技术领域technical field
本发明属于全无机钙钛矿量子点的制备领域，具体涉及一种铯铅卤无机钙钛矿量子点/透明高分子复合薄膜。The invention belongs to the field of preparation of all inorganic perovskite quantum dots, in particular to a cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film.
背景技术Background technique
全无机钙钛矿量子点CsPbX3(X＝Cl,Br,Cl)因具有优异的光学性能，在光电领域引起了极大的关注，如背光源显示，三色发光二极管，太阳能电池，光电探测器以及荧光探针等。量子点(quantum dots,QDs)是一种在零维量子系统定义的纳米材料，在三维方向上都受到限制的粒子。量子效应有量子尺寸效应，量子限域效应，表面效应，当粒子尺寸小于一定数值时，费米能级附近的电子级变为不连续的能级，出现能隙变宽的现象，电子处于束缚状态，容易形成激子，并且量子点的比表面积很大，表面活性高容易产生缺陷。量子效应对材料光学性质的影响主要为：通过调节量子点的尺寸可以调节光谱的波长，并且具有较窄的发射谱带，较大的光吸收截面。All-inorganic perovskite quantum dots CsPbX3 (X=Cl,Br,Cl) have attracted great attention in the field of optoelectronics due to their excellent optical properties, such as backlight display, three-color light-emitting diodes, solar cells, photodetection devices and fluorescent probes. Quantum dots (quantum dots, QDs) are nanomaterials defined in a zero-dimensional quantum system, particles that are restricted in three dimensions. Quantum effects include quantum size effects, quantum confinement effects, and surface effects. When the particle size is smaller than a certain value, the electron level near the Fermi level becomes a discontinuous energy level, and the phenomenon of widening the energy gap occurs, and the electrons are bound. state, it is easy to form excitons, and the specific surface area of quantum dots is large, and the surface activity is high and defects are easy to occur. The influence of quantum effects on the optical properties of materials is mainly: by adjusting the size of quantum dots, the wavelength of the spectrum can be adjusted, and it has a narrow emission band and a large light absorption cross section.
与传统半导体量子点相比，CsPbX3量子点材料具有以下性能优势：(1)通过卤素比例调节，可改变纳米晶的带隙宽度，使其发光可覆盖整个可见光范围，(2)宽激发，即不同发射波长的纳米晶可以被波长在350～400nm范围内的单一光源激发；(3)色纯度高，发射峰的半高宽只有12～42nm，比传统量子点及有机染料要窄很多；(4)较高的缺陷容忍度，使其在没有钝化修饰的情况下，荧光量子产率可达到100％。这些优点奠定了其在光电器件和生物医学等领域的应用基础。因为钙钛矿量子点的荧光峰半峰宽非常窄，所以具有高亮度的荧光和高饱和度的色彩，这正好满足了宽色域液晶显示和高显色指数照明的要求。钙钛矿量子点提供的色彩纯净度相当高，它可以发出相当纯净的红、绿、蓝三色光，NTSC标准下的色域值高达140％，与传统量子点相比，CsPbX3(X＝Cl,Br,Cl)拥有极高的缺陷容忍能力。随着全无机铯铅卤钙钛矿纳米晶合成工艺的不断改进和性能的提高，直接推动了其作为荧光材料在诸多研究领域的应用。Compared with traditional semiconductor quantum dots, CsPbX3 quantum dot materials have the following performance advantages: (1) By adjusting the halogen ratio, the bandgap width of nanocrystals can be changed, so that the luminescence can cover the entire visible light range; (2) wide excitation, That is, nanocrystals with different emission wavelengths can be excited by a single light source with a wavelength in the range of 350-400nm; (3) the color purity is high, and the half-maximum width of the emission peak is only 12-42nm, which is much narrower than traditional quantum dots and organic dyes; (4) High defect tolerance, so that the fluorescence quantum yield can reach 100% without passivation modification. These advantages have laid the foundation for its application in the fields of optoelectronic devices and biomedicine. Because the half-maximum width of the fluorescence peak of perovskite quantum dots is very narrow, it has high brightness fluorescence and high saturation color, which just meets the requirements of wide color gamut liquid crystal display and high color rendering index lighting. The color purity provided by perovskite quantum dots is quite high. It can emit quite pure red, green and blue light. The color gamut value under the NTSC standard is as high as 140%. Compared with traditional quantum dots, CsPbX3 (X= Cl, Br, Cl) have extremely high defect tolerance. With the continuous improvement of the synthesis process and performance of all-inorganic cesium lead halide perovskite nanocrystals, it has directly promoted its application as a fluorescent material in many research fields.
