A photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter and a preparation method thereof

Abstract

The application discloses a kind of based on photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter and preparation method thereof, color filter is formed by opal photonic crystal template of nanometer microsphere and dye-transparent polymer composite filled in the interspace of opal photonic crystal template, by the composite of nanometer microsphere, dye and transparent polymer, wherein photonic crystal and dye can synergistically filter specific wavelength visible light, with reflection and transmission two filter modes;The light absorption characteristics of dye can widen the absorption peak width of photonic crystal, produce high-purity filter effect under reflection mode;The photonic band gap of photonic crystal can adjust the light cut-off wave band of dye, form high-purity filter effect under transmission mode, finally realize high-purity color output photonic crystal-dye-transparent polymer composite reflection / transmission integrated color filter, and stable in nature, it has wide application prospect in display and optical instrument and other fields.

Description

Technical Field

[0001] This invention relates to the field of optical filter technology, and more specifically, to a photonic crystal-dye-transparent polymer composite reflective / transmitting integrated color filter and its preparation method. Background Technology

[0002] In today's increasingly technology-driven world, optical filters are simple optical control devices. They are widely used in laser experiments, displays, spectral analysis, and optical measurements (Nat. Nanotechnol. 2012, 7, 557.; LabChip, 2006, 6, 981-987). High-purity filters not only enable high-precision imaging and detection of biological samples but are also used in laser surgery and laser therapy equipment. By precisely controlling the laser wavelength and power, they enable precise cutting and repair of diseased tissues (Sensor actuat B-chem., 2017, 242, 318-323). Furthermore, high-purity filters applied to displays not only provide an immersive visual experience but also offer high-quality display effects that are virtually harmless to the human eye.

[0003] Optical filters are mainly divided into two categories: dye absorption filters and structural filters (Adv. Opt. Mater. 2020, 8, 2000317.). Dye absorption filters achieve their filtering effect based on the absorption of light by dyes. Although dye filters have high transmittance, the molecular structure of dyes is complex, and existing filters or coatings based on traditional dyes or pigments are susceptible to various damages under prolonged ultraviolet (UV) irradiation and high temperatures (Adv. Opt. Mater. 2017, 5, 1700029.). The other type of filter is the micro / nano structure filter developed based on micro / nano structures and the diffraction, interference, and scattering effects of light. These micro / nano structures include photonic crystals, all-metal structures, and all-dielectric structures. The colors produced by these micro / nano structures are typically tunable in terms of wavelength and full width at half maximum (FWHM). Therefore, micro / nano structure filters offer advantages such as color tunability and optical and thermal stability. However, the difference in 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 reduces its average visible light transmittance, which to some extent limits the improvement of the color saturation / purity of the device.

[0004] Therefore, researchers have attempted to combine dyes and structural colors to synergistically construct high-purity filters. For example, L. Jay Guo et al. incorporated ultrathin dye films into a 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 thin 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-structural color composite filters are limited to the fabrication of reflective filters. Therefore, achieving a color filter with integrated reflection / transmission and high-purity filtering effect remains a challenge. Summary of the Invention

[0005] The purpose of this invention is to overcome the aforementioned defects in the prior art and provide a photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filter and its preparation method. The filter consists of an opal photonic crystal template formed from nanospheres and a dye-transparent polymer composite filling the voids in the opal photonic crystal template. The dye absorbs and purifies the light reflected from the photonic crystal bandgap by absorbing light that does not overlap with the photonic bandgap. Simultaneously, the photonic crystal and dye can synergistically filter visible light of specific wavelengths, providing both reflective and transmissive filtering modes. The dye's absorption characteristics broaden the absorption peak width of the photonic crystal, producing a high-purity filtering effect in the reflective mode. The photonic bandgap of the photonic crystal can adjust the cutoff wavelength of the dye, forming a high-purity filtering effect in the transmissive mode. Ultimately, high-purity color output is achieved on both sides of the filter.

