CN111690400A - Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof - Google Patents
Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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Abstract
一种稀土‑量子点长余辉复合发光材料及其制备方法和应用。所述复合材料由稀土长余辉发光材料和量子点两部分组成。本发明的复合材料制备简单，只需将稀土长余辉发光材料和量子点旋涂成膜或直接混合即可。通过调控稀土长余辉发光材料与量子点的种类和比例，该复合材料可实现全可见谱段的高效长余辉发光。本发明复合材料克服了传统稀土长余辉材料余辉发射半峰宽较大，发光波段受限于材料本身的缺陷，实现了可见光波段的连续可调。本发明对材料的的余辉光谱进行了精细调控，该复合材料可应用于生物监测、生物成像、光学编码、防伪、显示等领域。
A rare earth-quantum dot long afterglow composite luminescent material, preparation method and application thereof. The composite material is composed of rare earth long afterglow luminescent material and quantum dots. The composite material of the invention is simple to prepare, and only needs to spin-coat or directly mix the rare earth long afterglow luminescent material and the quantum dots. By adjusting the types and ratios of rare earth long afterglow luminescent materials and quantum dots, the composite material can achieve high-efficiency long afterglow luminescence in the full visible spectrum. The composite material of the invention overcomes the defects of the traditional rare earth long afterglow material that the afterglow emission half-peak width is large and the emission band is limited by the material itself, and realizes the continuous adjustment of the visible light band. The invention finely regulates the afterglow spectrum of the material, and the composite material can be applied to the fields of biological monitoring, biological imaging, optical coding, anti-counterfeiting, display and the like.
Description
技术领域technical field
本发明属于发光材料技术领域，具体涉及一种量子点-稀土长余辉复合发光材料及其制备方法和应用。The invention belongs to the technical field of luminescent materials, in particular to a quantum dot-rare earth long afterglow composite luminescent material and a preparation method and application thereof.
背景技术Background technique
长余辉发光材料是一种将激发高能光子部分存储后在激发光停止后以光的形式缓慢释放出来实现长时间光发射的光致发光材料。长余辉材料广泛应用于安全标识、信息显示以及防伪、应力探测、生物成像等领域。(参考文献：B.K.Gupta et al.,J.Appl.Phys.2015,117,243104)The long afterglow luminescent material is a photoluminescent material that stores the excited high-energy photons and releases them slowly in the form of light after the excitation light stops to achieve long-term light emission. Long afterglow materials are widely used in security signs, information display and anti-counterfeiting, stress detection, biological imaging and other fields. (Reference: B.K.Gupta et al., J.Appl.Phys.2015, 117, 243104)
稀土长余辉发光材料是一种新型环保节能材料，其发光亮度高、余辉时间长、化学稳定性良好，受到国内外广泛关注。利用稀土独特的电子结构和丰富的跃迁能级，稀土长余辉材料可产生可见光波段的多种色彩发光。通过调控稀土离子及基质离子的组成可对其余辉发光波长进行精细调控，这需要对不同稀土离子及其掺杂浓度进行大量的尝试。此外由于稀土离子的能级结构特点，稀土长余辉材料有着不同的余辉时长及半峰宽，因此无法实现对整个可见光谱段的窄带发射，限制了其发光调控的自由度。Rare earth long afterglow luminescent material is a new type of environmentally friendly and energy-saving material, which has high luminous brightness, long afterglow time and good chemical stability, and has attracted widespread attention at home and abroad. Utilizing the unique electronic structure and abundant transition energy levels of rare earths, rare earth long afterglow materials can produce a variety of color luminescence in the visible light band. The afterglow wavelength can be fine-tuned by manipulating the composition of rare earth ions and host ions, which requires a lot of experimentation with different rare earth ions and their doping concentrations. In addition, due to the energy level structure characteristics of rare earth ions, rare earth long afterglow materials have different afterglow durations and half-peak widths, so they cannot achieve narrow-band emission in the entire visible spectrum, limiting their freedom of luminescence regulation.
发明内容SUMMARY OF THE INVENTION
为改善稀土长余辉发光材料在应用中的不足，本发明提供一种量子点-稀土长余辉复合发光材料，所述复合材料主要由稀土长余辉发光材料和量子点共混组成。In order to improve the deficiencies in the application of rare earth long afterglow luminescent materials, the present invention provides a quantum dot-rare earth long afterglow composite luminescent material, the composite material is mainly composed of rare earth long afterglow luminescent materials and quantum dots.
根据本发明的实施方案，复合材料中所述稀土长余辉发光材料和量子点的摩尔比为1:(0.001-1000)，优选为1:(0.01-100)，进一步优选为1:(0.01-20)，例如为(5-20):1。According to an embodiment of the present invention, the molar ratio of the rare earth long afterglow luminescent material and the quantum dots in the composite material is 1:(0.001-1000), preferably 1:(0.01-100), more preferably 1:(0.01-1000) 20), for example (5-20):1.
根据本发明的实施方案，所述稀土长余辉发光材料的基质选自氧化物、氟化物、硫化物、卤化物、氮化物、磷化物、砷化物、硒化物、碲化物、铝氧化物、氟卤化物、硫氧化物、硅氧化物、钒酸盐、磷酸盐、硼酸盐、硅酸盐、铝酸盐、锗酸盐、钨酸盐、钼酸盐、钛酸盐、硫酸盐、钽酸盐、铌酸盐、铬酸盐、镓酸盐中的一种、两种或多种；优选为氧化物、硫氧化物中的至少一种；例如选自CaAl2O4、SrAl2O4中的一种或两种；According to an embodiment of the present invention, the host of the rare earth long afterglow luminescent material is selected from oxides, fluorides, sulfides, halides, nitrides, phosphides, arsenides, selenides, tellurides, aluminum oxides, fluorides Halides, oxides of sulfur, oxides of silicon, vanadates, phosphates, borates, silicates, aluminates, germanates, tungstates, molybdates, titanates, sulfates, tantalum One, two or more of salts, niobates, chromates, and gallates; preferably at least one of oxides and oxysulfides; for example, selected from CaAl 2 O 4 , SrAl 2 O one or both of 4 ;
根据本发明的实施方案，所述稀土长余辉材料的稀土激活离子选自Er3+、Tm3+、Ho3 +、Pr3+、Gd3+、Ce3+、Nd3+、Tb3+、Eu2+、Sm3+、Dy3+、Mn2+、Cr3+中的一种或几种的组合；优选为Eu2+、Nd3+、Dy3+、Tm3+、Sm3+中的一种或几种的组合；进一步优选为Eu2+、Nd3+、Dy3+中的一种、两种或更多种的组合。According to an embodiment of the present invention, the rare earth active ions of the rare earth long afterglow material are selected from Er 3+ , Tm 3+ , Ho 3+ , Pr 3+ , Gd 3+ , Ce 3+ , Nd 3+ , Tb 3+ , Eu 2+ , Sm 3+ , Dy 3+ , Mn 2+ , Cr 3+ in one or a combination of several; preferably Eu 2+ , Nd 3+ , Dy 3+ , Tm 3+ , Sm 3 A combination of one or more of + ; more preferably, one or a combination of two or more of Eu 2+ , Nd 3+ , and Dy 3+ .
