WO2020077992A1 - 发光装置及其制备方法 - Google Patents

发光装置及其制备方法 Download PDF

Info

Publication number
WO2020077992A1
WO2020077992A1 PCT/CN2019/086932 CN2019086932W WO2020077992A1 WO 2020077992 A1 WO2020077992 A1 WO 2020077992A1 CN 2019086932 W CN2019086932 W CN 2019086932W WO 2020077992 A1 WO2020077992 A1 WO 2020077992A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
metal
layer
reflective layer
emitting device
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2019/086932
Other languages
English (en)
French (fr)
Inventor
张世忠
段银祥
田梓峰
周萌
徐虎
许颜正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Appotronics Corp Ltd
Original Assignee
Appotronics Corp Ltd
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 Appotronics Corp Ltd filed Critical Appotronics Corp Ltd
Publication of WO2020077992A1 publication Critical patent/WO2020077992A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07331—Connecting techniques
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors

Definitions

  • the invention relates to a light-emitting device and a preparation method thereof, which belong to the technical field of lighting and display.
  • the fixed light-emitting component is a new type of light-emitting device developed based on the traditional organic (silicone) / inorganic (glass powder) color wheel. Since there is no large and heavy motor-driven heat sink inside the component, the overall volume of the component is smaller and the mass Lighter, which meets people's requirements for light weight and portability of modern electronic products; in addition, because the component is always at rest during the light emission process, it has a more stable light effect than the rotating color wheel. Therefore, the fixed light-emitting component will be a type of light-emitting device with broad development prospects, and has great potential application value.
  • the heat generated by the wavelength conversion material in the fixed light-emitting assembly is mainly transferred to the outside through the reflective metal layer and the thermally conductive ceramic substrate connected thereto. Therefore, not only the reflective layer (silver thermal conductivity ⁇ 429w / m ⁇ k) and the ceramic thermally conductive substrate (AlN thermal conductivity ⁇ 320w / m ⁇ k) are required to have excellent thermal conductivity and heat dissipation ability, but also the two must be firmly bonded, otherwise the interface There will be a lot of air (thermal conductivity ⁇ 0.02w / m ⁇ k).
  • the presence of air will seriously damage the overall heat conduction capacity of the component, so that the heat generated in the wavelength conversion material cannot be quickly transmitted through the ceramic thermally conductive substrate, causing heat accumulation in the wavelength conversion material, premature lumen saturation, and even fluorescence quenching
  • the luminous performance of the module is seriously damaged; on the other hand, under the action of thermal excitation, the oxygen and sulfur in the air between the reflective silver layer and the interface are chemically reacted, causing the oxidation and sulfidation of the reflective silver layer, which greatly reduces the reflection of the reflective silver layer ability.
  • the characteristics of the covalent bond in the ceramic thermally conductive substrate and the metal bond in the reflective metal layer are too different, the interface between the two is not wetted, and the difference in their thermal expansion coefficients causes the interface to easily accumulate thermal stress.
  • the prior art mainly uses glue to bond the ceramic thermally conductive substrate and the reflective metal layer.
  • the existing glue has poor thermal conductivity (thermal conductivity ⁇ 0.02w / m ⁇ k), and is easily softened and decomposed at high temperature, causing the interface to fall off.
  • thermal conductivity thermal conductivity ⁇ 0.02w / m ⁇ k
  • more heat will be generated in the wavelength conversion material, which requires the component to have higher thermal conductivity and heat resistance. Therefore, how to tightly combine the ceramic thermally conductive substrate and the reflective metal layer is a problem that needs to be solved urgently.
  • the technical problem to be solved by the present invention is to provide a light-emitting device and a preparation method for the deficiencies of the prior art.
  • a bonding layer containing ceramic particles and Al alloy between the metal reflective layer and the ceramic thermal conductive substrate By adding a bonding layer containing ceramic particles and Al alloy between the metal reflective layer and the ceramic thermal conductive substrate, the improvement is improved.
  • the adhesion between the metal reflective layer and the ceramic thermally conductive substrate prevents the interface from sticking tightly, improves the adhesion of the interface, avoids the fluorescence quenching caused by heat accumulation, and extends the life of the light-emitting device.
