WO2013144777A1 - Phosphor in inorganic binder for led applications - Google Patents

Phosphor in inorganic binder for led applications Download PDF

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Publication number
WO2013144777A1
WO2013144777A1 PCT/IB2013/052194 IB2013052194W WO2013144777A1 WO 2013144777 A1 WO2013144777 A1 WO 2013144777A1 IB 2013052194 W IB2013052194 W IB 2013052194W WO 2013144777 A1 WO2013144777 A1 WO 2013144777A1
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WIPO (PCT)
Prior art keywords
binder
phosphor layer
phosphor
layer
porous
Prior art date
Application number
PCT/IB2013/052194
Other languages
French (fr)
Inventor
Grigoriy Basin
Stein Kuiper
Paul Scott Martin
Original Assignee
Koninklijke Philips N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Koninklijke Philips N.V. filed Critical Koninklijke Philips N.V.
Priority to CN201380017738.2A priority Critical patent/CN104185908B/en
Priority to EP13721402.9A priority patent/EP2831931B1/en
Priority to KR1020207021756A priority patent/KR102228997B1/en
Priority to US14/385,594 priority patent/US9337398B2/en
Priority to KR1020147030187A priority patent/KR102139777B1/en
Publication of WO2013144777A1 publication Critical patent/WO2013144777A1/en
Priority to US15/132,123 priority patent/US9537047B2/en

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    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • 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
    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1062—Prior to assembly

