TWI662104B - Siloxane organic phosphor and method for forming the same - Google Patents

Abstract

The invention provides a siloxane organic phosphor, which is an environmentally friendly and non-polluting material, has an easy manufacturing process, and has high conversion efficiency, high color rendering, wide color temperature range, and excellent photoelectric characteristics.

Description

Siloxane organic fluorescent powder and preparation method thereof

The invention relates to a method and application for preparing an organic light-emitting material, in particular a siloxane organic fluorescent powder.

Phosphors use electronic transitions to produce fluorescence. When the phosphor is stimulated by light, its electrons are excited to a high-energy-level excitation state, and then return to the original low-energy-level state, the energy will be radiated in the form of light.

So far, white light-emitting diodes are still dominated by blue light-emitting diodes that excite yellow (inorganic) phosphors, such as YAG (yttrium aluminum garnet) phosphors with blue light-emitting diodes. Although white light-emitting diodes produced in this way have high luminous efficiency, most of the light emitted by the components is cold white light with high color temperature and contains a large amount of blue light; except for the lack of red light band, the color rendering is low. It is also bad for human health. In addition, most white light emitting diodes on the market use fluorescent materials doped with rare earth elements. Rare earth elements are expensive and not environmentally friendly. In addition, the manufacturing method of this type of fluorescent powder uses solid-state sintering, and its process temperature is higher than 1000 ° C. It is also necessary to introduce hydrogen to reduce rare earth elements, so that the manufacturing cost and danger are high.

Taiwan Patent Application No. 102112135, the application date is April 3, 2013, entitled "Method for Making Zinc Sulfide Nanoparticles Doped with Metal Ions and Method for Applying Photoluminescence to Warm White Light", discloses a method for producing a dopant by solution method Heteromanganese zinc sulfide nano particles (or quantum dots) replace traditional fluorescent materials doped with rare earth elements. However, the optimal absorption wavelength of manganese-doped zinc sulfide nano-particles lies in the wavelength of ultraviolet light (that is, the wavelength is less than 400 nanometers (nm)), which is limited in application.

In addition, in recent years, manganese-doped zinc selenide nano particles (ZnSe: Mn) have also been developed to replace traditional rare earth element fluorescent materials. The synthesis methods of such nanoparticles are mostly nucleation doping, and metal organic compounds are used as a source of metal ions. In the nucleation doping process, a manganese ion precursor solution is injected into the selenium ion precursor solution. The selenium ion precursor solution is generally toxic, unfriendly to the environment, and expensive. In addition, the nucleation doping method requires two stages of growth of manganese selenide (MnSe) and zinc selenide (ZnSe), which grow at a high temperature of about 300 ° C, which is difficult to produce, and the manganese doped zinc selenide nanoparticles Poor dispersibility results in poor luminous efficiency. In addition, its optimal absorption wavelength is located in the ultraviolet light band, and its application is limited.

Taiwan Patent Application No. 104104303, filed on February 9, 2015, entitled "Method for Making the Rare Earth-Free Fluorescent Material with the Strongest Absorption Wavelength Between 410 nm (nm)-470 nm (nm) and Application of Light "Methods for white light emission", using cheap, environmentally friendly materials, and a simple and low-cost method to produce manganese-doped selenide excited by blue light (440-470 nm) and emitting 500-700 nm yellow orange light Zinc nanoparticles. Furthermore, using this rare earth-free fluorescent material and organic materials that emit green or orange light when excited by blue light, it can be made into a white fluorescent solution or a white fluorescent film, which can produce suitable for daily lighting, low color temperature, and will not harm the human body. White light.

On the other hand, conventional techniques also use organic phosphors to make white light-emitting diode elements. For example, the 2008 master's thesis "Research on the Application of Organic Phosphor C545P in White Light-Emitting Diode Encapsulation" published by Zhang Jingzheng of Cheng Kung University in 2008 did two studies: 1. Excitation with ultraviolet diode (380nm) C545P white light emitting diode of organic phosphor; 2. White light emitting diode of red / C545P mixed phosphor excited by blue light emitting diode (460nm). Both of the above methods can obtain white light emitting diode elements with high color rendering.