根据本发明的实施方案，所述稀土长余辉发光材料选自包括但不限于如下化合物：CaAl2O4:Eu2+,Nd3+(CAO)，SrAl2O4:Eu2+,Dy3+，CaAl2O4:Eu2+，CaAl2O4:Tb3+，Ca12Al14O33:Eu2 +,Nd3+，CaAl2O4:Tb3+，BaAl2O4:Ce3+,Dy3+，SrAl4O7:Eu2+,Dy3+，CaxSr1-xAl2O4:Eu2+,Nd3+(其中0<x<1)，MgAl2O4:Ce3+，SrAl2O4:Eu2+，CdSiO3:Sm3+，Ca2Al2SiO7:Ce3+，CaAl2Si2O8:Eu2+,Dy3+，MAl2O4:Eu2+,Dy3+,Nd3+(M＝Sr或Ca)，CdSiO3:Sm3+，CaMgSi2O6:Eu2+,Dy3+，Sr3MgSi2O8:Eu2+,Dy3 +，Sr2MgSi2O7:Eu2+,Dy3+，Sr2SiO4:Eu2+,Dy3+，CaTiO3:Pr3+，ZnS:Eu2+，CaS:Bi3+,Tm3+。According to an embodiment of the present invention, the rare earth long afterglow luminescent material is selected from compounds including but not limited to: CaAl 2 O 4 :Eu 2+ , Nd 3+ (CAO), SrAl 2 O 4 :Eu 2+ , Dy 3 + , CaAl 2 O 4 :Eu 2+ , CaAl2O 4 :Tb 3+ , Ca 12 Al 14 O 33 :Eu 2 + ,Nd 3+ ,CaAl 2 O 4 :Tb 3+ ,BaAl 2 O 4 :Ce 3+ , Dy 3+ , SrAl 4 O 7 : Eu 2+ , Dy 3+ , Ca x Sr 1-x Al 2 O 4 : Eu 2+ , Nd 3+ (where 0<x<1), MgAl 2 O 4 : Ce 3+ , SrAl 2 O 4 :Eu 2+ , CdSiO 3 :Sm 3+ , Ca 2 Al 2 SiO 7 :Ce 3+ , CaAl 2 Si2 O 8 :Eu 2+ ,Dy 3+ ,MAl 2 O 4 :Eu 2 + , Dy 3+ , Nd 3+ (M=Sr or Ca), CdSiO 3 : Sm 3+ , CaMgSi 2 O 6 : Eu 2+ , Dy 3+ , Sr 3 MgSi 2 O 8 : Eu 2+ , Dy 3 + , Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ ,Sr 2 SiO 4 :Eu 2+ ,Dy 3+ ,CaTiO 3 :Pr 3+ ,ZnS:Eu 2+ ,CaS:Bi 3+ ,Tm 3+ .
根据本发明的实施方案，所述稀土长余辉发光材料的尺寸可以为纳米级、微米级、或块材的晶体形式。According to an embodiment of the present invention, the size of the rare earth long afterglow luminescent material may be in nanoscale, microscale, or bulk crystal form.
根据本发明的实施方案，所述稀土长余辉发光材料的表面性质可以为油溶性、水溶性、或者油水均不溶。According to an embodiment of the present invention, the surface properties of the rare earth long afterglow luminescent material may be oil-soluble, water-soluble, or both oil- and water-insoluble.
根据本发明的实施方案，所述稀土长余辉发光材料样品包括其溶液、粉末、薄膜、块体，优选为其溶液、粉末和薄膜样品。According to an embodiment of the present invention, the rare earth long afterglow luminescent material sample includes its solution, powder, film, bulk, preferably its solution, powder and film samples.
根据本发明的实施方案，所述量子点选自卤化物钙钛矿量子点、氧化物量子点、硫化物量子点、硒化物量子点、碲化物量子点、氮化物量子点、磷化物量子点、砷化物量子点、碳量子点、碳化物量子点、硅量子点、硅化物量子点、锗量子点、锗化物量子点、及在所述量子点基础上形成的核壳结构或异质结中的至少一种。According to an embodiment of the present invention, the quantum dots are selected from halide perovskite quantum dots, oxide quantum dots, sulfide quantum dots, selenide quantum dots, telluride quantum dots, nitride quantum dots, phosphide quantum dots , Arsenide quantum dots, carbon quantum dots, carbide quantum dots, silicon quantum dots, silicide quantum dots, germanium quantum dots, germanide quantum dots, and core-shell structures or heterojunctions formed on the basis of the quantum dots at least one of them.
根据本发明的实施方案，所述量子点优选为CdS、CdSe、InP、CuInS2、或CdS、CdSe、InP、ZnS、CuInS2量子点基础上形成的核壳结构或异质结，或者，有机-无机杂化钙钛矿量子点、全无机钙钛矿量子点。According to an embodiment of the present invention, the quantum dots are preferably core-shell structures or heterojunctions formed on the basis of CdS, CdSe, InP, CuInS 2 , or CdS, CdSe, InP, ZnS, CuInS 2 quantum dots, or, organic -Inorganic hybrid perovskite quantum dots, all-inorganic perovskite quantum dots.
根据本发明的实施方案，所述量子点选自包括但不限于如下物质：CsPbCl3、CsPbCl1.5Br1.5、CsPbCl1Br2、CsPbBr3、CsPbBr2I1、CsPbBr1.5I1.5、CsPbBr1I2、CsPbI3、CdSe、InP@ZnS。According to an embodiment of the present invention, the quantum dots are selected from substances including but not limited to: CsPbCl 3 , CsPbCl 1.5 Br 1.5 , CsPbCl 1 Br 2 , CsPbBr 3 , CsPbBr 2 I 1 , CsPbBr 1.5 I 1.5 , CsPbBr 1 I 2 , CsPbI 3 , CdSe, InP@ZnS.
根据本发明的实施方案，所述量子点的表面性质可以为油溶性、水溶性、或者油水均不溶。According to an embodiment of the present invention, the surface properties of the quantum dots may be oil-soluble, water-soluble, or both oil- and water-insoluble.
根据本发明的实施方案，所述量子点样品包括其溶液、粉末、薄膜、块体，优选为溶液、粉末和薄膜样品。According to an embodiment of the present invention, the quantum dot samples include solutions, powders, films, bulks thereof, preferably solution, powder and film samples.