Definitions

  • This invention relates to a phosphor layer for use with light emitting diodes (LEDs) to wavelength convert the LED emission and, in particular, to a technique for forming the phosphor layer with an inorganic glass binder for improved performance.
  • LEDs light emitting diodes
  • Providing a phosphor layer over an LED is common.
  • a phosphor is provided over a blue LED to make white light. Blue light leaking through the phosphor, combined with the phosphor light, produces white light.
  • inorganic glass would be a relatively stable and reliable binder for the phosphor powder
  • molten glass is too chemically reactive at the high temperatures needed to form a phosphor-glass layer, since the glass would react chemically with the phosphors, especially red nitride phosphors.
  • a sol-gel for forming a glass layer may also be considered as a candidate to substitute for the silicone, but the sol-gel is also too reactive for the phosphor, leading to light attenuation. Further, the low viscosity of sol-gel would result in phosphor sedimentation and non-uniform phosphor density. Other problems would exist as well.
  • a phosphor layer is formed, having an inorganic glass binder, that can be used as a remote phosphor for LEDs or as a coating over LEDs to wavelength-convert the LED light.
  • the LED emits blue light, and the phosphor converts the light to white light.
  • phosphor powder is mixed with an organic polymer binder, such as inexpensive acrylate or nitrocellulose.
  • the mixture may be formed as a paste having a wide range of viscosities.
  • Such a mixture is then easily screen printed over a transparent substrate, such as a thin glass substrate.
  • the mixture can be screen printed over LED dies mounted on a submount wafer.
  • Other deposition techniques may be used.
  • the layer may be made to have an accurate thickness, such as +/- 2%.
  • the organic binder is then burned away in air, such as at 180-300 degrees C.
  • the mixture may be subject to an 0 2 plasma process.
  • the polymer is oxidized and evaporates.
  • the binder may also be chemically dissolved.
  • the resulting layer is a porous, sintered phosphor powder layer that is substantially uniformly distributed over the transparent substrate or LEDs.
  • the porous layer is relatively weak and subject to contamination.
  • the porous layer is impregnated with a sol-gel (e.g., a sol-gel of TEOS or MTMS) or liquid glass (e.g., sodium silicate or potassium silicate), also known as water glass, which saturates the porous structure.
  • a sol-gel e.g., a sol-gel of TEOS or MTMS
  • liquid glass e.g., sodium silicate or potassium silicate
  • the porous structure is then heated to cure the inorganic glass binder.
  • sol-gel the heating causes the sol-gel to become cross-linked to create a hard, scratch resistant glass layer.
  • the water component evaporates, leaving a hard layer.
  • Other glassy materials may be used.
  • the resulting inorganic binder material is extremely stable under the high heat and flux generated by the LEDs, it resists yellowing, it conducts heat much better than silicone or epoxy, it is much less expensive than silicone or epoxy, and it has greater mechanical strength and scratch resistance.
  • Fig. 1 is a cross-sectional view of a prior art blue or UV flip-chip LED die, mounted on a submount.
  • Fig. 2 is a top down view illustrating a simplified submount wafer populated by an array of LED dies, such as 500-4000 LEDs, where all LED dies on the wafer are
  • Fig. 3 illustrates the submount wafer of Fig. 2 having a phosphor layer being laminated or deposited over the LEDs.
  • Fig. 4 illustrates the submount wafer of Fig. 2, populated with LEDs encapsulated with a lens, having a phosphor layer being laminated or deposited over the lenses.
  • Fig. 5 is a cross-sectional view of the phosphor layer deposited on a substrate, where phosphor powder is distributed in a polymer binder.
  • the substrate may be a glass substrate or the LED dies on the submount wafer.
  • Fig. 6 illustrates the phosphor layer of Fig. 5 after the polymer binder has evaporated by oxidation in an 0 2 plasma or baked out in air, leaving a porous phosphor layer.
  • Fig. 7 illustrates a sol-gel glass, liquid glass, or other suitable transparent inorganic binder material saturating the porous phosphor layer, then being cured to form a robust inorganic binder.
  • Fig. 8 illustrates the phosphor layer of Fig. 5 being laminated over a submount wafer populated with LED dies.
  • Fig. 9 illustrates the phosphor layer of Fig. 8 conforming to the shape of the LED dies upon application of a vacuum or other form of pressure.
  • Fig. 10 is a cross-sectional view of a completed LED having a phosphor layer over it formed in accordance with one embodiment of the present invention, where the phosphor layer is formed over the entire surface of the submount wafer prior to singulation.
  • Fig. 1 1 is a cross-sectional view of a completed LED having a phosphor layer over it formed in accordance with another embodiment of the present invention, where the phosphor layer is affixed as a tile over the top of an LED die.
  • Fig. 12 is a flowchart summarizing techniques for fabricating the phosphor layer in accordance with some embodiments of the invention.
  • FIG. 1 illustrates a conventional flip chip LED die 10 mounted on a portion of a submount wafer 12. In a flip-chip, both the n and p contacts are formed on the same side of the LED die.
  • the term "submount wafer” is intended to mean a support for an array of LED dies, where electrical contacts on the wafer are bonded to electrodes on the LED dies, and the wafer is later singulated to form one or more LEDs on a single submount, where the submount has electrodes that are to be connected to a power supply.
  • the LED die 10 is formed of semiconductor epitaxial layers, including an n-layer 14, an active layer 15, and a p-layer 16, grown on a growth substrate, such as a sapphire substrate.
  • the growth substrate has been removed in Fig. 1 by laser lift-off, etching, grinding, or by other techniques.
  • the epitaxial layers are GaN based, and the active layer 15 emits blue light. LED dies that emit UV light are also applicable to the present invention.
  • a metal electrode 18 electrically contacts the p-layer 16, and a metal electrode 20 electrically contacts the n-layer 14.
  • the electrodes 18 and 20 are gold pads that are ultrasonically welded to anode and cathode metal pads 22 and 24 on a ceramic submount wafer 12.
  • the submount wafer 12 has conductive vias 24 leading to bottom metal pads 26 and 28 for bonding to a printed circuit board.
  • Many LEDs are mounted on the submount wafer 12 and will be later singulated to form individual LEDs/submounts. Further details of LEDs can be found in the assignee's U.S. Patent Nos. 6,649,440 and 6,274,399, and U.S. Patent Publications US 2006/0281203 Al and 2005/0269582 Al , all incorporated herein by reference.
  • Fig. 2 is a simplified top down view of an exemplary submount wafer 12 on which is mounted an array of LED dies 10 (only one LED is numbered but all of the squares on wafer 12 are LEDs). There may be 500-4000 LEDs on a single submount wafer 12. All LEDs on the wafer 12 will be processed simultaneously using the method described below.
  • Fig. 3 illustrates a portion of the submount wafer 12 having LED dies 10 mounted thereon.
  • the LED electrodes 18 and 20 are bonded to metal pads on the submount wafer 12 that are connected to more robust pads on the bottom surface of the wafer 12 by vias extending through the wafer 12.
  • the bottom pads may be soldered to pads on a printed circuit board.
  • a phosphor layer 38 is shown over the wafer 12, which represents that either the phosphor layer 38 will be laminated over the wafer 12 or that the phosphor layer 38 will be a remote layer separated from the LED dies 10.
  • the phosphor layer 38 may be singulated to form tiles, and each tile is affixed over an LED die 10. Further, in another embodiment, the phosphor layer 38 is laminated over an LED wafer prior to the LEDs being singulated. In that way, there is little waste of phosphor. Other uses of the phosphor layer 38 are envisioned.
  • Fig. 4 illustrates how the LED dies 10 may have a hemispherical lenses 36 molded over them to separate the phosphor layer 38 from the dies 10 after lamination. This reduces the intensity of heat and flux on the phosphor and improves color uniformity vs. angle.
  • Figs. 5-7 illustrate the formation of a phosphor layer in accordance with one embodiment of the invention.
  • a substrate 40 may be a transparent glass plate, or the surface of the submount wafer 12 populated with the LED dies 10, or any other suitable substrate.
  • the phosphor layer 38 (Figs. 3 and 4) is intended to be a self-supporting layer for a remote phosphor application, or is intended to be singulated as tiles and affixed on LED dies 10, then a glass substrate is preferred.
  • a remote phosphor, supported by a transparent glass plate and separated from the LED(s), may be preferred for high power applications using an array of interconnected LEDs, where the light and heat generated are very high, or in situations where the emitted color is desired to be selectable by selecting to use one of a variety of remote phosphor plates having different characteristics.