The stability of fluorescent materials used in light-emitting diodes (LEDs) is usually considered in two different levels: environmental stability and thermal stability. However, the production of white light-emitting diode elements with organic phosphors cannot meet the requirements in terms of these characteristics, and it cannot actually be applied to the industry. The industry still needs to develop a new fluorescent material to meet the requirements of environmental protection, easy process, high conversion efficiency (energy-conversion efficiency), high color rendering, wide-range color temperature range, and good reliability and photoelectric characteristics.

The invention relates to a method for preparing and applying a siloxane organic fluorescent powder.

According to an embodiment of the present invention, a siloxane organic phosphor includes an organic dye, a siloxane compound, and an organic layer. Organic dyes can absorb short-wavelength excitation light and emit long-wavelength radiation. The siloxane compound is bonded to the organic layer, and the organic layer is bonded to the organic dye. Thereby, the organic layer promotes the luminous efficiency of the organic dye, and the siloxane is isolated from the external environment.

According to another embodiment of the present invention, a method for manufacturing a siloxane organic phosphor includes the following steps: drying a siloxane polymer solution to form a siloxane polymer powder, wherein A polymer of the siloxane compound is bonded to an organic layer; the polymer powder of the siloxane compound and an organic base powder are dissolved in a solvent to form a first solution; and an organic dye powder is dissolved in the first solution. The solution; removing the solvent in the first solution to make it a solid, and grinding the solid to form a siloxane organic phosphor.

According to the embodiment of the present invention, the siloxane organic phosphor can be used to isolate the environment and increase the volume of the powder to improve the dispersibility of the organic dye. The organic layer can improve the produced siloxane organic phosphor. The photoelectric properties and reliability of the organic silicon phosphor produced by the siloxane are at least 90%.

According to another embodiment of the present invention, a siloxane organic phosphor includes a first organic dye and a second organic dye. The first organic dye can absorb blue excitation light and emit green light. The second organic dye can absorb blue excitation light and emit red light. The first organic dye and the second organic dye are respectively bonded to an organic layer, and the organic layer is bonded to a siloxane compound. As a result, after being excited by blue light, the siloxane organic phosphor can emit warm white light with a color rendering performance above 95 and a wide color temperature range between 2500K ~ 4000K.

Hereinafter, the embodiments of the present invention will be described in detail, and illustrated with the drawings. In addition to these detailed descriptions, the present invention can be widely practiced in other embodiments, and easy replacements, modifications, and equivalent changes of any of the embodiments are included in the scope of this case, and the scope of the following patents is quasi. In the description of the specification, in order to provide the reader with a more complete understanding of the present invention, many specific details are provided; however, the present invention may be implemented without omitting some or all of these specific details. In addition, well-known program steps or elements have not been described in details to avoid unnecessary limitations of the present invention.

An embodiment of the present invention discloses a siloxane organic phosphor, which includes an organic dye, a siloxane compound, and an organic layer. Organic dyes can absorb short-wavelength excitation light and emit long-wavelength radiation. The surface of the siloxane compound is modified to bond the organic layer, and the organic layer and the organic dye are bonded or react with each other. Thereby, the organic layer promotes the luminous efficiency of the organic dye, and the siloxane is isolated from the external environment.

In some embodiments, the siloxane compound comprises siloxane, silica, or other silane-containing polymers.

In one embodiment, the structure of the modified siloxane-bonded organic layer includes siloxide, and its chemical formula is R ₃ SiOM, where R is an organic group and M is a metal.

In some embodiments, the structure of the modified siloxane silane-bonded organic layer includes one or more of the following functional groups: Si-H, Si-R, and Si-O Radical (Si-O).

In some embodiments, the structure of the modified siloxane-bonded organic layer includes tetramethyltetradisiloxane, hexamethyldisilazane, hexamethylcyclotrisiloxane, Methylcyclotetrasiloxane.

In one embodiment, the siloxane compound includes a structure as shown in FIG. 2.

In some embodiments, the organic dye contains at least one of the following functional groups: Ester (ester), Nitrile (nitrile).