根据本发明的实施方案，所述量子点-稀土长余辉复合发光材料选自包括但不限于如下复合材料：CaAl2O4:Eu2+,Nd3+-CsPbCl3、CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5、CaAl2O4:Eu2+,Nd3+-CsPbCl2Br1、CaAl2O4:Eu2+,Nd3+-CsPbCl1Br2、CaAl2O4:Eu2+,Nd3+-CsPbBr3、CaAl2O4:Eu2+,Nd3+-CsPbBr2I1、CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5、CaAl2O4:Eu2+,Nd3+-CsPbBr1I2、CaAl2O4:Eu2+,Nd3+-CsPbI3、CaAl2O4:Eu3+,Nd3+-CsPbBr2.3I0.7、SrAl2O4:Eu2+,Dy3+-CsPbBr2I1、SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5、SrAl2O4:Eu2+,Dy3+-CsPbBr1I2、SrAl2O4:Eu2+,Dy3+-CsPbI3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr2I1、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1I2、Sr4Al14O25:Eu2+,Dy3+-CsPbI3、Sr2MgSi2O7:Eu2 +,Dy3+-CsPbBr3、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr2I1、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1I2、Sr2MgSi2O7:Eu2+,Dy3+-CsPbI3、Sr2SiO4:Eu2+,Dy3+-CsPbBr2I1、Sr2SiO4:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2SiO4:Eu2+,Dy3+-CsPbBr1I2、Sr2SiO4:Eu2+,Dy3 +-CsPbI3、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr3、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr2I1、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1I2、Sr3MgSi2O8:Eu2+,Dy3+-CsPbI3，Sr3MgSi2O8:Eu2+,Dy3+-InP@ZnS。According to an embodiment of the present invention, the quantum dot-rare earth long afterglow composite luminescent material is selected from composite materials including but not limited to: CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbCl 3 , CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbCl 1.5 Br 1.5 , CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbCl 2 Br 1 , CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbCl 1 Br 2 , CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 3 ,CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 2 I 1 ,CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 1.5 I 1.5 , CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 1 I 2 , CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbI 3 ,CaAl 2 O 4 :Eu 3+ ,Nd 3+ -CsPbBr 2.3 I 0.7 , SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 , SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 1.5 I 1.5 ,SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 , SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbI 3 , Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ -CsPbBr 3 ,Sr 4 Al 14 O 25 :Eu 2+ , Dy 3+ -CsPbBr 2 I 1 , Sr 4 Al 14 O 25 :Eu 2+ , Dy 3+ -CsPbBr 1.5 I 1.5 , Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 , Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ -CsPbI 3 , Sr 2 MgSi 2 O 7 :Eu 2 + ,Dy 3+ -CsPbBr 3 ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 , Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ -CsPbBr 1.5 I 1.5 , Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 , Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ -CsPbI 3 , Sr 2 SiO 4 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 ,Sr 2 SiO 4 :Eu 2+ ,Dy 3 + -CsPbBr 1.5 I 1.5 , Sr 2 SiO 4 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 , Sr 2 SiO 4 :Eu 2+ ,Dy 3 + -CsPbI 3 ,Sr 3 MgSi 2 O 8 :Eu 2 + ,Dy 3+ -CsPbBr 3 , Sr 3 MgSi 2 O 8 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 ,Sr 3 MgSi 2 O 8 :Eu 2+ ,Dy 3+ -CsPbBr 1.5 I 1.5 ,Sr 3 MgSi 2 O 8 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 ,Sr 3 MgSi 2 O 8 :Eu 2+ ,Dy 3+ -CsPbI 3 ,Sr 3 MgSi 2 O 8 :Eu 2+ ,Dy 3 + -InP@ZnS.
本发明还提供上述量子点-稀土长余辉复合发光材料的制备方法，包括如下步骤：将稀土长余辉发光材料、量子点旋涂成膜或者直接混合，即可获得所述量子点-稀土长余辉复合发光材料。The present invention also provides a method for preparing the above quantum dot-rare earth long afterglow composite luminescent material, comprising the following steps: spinning the rare earth long afterglow luminescent material and the quantum dot into a film or directly mixing to obtain the quantum dot-rare earth long afterglow luminescent material Composite luminescent material.
根据本发明的实施方案，所述混合的形式包括将稀土长余辉发光材料、量子点的溶液混合、粉末混合、薄膜层叠，还包括共混制成薄膜。According to an embodiment of the present invention, the mixing form includes solution mixing, powder mixing, thin film stacking, and blending of rare earth long afterglow luminescent materials and quantum dots to form a thin film.
根据本发明的实施方案，所述稀土长余辉发光材料和量子点的摩尔比为1:(0.001-1000)，优选为1:(0.01-100)，进一步优选为1:(0.01-20)。According to an embodiment of the present invention, the molar ratio of the rare earth long afterglow luminescent material and the quantum dots is 1:(0.001-1000), preferably 1:(0.01-100), more preferably 1:(0.01-20).
根据本发明示例性的实施方案，所述制备方法包括如下步骤：将稀土长余辉材料和量子点分别分散在聚二甲基硅氧烷(PDMS)或聚甲基丙烯酸甲酯(PMMA)中，分次旋涂、凝固，即可获得量子点-稀土复合长余辉复合发光材料。According to an exemplary embodiment of the present invention, the preparation method includes the steps of: dispersing the rare earth long afterglow material and quantum dots in polydimethylsiloxane (PDMS) or polymethylmethacrylate (PMMA), respectively, The quantum dot-rare earth composite long afterglow composite luminescent material can be obtained by spin coating and solidification step by step.
本发明还提供上述量子点-稀土长余辉复合发光材料的用途，包括用于生物检测、生物成像、光学编码、防伪、显示、光电探测器、太阳频谱转换方面。优选用于显示、光学编码和多重防伪。The present invention also provides uses of the quantum dot-rare earth long afterglow composite luminescent material, including biological detection, biological imaging, optical coding, anti-counterfeiting, display, photodetector, and solar spectrum conversion. Preferred for display, optical coding and multiple security.
本发明的有益效果在于：The beneficial effects of the present invention are:
(1)本发明的复合材料在紫外光激发下获得了可见光谱的窄带发射的连续调节，突破了单独使用长余辉材料时仅有宽带发射的瓶颈。(1) The composite material of the present invention obtains continuous regulation of the narrow-band emission of the visible spectrum under the excitation of ultraviolet light, which breaks through the bottleneck of only broadband emission when the long afterglow material is used alone.
(2)本发明的复合材料由稀土长余辉发光材料和量子点两部分组成：稀土长余辉发光材料通过将被缺陷存储的能量以发光的形式释放出来，量子点吸收释放的光能从而实现量子点的持续发光。这种辐射能量传递(或称辐射再吸收)突破了传统的荧光共振能量传递(FRET)给体与受体距离的限制；本发明合成方法简单、方便，容易推广和大规模制备。(2) The composite material of the present invention is composed of two parts: the rare earth long afterglow luminescent material and the quantum dots: the rare earth long afterglow luminescent material releases the energy stored by the defect in the form of luminescence, and the quantum dot absorbs the released light energy to realize quantum Continuous glow of the dots. This radiation energy transfer (or called radiation reabsorption) breaks through the limitation of the distance between the donor and the acceptor of the traditional fluorescence resonance energy transfer (FRET); the synthesis method of the invention is simple, convenient, easy to popularize and large-scale preparation.
(3)本发明复合材料中量子点的发光波长范围为420-1500nm，优选为450-700nm；通过调控稀土长余辉材料和量子点的种类和数目，可对整个可见谱段长余辉发光进行连续调控，这是传统长余辉发光材料无法实现的。(3) The emission wavelength range of the quantum dots in the composite material of the present invention is 420-1500 nm, preferably 450-700 nm; by regulating the type and number of rare earth long afterglow materials and quantum dots, the long afterglow emission of the entire visible spectrum can be continuously regulation, which cannot be achieved by traditional long-persistence luminescent materials.
(4)通过改变稀土长余辉材料和量子点的种类和数目，本发明可对材料的余辉光谱进行精细调控，从而构筑无数可以识别的光学标签，拓展了其在光学编码、多重防伪、显示等领域的应用前景。(4) By changing the types and numbers of rare earth long afterglow materials and quantum dots, the present invention can finely control the afterglow spectrum of the materials, thereby constructing countless identifiable optical labels, and expanding its applications in optical coding, multiple anti-counterfeiting, display, etc. application prospects in the field.