  • the phosphor layer 38 is intended to be laminated directly over the LEDs on submount wafer 12 or over an LED wafer, then the substrate 40 would be the submount wafer 12 populated with the LED dies 10 or an LED wafer.
  • phosphor powder 42 is mixed with an organic polymer binder 44, such as an acrylate, nitrocellulose, or other commercially available binder that can be later evaporated or dissolved away. Due to the conventional small grain size of the phosphor powder 42 and its density in the binder 44, the distribution of phosphor powder 42 in binder 44 is fairly homogenous which should achieve good color uniformity across the phosphor layer 38. The phosphor grain size and density is not critical; however, the density should be such that the grains contact each other after the binder 44 is later removed.
  • the phosphor powder 42 may be any conventional phosphor, including YAG, red, green, yellow, blue, or orange phosphor, or combinations thereof, depending on the application and the LED.
  • the polymer binder 44 does not have to have good optical properties, it may be much less expensive than silicone. Silicone for use with phosphors is about $900 US/kg.
  • the mixed binder/phosphor may form a paste or viscous liquid that is spray coated, dip coated, spun on, or screen printed onto the substrate 40.
  • the thickness is not critical for the invention, but the thickness and density of the phosphor powder 42 affects the emitted light color.
  • the deposited layer should have a thickness accuracy of +/- 2% to achieve good color uniformity.
  • the binder 44 is subjected to heat, such as 180-300 degrees C in an air environment for a time to evaporate the binder 44.
  • heat such as 180-300 degrees C
  • an 0 2 plasma may be used to oxidize the binder 40 to convert the binder 44 to a gas, or the binder may be chemically dissolved and heated.
  • the combination of heat and the removal of the binder 44 results in the phosphor powder 42 grains being sintered together and to the substrate 40 to form a relatively uniform layer of phosphor powder 42.
  • the phosphor powder 42 forms a porous layer or a web.
  • the porous layer is then impregnated and saturated with a sol-gel (for forming a glass) or liquid glass, also known as water glass. This may be done by spray coating, dip coating, or other well-known method.
  • the liquid glass or sol-gel is cured to dehydrate the material, leaving a robust glass binder 48 surrounding the phosphor powder 42.
  • curing is performed by heat or dehydrating at a longer time at room temperature, or performed using a chemical curing agent.
  • Liquid glass (sodium silicate or potassium silicate) is made by fusing varying portions of sand (Si0 2 ) and soda ash (Na 2 C0 3 ), where C0 2 is driven off. The ratio of these portions determines the properties of the final product. This product is specified as a ratio of
  • the sodium may also be replaced by potassium or lithium in order to obtain different properties.
  • the water is evaporated, leaving a solid glass coating behind.
  • Lower Si02/Na 2 0 ratios tend to retain water better and hence evaporate slower.
  • Higher ratio solutions (approx. 2.8-3.22) are preferred if increased durability is desired.
  • Complete dehydration typically requires heat during the drying process.
  • the silicate layers may be cured at a temperature of 250°C, which is well below the temperature that luminescent materials can stand (nitride-based luminescent materials can stand temperatures up to 350°C and YAG-based luminescent materials even much higher).
  • Chemical setting agents that can be used in this manner include mineral and organic acids, C0 2 gas, and acid salts such as sodium bicarbonate.
  • silicate films When silicate films are completely dehydrated, they provide excellent resistance to high temperatures. Most silicates have flow points around 850°C. In LEDs, such
  • Liquid glass is transparent for visible light, and the transmission drops off rapidly below 400 nm, exhibiting a value of approximately 40% at 325 nm. For LEDs that convert blue to white light, this range is sufficient.
  • Silicate coatings may be brittle. If a higher degree of flexibility is required, typically 5% by weight of glycerine can be added. Glycerine has a very high transparency for blue light. Other materials may be added, such as ethyelene glycol, propylene glycol, an alcohol, etc.
  • sol-gel materials such as TEOS (tetraethylorthosiiicate), MTMS (methyl SharePointiethoxysilane), and MTES (triethoxysilane), all generally referred to as glass materials.
  • Sol-gel is relatively inexpensive (less than $20US kg), so the resulting phosphor layer is less expensive than phosphor powder in a silicone binder.
  • Glass has high thermo and photo-thermal stability and resists yellowing in the presence of the high heat and flux of an LED. Forming a sol-gel of such materials is well known for depositing the materials on a substrate.
  • the sol-gel process is a wet-chemical technique commonly used for the fabrication of a glassy coating.
  • sol evolves gradually towards the formation of a gel-like network containing both a liquid phase and a solid phase.
  • the micron-size or sub-micron-size glass particles become linked, forming the gel.
  • the formation of a TEOS, MTMS, MTES, or other glass layer using sol-gel is well-known and need not be described in detail.
  • the drying process serves to remove the liquid phase from the gel, yielding an amorphous glass (a linked silica network or matrix).
  • amorphous glass a linked silica network or matrix.
  • Subsequent thermal treatment (firing) may be performed in order to densify the glass to enhance its mechanical properties.
  • the thickness of the sol-gel or liquid glass should be adjusted to ensure complete coverage of the phosphor powder 42 after dehydration. Multiple applications and curing of the sol-gel or liquid glass may be desirable for complete coverage.
  • the glass layer may be formed to have a relatively high index of refraction, comparable to that of high index silicones, to provide good light extraction.
  • the film of Fig. 5 may be pre-formed as a flexible layer then laminated over the LED dies 10 and submount wafer 12, as shown in Figs. 8 and 9.
  • a flexible layer of the polymer binder 44 and phosphor power 42 mixture is formed on a releasable film (an embodiment of substrate 40).
  • the layer may be tested to determine its luminescent properties and matched to a particular bin of LED dies that emit a particular narrow range of blue light.
  • the flexible layer 58 is then laminated on the matched LED dies 10 with the releasable film facing up. A vacuum or mechanical downward pressure is used to ensure there are no air gaps and to conform the layer 58 to the LED dies 10.
  • the releasable film is removed before or after the layer 58 is fully laminated over the LED dies 10. Then, as shown in Fig. 9, the processes of Figs.
  • Fig. 10 illustrates the structure of Fig. 9 (using a laminated layer 58) after hemispherical lenses 60 are molded over the LED dies 10 and after the submount wafer 12 is singulated.
  • the structure may emit white light or any color of light.
  • the structure of Fig. 10 may also be formed by depositing the layer 44/42 of Fig. 5 directly over the LED dies 10 by spray coating, spin coating, etc., then performing the processes of Figs. 6 and 7.
  • Fig. 1 1 illustrates an LED structure where the luminescent structure of Fig. 7 has been singulated to form luminscent tiles 40/42/48, and each tile is affixed over an LED die.
  • the LED die has a YAG tile 64 affixed directly over the top surface of the die, and a luminescent tile 40/42/48 containing red phosphor powder, formed using the processes of Figs. 5-7, is affixed over the YAG tile 64 to create a warmer white light.
  • a thin glass layer, epoxy, or silicone may be used as the adhesive.
  • Fig. 12 is a flowchart summarizing various steps for forming the phosphor layer in accordance with some embodiments of the invention.
  • an LED wafer is fabricated, such as a wafer containing GaN-based blue LEDs.
  • step 71 the LED wafer is diced, and a submount wafer is populated with the LED dies.
  • step 72 a mixture of phosphor powder and an organic binder is created as a paste or a liquid for screen printing or other type of deposition, or created as a lamination layer.
  • step 73 the phosphor/binder mixture is printed or laminated on a glass plate (e.g., for a remote phosphor) or other substrate or over the LED dies.
  • step 74 the organic binder is removed by heating or subjecting the binder to an 0 2 plasma or other treatment, leaving a porous, sintered phosphor powder layer.
  • step 75 the phosphor "web" is impregnated with liquid glass, a sol-gel, or other suitable material by spray coating, dip coating, or other process.
  • step 76 the liquid glass or sol-gel is cured such as by heating to cross-link the sol- gel layer and/or evaporate any solution, such as water in the liquid glass.
  • Steps 75 and 76 may be performed multiple times due to shrinkage.

