Composite reflection / transmission integrated color filter based on photonic crystal-dye-transparent polymer and preparation method of composite reflection / transmission integrated color filter

Abstract

The invention discloses a reflection / transmission integrated color filter based on a photonic crystal-dye-transparent polymer composite and a preparation method thereof, and the color filter is composed of an opal photonic crystal template formed by nanometer microspheres and a dye-transparent polymer composite filled in gaps of the opal photonic crystal template. Through compounding of the nano-microspheres, the dye and the transparent polymer, the photonic crystal and the dye can cooperatively filter visible light with specific wavelength, and two filtering modes of reflection and transmission are achieved; the absorption peak width of the photonic crystal can be widened due to the light absorption characteristic of the dye, and a high-purity light filtering effect is generated in a reflection mode; the photonic band gap of the photonic crystal can adjust the light cut-off wave band of the dye, a high-purity light filtering effect is formed in a transmission mode, the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter with high-purity color output is finally achieved, the property is stable, and the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter has wide application prospects in the fields of display, optical instruments and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of optical filters, and more specifically, to a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter and a preparation method thereof. Background Art

[0002] In today's increasingly technology-driven world, filters are a simple optical control device. They are widely used in laser experiments, displays, spectral analysis, and optical measurements (Nat. Nanotechnol. 2012, 7, 557.; LabChip, 2006, 6, 981-987). Filters with high-purity filtering effects can not only achieve high-precision imaging and detection of biological samples, but are also used in laser surgery and laser treatment equipment to achieve precise cutting and repair of diseased tissues by precisely controlling laser wavelength and power (Sensor actuat B-chem., 2017, 242, 318-323). In addition, filters with high-purity filtering effects are used in displays, which can not only bring people an immersive visual enjoyment experience, but also the high-quality display effect is almost harmless to the human eye.

[0003] Filters are mainly divided into two categories: dye absorption filters and structured filters (Adv. Opt. Mater. 2020, 8, 2000317.). Dye absorption filters achieve filtering effects based on the absorption of light by dyes. Although dye filters have high transmittance, the molecular design of dye structures is complex, and existing filters or coatings based on traditional dyes or pigments are susceptible to various damages under long-term ultraviolet (UV) irradiation and high temperatures (Adv. Opt. Mater. 2017, 5, 1700029.). Another type of filter is a micro-nano structure filter developed based on the diffraction, interference and scattering effects of micro-nano structures and light. Among them, micro-nano structures include photonic crystals, all-metal and all-medium structures. The colors produced by such micro-nano structures are usually adjustable in wavelength and half-peak width. Therefore, micro-nano structure filters have the advantages of color tunability and light and thermal stability. However, the difference in the refractive index of the medium often leads to an increase in light scattering in the structure, which greatly weakens the purity and intensity of the reflected light of the filter, and its average visible light transmittance decreases, which to a certain extent limits the improvement of the color saturation / purity of the device.

[0004] Therefore, people try to combine dyes with structural colors to synergistically construct high-purity filters. For example, L. Jay Guo et al. integrated ultrathin dye films into the traditional dielectric-absorber-dielectric-metal resonator configuration to generate high-purity reflective structural colors (Adv. Opt. Mater. 2017, 5, 1700029.). Yong Li et al. reported the development of a dichroic dye-doped flexible cholesterol polymer film optical filter with a double-layer structure, which exhibited excellent stability, high optical density and good visibility (Adv. Opt. Mater. 2021, 9, 2001861.). However, the above dye and structural color composite filters are limited to the preparation of reflective filters. Therefore, it is still a challenge to realize a reflective / transmitting integrated color filter with a high-purity filtering effect. Summary of the invention