附图说明Description of drawings
图1对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbX3(其中X为一种或两种卤素)复合材料中(a)CsPbCl3，(b)CsPbCl1.5Br1.5，(c)CsPbBr3，(d)CsPbBr1.5I1.5，(e)CsPbI3钙钛矿量子点的透射电镜照片和(f)X射线粉末衍射图。Figure 1 corresponds to (a) CsPbCl 3 , (b) CsPbCl 1.5 Br 1.5 in the composite material of CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbX 3 (wherein X is one or two halogens) in Example 1, (c) Transmission electron micrographs and (f) X-ray powder diffraction patterns of CsPbBr 3 , (d) CsPbBr 1.5 I 1.5 , and (e) CsPbI 3 perovskite quantum dots.
图2对应实施例1中CsPbCl3，CsPbCl2Br1，CsPbCl1.5Br1.5，CsPbCl1Br2，CsPbBr3，CsPbBr2I1，CsPbBr1.5I1.5，CsPbBr1I2，CsPbI3钙钛矿量子点的荧光发射光谱图(激发波长为365nm)和吸收谱图(图2中虚线表示吸收曲线，实线表示发射曲线)。Figure 2 corresponds to CsPbCl 3 , CsPbCl 2 Br 1 , CsPbCl 1.5 Br 1.5 , CsPbCl 1 Br 2 , CsPbBr 3 , CsPbBr 2 I 1 , CsPbBr 1.5 I 1.5 , CsPbBr 1 I 2 , CsPbI 3 perovskite quantum dots in Example 1 The fluorescence emission spectrum (excitation wavelength is 365nm) and absorption spectrum (the dotted line in Figure 2 represents the absorption curve, and the solid line represents the emission curve).
图3对应实施例1中CsPbCl3，CsPbCl1.5Br1.5，CsPbBr3，CsPbBr2I1，CsPbBr1.5I1.5，CsPbI3钙钛矿量子点的荧光寿命图，激发波长为375nm。3 corresponds to the fluorescence lifetime diagram of the CsPbCl 3 , CsPbCl 1.5 Br 1.5 , CsPbBr 3 , CsPbBr 2 I 1 , CsPbBr 1.5 I 1.5 , and CsPbI 3 perovskite quantum dots in Example 1, and the excitation wavelength is 375 nm.
图4对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbX3(其中X为一种或两种卤素)复合材料的薄膜，分别是(a)CAO、(b)CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)、(c)CaAl2O4:Eu2+,Nd3+-CsPbBr3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr3摩尔比为14:1)、(d)CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2I1摩尔比为15:1)、(e)CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1.5I1.5摩尔比为18:1)和(f)CaAl2O4:Eu2+,Nd3+-CsPbI3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbI3摩尔比为20:1)在常光下(第一行)的照片和余辉发射光的照片(第二行)(其中，第一行a为白色，b为浅绿色，c为浅黄色，d为橙色，e为暗红色，f为暗红色；第二行a为蓝紫色发光，b为蓝色发光，c为绿色发光，d为橙色发光，e为红色发光，f为暗红色发光。Figure 4 corresponds to the thin film of the composite material of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 (wherein X is one or two halogens) in Example 1, respectively (a) CAO, (b) CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1.5 Br 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbCl 1.5 Br 1.5 in the composite material is 12:1), (c) CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbBr 3 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ to CsPbBr 3 is 14:1), (d) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 2 I 1 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ and CsPbBr 2 I 1 is 15:1), (e) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1.5 I 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ to CsPbBr 1.5 I 1.5 in the composite material is 18:1) and (f)CaAl 2 O 4 :Eu 2+ ,Nd Photographs of 3+ -CsPbI 3 (CaAl 2 O 4 :Eu 2+ , Nd 3+ to CsPbI 3 molar ratio in the composite material is 20:1) under normal light (first row) and afterglow emission (second row) Line) (wherein the first line a is white, b is light green, c is light yellow, d is orange, e is dark red, and f is dark red; the second line a is blue-purple luminescence, b is blue luminescence , c is green emission, d is orange emission, e is red emission, f is dark red emission.
图5对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbX3(其中X为一种或两种卤素)复合材料的薄膜，分别是(a)CAO、(b)CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)、(c)CaAl2O4:Eu2+,Nd3+-CsPbCl1Br2(复合材料中CaAl2O4:Eu2 +,Nd3+与CsPbCl1Br2摩尔比为12:1)、(d)CaAl2O4:Eu2+,Nd3+-CsPbBr3(复合材料中CaAl2O4:Eu2 +,Nd3+与CsPbBr3摩尔比为14:1)、(e)CaAl2O4:Eu2+,Nd3+-CsPbBr2.3I0.7(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2.3I0.7摩尔比为14:1)、(f)CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2I1摩尔比为15:1)、(g)CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1.5I1.5摩尔比为18:1)、(h)CaAl2O4:Eu2+,Nd3+-CsPbBr1I2(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1I2摩尔比为20:1)和(i)CaAl2O4:Eu2+,Nd3+-CsPbI3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbI3摩尔比为20:1)的余辉发光谱图(左图)、余辉衰减曲线(中图)及其CIE色坐标位置(右图)。Figure 5 corresponds to the thin film of the composite material of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 (wherein X is one or two halogens) in Example 1, respectively (a) CAO, (b) CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1.5 Br 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbCl 1.5 Br 1.5 in the composite material is 12:1), (c) CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbCl 1 Br 2 (CaAl 2 O 4 : Eu 2 + , Nd 3+ and CsPbCl 1 Br 2 molar ratio in the composite material is 12:1), (d) CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbBr 3 (CaAl 2 O 4 :Eu 2 + in the composite material, the molar ratio of Nd 3+ to CsPbBr 3 is 14:1), (e) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 2.3 I 0.7 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ to CsPbBr 2.3 I 0.7 is 14:1), (f)CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 2 I 1 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ to CsPbBr 2 I 1 in the composite material is 15:1), (g) CaAl 2 O 4 :Eu 2+ ,Nd 3 + -CsPbBr 1.5 I 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbBr 1.5 I 1.5 in the composite material is 18:1), (h)CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 1 I 2 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ to CsPbBr 1 I 2 in the composite material is 20:1) and (i) CaAl 2 O 4 :Eu 2+ ,Nd 3+ - Afterglow emission spectrum (left image), afterglow decay curve (middle image) and CIE color coordinates of CsPbI 3 (CaAl 2 O 4 :Eu 2+ , Nd 3+ and CsPbI 3 molar ratio in the composite material is 20:1) location (right).