Abstract

A method for fabricating an LED/phosphor structure is described where an array of blue light emitting diode (LED) dies are mounted on a submount wafer. A phosphor powder is mixed with an organic polymer binder, such as an acrylate or nitrocellulose. The liquid or paste mixture is then deposited over the LED dies or other substrate as a substantially uniform layer. The organic binder is then removed by being burned away in air, or being subject to an 02 plasma process, or dissolved, leaving a porous layer of phosphor grains sintered together. The porous phosphor layer is impregnated with a sol-gel (e.g., a sol-gel of TEOS or MTMS) or liquid glass (e.g., sodium silicate or potassium silicate), also known as water glass, which saturates the porous structure. The structure is then heated to cure the inorganic glass binder, leaving a robust glass binder that resists yellowing, among other desirable properties.

Description

PHOSPHOR IN INORGANIC BINDER FOR LED APPLICATIONS
FIELD OF THE INVENTION
This invention relates to a phosphor layer for use with light emitting diodes (LEDs) to wavelength convert the LED emission and, in particular, to a technique for forming the phosphor layer with an inorganic glass binder for improved performance.
BACKGROUND
Providing a phosphor layer over an LED is common. Typically, a phosphor is provided over a blue LED to make white light. Blue light leaking through the phosphor, combined with the phosphor light, produces white light. There are many ways to provide the phosphor layer over the LED, and one prior art technique is described below.
It is known to pre-form a layer of phosphor powder mixed with silicone and then laminate the layer over blue-emission LED dies mounted on a submount wafer. The wafer is then singulated. The resulting dies emit white light. This is described in United Stated patent application publications 20110031516 and 201 10266569, by Grigoriy Basin et al., assigned to the present assignee and incorporated by reference. Other techniques also mix the phosphor powder in an organic polymer binder (e.g., silicone or epoxy) and then deposit (e.g., print, mold, etc.) the liquid/paste layer directly over the LEDs. The binder is then cured to harden it.
However, the heat and high flux from the LEDs tend to oxidize the organic binder surrounding the phosphor particles, causing the binder to yellow and color shift the light. Further, high quality silicone and epoxy are relatively expensive, which is a significant concern for large remote phosphor components.
What is needed in a process for forming a phosphor layer that can be either formed directly over LEDs or formed on a transparent substrate and which does not use silicone or other organic polymer as a binder.
Although inorganic glass would be a relatively stable and reliable binder for the phosphor powder, molten glass is too chemically reactive at the high temperatures needed to form a phosphor-glass layer, since the glass would react chemically with the phosphors, especially red nitride phosphors.
A sol-gel for forming a glass layer may also be considered as a candidate to substitute for the silicone, but the sol-gel is also too reactive for the phosphor, leading to light attenuation. Further, the low viscosity of sol-gel would result in phosphor sedimentation and non-uniform phosphor density. Other problems would exist as well.
SUMMARY
A phosphor layer is formed, having an inorganic glass binder, that can be used as a remote phosphor for LEDs or as a coating over LEDs to wavelength-convert the LED light. In one embodiment, the LED emits blue light, and the phosphor converts the light to white light.
Initially, phosphor powder is mixed with an organic polymer binder, such as inexpensive acrylate or nitrocellulose. The mixture may be formed as a paste having a wide range of viscosities. Such a mixture is then easily screen printed over a transparent substrate, such as a thin glass substrate. Alternatively, the mixture can be screen printed over LED dies mounted on a submount wafer. Other deposition techniques may be used. The layer may be made to have an accurate thickness, such as +/- 2%.
The organic binder is then burned away in air, such as at 180-300 degrees C.
Alternatively, the mixture may be subject to an 02 plasma process. In either case, the polymer is oxidized and evaporates. The binder may also be chemically dissolved.
The resulting layer is a porous, sintered phosphor powder layer that is substantially uniformly distributed over the transparent substrate or LEDs. The porous layer is relatively weak and subject to contamination.
Next, the porous layer is impregnated with a sol-gel (e.g., a sol-gel of TEOS or MTMS) or liquid glass (e.g., sodium silicate or potassium silicate), also known as water glass, which saturates the porous structure. The structure is then heated to cure the inorganic glass binder. In the case of sol-gel, the heating causes the sol-gel to become cross-linked to create a hard, scratch resistant glass layer. In the case of liquid glass, the water component evaporates, leaving a hard layer. Other glassy materials may be used. The resulting inorganic binder material is extremely stable under the high heat and flux generated by the LEDs, it resists yellowing, it conducts heat much better than silicone or epoxy, it is much less expensive than silicone or epoxy, and it has greater mechanical strength and scratch resistance.
Other embodiments are disclosed. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cross-sectional view of a prior art blue or UV flip-chip LED die, mounted on a submount.
Fig. 2 is a top down view illustrating a simplified submount wafer populated by an array of LED dies, such as 500-4000 LEDs, where all LED dies on the wafer are
simultaneously processed.
Fig. 3 illustrates the submount wafer of Fig. 2 having a phosphor layer being laminated or deposited over the LEDs.
Fig. 4 illustrates the submount wafer of Fig. 2, populated with LEDs encapsulated with a lens, having a phosphor layer being laminated or deposited over the lenses. Fig. 5 is a cross-sectional view of the phosphor layer deposited on a substrate, where phosphor powder is distributed in a polymer binder. The substrate may be a glass substrate or the LED dies on the submount wafer.
Fig. 6 illustrates the phosphor layer of Fig. 5 after the polymer binder has evaporated by oxidation in an 02 plasma or baked out in air, leaving a porous phosphor layer. Fig. 7 illustrates a sol-gel glass, liquid glass, or other suitable transparent inorganic binder material saturating the porous phosphor layer, then being cured to form a robust inorganic binder.
Fig. 8 illustrates the phosphor layer of Fig. 5 being laminated over a submount wafer populated with LED dies.
Fig. 9 illustrates the phosphor layer of Fig. 8 conforming to the shape of the LED dies upon application of a vacuum or other form of pressure.
Fig. 10 is a cross-sectional view of a completed LED having a phosphor layer over it formed in accordance with one embodiment of the present invention, where the phosphor layer is formed over the entire surface of the submount wafer prior to singulation.