[0005] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter and a preparation method thereof, which is composed of an opal photonic crystal template formed by nano-microspheres and a dye-transparent polymer composite filled in the gaps of the opal photonic crystal template; wherein, the photonic crystal band gap reflected light is absorbed and purified by using a dye that absorbs non-overlapping light in the photonic band gap, and at the same time, the photonic crystal and the dye can cooperatively filter visible light of a specific wavelength, and have two filtering modes of reflection and transmission; the light absorption characteristics of the dye can broaden the absorption peak width of the photonic crystal, and produce a high-purity filtering effect in the reflection mode; the photonic band gap of the photonic crystal can adjust the light cutoff band of the dye, and form a high-purity filtering effect in the transmission mode, and finally achieve high-purity color output on both sides of the filter.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] A photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter, the color filter is composed of an opal photonic crystal template formed by nano-microspheres and a dye-transparent polymer composite filled in the gaps of the opal photonic crystal template. Through the composite of the nano-microspheres, the dye and the transparent polymer, the color filter has two filtering modes of reflection and transmission.

[0008] Optionally, the color filter comprises the following components in volume percentage: 10% to 74% of nano-microspheres and 26% to 90% of a dye-transparent polymer composite; wherein the mass ratio of the dye to the transparent polymer in the dye-transparent polymer composite is 1:(10 to 1000).

[0009] Optionally, the reflection wavelength of the color filter is 380nm to 780nm.

[0010] Optionally, the cross-sectional thickness of the opal photonic crystal template is 1 um to 90 μm.

[0011] Optionally, the nanospheres include one or more of silica-coated cerium dioxide, silica-coated zinc sulfide, silica-coated titanium dioxide, silica-coated zinc oxide, silica-coated cadmium sulfide, silica-coated polystyrene, titanium dioxide-coated silica, silica, polystyrene, cerium dioxide, titanium dioxide, cadmium sulfide, zinc oxide, and zinc sulfide nanospheres.

[0012] Optionally, the diameter of the nano-microspheres is 100 nm to 800 nm, and the particle size distribution is 0.01 to 0.20.

[0013] Optionally, the dye includes one or more of perylene dye derivatives, azo dye derivatives, anthraquinone dye derivatives and phthalocyanine dye derivatives.

[0014] Optionally, the perylene dye derivative includes one or more of 1,6,7,10-dibromoperylene diimide, 1,6,7,10-dialkoxyperylene diimide, 1,6,7,10-diaryloxyperylene diimide, 1,6,7,10-dialkylaminoperylene diimide, 1,7-dibromoperylene diimide, 1,7-dialkoxyperylene diimide, 1,7-diaryloxyperylene diimide, 1,7-dialkylaminoperylene diimide, perylene dicarboxylate, and perylene tetracarboxylate.

[0015] Optionally, the azo dye derivative includes one or more of pyrazolone, pyridone, thiazole and aromatic amine derivatives.

[0016] Optionally, the anthraquinone dye derivative includes one or more of 1,4-dialkylamino substituted anthraquinone dye, 1,4-diarylamino substituted anthraquinone dye, 1,5-dialkylamino substituted anthraquinone dye, 1,5-diarylamino substituted anthraquinone dye, 1,8-dialkylamino substituted anthraquinone dye, 1,8-diarylamino substituted anthraquinone dye, 1,8-hydroxyanthraquinone, 1,8-aminoanthraquinone, 1,8-dichloroanthraquinone, 1,4-hydroxyanthraquinone, 1,4-aminoanthraquinone, 1,4-dichloroanthraquinone, 1,5-hydroxyanthraquinone, 1,5-aminoanthraquinone and 1,5-dichloroanthraquinone.

[0017] Optionally, the phthalocyanine dye derivative includes one or more of lanthanum phthalocyanine, silicon phthalocyanine, aluminum phthalocyanine, copper phthalocyanine, nickel phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine and iron phthalocyanine.

[0018] Optionally, the transparent polymer is formed by polymerizing polyimide, polycarbonate, polyurethane, polysulfone, epoxy resin, polystyrene, acrylate compounds and acrylic compounds as monomer components.

[0019] The present invention also discloses a method for preparing the above-mentioned photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter, comprising the following steps:

[0020] Opal photonic crystal templates were obtained by self-assembly using nanospheres as raw materials;

[0021] dissolving a transparent polymer and a dye in a solvent to obtain a mixed solution;

[0022] The mixed liquid is filled into the gaps of the opal photonic crystal template, and heated and cured at 50° C. to 120° C. for 2 min to 600 min to obtain the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter.