  • the invention provides a light-emitting device comprising a light-emitting layer, a metal reflective layer and a ceramic heat-conducting substrate stacked in sequence, and an adhesive layer is provided between the metal reflective layer and the ceramic heat-conducting substrate, and the adhesive layer comprises For AlN ceramic particles, the bonding layer further includes metallic Al or Al-Me alloy, where Me is a metal material different from Al.
  • the Me is Ag, Au or Cu
  • the material of the metal reflective layer is Al, Ag, Au or Cu.
  • the material of the light-emitting layer is Ce 3 + -doped YAG ceramic, YAG phase and Al 2 O 3 composite yellow light ceramic and (Sr, Ca) AlSiN 3 : Eu 2+ , (Sr, Ca) 2 Si 5 N 8 : one of Eu 2+ red ceramics; the material of ceramic thermal conductive substrate is AlN.
  • the Al-Me alloy is disposed on the side of the bonding layer facing the metal reflective layer, and the AlN ceramic particles are disposed on the side of the bonding layer away from the metal reflective layer.
  • the thickness of the adhesive layer is 5 ⁇ m-20 ⁇ m; the thickness of the metal reflective layer is 40 ⁇ m-120 ⁇ m.
  • the thickness of the adhesive layer is 10 ⁇ m-15 ⁇ m; the thickness of the metal reflective layer is 60 ⁇ m-100 ⁇ m.
  • the invention also proposes a preparation method of a light-emitting device, the preparation method comprising:
  • the material of the metal powder is Al, Ag, Au or Cu
  • the binding powder is Al powder, or Me powder and Al powder
  • the Me is a metal material different from Al.
  • the mass ratio of the binding powder and the organic carrier is 1: (0.05-0.2); in S4, the mass ratio of the metal powder and the organic carrier is 1: (0.05-0.2).
  • the mass ratio of the binding powder and the organic carrier is 1: (0.08-0.12); in S4, the mass ratio of the metal powder and the organic carrier is 1: (0.08-0.12).
  • the baking temperature is 130 ° C, and the baking time is 30min-60min; in S6, the drying temperature is 270 ° C-420 ° C, drying The time is 120min-240min; in S7, the pressing uses a cold isostatic pressing process, the pressing pressure is 80MPa-100MPa, and the holding time is 30s-60s.
  • the material of the metal powder is Ag.
  • the sintering temperature of the sintering is 800 ° C-860 ° C, and the sintering time is 10min-60min.
  • the present invention improves the adhesion between the metal reflective layer and the ceramic thermal conductive substrate by adding a bonding layer containing ceramic particles and Al alloy between the metal reflective layer and the ceramic thermal conductive substrate, and prevents the interface from sticking It improves the adhesion of the interface, avoids the quenching of fluorescence caused by heat accumulation, and extends the service life of the light-emitting device.
  • FIG. 1 is a cross-sectional view of the structure of the light-emitting device of the present invention.
  • FIG. 2 is a plan view of the structure of the light-emitting device of the present invention.
  • Figure 3 is the phase diagram of the Ag-Al binary alloy
  • FIG. 5 is a schematic diagram of a light-emitting device in the prior art after being subjected to a destruction test
  • FIG. 6 is a schematic diagram of the light-emitting device of the present invention after a destruction test.
  • FIG. 1 is a cross-sectional view of the structure of the light-emitting device of the present invention
  • FIG. 2 is a top view of the structure of the light-emitting device of the present invention.
  • the present invention provides a light-emitting device and a method for manufacturing the same.
  • the light-emitting device includes a light-emitting layer 40, a metal reflective layer 30, and a ceramic thermally conductive substrate 10 that are sequentially stacked, wherein the metal reflective layer 30
  • An adhesive layer 20 is provided between the ceramic thermal conductive substrate 10 and the adhesive layer 20 is used to connect the metal reflective layer 30 and the ceramic thermal conductive substrate 10 and achieve heat transfer therebetween.
  • the light-emitting device can be used alone as a fixed light-emitting component, or can be used in conjunction with a motor-driven heat dissipation device as a color wheel.
  • the function of the light-emitting layer 40 is to receive the irradiation of excitation light and convert the excitation light into laser beams with different wavelengths.
  • the invention does not limit the shape and material of the light-emitting layer 40.
