TW202334720A - Wavelength conversion film and display device including the same - Google Patents

Abstract

Described herein is an improved wavelength converting film with composite materials that have improved quantum efficiency and color gamut. The film includes narrow FWHM green and red emitting dyes.

Description

Wavelength conversion film and display device containing the same

The present invention relates to a wavelength conversion film and a light emitting display device including the same.

Photoluminescent substances are materials that emit light after absorbing energy in the form of light or electricity. Depending on the components forming the photoluminescent substance and the luminescence mechanism, the photoluminescent substance can be classified into inorganic photoluminescent substances (or dyes), organic photoluminescent dyes, nanocrystalline photoluminescent substances and the like.

Recently, various attempts have been described to use such photoluminescent substances to modify the spectrum of light sources. Photoluminescent substances absorb light of a specific wavelength from a light source, convert it into light with a longer wavelength in the visible light region, and emit the light. Depending on the luminescence properties of the photoluminescent substance, the brightness, color purity, color gamut, etc. of the emitted light can be greatly enhanced. Inorganic photoluminescent materials can be formed from parent compounds such as thioethers, oxides, or nitrides and activator ions, and can be used in high-quality display devices with excellent physical and chemical stability and high color purity reproduction. However, the disadvantages are that such inorganic photoluminescent materials are extremely expensive, have low light emission efficiency and are limited in the emission of light in the near ultraviolet or blue light region of 400 nm or higher.

Quantum dot technology has achieved high levels of quantum efficiency and color gamut. However, cadmium-based quantum dots can be extremely toxic and are restricted in many countries due to health safety concerns. Additionally, some quantum dots have much lower quantum efficiency at converting blue LED light into green or red light. In addition, quantum dots can have low stability when exposed to moisture and oxygen, often requiring expensive packaging processes. Quantum dots can be costly because it can be difficult to control dimensional uniformity during their production.

Therefore, there is a need for new photoluminescent films with high quantum efficiency, high color gamut output, and lower cost relative to quantum dots and other existing films containing photoluminescent dyes.

Some embodiments include a wavelength conversion film comprising: a polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and emits strictly green with an emission spectrum with a half-maximum width less than 40 nm. wavelength light; a second photoluminescence, the second photoluminescence dye absorbs blue or green wavelength light and strictly emits red wavelength light with an emission spectrum with a half-maximum width less than 55 nm; and a light scattering center; wherein the first The photoluminescent dye, the second photoluminescent dye and the light scattering center are disposed within the polymer matrix.

In some embodiments, the first photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinolinyl group. In some embodiments, the first photoluminescent dye can be: (FD-1), and/or (FD-3).

In some embodiments, the first photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalenedicarboxylic acid imide group. In some embodiments, the first photoluminescent dye can be: (FD-2).

In some embodiments, the second photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinolinyl group. In some embodiments, the second photoluminescent dye can be: (SD-1), (SD-2), and/or (SD-4).

In some embodiments, the second photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalenedimide group. In some embodiments, the second photoluminescent dye can be: .

In some embodiments, the second photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted perylene group. In some embodiments, the second photoluminescent dye can include: .

In some embodiments, the film can have an internal quantum yield greater than 80%. In some embodiments, the film can have an external quantum yield greater than 50%. In some embodiments, the film can have a color gamut greater than 90% of the BT.2020 standard or Rec.2020 standard. In some embodiments, the film may have a thickness of less than 50 microns.

Some embodiments include a light emitting device including a photoluminescent wavelength conversion film described herein.

Some embodiments include a backlight device with a blue light source that includes a photoluminescent wavelength conversion film described herein.

These and other embodiments are described in greater detail below.

The present invention relates to wavelength conversion films, which contain photoluminescent compounds (or dyes) with high quantum efficiency, high color gamut output and low cost.

The term "BODIPY" as used herein refers to an optionally substituted chemical moiety having the formula: , where the ring indicated by the dotted line exists depending on the situation.

The BODIPY moiety contains a dipyrromethene complexed to a disubstituted boron atom (usually a BF ₂ unit). The IUPAC name of the core of BODIPY is 4,4-difluoro-4-boron-3a,4a-diaza-s-dicyclopentacene.

The term "perylene" or "perylene derivative" as used herein refers to an optionally substituted chemical moiety having the formula:

The term "naphthalenedicarboxylic acid imide" or "naphthalenedicarboxylic acid derivative" as used herein refers to an optionally substituted chemical moiety having the following formula: , where X = NR, where R can be a linking group or an aryl group.

As used herein, the term "isoquinoline" or "isoquinoline derivative" or "isoquinoline" "isoquinoline derivative" means an optionally substituted chemical moiety having the following formula: _{, where}

The term "naphthalenedimine" or "naphthalenedimine derivative" as used herein refers to an optionally substituted chemical moiety having the formula: where R ⁰ can be hydrogen (H), substituted or unsubstituted aryl or CF ₃ , where X can be oxygen (O) or sulfur (S), where R ¹ can be hydrogen, substituted or unsubstituted Aryl group (such as phenyl, fluoroalkylphenyl (such as 4-trifluoromethylphenyl), etc.) or C ₁ -C ₅ alkyl group.

In some embodiments, the BODIPY moiety is linked to the perylene moiety via a linking group. In some embodiments, the BODIPY moiety is linked to the naphthalenedicarboxylic acid imine moiety via a linking group. In some embodiments, the BODIPY moiety is linked to the isoquinoline moiety via a linking group. In some embodiments, the BODIPY moiety is linked to the naphthalenedimine moiety via a linking group.

Use of the terms "may" or "may be" shall be taken to mean "is" or "is not" or alternatively "does" or "does not" )" or "will (will)" or "will not (will not)", etc. For example, the statement "the film may comprise a scattering center disposed within a polymeric matrix" should be interpreted to mean, for example, "In some embodiments, the film comprises a scattering center disposed within a polymeric matrix" or "In some embodiments , the film does not contain scattering centers disposed within the polymer matrix".

The term ITU-R Recommendation BT.2020 (more commonly known by the abbreviation Rec.2020 or BT.2020) refers to the color display standard for color gamut. The RGB primary colors used in Rec.2020 are equivalent to monochromatic light sources on the CIE 1931 spectral locus. The wavelengths of the Rec.2020 primary colors are as follows: the red primary color is 630 nm, the green primary color is 532 nm, and the blue primary color is 467 nm. The Rec.2020 color space covers 75.8% of the CIE 1931 color space (the area within the determined triangle). Rec.2020 uses CIE standard illuminant D65 as the white point and the following color coordinates: Xw = 0.3127; Yw = 0.3290; XR = 0.708, YR = 0.292, XG = 0.17, YG = 0.797;

Some embodiments include a wavelength converting film including a polymer matrix, a first organic photoluminescent compound, and a second organic photoluminescent compound. In some embodiments, the film may include a first organic photoluminescent dye that emits green light and has an emission peak with a half-maximum width less than 30 nm or 40 nm. In some embodiments, the film may include a second organic photoluminescent dye that emits red light and has an emission peak with a half-maximum width less than 55 nm. In some embodiments, the film may contain light scattering centers. In some examples, a first organic photoluminescent dye (emitting green light), a second organic photoluminescent dye (emitting red light), and a scattering center are disposed within a polymer matrix. In some embodiments, the membrane provides high quantum yield. In some embodiments, the film provides greater than 90% of a wide color gamut. A suitable means of determining color gamut percentage is to measure the area under the resulting 1931 CIE color space. In some embodiments, the film can be between 89% and 99.9% of the color gamut, such as 91-92%, 92-93%, 93-94%, 98-99.9%, 89-93%, 93-96% and/or 96-99.9%, or a range limited by any such value. Some embodiments include an LCD backlight including the aforementioned film.

In some embodiments, the membrane may comprise a polymer matrix. In some embodiments, the polymer matrix can have a transparency of greater than 75%, greater than 80%, greater than 90%, or greater than 95%. In some embodiments, the polymer matrix may include hydrophilic or hydrophobic polymers. In some embodiments, the polymer matrix may include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or polyacrylate. In some embodiments, the polymer matrix may include polyvinyl butyral (PVB). In some embodiments, the polyacrylate can be a polyalkyl acrylate. In some embodiments, the polyalkyl acrylate can be polymethylmethacrylate (PMMA).

In some embodiments, the photoluminescent compound (and/or the photoluminescent wavelength conversion film including the photoluminescent compound) has a narrow absorption or emission band such that a small amount of visible wavelength light is emitted. The absorption or emission band can be characterized by the full width at half maximum (FWHM). In the present invention, FWHM defines the width in nanometers of an absorption or emission spectrum at half the absorption or emission peak wavelength. In some embodiments, the photoluminescent compound has a FWHM value less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 35 nm, less than or equal to 30 nm, or less than or an absorption band equal to 25 nm. In some embodiments, the photoluminescent compound has an emission with a FWHM value less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 35 nm, or less than or equal to 30 nm when dispersed in a substantially transparent polymer matrix. belt.

