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WO2024236144A1 - Siloxanes modifiés, procédé de modification de siloxanes et leur utilisation - Google Patents

Siloxanes modifiés, procédé de modification de siloxanes et leur utilisation Download PDF

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Publication number
WO2024236144A1
WO2024236144A1 PCT/EP2024/063598 EP2024063598W WO2024236144A1 WO 2024236144 A1 WO2024236144 A1 WO 2024236144A1 EP 2024063598 W EP2024063598 W EP 2024063598W WO 2024236144 A1 WO2024236144 A1 WO 2024236144A1
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siloxane
filler
properties
matrix
pimos
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Cathy TRUMBLE
Alan Piquette
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Ams Osram International GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/32—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the present application claims priority of US application US 63/503,081 dated May 18, 2023, the content of which is incorporated herein by reference in its entirety.
  • the present invention concerns modified siloxanes, a method for modifying siloxanes, use of the modified siloxanes as filler, a filler containing or consisting of said modified siloxanes and optoelectronic devices containing said fillers.
  • BACKGROUND Filler materials are commonly added to various types of chemical formulations to alter properties (such as physical, optical, and/or mechanical properties) to optimize performance or robustness of the resulting component/product.
  • filler material includes a wide range of solid materials that can take various physical forms such as powders, fibres, whiskers, platelets, and nano-materials.
  • the chemical make-up of the filler material varies depending on the desired properties of the filler.
  • filler materials can be used in optoelectronic devices that make use of phosphor-converted LEDs (Light Emitting Diodes) to generate light with a desired emission spectrum.
  • a particular class of wavelength converter are phosphor-in-matrix-on-substrate (PiMoS) and phosphor-in matrix (PiM) wavelength converter. Fillers can be added to the matrix phase to optimize properties and performance of the optoelectronic device.
  • the most common fillers for PiMoS and PiM converter elements include fumed silica, fused silica powder (0.5-10 ⁇ m particle size) and polymethylsiloxane powders (0.8-8 ⁇ m particle size). While these materials are available as spherical powders with similar particle sizes, the material properties are very different.
  • the polymethylsilioxane powders hybrid organic/inorganic structure
  • silica powders are high temperature inorganic materials that have very low coefficient of thermal expansion (CTE).
  • the significant difference in 2022PF02477 - 2 - physical properties between polymethysiloxane and fused silica powders leaves a large gap where fillers with intermediate properties would be beneficial to meet the demands of various end-use applications. This issue will be described in the following in more detail.
  • the primary filler material for PiMoS wavelength converters is fused silica powder. Fused silica fillers are commonly made using a powder flame- spray process, where the powder typically has spherical shaped particles with a fairly-wide particle size distribution. The chemical purity of the material depends on the precursor material used in the process. A second class of silica filler is produced using high purity precursors and a sol-gel processing method.
  • Silica powders can be made with spherical particles, narrow particles distribution and high chemical purity. These type of silica fillers are currently being evaluated in PiMoS wavelength converters. Siloxane (polymethylsiloxane) powder materials are currently being evaluated for use in PiMoS and PiM wavelength converters. While siloxane powders are used for various technical applications, they are widely used in the cosmetic industry; they are available from many vendors in a wide range of particle sizes and typically have narrow particle size distributions. Siloxane powders have very different material properties than fused silica.
  • modifying means that the chemical composition and/or the properties of the siloxane after the heat treatment in an oxygen-containing environment (modified siloxane) are different from the chemical composition and/or properties of the siloxane used as the starting material.
  • Siloxanes are chemical compounds that comprise a backbone of alternating silicon-oxygen [Si-O] units with organic side groups attached to each silicon atom.
  • Oligomeric or polymeric organosiloxanes silicones. They have long Si-O main chains and are viscous or permanently elastic, depending on their molar mass and crosslinking. If they are liquid, they are also called silicone oils.
  • siloxanes used can be those siloxanes which are known to be used in filler materials in optoelectronic devices which for example make use of phosphor-converted LEDs (Light Emitting Diodes) to generate light with a desired emission spectrum, for example phosphor-in-matrix- on substrate (PiMoS) and phosphor-in-matrix (PiM). 2022PF02477 - 4 -
  • siloxane powders used as the starting material in the present invention are based on CH 3 (SiO 3/2 ) (T-units).
  • polysiloxane materials that contain a combination of Q-unit, T-unit, D-unit and M-unit bonding and some combination of methyl and phenyl groups could be used.
  • the general formula for the starting polysiloxane powder would be [RSiO 3/2 ] x [R 2 SiO] y [R 3 SiO 1/2 ] z , where R can be any combination of methyl and phenyl groups, and x, y, and z are the relative amounts of T-unit, D-unit, and M-unit siloxane bonding, respectively.
  • x + y + z 1, 0.5 ⁇ x 1.0, 0 0.5, and 0 z ⁇ 0.1.
  • the ability to tune the properties of the filler is for example suitable when working to balance (or optimize) the properties of PiMoS or PiM wavelength converters.