铯铅卤量子点对极性溶剂的敏感直接影响它的应用。处于极性溶剂(如水)环境中，量子点荧光特性短时间迅速退化直至消失。铯铅卤钙钛矿在极性溶剂中的溶解度很高，即使低剂量的极性溶剂也会导致量子点的分解，进而破坏量子点结构，影响量子点发光。研究表明，水中浸泡3h后，量子点荧光性能下降80％左右。另外，钙钛矿量子点长期处于空气中时，量子点在空气中水氧的共同作用下发生分解，严重影响其长期稳定性。The sensitivity of cesium lead halide quantum dots to polar solvents directly affects its application. In a polar solvent (such as water) environment, the fluorescence characteristics of quantum dots degrade rapidly in a short time until they disappear. The solubility of cesium lead halide perovskite in polar solvents is very high, even a low dose of polar solvents can cause the decomposition of quantum dots, thereby destroying the structure of quantum dots and affecting the light emission of quantum dots. Studies have shown that after soaking in water for 3 hours, the fluorescence performance of quantum dots decreases by about 80%. In addition, when the perovskite quantum dots are in the air for a long time, the quantum dots will decompose under the combined action of water and oxygen in the air, which will seriously affect their long-term stability.
申请公布号为CN108034391A的中国发明专利申请公开了一种具有光转换功能的太阳能电池EVA封装胶膜材料及其制备方法，其是将EVA溶解在二氯甲烷中形成EVA的二氯甲烷溶液，将铯铅卤量子点分散到有机溶剂中形成分散液，分散液加入到EVA的二氯甲烷溶液中，再加入交联剂反应后烘干成膜，制成透明光转换胶膜材料。The Chinese invention patent application with the application publication number CN108034391A discloses a solar cell EVA encapsulating adhesive film material with light conversion function and a preparation method thereof, in which EVA is dissolved in dichloromethane to form a dichloromethane solution of EVA. The cesium lead halide quantum dots are dispersed in an organic solvent to form a dispersion liquid, the dispersion liquid is added to the dichloromethane solution of EVA, and then a cross-linking agent is added to react and then dried to form a film to make a transparent light conversion film material.
现有复合薄膜材料是利用铯铅卤量子点分散液和EVA溶液混合制备薄膜材料，该制备过程中，铯铅卤量子点经历了反应生成、分离沉淀、再分散等多个阶段，由于全无机铯铅卤量子点对空气、水、极性溶剂敏感导致其稳定性差，以上多个操作及转移过程，容易破坏量子点的结构，从而使薄膜制品的发光性能变差。Existing composite thin film materials are prepared by mixing cesium lead halogen quantum dot dispersion liquid and EVA solution. Cesium-lead-halogen quantum dots are sensitive to air, water, and polar solvents, resulting in poor stability. The above multiple operations and transfer processes can easily damage the structure of quantum dots, thereby deteriorating the luminescent properties of thin-film products.
发明内容Contents of the invention
本发明的目的在于提供一种铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，以解决现有方法容易破坏量子点结构，导致量子点的发光性能变差的问题。The purpose of the present invention is to provide a cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film to solve the problem that the existing method is easy to destroy the quantum dot structure and cause the luminous performance of the quantum dot to deteriorate.