  • the shape may be, for example, a square, round, or fan-shaped sheet, or may have a curved profile, which is subject to practical application.
  • the present invention will use a sheet-shaped light-emitting layer as an example; the material may be a yellow-emitting fluorescent ceramic It can also be a fluorescent glass that emits yellow light, or a fluorescent ceramic or fluorescent glass that emits light of other colors after being stimulated, such as yellow light-emitting cerium (Ce 3+ ) doped YAG ceramic, YAG phase, and Al 2 O 3 composite yellow light ceramics and (Sr, Ca) AlSiN 3 : Eu 2+ , (Sr, Ca) 2 Si 5 N 8 : Eu 2+ red light ceramics and other series of luminescent ceramic materials.
  • the main function of the metal reflective layer 30 is to reflect the received laser light, and any material with high reflectivity can be used as the metal reflective layer 30, such as Al, Ag, Au, Cu, or the like.
  • Table 1 shows the reflectance and other information of several metals under different wavelengths of light. Since the metal Ag has a high reflectance in the visible light range of 400nm-800nm, the metal reflective layer 30 in this embodiment
  • the material is preferably Ag. It should be added that because different metals have different reflectances for different wavelengths of light, certain metals have higher reflectances for specific wavelengths and lower reflectances for other wavelengths. Such metals can also be used as metal reflections
  • the material of layer 30 is used to reflect light of a specific wavelength.
  • the material of the ceramic thermal conductive substrate 10 may be a variety of ceramic materials with excellent thermal conductivity, such as Al 2 O 3 ceramics, AlN ceramics, SiN ceramics, etc., preferably AlN ceramics, which mainly conducts heat generated by the light emitting layer 40, Thereby reducing the overall temperature of the light emitting device.
  • the bonding layer 20 includes AlN ceramic particles 22, and the bonding layer 20 further includes metal Al or Al-Me alloy 21.
  • the Al-Me alloy of the present invention is a metal other than Al and Al.
  • the Al-Me alloy 21 is disposed on the side of the bonding layer 20 facing the metal reflective layer 30, and the AlN ceramic particles 22 are disposed on the side of the bonding layer 20 away from the metal reflective layer 30.
  • the arrangement of the Al-Me alloy 21 and the AlN ceramic particles 22 in the bonding layer 20 can be understood as that the Al-Me alloy 21 is enriched on the side of the bonding layer 20 close to the metal reflective layer 30, while the AlN ceramic particles 22 are rich It is collected on the side of the adhesive layer 20 away from the metal reflective layer 30, for example, on the side close to the ceramic thermal conductive substrate 10. Due to the similar miscibility principle, the AlN ceramic particles 22 diffuse to the ceramic thermally conductive substrate 10 side at high temperature and are closely adhered to the surface of the ceramic thermally conductive substrate 10; and the Al-Me alloy 21 is closely adhered to the metal reflective layer 30 Excellent connection performance.
  • the adhesive layer 20 can improve the adhesion between the metal reflective layer 30 and the ceramic thermal conductive substrate 10, improve the interface adhesion, prevent the difficulty of heat conduction and heat accumulation caused by the weak interface adhesion, and avoid light saturation. Even the phenomenon of fluorescence quenching, at the same time, the bonding layer 20 can reduce the contact between the metal reflective layer 30 and the air, and prevent the metal reflective layer 30 from reacting with oxygen and sulfur in the air when thermally excited to cause a significant drop in reflectivity.
  • Me can theoretically be any metal different from Al, such as Al, Ag, Au, Cu, or the like.
  • the metal reflective layer 30 that is used as a reflection in the light-emitting device of the present invention can be considered to be made of any metal that has a high reflectivity to a predetermined wavelength, such as a high reflection in the visible light range of 400nm-800nm Rated metal Ag, metal Au with high reflectivity to infrared light.
  • the material of the metal reflective layer 30 may be the same as at least one metal in the Al-Me alloy, for example, when Me is specifically Ag, the metal reflective layer is an Ag reflective layer, and the alloy in the bonding layer is Al-Ag alloy; or The metal reflective layer is an Al reflective layer, and the alloy in the bonding layer is an Al-Ag alloy.
  • the material of the metal reflective layer 30 may also be different from any metal in the Al-Me alloy.