[0023] Optionally, the solvent includes N,N'-dimethylformamide (DMF).

[0024] Optionally, the self-assembly method comprises one of pulling, spraying, vertical deposition, screen printing and inkjet printing.

[0025] Implementing the embodiments of the present invention will have the following beneficial effects:

[0026] The present invention provides a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter. By combining the dye with the photonic crystal structure, the optical absorption of the dye can be used to broaden the absorption peak width of the photonic crystal structure color, and a high-purity filtering effect is produced in the reflection mode; the photonic band gap of the photonic crystal can adjust the optical cutoff band of the dye. At the same time, in the composite structure, the photonic crystal structure and the dye both have a filtering effect, thereby cooperatively filtering visible light of a specific wavelength, and having two filtering modes of reflection and transmission. Finally, a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter with high-purity color output is realized. At the same time, the present invention simplifies the design process of high-purity colors, avoids the trouble of designing ideal materials, and has stable properties. It has great potential in various applications such as color displays, optical decoration and optical detection, and is expected to have great application value in fields such as information security and display. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The present invention is a flow chart for preparing the photonic crystal-dye-transparent polymer composite color filter.

[0028] Figure 2The molecular formula and structural characterization diagram of azopyrazolone Y-1 prepared in Example 1 of the present invention; wherein a is the molecular formula diagram of azopyrazolone; b is the structural characterization diagram of azopyrazolone; and c is the Fourier infrared spectrum diagram of azopyrazolone.

[0029] Figure 3 The molecular formula and structural characterization diagram of perylene diimide M-1 prepared in Examples 10 to 17 of the present invention; wherein a is the molecular formula diagram of perylene diimide M-1; b is the structural characterization diagram of perylene diimide M-1; c is the Fourier infrared spectrum diagram of perylene diimide M-1.

[0030] Figure 4 The molecular formula and structural characterization diagram of phthalocyanine C-1 prepared in Examples 18 to 25 of the present invention; wherein a is the molecular formula diagram of phthalocyanine C-1; b is the structural characterization diagram of phthalocyanine C-1; c is the Fourier infrared spectrum diagram of phthalocyanine C-1.

[0031] Figure 5 The molecular formula of anthraquinone B-1 prepared in Examples 26 to 33 of the present invention.

[0032] Figure 6 The molecular formula of anthraquinone B-2 prepared in Example 34 of the present invention.

[0033] Figure 7 The molecular formula of anthraquinone B-3 prepared in Examples 35 to 42 of the present invention.

[0034] Figure 8 The anthraquinone R-1 molecular formula prepared in Examples 43 to 50 of the present invention.

[0035] Fig. 9 The anthraquinone R-2 molecular formula prepared in Examples 51 to 58 of the present invention.

[0036] Fig.10 The molecular formula of azo Y-2 prepared in Examples 59 to 66 of the present invention.

[0037] Fig.11 The molecular formula of azo O-1 prepared in Example 67 of the present invention.

[0038] Fig.12 The molecular formula of perylene diimide C-2 prepared in Examples 68 to 75 of the present invention is as follows.

[0039] Fig.13 The molecular formula of perylene diimide R-3 prepared in Examples 76 to 83 of the present invention is:

[0040] Fig.14 The molecular formula of perylene diimide R-4 prepared in Examples 84 to 91 of the present invention is:

[0041] Fig.15The molecular formula of perylene diimide C-3 prepared in Examples 92 to 99 of the present invention is as follows.

[0042] Fig.16 The molecular formula of perylene tetracarboxylic acid ester Y-3 prepared in Examples 100 to 107 of the present invention is:

[0043] Fig.17 The molecular formula of perylene dicarboxylate Y-4 prepared in Examples 108 to 115 of the present invention is:

[0044] Fig.18 This is an electron scanning microscope image of the monodisperse silica-coated cerium dioxide prepared in Example 1 of the present invention.

[0045] Fig.19 This is a field emission scanning electron microscope image of the monodisperse silica-coated ceria opal photonic crystal template prepared in Example 1 of the present invention.