为实现上述目的，本发明的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜的技术方案是：In order to achieve the above object, the technical scheme of cesium lead halide inorganic perovskite quantum dot/transparent polymer composite thin film of the present invention is:
一种铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，由包括以下步骤的方法进行制备：A cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film is prepared by a method comprising the following steps:
1)将卤化铅、卤化铯、表面配体溶解于第一溶剂中，制备前驱体溶液；1) dissolving lead halide, cesium halide, and surface ligands in the first solvent to prepare a precursor solution;
2)在搅拌下将前驱体溶液滴加到高分子溶液中，得到胶体溶液；利用胶体溶液制膜即可；高分子溶液由透明高分子材料溶解于第二溶剂中制成，所述第二溶剂不溶解铯铅卤量子点。2) Add the precursor solution dropwise into the polymer solution under stirring to obtain a colloidal solution; it is enough to use the colloidal solution to form a film; the polymer solution is made by dissolving a transparent polymer material in a second solvent, and the second Solvents do not dissolve cesium lead halide quantum dots.
本发明提供的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，利用超饱和重结晶的方法使铯铅卤量子点在第二溶剂中结晶析出，并且在合成量子点的同时，使量子点处于高分子树脂的网络结构中，干燥后树脂包裹量子点，形成复合薄膜材料。利用超饱和重结晶的方法所得量子点的粒径小且均匀、分散性好，具有良好的发光性能，而且该方法实现了量子点的生成和高分子树脂原位封装，整个工艺流程简单，可重复性强，生产过程污染小，能耗少，原料来源广泛，可实现批量生产，具有良好的实用效果。The cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film provided by the present invention utilizes the method of supersaturated recrystallization to crystallize the cesium lead halide quantum dot in the second solvent, and at the same time of synthesizing the quantum dot, make The quantum dots are in the network structure of the polymer resin, and after drying, the resin wraps the quantum dots to form a composite film material. The particle size of quantum dots obtained by supersaturated recrystallization method is small, uniform, good dispersion, and has good luminescence performance, and this method realizes the generation of quantum dots and in-situ encapsulation of polymer resin, the whole process is simple and can be The repeatability is strong, the production process is less polluted, the energy consumption is less, and the source of raw materials is extensive, which can realize mass production and has good practical effect.
为促进形成粒径小、分散好、避免团聚的铯铅卤量子点，优选的，步骤2)中，前驱体溶液与高分子溶液的体积比为(0.1-2):(10-20)。In order to promote the formation of cesium lead halide quantum dots with small particle size, good dispersion and avoid agglomeration, preferably, in step 2), the volume ratio of the precursor solution to the polymer solution is (0.1-2):(10-20).
为加快铯铅卤量子点的快速合成，并促进析出细小晶体结构，优选的，步骤2)中，高分子溶液的温度为60-90℃。In order to speed up the rapid synthesis of cesium lead halide quantum dots and promote the precipitation of fine crystal structures, preferably, in step 2), the temperature of the polymer solution is 60-90°C.
为进一步优化前驱体溶液在高分子溶液中的析晶效果，优选的，步骤1)中，前驱体溶液中，卤化铅的浓度为0.01-0.05mol/L；步骤2)中，高分子溶液的浓度为0.01-1g/mL。In order to further optimize the crystallization effect of the precursor solution in the polymer solution, preferably, in step 1), in the precursor solution, the concentration of lead halide is 0.01-0.05mol/L; in step 2), the concentration of the polymer solution The concentration is 0.01-1g/mL.
卤化铅、卤化铯、表面配体的选择可参考相关现有技术，为实现更好钝化和稳定效果，优选的，步骤1)中，所述表面配体为油酸和油胺，油酸和油胺的体积比为(1.5-2.5):1，油酸与卤化铅的摩尔比为(7-9):1。The selection of lead halide, cesium halide, and surface ligands can refer to relevant prior art. In order to achieve better passivation and stabilization effect, preferably, in step 1), the surface ligands are oleic acid and oleylamine, oleic acid The volume ratio of oleylamine and oleylamine is (1.5-2.5):1, and the molar ratio of oleic acid to lead halide is (7-9):1.
第一溶剂能够溶解卤化铅、卤化铯和表面配体即可，从原料成本方面考虑，优选的，所述第一溶剂为N,N-二甲基甲酰胺或二甲基亚砜。第二溶剂的选择以铯铅卤量子点的溶解度越小越好，优选的，步骤2)中，所述第二溶剂为甲苯或正己烷。It is sufficient that the first solvent can dissolve lead halide, cesium halide and surface ligands. In view of raw material cost, preferably, the first solvent is N,N-dimethylformamide or dimethyl sulfoxide. The choice of the second solvent is the smaller the solubility of the cesium lead halide quantum dots, the better. Preferably, in step 2), the second solvent is toluene or n-hexane.