In some embodiments, the film may include a first organic photoluminescent compound (or dye). In some embodiments, the first organic photoluminescent dye (and/or the photoluminescent wavelength conversion film including the first organic photoluminescent dye) may have a wavelength between 510 and 520 nm or between 520 and 530 nm, or by any The emission peak (emitting green light) within the range defined by these equivalent values. In some embodiments, the emission spectrum of the first organic photoluminescent dye and/or the photoluminescent wavelength conversion film may have a full width at half maximum (FWHM) of less than 35 nm, less than 30 nm, or less than 20 nm.

In some embodiments, the first organic photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinolinyl group. In some embodiments, the optionally substituted isoquinolyl group can be an optionally substituted isoquinoline derivative group. In some embodiments, the optionally substituted isoquinolinyl group can be the optionally substituted isoquinolyl group And isoquinoline derivative group. In some embodiments, the optionally substituted BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to an optionally substituted isoquinolinyl group. In other embodiments, the linking group is covalently bonded to an optionally substituted isoquinoline derivative group. In other embodiments, the linking group is covalently bonded to an optionally substituted Isoquinoline derivative group.

In some embodiments, the first organic photoluminescent dye can include an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalenedicarboxylic acid imide group. In some embodiments, the optionally substituted naphthalenedicarboxylic acid imide group may be an optionally substituted naphthalenedicarboxylic acid derivative group. In some embodiments, the optionally substituted BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to an optionally substituted naphthalenedicarboxylic acid imide group. In other embodiments, the linking group is covalently bonded to an optionally substituted naphthalenedicarboxylic acid derivative group.

In some embodiments, the first organic photoluminescent dye can be selected from the photoluminescent dyes described in the following co-pending application: U.S. Provisional Application No. 63/152,309, filed February 22, 2021 , whose discussion of photoluminescent dyes is incorporated herein by reference; and U.S. Provisional Application No. 63/278,904, filed on November 12, 2021, Attorney Docket No. N3253.10133US02, are incorporated by reference. into this article.

In some embodiments, the first organic photoluminescent dye can be selected from FD-1, FD-2, or FD-3: (FD-1), (FD-2), (FD-3), or combinations thereof.

In some embodiments, the wavelength conversion film may include a second organic photoluminescent dye. In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength conversion film including the second organic photoluminescent dye) may have an absorption peak between 400 and 470 nm (absorbing blue light). In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength conversion film including the second organic photoluminescent dye) may have a wavelength between 610 and 620 nm or between 620 and 630 nm, or by any The emission peak (red light emission) within the range defined by these equivalent values. In some embodiments, the emission spectrum of the second organic photoluminescent dye and/or the photoluminescent wavelength conversion film may have a half-height of less than 65 nm, 55 nm, 50 nm, 45 nm, less than 40 nm, or less than 35 nm. Width (FWHM).

In some embodiments, the second organic photoluminescent dye can include a BODIPY group, a linking group, and a perylene group. In some embodiments, the perylene group can be a perylene derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the perylene group. In other embodiments, the linking group is covalently bonded to the perylene derivative group.

In some embodiments, the second organic photoluminescent dye can include a BODIPY group, a linking group, and an isoquinolinyl group. In some embodiments, the isoquinolyl group can be an isoquinoline derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the isoquinolinyl group. In other embodiments, the linking group is covalently bonded to the isoquinoline derivative group.

In some embodiments, the second organic photoluminescent dye can include a BODIPY group, a linking group, and a naphthalenedimide group. In some embodiments, the naphthalenedimine group can be a naphthalenedimine derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the naphthalenedimine group. In other embodiments, the linking group is covalently bonded to the naphthalenedimine derivative group.

In some embodiments, the first organic photoluminescent dye can be selected from the photoluminescent dyes described in the following co-pending application: U.S. Provisional Application No. 63/248,863, filed September 27, 2021 , whose discussion of photoluminescent dyes is incorporated herein by reference; U.S. Provisional Application No. 63/278,904, filed on November 19, 2021, Attorney Docket No. N3252.10147US02, is incorporated by reference. herein; and PCT Patent Publication WO2020/210761, are incorporated herein by reference. In some embodiments, the second organic photoluminescent dye can be selected from SD-1, SD-2, SD-3, SD-4 or SD-5: (SD-1), (SD-2), (SD-3), (SD-4), , or a combination thereof.

In some embodiments, the first photoluminescent compound can absorb light in the UV/blue absorption spectrum and emit light in the green emission spectrum, thereby enhancing the perception of the emitted green light. In other embodiments, the second photoluminescent compound can absorb light in the green and/or blue absorption spectrum and emit light in the red emission spectrum, thereby enhancing the perception of the emitted red light. In some embodiments, the first and second photoluminescent dyes can absorb light within the UV/blue light absorption spectrum and emit light at other wavelengths, where the resulting combined light can be perceived as white light. In some examples, perceived white light may have a color temperature described as cool. In some embodiments, perceived white light may have a color temperature described as warm.

In some embodiments, the first photoluminescent dye and the second photoluminescent dye can absorb about 60-70% of a light source emitting light in the blue spectrum. In some embodiments, the resulting white light includes 30-50% blue light, 20-30% red light emitted from the wavelength conversion film, and 20-30% green light emitted from the wavelength conversion film. The thickness of the film can be adjusted to adjust the percentage of blue light absorbed by the wavelength conversion film and the percentage of blue light that passes through the wavelength conversion film to contain the resulting white light. In some embodiments, the photoluminescent wavelength conversion film can have any suitable thickness, such as less than about 500 µm, less than about 200 µm, or less than about 100 µm, such as about 1-20 µm, about 10-40 µm, about 20- 30 µm, about 30-40 µm, about 40-50 µm, about 50-80 µm, about 80-120 µm, about 120-200 µm, about 200-300 µm or about 300-500 µm.

In some embodiments, the thickness of the wavelength conversion film may decrease or increase according to Beer-Lambert's law. In particular, the Beer-Lambert law can be used to derive the relationship between the film thickness and the concentration of the first photoluminescent dye and the second photoluminescent dye to obtain 60-70% of the blue light emitted from the light source. In some embodiments, the dye concentration can be reduced and the thickness increased to allow for 60-70% absorption of blue light. In some embodiments, the dye concentration can be increased and the thickness reduced to allow for 60-70% absorption of blue light. In some embodiments, the photoluminescent wavelength conversion film may have a suitable thickness greater than 20 µm and less than 30 µm for most of the dye concentrations shown in Table 1 of the Examples section below.

In some embodiments, the length of the linking group can be adjusted to optimize the solubility of the first photoluminescent dye and the second photoluminescent dye. In some embodiments, the solubility of the first photoluminescent dye and the second photoluminescent dye can be greater than 0.15%. In some embodiments, the solubility of the first photoluminescent dye and the second photoluminescent dye may be about .03%-0.8%, about 0.8%-2%, or about 2%-3%, or any of the above values. solubility within a limited range.

The ratio of the amounts of the first photoluminescent dye and the second photoluminescent dye can be adjusted to adjust the color characteristics of the photoluminescent wavelength conversion film. For example, the weight ratio of the first photoluminescent dye to the second photoluminescent dye may be about 0.01-100 (the ratio of 1 mg of the first photoluminescent dye to 100 mg of the second photoluminescent dye is 0.01), About 0.01-0.2, about 0.2-0.4, about 0.4-0.6, about 0.6-0.8, about 0.8-1, about 1-2, about 2-3, about 3-4, about 4-5, about 5-6, About 6-7, about 7-8, about 8-9, about 9-10, about 10-20, about 20-40, about 40-70, about 70-100, about 0.43, about 0.91, about 1.8 or about 3.0.

In some embodiments, the film may include scattering centers disposed within a polymer matrix. In some embodiments, the scattering centers can be solid particles that contain scattering material with a refractive index (RI) different from that of the polymeric matrix material. The scattering material may be a material with a different refractive index than the RI of the polymer matrix. Scattering materials can be used to increase the external quantum yield, for example by reducing total internal reflection. Material RI PMMA 1.49 PVB 1.49 Silicon 1.42 air pockets or voids 1.00

In some embodiments, the difference in RI between the polymer matrix material and the light scattering material can be at least 0.05, 0.1, at least 0.2, at least 0.3, at least 0.4, or at least 0.5, up to 1 or 2.

In some embodiments, the scattering material may be polysilicone beads. In some embodiments, the scattering centers may comprise voids defined within the polymer matrix. In some embodiments, the average diameter of the scattering center may be 1 micron (µm) to 10 microns (µm), about 1-2 µm, about 2-3 µm, about 3-4 µm, about 4-5 µm, about 5-6 µm, about 6-7 µm, about 7-8 µm, about 8-9 µm, about 9-10 µm, or about any value within the range defined by any of these values. In some embodiments, the scattering centers can be substantially uniformly dispersed within the polymer matrix. In some embodiments, the top portion of the film (eg, the side away from the blue light emitting source) may have a scattering center greater than 50%. In some embodiments, the scattering centers can be evenly distributed throughout the polymer matrix.

In some embodiments, the photoluminescent wavelength conversion film may have at least about 70%, at least about 80%, or at least about 90% at the red or green light emission maximum; and/or at most about 80%, at most about Internal quantum yield (IQE) of 90%, up to about 100%. In some embodiments, the photoluminescent wavelength conversion film may have at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% at a red or green light emission maximum; and/or an external quantum yield (EQE) of up to about 80%, up to about 90%, or up to about 100%.