图6对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbCl2Br1不同组成比例的复合材料的余辉光谱图，其中CAO的含量固定为0.2mmol(0表示使用0μmolCsPbCl2Br1与0.2mmolCAO制备的复合材料样品；1表示使用1μmol CsPbCl2Br1与0.2mmol CAO制备的复合材料样品，余下依次类推)。Figure 6 corresponds to the afterglow spectra of composites with different composition ratios of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 2 Br 1 in Example 1, wherein the content of CAO is fixed at 0.2 mmol (0 means using 0 μmol of
图7对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5不同组成比例的复合材料的余辉光谱图，其中CAO的含量固定为0.2mmol(0表示使用0μmolCsPbBr1.5I1.5与0.2mmolCAO制备的复合材料样品；2表示使用2μmolCsPbBr1.5I1.5与0.2mmolCAO制备的复合材料样品，余下依次类推)。Figure 7 corresponds to the afterglow spectra of the composites with different composition ratios of CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1.5 I 1.5 in Example 1, wherein the content of CAO is fixed at 0.2 mmol (0 means using 0 μmol CsPbBr 1.5 I 1.5 and 0.2 mmol CAO composite samples; 2 represents composite samples prepared using 2 μmol CsPbBr 1.5 I 1.5 and 0.2 mmol CAO, and the rest are analogous).
图8对应实施例1中CaAl2O4:Eu2+,Nd3+-CsPbX3(其中X为一种或两种卤素)复合材料的薄膜，分别是(a)CAO、(b)CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)、(c)CaAl2O4:Eu2+,Nd3+-CsPbBr3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr3摩尔比为14:1)、(d)CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2I1摩尔比为15:1)、(e)CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1.5I1.5摩尔比为18:1)和(f)CaAl2O4:Eu2+,Nd3+-CsPbI3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbI3摩尔比为20:1)在100K温度条件下测得的CAO的荧光寿命，激发波长375nm，监测波长为440nm。Figure 8 corresponds to the thin film of the composite material of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 (wherein X is one or two halogens) in Example 1, respectively (a) CAO, (b) CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1.5 Br 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbCl 1.5 Br 1.5 in the composite material is 12:1), (c) CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbBr 3 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ to CsPbBr 3 is 14:1), (d) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 2 I 1 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ and CsPbBr 2 I 1 is 15:1), (e) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1.5 I 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ to CsPbBr 1.5 I 1.5 in the composite material is 18:1) and (f)CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbI 3 (CaAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Nd 3+ to CsPbI 3 is 20:1) Fluorescence lifetime of CAO measured at 100K temperature, excitation wavelength 375nm, monitoring wavelength is 440nm.
图9对应实施例1中(a)CAO、(b)CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)、(c)CaAl2O4:Eu2+,Nd3+-CsPbBr3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr3摩尔比为14:1)、(d)CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1.5I1.5摩尔比为18:1)的热释曲线，测试范围200K-550K，升温速率30K-min。Figure 9 corresponds to (a) CAO, (b) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbCl 1.5 Br 1.5 in Example 1 (CaAl 2 O 4 :Eu 2+ , Nd 3+ and CsPbCl in the composite material 1.5 Br 1.5 molar ratio is 12:1), (c) CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 3 (CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbBr 3 molar ratio in the composite material is 14:1), (d) CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1.5 I 1.5 (in the composite material, the molar ratio of CaAl 2 O 4 :Eu 2+ , Nd 3+ and CsPbBr 1.5 I 1.5 is 18:1) pyrolysis curve, the test range is 200K-550K, and the heating rate is 30K-min.
图10对应实施例1中CaAl2O4:Eu2+,Nd3+通过辐射能量传递过程敏化钙钛矿量子点发光示意图。FIG. 10 corresponds to the schematic diagram of the luminescence of perovskite quantum dots sensitized by CaAl 2 O 4 :Eu 2+ , Nd 3+ through radiation energy transfer process in Example 1.
图11为实施例2制备的几种复合材料的余辉发光谱图，其中a为SrAl2O4:Eu2+,Dy3 +，b为SrAl2O4:Eu2+,Dy3+-CsPbBr3(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr3摩尔比为8:1)，c为SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr2I1摩尔比为9:1)，d为SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1.5I1.5摩尔比为10:1)，e为SrAl2O4:Eu2+,Dy3+-CsPbBr1I2的检测结果(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1I2摩尔比为10:1)。Figure 11 is the afterglow emission spectra of several composite materials prepared in Example 2, wherein a is SrAl2O4:Eu 2+ , Dy 3 + , b is SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 3 (composite In the material SrAl 2 O 4 :Eu 2+ , the molar ratio of Dy 3+ and CsPbBr 3 is 8:1), c is SrAl 2 O 4 :Eu 2+ , Dy 3+ -CsPbBr 2 I 1 (SrAl 2 in the composite material O 4 :Eu 2+ , the molar ratio of Dy 3+ and CsPbBr 2 I 1 is 9:1), d is SrAl 2 O 4 :Eu 2+ , Dy 3+ -CsPbBr 1 .5 I 1.5 (SrAl 2 O 4 :Eu in the composite material 2+ , Dy 3+ and CsPbBr 1.5 I 1.5 molar ratio of 10:1), e is the detection result of SrAl 2 O 4 :Eu 2+ , Dy 3+ -CsPbBr 1 I 2 (SrAl 2 O4 :Eu in the composite material 2+ , Dy 3+ and CsPbBr 1 I2 molar ratio of 10:1).
具体实施方式Detailed ways
以下结合具体实施例对本发明作进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，但不应将这些实施例解释为对本发明保护范围的限制。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only illustrative to illustrate and explain the present invention, but these examples should not be construed as limiting the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.
仪器和设备：Instruments and Equipment:
本发明实施例产品进行粉末衍射表征使用的仪器型号为MiniFlex2，厂家为Rigaku，铜靶辐射波长为λ＝0.154187nm。The model of the instrument used for powder diffraction characterization of the product of the embodiment of the present invention is MiniFlex2, the manufacturer is Rigaku, and the radiation wavelength of the copper target is λ=0.154187 nm.
本发明实施例产品进行X射线能谱分析使用的仪器型号为JEM-2010，厂家为JEOL。The model of the instrument used for the X-ray energy spectrum analysis of the product of the embodiment of the present invention is JEM-2010, and the manufacturer is JEOL.
本发明实施例产品进行透射电镜检测使用的仪器型号为TECNAI G2F20，厂家为FEI。The model of the instrument used for the transmission electron microscope detection of the products of the embodiment of the present invention is TECNAI G 2 F20, and the manufacturer is FEI.
本发明实施例产品进行紫外可见吸收光谱表征使用的仪器型号为Lambda365，厂家为Perkin-Elmer。The model of the instrument used for the UV-Vis absorption spectrum characterization of the product of the embodiment of the present invention is Lambda365, and the manufacturer is Perkin-Elmer.
本发明实施例产品进行荧光发射光谱、荧光寿命表征使用的仪器型号为FLS980，厂家为Edinburgh，激发光源为氙灯和390nm LD脉冲激光器。The instrument used for the characterization of the fluorescence emission spectrum and the fluorescence lifetime of the product of the embodiment of the present invention is FLS980, the manufacturer is Edinburgh, and the excitation light source is a xenon lamp and a 390 nm LD pulsed laser.