  • the composite structure of the PiMoS or PiM converter is sensitive to any change in properties, where there is a fine balance required to achieve the desired properties.
  • Modified siloxane-based fillers can be tuned to fill the large gap in properties between siloxane and fused silica fillers.
  • the present invention provides a method to make filler materials that range in properties from siloxane-like to silica-like so that for example PiM and PiMoS converter properties can be optimized for performance and reliability.
  • siloxane powders can be modified with controlled thermal treatment (for example in air) of the powder at specified temperatures as indicated above to decrease the silanol (Si- OH) and CH 3 -group content of the material.
  • Material properties can be 2022PF02477 - 5 - tuned from siloxane-like to silica-like, by using different thermal treatments, to optimize the performance of the end-use application.
  • the ability to tune the properties of the filler is important when working to balance (or optimize) the properties of PiMoS or PiM wavelength converters.
  • the composite structure of the PiMoS or PiM converter is sensitive to any change in properties, where there is a fine balance required to achieve the desired properties.
  • the siloxane powders have a high purity and are low-cost precursor materials for fabrication of heat-treated modified siloxane fillers.
  • a basic thermal process is used to modified siloxane fillers once the appropriate thermal profile has been identified.
  • a range of siloxane- based filler properties can be achieved by altering the thermal profile.
  • the primary advantage of this invention is the ability to tune properties of the siloxane-based filler material to meet the specifications of the end-product, which in this case is a wavelength converter for LED optoelectronic devices.
  • PiMoS wavelength converters have a complex, composite structure that requires a fine- tuned balance/optimization of properties.
  • a tunable filler is advantageous in striking a balance in the overall properties, performance, and reliability of the LED optoelectronic device.
  • the siloxane powder precursor material is a high purity material that is readily available as spherical particles in the 0.8 to 15 ⁇ m range, with narrow particles size distributions. These siloxane powders are commercially available wherein the vendor indicates the particle size.
  • the siloxanes are subjected to a heat treatment at a temperature of about 200 °C to about 500 °C, for example about 200 °C to about 425 °C, like about 370 °C to about 410 °C.
  • the heating can be achieved in any apparatus suitable for adjusting these temperatures.
  • the apparatus can be a usual furnace.
  • the heat treatment is carried out in that the siloxane used as the starting material is maintained at the desired temperature as outlined above. According to the present invention, it is possible that the heat treatment is carried out at one temperature or alternatively at at at least two different temperatures, for example 2, 3, 4 or 5 different temperatures, each lying within the temperature range of about 200 °C to about 500 °C.
  • the siloxane can be maintained at a first temperature for a certain time and then at a second and optionally further temperatures for further periods of time, wherein the temperatures are different from each other and each of the temperature is lying within the temperature range of about 200 °C to about 500 °C.
  • the temperature in order to reach the desired temperature for the heat treatment, can be increased from ambient temperature, for example room temperature, or at least a temperature lower than the temperature of the heat treatment, in a thermal ramp rate of about 1.0°C/min. to about 20°C/min., for example about 2 °C/min. to about 5°C/min., like about 2°C/min.
  • the heat treatment can be carried out for about 0.5 hour to about 24 hours, for example about 2 hours to about 8 hours, like about 6 hours for achieving the heat treatment.
  • oxygen-containing environment used according to the present invention means that the siloxane used as the starting material is surrounded by a gas/gaseous mixture at least containing oxygen.
  • gas/gaseous mixture containing oxygen can be the mixture of oxygen with other gases, for example inert gases, like nitrogen and/or argon.
  • the oxygen-containing environment can contain about 5 vol.-% to about 30 vol.-% oxygen.
  • the oxygen-containing environment is air. 2022PF02477 - 7 - This excludes that the siloxane to be modified is present in a solid matrix.
  • Siloxane (polymethysiloxane) fillers have the chemical composition of CH 3 (SiO 3/2 ), while silica fillers have the chemical composition of SiO 2 .
  • Heating siloxanes to temperatures of about 200°C to about 500°C results in decreasing the silanol (Si-OH) content by forming Si-O-Si bonds (i.e., condensation reactions), thus changing the properties of the filler.
  • modified siloxane fillers can be made by using slightly different thermal treatments, thus producing fillers with a range of properties that fill the gap between siloxane and fused silica fillers.
  • modified siloxane filler (with silica-like properties) according to the present invention was substituted for siloxane filler for a PiMoS converter.
  • the delamination at the PiM-substrate interface decreased from 14% to 2.2% following a slow thermal ramp 200 °C cure.
  • the PiMoS converter platelets showed increased brightness vs. use of the fused silica filler (made with powder flame-spray process). Tuning the properties of the filler resulted in optimizing the properties of the PiMoS converter.
  • the present invention relates to the use of the modified siloxane according to the present invention or the modified siloxane obtained by the method according to the present invention as a filler, for example as a filler employed in a wavelength converter, wherein the wavelength converter for example can be a phosphor-in- matrix wavelength converter or a phosphor-in-matrix-on-substrate wavelength converter.