In some embodiments, a display device may be represented by device 10 . As shown in FIG. 1 , device 10 may include light source 12 . In some embodiments, display device 10 may include a wavelength conversion (WLC) film 16 . In some embodiments, WLC film 16 can be in optical communication with light source 12 such that the effectiveness of transmitting generated light from light source 12 to viewer 20 can be increased.

In some embodiments, the display device may be schematically represented by FIG. 2 . As shown in FIG. 2 , a display device such as device 10 may include a light source 12 . In some embodiments, display device 10 may include back reflector 14 . In some embodiments, display device 10 may include a wavelength conversion (WLC) film 16 . In some embodiments, display device 10 may include mask 18 . In some embodiments, WLC film 16 can be in optical communication with light source 12 such that the effectiveness of transmitting generated light from light source 12 to viewer 20 can be increased.

In some embodiments, the display device may be schematically represented by FIG. 3 . As shown in FIG. 3 , a display device is depicted, which device 10 may include a light source 12 . In some embodiments, display device 10 may include back reflector 14 . In some embodiments, display device 10 may include a wavelength conversion (WLC) film 16 . In some embodiments, the display device may include a mask 18 . In some embodiments, WLC film 16 may be in optical communication with light source 12 and/or interposed between light source 12 and viewer 20 and/or mask 18 such that transmission of generated light from light source 12 to the viewer may be enhanced. 20 effectiveness.

As shown in Figures 3 and 4, in some embodiments, the display device 10 may include one or more brightness enhancing films (BEF) 22, such as Vikuiti brand BEF (3M Minneapolis, MN, USA). In some embodiments, display device 10 may include one or more polarizers and/or brightness enhancement films, such as dual brightness enhancement film (DBEF) 24, such as DBEF II (3M Minneapolis, MN, USA). In some embodiments, the use of one or more brightness enhancing films may be referred to as an optical film stack.

Some embodiments include a method for manufacturing an LED light source. In some embodiments, methods can include making an undried wavelength-shifting polymeric layer using an organic solvent and a photoluminescent dye described herein. In some embodiments, methods may include mixing polymers and/or monomers with organic solvents. In some embodiments, polymer and/or monomer precursors can be dispersed, dissolved, and/or mixed with solvents. In some embodiments, solvents can be used to create layers of materials. In some embodiments, the solvent may be a non-polar solvent. In some embodiments, non-polar solvents may include, but are not limited to, xylene, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. In some embodiments, the solvent may be a polar solvent. In some embodiments, the polar solvent may include ethanol, dimethylformamide (DMF), or combinations thereof. In some embodiments, the solvent can be a combination of non-polar and polar solvents.

In some embodiments, the method may include immersing the undried polymeric photocatalytic WLC layer in an aqueous solution. In some embodiments, the aqueous solution may include water. In some embodiments, the aqueous solution may contain at least 90% water. In some embodiments, the water can be deionized water. In some embodiments, the undried polymeric photocatalytic WLC layer can be immersed in the aqueous solution for 5 minutes to about 1 hour.

In some embodiments, the method may include removing the undried polymerized photocatalytic WLC layer from the aqueous solution. In some embodiments, the method may include drying the undried polymerized photocatalytic WLC layer. It is believed that fabricating the polymeric photocatalytic WLC layer in this manner provides a plurality of voids defined in the emissive or distal surface of the polymeric photocatalytic WLC layer. In some embodiments, the voids are substantially entirely within about 1 micron to about 5 microns of the emissive surface of the polymeric photocatalytic WLC layer.

In some embodiments, the polymeric material includes about 2 wt% to about 50 wt% polymer, about 2-5 wt%, about 5-10 wt%, about 10-15 wt%, about 15-20 wt%, about 20-25 wt%, about 25-30 wt%, about 30-35 wt%, about 35-40 wt%, about 40-45 wt%, about 45-50 wt%, about 2.5 to 30 wt%, about 5 - an aqueous solution of 15 wt%, about 15-25 wt%, about 25-35 wt%, or about 30 wt% polymer, or about any value within the range defined by these values. Examples Example 1. A wavelength conversion film, comprising: a polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and has an emission spectrum with a half-maximum width less than 30 nm. Emitting green wavelength light; a second photoluminescent dye that absorbs blue or green wavelength light and strictly emits red wavelength light with an emission spectrum with a half-maximum width less than 55 nm; and a light scattering center, wherein The first photoluminescent dye, the second photoluminescent dye and the light scattering center are disposed within the polymer matrix. Embodiment 2. The wavelength conversion film of Embodiment 1, wherein the first photoluminescent dye includes a BODIPY group, a linking group and an isoquinolinyl group. Embodiment 3. The wavelength conversion film of Embodiment 2, wherein the first photoluminescent dye is selected from: (FD-1), or (FD-3). Embodiment 4. The wavelength conversion film of Embodiment 1, wherein the first photoluminescent dye includes a BODIPY group, a linking group and a naphthalenedicarboxylic acid imide group. Embodiment 5. The wavelength conversion film of Embodiment 4, wherein the first photoluminescent dye is selected from: (FD-2). Embodiment 6. The wavelength conversion film of Embodiment 1, wherein the second photoluminescent dye includes a BODIPY group, a linking group and an isoquinolinyl group. Embodiment 7. The wavelength conversion film of Embodiment 6, wherein the second photoluminescent dye is selected from: (SD-1), (SD-2), or (SD-4). Embodiment 8. The wavelength conversion film of Embodiment 1, wherein the second photoluminescent dye includes a BODIPY group, a linking group and a naphthalenedimide group. Embodiment 9. The wavelength conversion film of Embodiment 8, wherein the second photoluminescent dye is selected from: . Embodiment 10. The wavelength conversion film of Embodiment 1, wherein the second photoluminescent dye includes a BODIPY group, a linking group and a perylene group. Embodiment 11. The wavelength conversion film of Embodiment 8, wherein the second photoluminescent dye is selected from: (SD-3). Embodiment 12. The wavelength conversion film of embodiments 1 to 11, wherein the wavelength conversion film has an internal quantum yield greater than 80%. Embodiment 13. The wavelength conversion film of embodiments 1 to 11, wherein the wavelength conversion film has an external quantum yield greater than 50%. Embodiment 14. The wavelength conversion film of embodiments 1 to 11, wherein the wavelength conversion film has a color gamut greater than 90% of the BT.2020 standard. Embodiment 15. The wavelength conversion film of embodiments 1 to 11, wherein the wavelength conversion film has a thickness between 10 µm and 40 µm. Embodiment 16. A light-emitting device comprising the wavelength conversion film of embodiments 1 to 15. Embodiment 17. A backlight device with a blue light source, the device includes the wavelength conversion film of Embodiments 1 to 15. Example

Embodiments of films including the photoluminescent complexes described herein have been found to have improved performance compared to other forms of color conversion films. These benefits are further demonstrated by the following examples, which are intended to illustrate the invention but are not intended to limit the scope or underlying principles in any way. Synthetic procedure for synthesizing the first photoluminescent dye compound FD-1 Compound FD-1.1 :

Make 2,4-dimethyl-1H-pyrrole-3-carboxylic acid ethyl ester (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and p-toluenesulfonate. A mixture of acid (50 mg, 0.29 mmol) in 50 mL 1,2-dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis showed one main peak with m/e+ = 467.

DDQ (0.817 g, 3.6 mmol) was added to the resulting solution, followed by stirring at room temperature for 30 min. LCMS analysis showed conversion of all starting material to the desired product with m/e+ =465.

Under ice bath cooling, 1.7 mL triethylamine and 2.2 mL BF3-ethyl ether were added sequentially to the mixture from step 2. All heated at 50°C for one hour. LCMS analysis showed approximately 30% conversion. Add another 1 mL of triethylamine and 1 mL of BF3-ethyl ether to the mixture, and heat all at 50°C for another hour. LCMS analysis showed conversion of all of the material to the desired BODIPY product with m/e+ = 513 and m/e- = 512. The reaction mixture was presented directly to silica gel and purified by flash chromatography using the eluant hexane/ethyl acetate (0% to 30% ethyl acetate). The main desired peak was collected and the solvent was removed to give an orange solid (1.0 g, 65% yield). LCMS (APCI): Calculated for C27H32BF2N2O5 (M+H): 513.2; found: 513. 1H NMR (400 MHz, chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q , J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Compound FD-1.2 :

2-Nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) were mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 min, then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. All were degassed and then heated to reflux for 1.5 hr. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture and allowed to stand for 2 hr. The precipitate was collected by filtration and then dried under vacuum overnight to give a yellow-brown solid (4.6 g). Further purification was performed by stirring in refluxing acetic acid (50 mL) for 2 hr, followed by cooling to room temperature. Filtration and drying in air gave a yellow solid (3.0 g, 41% yield). Confirmed by LCMS (APCI): Calculated value (M+H) of C18H10NO6: 336.0; Experimental value: 336. ¹ H NMR (400 MHz, chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H ), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H). Compound FD-1.3 :

Compound FD - 1.2 4-(2-nitrophenoxy)-1,8-naphthalenedicarboxylic anhydride (2.0 g, 6 mmol) and iron powder (<10 um, 0.91 g, 16 mmol) were dissolved in acetic acid (75 mL) and heated to reflux for 30 min. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration and washed with water, dried thoroughly in air and then under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed by LCMS (APCI): Calculated for C ₁₈ H ₁₂ NO ₄ (M+H): 306.1; Found: 306. Compound FD-1.4 :