高分子基体的选择没有特殊限制，为使薄膜材料具有良好的防水、透明和高柔韧性的特点，优选的，所述透明高分子材料为乙烯-醋酸乙烯共聚物(EVA)。利用EVA将铯铅卤钙钛矿量子点包裹起来，可避免量子点与空气中水氧分子的接触，提高量子点薄膜的稳定性，相关制品在白光LED和柔性显示等领域预期有良好应用。The selection of the polymer matrix is not particularly limited. In order to make the film material have the characteristics of good waterproof, transparency and high flexibility, preferably, the transparent polymer material is ethylene-vinyl acetate copolymer (EVA). Using EVA to wrap cesium lead halide perovskite quantum dots can avoid the contact between quantum dots and water oxygen molecules in the air, and improve the stability of quantum dot films. Related products are expected to have good applications in the fields of white light LED and flexible display.
附图说明Description of drawings
图1为本发明实施例1所得铯铅卤无机钙钛矿量子点的TEM(a)、HRTEM(b)和尺寸分布图(c)；Fig. 1 is TEM (a), HRTEM (b) and size distribution diagram (c) of cesium lead halide inorganic perovskite quantum dots obtained in Example 1 of the present invention;
图2为本发明实施例和对比例的薄膜材料的XRD图；Fig. 2 is the XRD figure of the thin film material of the embodiment of the present invention and comparative example;
图3为本发明实施例和对比例的薄膜材料的FT-IR图；Fig. 3 is the FT-IR figure of the film material of the embodiment of the present invention and comparative example;
图4为本发明实施例1制备的CsPbBr3/EVA薄膜的表面SEM(a)及EDS能谱图，EDS能谱图分别为：(b)C，(c)Cs，(d)Br，(e)Pb四种元素；Fig. 4 is the surface SEM (a) and EDS spectrum of the CsPbBr3 /EVA thin film prepared in Example 1 of the present invention, and the EDS spectrum is respectively: (b) C, (c) Cs, (d) Br, ( e) Pb four elements;
图5为本发明实施例和对比例的薄膜材料的光致发光(PL)光谱图；Fig. 5 is the photoluminescence (PL) spectrogram of the thin film material of the embodiment of the present invention and comparative example;
图6为本发明实施例和对比例的薄膜材料的半高宽(FWHM)图；Fig. 6 is the full width at half maximum (FWHM) figure of the film material of the embodiment of the present invention and comparative example;
图7为本发明实施例1的复合薄膜材料在不同浸水时间后的PL光谱图；Fig. 7 is the PL spectrogram of the composite film material of Example 1 of the present invention after different immersion times;
图8为本发明实施例1的复合薄膜材料在不同浸水时间后的强度保持率图；Figure 8 is a diagram of the strength retention rate of the composite film material of Example 1 of the present invention after different immersion times;
图9为本发明实施例1的复合薄膜材料在长期放置后的PL光谱图；Fig. 9 is the PL spectrogram of the composite film material of Example 1 of the present invention after long-term storage;
图10为本发明实施例1的复合薄膜材料在长期放置后的强度保持率图。Fig. 10 is a diagram of the strength retention rate of the composite film material in Example 1 of the present invention after long-term storage.
具体实施方式Detailed ways
下面结合具体实施例对本发明的实施方式作进一步说明。The embodiments of the present invention will be further described below in conjunction with specific examples.