According to the embodiment of the present invention, the organic dye can absorb short-wavelength excitation light and emit long-wavelength radiant light, and different types of organic dyes are selected according to the required color of the radiant light. For example, the organic dye used to emit green light can be selected from one or a combination of the following groups: C545T, C545P, Alq3, BA-NPB, TPA. Organic dyes used to emit red light can be selected from one or a combination of the following groups: DCJTB, DCQTB (C ₂₈ H ₃₁ N ₃ O), PtOEP, Ir (dpm) (piq) 2, Ru (dtb-bpy) 3 ∙ 2 (PF6).

The Chinese name of the organic dye C545T is 2-tert-butyl-4- (dicyanomethylene) -6- [2- (1,1,7,7-tetramethyljulonidin-9-yl) Vinyl] -4H-pyran, English name is 2-tert-Butyl-4- (dicyanomethylene) -6- [2- (1,1,7,7-tetramethyljulolidin-9-yl) vinyl] -4H-pyran The chemical formula is C ₂₆ H ₂₆ N ₂ O ₂ S. The Chinese name of Alq3 is 8-hydroxyquinoline aluminum, the English name is Tris (8-quinolato) aluminium (III), and the chemical formula is C ₂₇ H ₁₈ AlN ₃ O ₃ . The Chinese name of BA-NPB is N, N'-di-1-naphthyl-N, N'-diphenyl- [9,9'-bianthracene] -10,10'-diamine, and the English name is N10 , N10'-diphenyl-N10, N10'-dinaphthalenyl-9,9'-bianthracene-10,10'-diamine, and the chemical formula is C ₆₀ H ₄₀ N ₂ . The Chinese name of TPA is triphenylamine, the English name is Tripheneylamine, and the chemical formula is C ₁₈ H ₁₅ N. The Chinese name of DCJTB is 2-tert-butyl-4- (dicyanomethylene) -6- [2- (1,1,7,7-tetramethyljulonidin-9-yl) vinyl ] -4H-pyran, English name is 2-tert-Butyl-4- (dicyanomethylene) -6- [2- (1,1,7,7-tetramethyljulolidin-9-yl) vinyl] -4H-pyran, C30H ₃₆ N ₃ O. The chemical formula of DCQTB is C ₂₈ H ₃₁ N ₃ O. The Chinese name of PtOEP is octaethylporphine platinum, and its chemical formula is C ₃₆ H ₄₄ N ₄ Pt. The chemical formula of Ir (dpm) (piq) 2 is C ₄₁ H ₃₉ IrN ₂ O ₂ . The chemical formula of RU (DTB-BPY) 3 · 2 (PF6) is C ₅₄ H ₇₂ F ₁₂ N ₆ P ₂ Ru.

FIG. 1 is a flowchart showing a method for producing a siloxane organic phosphor according to the foregoing embodiment of the present invention. Referring to FIG. 1 and step 10, drying a siloxane polymer solution to form a siloxane polymer powder, wherein the siloxane polymer is bonded to an organic layer after surface modification. . For example, the siloxane polymer solution is placed in a vacuum oven and baked at a temperature of 150 to 180 ° C. for about 1 to 3 hours to form a siloxane polymer powder including an organic layer.

As shown in FIG. 1, in step 11, the siloxane polymer powder and an organic base powder are dissolved in a solvent to form a first solution. The solvent may include, but is not limited to, polar or non-polar solvents such as n-hexane, cyclohexanone, ethyl acetate, acetone, methanol, ethanol, isopropanol, and tetrahydrofuran. An ultrasonic vibrator can be used to accelerate the dissolution process. The function of the organic base can balance the acidity of the siloxane polymer and improve the environmental stability, thermal stability, and reliability of the siloxane organic fluorescent powder produced. The organic base may include, but is not limited to, sodium methoxide, potassium ethoxide, potassium t-butoxide, butyllithium, phenyllithium, or an organic compound containing an amino group in the molecule.

As shown in FIG. 1, in step 12, an organic dye powder is dissolved in the first solution. As described above, a suitable organic dye and a solvent capable of dissolving the organic dye and the polymer of the siloxane compound are selected according to the emission band to be emitted. An ultrasonic vibrator can be used to accelerate the dissolution process.