[0046] Fig. 20 This is a scanning electron microscope image of the cross section of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1.

[0047] Fig.21 This is a reflection spectrum diagram of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1 before and after the light stability test.

[0048] Fig. 22 This is a transmission spectrum diagram of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1 before and after the light stability test.

[0049] Fig.23 Actual pictures of the photonic crystal-dye-transparent polymer composite color filters prepared in Examples 1, 10, and 18. DETAILED DESCRIPTION

[0050] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited in any way.

[0051] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0052] Example 1

[0053] Preparation of SiO2 seed solution: First, add 5.5mL of tetraethyl orthosilicate to 87mL of water, and add 0.087g of arginine as a surfactant, and then react at 70℃ for 24h to prepare a SiO2 seed solution with a diameter of 20nm. Preparation of CeO2@SiO2 nanospheres: Add 2.5g of polypyrrolidone (PVP), 5.2g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 250μL of SiO2 seed solution to 20mL of ethylene glycol (EG), and stir at 65℃ to dissolve it. Then, heat the transparent solution to 155℃ under a nitrogen atmosphere, and the solution gradually turns into a yellow turbid liquid after reaching the reaction temperature. Nanoparticles can be obtained by reacting at 155℃ for 1h. After collecting the colloidal particles by centrifugation and washing them three times with ethanol, the nanoparticles were calcined at 500°C for 3h to obtain CeO2 particles. Then, 10mL of 2wt% CeO2 particle suspension was dispersed in 30mL of ethanol, and 9mL of ammonia and 10mL of deionized water were added. The mixed solution was rapidly stirred at 500rpm and raised to 50°C. In order to control the shell thickness, 2.5mL of tetraethyl orthosilicate (TEOS) was dissolved in 20mL of ethanol and dripped into the bottle through an automatic syringe pump. After Stober reaction for 1h, CeO2@SiO2 nanospheres with a particle size of ~178nm (monodispersity index (PDI) of 0.02) were purified by multiple centrifugation and ethanol redispersion.

[0054] CeO2@SiO2 photonic crystal structure construction: CeO2@SiO2 opal photonic crystal template obtained by pulling self-assembly, the cross-sectional thickness of the photonic crystal is 1um.

[0055] Preparation of filling dispersion: Weigh 20g polysulfone (PSU) masterbatch, 0.2g azopyrazolone dye Y-1, molecular structure as Figure 2 As shown, the above two substances are dispersed in 100 g of N,N'-dimethylformamide (DMF) solvent, and the mass ratio of the dye to the transparent polymer is 1:100 to obtain a dye-polymer dispersion.

[0056] Preparation of CeO2@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on the opal photonic crystal template, a mixed precursor liquid of transparent polymer, dye and solvent is filled into the gaps of the opal template to make the volume fraction of nano-microspheres 10% and the volume fraction of dye-dispersed polymer 90%. Then, a heating table is used to heat to 50°C and cure for 600 minutes to obtain a composite photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter with a reflection wavelength of 443nm.

[0057] Embodiments 2 to 9

[0058] Compared with Example 1, Examples 2 to 9 differ in that the transparent polymers are respectively polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0059] Compared with Example 1, Examples 2 to 9 are different in that the mass ratio of the dye to the transparent polymer in the dye polymer dispersion is 1:10.

[0060] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 2 to 9 were prepared according to the preparation method of Example 1.

[0061] Examples 10 to 17

[0062] Compared with Example 1, Examples 10 to 17 differ in that: the transparent polymers are polymers formed by polymerization of polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and acrylate compounds and acrylic acid compounds as monomer components;

[0063] Compared with Example 1, Examples 10 to 17 are different in that: the amount of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) is adjusted to 5.1 g, and CeO2@SiO2 with a particle size of 220 nm (PDI is 0.02) is prepared; the dye is M-1, and the molecular structure and its characterization are as follows Figure 3 ; The mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:500.

[0064] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 10 to 17 with a reflection wavelength of 540 nm were prepared according to the preparation method of Example 1.