Fig. 1 1 is a cross-sectional view of a completed LED having a phosphor layer over it formed in accordance with another embodiment of the present invention, where the phosphor layer is affixed as a tile over the top of an LED die.
Fig. 12 is a flowchart summarizing techniques for fabricating the phosphor layer in accordance with some embodiments of the invention.
Elements that are the same or similar are labeled with the same numeral.
DETAILED DESCRIPTION
Although the present invention of a phosphor layer does not rely on its use with any particular LED, an example of an LED structure will be described to illustrate the phosphor layer's use with an LED.
Prior art Fig. 1 illustrates a conventional flip chip LED die 10 mounted on a portion of a submount wafer 12. In a flip-chip, both the n and p contacts are formed on the same side of the LED die.
In this disclosure, the term "submount wafer" is intended to mean a support for an array of LED dies, where electrical contacts on the wafer are bonded to electrodes on the LED dies, and the wafer is later singulated to form one or more LEDs on a single submount, where the submount has electrodes that are to be connected to a power supply.
The LED die 10 is formed of semiconductor epitaxial layers, including an n-layer 14, an active layer 15, and a p-layer 16, grown on a growth substrate, such as a sapphire substrate. The growth substrate has been removed in Fig. 1 by laser lift-off, etching, grinding, or by other techniques. In one example, the epitaxial layers are GaN based, and the active layer 15 emits blue light. LED dies that emit UV light are also applicable to the present invention.
A metal electrode 18 electrically contacts the p-layer 16, and a metal electrode 20 electrically contacts the n-layer 14. In one example, the electrodes 18 and 20 are gold pads that are ultrasonically welded to anode and cathode metal pads 22 and 24 on a ceramic submount wafer 12. The submount wafer 12 has conductive vias 24 leading to bottom metal pads 26 and 28 for bonding to a printed circuit board. Many LEDs are mounted on the submount wafer 12 and will be later singulated to form individual LEDs/submounts. Further details of LEDs can be found in the assignee's U.S. Patent Nos. 6,649,440 and 6,274,399, and U.S. Patent Publications US 2006/0281203 Al and 2005/0269582 Al , all incorporated herein by reference.
Fig. 2 is a simplified top down view of an exemplary submount wafer 12 on which is mounted an array of LED dies 10 (only one LED is numbered but all of the squares on wafer 12 are LEDs). There may be 500-4000 LEDs on a single submount wafer 12. All LEDs on the wafer 12 will be processed simultaneously using the method described below.
Fig. 3 illustrates a portion of the submount wafer 12 having LED dies 10 mounted thereon.The LED electrodes 18 and 20 are bonded to metal pads on the submount wafer 12 that are connected to more robust pads on the bottom surface of the wafer 12 by vias extending through the wafer 12. When the wafer 12 is later singulated, the bottom pads may be soldered to pads on a printed circuit board.
A phosphor layer 38 is shown over the wafer 12, which represents that either the phosphor layer 38 will be laminated over the wafer 12 or that the phosphor layer 38 will be a remote layer separated from the LED dies 10. In another embodiment, the phosphor layer 38 may be singulated to form tiles, and each tile is affixed over an LED die 10. Further, in another embodiment, the phosphor layer 38 is laminated over an LED wafer prior to the LEDs being singulated. In that way, there is little waste of phosphor. Other uses of the phosphor layer 38 are envisioned.
Fig. 4 illustrates how the LED dies 10 may have a hemispherical lenses 36 molded over them to separate the phosphor layer 38 from the dies 10 after lamination. This reduces the intensity of heat and flux on the phosphor and improves color uniformity vs. angle.
Figs. 5-7 illustrate the formation of a phosphor layer in accordance with one embodiment of the invention.
In Fig. 5, a substrate 40 may be a transparent glass plate, or the surface of the submount wafer 12 populated with the LED dies 10, or any other suitable substrate. If the phosphor layer 38 (Figs. 3 and 4) is intended to be a self-supporting layer for a remote phosphor application, or is intended to be singulated as tiles and affixed on LED dies 10, then a glass substrate is preferred. A remote phosphor, supported by a transparent glass plate and separated from the LED(s), may be preferred for high power applications using an array of interconnected LEDs, where the light and heat generated are very high, or in situations where the emitted color is desired to be selectable by selecting to use one of a variety of remote phosphor plates having different characteristics. If the phosphor layer 38 is intended to be laminated directly over the LEDs on submount wafer 12 or over an LED wafer, then the substrate 40 would be the submount wafer 12 populated with the LED dies 10 or an LED wafer.
Initially, phosphor powder 42 is mixed with an organic polymer binder 44, such as an acrylate, nitrocellulose, or other commercially available binder that can be later evaporated or dissolved away. Due to the conventional small grain size of the phosphor powder 42 and its density in the binder 44, the distribution of phosphor powder 42 in binder 44 is fairly homogenous which should achieve good color uniformity across the phosphor layer 38. The phosphor grain size and density is not critical; however, the density should be such that the grains contact each other after the binder 44 is later removed. The phosphor powder 42 may be any conventional phosphor, including YAG, red, green, yellow, blue, or orange phosphor, or combinations thereof, depending on the application and the LED.
Since the polymer binder 44 does not have to have good optical properties, it may be much less expensive than silicone. Silicone for use with phosphors is about $900 US/kg.
The mixed binder/phosphor may form a paste or viscous liquid that is spray coated, dip coated, spun on, or screen printed onto the substrate 40. The thickness is not critical for the invention, but the thickness and density of the phosphor powder 42 affects the emitted light color. The deposited layer should have a thickness accuracy of +/- 2% to achieve good color uniformity.
In Fig. 6, the binder 44 is subjected to heat, such as 180-300 degrees C in an air environment for a time to evaporate the binder 44. Alternatively, an 02 plasma may be used to oxidize the binder 40 to convert the binder 44 to a gas, or the binder may be chemically dissolved and heated. The combination of heat and the removal of the binder 44 results in the phosphor powder 42 grains being sintered together and to the substrate 40 to form a relatively uniform layer of phosphor powder 42. The phosphor powder 42 forms a porous layer or a web.
In Fig. 7, the porous layer is then impregnated and saturated with a sol-gel (for forming a glass) or liquid glass, also known as water glass. This may be done by spray coating, dip coating, or other well-known method.