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

[0007] A color filter based on a photonic crystal-dye-transparent polymer composite for integrated reflection / transmission is disclosed. The color filter is composed of an opal photonic crystal template formed by nanospheres and a dye-transparent polymer composite filling the voids in the opal photonic crystal template. Through the composite of the nanospheres, dye and transparent polymer, the color filter has both reflection and transmission filtering modes.

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

[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 μm to 90 μm.

[0011] Optionally, the nanospheres include one or more of the following: 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 nanospheres have a diameter of 100 nm to 800 nm and a particle size distribution of 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 derivatives include one or more of the following: 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 the following: 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.

[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] This invention also discloses a method for preparing a composite reflective / transmitting color filter based on a photonic crystal-dye-transparent polymer as described above, comprising the following steps:

[0020] Opal photonic crystal templates were obtained from nanospheres via a self-assembly method.

[0021] The transparent polymer and dye are dissolved in a solvent to obtain a mixture;

[0022] The mixture is filled into the voids of the opal photonic crystal template and heated and cured at 50℃~120℃ for 2min~600min to obtain the integrated color filter based on photonic crystal-dye-transparent polymer composite reflection / transmission.

[0023] Optional solvents include N,N'-dimethylformamide (DMF).

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

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

[0026] This invention provides a photonic crystal-dye-transparent polymer composite integrated reflective / transmittive color filter. By combining a dye with a photonic crystal structure, the optical absorption of the dye can broaden the absorption peak width of the photonic crystal structure color, producing a high-purity filtering effect in reflection mode. The photonic bandgap of the photonic crystal can adjust the light cutoff band of the dye. Simultaneously, in this composite structure, both the photonic crystal structure and the dye have filtering effects, thus synergistically filtering visible light of specific wavelengths, providing both reflection and transmission filtering modes. Ultimately, this results in a photonic crystal-dye-transparent polymer composite integrated reflective / transmittive color filter with high-purity color output. Furthermore, this invention simplifies the design process for high-purity colors, avoids the hassle of designing ideal materials, and exhibits stable properties. It has great potential in various applications such as color displays, optical decoration, and optical inspection, and is expected to have significant application value in fields such as information security and displays. Attached Figure Description

[0027] Figure 1 This is a flowchart illustrating the preparation process of the photonic crystal-dye-transparent polymer composite color filter of the present invention.

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

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

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

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

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

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

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

[0035] Figure 9 The molecular formula of anthraquinone R-2 prepared in Examples 51-58 of this invention.

[0036] Figure 10 The molecular formula of azo Y-2 prepared in Examples 59-66 of this invention.

[0037] Figure 11 The molecular formula of azo O-1 prepared in Example 67 of this invention.

[0038] Figure 12 The molecular formula of perylene diamide C-2 prepared in Examples 68-75 of this invention.

[0039] Figure 13 The molecular formula of perylene diimide R-3 prepared in Examples 76-83 of this invention.

[0040] Figure 14 The molecular formula of perylene diimide R-4 prepared in Examples 84-91 of this invention.

[0041] Figure 15The molecular formula of perylene diimide C-3 prepared in Examples 92-99 of this invention.

[0042] Figure 16 The molecular formula of perylene tetracarboxylate Y-3 prepared in Examples 100-107 of this invention.

[0043] Figure 17 The molecular formula of perylene dicarboxylic acid ester Y-4 prepared in Examples 108-115 of this invention.

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

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

[0046] Figure 20 The image shows a cross-sectional scanning electron microscope image of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1.

[0047] Figure 21 The reflection spectra of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1 before and after photostability testing are shown.

[0048] Figure 22 The transmission spectra of the photonic crystal-dye-transparent polymer composite color filter prepared in Example 1 before and after photostability testing are shown.

[0049] Figure 23 The images show actual photos of the photonic crystal-dye-transparent polymer composite color filters prepared in Examples 1, 10, and 18. Detailed Implementation

[0050] The present invention will be further described below with reference to specific embodiments, but this does not limit the present invention in any way.