  • a filler for example can be a phosphor-in- matrix wavelength converter or a phosphor-in-matrix-on-substrate wavelength converter.
  • Such converters are known to the person skilled in the art so that the skilled person knowns how to use the fillers of the present invention in a matrix of such converters.
  • a filler containing or consisting of the modified siloxane according to 2022PF02477 - 8 - the present invention and/or the modified siloxane obtainable by the method according to the present invention.
  • the filler can have the form of spherical powders with various particle sizes.
  • the filler can have an average size of about 0.8 ⁇ m to about 10 ⁇ m, for example about 0.8 ⁇ m to about 8 ⁇ m.
  • the average particle size mentioned in the present application means the d50 value.
  • the siloxanes are commercially available and the particle sizes have been indicated by the vendors.
  • an LED optoelectronic device component having a matrix containing a filler, wherein the filler comprises or consist of the modified siloxane according to the present invention and/or the modified siloxane obtained by the method according to the present invention.
  • LED optoelectronic device components are phosphor-in-matrix-on- substrate and phosphor-in-matrix wavelength converters.
  • Matrix Material The matrix material can be a polysiloxane.
  • the polysiloxane can be a methyl polysiloxane with exclusively T-unit bonding.
  • Alternative embodiments would allow for some combination of T-unit, D-unit, and M- unit bonding and some combination of methyl and phenyl groups.
  • the general formula for the cured polysiloxane would be [RSiO 3/2 ] x [R 2 SiO] y [R 3 SiO 1/2 ] z , where R could be any combination of methyl and phenyl groups, and x, y, and z are the relative amounts of T-unit, D-unit, and M-unit siloxane bonding, respectively.
  • x + y + z 1, and 0.5 z ⁇ 0.1.
  • the matrix material could also be a type of glass. There should be no carbon-carbon bonds in the polymer chain.
  • the crosslinking throughout the entire matrix should be made from silicon-oxygen bonds.
  • R phenyl
  • This lack of carbon-carbon bonds in the main polymer chain differentiates 2022PF02477 - 9 - this invention from any invention that uses silicones (or siloxanes) that are based on addition curing, i.e., systems that crosslink via a Si-H group on one material and vinyl group on another.
  • Optional Fillers 2022PF02477 - 10 - Fumed silica could be present in the phosphor-in-matrix layer in the range of 0vol.-% to 15vol-.%.
  • the fumed silica would be preferably of hydrophobic type and have surface area greater than 175m 2 /g.
  • Fused silica could be present in the phosphor-in-matrix layer in the range of 0vol.-% to 35vol.-%.
  • the fused silica particle diameter would be in the range of 0.1 ⁇ m to 15 ⁇ m.
  • the fused silica should be spherical- like in shape.
  • the particles could be porous or non-porous.
  • Polysilsesquioxane particles could be present in the phosphor-in-matrix layer in the range of 0vol.-% to 35vol.-%.
  • the polysilsesquioxane particles can be spherical-like in shape and be in the size range of 0.1 ⁇ m to 10 ⁇ m.
  • Filler material should not be limited to the above examples. It could be sapphire spheres, ZnO, TiO 2 , etc. or materials transparent in the UV/visible/IR wavelengths.
  • Substrate The substrate can be glass.
  • the type of glass can be borosilicate, but other types of glass could be used, such as aluminosilicate or others.
  • the substrate can also be fused silica.
  • the substrate can be sapphire, quartz, or any other transparent crystalline or polycrystalline material.
  • the surface of the substrate, opposite the phosphor-in-matrix layer, could be modified to change the way light propagates through the converter.
  • an anti-reflective coating can be applied to the exit surface of the substrate.
  • a dielectric stack can be coated on the exit surface of the substrate to modify the transmittance of the light as a function of wavelength and/or angle.
  • the exit surface of the substrate can be roughened to change the light extraction behavior.
  • a micro-lens array, meta-lens, or photonic crystal can be made on the exit surface of the substrate to alter the light propagation according to the needs of a given application.
  • FIG. 1 shows schematically a phosphor-in-matrix-on-substrate (PiMoS) wavelength converter.
  • Figure 2 shows an overview of polymethysiloxane (siloxane) filler and fused silica filler properties with respect to PiM formulations; a large gap in properties exists between these two filler materials.
  • Figure 3 illustrates schematically a polymethylsiloxane (siloxane) particle based on CH 3 (SiO 3/2 ) chemistry, containing T-units in a 3- dimentional structure; the T-unit content in the structure may vary for various commercially available products.
  • Figure 4 shows a TGA plot of weight loss of siloxane powders as a function of temperature; TGA evaluation at 10°C/min to 600°C in air.
  • Figure 5 shows a TGA evaluation of the heat-treated 4 ⁇ m siloxane powders to determine the weight loss of the powder as a function of temperature, i.e., how much silanol and CH 3 is left in the structure following thermal treatment of the powder. TGA evaluation at 10°C/min to 600°C in air.
  • Figure 6 shows SEM images of original siloxane powders and heat-treated modified siloxane powders (5,000x magnification for all powders).