本申请中使用的CsPbX3(其中X为一种或两种卤素)的制备方法为：The preparation method of CsPbX 3 (wherein X is one or two halogens) used in this application is:
所述CsPbX3(X＝Cl,Br,I)量子点可以通过热注射法制备。将Cs2CO3、Pb(CH3COO)2溶解于十八烯、油酸、油胺混合溶剂中，高温注射HX(X＝Cl,Br,I)溶剂获得CsPbX3量子点。其发射光谱在400-700nm范围之间连续可调。具体制备方法列举在下文。The CsPbX 3 (X=Cl, Br, I) quantum dots can be prepared by a thermal injection method. Dissolve Cs 2 CO 3 and Pb(CH 3 COO) 2 in a mixed solvent of octadecene, oleic acid and oleylamine, and inject HX (X=Cl, Br, I) solvent at high temperature to obtain CsPbX 3 quantum dots. Its emission spectrum is continuously tunable in the range of 400-700nm. Specific preparation methods are listed below.
制备例1 CsPbCl3钙钛矿量子点的制备Preparation Example 1 Preparation of CsPbCl 3 Perovskite Quantum Dots
称取0.5mmol醋酸铅、0.1mmol碳酸铯，然后加入1mL油酸、1mL油胺、1mL三正辛基膦和10mL十八烯，通氮气加热至120℃并保温10分钟，形成透明溶液A，然后升温至180℃；向溶液A中快速注射124μL盐酸，保温10秒，用冰浴快速冷却(冷却速度约为10-15℃/秒)至室温；先离心分离再用10mL环己烷和10mL丙酮洗涤1次，并将沉淀物分散在30mL环己烷中，得到CsPbCl3钙钛矿量子点。Weigh 0.5 mmol of lead acetate and 0.1 mmol of cesium carbonate, then add 1 mL of oleic acid, 1 mL of oleylamine, 1 mL of tri-n-octyl phosphine and 10 mL of octadecene, and heat to 120°C with nitrogen and keep it for 10 minutes to form a transparent solution A, then The temperature was raised to 180°C; 124 μL of hydrochloric acid was rapidly injected into solution A, incubated for 10 seconds, and rapidly cooled with an ice bath (the cooling rate was about 10-15°C/second) to room temperature; centrifuged first, then used 10 mL of cyclohexane and 10 mL of acetone Wash once, and disperse the precipitate in 30 mL of cyclohexane to obtain CsPbCl 3 perovskite quantum dots.
制备例2 CsPbCl1.5Br1.5钙钛矿量子点的制备Preparation Example 2 Preparation of CsPbCl 1.5 Br 1.5 Perovskite Quantum Dots
称取0.5mmol醋酸铅、0.05mmol碳酸铯，然后加入0.5mL油酸、0.5mL油胺和6mL十八烯，通氮气加热至120℃并保温30分钟，形成透明溶液A，然后升温至190℃；向溶液A中快速注射62μL盐酸和87μL溴化氢，保温5秒，用冰水浴快速冷却至室温；先离心分离再用5mL环己烷和5mL丙酮洗涤1次，并将沉淀物分散在30mL环己烷中，得到CsPbCl1.5Br1.5钙钛矿量子点。Weigh 0.5 mmol of lead acetate and 0.05 mmol of cesium carbonate, then add 0.5 mL of oleic acid, 0.5 mL of oleyl amine and 6 mL of octadecene, pass nitrogen and heat to 120 °C and keep the temperature for 30 minutes to form a transparent solution A, which is then heated to 190 °C; Quickly inject 62 μL of hydrochloric acid and 87 μL of hydrogen bromide into solution A, incubate for 5 seconds, and rapidly cool to room temperature with an ice-water bath; firstly centrifuge and then wash once with 5 mL of cyclohexane and 5 mL of acetone, and disperse the precipitate in a 30 mL ring. In hexane, CsPbCl 1.5 Br 1.5 perovskite quantum dots were obtained.
制备例3 CsPbBr3钙钛矿量子点的制备Preparation Example 3 Preparation of CsPbBr 3 Perovskite Quantum Dots
称取0.5mmol醋酸铅、0.08mmol碳酸铯，然后加入1.5mL油酸、1.5mL油胺和8mL十八烯，通氮气加热至120℃并保温30分钟，形成透明溶液A，然后升温至170℃；向溶液A中快速注射173μL溴化氢，保温10秒，用冰浴快速冷却(冷却速度约为10-15℃/秒)至室温；先离心分离再用5mL环己烷和5mL丙酮洗涤1次，并将沉淀物分散在30mL环己烷中，得到CsPbBr3钙钛矿量子点。Weigh 0.5 mmol of lead acetate and 0.08 mmol of cesium carbonate, then add 1.5 mL of oleic acid, 1.5 mL of oleyl amine and 8 mL of octadecene, pass nitrogen and heat to 120°C and keep the temperature for 30 minutes to form a transparent solution A, which is then heated to 170°C; Quickly inject 173 μL of hydrogen bromide into solution A, hold for 10 seconds, and rapidly cool with an ice bath (the cooling rate is about 10-15 °C/second) to room temperature; first centrifuge and then wash with 5 mL of cyclohexane and 5 mL of acetone once , and the precipitate was dispersed in 30 mL of cyclohexane to obtain CsPbBr3 perovskite quantum dots.
制备例4 CsPbBr2I1钙钛矿量子点的制备Preparation Example 4 Preparation of CsPbBr2I1 Perovskite Quantum Dots
称取0.5mmol醋酸铅、0.2mmol醋酸铯，然后加入1.5mL油酸、1.5mL油胺和10mL十八烯，通氮气加热至120℃并保温40分钟，形成透明溶液A，然后升温至160℃；向溶液A中快速注射116μL溴化氢和66μL碘化氢，保温10秒，用冰浴快速冷却至室温；先离心分离再用1mL环己烷洗涤1次，并将沉淀物分散在30mL环己烷中，得到CsPbBr2I1钙钛矿量子点。Weigh 0.5 mmol of lead acetate and 0.2 mmol of cesium acetate, then add 1.5 mL of oleic acid, 1.5 mL of oleylamine and 10 mL of octadecene, pass nitrogen and heat to 120°C and keep the temperature for 40 minutes to form a transparent solution A, which is then heated to 160°C; Quickly inject 116 μL of hydrogen bromide and 66 μL of hydrogen iodide into solution A, incubate for 10 seconds, and rapidly cool to room temperature with an ice bath; firstly centrifuge and then wash with 1 mL of cyclohexane once, and disperse the precipitate in 30 mL of cyclohexane In alkane, CsPbBr 2 I 1 perovskite quantum dots were obtained.
参考上述制备例的方法，改变卤素与其他原料的摩尔比还制备了如下几种量子点：CsPbBr1.5I1.5、CsPbI3、CsPbCl2Br1、CsPbCl1Br2、CsPbBr1.5I1.5、CsPbBr1I2、CsPbCl1.5Br1.5、CsPbBr2.3I0.7。Referring to the method of the above preparation example, the following quantum dots were also prepared by changing the molar ratio of halogen to other raw materials: CsPbBr 1.5 I 1.5 , CsPbI 3 , CsPbCl 2 Br 1 , CsPbCl 1 Br 2 , CsPbBr 1.5 I 1.5 , CsPbBr 1 I 2. CsPbCl 1.5 Br 1.5 , CsPbBr 2.3 I 0.7 .