  • the alloy in the bonding layer is Al-Ag alloy
  • the metal reflective layer is Au reflective layer Or Cu reflective layer, etc.
  • the metal reflective layer is an Ag reflective layer
  • the Al-Me alloy is an Al-Ag alloy as an example.
  • the ceramic thermal conductive substrate can be cleaned with absolute ethanol, and then baked at 80 ° C. for 2 hours to obtain a ceramic thermal conductive substrate with a clean surface and no dirt.
  • the binding powder and the organic vehicle are uniformly mixed to prepare a binding layer slurry.
  • the binding powder and the organic carrier can be placed in a planetary stirring device and mixed for 10 minutes to achieve uniform dispersion of the binding powder in the organic carrier.
  • the mass ratio of the binding powder and the organic carrier is 1: (0.05-0.2), preferably 1: (0.08-0.12).
  • the organic carrier is at least one of ethyl cellulose, terpineol, butyl carbitol, and butyl carbitol ester.
  • the bonding powder may be Al powder, or Me powder and Al powder.
  • the present invention does not limit the ratio of Me powder and Al powder, as long as the bonding layer and heat conduction in the light-emitting device formed by the preparation method of the present invention can be achieved
  • the adhesion of the substrate may be greater than the adhesion between the metal reflective layer of the light-emitting device without the adhesive layer and the thermally conductive substrate in the prior art.
  • the baking temperature is 130 °C, and the baking time is 30min-60min.
  • a person skilled in the art can select the thickness of the coating adhesive layer slurry according to the experiment to control the thickness of the adhesive layer.
  • the thickness of the adhesive layer is preferably 5 ⁇ m-20 ⁇ m, more preferably 10 ⁇ m-15 ⁇ m.
  • the metal powder and the organic vehicle are uniformly mixed to prepare a reflective layer slurry.
  • the metal powder and the organic carrier can be placed in a planetary stirring device and mixed for 10 minutes to achieve uniform dispersion of the metal powder in the organic carrier.
  • the mass ratio of metal powder to organic carrier is 1: (0.05-0.2), preferably 1: (0.08-0.12).
  • the organic carrier is at least one of ethyl cellulose, terpineol, butyl carbitol, and butyl carbitol ester.
  • S5 Brush the reflective layer paste on the baked adhesive layer paste, cover the light emitting layer on the reflective layer paste, and bake to obtain a semi-finished product.
  • the baking temperature is 130 °C
  • the baking time is 30min-60min.
  • the thickness of the reflective layer paste is preferably 40 ⁇ m-120 ⁇ m, more preferably 60 ⁇ m-100 ⁇ m.
  • S6 Dry the semi-finished product.
  • the drying temperature is 270 ° C-420 ° C, and the drying time is 120min-240min, to remove the organic carrier in the adhesive layer slurry and the reflective layer slurry.
  • S7 Press and dry the semi-finished product to enhance the interface adhesion between the layers.
  • a cold isostatic pressing process pressurize at a pressure rate of 1 MPa / s-2 MPa / s to the pressing pressure, and then hold the pressure for a certain period of time.
  • the pressing pressure is preferably 80MPa-100MPa, and the holding time is preferably 30s-60s.
  • S8 Sintered and pressed semi-finished product is sintered under N 2 atmosphere to form a light-emitting device.
  • the sintering temperature is preferably 800 ° C-860 ° C
  • the sintering time is preferably 10min-60min, more preferably 15min-30min.
  • the present invention is not limited to this, and those skilled in the art may select different sintering temperatures according to different materials of the metal reflective layer 30.
  • Figure 3 is the phase diagram of the Ag-Al binary alloy.
  • the melting point of pure silver is about 962 ° C, so as long as the sintering temperature is in the range of 800 ° C-900 ° C, the Ag metal reflective layer will not melt;
  • the melting temperature of the Al-Ag alloy solid solution can also be maintained at 800 ° C-900 ° C sintering temperature without melting; therefore, the sintering temperature is preferably 800 ° C-860 ° C.
  • the metal powder in the reflective layer paste achieves sintering densification, and the Al powder in the adhesive layer paste that contacts the reflective layer paste is dissolved into a certain thickness in the metal powder, thereby forming a thin layer at the interface between the two Al-Me alloy to enhance the interface adhesion between the two.