[0065] Embodiments 18 to 25

[0066] Compared with Example 1, the difference between Examples 18 to 25 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0067] Compared with Example 1, Examples 18 to 25 are different in that: the amount of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) is adjusted to 4.9 g to prepare CeO2@SiO2 with a particle size of 250 nm (PDI is 0.09); the dye is C-1, and the molecular structure and characterization thereof are as follows Figure 4; The mass ratio of the dye to the transparent polymer in the dye polymer dispersion is 1:100.

[0068] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 18 to 25 with a reflection wavelength of 650 nm were prepared according to the preparation method of Example 1.

[0069] Embodiments 26 to 33

[0070] Compared with Example 1, the difference between Examples 26 to 33 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0071] Compared with Example 1, Examples 26 to 33 are different in that the amount of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) is adjusted to 5.0 g to prepare CeO2@SiO2 with a particle size of 230 nm. 2； The dye is B-1, and its molecular structure is as follows Figure 5 ; The mass ratio of the dye to the transparent polymer in the dye polymer dispersion is 1:600.

[0072] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 26 to 33 were prepared according to the preparation method of Example 1.

[0073] Embodiment 34

[0074] Polystyrene colloidal nanospheres were synthesized by emulsion polymerization. 0.65g sodium dodecyl sulfate emulsifier and 900mL deionized water were added to a 2000mL three-necked round-bottom flask equipped with a mechanical stirrer. The oil bath was heated to 85°C and mechanically stirred at 350r / min for 1h. 90g styrene (St) monomer was added and stirring was continued for 30min. 1g potassium persulfate (KPS) initiator was dissolved in 5g deionized water and added to the above round-bottom flask. The reaction was completed after 5h to obtain a white polystyrene microsphere emulsion (particle size was 185nm, PDI was 0.20, and surface potential was -38.9mV).

[0075] Silicon dioxide coated polystyrene core-shell nanospheres were modified Method, by hydrolyzing vinyl triethoxysilane in polystyrene microsphere emulsion, a dense silica shell layer is coated on its surface to obtain. Take 30mL of the above polystyrene microsphere emulsion in a 250mL single-hole round-bottom flask, add 100mL deionized water, 15mL ammonia water, add a magnetic particle, and ultrasonically disperse it evenly. Place the round-bottom flask under a magnetic stirrer at 300r / min and stir at room temperature. Use a micro-injection pump to add 8mL of vinyl triethoxysilane dropwise into the flask for 3h. After 18h of reaction, the obtained silica-coated polystyrene core-shell nano-microspheres have a particle size of 220nm, a PDI of 0.035, and a surface potential of -43.1mV. The obtained microsphere dispersion is washed 3 times with anhydrous ethanol, and finally prepared into a nano-microsphere concentrate with a mass fraction of 30wt% with ethanol for standby use.

[0076] PS@SiO2 photonic crystal structure construction: PS@SiO2 opal photonic crystal template obtained by pulling self-assembly, the cross-sectional thickness of the photonic crystal is 90um.

[0077] Preparation of filling dispersion: Weigh 20g PSU masterbatch and 0.2g dye B-2, the molecular formula is Figure 6 The above two substances are dispersed in 100g of dimethyl sulfoxide (DMSO) solvent, and the mass ratio of dye to transparent polymer is 1:100 to obtain a dye-polymer dispersion.

[0078] Preparation of PS@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on the opal photonic crystal template, a mixed precursor liquid of transparent polymer, dye and solvent is filled into the gaps of the opal template to make the volume fraction of nanospheres 74% and the volume fraction of dye-dispersed polymer 26%. Then, a heating table is used to heat to 120°C and cure for 2 minutes to obtain a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter.

[0079] Embodiments 35 to 42

[0080] Compared with Example 34, the difference between Examples 35 to 42 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0081] Compared with Example 34, Examples 35 to 42 are different in that the dye is B-3, with the molecular formula Figure 7 ;;The mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:800.

[0082] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 35 to 42 were prepared according to the preparation method of Example 34.