After the saturation step, the liquid glass or sol-gel is cured to dehydrate the material, leaving a robust glass binder 48 surrounding the phosphor powder 42. In some cases, curing is performed by heat or dehydrating at a longer time at room temperature, or performed using a chemical curing agent.
Liquid glass (sodium silicate or potassium silicate) is made by fusing varying portions of sand (Si02) and soda ash (Na2C03), where C02 is driven off. The ratio of these portions determines the properties of the final product. This product is specified as a ratio of
Si02/Na20 and as a concentration in water. The sodium may also be replaced by potassium or lithium in order to obtain different properties. After applying liquid glass as a thin film, the water is evaporated, leaving a solid glass coating behind. Lower Si02/Na20 ratios tend to retain water better and hence evaporate slower. Higher ratio solutions (approx. 2.8-3.22) are preferred if increased durability is desired. Complete dehydration typically requires heat during the drying process. The silicate layers may be cured at a temperature of 250°C, which is well below the temperature that luminescent materials can stand (nitride-based luminescent materials can stand temperatures up to 350°C and YAG-based luminescent materials even much higher).
Another method to make the coatings durable is to make use of chemical setting. Chemical setting agents that can be used in this manner include mineral and organic acids, C02 gas, and acid salts such as sodium bicarbonate.
When silicate films are completely dehydrated, they provide excellent resistance to high temperatures. Most silicates have flow points around 850°C. In LEDs, such
temperatures will never be reached.
Liquid glass is transparent for visible light, and the transmission drops off rapidly below 400 nm, exhibiting a value of approximately 40% at 325 nm. For LEDs that convert blue to white light, this range is sufficient.
Silicate coatings may be brittle. If a higher degree of flexibility is required, typically 5% by weight of glycerine can be added. Glycerine has a very high transparency for blue light. Other materials may be added, such as ethyelene glycol, propylene glycol, an alcohol, etc.
There are many suitable sol-gel materials, such as TEOS (tetraethylorthosiiicate), MTMS (methyltrittiethoxysilane), and MTES (triethoxysilane), all generally referred to as glass materials. Sol-gel is relatively inexpensive (less than $20US kg), so the resulting phosphor layer is less expensive than phosphor powder in a silicone binder. Glass has high thermo and photo-thermal stability and resists yellowing in the presence of the high heat and flux of an LED. Forming a sol-gel of such materials is well known for depositing the materials on a substrate. The sol-gel process is a wet-chemical technique commonly used for the fabrication of a glassy coating. In this process, the sol (or solution) evolves gradually towards the formation of a gel-like network containing both a liquid phase and a solid phase. The micron-size or sub-micron-size glass particles become linked, forming the gel. The formation of a TEOS, MTMS, MTES, or other glass layer using sol-gel is well-known and need not be described in detail.
The drying process serves to remove the liquid phase from the gel, yielding an amorphous glass (a linked silica network or matrix). Subsequent thermal treatment (firing) may be performed in order to densify the glass to enhance its mechanical properties.
Since there will be shrinkage after dehydration, the thickness of the sol-gel or liquid glass should be adjusted to ensure complete coverage of the phosphor powder 42 after dehydration. Multiple applications and curing of the sol-gel or liquid glass may be desirable for complete coverage.
The glass layer may be formed to have a relatively high index of refraction, comparable to that of high index silicones, to provide good light extraction.
As an alternative to depositing the film of Fig. 5 directly over the LED dies 10 or depositing the film on a glass substrate, the film may be pre-formed as a flexible layer then laminated over the LED dies 10 and submount wafer 12, as shown in Figs. 8 and 9.
In one embodiment, a flexible layer of the polymer binder 44 and phosphor power 42 mixture is formed on a releasable film (an embodiment of substrate 40). The layer may be tested to determine its luminescent properties and matched to a particular bin of LED dies that emit a particular narrow range of blue light. As shown in Fig. 8, the flexible layer 58 is then laminated on the matched LED dies 10 with the releasable film facing up. A vacuum or mechanical downward pressure is used to ensure there are no air gaps and to conform the layer 58 to the LED dies 10. The releasable film is removed before or after the layer 58 is fully laminated over the LED dies 10. Then, as shown in Fig. 9, the processes of Figs. 6 and 7 are performed to create a robust inorganic glass layer 59 containing the phosphor powder 42. Fig. 10 illustrates the structure of Fig. 9 (using a laminated layer 58) after hemispherical lenses 60 are molded over the LED dies 10 and after the submount wafer 12 is singulated. The structure may emit white light or any color of light. The structure of Fig. 10 may also be formed by depositing the layer 44/42 of Fig. 5 directly over the LED dies 10 by spray coating, spin coating, etc., then performing the processes of Figs. 6 and 7.
Fig. 1 1 illustrates an LED structure where the luminescent structure of Fig. 7 has been singulated to form luminscent tiles 40/42/48, and each tile is affixed over an LED die. In one embodiment, the LED die has a YAG tile 64 affixed directly over the top surface of the die, and a luminescent tile 40/42/48 containing red phosphor powder, formed using the processes of Figs. 5-7, is affixed over the YAG tile 64 to create a warmer white light. A thin glass layer, epoxy, or silicone may be used as the adhesive.
Fig. 12 is a flowchart summarizing various steps for forming the phosphor layer in accordance with some embodiments of the invention.
In step 70, an LED wafer is fabricated, such as a wafer containing GaN-based blue LEDs.
In step 71 , the LED wafer is diced, and a submount wafer is populated with the LED dies.
In step 72, a mixture of phosphor powder and an organic binder is created as a paste or a liquid for screen printing or other type of deposition, or created as a lamination layer. In step 73, the phosphor/binder mixture is printed or laminated on a glass plate (e.g., for a remote phosphor) or other substrate or over the LED dies.
In step 74, the organic binder is removed by heating or subjecting the binder to an 02 plasma or other treatment, leaving a porous, sintered phosphor powder layer.
In step 75, the phosphor "web" is impregnated with liquid glass, a sol-gel, or other suitable material by spray coating, dip coating, or other process. In step 76, the liquid glass or sol-gel is cured such as by heating to cross-link the sol- gel layer and/or evaporate any solution, such as water in the liquid glass.
Steps 75 and 76 may be performed multiple times due to shrinkage.
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of this invention.