一、本发明的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜的具体实施例One, the specific embodiment of cesium lead halide inorganic perovskite quantum dot/transparent polymer composite thin film of the present invention
实施例1Example 1
本实施例的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，采用以下步骤进行制备：The cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film of this embodiment is prepared by the following steps:
1)称取0.0734g PbBr2、0.0425g CsBr粉体，溶入5mL N，N-二甲基甲酰胺(DMF)中，搅拌30min(搅拌转速为200rpm)使充分溶解；然后逐滴滴加表面配体油酸0.5mL(OA)及油胺0.25mL(OAm)，搅拌5min(搅拌转速为200rpm)，待完全溶解后得前驱体溶液；1) Weigh 0.0734g of PbBr2 and 0.0425g of CsBr powder, dissolve them in 5mL of N,N-dimethylformamide (DMF), stir for 30min (stirring speed is 200rpm) to fully dissolve; then drop by drop on the surface Ligand oleic acid 0.5mL (OA) and oleylamine 0.25mL (OAm), stirred for 5min (stirring speed is 200rpm), after being completely dissolved, the precursor solution was obtained;
2)将乙烯-醋酸乙烯共聚物(EVA)树脂颗粒与聚四氟乙烯圆形模具放入无水乙醇中超声30min(超声功率400W)，干燥待用，模具直径为1.5mm，槽深0.5mm；称取1g EVA树脂颗粒加入10mL甲苯中，于70℃下搅拌30min(搅拌转速为200rpm)使充分溶解，得到EVA溶液。2) Put ethylene-vinyl acetate copolymer (EVA) resin particles and polytetrafluoroethylene circular mold into absolute ethanol for 30 minutes (ultrasonic power 400W), dry and set aside, the diameter of the mold is 1.5mm, and the groove depth is 0.5mm Weigh 1g of EVA resin particles into 10mL of toluene, stir at 70°C for 30min (stirring speed is 200rpm) to fully dissolve to obtain EVA solution.
3)用滴管吸取0.2mL前驱体溶液，在70℃、200rpm下滴加到EVA中，溶液由无色透明状态变为黄色状态，由于反应过程非常迅速，在几秒内即可反应完成，滴加完毕后即可得到全无机钙钛矿量子点(CsPbBr3)胶体溶液。这一过程CsPbBr3在甲苯中的溶解度远小于其在DMF中的溶解度，CsPbBr3结晶析出并在表面配体的作用下形成块状CsPbBr3量子点。3) Use a dropper to absorb 0.2mL precursor solution, drop it into EVA at 70°C and 200rpm, the solution changes from a colorless transparent state to a yellow state. Since the reaction process is very fast, the reaction can be completed within a few seconds. After the dropwise addition, an all-inorganic perovskite quantum dot (CsPbBr3 ) colloidal solution can be obtained. In this process, the solubility ofCsPbBr3 in toluene is much smaller than its solubility in DMF, andCsPbBr3 crystallizes out and forms bulkCsPbBr3 quantum dots under the action of surface ligands.
4)取步骤3)所得胶体溶液滴加于聚四氟乙烯模具槽内，置于70℃烘箱干燥3h，脱模，即得CsPbBr3/EVA薄膜复合材料。4) The colloidal solution obtained in step 3) was added dropwise into a polytetrafluoroethylene mold groove, dried in an oven at 70° C. for 3 hours, and demolded to obtain a CsPbBr3 /EVA film composite material.
实施例2-5Example 2-5
本实施例的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，与实施例1的制备方法的区别仅在于，步骤3)中，前驱体溶液的滴加量为0.1mL、0.4mL、0.6mL、0.8mL。The difference between the cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film of this example and the preparation method of Example 1 is that in step 3), the dropping amount of the precursor solution is 0.1mL, 0.4mL , 0.6mL, 0.8mL.
实施例6Example 6
本实施例的铯铅卤无机钙钛矿量子点/透明高分子复合薄膜，与实施例1的制备方法的区别仅在于，步骤3)中，搅拌的速度为300rpm；高分子溶液的温度为80℃。The difference between the cesium lead halide inorganic perovskite quantum dot/transparent polymer composite film of the present embodiment and the preparation method of embodiment 1 is that in step 3), the stirring speed is 300rpm; the temperature of the polymer solution is 80 ℃.
二、对比例2. Comparison ratio
对比例的薄膜的制备方法，与实施例1的区别在于，步骤3)中，前驱提溶液的加入量为0mL。The difference between the preparation method of the film of the comparative example and that of Example 1 is that in step 3), the amount of the pre-extraction solution added is 0 mL.
三、实验例3. Experimental example
实验例1Experimental example 1
本实验例检测实施例1所得铯铅卤无机钙钛矿量子点的TEM、HRTEM和尺寸分布，结果如图1所示。In this experimental example, the TEM, HRTEM and size distribution of the cesium lead halide inorganic perovskite quantum dots obtained in Example 1 were detected, and the results are shown in FIG. 1 .