Compound FD-1.3 4-(2-aminophenoxy)-1,8-naphthalenedicarboxylic anhydride (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0°C. While stirring, precooled hydrochloric acid (3 mL, 37 mmol) was added, followed by a solution of sodium nitrite (3.29 g, 46 mmol) in 12 mL of water dropwise at 0°C. All was stirred at 0°C for one hour, then transferred to another funnel and dropped into refluxing copper sulfate solution (5.08 g, 20 mmol in 50 mL water) over a period of one hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water, and then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): Calculated for C ₁₈ H ₈ O ₄ (M-): 288.0; Found: 288. ¹ H NMR (400 MHz, chloroform-d) δ 8.61 (dd, J = 17.1, 8.1 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.40 (t, J = 8.1 Hz, 2H), 7.33 (d, J = 8.4 Hz, 1H). Compound FD-1.5 :

Heating compound FD-1.4 1H,3H-isobenzopirano[6,5,4-mna]𠮿 in a microwave reactor at 165°C -A mixture of 1,3-dione (100 mg, 0.347 mmol), 4-(4-aminophenyl)butyric acid (125 mg, 0.7 mmol) in 5 mL DMF for 2.5 hr. 15 mL of acetone was added to the mixture, and the resulting precipitate was collected by filtration and dried in air to obtain a yellow solid (120 mg, 77% yield). Confirmed by LCMS (APCI): Calculated for C ₂₈ H ₁₉ NO ₅ (M-): 449.1; Found: 449. ¹ H NMR (400 MHz, DMSO-d6) δ 8.38 (d, J = 41.6 Hz, 4H), 7.81 - 6.97 (m, 8H), 2.69 - 2.64 (m, 2H), 2.26 (t, J = 7.2 Hz , 2H), 1.87 (p, J = 7.2 Hz, 2H). Compound FD-1 :

Compound FD-1.5 (45 mg, 0.1 mmol), compound FD-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59 mg, 0.2 mmol) and DIC (0.1 mL, 0.63 mmol) were stirred at room temperature. The mixture in 5 mL DCM was incubated overnight and then stirred at 45°C for 2 hr. The reaction mixture was submitted to silica gel and purified by flash chromatography using the eluant DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (46 mg, 62% yield). Confirmed by LCMS (APCI): Calculated for C ₅₅ H ₄₉ BF ₂ N ₃ O ₉ (M+H): 944.3; Found: 944. ¹ H NMR (400 MHz, d2-TCE) δ 8.54 (dd, J = 18.7, 8.1 Hz, 2H), 7.40 - 7.25 (m, 5H), 7.20 (d, J = 8.3 Hz, 2H), 6.93 (s , 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.80 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.10 (t , J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthetic procedure of compound FD-2 Compound FD-2.1 :

Make 2,4-dimethyl-1H-pyrrole-3-carboxylic acid ethyl ester (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and p-toluenesulfonate. A mixture of acid (p-TsOH) (50 mg, 0.29 mmol) in 50 mL dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography mass spectrometry (LCMS) analysis showed that the reaction was complete, with the main peak having m/e ⁺ = 467. To the mixture obtained above was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817 g, 3.6 mmol) and the whole was stirred at room temperature for 30 min. LCMS analysis indicated completion of the reaction with the main peak having m/e ⁺ = 465. Under ice bath cooling, triethylamine (1.7 mL, 12 mmol) and BF ₃ -ethyl ether (2.2 mL, 18 mmol) were added to the mixture obtained above, and the resulting mixture was stirred at 50°C for one hour. An additional 1 mL of triethylamine and 1 mL of BF ₃ -ethyl ether were added and all heated for another hour. LCMS analysis indicated conversion of all dipyrromethine starting material to the BODIPY product with m/e ⁺ = 513. After cooling to room temperature, the reaction mixture was transferred to silica gel and purified by flash chromatography using the eluant hexane/ethyl acetate (0% to 30% ethyl acetate). Collect the required fractions. After removal of the solvent, the desired product was obtained as an orange solid (1.0 g, 65% yield). ¹ H NMR (400 MHz, chloroform-d) δ 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): Calculated for C ₂₇ H ₃₂ BF ₂ N ₂ O ₅ (M+H) = 513.2; found: 513. Compound FD-2 :

Compounds FD-2.1 (100 mg, 0.195 mmol), FD-2.2 (4-(4-(6-(4-(diphenylamine)phenyl))-1,3-dilateral oxy- 1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butyric acid) (132 mg, 0.22 mmol), diisopropylcarbodiimide (DIC) (0.1 mL, 0.63 mmol) and a mixture of dimethylaminopyridine (DMAP)/p-TsOH (118 mg, 0.4 mmol) in dichloromethane (DCM) (6 mL) overnight, then loaded on silica and eluted by flash chromatography. Purify using DCM/ethyl acetate (0% to 5% ethyl acetate). Collect the desired major orange fraction. After removal of the solvent, the solid obtained was reprecipitated in DCM/MeOH. After filtration and drying in air the desired product was obtained as an orange solid (145 mg, 68% yield). ¹ H NMR (400 MHz, d2-TCE) δ 8.56 (dd, J = 7.4, 4.7 Hz, 2H), 8.43 (d, J = 8.3 Hz, 1H), 7.79 - 7.64 (m, 2H), 7.41 - 7.18 (m, 10H), 7.18 - 7.12 (m, 6H), 7.03 (t, J = 7.3 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.81 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.11 (t, J = 7.5 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). LCMS (APCI-): Calculated for C ₆₇ H ₅₉ BF ₂ N ₄ O ₈ (M-) = 1096.4; found: 1096. Synthetic procedure of compound FD-3 Synthesis procedure of FD-3.1 - 2-(4-(9- bromo -1,3- bilateral oxygen -1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H) -yl ) phenyl ) acetic acid :

Degas a mixture of SD-2.6 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) at room temperature. . The mixture was then heated to 165°C and maintained at this temperature for 3 hr. TLC and LCMS showed about 95% conversion rate and no observable side reactions. The mixture was cooled to 50°C. This was then poured into an acetone solution (40 mL) that had been pre-cooled by a water-ice bath. The mixture was kept at 0°C for 2 hr and kept stirring at room temperature overnight. The solid was collected via vacuum filtration and washed with acetone (4 mL). And by drying in a vacuum oven at 100°C for 3 hr, pure compound FD-3.1 (395.0 mg, 73% yield) was obtained as a yellow-brown solid. MS (APCI): Calculated value of C ₂₆ H ₁₄ BrNO ₅ ([M+H]+) =500 Experimental value: 500. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H ), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 ( d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H). Synthesis procedure of compound SD-5.1-2- (4-(1,3- dilateral oxygen -9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H) -yl ) phenyl ) acetic acid :

The 100 mL vial is equipped with a stir bar. In a vial, mix compound FD-3.1 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Degas Pd(dppf)Cl ₂ (41.0 mg, 0.056 mmol) and K ₂ CO ₃ (298.0 mg, 2.2 mmol) in THF/DMF/H ₂ O (22 ml/4.4 ml/2.2 ml). The reaction mixture was heated to 80°C and the reaction was maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was treated by adding 0.1 N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted with THF (150 ml×3). The combined organic phases were dried over anhydrous Na ₂ SO ₄ , concentrated on a rotary evaporator and purified by flash chromatography using DCM/EtOAc (0-40% with 0.1% TFA) as eluent to give a yellow/yellow color Pure RL-naphthalenedimine derivative SD-5.1 is a brown solid. 363.0 mg, 80% yield. MS (APCI): Calculated value for C ₃₃ H ₁₈ F ₃ NO ₅ ([M+H]+) = 566 Experimental value: 566. ¹ H NMR (400 MHz, DMSO-d6) 8.76 (m, 1H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz , 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H). Procedure for compound FD-3 :

Compound SD-5.1 (50 mg, 0.089 mmol), compound FD-2.1 (30 mg, 0.059 mmol), DMAP/TsOH salt (15 mg, 0.051 mmol) and EDC·HCl (60 mg, 0.31 mmol) were stirred at room temperature. ) in 5 mL DCM overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using the eluant DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was reprecipitated with ethyl acetate/methanol and dried in air to give an orange solid (45 mg, 72%). LCMS (APCI-): Calculated for C ₆₀ H ₄₇ BF ₅ N ₃ O ₉ : 1059.33; found: 1059. ¹ H NMR (400 MHz, dichloromethane-d2) δ 8.73 (d, J = 7.9 Hz, 1H), 8.66 (d, J = 8.3 Hz, 1H), 8.39 (d, J = 2.2 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H), 7.86 (dt, J = 11.4, 8.4 Hz, 5H), 7.64 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.6 Hz, 1H), 7.43 (d, J = 8.3 Hz, 1H), 7.41 - 7.35 (m, 2H), 7.09 (s, 2H), 4.30 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 2.84 (s , 6H), 2.18 (s, 6H), 1.77 (s, 6H), 1.36 (t, J = 7.1 Hz, 6H). Synthetic procedure of the second photoluminescent dye Synthetic procedure of compound SD-1 Compound SD -1.1 (2-(4- bromophenyl )-4- phenyl -1 H -pyrrole ) : synthesized according to the following literature procedure: Synlett, 2016, 27(11), 1738-1742. Compound SD-1.2 :