Claims

CLAIMS What is claimed is:
1. A method for fabricating a luminescent structure comprising: a. depositing an intermediate phosphor layer on a supporting structure, the intermediate phosphor layer comprising phosphor powder mixed with a first binder; b. removing the first binder, leaving a porous phosphor layer on the supporting structure; c. infusing the porous phosphor layer with liquid glass; and d. curing the liquid glass to form an inorganic transparent glass binder.
2. The method of Claim 1 wherein the step of removing the first binder comprises heating the first binder to evaporate the first binder.
3. The method of Claim 1 wherein the step of removing the first binder comprises subjecting the first binder to an 02 plasma to oxidize the first binder.
4. The method of Claim 1 wherein the step of removing the first binder comprises dissolving the first binder.
5. The method of Claim 1 wherein the first binder comprises acrylate.
6. The method of Claim 1 wherein the supporting structure comprises a glass substrate.
7. The method of Claim 1 further comprising singulating the supporting structure to form luminescent tiles and affixing one of the tiles over a light emitting diode.
8. The method of Claim 1 wherein the supporting structure comprises a submount wafer populated with light emitting diode dies.
9. The method of Claim 1 wherein the supporting structure comprises a releasable film, where the method further comprises: laminating the intermediate phosphor layer on the releasable film over light emitting diodes mounted on a submount wafer; removing the releasable film; and then performing steps b through d.
10. The method of Claim 1 wherein the supporting structure comprises a lens over a light emitting diode.
1 1. The method of Claim 1 wherein the liquid glass, after curing, forms a layer of either sodium silicate or potassium silicate.
12. A light emitting device comprising: a light emitting diode (LED) die mounted on a submount; a porous phosphor layer located over the LED die; and an inorganic transparent silicate binder substantially filling spaces in the porous phosphor layer, the silicate binder being formed by curing a liquid glass infused in the porous phosphor layer.
13. The device of Claim 12 wherein the porous phosphor layer comprises phosphor grains sintered together.
14. The device of Claim 12 wherein the porous phosphor layer is supported by a glass substrate, which overlies the LED die.
15. A structure comprising: a porous phosphor layer comprising sintered phosphor particles; and an inorganic transparent silicate binder substantially filling spaces in the porous phosphor layer, the silicate binder being formed by curing a liquid glass infused in the porous phosphor layer after the porous phosphor layer was formed.
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KR1020207021756A KR102228997B1 (en) 2012-03-29 2013-03-20 Phosphor in inorganic binder for led applications
US14/385,594 US9337398B2 (en) 2012-03-29 2013-03-20 Phosphor in inorganic binder for LED applications
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150204494A1 (en) * 2014-01-21 2015-07-23 Toyoda Gosei Co., Ltd. Light-Emitting Device and Method of Manufacturing the Same
EP2903040A1 (en) * 2014-01-29 2015-08-05 Sharp Kabushiki Kaisha Wavelength conversion member, light-emitting device, and method for producing wavelength conversion member
JP2016100594A (en) * 2014-11-18 2016-05-30 アクロラックス・インコーポレーテッド Package structure, manufacturing method therefor and molding base material
WO2016094799A1 (en) * 2014-12-11 2016-06-16 Luminus, Inc. Led flip chip structures with extended contact pads formed by sintering silver
US9401468B2 (en) 2014-12-24 2016-07-26 GE Lighting Solutions, LLC Lamp with LED chips cooled by a phase transformation loop
CN105814700A (en) * 2013-12-19 2016-07-27 奥斯兰姆奥普托半导体有限责任公司 Conversion element, method for the production of a conversion element, optoelectronic component comprising a conversion element
WO2018158194A1 (en) * 2017-02-28 2018-09-07 Osram Opto Semiconductors Gmbh Optoelectronic component and method for producing an optoelectronic component
WO2018162375A2 (en) 2017-03-08 2018-09-13 Merck Patent Gmbh Luminophore mixtures for use in dynamic lighting systems
WO2019002328A1 (en) 2017-06-30 2019-01-03 Merck Patent Gmbh Wavelength converting component

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10439112B2 (en) * 2012-05-31 2019-10-08 Cree, Inc. Light emitter packages, systems, and methods having improved performance
US20150364650A1 (en) * 2014-06-12 2015-12-17 Epistar Corporation Light-emitting device and method of manufacturing the same
CN106154365B (en) * 2015-04-16 2019-01-08 深圳市光峰光电技术有限公司 A kind of preparation method and Wavelength converter of diffusing reflection layer
JP6920859B2 (en) * 2016-04-04 2021-08-18 スタンレー電気株式会社 Light emitting device and its manufacturing method
JP6790563B2 (en) * 2016-08-05 2020-11-25 日本電気硝子株式会社 Manufacturing method of wavelength conversion member
TWI787326B (en) * 2017-09-08 2022-12-21 日商杜邦東麗特殊材料股份有限公司 Manufacturing method of sealed optical semiconductor element
TWI779077B (en) * 2017-09-08 2022-10-01 日商杜邦東麗特殊材料股份有限公司 Manufacturing method of encapsulated photo-semiconductor element
CN110311026A (en) * 2018-03-27 2019-10-08 白金光学科技（苏州）有限公司 A kind of light-emitting diode encapsulation structure and its manufacturing method
US11201267B2 (en) * 2018-12-21 2021-12-14 Lumileds Llc Photoresist patterning process supporting two step phosphor-deposition to form an LED matrix array
WO2020176964A1 (en) 2019-03-01 2020-09-10 Daryl James Fluorescence time decay sensing apparatus and methods of manufacturing same
KR102272829B1 (en) * 2019-09-11 2021-07-05 한국광기술원 Phosphor Plate Emitting a Visible Light and Near-infrared Wavelength Band and Method for Manufacturing Thereof
US20220320380A1 (en) * 2021-03-31 2022-10-06 Lumileds Llc Thin Compact Wavelength Converting Structure for pcLED
CN114512588B (en) * 2022-02-25 2023-06-16 苏州芯聚半导体有限公司 Micro light emitting diode structure, manufacturing method and display panel

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274399B1 (en) 1998-06-05 2001-08-14 Lumileds Lighting, U.S. Llc Method of strain engineering and impurity control in III-V nitride semiconductor films and optoelectronic devices
EP1199757A2 (en) * 2000-10-17 2002-04-24 Philips Corporate Intellectual Property GmbH Light emitting device with with coated phosphor
US6649440B1 (en) 1999-06-08 2003-11-18 Lumileds Lighting U.S., Llc Aluminum indium gallium nitride-based LED having thick epitaxial layer for improved light extraction
US20050269582A1 (en) 2004-06-03 2005-12-08 Lumileds Lighting, U.S., Llc Luminescent ceramic for a light emitting device
US20060281203A1 (en) 2005-06-09 2006-12-14 Lumileds Lighting U.S, Llc Method of removing the growth substrate of a semiconductor light emitting device
WO2009090580A1 (en) * 2008-01-15 2009-07-23 Koninklijke Philips Electronics N.V. Light scattering by controlled porosity in optical ceramics for leds
DE102009010468A1 (en) * 2008-11-13 2010-05-20 Osram Opto Semiconductors Gmbh Method for manufacturing layer of radiation-emitting functional material arranged with light conversion material particle for substrate, involves supplying composition, which contains solvent and organic bonding agent
US20110031516A1 (en) 2009-08-07 2011-02-10 Koninklijke Philips Electronics N.V. Led with silicone layer and laminated remote phosphor layer
JP2011168627A (en) * 2010-02-16 2011-09-01 National Institute For Materials Science Wavelength converting member, method for manufacturing the same and light-emitting equipment using the same
US20110266569A1 (en) 2010-04-30 2011-11-03 Philips Lumileds Lighting Company, Llc Led wafer with laminated phosphor layer