As shown in FIG. 1, in step 13, the solvent in the first solution is removed to become a solid, and the solid is ground to form a siloxane organic fluorescent powder. For example, the first solution is placed in a vacuum oven and baked at a temperature of 100 to 180 ° C. for about 3 to 5 hours. After curing, the first solution is ground with a grinder to form a siloxane organic fluorescent powder.

3 and 4 are Raman spectrum and Fourier transform infrared spectrum (FTIR) diagrams of a siloxane compound after surface modification bonding an organic layer according to an embodiment of the present invention. From the above figure and experimental results, it can be seen that the ester (Ester) RCOOR functional group of the organic dye reacts with the modified siloxane (Si-O) functional group of the siloxane, and is converted into the silicon of the siloxane organic phosphor. Silyl ester RCOOSiR functional group.

Example 1

In this example, C545T is selected as the organic dye, and a siloxane as shown in FIG. 2 is used, and an organic fluorescent powder is prepared by the method as shown in FIG. 1. FIG. 5 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 1. The excitation spectrum is the absorption spectrum. At the same time, the PL excitation spectrum (left) and PL emission spectrum (right) of the pure organic dye C545T are also put on for comparison. As shown in FIG. 5, the optimal excitation range of the siloxane organic phosphor produced in Example 1 falls between 440-470 nm (the emission range of a commercial blue LED), and the wavelength of the emitted light falls between 500-530 nm. The conversion efficiency of this green-emitting siloxane organic phosphor is higher than 95%, and its luminous efficiency is better than that of the organic dye C545T.

Example 2

In this example, the organic dye is DCJTB, and a siloxane as shown in FIG. 2 is used, and a siloxane organic phosphor is prepared by the method shown in FIG. 1. FIG. 6 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 2. At the same time, the PL excitation spectrum (left) and PL emission spectrum (right) of the pure organic dye DCJTB are also put on for comparison. As shown in FIG. 6, the optimal excitation range of the siloxane organic phosphor manufactured in Example 2 falls between 440-470 nm (the emission range of a commercial blue LED), and the wavelength of the emitted light falls between 600-630 nm. The conversion efficiency of this red-emitting siloxane organic phosphor is more than 90%, and its luminous efficiency is better than that of the organic dye DCJTB.

Example 3

In this example, TPA is used as the organic dye, and a siloxane as shown in FIG. 2 is used, and a siloxane organic phosphor is prepared by the method shown in FIG. 1. FIG. 7 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 3. At the same time, the PL excitation spectrum (left) and PL emission spectrum (right) of the pure organic dye TPA are put on for comparison. As shown in FIG. 7, the optimal excitation range of the siloxane organic phosphor manufactured in Example 3 falls between 440-470 nm (the emission range of a commercial blue LED), and the emission wavelength falls between 500-530 nm. The conversion efficiency of this green-emitting siloxane organic phosphor is more than 90%, and its luminous efficiency is better than that of the organic dye TPA.

Example 4 (application)

The green light-emitting siloxane organic phosphor produced in Example 1 and the red light-emitting siloxane organic phosphor produced in Example 2 were doped in a lens, or coated and formed on a substrate, and then By using a blue LED with an emission wavelength between 440-470nm as the excitation light source, white light with a color rendering greater than 95% and a conversion efficiency higher than 90% can be obtained. The mixing ratio of the green siloxane organic phosphor and the red siloxane organic phosphor is in the range of 1: 1 to 1: 3.4 (unit: gram), and the silica with a color temperature range of 2500K to 4000K can be obtained. Alkane organic phosphor.

FIG. 8A shows the PL emission spectrum of the warm white light-emitting siloxane organic phosphor produced in Example 4, wherein the mixing ratio of the green siloxane organic phosphor and the red siloxane organic phosphor is 1: 3.4, The excitation light has a wavelength of 450 nm. FIG. 8B shows a color coordinate diagram CIE-1931 (X: 0.4691, Y 0.4735) of the siloxane organic phosphor with warm white light produced in Example 4. FIG. (The mixing ratio of the green light siloxane organic phosphor and the red light siloxane organic phosphor is 1: 3.4; color temperature: 3000K)

characteristic

According to the embodiment of the present invention, a siloxane organic fluorescent powder is synthesized from a surface-modified siloxane, so that the dispersibility of the organic dye is increased, and the prepared siloxane organic fluorescent powder has good luminous efficiency.