  • Figure 7 shows the % reflectance as a function of wavelength for various siloxane powder fillers (powder plaque measurements with a spectrophotometer).
  • Figures 8a and b show heat-treated siloxane powders: (a) high processing temperatures and limited air flow resulted in carbon trapped in the structure, as indicated by the grey powder, and (b) optimized processing temperatures and improved air flow resulted in a high purity modified siloxane powder.
  • Figure 9 shows a % reflectance comparison for the original 4 ⁇ m siloxane powder vs. modified 4 ⁇ m-HT400.
  • Figure 10 shows methyl polysiloxane-based matrix samples containing various filler types: siloxane, modified siloxane, and fused silica powder.
  • Figure 11 shows % transmittance spectra for matrix samples containing various filler types: siloxane, modified siloxane, and powders (samples were 0.34-0.35mm thick).
  • Figures 12a, b and c show % transmittance curves for matrix samples containing various filler types: (a) siloxane, (b) modified siloxane and (c) silica powder, subjected to thermal storage at 250°C for 24 hours.
  • Figures 13a and b show mechanical properties (3-point bend test) for matrix samples containing various filler types: siloxane, modified siloxane, and silica powder, (a) Breaking Force and (b) Youngs Modulus.
  • Figure 14a and b show an overview for two different thermally modified siloxane fillers: (a) 4 ⁇ m-HT360 is siloxane-like with improved thermal stability, and (b) 4 ⁇ m-HT410 is silica-like with lower CTE, higher breaking force and some scattering.
  • the 4 ⁇ m-HT360 modified siloxane powder is not moisture sensitive and has a good thermal stability (>400°C); the CH 3 content is still the same as the starting siloxane powder.
  • the thermal stability of the material has been significantly improved without losing the benefits of having an organic/inorganic hybrid structure. Properties will be siloxane-like but without a weight loss until >400°C.
  • the 4 ⁇ m-HT410 modified siloxane powder is most likely porous with a moisture sensitivity. The powder has a good thermal 2022PF02477 - 13 - stability (500°C) and only little if any CH 3 groups left.
  • the thermal stability of the material has been significantly improved and the properties will be silica-like. A low CTE of the material can help decrease stress when blended with Methyl Polysiloxane.
  • Figure 15 shows an overview of polymethysiloxane (siloxane) and fused silica filler properties with respect to PiM formulations; modified siloxane fillers can be prepared with a range of properties that falls between these filler materials to optimize wavelength converters for LED optoelectronic device performance and robustness.
  • the CH 3 content may vary. It is available in a wide range of sizes, with high purity available.
  • the Fused Silica powder contains SiO 2 with high purity available, a low CTE, blending with LRI (low refractive index) liquid Siloxanes and high temperature stability.
  • the modified Siloxane powder according to the present invention combines the benefits and advantages of both with additional a variable CTE, variable scattering in LRI liquid siloxanes, high thermal stability (>400°C) and variable mechanical properties.
  • Figure 16 shows % reflectance as a function of wavelength for siloxane and modified siloxane powder plaque measurements.
  • Figures 17a and 17b show a Trial 1 delamination at the PiM-glass interface was evaluated using an optical microscope with coaxial lighting, where the light-colored regions indicate delamination: (a) shows about 21% delamination for PiMoS converters cured at 200°C, while (b) shows about 14% delamination for PiMoS converters cured at 200°C using a slow thermal ramp rate.
  • Figures 18a and 18b show a Trial 2 delamination at the PiM-glass interface was evaluated using an optical microscope with coaxial lighting, where the light-colored regions indicate delamination: (a) shows about 6.5% delamination for PiMoS converters cured at 200°C, while (b) shows about 2.2% delamination for PiMoS converters cured at 200°C using a slow thermal ramp rate, which helped to reduce stress. 2022PF02477 - 14 - Figure 19 shows probability plots of surface roughness measurements for Trial 2 PiMoS 1” x 1” coupon; Sa, Sp, Sv and Sz are specified.
  • Figure 20a and 20b show SEM images of Trial 2 PiMoS surface at 3,000x magnification to evaluate surface features: (a) electron backscatter mode, and (b) topography mode.
  • Figures 21a and 21b show photometry data for Trial 2 PiMoS converter platelets, with comparison to the control PiMoS converter platelets: (a) color coordinate comparison, and (b) conversion efficiency comparison.
  • Figures 22a and 22b show delamination as a function of thermal storage at 250°C storage (1,188 hours) for Trial 2 PiMoS converter platelets: (a) Trial 2 cured with standard 200°C profile, and (b) Trial 2 cured with slow thermal ramp rate 200°C profile.
  • Inserted photos show delamination measurements of platelets, where the light-colored regions indicate delamination at the PiM-glass interface.
  • Figures 23a and 23b show color coordinate (Cx) thermal stability at 250°C storage (1,188 hours) for Trial 2 PiMoS converter platelets: (a) Trial 2 cured with 200°C profile, and (b) Trial 2 cured with slow thermal ramp rate 200°C profile.