  • FIG. 4 is a schematic diagram of preparing AlN powder by direct nitridation of Al powder.
  • the Al powder in contact with the ceramic thermally conductive substrate in the adhesive layer slurry reacts with nitrogen gas at high temperature to generate AlN ceramic particles (2Al + N 2 ⁇ 2AlN), and the AlN ceramic particles are directed toward the ceramic thermally conductive substrate
  • the surface diffuses and pegs the ceramic thermally conductive substrate to enhance the adhesion between the two.
  • the thickness of the metal reflective layer is preferably 40 ⁇ m-120 ⁇ m, and when the thickness of the metal reflective layer is 10 ⁇ m, the technical effect of reflecting and receiving laser light can be achieved, that is, in this embodiment, the metal reflective layer is removed
  • the thickness in contact with the adhesive layer is still at least 30 ⁇ m thick, which can prevent the Al-Me alloy in contact with the metal reflective layer from affecting the reflection effect of the metal reflective layer.
  • AlN ceramic particles 22 may appear near the Al-Me alloy, but due to the presence of the metal Me, the Al near the metal reflective layer tends to form an Al-Me alloy, so although A small amount of AlN ceramic particles will be formed in the Al-Me alloy portion of the junction layer, but this situation does not affect the metal reflective layer 30, but can further enhance the adhesion between the interfaces.
  • FIG. 5 is a schematic diagram of a light-emitting device in the prior art after being destroyed
  • FIG. 6 is a schematic diagram of the light-emitting device of the present invention after being destroyed.
  • the reflective metal layer in the light-emitting device in which the ceramic thermal conductive substrate and the reflective metal layer are bonded by glue in the prior art is peeled off, and the present invention passes
  • the reflective metal layer in the light-emitting device connected by the adhesive layer is closely attached to the surface of the ceramic thermal conductive substrate.