According to the embodiment of the present invention, the siloxane-bonded organic layer can effectively improve the photoelectric properties and reliability of the produced siloxane organic phosphor. FIG. 9 is an excitation spectrum and an emission spectrum of a siloxane organic phosphor made of a general SOG silicon oxide (without an organic layer) and a siloxane oxide having an organic layer in this case. As shown in Figure 9, the number of photons emitted by the siloxane organic phosphor of this case (56308 total spectral integration) is compared with the emitted light of organic phosphors made with general SOG silicon oxide (without organic layer). The number of photons (the total number of spectral integrations is 17937) is increased by at least 70%. This proves that the siloxane organic fluorescent powder made from the modified siloxane bonded organic layer can greatly improve the luminous efficiency of the siloxane organic fluorescent powder.

The siloxane organic fluorescent powder provided according to the embodiment of the present invention is an environment-friendly and non-polluting material without rare earths. The manufacturing process does not require high temperature and high pressure conditions, and the process is simple. In addition, this novel siloxane organic phosphor has high conversion efficiency, high color rendering, good reliability, a wide range of color temperature, and good thermal stability, which can make up for the lack of color rendering of today's rare earth phosphors (such as The color rendering of YAG: Ce yellow phosphor is only about 70), the color temperature is not easy to adjust, and it lacks some emission bands (such as β-SiAlON: Eu green phosphor has a 540-550nm emission wavelength that is too yellow and green).

For each / all embodiments disclosed in this specification, those skilled in the art can make various modifications, changes, combinations, exchanges, omissions, substitutions, equivalent changes accordingly, as long as they are not mutually exclusive, they all belong to the concept of the present invention. , Belongs to the scope of the present invention. Structures or methods that may correspond to or be related to the features of the embodiments described in this case, and / or any application, abandonment, or approved application by the inventor or assignee are incorporated herein as part of the description of this case. The incorporated part includes part or all of its corresponding, related, and modified, (1) operable and / or constructable (2) modified into operable and / or constructable according to those skilled in the art (3) Implement / manufacture / use or incorporate any part of the description of this case, the related applications of this case, and the common sense and judgment of those skilled in the art.

Unless otherwise specified, some conditionals or auxiliary words, such as "can", "could", "might", or "may", usually attempt to express that the embodiment in this case has, but It may also be interpreted as a feature, element, or step that may not be needed. In other embodiments, these features, elements, or steps may not be required.

The contents of the aforementioned documents are incorporated herein as part of the description of this case. The embodiments provided by the present invention are merely examples, and are not intended to limit the scope of the present invention. The features or other features mentioned in the present invention include method steps and techniques, and can be combined or changed in any way with the features or structures described in related applications, in part or in whole, which can be regarded as unequal, separate, Irreplaceable embodiment. The corresponding or related features and methods disclosed in the present invention include those that can be derived from the text, non-mutually exclusive, and modifications made by those skilled in the art, some or all of which can be (1) operable and / Or constructable (2) modified to be operable and / or constructable according to the knowledge of those skilled in the art (3) implemented / manufactured / used or combined with any part of the description of the case, including (I) the present invention or Any one or more parts of a structure and method, and / or (II) any alteration and / or combination of the content of any one or more inventive concepts and parts thereof, including any one or more of the features Or any changes and / or combinations of the content of the embodiments.

10-14‧‧‧Manufacturing steps of siloxane organic phosphor

FIG. 1 is a flowchart illustrating a method for preparing a siloxane organic phosphor according to an embodiment of the present invention.

FIG. 2 shows a structure of a siloxane according to an embodiment of the present invention.

3 and 4 are Raman spectrum and Fourier transform infrared spectrum (FTIR) diagrams of a siloxane compound after surface modification bonding an organic layer according to an embodiment of the present invention.

FIG. 5 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 1 and a comparative sample.

FIG. 6 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 2 and a comparative sample.

FIG. 7 shows the PL excitation spectrum (left) and PL emission spectrum (right) of the siloxane organic phosphor produced in Example 3 and a comparative sample.