  • Cx color coordinate
  • FIG. 23a and 23b show color coordinate (Cx) thermal stability at 250°C storage (1,188 hours) for Trial 2 PiMoS converter platelets: (a) Trial 2 cured with 200°C profile, and (b) Trial 2 cured with slow thermal ramp rate 200°C profile.
  • DETAILED DESCRIPTION The following embodiments and examples disclose various aspects and their combinations according to the proposed principle. The embodiments and examples are not always to scale. Likewise, different elements can be displayed enlarged or reduced in size to emphasize individual aspects.
  • HT360 means heat treated (HT) at 360°C.
  • Particle sizes mentioned throughout the present application that are stated for the siloxane and silica powders were provided from the vendors; the particle size is the d50 value.
  • SEM evaluation of powders was done at ams-OSRAM to compare the starting Siloxane powder vs. the modified Siloxane powder with regard to general particle size, particle distribution and whether or not significant fusing/agglomeration of the particles occurred during the thermal treatment.
  • Filler materials are commonly added to various types of chemical formulations to alter properties (such as physical, optical, and/or mechanical), to optimize performance or robustness of the resulting component/product.
  • the term “filler” material includes a wide range of solid materials that can take various physical forms such as powders, fibers, whiskers, platelets, and/or nano-materials.
  • the chemical make-up of the filler material varies depending on the desired properties of the material.
  • Filler materials can be used in optoelectronic devices that make use of phosphor-converted LEDs (Light Emitting Diodes) to generate light with a desired emission spectrum.
  • the main purpose of the phosphor component of such a device is to convert light of one wavelength range to another wavelength range, typically from higher energy to lower energy, e.g., blue to green.
  • These wavelength converters can come in 2022PF02477 - 16 - many different forms.
  • This invention addresses optimized performance of a particular class of wavelength converter: phosphor-in-matrix-on- substrate (PiMoS) and phosphor-in-matrix (PIM). Fillers can be added to the matrix phase of the wavelength converter to optimize properties and performance of the LED optoelectronic device.
  • PIMoS phosphor-in-matrix-on- substrate
  • PIM phosphor-in-matrix
  • Fillers can be added to the matrix phase of the wavelength converter to optimize properties and performance of the LED optoelectronic device.
  • a schematic of a PiMoS wavelength converter is shown in Figure 1, where the PiM layer is attached (bonded) to a substrate.
  • PiM wavelength converters are stand-alone converters where there is no substrate.
  • Figure 1 shows schematically a PiMoS wavelength converter.
  • the substrate is some type of glass
  • the matrix is some type of polymer, or polymer blend.
  • Other substrate materials could be used, e.g., sapphire, and other matrix materials could be used, e.g., low melting glass.
  • substrate, phosphor, and matrix materials There are many combinations of substrate, phosphor, and matrix materials that could be used.
  • the PiMoS is a complex composite structure that relies on a balance of properties to meet performance and reliability requirements. Modifying the matrix phase is one way to optimize the PiMoS converter performance.
  • This invention focuses on modification of the matrix phase using solid filler additions, where the primary component of the matrix is a polysiloxane, and the polysiloxane can be a methy polysiloxane. Filler materials can be added to the matrix formulation to tune the properties for optimum performance of the phosphor-converted LED.
  • Fillers can be added to the matrix phase to: ⁇ alter the rheology of the PiM slurry, ⁇ increase solids loading to decrease the shrinkage of the liquid methyl polysiloxane during the curing process, thus decreasing stress in the PiMoS, ⁇ modify matrix properties such as storage modulus, thermal expansion coefficient, optical scattering, thermal stability, and robustness/reliability, ⁇ decrease the surface roughness of the top surface of PiMoS or PiM, ⁇ decrease cracking in the PiM layer of the PiMoS or PiM, ⁇ decrease delamination at the PiM and substrate interface.
  • filler materials for the matrix phase is limited to materials with select properties such as: ⁇ high purity, ⁇ low absorbance in the visible wavelength region, ⁇ thermal stability at minimum of 200°C, and in particular thermal stability at 250°C for extended times (e.g., 1,000 hours), ⁇ variable particle sizes in particular in the range of 10s of nanometers to 15 ⁇ m, ⁇ narrow size particle range desired, ⁇ and readily available in large quantities and low cost desired.
  • Optoelectronic devices that make use of phosphor-converted LEDs, can have different end-use applications where construction of the PiMoS has different materials (e.g., different phosphors or phosphor loading) and construction parameters (e.g., PiM and substrate layer thicknesses). For this reason, there is need for a variety of filler materials to be able to tune the PiMoS properties for different end- use applications.
  • the most common fillers for PiMoS and PiM converter elements include fumed silica, fused silica powder (0.5-10 ⁇ m particle size) and polymethylsiloxane powders (0.8- 10 ⁇ m particle size). Fumed silica is often used to adjust the rheology of the matrix.
  • FIG. 2 provides an overview of the properties and uses of polymethylsiloxane and fused silica fillers in PiM formations. While both of these materials are available as spherical powders with similar particle sizes, the material properties are very different.