Heat SD-1.1 (2-(4-bromophenyl)-4-phenyl-1H-pyrrole) (1.0 g, 3.36 mmol), 2,4,6-trimethylbenzaldehyde (0.249 g) at 50°C. , 1.68 mmol) and a mixture of p-toluenesulfonic acid (50 mg) in 1,2-dichloroethane (80 mL) for 24 hr. LCMS analysis showed that the main peak was the desired product with m/e ⁺ = 727. DDQ (454 mg, 2 mmol) was added to the mixture and stirred at room temperature for one hour. LCMS analysis showed that the reaction was complete, with one of the main peaks having m/e ^- = 724. Triethylamine (0.85 mL, 6 mmol), BF ₃ -ethyl ether (1.1 mL, 9 mmol) were added to the mixture at 0°C. All heated at 50°C for one hour. Another portion of triethylamine (0.5 mL) and BF3-ethyl ether (0.5 mL) were added and the mixture was heated at 50°C for an additional hour. LCMS showed that the reaction was complete, with m/e of the main peak ^- = 772. The mixture was diluted with 50 mL DCM and washed twice with water and once with brine, then concentrated to 100 mL and loaded onto silica gel and purified by flash chromatography using the eluant hexane/DCM (40% to 100% DCM). The main desired peaks were collected, and after removing the solvent under reduced pressure, the desired product (1.06 g, 81.6% yield) was obtained as a purple solid. Confirmed by LCMS (APCI): Calculated for C ₄₂ H ₃₁ BBr ₂ F ₂ N ₂ (M-): 770.1; found 770. ¹ H NMR (400 MHz, chloroform-d) δ 7.81 - 7.73 (m, 4H), 7.61 - 7.53 (m, 4H), 6.99 - 6.90 (m, 2H), 6.85 (dd, J = 8.3, 6.9 Hz, 4H), 6.78 - 6.71 (m, 4H), 6.42 (s, 2H), 6.00 (s, 2H), 1.98 (s, 6H), 1.85 (s, 3H). Compound SD-1.3 :

Compound SD-1.2 (160 mg, 0.207 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (184 mg, A mixture of Pd(dppf)Cl ₂ (16 mg, 0.022 mol), potassium carbonate (140 mg, 1.01 mmol) in THF/water (8 mL/1 mL) was degassed and heated at 80 °C. 120 minutes. The resulting mixture was diluted with 20 mL DCM, loaded on silica gel and purified by flash chromatography using the eluant DCM/ethyl acetate (0% to 20% ethyl acetate). The desired main peak was collected, and after removing the solvent under reduced pressure, the desired product (130 mg, 79% yield) was obtained as a dark solid. ¹ H NMR (400 MHz, TCE-d2) δ 7.98 - 7.91 (m, 4H), 7.62 - 7.54 (m, 4H), 7.54 - 7.46 (m, 4H), 6.92 - 6.85 (m, 4H), 6.84 ( d, J = 2.1 Hz, 2H), 6.82 - 6.74 (m, 4H), 6.73 - 6.66 (m, 4H), 6.46 (s, 2H), 5.92 (s, 2H), 4.88 (s, 2H), 1.92 (s, 6H), 1.78 (s, 3H). Compound SD-1 :

Stir compound SD-1.3 (80 mg, 0.1 mmol), compound SD-1.4 (100 mg, 0.222 mmol), DMAP/TsOH salt (59 mg, 0.2 mmol), and DIC (0.15 mL) in 6 mL DCM at room temperature. The mixture was left overnight and then stirred at 45°C for 2 hr. The resulting mixture was loaded on silica gel and purified by flash chromatography using the eluant DCM/ethyl acetate (0% to 10% ethyl acetate). The desired secondary coupling product was collected as the second major peak. After removing the solvent, washing with methanol and drying in air, the desired product was obtained as a dark solid (100 mg, 60% yield). Confirmed by ¹ H NMR. ¹ H NMR (400 MHz, d2-TCE) δ 8.49 (dd, J = 16.0, 8.1 Hz, 4H), 7.99 (d, J = 8.2 Hz, 6H), 7.85 (d, J = 8.0 Hz, 2H), 7.63 (dd, J = 8.5, 3.7 Hz, 8H), 7.50 (t, J = 7.8 Hz, 2H), 7.42 - 7.25 (m, 8H), 7.25 - 7.08 (m, 10H), 6.84 (dt, J = 36.5, 7.3 Hz, 6H), 6.70 (d, J = 7.5 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.7 Hz, 4H), 2.63 (t, J = 7.4 Hz, 4H), 2.11 (t, J = 7.7 Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H). Synthetic Procedure for Compound SD-2 General Procedure for Preparing Compounds SD-2.1 , SD-2.2 and SD-2.3 Compound SD-2.1 :

To a solution of 1-benzocycloheptanone (10.0 mmol, 1.46 mL) in 3:1 H ₂ O/EtOH (32.5 mL) was added NH ₂ OH·HCl (15.0 mmol, 1.04 g) and Sodium acetate (25.0 mmol, 2.05 g), and the reaction mixture was stirred at 95 °C for 1 h. Then it was cooled to room temperature, filtered, washed with water (150 mL) and lyophilized for 16 h to obtain 1.64 g of 6,7,8,9-tetrahydro-5H-benzo[7]annene-5- as a colorless solid. The ketoxime (94% yield) was used in the subsequent synthetic step without further purification.

To a solution of 6,7,8,9-tetrahydro-5H-benzo[7]annen-5-one oxime (5.71 mmol, 1.00 g) in DMSO (9.00 mL) at room temperature was added KOH ( 17.1 mmol, 959 mg), and the reaction mixture was heated to 140°C, then DMSO (2.00 mL) containing 1,2-dichloroethane (11.4 mmol, 897 µL) was added via a syringe pump over 3 h. The mixture was then cooled to room temperature, quenched with 1 M aqueous NH ₄ Cl (30.0 mL) and extracted with CH ₂ Cl ₂ (3×30.0 mL). The combined organics were dried ( _MgSO4 ) and concentrated under reduced pressure. Flash chromatography (Hexane → 9:1, Hexane/EtOAc) afforded 262 mg of SD-2.1 as a yellow solid (25% yield). ¹ H NMR (400 MHz, chloroform-d) δ 8.18 (br s, 1H), 7.34 (dd, J = 7.8, 1.3 Hz, 1H), 7.25 - 7.19 (m, 1H), 7.16 (dd, J = 7.6 , 1.6 Hz, 1H), 7.13 - 7.07 (m, 1H), 6.84 (t, J = 2.8 Hz, 1H), 6.17 (t, J = 2.8 Hz, 1H), 2.91 (t, J = 6.8 Hz, 2H ), 2.86 - 2.80 (m, 2H), 2.07 - 1.98 (m, 2H); ¹³ C NMR (101 MHz, chloroform-d) δ 140.4, 131.8, 129.3, 126.8, 125.9, 125.2, 123.2, 121.8, 118. 3, 111.1, 34.9, 27.8, 26.7. Compound SD-2.3 :

The 100 mL 2-neck round bottom flask is equipped with an air condenser and a stirring rod. Add compounds SD-2.1 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (813.1 mg, 4.4 mmol) and SD-2.2 4-hydroxy to the flask. -2,6-Dichlorobenzaldehyde (424.3 mg, 2.2 mmol), followed by anhydrous dichloroethane (55 ml). The reaction mixture was bubbled with Ar for 30 min, then TFA (4 drops) was added. The reaction solution was stirred at room temperature overnight. After the reaction was cooled to 0°C in an ice-water bath, tetrachloro-p-benzoquinone (731.8 mg, 2.98 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (3.0 mL, 24.1 mmol) and Et ₃ N (1.9 mL, 13.3 mmol) were added at 0°C. The reaction mixture was heated to 50°C for 3 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM/hexane (0-80-90%) as the eluant to obtain pure BODIPY SD-2.3 as a golden brown solid (476.0 mg, 36% yield). MS (APCI): Calculated for C ₃₃ H ₂₄ BCl ₂ F ₂ N ₂ O ([MH]-) = 584 Found 584. ¹ H NMR (400 MHz, CDCl3) 8.09 (dd, J = 4.0 Hz, 2.0 Hz, 2H), 7.32 (dddd, J = 13.2 Hz, 7.2 Hz, 7.2 Hz, 2.0 Hz, 4H), 7.22 (dd, J = 6.4 Hz, 2.0 Hz, 2H), 6.99 (s, 2H), 6.43 (s, 2H), 5.77 (bs, 1H), 2.63 (dd, J = 6.8 Hz, 6.8 Hz, 4H), 2.32 (bs, 4H), 2.03 (ddd, J = 14.0 Hz, 6.8 Hz, 6.8 Hz, 4H). Compound SD-2.4 :