FIG. 8A shows the PL emission spectrum of the warm white light siloxane organic phosphor produced in Example 4. FIG.

FIG. 8B shows a color coordinate diagram of the warm white light-emitting siloxane organic phosphor manufactured in Example 4. FIG.

Figure 9 shows the test results of the photoelectric properties of the siloxane organic phosphor of the present case and comparative samples.

Claims (9)

A siloxane organic phosphor includes: an organic dye that absorbs short-wavelength excitation light and emits long-wavelength radiation. The organic dye includes at least one of the following functional groups: Ester (ester), Nitrile (nitrile); Siloxane; and an organic layer, wherein the siloxane is bonded to the organic layer, the organic layer is bonded to the organic dye, and the structure of the siloxane bonded to the organic layer includes tetramethyldisilazide Oxane, hexamethyldisilaxane, hexamethylcyclotrisiloxane, or tetramethylcyclotetrasiloxane; by this, the organic layer promotes the luminous efficiency of the organic dye, and the siloxane oxide is isolated external environment. For example, the siloxane organic phosphor according to item 1 of the patent application scope, wherein the siloxane compound includes siloxane, silica, or other silane-containing polymers. For example, the siloxane organic phosphor of the first scope of the patent application, wherein the structure of the siloxane bond to the organic layer includes one or more of the following functional groups: Si-H, Si-H -R), siloxane (Si-O). For example, the siloxane organic phosphor of the first scope of the patent application, wherein the siloxane oxide contains the following structure: For example, the siloxane organic phosphor of the first patent application scope, wherein the organic dye contains C545T, C545P, Alq3, BA-NPB, TPA, DCJTB, DCQTB, PtOEP, Ir (dpm) (piq) 2, or Ru (dtb-bpy) _3. (PF6). A method for manufacturing a siloxane organic fluorescent powder includes the following steps: drying a siloxane polymer solution to form a siloxane polymer powder, wherein the polymer bond of the siloxane is An organic layer is formed, and the structure in which the siloxane compound is bonded to the organic layer includes tetramethyldisilaxane, hexamethyldisilaxane, hexamethylcyclotrisiloxane, or tetramethylcyclotetrasiloxane Siloxane; dissolving the polymer powder of siloxylate and an organic base powder in a solvent to form a first solution; dissolving an organic dye powder in the first solution, the organic dye powder including the following At least one functional group: Ester (ester), Nitrile (nitrile); removing the solvent in the first solution to form a solid, and grinding the solid to form a siloxane organic fluorescent powder. For example, the method for manufacturing a siloxane organic phosphor powder according to item 6 of the patent application, wherein the organic base powder comprises: sodium methoxide, potassium ethoxide, potassium t-butoxide, butyllithium, phenyllithium, or an amino group in the molecule Organic compounds. A siloxane organic fluorescent powder includes: a first organic dye that absorbs blue excitation light and emits green light; a second organic dye that absorbs blue excitation light and emits red light; wherein the first organic dye The dye and the second organic dye are respectively bonded to an organic layer, and the organic layer is bonded to a siloxane. The structure of the siloxane bonded to the organic layer includes tetramethyldisilazane and hexamethyl. Disiloxane, hexamethylcyclotrisiloxane, or tetramethylcyclotetrasiloxane, the first organic dye and the second organic dye contain at least one of the following functional groups: Ester (ester), Nitrile (nitrile ); In this way, after being excited by blue light, the siloxane organic phosphor can emit white light with an excellent temperature range of 2500K ~ 4000K. A siloxane organic phosphor includes: an organic dye that absorbs short-wavelength excitation light and emits long-wavelength radiation. The organic dye includes at least one of the following functional groups: Ester (ester), Nitrile (nitrile); Siloxane; and an organic layer, wherein the siloxane is bonded to the organic layer, the organic layer is bonded to the organic dye, and the structure after the siloxane is bonded to the organic layer includes a siloxy group A metal (siloxide) having a chemical formula of R ₃ SiOM, wherein R is an organic group and M is a metal; thereby, the organic layer promotes the luminous efficiency of the organic dye, and the siloxane isolates the external environment.