  • the sintering temperature of other mixed metal embodiments in the method provided by the present invention can be obtained, and a structure similar to the adhesive layer in this case can be prepared. It should be understood that even without a binary alloy phase diagram, based on the melting temperatures of the two metals, an approximate sintering temperature range can be obtained through experiments.
  • the present invention improves the adhesion between the metal reflective layer and the ceramic thermal conductive substrate by adding a bonding layer containing ceramic particles and Al alloy between the metal reflective layer and the ceramic thermal conductive substrate, and prevents the interface from sticking It improves the adhesion of the interface, avoids the quenching of fluorescence caused by heat accumulation, and extends the service life of the light-emitting device.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Led Device Packages (AREA)

Abstract

一种发光装置及其制备方法，所述发光装置包含依次层叠的发光层(40)、金属反射层(30)以及陶瓷导热基板(10)，所述金属反射层(30)与陶瓷导热基板(10)之间设有粘结层(20)，所述粘结层(20)包含AlN陶瓷颗粒(22)，所述粘结层(20)还包含金属Al或者Al-Me合金(21)，其中，所述Me为不同于Al的金属材料。本发明通过在金属反射层与陶瓷导热基板之间增设包含陶瓷颗粒和Al合金的粘结层，改善了金属反射层与陶瓷导热基板间的粘接情况，防止界面粘接不牢，提高了界面的粘接力，避免了热量积聚而导致的荧光淬灭现象，延长了发光装置的使用寿命。

Description

发光装置及其制备方法 技术领域
本发明涉及一种发光装置及其制备方法，属于照明及显示技术领域。
背景技术
固定式发光组件是基于传统有机(硅胶类)/无机(玻璃粉)色轮发展起来的一种新型发光装置，由于组件内部不存在大而重的马达驱动散热器件，组件整体体积更小，质量更轻，满足了人们对现代电子产品质轻、便携的要求；此外，由于发光过程中，组件始终处于静止状态，其具有较转动式色轮更加稳定的发光光效。因而，固定式发光组件将是一类具有广大发展前景的发光装置，具备极大的潜在应用价值。
然而，由于缺少马达驱动散热装置，固定式发光组件中波长转换材料产生的热量主要通过与其连接的反射金属层及导热陶瓷基板向外传递。因而，不仅要求反射层(银导热系数≈429w/m·k)及陶瓷导热基板(AlN导热系数≈320w/m·k)具有优异的导热散热能力，而且需要两者粘接牢固，否则界面中会出现大量的空气(导热系数≈0.02w/m·k)。空气的存在一方面会严重损害组件整体热量传导能力，使得波长转换材料中产生的热量无法快速通过陶瓷导热基板传输出去，造成波长转化材料中热量积聚，过早发生流明饱和，甚至荧光淬灭现象，组件的发光性能被严重损害；另一方面，在热激发作用下，反射银层与界面空气中的氧及硫发生化学作用，造成反射银层的氧化硫化，极大降低反射银层的反射能力。除此之外，陶瓷导热基板内共价键和反射金属层内金属键的特性相差太大，二者界面不润湿，且其热膨胀系数的不同导致二者界面易积聚热应力。
现有技术主要是通过胶水将陶瓷导热基板和反射金属层粘接起 来，而现有胶水的导热能力较差(导热系数≈0.02w/m·k)，高温下易软化分解，造成界面脱落。随固定式发光组件朝高亮，高流明领域发展，波长转换材料中将产生更多的热量，从而要求组件整体具有更高的导热、耐热能力。因此，如何使陶瓷导热基板和反射金属层紧密结合，是目前亟待解决的问题。
发明内容
本发明所要解决的技术问题在于针对现有技术的不足，提供一种发光装置及其制备方法，通过在金属反射层与陶瓷导热基板之间增设包含陶瓷颗粒和Al合金的粘结层，改善了金属反射层与陶瓷导热基板间的粘接情况，防止界面粘接不牢，提高了界面的粘接力，避免了热量积聚而导致的荧光淬灭现象，延长了发光装置的使用寿命。
本发明所要解决的技术问题是通过如下技术方案实现的：
本发明提供一种发光装置，所述发光装置包含依次层叠的发光层、金属反射层以及陶瓷导热基板，所述金属反射层与陶瓷导热基板之间设有粘结层，所述粘结层包含AlN陶瓷颗粒，所述粘结层还包含金属Al或者Al-Me合金，其中，所述Me为不同于Al的金属材料。
优选地，所述Me为Ag、Au或Cu，所述金属反射层的材质为Al、Ag、Au或Cu。