实施例1 CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5的制备Example 1 Preparation of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1.5 Br 1.5
称取经过研磨至亚微米级的CaAl2O4:Eu2+,Nd3+(CAO)稀土长余辉发光材料0.24mmol、聚二甲基硅氧烷(Dowcorning 184(PDMS))0.1g，混合均匀后，置于手套箱中，抽出混合物中的空气，然后旋涂于石英片上，并置于90℃干燥箱中恒温30mins，得到固化的CaAl2O4:Eu2+,Nd3+薄膜。然后称取CsPbCl1.5Br1.5 20μmol，聚二甲基硅氧烷(Dowcorning184)0.1g，混合均匀后抽除其中的空气，并旋涂于CaAl2O4:Eu2+,Nd3+薄膜上，再次置于90℃干燥箱中恒温30mins，得到固化的CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)薄膜。Weigh out 0.24 mmol of CaAl 2 O 4 :Eu 2+ ,Nd 3+ (CAO) rare earth long afterglow luminescent material, 0.1 g of polydimethylsiloxane (Dowcorning 184 (PDMS)), and mix After homogenization, put it in a glove box, extract the air in the mixture, spin-coat it on a quartz plate, and place it in a drying oven at 90 °C for 30 mins to obtain a cured CaAl 2 O 4 :Eu 2+ , Nd 3+ film. Then weigh CsPbCl 1.5 Br 1.5 20μmol, polydimethylsiloxane (Dowcorning 184) 0.1g, mix evenly, remove the air, and spin-coat on the CaAl 2 O 4 :Eu 2+ ,Nd 3+ film, It was placed in a drying oven at 90°C for 30 mins at a constant temperature to obtain solidified CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbCl 1.5 Br 1.5 (CaAl 2 O 4 : Eu 2+ , Nd 3+ and CsPbCl 1.5 in the composite material Br 1.5 molar ratio 12:1) film.
参考如上实施例1的方法还制备了如下复合材料：CaAl2O4:Eu2+,Nd3+-CsPbBr3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr3摩尔比为14:1)、CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2I1摩尔比为15:1)、CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1.5I1.5摩尔比为18:1)、CaAl2O4:Eu2+,Nd3+-CsPbI3(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbI3摩尔比为20:1)、CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1.5Br1.5摩尔比为12:1)、CaAl2O4:Eu2+,Nd3+-CsPbCl1Br2(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbCl1Br2摩尔比为12:1)、CaAl2O4:Eu2+,Nd3+-CsPbBr2.3I0.7(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr2.3I0.7摩尔比为14:1)、CaAl2O4:Eu2+,Nd3+-CsPbBr1I2(复合材料中CaAl2O4:Eu2+,Nd3+与CsPbBr1I2摩尔比为20:1)。Referring to the method of Example 1 above, the following composite materials were also prepared: CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbBr 3 (the molar ratio of CaAl 2 O 4 : Eu 2+ , Nd 3+ to CsPbBr 3 in the composite material 14:1), CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 2 I 1 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ to CsPbBr 2 I 1 in the composite material is 15:1 ), CaAl 2 O 4 : Eu 2+ , Nd 3+ -CsPbBr 1.5 I 1.5 (the molar ratio of CaAl 2 O 4 : Eu 2+ , Nd 3+ and CsPbBr 1.5 I 1.5 in the composite material is 18:1), CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbI 3 (CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbI 3 molar ratio in the composite material is 20:1), CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1.5 Br 1.5 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbCl 1.5 Br 1.5 in the composite material is 12:1), CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 1 Br 2 (the molar ratio of CaAl 2 O 4 :Eu 2+ ,Nd 3+ and CsPbCl 1 Br 2 in the composite material is 12:1), CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 2.3 I 0.7 ( In the composite material, the molar ratio of CaAl 2 O 4 :Eu 2+ , Nd 3+ and CsPbBr 2.3 I 0.7 is 14:1), CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1 I 2 (CaAl 2 O 4 :Eu 2+ , Nd 3+ -CsPbBr 1 I 2 in the composite material The molar ratio of 2 O 4 :Eu 2+ , Nd 3+ and CsPbBr 1 I 2 is 20:1).
实施例2 SrAl2O4:Eu2+,Dy3+-CsPbBr3的制备Example 2 Preparation of SrAl 2 O 4 : Eu 2+ , Dy 3+ -CsPbBr 3
称取经过研磨至亚微米级的SrAl2O4:Eu2+,Dy3+稀土长余辉发光材料(SrAl2O4中Eu2 +,Dy3+掺入含量均为3％)0.08mmol、聚二甲基硅氧烷(Dowcorning 184(PDMS))0.1g，混合均匀后，置于手套箱中，抽出混合物中的空气，然后旋涂于石英片上，并置于90℃干燥箱中恒温30mins，得到固化的SrAl2O4:Eu2+,Dy3+薄膜。然后称取CsPbBr3 10μmol，聚二甲基硅氧烷(Dowcorning 184)0.1g，混合均匀后抽除其中的空气，并旋涂于SrAl2O4:Eu2+,Dy3+薄膜上，再次置于90℃干燥箱中恒温30mins，得到固化的SrAl2O4:Eu2+,Dy3+-CsPbBr3(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr3摩尔比为8:1)薄膜。参考实施例2的方法还制备了如下复合材料：SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr2I1摩尔比为9:1)、SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1.5I1.5摩尔比为10:1)、SrAl2O4:Eu2+,Dy3+-CsPbBr1I2(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1I2摩尔比为10:1)。Weigh SrAl 2 O 4 :Eu 2+ ,Dy 3+ rare earth long afterglow luminescent material ground to submicron level (Eu 2 + in SrAl 2 O 4 ,Dy 3+ doping content are both 3%)0.08mmol, Polydimethylsiloxane (Dowcorning 184 (PDMS)) 0.1g, after mixing evenly, put it in a glove box, extract the air from the mixture, spin-coat it on a quartz plate, and place it in a drying oven at 90°C for 30mins , to obtain a cured SrAl 2 O 4 :Eu 2+ ,Dy 3+ thin film. Then weigh 10 μmol of CsPbBr 3 and 0.1 g of polydimethylsiloxane (Dowcorning 184), mix them evenly, remove the air, and spin-coat it on the SrAl 2 O 4 :Eu 2+ ,Dy 3+ film, again Place in a drying oven at 90°C for 30mins at a constant temperature to obtain solidified SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 3 (in the composite material, the molar ratio of SrAl 2 O 4 :Eu 2+ ,Dy 3+ to CsPbBr 3 is 8:1) Film. The method of Reference Example 2 also prepared the following composite materials: SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 (SrAl 2 O 4 :Eu 2+ ,Dy 3+ and CsPbBr 2 I in the composite material 1 molar ratio is 9:1), SrAl 2 O 4 :Eu 2+ , Dy 3+ -CsPbBr 1.5 I 1.5 (in the composite material SrAl 2 O 4 :Eu 2+ , Dy 3+ and CsPbBr 1.5 I 1.5 molar ratio is 10:1), SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 1 I 2 (the molar ratio of SrAl 2 O 4 :Eu 2+ ,Dy 3+ to CsPbBr 1 I 2 in the composite material is 10:1) .