A mixture of 4-bromo-1,8-naphthalenedicarboxylic anhydride (2.77 g, 10 mmol) and 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was vacuum degassed for 30 min, followed by the addition of anhydrous NMP ( 50 mL), then add sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was bubbled with argon for 20 min and subsequently heated at 180 °C overnight under an argon atmosphere. After cooling to room temperature, 50 mL of 20% aqueous hydrochloric acid solution was added dropwise to the solution, followed by 50 mL of water. The resulting mixture was allowed to stand for 3 hr, then filtered to collect the precipitate and dried under vacuum to obtain 4.6 g of crude product. The crude product was dispersed in 30 mL acetone and stirred at room temperature overnight to dissolve impurities. Filtration and vacuum drying gave a brown solid as the desired product (3.3 g, 80% yield). LCMS (APCI+): Calculated for C ₁₈ H ₉ BrNO ₆ (M+H) = 413.95; Found: 414. ¹ H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H ), 8.24 (d, J = 2.4 Hz, 1H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). Compound SD-2.5 :

A mixture of compound SD-2.4 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125°C for 30 min. After cooling to room temperature, 100 mL of water was added to the mixture while stirring. The resulting mixture was filtered and washed with water, dried in air and under vacuum to give a solid (1.35 g, 82% yield). LCMS (APCI-): Calculated for C ₁₈ H ₁₀ BrNO ₄ = 382.98; Found: 383. ¹ H NMR (400 MHz, DMSO-d6) δ 9.01 - 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). Compound SD-2.6 :

Compound SD-2.5 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL)/water (10 mL) and cooled to 0°C. While stirring, precooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, followed by a solution containing sodium nitrite (3.57 g, 52 mmol) in 15 mL of water dropwise at 0°C. All was stirred at 0°C for one hour, then transferred to another funnel and copper sulfate solution (12 g, 47 mmol in 140 mL water) added dropwise at 130°C over a period of one hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL×3), and then stirred in 50 mL acetone at 40°C for 30 min. Filtration, drying in air, then vacuum drying gave a tan solid (1.76 g, 70% yield). LCMS (APCI+): Calculated for C ₁₈ H ₈ BrO ₄ (M+H) = 366.95; Found: 367. ¹ H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). Compound SD-2.7 :

Compounds SD-2.6 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butyric acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) were heated in a microwave reactor at 165°C. Mix in 10 mL DMF for 2.5 hr. The resulting solution was dropped into 50 mL of acetone while stirring. A precipitate formed and was filtered and dried in a vacuum oven at 60°C overnight to give the desired product as a tan solid (0.49 g, 62% yield). LCMS (APCI-): Calculated for C ₂₈ H ₁₈ BrNO ₅ = 527.04; found 527. ¹ H NMR (400 MHz, DMSO-d6) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H ), 2.63 - 2.55 (m, 2H), 2.27 - 2.15 (m, 2H), 1.87 - 1.73 (m, 2H). Compound SD-2.8 :

Dissolve compound SD-2.7 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd(dppf)Cl2 (36 mg, 0.05 mmol), and potassium carbonate (276 mg, 2 mmol) in THF/DMF /water (20 L/4 mL/2 mL) in co-solvent was degassed and then heated at 80°C overnight. The mixture was treated with 200 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. Extract the aqueous phase with ethyl acetate (100 mL×2). The organic phase was collected and washed with brine (100 mL×2), dried over sodium sulfate, then dried and loaded on silica gel and subjected to flash chromatography using the eluant DCM/EA (0% to 40% EA, containing 0.1% TFA) Purification. The main desired fractions were collected and the solvent was removed under reduced pressure to obtain a yellow solid (250 mg, 65% yield). LCMS (APCI-): Calculated for C ₃₄ H ₂₃ NO ₅ = 525.16; Found: 525. ¹ H NMR (400 MHz, TCE-d2) δ 8.55 (dd, J = 19.5, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.72 (dd, J = 8.6, 2.1 Hz, 1H), 7.62 (d, J = 7.3 Hz, 2H), 7.51 - 7.28 (m, 7H), 7.17 (d, J = 8.2 Hz, 2H), 2.72 (t , J = 7.7 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.2 Hz, 2H). Compound SD-2 :

Compound SD-2.3 (31 mg, 0.053 mmol), compound SD-2.8 (43 mg, 0.082 mmol), EDC·HCl (100 mg, 0.52 mmol) and DMAP/p-TsOH (16 mg, 0.054 mmol) in DCM (8 mL) overnight. The resulting mixture was then loaded on silica gel and purified by flash chromatography using the eluent DCM/ethyl acetate (0%-5% ethyl acetate). The main red fraction was collected and concentrated under reduced pressure to about 1 mL, and then 10 mL of methanol was added. The resulting precipitate was filtered and dried in air to give a dark red solid (41 mg, 70.8% yield). LCMS (APCI-): Calculated for C ₆₇ H ₄₆ BCl ₂ F ₂ N ₃ O ₅ = 1091.29; found 1091. ¹ H NMR (400 MHz, d2-TCE) δ 8.56 (dd, J = 19.3, 8.1 Hz, 2H), 8.21 (d, J = 2.2 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.97 (t, J = 4.7 Hz, 2H), 7.73 (dd, J = 8.6, 2.1 Hz, 1H), 7.63 (dd, J = 7.2, 1.7 Hz, 2H), 7.50 - 7.41 (m, 3H), 7.38 (dd, J = 8.0, 2.2 Hz, 3H), 7.34 - 7.25 (m, 7H), 7.25 - 7.18 (m, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H), 2.60 - 2.49 (m, 4H), 2.24 (s, 4H), 2.18 - 2.07 (m, 2H), 2.03 - 1.90 (m, 4H). Synthetic procedure of compound SD-3 General Procedure for Preparing SD-3.2

AlCl ₃ (78.0 g, 585 mmol, 31.9 mL, 1.80 equiv) was added to anhydrous DCM (1.50 L) at 0-10 °C. The mixture was stirred at 0 °C for 30 min. A mixture of compound SD-3.1A (88.1 g, 585 mmol, 72.2 mL, 1.80 equiv) in anhydrous DCM (100 mL) was added to the mixture at 0-10 °C under _N2 . Compound SD-3.1 (82 g, 325 mmol, 1.00 equiv) was added portionwise to the mixture and the mixture was stirred at 25-30°C for 30 min. The mixture was stirred at 50°C for 12 hr. Thin layer chromatography (TLC) (petroleum ether/ethyl acetate = 10/1) showed the reaction was complete. The mixture was cooled to 25-30°C and poured into water (1.00 L). The mixture was separated and the aqueous phase was extracted with DCM (500 mL×2). The combined organic layers were dried _{over Na2SO4} and concentrated. The product was purified by MPLC (100-200 mesh silica gel, DCM). SD-3.2 was obtained as an orange solid (82.0 g, 223 mmol, 68.8% yield). LCMS (APCI+), calculated for C ₂₅ H ₁₈ O ₃ = 366.1; found 366. ¹ H NMR (400 MHz, chloroform-d) δ 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30 - 8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d , J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64 - 7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H). General procedure for the preparation of compound SD-3.3

Trifluoroacetic acid (TFA) (231 g, 2.03 mol, 150 mL, 9.90 equiv) was added to SD-3.2 (75.0 g, 204 mmol, 1.00 equiv) in anhydrous DCM (600 mL) at 0-10 °C. in the mixture. Stir the mixture at 0-10 °C for 30 min. Triethylsilane ( _Et3SiH ) (71.4 g, 614 mmol, 98.1 mL, 3.00 equiv) was added to the mixture at 0-10°C and the mixture was stirred at 25°C for 16 hr. TLC (petroleum ether/ethyl acetate = 3/1) showed the reaction was complete. The mixture was concentrated to give crude product. The crude product was wet-triturated with methyl tertiary butyl ether (MTBE) (400 mL) at 25-30°C for 30 min. The mixture was filtered and the filter cake was washed with MTBE (100 mL). Dry the filter cake under vacuum. The mother liquor was concentrated and purified by silica gel chromatography (100-200 mesh silica gel, petroleum ether/ethyl acetate = 100/1-2/1). Compound SD-3.3 was obtained as a yellow solid (62.0 g, 176 mmol, 85.9% yield). ¹ H NMR (400MHz, CDCl ₃ ) δ 8.27 - 8.08 (m, 4H), 7.91 (d, J = 8.3 Hz, 1H), 7.68 (dd, J = 5.5, 7.9 Hz, 2H), 7.53 (t, J = 8.0 Hz, 1H), 7.48 (dt, J = 1.5, 7.9 Hz, 2H), 7.34 (d, J = 7.7 Hz, 1H), 3.71 (s, 3H), 3.07 (t, J = 7.8 Hz, 2H ), 2.47 (t, J = 7.2 Hz, 2H), 2.12 (quin, J = 7.5 Hz, 2H) General procedure for the preparation of compound 3.4

Add N- bromosuccinimide (NBS) (88.4 g, 496 mmol, 3.40 equiv) portionwise to SD-3.3 (51.5 g, 146 mmol, 1.00 equiv) in CHCl ₃ (2.00 L) at 25 °C. in the mixture. The mixture was stirred at 25°C for 16 hr and kept in the dark. LCMS (ET39890-22-P1A) showed the reaction was complete. _The mixture was washed with _Na2SO3 (1 N, 1.00 L). The mixture was separated and the aqueous phase was extracted with DCM (200 mL). The combined organic layers were concentrated to obtain crude product. The product was purified by silica gel chromatography (100-200 mesh silica gel, petroleum ether/ethyl acetate = 1/0-1/1). SD-3.4 was obtained as reddish brown oil (69.2 g, 102 mmol, 69.9% yield, 87.0% purity). LCMS (APCI+), calculated for C ₂₅ H ₁₇ Br ₃ O ₂ = 585.88; found: 589. General Procedure for Preparing SD-3.5