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

[0052] Example 1

[0053] Preparation of SiO2 seed solution: First, 5.5 mL of tetraethyl orthosilicate was added to 87 mL of water, and 0.087 g of arginine was added as a surfactant. The mixture was then reacted at 70 °C for 24 h to prepare a SiO2 seed solution with a diameter of 20 nm. Preparation of CeO2@SiO2 nanospheres: 2.5 g of polypyrrolidone (PVP), 5.2 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O), and 250 μL of SiO2 seed solution were added to 20 mL of ethylene glycol (EG) and stirred at 65 °C until dissolved. The transparent solution was then heated to 155 °C under a nitrogen atmosphere. Upon reaching the reaction temperature, the solution gradually turned into a yellow turbid liquid. Nanoparticles were obtained by reacting at 155 °C for 1 h. After centrifugation to collect colloidal particles and washing them three times with ethanol, the nanoparticles were calcined at 500℃ for 3 h to obtain CeO2 particles. 10 mL of a 2 wt% CeO2 particle suspension was then dispersed in 30 mL of ethanol, with 9 mL of ammonia and 10 mL of deionized water added. The mixture was rapidly stirred at 500 rpm and the temperature was raised to 50℃. To control the shell thickness, 2.5 mL of tetraethyl orthosilicate (TEOS) was dissolved in 20 mL of ethanol and added dropwise to the bottle using an auto-injector pump. After a Stobol reaction for 1 h, CeO2@SiO2 nanospheres with a particle size of ~178 nm (monodispersibility index (PDI) of 0.02) were obtained through purification by multiple centrifugations and ethanol redispersion.

[0054] Construction of CeO2@SiO2 photonic crystal structure: CeO2@SiO2 opal photonic crystal template obtained by Czochralski self-assembly, with a cross-sectional thickness of 1µm.

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

[0056] Preparation of CeO2@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on an opal photonic crystal template, a mixed precursor solution of transparent polymer, dye and solvent is filled into the gaps of the opal template to make the volume fraction of nanospheres 10% and the volume fraction of dye-dispersed polymer 90%. Then, it is heated to 50℃ and cured for 600 min using a heating stage to obtain a composite photonic crystal-dye-transparent polymer composite reflective / transmittive color filter with a reflection wavelength of 443nm.

[0057] Examples 2-9

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

[0059] The difference between Examples 2-9 and Example 1 is that the mass ratio of dye to transparent polymer in the dye polymer dispersion is 1:10.

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

[0061] Examples 10-17

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

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

[0064] Photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filters with a reflection wavelength of 540 nm, as described in Examples 10-17, were prepared according to the preparation method of Example 1.

[0065] Examples 18-25

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

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

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

[0069] Examples 26-33

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

[0071] Examples 26-33 differ from Example 1 in that the amount of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) was adjusted to 5.0 g to prepare CeO2@SiO 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 dye to transparent polymer in the dye polymer dispersion is 1:600.

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

[0073] Example 34

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

[0075] Silica-coated polystyrene core-shell nanospheres employ improved... The method involves hydrolyzing vinyltriethoxysilane in a polystyrene microsphere emulsion to coat the surface of the microspheres with a dense silica shell. 30 mL of the polystyrene microsphere emulsion was placed in a 250 mL single-hole round-bottom flask, along with 100 mL of deionized water and 15 mL of ammonia. A magnetic stir bar was added, and the mixture was ultrasonically dispersed until homogeneous. The flask was then stirred at room temperature using a magnetic stirrer at 300 rpm. 8 mL of vinyltriethoxysilane was added dropwise to the flask over 3 hours using a micro-injection pump. The reaction was stopped after 18 hours. The resulting silica-coated polystyrene core-shell nanospheres had a particle size of 220 nm, a PDI of 0.035, and a surface potential of -43.1 mV. The resulting microsphere dispersion was washed three times with anhydrous ethanol, and finally, a 30 wt% concentrated nanosphere solution was prepared with ethanol for later use.