实施例3性能测试Example 3 Performance Test
CsPbX3(X＝Cl,Br,I)量子点的透射电镜照片(图1a)和X射线粉末衍射图(图1b)表明这类量子点为立方相结构，具有良好的分散性和晶化，粒径约为10-16nm。荧光光谱和吸收光谱(图2)表明在紫外光激发下，CsPbX3钙钛矿量子点具有窄带发射，其半峰宽为9-31nm以及较宽的吸收范围。图3表明了CsPbX3钙钛矿量子点的荧光寿命为7.7-103ns。上述实施例制备的CaAl2O4:Eu2+,Nd3+-CsPbX3复合材料薄膜照片(图4)及其余辉发光照片表明所述复合材料在紫外光照射后可持续呈现出明亮的蓝紫色、绿色、红色的连续可调发光，对应的余辉发光谱图、余辉衰减曲线和色坐标图(图5)说明了上述实施例制备的复合材料薄膜继承了钙钛矿量子点具有的较窄发射峰宽和余辉发光时长大于8h。几种复合材料的色域范围可达130％NTSC色域标准(即薄膜余辉发光波长的色坐标位置所组成面积进行积分与NTSC三刺激值组成的积分面积相比计算得到的结果)。上述实施例制备的CaAl2O4:Eu2+,Nd3+-CsPbCl2Br1不同组成比例的复合材料(CAO为0.2mmol)的余辉光谱(图6)表明了随着复合材料中CsPbCl2Br1占比的提升，CsPbCl2Br1吸收更多CAO的发光，从而占据主导。上述实施例制备的CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5不同组成比例的复合材料(CAO为0.2mmol)的余辉光谱(图7)表明随着复合材料中CsPbBr1.5I1.5占比的提升，其可以完全吸收CAO的余辉发光从而呈现出钙钛矿量子点的荧光发射。上述实施例制备的CaAl2O4:Eu2+,Nd3+-CsPbX3复合材料的薄膜在100K温度条件下测得的CAO的荧光寿命(图8)表明复合材料中的CAO荧光寿命基本没有变化，说明CAO与钙钛矿量子点之间不存在共振能量传递，而是单纯的辐射再吸收过程。热释谱(图9)表明监测上述实施例制备的CaAl2O4:Eu2+,Nd3+-CsPbX3复合材料中CsPbX3量子点的发射峰强度随温度的变化趋势发现，CsPbX3量子点与CAO的热释谱图相比，热释曲线无明显变化，说明CsPbX3量子点能够对CAO的发光实现高效的吸收。图10为长余辉发光材料与量子点之间辐射再吸收的原理示意图。The TEM image (Fig. 1a) and X-ray powder diffraction pattern (Fig. 1b) of CsPbX 3 (X=Cl, Br, I) quantum dots show that these quantum dots have a cubic phase structure with good dispersibility and crystallization. The particle size is about 10-16nm. Fluorescence and absorption spectra (Figure 2) show that CsPbX3 perovskite QDs have a narrow-band emission with a half-peak width of 9–31 nm and a broad absorption range under UV excitation. Figure 3 demonstrates the fluorescence lifetime of CsPbX3 perovskite QDs in the range of 7.7-103 ns. The photo of the CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 composite film prepared in the above example (Fig. 4) and the afterglow photo show that the composite material can continue to present a bright blue color after being irradiated by ultraviolet light. The continuous tunable emission of purple, green and red, the corresponding afterglow emission spectrum, afterglow decay curve and color coordinate diagram (Fig. 5) illustrate that the composite film prepared in the above example inherits the narrowness of perovskite quantum dots. The emission peak width and afterglow luminescence duration are greater than 8h. The color gamut range of several composite materials can reach 130% of the NTSC color gamut standard (that is, the result obtained by integrating the area composed of the color coordinates of the afterglow wavelength of the film and the integral area composed of the NTSC tristimulus values). The afterglow spectra (Fig. 6) of the composites with different composition ratios of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbCl 2 Br 1 (CAO is 0.2 mmol) prepared in the above examples showed that with the CsPbCl 2 in the composites With the increase of the proportion of Br 1 , CsPbCl 2 Br 1 absorbs more luminescence of CAO, and thus dominates. The afterglow spectra (Fig. 7) of the composites with different composition ratios of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbBr 1.5 I 1.5 (CAO is 0.2 mmol) prepared in the above examples show that with the increase of CsPbBr 1.5 I in the composites With an increase of 1.5% , it can completely absorb the afterglow luminescence of CAO to show the fluorescence emission of perovskite quantum dots. The fluorescence lifetime of CAO measured at the temperature of 100K for the thin films of CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 composite prepared in the above example (Fig. 8) shows that the CAO fluorescence lifetime in the composite material is basically not The change indicates that there is no resonance energy transfer between CAO and perovskite quantum dots, but a simple radiation reabsorption process. The pyrolysis spectrum (Fig. 9) shows that monitoring the change trend of the emission peak intensity of CsPbX 3 quantum dots in the CaAl 2 O 4 :Eu 2+ ,Nd 3+ -CsPbX 3 composite material prepared in the above example with temperature, it is found that C s PbX Compared with the pyrolysis spectrum of CAO, the pyrolysis curve of 3 quantum dots has no obvious change, indicating that CsPbX 3 quantum dots can achieve efficient absorption of the luminescence of CAO. FIG. 10 is a schematic diagram of the principle of radiation reabsorption between the long afterglow luminescent material and the quantum dots.
实施例4：SrAl2O4:Eu2+,Dy3+-CsPbX3(其中X为一种或两种卤素)复合材料的发光性能Example 4: Luminescence properties of SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbX 3 (wherein X is one or two halogens) composite material
图11为SrAl2O4:Eu2+,Dy3+-CsPbX3复合材料继承了量子点具有的较窄发射峰宽和长余辉发光材料具有的余辉发光检测结果。其中a为SrAl2O4:Eu2+,Dy3+，b为SrAl2O4:Eu2+,Dy3 +-CsPbBr3(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr3摩尔比为8:1)，c为SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr2I1摩尔比为9:1)，d为SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1.5I1.5摩尔比为10:1)，e为SrAl2O4:Eu2 +,Dy3+-CsPbBr1I2(复合材料中SrAl2O4:Eu2+,Dy3+与CsPbBr1I2摩尔比为10:1)的检测结果。Figure 11 shows the detection result of the afterglow luminescence of the SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbX 3 composite material, which inherits the narrow emission peak width of quantum dots and the afterglow luminescence of long afterglow luminescent materials. where a is SrAl 2 O 4 :Eu 2+ ,Dy 3+ ,b is SrAl 2 O 4 :Eu 2+ ,Dy 3 + -CsPbBr 3 (in the composite material SrAl 2 O 4 :Eu 2+ ,Dy 3+ and CsPbBr 3 molar ratio is 8:1), c is SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 2 I 1 (SrAl 2 O 4 :Eu 2+ ,Dy 3+ and CsPbBr 2 I 1 in the composite material The molar ratio is 9:1), d is SrAl 2 O 4 :Eu 2+ ,Dy 3+ -CsPbBr 1.5 I 1.5 (in the composite material SrAl 2 O 4 :Eu 2+ ,Dy 3+ and CsPbBr 1.5 I 1.5 molar ratio is 10:1), e is SrAl 2 O 4 :Eu 2 + , Dy 3+ -CsPbBr 1 I 2 (SrAl 2 O 4 :Eu 2+ in the composite material, the molar ratio of Dy 3+ to CsPbBr 1 I 2 is 10 :1) of the test results.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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