SD-3.4A (228 g, 1.19 mol, 151 mL, 10.0 equiv) was added to SD-3.4 (70.0 g, 119 mmol, 1.00 equiv) and CuI (113 g, 594 mmol, 5.00 equiv) at 25°C. DMA (490 mL) in a mixture. The mixture was stirred at 160 °C under _N2 for 3 hr. LCMS (ET39890-26-P1A) showed the reaction was complete. The mixture was cooled to 25-30°C and diluted with water (1.50 L) and ethyl acetate (EtOAc) (1.00 L). The mixture was filtered through a pad of celite. Wash the filter cake by EtOAc (500 mL×2). The combined filtrates were separated and the aqueous phase was extracted with EtOAc (500 mL×2). The combined organic layers were concentrated to obtain crude product. The product was purified by silica gel chromatography (100-200 mesh silica gel, petroleum ether/ethyl acetate = 1/0 to 1/1). SD-3.5 was obtained as reddish brown oil (40.0 g, 71.9 mmol, 60.5% yield). General procedure for the preparation of compound SD-3.6

Add sodium hydroxide (NaOH) (8.63 g, 215 mmol, 3.00 equiv) to SD-3.5 (40.0 g, 71.9 mmol, 1.00 equiv) in tetrahydrofuran (THF) (200 mL), methanol (MeOH) at 25°C. (200 mL) and H ₂ O (200 mL). The mixture was stirred at 25°C for 2 hr. TLC (petroleum ether/ethyl acetate = 10/1) showed the reaction was complete. The mixture was acidified to pH = 1-2 by hydrochloric acid (HCl) solution (1 N). The mixture was concentrated to remove solvent. The residue was diluted with water (150 mL) and extracted with EtOAc (100 mL×2). The combined organic layers were concentrated. The product was purified by silica gel chromatography (100-200 mesh silica gel, petroleum ether/ethyl acetate = 1/0-0/1). SD-3.6 was obtained as a yellow solid (26.2 g, 48.1 mmol, 66.9% yield, 99.6% purity). ¹ HNMR (400MHz, CDCl ₃ ) δ 8.37 - 7.93 (m, 6H), 7.91 - 7.50 (m, 2H), 3.47 - 3.13 (m, 2H), 2.68 - 2.53 (m, 2H), 2.26 - 2.13 (m , 2H). General procedure for the preparation of compound SD-3 Compound SD-3.7 :

To 2,6-dichloro-4-hydroxybenzaldehyde (0.335 mmol, 64 mg), 4-(trifluoromethyl)perylene-3-yl)butyric acid (0.369 mmol, 200 mg) and DMAP·pTsOH To a solution of the salt (0.034 mmol, 10 mg) in _CH2Cl2 (1.68 mL) was added DIC (1.34 mmol, ₂₁₀ µL), and the reaction mixture was stirred at room temperature for 2 hr. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene) afforded 187 mg of SD-3.7 as a yellow solid (78% yield). ¹ H NMR (400 MHz, chloroform-d) δ 10.50 - 10.33 (m, 1H), 8.48 - 7.50 (m, 8H), 7.19 - 7.14 (m, 2H), 3.45 - 3.25 (m, 2H), 2.83 - 2.59 (m, 2H), 2.33 - 2.03 (m, 2H). Compound SD-3 :

To a solution of SD-2.1 (0.461 mmol, 84 mg) and SD-3.7 (0.210 mmol, 150 mg) in CH ₂ Cl ₂ (4.50 mL) was added p- TsOH·H ₂ O (0.021 mmol, 3 mg) , and the reaction mixture was stirred at room temperature for 1 h. DDQ (0.252 mmol, 57 mg) was then added and the mixture was stirred at room temperature for 1 h. Triethylamine (TEA) (1.26 mmol, 175 µL) was added and the mixture was stirred at room temperature for 1 h, followed by BF ₃ ·OEt ₂ (1.89 mmol, 233 µL), and the mixture was stirred at room temperature for 2 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCl (3×30.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexane→toluene) afforded 106 mg of SD-3 as a purple solid (45% yield). ¹ H NMR (400 MHz, dichloromethane-d2) δ 8.61 - 7.60 (m, 10H), 7.39 - 7.11 (m, 8H), 6.54 - 6.40 (m, 2H), 3.46 - 3.30 (m, 2H), 2.90 - 2.55 (m, 6H), 2.39 - 2.09 (m, 6H), 2.08 - 1.94 (m, 4H). Synthetic procedure of compound SD-4 General procedure for the synthesis of compound SD-4

The 10 mL vial is equipped with a stir bar. Compounds SD-2.3 (25.0 mg, 0.043 mmol), FD-1.5 (24.0 mg, 0.053 mmol), EDC·HCl (40.9 mg, 0.21 mmol) and DMAP·TsOH (25.6 mg, 0.085 mmol) were added to the vial, followed by Add anhydrous DCM (1.5 ml). The reaction mixture was heated to 40°C overnight. After the reaction was cooled to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using DCM/EtOAc (0-5%) as the eluent to obtain pure RL-naphthalenedidine as a dark purple solid. Amine-BODIPY 1605-23-3. Further wet trituration of the solid with MeOH (10 ml) afforded RL-naphthalenedimide-BODIPY SD-4 (21.0 mg, 48% yield). MS (APCI): Calculated value for C ₆₁ H ₄₁ Cl ₂ F ₂ N ₃ O ₅ ([MH]-) = 1015 Experimental value: 1015. ¹ H NMR (400 MHz, CDCl3) δ 8.66 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.10 (m, 3H), 7.99 (d, J =8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.36 (m, 13H), 7.22 (dd, J = 6.8 Hz, 2.0 Hz, 2H), 6.45 (s, 2H) 2.88 (t, J = 7.6 Hz, 2H ), 2.72 (t, J = 7.2 Hz, 2H), 2.63 (m, 4H), 2.20 (m, 6H), 2.04 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H). Synthetic procedure of compound SD-5 General procedure for the synthesis of compound SD-5

The 25 mL vial is equipped with a stir bar. Add compounds SD-2.3 (40.0 mg, 0.068 mmol), 1605-99 SD-5.1 (77.5 mg, 0.137 mmol), EDC·HCl (65.2 mg, 0.340 mmol), and DMAP·TsOH (41.1 mg, 0.137 mmol) to the vial. ), after which anhydrous DCM (4 ml) was added. The reaction mixture was heated to 40°C overnight. After cooling the reaction to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using DCM/EtOAc (0-4%) as the eluent to obtain pure RL-naphthalenedidine as a dark blue solid. Amine-BODIPY SD-5 . Further wet trituration of the solid with MeOH (15 ml) afforded RL-naphthalenedimide-BODIPY SD-5 (46.0 mg, 60% yield). MS (APCI): Calculated for C ₆₆ H ₄₁ BCl ₂ F ₅ N ₃ O ₅ ([MH]-) = 1132 Found: 1132. ¹ H NMR (400 MHz, CDCl2CDCl2) δ 8.69 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 8.06 (m, 2H), 7.82 (m, 5H), 7.65 (m, 2H), 7.55 (d, J = 8.0 Hz, 1H), 7.39 (m, 9H), 7.30 ( m, 2H), 6.48 (s, 2H), 4.07 (s, 2H), 2.63 (m, 4H), 2.33 (bs, 3H), 2.06 (m, 4H). Preparation of polymer solution Preparation of 25% PMMA polymer solution

Weigh 30 g of PMMA polymer (grade unknown) and add to a 250 mL glass bottle. Use a volumetric cylinder to measure 90 mL of cyclopentanone or toluene and add to the same glass bottle. Stir the solution on a stirring stand with a stirring rod and heat at 50°C until completely dissolved. Preparation of Dye Polymer Solution

0.2 mg FD-1 , 0.16 mg compound SD-3 and 150 mg polysiloxane particles (TSR9000, momentive). Add 4 mL of 25% PMMA solution to the solution. Mix the solution thoroughly by vortexing for 1 minute, then sonicate for 15 minutes, then stir on a stir plate at moderate speed. Membrane Fabrication Individual Dye Polymer Films

Dye polymer films are evaluated for basic optical properties. Dissolve the scattering center (20% silica beads, average size 2-3 µm) and appropriate weight of dye in more than 3 mL of 25% PMMA/toluene solution to prepare a 2 mmol/L dye polymer solution. The solution was mixed thoroughly by vortexing for 1 minute and then sonicated for 15 minutes. Clean several 1''×1'' glass substrates with soapy water and air dry them. The glass substrate was then placed on the spin coater holder and the dye polymer solution was poured onto the glass substrate. Spin coat the film at a spin speed set to 1000 RPM for 20 seconds. The wet coated film was then dried at room temperature for 1 hour and heated at 130°C for 30 minutes. Green and red dye polymer films

To convert blue light into white light that is a mixture of R, G, and B colors, green dye and red dye are mixed into a film. Clean the 2"x2" glass substrate with soapy water and air dry. The glass substrate was then placed on the spin coater holder and the dye polymer solution was poured onto the glass substrate. Spin coat the film at a spin speed set to 1000 RPM. The wet coated film was then dried at room temperature for 1 hour and heated at 130°C for 30 minutes. Once the membrane was dry, the membrane was detached from the glass by immersion in water for 5 minutes.