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

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

[0078] Preparation of PS@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on an 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, it is heated to 120℃ and cured for 2 minutes to obtain a photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filter.

[0079] Examples 35-42

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

[0081] The difference between Examples 35-42 and Example 34 is that the dye is B-3, with the molecular formula as follows: 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 reflective / transmittive integrated color filters of Examples 35-42 were prepared according to the preparation method of Example 34.

[0083] Examples 43-50

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

[0085] The difference between Examples 43-50 and Example 34 is that the amount of styrene was adjusted to 95g to prepare PS@SiO2 with a particle size of 230nm (PDI was 0.02); the dye was R-1, with the 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 reflective / transmittive integrated color filters of Examples 43-50 were prepared according to the preparation method of Example 34.

[0087] Examples 51-58

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

[0089] Examples 51-58 differ from Example 34 in that: PS@SiO2 with a particle size of 240 nm (PDI = 0.09) was prepared by adjusting the amount of 98 g styrene; the dye used was R-2, and its molecular structure and characterization are as follows: Figure 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 reflective / transmittive integrated color filters of Examples 51-58 were prepared according to the preparation method of Example 34.

[0091] Examples 59-66

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

[0093] The difference between Examples 58-64 and Example 34 is that the amount of styrene was adjusted to 80g to prepare PS@SiO with a particle size of 223nm. 2； The dye is Y-2, with the molecular formula as follows: Figure 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 reflective / transmittive integrated color filters of Examples 59-66 were prepared according to the preparation method of Example 34.

[0095] Example 67

[0096] Preparation of ZnS microspheres: First, 3.50 g of polyvinylpyrrolidone (PVP) was dissolved in 75.0 mL of deionized water. After complete dissolution, the solution was sonicated for 10 min. The solution was then transferred to a three-necked round-bottom flask (250 mL) and heated to 70 °C. 40.0 mmol of thioacetamide (TAA) was added to the flask. After stirring and dissolving for 15 min, 100 μL of concentrated nitric acid was injected into the flask. Stirring was continued for 15 min. 7.0 mmol of zinc nitrate hexahydrate (Zn(NO3)2·6H2O) pre-dissolved in 5.00 mL of deionized water was quickly poured into the flask, and the solution in the three-necked flask was stirred rapidly for 2 min (~1500 rpm). Then, after the reaction was carried out for 3 hours 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: 0.40 g of ZnS microspheres were dispersed in 80 mL of anhydrous ethanol, sonicated, and then transferred to a three-necked flask (250 mL). Then, 3.00 mL of ammonia and 6.00 mL of deionized water were added, mixed, and stirred for 1 h. Finally, a certain volume of tetraethyl orthosilicate (0.50–6.00 mL) was added to the solution, and the reaction was continued at 25 °C for 5 h. The prepared ZnS@SiO2 microspheres were separated by centrifugation, washed three times with anhydrous ethanol, dried, and weighed. Taking the addition of 3.0 mL 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 185 nm were synthesized.

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

[0099] Preparation of the packed dispersion: Weigh 20g of PSU masterbatch and 0.2g of perylene diimide O-1, molecular structure as shown below. Figure 11 As shown, the two substances were dispersed in 100g of N,N'-dimethylformamide (DMF) solvent, and the dye-to-transparent polymer mass ratio was 1:100, resulting in a dye-polymer dispersion.

[0100] Preparation of ZnS@SiO2 photonic crystal-dye-transparent polymer composite color filter: Based on an 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, it is heated to 70℃ and cured for 120 min to obtain a photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filter.

[0101] Examples 68-75

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

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

[0104] Examples 76-83

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

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

[0107] Examples 84-91

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

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

[0110] Examples 92-99

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

[0112] The photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filters of Examples 92-99 were prepared according to the preparation method of Example 67.