[0083] Embodiments 43 to 50

[0084] Compared with Example 34, the difference between Examples 43 to 50 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0085] Compared with Example 34, Examples 43 to 50 are different in that: the amount of styrene is adjusted to 95 g to prepare PS@SiO2 with a particle size of 230 nm (PDI is 0.02); the dye is R-1, with a molecular formula as follows Figure 8 ; The mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:900.

[0086] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 43 to 50 were prepared according to the preparation method of Example 34.

[0087] Examples 51 to 58

[0088] Compared with Example 34, the difference between Examples 51 to 58 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0089] Compared with Example 34, Examples 51 to 58 are different in that: the amount of styrene is adjusted to 98 g to prepare PS@SiO2 with a particle size of 240 nm (PDI is 0.09); the dye is R-2, and the molecular structure and characterization thereof are as follows: Fig. 9 ; The mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:900.

[0090] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 51 to 58 were prepared according to the preparation method of Example 34.

[0091] Examples 59 to 66

[0092] Compared with Example 34, the difference between Examples 59 to 66 is that the transparent polymers are polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), and polymers formed by polymerization of acrylate compounds and acrylic compounds as monomer components.

[0093] Compared with Example 34, Examples 58 to 64 are different in that: the amount of styrene is adjusted to 80 g to prepare PS@SiO with a particle size of 223 nm. 2； The dye is Y-2, with the molecular formula Fig.10 ; The mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:200.

[0094] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 59 to 66 were prepared according to the preparation method of Example 34.

[0095] Embodiment 67

[0096] Preparation of ZnS microspheres: First, dissolve 3.50 g of polyvinyl pyrrolidone (PVP) in 75.0 mL of deionized water; after it is completely dissolved, perform ultrasonic treatment for 10 minutes, transfer the solution to a three-necked round-bottom flask (250 mL) and heat to 70°C, add 40.0 mmol of thioacetamide (TAA) to the flask; after stirring and dissolving for 15 minutes, inject 100 uL of concentrated nitric acid into the flask, continue stirring for 15 minutes, quickly pour 7.0 mmol of zinc nitrate hexahydrate (Zn(NO3)2·6H2O) pre-dissolved in 5.00 mL of deionized water into the flask, and quickly stir the solution in the three-necked flask for 2 minutes (~1500 rpm). Then, after the reaction was allowed to proceed for 3 h with slow stirring (~500 rpm), 10.0 mL of Zn(NO3)2-6H2O aqueous solution (2.0 mol / L) was added at a rate of 0.03 mL / min using a constant flow pump according to the target particle size. Finally, after the Zn(NO3)2·6H2O aqueous solution was completely added, heating was stopped and the ZnS microspheres were separated by centrifugation.

[0097] Preparation of ZnS@SiO2 microspheres: 0.40g of ZnS microspheres were dispersed in 80mL of anhydrous ethanol, and transferred to a three-necked flask (250mL) after ultrasonic treatment. Then, 3.00mL of ammonia water and 6.00mL of deionized water were added and mixed and stirred for 1h. Finally, a certain volume of tetraethyl orthosilicate (0.50-6.00mL) was added to the solution, and the reaction lasted for 5h at 25°C. The ZnS@SiO2 microspheres prepared by centrifugation were then washed 3 times with anhydrous ethanol, dried and weighed. Taking the addition of 3.0mL of tetraethyl orthosilicate as an example, the yield was calculated based on the amount of tetraethyl orthosilicate added, and ZnS@SiO2 nanospheres with a particle size of 185nm were synthesized.

[0098] Preparation of ZnS@SiO2 photonic crystal: The ZnS@SiO2 opal photonic crystal template was obtained by spraying, and the cross-sectional thickness of the photonic crystal was 30um.

[0099] Preparation of filling dispersion: Weigh 20g PSU masterbatch, 0.2g perylene diimide O-1, molecular structure Fig.11 As shown, the above two substances are dispersed in 100 g of N,N'-dimethylformamide (DMF) solvent, and the mass ratio of the dye to the transparent polymer is 1:100 to obtain a dye-polymer dispersion.

