1 or 4.8:1 etc..

Preferably, the temperature of the reaction be 180~230 DEG C, such as 185 DEG C, 190 DEG C, 192 DEG C, 195 DEG C, 198 DEG C, Specific point value between 200 DEG C, 202 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C or 228 DEG C and above-mentioned point value, As space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes, further preferably It is 200 DEG C.

Preferably, the time of the reaction be 2~8h, such as 2.3h, 2.5h, 2.8h, 3h, 3.3h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h, 6h, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h or 7.8h, Yi Jishang The specific point value between point value is stated, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes Specific point value, further preferably 4~7h.

It preferably, further include sulphur powder in the raw material of the reaction.

Preferably, the mass ratio of the sulphur powder and acrylic monomer is (0.1~1): 1, such as 0.15:1,0.2:1, 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1 or 0.9:1 etc., further preferably (0.3~0.7): 1.

Preferably, the sulphur powder is the sulphur powder being dissolved in tri octyl phosphine.

Reaction raw materials in preparation method of the present invention, can be in addition to quantum dot dispersion liquid and acrylic monomer Including sulphur powder, wherein sulphur powder can fill up the defect of quantum dot surface to a certain extent, facilitate the promotion of quantum dot performance.

Preferably, the preparation method further includes the post-processing of product.

Preferably, the post-processing includes separation, washing and drying.

Preferably, the isolated method is centrifuge separation.

Preferably, the cleaning solution of the washing is n-hexane.

Preferably, the preparation method specifically includes the following steps:

By concentration be 30~80mg/mL quantum dot solution and octadecylene with volume ratio 1:(5~20) mixing, obtain quantum Point dispersion liquid；The quantum dot dispersion liquid is reacted into 2~8h with acrylic monomer mixing, 180~230 DEG C, separate, wash, It is dry, obtain the acrylic polymer coated quantum dots；Wherein, the mass ratio (1 of the acrylic monomer and quantum dot ~5): 1, the acrylic monomer is selected from acrylic acid, acrylate, methacrylic acid, methacrylate, methacrylic acid In metal salt or acrylate metal salt any one or at least two combination.

On the other hand, the present invention provides a kind of acrylic polymer that preparation method as described above obtains cladding quantum Point.

On the other hand, the present invention provides a kind of acrylic polymer coated quantum dots as described above in luminescent material Application.

Compared with the existing technology, the invention has the following advantages:

In the preparation method of acrylic polymer coated quantum dots provided by the invention, quantum dot dispersion liquid and acrylic acid It directly reacts after the mixing of class monomer, acrylic monomer carries out the acrylic polymer that in-situ polymerization obtains in quantum dot surface It closes object and is evenly coated at quantum dot surface, make to form polymer protective layer outside quantum dot.The preparation method causes without being added Agent or catalyst change into water phase without the quantum dot for being combined to oil, avoid ligand exchange or ligand from being lost and make to quantum dot Its luminous efficiency and stability is caused to decline at defect, solving the modification of quantum dot later period from the root influences its luminescent properties The problem of.The acrylic polymer coated quantum dots obtained based on preparation method of the present invention are lighted on InGaN chip Its green light power is the 81.2% of initial value after 240h, and stability significantly improves compared with uncoated quantum dot；Its fluorescence Quantum yield is 53~61%, good luminous performance.Therefore, preparation method provided by the invention is easy to operate, the reaction time is short, effect Rate is high, the product of available stable high luminescence energy, while being suitable for industrialized mass production, has wide application Prospect.

Detailed description of the invention

Fig. 1 is the transmission electron microscope picture of acrylic polymer coated quantum dots prepared by the embodiment of the present invention 1；

Fig. 2 is the transmission electron microscope picture of acrylic polymer coated quantum dots prepared by the embodiment of the present invention 1；

Fig. 3 is the transmission electron microscope picture of the quantum dot without polymer overmold of comparative example 1 of the present invention preparation；

Fig. 4 is the fluorescence spectra of acrylic polymer coated quantum dots prepared by the embodiment of the present invention 1；

Fig. 5 is the fluorescence spectra of the quantum dot without polymer overmold of comparative example 1 of the present invention preparation；

Fig. 6 is that the LED green light power stability of acrylic polymer coated quantum dots prepared by the embodiment of the present invention 1 declines Subtract figure；

Fig. 7 is that the LED green light power stability of acrylic polymer coated quantum dots prepared by the embodiment of the present invention 2 declines Subtract figure.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.

Used quantum dot can be obtained by market approach in following embodiment of the present invention, and the present invention is not to its source Carry out particular determination.