  • the polymethylsilioxane powders hybrid organic/inorganic structure
  • silica powders are high temperature inorganic materials that have very low thermal expansion coefficient.
  • siloxane powders polymethylsiloxane powders
  • This invention describes a method for preparing modified siloxane powder fillers to tune the properties from siloxane-like to silica- like powders, thus spanning the gap shown in Figure 2.
  • the siloxane structure is a hybrid, organic/inorganic material that is based on a 3-dimension structure that contains T-units (CH 3 -groups), as shown in Figure 3; the actual number of T-units may be different for various commercially available siloxane powder products.
  • the structure and properties of siloxane powders can be modified with controlled thermal treatment (for example in air) of the powder at specified temperatures to decrease the silanol (Si-OH) and CH 3 -group content of the material.
  • Figure 4 shows TGA (thermogravimetric analysis) measurements for weight loss of siloxane powders (0.8-6 ⁇ m size particles) as a function of temperature.
  • Thermal treatment of 4 ⁇ m siloxane powder was conducted at different temperatures to produce filler materials with a range of CH 3 -grous (T- groups); as CH 3 -groups decompose from the structure the properties of the powder become more silica-like.
  • Thermal treatment (i.e., modification) of siloxane powder was conducted using the following procedure. 2022PF02477 - 19 - ⁇ Siloxane powder was placed in a furnace with air atmosphere; air is required for a clean burn-out of CH 3 -groups. ⁇ Slow thermal ramp rate (about 2°C/min) to the target temperatures: 360°C, 370°C, 390°C, and 410°C. ⁇ Hold at target temperature for 6 hours to allow reactions to stabilize.
  • siloxane-based filler materials can be made that have properties ranging from siloxane-like to silica- like, thus the ability to tune filler properties.
  • FIG. 6 shows SEM evaluation of the original and heat- treated powders for 0.8 ⁇ m, 2 ⁇ m and 4 ⁇ m siloxane powders.
  • the siloxane powders shown in Figure 6 have a spherical shape with narrow particle size distribution (PSD).
  • PSD narrow particle size distribution
  • Thermal treatment of the powders shown in Figure 6 ranged from 390°C to 500°C, with significant CH 3 loss for all powders. Comparison of SEM images indicate that there was minimal change in the particle size/shape and nominal particle fusing was observed.
  • the original 4 ⁇ m powder, and heat- treated 4 ⁇ -HT400 and 4 ⁇ m-HT500 powders there are some fused particles in both the original and the heat-treated powders.
  • the original siloxane powders are high purity and show very high reflectance values (powder plaque measurement with a spectrophotometer), as shown in Figure 7.
  • High purity, low absorption filler materials are essential to maximizing the brightness of phosphor-converted LEDs.
  • Thermal treatment of the siloxane powders requires processing parameters such that the CH 3 -groups decompose, but carbon does not get trapped in the structure. Residual carbon in the structure results in strong absorption in the visible spectrum.
  • Figures 8a and b show samples of heat-treated siloxane powders with different thermal processing conditions.
  • Modified siloxane powders can be included as candidates for high purity filler materials for PiM formulations.
  • Modified siloxane powders can be made from thermal treatment of siloxane powders; siloxane powders from vendor A are a high purity, low cost material that is available in many particle sizes.
  • Modified siloxane powder properties and % reflectance values look promising for use as filler in PiM formulations.
  • Matrix formulations were prepared with various fillers to evaluate potential advantages of using modified siloxane fillers; the general matrix formulation is shown in Table 2a, while the fillers are provided in Table 2b.
  • High purity fillers include siloxane powders, modified siloxane powders and fused silica powders; a blend of 1, or 0.8 ⁇ m, and 4 ⁇ m particle sizes were used for each filler type.
  • Samples were prepared using the following procedure: ⁇ matrix components were blended with planetary mixing and 3-roll milling of the slurry (no solvent), ⁇ Dr. Blade cast on mylar using a blade gap sufficient for a dried film thickness of approximately 0.35 mm, ⁇ room temperature cure at about 50% RH for 4 days, ⁇ samples cut and trimmed, ⁇ 200°C cure.
  • Blend Component Formulation Siloxane 0.8 and 4 ⁇ m blend Methyl Siloxane 58.2v% 0.8 and 4 ⁇ m blend Modified Siloxane Fumed Silica 11.5v% 0.8 ⁇ m- HT390 4 ⁇ m- HT400 Filler Material 30.3v% Silica 1 and 4 ⁇ m blend (a) (b) Table 2a and b. General matrix formulation shown in (a), and various filler blends are provided in (b). 2022PF02477 - 23 - Figure 10 provides a visual comparison of cured matrix samples (about 0.35mm thick).
  • the siloxane filler matrix sample is colorless and transparent; this is expected because the siloxane filler has essentially the same chemistry and refractive index as the methyl polysiloxane.
  • the modified siloxane filler sample shows a hazy appearance, while the fused silica filler sample had a cloudy appearance. Transmittance measurements, shown in Figure 11, help to quantify the differences in these samples.