[0100] Preparation of ZnS@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on the opal photonic crystal template, a mixed precursor liquid of transparent polymer, dye and solvent is filled into the gaps of the opal template to make the volume fraction of nanospheres 64% and the volume fraction of dye-dispersed polymer 36%. Then, a heating table is used to heat to 70°C and cure for 120 minutes to obtain a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter.

[0101] Embodiments 68 to 75

[0102] The only difference between Examples 68 to 75 and Example 67 is that: the amount of Zn(NO3)2·6H2O is adjusted to 7.5 mmol to prepare ZnS@SiO2 with a particle size of 250 nm; the dye is C-2, with a molecular structure as shown in Fig.12 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0103] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 68 to 75 were prepared according to the preparation method of Example 67.

[0104] Embodiments 76 to 83

[0105] The only difference between Examples 76 to 83 and Example 67 is that: the amount of Zn(NO3)2·6H2O is adjusted to 7.5 mmol to prepare ZnS@SiO2 with a particle size of 210 nm; the dye is R-3, and the molecular structure is as follows Fig.13 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0106] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 76 to 83 were prepared according to the preparation method of Example 67.

[0107] Embodiments 84 to 91

[0108] The difference between Examples 84 to 91 and Example 67 is that the amount of Zn(NO3)2·6H2O was adjusted to 7.5 mmol to prepare ZnS@SiO with a particle size of 210 nm. 2； The dye is R-4, and its molecular structure is as follows Fig.14 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0109] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters of Examples 84 to 91 were prepared according to the preparation method of Example 67.

[0110] Embodiments 92 to 99

[0111] The only difference between Examples 92 to 99 and Example 67 is that: the amount of Zn(NO3)2·6H2O is adjusted to 7.5 mmol to prepare ZnS@SiO2 with a particle size of 250 nm; the dye is C-3, with a molecular structure as shown in Fig.15 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0112] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter of Examples 92 to 99 was prepared according to the preparation method of Example 67.

[0113] Embodiments 100 to 107

[0114] The difference between Examples 100 to 107 and Example 67 is that: the amount of Zn(NO3)2·6H2O is adjusted to 7.5 mmol to prepare ZnS@SiO2 with a particle size of 190 nm; the dye is Y-3, and the molecular structure is as follows Fig.16 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0115] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter of Example 67 was prepared according to the preparation methods of Examples 100 to 107.

[0116] Embodiments 108 to 115

[0117] The difference between Examples 108 to 115 and Example 67 is that: the amount of Zn(NO3)2·6H2O is adjusted to 7.5 mmol to prepare ZnS@SiO2 with a particle size of 190 nm; the dye is Y-4, with a molecular structure as shown in Fig.17 ; The transparent polymer is formed by polymerizing polyimide (PI), polycarbonate (PC), polyurethane (PU), polysulfone (PSU), epoxy resin, polystyrene (PS), acrylate compounds and acrylic acid compounds as monomer components; the mass ratio of the dye in the dye polymer dispersion to the transparent polymer is 1:500.

[0118] The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter of Example 67 was prepared according to the preparation methods of Examples 108 to 115.

[0119] Test Case

[0120] 1. The electron scanning microscopy images of the CeO2@SiO2 nanospheres and CeO2@SiO2 photonic crystal structures prepared in Example 1 are shown in FIG. Figure 18-19 and the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter prepared in Example 1 was observed by electron scanning microscope, as shown in FIG. Fig. 20 shown.

[0121] 2. The digital photo and reflection spectrum of the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter prepared in Example 1 are as follows: Fig.21 As shown, a is a digital photo of the photonic crystal-dye-transparent polymer composite color filter; b is the reflection spectrum of the photonic crystal-dye-transparent polymer composite color filter,

[0122] 3. The spectra of the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter prepared in Example 1 before and after the light stability test are as follows: Fig. 22 As shown, the transmission spectra of the colored film prepared by the composite of dye and photonic crystal almost overlap after irradiation with 365nm ultraviolet light, which proves that the film does not undergo photodegradation or photooxidation due to light irradiation, reflecting the excellent photostability of the composite film.