[0113] Examples 100-107

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

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

[0116] Examples 108-115

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

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

[0119] Test case

[0120] 1. Scanning electron microscope images of the CeO2@SiO2 nanospheres and CeO2@SiO2 photonic crystal structure prepared in Example 1 are shown below. Figure 18-19 As shown; and the photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filter prepared in Example 1 was observed by scanning electron microscopy, as follows. Figure 20 As shown.

[0121] 2. Digital photographs and reflection spectra of the photonic crystal-dye-transparent polymer composite reflective / transmittive color filter prepared in Example 1 are as follows: Figure 21 As shown, a is a digital photograph of the photonic crystal-dye-transparent polymer composite color filter; b is the reflectance spectrum of the photonic crystal-dye-transparent polymer composite color filter.

[0122] 3. The photostograms before and after the photostability test of the photonic crystal-dye-transparent polymer composite reflective / transmittive color filter prepared in Example 1 are shown below. Figure 22 As shown, the transmission spectra of the colored thin film prepared by combining dye and photonic crystal almost overlapped after irradiation with 365nm ultraviolet light, which proves that the film did not undergo photodegradation or photooxidation due to light irradiation, demonstrating the excellent photostability of the composite film.

[0123] 4. Physical images of the photonic crystal-dye-transparent polymer composite reflective / transmittive integrated color filters prepared in Examples 1, 10, and 18 are shown below. Figure 23 As shown, the colored thin films prepared by combining dyes and photonic crystals reflect blue, green, and red colors, respectively, and their transmitted light is the complementary color of their reflected light, namely yellow, magenta, and cyan.

[0124] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A composite color filter based on photonic crystal-dye-transparent polymer for integrated reflection / transmission, characterized in that, The color filter is composed of an opal photonic crystal template formed by nanospheres and a dye-transparent polymer composite filling the voids in the opal photonic crystal template. Through the composite of the nanospheres, dye and transparent polymer, the color filter has both reflection and transmission filtering modes. The color filter comprises the following components by volume percentage: The composition comprises 10% to 74% nanospheres and 26% to 90% dye-transparent polymer composites; wherein the mass ratio of dye to transparent polymer in the dye-transparent polymer composite is 1:10 to 1:1000. The nanospheres include one or more of the following: 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. The dyes include one or more of the following: perylene dye derivatives, azo dye derivatives, anthraquinone dye derivatives, and phthalocyanine dye derivatives; The transparent polymer is formed by polymerizing polyimide, polycarbonate, polyurethane, polysulfone, epoxy resin, polystyrene, acrylate compounds and acrylic compounds as monomer components.

2. The photonic crystal-dye-transparent polymer composite integrated reflective / transmittive color filter according to claim 1, characterized in that, The color filter has a reflection wavelength of 380 nm to 780 nm.

3. The photonic crystal-dye-transparent polymer composite integrated reflective / transmittive 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.

4. The photonic crystal-dye-transparent polymer composite integrated reflective / transmittive color filter according to claim 1, characterized in that, The nanospheres have a diameter of 100 nm to 800 nm and a particle size distribution of 0.01 to 0.

20.

5. The photonic crystal-dye-transparent polymer composite integrated reflective / transmittive color filter according to claim 1, characterized in that, The perylene dye derivatives include one or more of the following: 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 the following as coupling components: pyrazolone, pyridone, thiazole, and aromatic amine derivatives. The anthraquinone dye derivatives include one or more of the following: 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 derivatives include one or more of lanthanum phthalocyanine, silicon phthalocyanine, aluminum phthalocyanine, copper phthalocyanine, nickel phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, and iron phthalocyanine.

6. A method for preparing a composite reflective / transmittive color filter based on a photonic crystal-dye-transparent polymer composite as described in any one of claims 1-5, characterized in that, Includes the following steps: Opal photonic crystal templates were obtained from nanospheres via a self-assembly method. The transparent polymer and dye are dissolved in a solvent to obtain a mixture; The mixture is filled into the voids of the opal photonic crystal template and heated and cured at 50℃~120℃ for 30min~600min to obtain the integrated color filter based on photonic crystal-dye-transparent polymer composite reflection / transmission.

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