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6409564B1 (en) * 1998-05-14 2002-06-25 Micron Technology Inc. Method for cleaning phosphor screens for use with field emission displays
US20030129415A1 (en) * 2000-06-07 2003-07-10 Micron Technology, Inc. Method for binding phosphor particles in a field emission display device
US8748923B2 (en) * 2005-03-14 2014-06-10 Philips Lumileds Lighting Company Llc Wavelength-converted semiconductor light emitting device
US7341878B2 (en) * 2005-03-14 2008-03-11 Philips Lumileds Lighting Company, Llc Wavelength-converted semiconductor light emitting device
CN101171205A (en) * 2005-05-11 2008-04-30 日本电气硝子株式会社 Fluorescent composite glass, fluorescent composite glass green sheet and process for production of fluorescent composite glass
JP2006319238A (en) * 2005-05-16 2006-11-24 Koito Mfg Co Ltd Light emitting device and vehicle-mounted lighting fixture
US7795600B2 (en) * 2006-03-24 2010-09-14 Goldeneye, Inc. Wavelength conversion chip for use with light emitting diodes and method for making same
US7999398B2 (en) * 2006-08-03 2011-08-16 Toyoda Gosei Co., Ltd. Solid state device
DE102007053285A1 (en) * 2007-11-08 2009-05-14 Merck Patent Gmbh Process for the preparation of coated phosphors
US8058088B2 (en) * 2008-01-15 2011-11-15 Cree, Inc. Phosphor coating systems and methods for light emitting structures and packaged light emitting diodes including phosphor coating
TWI438262B (en) * 2008-02-07 2014-05-21 Mitsubishi Chem Corp A semiconductor light emitting device, a backlight, a color image display device, and a phosphor
US7858409B2 (en) * 2008-09-18 2010-12-28 Koninklijke Philips Electronics N.V. White point compensated LEDs for LCD displays
JP2010135488A (en) * 2008-12-03 2010-06-17 Toshiba Corp Light-emitting device, and method of manufacturing the same
KR101102237B1 (en) * 2008-12-23 2012-01-03 (주) 아모엘이디 LED package, method of manufacturing LED package, back light unit and lighting device
BR112012002964A2 (en) * 2009-08-12 2020-03-31 Koninklijke Philips Electrnics N. V. COMPOSITION OF LIGHTING DEVICES AND METHOD FOR CONNECTING A FIRST BODY TO A SECOND BODY THROUGH A HIGH REPARATIVE CONNECTION
US9057511B2 (en) * 2010-03-03 2015-06-16 Cree, Inc. High efficiency solid state lamp and bulb
TW201219543A (en) * 2011-04-01 2012-05-16 Chi Mei Corp having the formula of Ii-Mm-Aa-Bb-Ot-Nn:Zr and providing the high luminance and durability

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274399B1 (en) 1998-06-05 2001-08-14 Lumileds Lighting, U.S. Llc Method of strain engineering and impurity control in III-V nitride semiconductor films and optoelectronic devices
US6649440B1 (en) 1999-06-08 2003-11-18 Lumileds Lighting U.S., Llc Aluminum indium gallium nitride-based LED having thick epitaxial layer for improved light extraction
EP1199757A2 (en) * 2000-10-17 2002-04-24 Philips Corporate Intellectual Property GmbH Light emitting device with with coated phosphor
US20050269582A1 (en) 2004-06-03 2005-12-08 Lumileds Lighting, U.S., Llc Luminescent ceramic for a light emitting device
US20060281203A1 (en) 2005-06-09 2006-12-14 Lumileds Lighting U.S, Llc Method of removing the growth substrate of a semiconductor light emitting device
WO2009090580A1 (en) * 2008-01-15 2009-07-23 Koninklijke Philips Electronics N.V. Light scattering by controlled porosity in optical ceramics for leds
DE102009010468A1 (en) * 2008-11-13 2010-05-20 Osram Opto Semiconductors Gmbh Method for manufacturing layer of radiation-emitting functional material arranged with light conversion material particle for substrate, involves supplying composition, which contains solvent and organic bonding agent
US20110031516A1 (en) 2009-08-07 2011-02-10 Koninklijke Philips Electronics N.V. Led with silicone layer and laminated remote phosphor layer
JP2011168627A (en) * 2010-02-16 2011-09-01 National Institute For Materials Science Wavelength converting member, method for manufacturing the same and light-emitting equipment using the same
US20110266569A1 (en) 2010-04-30 2011-11-03 Philips Lumileds Lighting Company, Llc Led wafer with laminated phosphor layer
WO2011135528A1 (en) * 2010-04-30 2011-11-03 Koninklijke Philips Electronics N.V. Led wafer with laminated phosphor layer

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10418529B2 (en) 2013-12-19 2019-09-17 Osram Opto Semiconductors Gmbh Conversion element, method of producing a conversion element, optoelectronic device comprising a conversion element
CN105814700A (en) * 2013-12-19 2016-07-27 奥斯兰姆奥普托半导体有限责任公司 Conversion element, method for the production of a conversion element, optoelectronic component comprising a conversion element
US9576941B2 (en) * 2014-01-21 2017-02-21 Toyoda Gosei Co., Ltd. Light-emitting device and method of manufacturing the same
US20150204494A1 (en) * 2014-01-21 2015-07-23 Toyoda Gosei Co., Ltd. Light-Emitting Device and Method of Manufacturing the Same
EP2903040A1 (en) * 2014-01-29 2015-08-05 Sharp Kabushiki Kaisha Wavelength conversion member, light-emitting device, and method for producing wavelength conversion member
JP2016100594A (en) * 2014-11-18 2016-05-30 アクロラックス・インコーポレーテッド Package structure, manufacturing method therefor and molding base material
WO2016094799A1 (en) * 2014-12-11 2016-06-16 Luminus, Inc. Led flip chip structures with extended contact pads formed by sintering silver
US9401468B2 (en) 2014-12-24 2016-07-26 GE Lighting Solutions, LLC Lamp with LED chips cooled by a phase transformation loop
WO2018158194A1 (en) * 2017-02-28 2018-09-07 Osram Opto Semiconductors Gmbh Optoelectronic component and method for producing an optoelectronic component
US11430922B2 (en) 2017-02-28 2022-08-30 Oskam Oled Gmbh Optoelectronic component and method for producing an optoelectronic component
WO2018162375A2 (en) 2017-03-08 2018-09-13 Merck Patent Gmbh Luminophore mixtures for use in dynamic lighting systems
WO2019002328A1 (en) 2017-06-30 2019-01-03 Merck Patent Gmbh Wavelength converting component
US11466839B2 (en) 2017-06-30 2022-10-11 Merck Patent Gmbh Wavelength converting component

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EP2831931B1 (en) 2019-10-02
US20160233377A1 (en) 2016-08-11
US9337398B2 (en) 2016-05-10
US9537047B2 (en) 2017-01-03
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EP2831931A1 (en) 2015-02-04

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