Additional examples of films were made by varying the weight of the first photoluminescent dye, the second photoluminescent dye, the scattering particles, and/or the polymeric matrix material as set forth in Table 1 below. parts( weight) polymer PMMA 100 thickness 20-30 µm - first photoluminescent dye green dye 0.01-0.06 Second photoluminescent dye red dye 0.01-0.06 scattering particles 20% silicone beads, average size 2-3 µm 25-30 Table 1. Characterization of dye compounds. Absorption and emission spectra. The absorption and emission spectra of individual dyes in polymer films were measured by UV-vis (Shimadzu uv-vis 3600 spectrophotometer) and Fluorolog 3 (Horiba) respectively. Dye absolute quantum yield

The absolute quantum yield of the dye film was measured by an absolute PL quantum yield spectrometer C11347 (Hamamatsu) at a wavelength of 450 nm. Characterization of Blue Light Converting WLC Films External Quantum Yield of WLC Films on LED Backlight Devices

The external quantum yield and other optical characteristics of WLC films for LED backlight display applications were tested using test equipment configured as illustrated in Figure 4 . BEF stands for Vikuiti BEF (3M) Brightening Film. DBEF is polarizer/enhancement film (3M). The blue LED edge-lit backlight is part of the lighting device. MCPD stands for Multi-Channel Photon Detection (MCPD-9800, Otsuka Electronics). Calculate EQE based on the following equation: Color Gamut - BT.2020 Ratio

A color gamut is a subset of complete colors. It can be represented by a triangle within the chromaticity diagram. The three angles of a triangle are primary colors. The more colors a monitor can display, the larger the area of the triangle will be, and therefore the wider the color gamut. BT.2020 is the color gamut standard for UHD projectors and TVs recommended by the ITU (International Telecommunications Union).

The spectrum measured with the setup described in Figure 4 is converted into a gamut triangle in the CIE1931 chromaticity diagram, and the triangle area is then estimated and divided by the triangle area of BT.2020 to obtain the BT mentioned in this article. 2020 ratio. The larger the ratio, the wider and wider the color gamut of the WLC film. In order to achieve a wide color gamut, the emission spectral shape of each primary color should be as narrow as possible. A narrow spectral shape may be characterized by a small FWHM of the emission spectrum. Compare examples

Table 2 below identifies Comparative Examples 1 and 2, which are examples disclosed in US Patent Application No. 63/001,924. Red dye SD-X corresponds to SD-1 in US Patent Application No. 63/001,924. As can be seen in Table 2, Example 1 has a large color gamut (94% BT.2020 ratio), yet its red emission spectrum has a FWHM of 68 nm, which is not too narrow. Example 2 obtains a narrower FWHM of the red emission spectrum at the cost of a smaller color gamut (88% BT.2020 ratio).

Instance number green dye red dye Emission peak/FWHM EQE BT.2020 ratio 1 522nm, 25nm 642 nm, 68 nm 48% 94% 2 534 nm, 29 nm 638 nm, 38 nm 47% 88% surface 2 Example

The membranes in the Examples listed in Table 4 below and in the Comparative Examples listed in Table 2 above were all made by the methods described in the section titled "Film Manufacturing" above. Examples 3 through 9 of Table 5 were produced using the dyes identified in Tables 2 and 3. All green-emitting dyes appear to have a FWHM less than 25 nm, and most red-emitting dyes have a FWHM less than 44 nm. All dyes have internal quantum yields greater than 80%, and some have quantum yields greater than 95%.

The permeability of Examples 3 to 11 of Table 5 was evaluated by the method described above in the section titled "Characterization of Blue Light Converting WLC Films." Most examples show an EQE greater than 51%, an average increase of 10% compared to the comparative examples in Table 2. This is mainly due to the internal quantum yield of the dyes in Tables 3 and 4. In addition, all films have a green emission spectrum FWHM less than 33 nm and a red emission spectrum FWHM less than 63 nm, and a BT.2020 ratio greater than 90%. green dye Emission peak wavelength (nm) FWHM (nm) dye quantum yield FD-1 513 twenty three 96% FD-2 515 twenty four 88% FD-3 513 twenty three 94% Table 3 red dye Emission peak wavelength (nm) FWHM (nm) dye quantum yield SD-1 617 44 95% SD-2 611 35 97% SD-3 612 35 84% SD-4 614 35 90% SD-5 608 32 89% Table 4 membrane green dye red dye Emission peak/FWHM EQE BT.2020 Ratio Example 3 FD-2 (0.7 mM) SD-4 (0.15 mM) 524 nm 26 nm 618 nm 41 nm 53% 93% Example 4 FD-1 (0.4 mM) SD-4 (0.2 mM) 521 nm 24 nm 619 nm 43 nm 52% 93% Example 5 FD-2 (0.7 mM) SD-2 (0.18 mM) 524 nm 25 nm 622 nm 44 nm 52% 92% Example 6 FD-1 (0.4 mM) SD-2 (0.2 mM) 522 nm 25 nm 619 nm 42 nm 53% 93% Example 7 FD-2 (0.7 mM) SD-1 (0.12 mM) 523 nm 27 nm 620 nm 51 nm 52% 91% Example 8 FD-1 (0.4 mM) SD-1 (0.1 mM) 521 nm 25 nm 621 nm 50 nm 51% 91% Example 9 FD-2 (0.7 mM) SD-3 (0.25 mM) 525 nm 32 nm 639 nm 63 nm 40% 94% Example 10 FD-1 (0.4 mM) SD-3 (0.25 mM) 521 nm 25 nm 621 nm 50 nm 49% 94% Example 11 FD-3 (0.4 mM) SD-5 (0.2 mM) 522 nm 24 nm 621 nm 45 nm 54% 94% Table 5 Cross-reference of related applications

This application claims priority to U.S. Provisional Application No. 63/278,923, filed on November 12, 2021, which is incorporated herein by reference in its entirety.

10:Display device 12:Light source 14:Back reflector 16:Wavelength conversion film 18: Mask 20:Viewer 22:Brightening film 24:Double brightening film

Figure 1 is a schematic diagram of an embodiment of a display device incorporating a modified WLC film described herein. Figure 2 is a schematic diagram of an embodiment of a display device incorporating a modified WLC film described herein. Figure 3 is a schematic diagram of an embodiment of a display device incorporating a modified WLC film described herein. Figure 4 is a schematic diagram of a test configuration including film embodiments described herein.

10:Display device

12:Light source

16:Wavelength conversion film

20:Viewer

Claims (17)

A wavelength conversion film containing: polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and emits green wavelength light with an emission spectrum with a half-maximum width less than 40 nm; a second photoluminescent dye that absorbs blue or green wavelength light and emits red wavelength light with an emission spectrum with a half-maximum width less than 55 nm; and light scattering center, The first photoluminescent dye, the second photoluminescent dye and the light scattering center are arranged in the polymer matrix. The wavelength conversion film of claim 1, wherein the first photoluminescent dye includes an optionally substituted BODIPY group, a linking group and an optionally substituted isoquinolinyl group. The wavelength conversion film of claim 2, wherein the first photoluminescent dye is: ,or . The wavelength conversion film of claim 1, wherein the first photoluminescent dye includes an optionally substituted BODIPY group, a linking group and an optionally substituted naphthalenedicarboxylic acid imide group. The wavelength conversion film of claim 4, wherein the first photoluminescent dye is: . The wavelength conversion film of claim 1, wherein the second photoluminescent dye includes an optionally substituted BODIPY group, a linking group and an optionally substituted isoquinolinyl group. The wavelength conversion film of claim 6, wherein the second photoluminescent dye is: . The wavelength conversion film of claim 1, wherein the second photoluminescent dye includes an optionally substituted BODIPY group, a linking group and an optionally substituted naphthalene dimethylimide group. The wavelength conversion film of claim 8, wherein the second photoluminescent dye is: . The wavelength conversion film of claim 1, wherein the second photoluminescent dye includes an optionally substituted BODIPY group, a linking group and an optionally substituted perylene group. The wavelength conversion film of claim 8, wherein the second photoluminescent dye is: . The wavelength conversion film of any one of claims 1 to 11, wherein the wavelength conversion film has an internal quantum yield greater than 80%. The wavelength conversion film of any one of claims 1 to 11, wherein the wavelength conversion film has an external quantum yield greater than 50%. The wavelength conversion film of any one of claims 1 to 11, wherein the wavelength conversion film has a color gamut greater than 90% of the BT.2020 standard. The wavelength conversion film of any one of claims 1 to 11, wherein the wavelength conversion film has a thickness between 10 µm and 40 µm. A light-emitting device comprising the wavelength conversion film according to any one of claims 1 to 11. A backlight device with a blue light source, the device includes the wavelength conversion film according to any one of claims 1 to 11.