  • Figure 11 shows distinct differences between the matrix samples, with % transmittance decreasing across the visible spectrum as the filler material goes from siloxane to silica; the modified siloxane filler falls in-between. All filler powders show high reflectance for powder plaque measurements, so material absorption losses should be low.
  • Matrix samples were subjected to thermal storage at 250°C for 24 hours, with the % transmittance curves shown in Figures 12a, b and c.
  • Table 3 summarizes the transmittance data at 450nm wavelength.
  • the matrix containing siloxane filler showed a small shift in the transmittance curve, but overall, there was very good thermal stability at 250°C.
  • the modified siloxane and silica fillers showed a significant shift in the curve to lower transmittance values, indicating a further increase in scattering.
  • these matrix formulations show a range of 2022PF02477 - 24 - behavior, with the modified siloxane filler filling the gap between siloxane and silica filler properties.
  • Figures 13a and b show the range of breaking force and Youngs modulus for matrix samples prepared with various fillers (see Table 2a and b). Siloxane filler additions result in the lowest values, while silica filler additions show the highest values for both breaking force and Youngs modulus. Modified siloxane fillers can be made to have intermediate mechanical properties, thus providing a lot of flexibility in tuning the properties of the wavelength converter.
  • Figures 14a and 14b profile two different modified siloxane powders: (a) shows siloxane-like properties, while (b) displays silica-like properties. Modified siloxane powders can be prepared to fill the gap between these examples to tune the properties of PiMoS and PiM wavelength converters.
  • FIG. 15 provides an updated view of Figure 1, where modified siloxane powders can be prepared with tunable properties from siloxane- 2022PF02477 - 25 - like to silica-like and can be used to optimize optoelectronic devices that use phosphor-converted LEDs.
  • the properties of PiMoS wavelength converters for use in automotive headlamp optoelectronic devices are sensitive to the absorption/scattering properties of filler materials in the PiM layer.
  • the chemical purity of the filler material and the filler content in the PiM layer can impact the brightness of the wavelength converter, where increased impurity and increased filler content can result in decreased brightness.
  • the chemical purity of fused silica filler made by the flame-spray process depends on the precursor material and can vary for different sources. Studies are ongoing to evaluate new silica filler sources and new filler materials to increase brightness, while maintaining other converter properties such as low delamination and excellent thermal stability.
  • Filler Materials The search for new filler materials has stressed the need for high purity (high reflectance) materials.
  • FIG. 16 shows the reflectance spectra for siloxane and modified siloxane powder fillers compared to the flame-sprayed fused silica filler.
  • the siloxane and modified siloxane powders show excellent reflectance and move forward for evaluation in wavelength converter formulations.
  • the PiM formulation and fillers used for evaluation are shown in Tables 4a and b.
  • the base matrix formulation is similar to an automotive white headlamp PiMoS matrix formulation. New fillers were evaluated as a direct volume percent substitution for the fused silica filler.
  • the polymer precursor can be a low molecular weight methyl methoxy siloxane.
  • the siloxane bonding would be primarily T-unit bonding, meaning that each silicon atom in the siloxane is connected to three oxygen atoms and one carbon atom.
  • T-unit bonding is important for two reasons: (i) T-unit siloxanes often cure into harder materials than traditional D-unit types, and (ii) T- unit siloxanes, like the ones claimed here, do not have any carbon- carbon bonds in the polymer chain.
  • the benefit of these two features is that the harder siloxanes can be saw diced without smudging or tearing and the lack of any C-C bonds means the cured polysiloxane is more thermally stable than a typical silicone.
  • the phosphor powder(s) could be any of the known LED phosphors.
  • a cerium doped yttrium aluminum garnet phosphor would be used to make cool white devices.
  • Fumed silica is added to give the slurry the rheological properties needed for coating the substrate with a uniform layer. Fillers could be added optionally to tune mechanical, thermal, or optical properties.
  • a curing agent is added to the slurry.
  • the curing agent could be a metal alkoxide such as titanium n-butoxide, or any other curing agent known to cure methoxy siloxanes.
  • the slurry is coated onto the hard substrate by either spray-coating, doctor-blading, tape-casting, slot-die coating, etc.
  • the substrate can be a borosilicate glass.
  • the siloxane precursor will react with the curing agent, and moisture 2022PF02477 - 27 - from the air, via hydrolysis and condensation to produce a cured film (PiM) on the glass.
  • Final curing of the coating is achieved by heating the PiMoS to a temperature of 200°C.
  • the formula of the fundamental repeat unit of the cured siloxane is [(CH 3 )SiO 3/2 ]. The result is a highly crosslinked polysiloxane matrix with phosphor and filler particles contained therein.
  • the PiMoS can be evaluated at the wafer/sheet level or proceed to singulation into platelets. Properties such as surface roughness and delamination at the PiM and glass interface is often checked at the wafer/sheet of PiMoS first, and then the PiMoS is ready for the singulation process.
  • the singulation process is carried out using saw dicing, using specified converter platelet dimensions. In the case of this study the converter platelets were diced to 1150 ⁇ m x 1150 ⁇ m. Data provided in this section were taken on both sheet level samples and converter platelet samples; sample type will be specified for each measurement.