由图1可知，实施例制备的CsPbBr3量子点的尺寸分布非常均匀，具体尺寸均匀分布于8.5-11.5nm，平均尺寸为10nm。量子由于存在量子尺寸效应，量子点尺寸的增大或减小会造成对应波长的红移或蓝移，尺寸分布范围的增大则表明存在尺寸过大或过小的量子点，这都会引起波长的宽化，FWHM增大。因此，制备小且均匀的CsPbBr3量子点的可赋予量子点较高的量子效率和发光性能的一致性，从而提高相关制品的性能表现。It can be seen from Figure 1 that the size distribution of the CsPbBr3 quantum dots prepared in the embodiment is very uniform, the specific size is uniformly distributed in the range of 8.5-11.5nm, and the average size is 10nm. Due to the quantum size effect, the increase or decrease of the quantum dot size will cause the red shift or blue shift of the corresponding wavelength, and the increase of the size distribution range indicates that there are quantum dots with too large or too small size, which will cause the wavelength widening, FWHM increases. Therefore, the preparation of small and uniform CsPbBr3 quantum dots can endow the quantum dots with higher quantum efficiency and consistency of luminescent properties, thereby improving the performance of related products.
实验例2Experimental example 2
本实施例对实施例和对比例的薄膜材料进行XRD分析和FT-IR分析，结果如图2和图3所示。In this embodiment, XRD analysis and FT-IR analysis are carried out on the thin film materials of the embodiment and the comparative example, and the results are shown in FIG. 2 and FIG. 3 .
图2中，显示的特征峰为在21°左右出现的宽衍射峰对应的是EVA，在15°、22°、31°出现的衍射峰和单斜相的CsPbBr3相符合。In Figure 2, the characteristic peaks shown are the broad diffraction peaks that appear around 21°, which correspond to EVA, and the diffraction peaks that appear at 15°, 22°, and 31° are consistent with the monoclinic CsPbBr3 .
图3中，与对照组(纯EVA薄膜)相比，加入不同含量前驱体溶液制备的CsPbBr3/EVA薄膜的红外光谱图基本上没有变化，表明CsPbBr3量子点与EVA树脂的复合并未对EVA树脂的结构产生明显的破坏。In Fig. 3, compared with the control group (pure EVA film), the infrared spectrograms of theCsPbBr3 /EVA film prepared by adding different content precursor solutions are basically unchanged, indicating that the composite ofCsPbBr3 quantum dots and EVA resin has no effect on The structure of EVA resin is obviously damaged.
由图2和图3的分析结果可知，利用实施例的方法可方便合成CsPbBr3量子点。It can be known from the analysis results in Fig. 2 and Fig. 3 that CsPbBr3 quantum dots can be conveniently synthesized by using the method of the embodiment.
实验例3Experimental example 3
本实验例对实施例1制备的CsPbBr3/EVA薄膜进行表面SEM及EDS能谱分析，结果如图4所示。In this experimental example, the surface SEM and EDS analysis of the CsPbBr3 /EVA thin film prepared in Example 1 was carried out, and the results are shown in FIG. 4 .
由图4可知实施例1制备的CsPbBr3/EVA薄膜具有粗糙的表面，Cs、Br、Pb元素均匀的分布于基体中，说明CsPbBr3量子点在EVA中的分布非常均匀。It can be seen from Figure 4 that the CsPbBr3 /EVA film prepared in Example 1 has a rough surface, and Cs, Br, and Pb elements are uniformly distributed in the matrix, indicating that the distribution of CsPbBr3 quantum dots in EVA is very uniform.
实验例4Experimental example 4
本实验例对实施例和对比例的薄膜材料的光致发光(PL)光谱和半高宽(FWHM)进行分析，结果图5和图6所示。In this experimental example, the photoluminescence (PL) spectrum and full width at half maximum (FWHM) of the thin film materials of the embodiment and the comparative example were analyzed, and the results are shown in FIGS. 5 and 6 .