[0123] 4. The actual pictures of the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filters prepared in Examples 1, 10, and 18 are shown in FIG. Fig.23 As shown, the reflection colors of the colored film prepared by the composite of dye and photonic crystal are blue, green and red respectively, and the transmitted light thereof is the complementary color of its reflected light, which are yellow, magenta and cyan respectively.

[0124] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter, characterized in that: The color filter is composed of an opal photonic crystal template formed by nano-microspheres and a dye-transparent polymer composite filled in the gaps of the opal photonic crystal template. Through the composite of the nano-microspheres, the dye and the transparent polymer, the color filter has two filtering modes: reflection and transmission.

2. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The color filter comprises the following components in volume percentage: 10% to 74% of nano-microspheres and 26% to 90% of a dye-transparent polymer composite; wherein the mass ratio of the dye to the transparent polymer in the dye-transparent polymer composite is 1:(10 to 1000).

3. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The reflection wavelength of the color filter is 380nm-780nm.

4. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The cross-sectional thickness of the opal photonic crystal template is 1 μm to 90 μm.

5. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The nano-microspheres include one or more of silica-coated cerium dioxide, silica-coated zinc sulfide, silica-coated titanium dioxide, silica-coated zinc oxide, silica-coated cadmium sulfide, silica-coated polystyrene, titanium dioxide-coated silica, silica, polystyrene, cerium dioxide, titanium dioxide, cadmium sulfide, zinc oxide, and zinc sulfide nano-microspheres.

6. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The diameter of the nano-microspheres is 100nm-800nm, and the particle size distribution is 0.01-0.

20.

7. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The dye includes one or more of perylene dye derivatives, azo dye derivatives, anthraquinone dye derivatives and phthalocyanine dye derivatives.

8. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 7, characterized in that: The perylene dye derivatives include one or more of 1,6,7,10-dibromoperylene diimide, 1,6,7,10-dialkoxyperylene diimide, 1,6,7,10-diaryloxyperylene diimide, 1,6,7,10-dialkylaminoperylene diimide, 1,7-dibromoperylene diimide, 1,7-dialkoxyperylene diimide, 1,7-diaryloxyperylene diimide, 1,7-dialkylaminoperylene diimide, perylene dicarboxylate, and perylene tetracarboxylate; The azo dye derivatives include azo dyes with one or more of pyrazolone, pyridone, thiazole and aromatic amine derivatives as coupling components; The anthraquinone dye derivatives include one or more of 1,4-dialkylamino-substituted anthraquinone dyes, 1,4-diarylamino-substituted anthraquinone dyes, 1,5-dialkylamino-substituted anthraquinone dyes, 1,5-diarylamino-substituted anthraquinone dyes, 1,8-dialkylamino-substituted anthraquinone dyes, 1,8-diarylamino-substituted anthraquinone dyes, 1,8-hydroxyanthraquinone, 1,8-aminoanthraquinone, 1,8-dichloroanthraquinone, 1,4-hydroxyanthraquinone, 1,4-aminoanthraquinone, 1,4-dichloroanthraquinone, 1,5-hydroxyanthraquinone, 1,5-aminoanthraquinone and 1,5-dichloroanthraquinone; The phthalocyanine dye derivative includes one or more of lanthanum phthalocyanine, silicon phthalocyanine, aluminum phthalocyanine, copper phthalocyanine, nickel phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine and iron phthalocyanine.

9. The photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to claim 1, characterized in that: The transparent polymer is formed by polymerizing polyimide, polycarbonate, polyurethane, polysulfone, epoxy resin, polystyrene, acrylate compounds and acrylic compounds as monomer components.

10. A method for preparing a photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter according to any one of claims 1 to 9, characterized in that: The following steps are involved: Opal photonic crystal templates were obtained by self-assembly using nanospheres as raw materials; dissolving a transparent polymer and a dye in a solvent to obtain a mixed solution; The mixed liquid is filled into the gaps of the opal photonic crystal template, and heated and cured at 50° C. to 120° C. for 30 min to 600 min to obtain the photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter.

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