  • Trial 1 was conducted using siloxane powders (4 and 6 ⁇ m blend) according to the formulation provided in Table 4a, where the substrate was a borosilicate glass.
  • Trial 2 PiMoS was singulated using saw dicing to prepare converter platelets for further evaluation; platelets were diced and cleaned. The main goal of this investigation is to identify filler materials that show potential in improving brightness for HL PiMoS optoelectronic devices.
  • the next step in Trial 2 platelet evaluation is to measure 2022PF02477 - 29 - color coordinates and brightness (i.e., conversion efficiency) of the PiMoS platelets.
  • Figures 21a and b provide the photometry results for Trial 2 PiMoS platelets: (a) color coordinates, and (b) conversion efficiency; data is plotted together with control HL PiMoS platelets that were measured at the same time.
  • Color coordinates for Trial 2 with modified siloxane filler fall on the same color conversion line as the control HL PiMoS (see Figure 21a). Color steering for the Trial 2 formulation can be done by varying the PiM coating thickness.
  • Figure 21b shows the conversion efficiency for Trial 2 PiMoS compared to the control HL PiMoS. Conversion efficiency (at the same Cx) is higher (brighter) for Trial 2 platelets with modified siloxane filler than for the control HL PiMoS.
  • thermal stability at 250°C is robustness, in particular, thermal stability at 250°C.
  • Thermal stability at 250°C for control HL PiMoS containing fused silica filler is excellent; very stable delamination and color (Cx).
  • Thermal stability at 250°C for Trial 2 PiMoS containing modified siloxane filler (silica-like) is shown in Figure 22 for delamination, and Figure 23 for color coordinate (Cx) stability; data are shown for both 200°C curing profiles.
  • Figures 22a and b show that delamination can be decreased by using a slow thermal ramp rate 200°C cure profile.
  • Figures 22a and 22b show that delamination is very stable for thermal storage at 250 °C for up to 1,188 hours. While the delamination starting values are significantly different for the two thermal profiles, the delamination level remains stable for 250°C storage.
  • Figure 21b shows the case (slow thermal ramp rate 200°C curing profile) where the delamination remains very low following 250°C storage.
  • Figures 23a and 23b show that color coordinate Cx is very stable for thermal storage at 250°C for up to 1,188 hours.
  • Figure 23b shows the case (slow thermal ramp rate 200°C curing profile to decrease stress) where delamination values are very low (Figure 22b), and both delamination and color coordinate Cx show excellent stability for 250°C thermal storage.

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Abstract

L'invention concerne des siloxanes modifiés pouvant être obtenus par soumission d'un siloxane à un traitement thermique à une température d'environ 200 °C à environ 500 °C dans un environnement contenant de l'oxygène. L'invention concerne en outre un procédé de modification de siloxanes, l'utilisation des siloxanes modifiés en tant que charge, une charge contenant lesdits siloxanes modifiés et un convertisseur de longueur d'onde pour un dispositif à LED à conversion de phosphore contenant lesdites charges.
PCT/EP2024/063598 2023-05-18 2024-05-16 Siloxanes modifiés, procédé de modification de siloxanes et leur utilisation Pending WO2024236144A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2653155A1 (fr) * 2006-06-02 2007-12-13 Degussa Novara Technology S.P.A. Silice agglomeree
US20100286311A1 (en) * 2008-03-04 2010-11-11 Evonik Degussa Gmbh Silica and also epoxy resins
CN108083286A (zh) * 2018-01-05 2018-05-29 江苏联瑞新材料股份有限公司 一种球形二氧化硅微粉及其制备方法和应用
US20200203579A1 (en) * 2018-12-21 2020-06-25 Lumileds Holding B.V. Photoresist patterning process supporting two step phosphor-deposition to form an led matrix array
US20220354757A1 (en) 2021-05-04 2022-11-10 Momentive Performance Materials Japan Llc Method for producing silica particles and their use in cosmetic compositions
CN115974089A (zh) * 2023-02-17 2023-04-18 江苏海格新材料有限公司 一种活性硅微粉的生产方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2653155A1 (fr) * 2006-06-02 2007-12-13 Degussa Novara Technology S.P.A. Silice agglomeree
US20100286311A1 (en) * 2008-03-04 2010-11-11 Evonik Degussa Gmbh Silica and also epoxy resins
CN108083286A (zh) * 2018-01-05 2018-05-29 江苏联瑞新材料股份有限公司 一种球形二氧化硅微粉及其制备方法和应用
US20200203579A1 (en) * 2018-12-21 2020-06-25 Lumileds Holding B.V. Photoresist patterning process supporting two step phosphor-deposition to form an led matrix array
US20220354757A1 (en) 2021-05-04 2022-11-10 Momentive Performance Materials Japan Llc Method for producing silica particles and their use in cosmetic compositions
CN115974089A (zh) * 2023-02-17 2023-04-18 江苏海格新材料有限公司 一种活性硅微粉的生产方法

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