使用361nm的紫外光进行激发，实施例的发光峰位于521nm，半高宽为21nm，具有色纯度高，半高宽窄的特点。由图可以看出，前驱体滴加量为0.2mL时，相应的薄膜材料具有最高的发光强度，随着前驱体滴加量的增加，发光强度呈现减小的趋势，这与生成的量子点的粒径增加有一定的关系。当加入的前驱液较少时，钙钛矿晶体可以在其中很好的分散析出，形成钙钛矿量子点，并随着滴入前驱液的增多，钙钛矿量子点产量增大，发光增强；当滴入的前驱液体积量超过其定量甲苯溶液的分散承载能力之后，其在一定空间内析出的钙钛矿量子点浓度增大，使其量子点间的间距减小，而导致由于自焊接效应，量子点继续生长，形成了尺寸更大的纳米晶体，超出了量子点零维材料的范畴，进而受到激光激发，转变为晶体发光，发光减弱。Using 361nm ultraviolet light for excitation, the luminescence peak of the embodiment is located at 521nm, and the half maximum width is 21nm, which has the characteristics of high color purity and narrow half maximum width. It can be seen from the figure that when the amount of precursor added is 0.2mL, the corresponding thin film material has the highest luminous intensity. With the increase of the amount of precursor added, the luminous intensity shows a decreasing trend, which is consistent with the generated quantum dots. There is a certain relationship with the increase of particle size. When less precursor liquid is added, perovskite crystals can be well dispersed and precipitated to form perovskite quantum dots, and as the amount of precursor liquid added increases, the yield of perovskite quantum dots increases and the luminescence is enhanced ; when the volume of the dropped precursor solution exceeds the dispersion carrying capacity of its quantitative toluene solution, the concentration of the perovskite quantum dots that it precipitates in a certain space increases, so that the distance between the quantum dots decreases, resulting in Due to the welding effect, quantum dots continue to grow and form larger nanocrystals, which exceed the scope of quantum dot zero-dimensional materials, and then are excited by lasers to transform into crystals that emit light, and the light emission is weakened.
实验例5Experimental example 5
本实验例对实施例1的复合薄膜材料在不同浸水时间后的PL光谱和强度保持率进行分析，PL光谱的测试条件与实施例4相同，结果图7和图8所示。In this experimental example, the PL spectrum and strength retention rate of the composite thin film material in Example 1 after different immersion times are analyzed. The test conditions of the PL spectrum are the same as in Example 4, and the results are shown in Figures 7 and 8.
由图7和图8可以看出，实施例1制备的复合薄膜材料，浸水5h荧光强度保持率为99.0％，浸水15h强度保持率为81.1％，该复合薄膜材料在水中的稳定好，具有良好的耐水性。As can be seen from Figures 7 and 8, the composite film material prepared in Example 1 has a fluorescence intensity retention rate of 99.0% after immersion in water for 5 hours, and an intensity retention rate of 81.1% after immersion in water for 15 hours. The composite film material has good stability in water and has a good water resistance.
实验例6Experimental example 6
本实施例对实施例1的复合薄膜材料的长期放置性能进行分析。在空气中放置3个月后，实施例1的薄膜材料的PL光谱和强度保持率如图9和图10所示。In this example, the long-term storage performance of the composite film material in Example 1 is analyzed. After being placed in the air for 3 months, the PL spectrum and strength retention rate of the film material of Example 1 are shown in Figure 9 and Figure 10 .
由图9和图10可看出，实施例1的复合薄膜材料的长期放置性能良好，30d放置后的荧光强度保持率为67.4％，90d放置后的荧光强度保持率为63.4％。It can be seen from Figures 9 and 10 that the long-term storage performance of the composite thin film material in Example 1 is good, the fluorescence intensity retention rate after 30d storage is 67.4%, and the fluorescence intensity retention rate after 90d storage is 63.4%.
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| CN201910894972.2ACN110551304A (en) | 2019-09-20 | 2019-09-20 | Cesium-lead halogen inorganic perovskite quantum dot/transparent polymer composite film |
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| CN201910894972.2ACN110551304A (en) | 2019-09-20 | 2019-09-20 | Cesium-lead halogen inorganic perovskite quantum dot/transparent polymer composite film |
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