优选地，所述发光层的材质为Ce 3+掺杂的YAG陶瓷、YAG相和Al 2O 3相复合的黄光陶瓷以及(Sr,Ca)AlSiN 3:Eu 2+、(Sr,Ca) 2Si 5N 8：Eu 2+红光陶瓷中的一种；陶瓷导热基板的材质为AlN。
为了粘接金属反射层，所述Al-Me合金设置在所述粘结层朝向金属反射层的一侧，所述AlN陶瓷颗粒设置在所述粘结层远离金属反射层的一侧。
优选地，所述粘结层的厚度为5μm-20μm；所述金属反射层的厚度为40μm-120μm。
优选地，所述粘结层的厚度为10μm-15μm；所述金属反射层的厚度为60μm-100μm。
本发明还提动一种发光装置的制备方法，所述制备方法包含：
S1：清洁陶瓷导热基板；
S2：将粘结粉和有机载体均匀混合以制备粘结层浆料；
S3：在所述陶瓷导热基板表面涂刷并烘烤所述粘结层浆料；
S4：将金属粉和有机载体均匀混合以制备反射层浆料；
S5：在烘烤后的粘结层浆料上涂刷所述反射层浆料，并将发光层盖在反射层浆料上后烘烤以得到半成品；
S6：烘干所述半成品；
S7：压制烘干后的半成品；
S8：在N 2气氛下烧结压制后的半成品，以形成发光装置；
其中，所述金属粉的材质为Al、Ag、Au或Cu，所述粘结粉为Al粉、或者Me粉和Al粉，所述Me为不同于Al的金属材料。
在S2中，所述粘结粉和有机载体的质量比为1：(0.05-0.2)；在S4中，所述金属粉和有机载体的质量比为1：(0.05-0.2)。
优选地，在S2中，所述粘结粉和有机载体的质量比为1：(0.08-0.12)；在S4中，所述金属粉和有机载体的质量比为1：(0.08-0.12)。
优选地，在S3和S5中，所述烘烤的烘烤温度为130℃，烘烤时间为30min-60min；在S6中，所述烘干的烘干温度为270℃-420℃，烘干时间为120min-240min；在S7中，所述压制采用冷等静压压制工艺，压制压力为80MPa-100MPa，保压时间为30s-60s。
优选地，所述金属粉的材质为Ag，在S8中，所述烧结的烧结温度为800℃-860℃，烧结时间为10min-60min。
综上所述，本发明通过在金属反射层与陶瓷导热基板之间增设包含陶瓷颗粒和Al合金的粘结层，改善了金属反射层与陶瓷导热基板间的粘接情况，防止界面粘接不牢，提高了界面的粘接力，避免了热量积聚而导致的荧光淬灭现象，延长了发光装置的使用寿命。
下面结合附图和具体实施例，对本发明的技术方案进行详细地说明。
附图说明
图1为本发明发光装置的结构剖视图；
图2为本发明发光装置的结构俯视图；
图3为Ag-Al二元合金相图；
图4为Al粉直接氮化法制备AlN粉末的示意图；
图5为现有技术中发光装置经破坏试验后的示意图；
图6为本发明发光装置经破坏试验后的示意图。
具体实施方式
图1为本发明发光装置的结构剖视图；图2为本发明发光装置的结构俯视图。如图1和图2所示，本发明提供一种发光装置及其制备方法，所述发光装置包含依次层叠的发光层40、金属反射层30以及陶瓷导热基板10，其中所述金属反射层30与陶瓷导热基板10之间设有粘结层20，所述粘结层20用于连接金属反射层30和陶瓷导热基板10，并实现二者之间的热传递。所述发光装置可以作为固定式发光组件单独使用，也可以与马达驱动散热装置配合，作为色轮使用。
所述发光层40的作用在于接收激发光的照射，并将激发光转换为波长不同的受激光。本发明并不对发光层40的形状、材料作限制。形状例如可以是方形、圆形或扇形的片状，也可以具有曲面的异形，具体以实际的应用为准，本发明将以片状的发光层为例；材料可以是发黄光的荧光陶瓷，也可以是发黄光的荧光玻璃，还可以是受激后发射其他颜色光的荧光陶瓷或荧光玻璃，例如发黄光的铈(Ce 3+)掺杂的YAG陶瓷、YAG相和Al 2O 3相复合的黄光陶瓷以及(Sr,Ca)AlSiN 3:Eu 2+、(Sr,Ca) 2Si 5N 8：Eu 2+红光陶瓷等系列发光陶瓷材料。
所述金属反射层30的主要作用为反射所述受激光，反射率高的材质均可作为金属反射层30，例如可以为Al、Ag、Au或Cu等。表1示出了几种金属在不同波长光线照射下的反射率等信息，由于金属Ag在波长为400nm-800nm的可见光范围内具有较高反射率，因此，本实施例中金属反射层30的材质优选为Ag。需要补充的是，由于不同金属对不同波长光线的反射率不同，某些特定金属对于特定波长光线的反射率较高，而对其他波长光线的反射率较低，此种金属也可作为金 属反射层30的材料，用于反射特定波长的光线。
表1
Figure PCTCN2019086932-appb-000001
所述陶瓷导热基板10的材质可以为多种导热性优良的陶瓷材料，例如Al 2O 3陶瓷、AlN陶瓷、SiN陶瓷等，优选为AlN陶瓷，其主要作用为传导发光层40产生的热量，从而降低发光装置的整体温度。
所述粘结层20包含AlN陶瓷颗粒22，所述粘结层20还包含金属Al或者Al-Me合金21，应当理解的是，本发明的Al-Me合金为Al和Al以外的其他金属经熔化、混合、冷却、凝固后得到的具有金属性质的固体产物。所述Al-Me合金21设置在粘结层20朝向金属反射层30的一侧，所述AlN陶瓷颗粒22设置在粘结层20远离金属反射层30的一侧。上述粘结层20中的Al-Me合金21和AlN陶瓷颗粒22的设置可理解为，Al-Me合金21富集在粘结层20靠近金属反射层30的一侧，而AlN陶瓷颗粒22富集在粘结层20远离金属反射层30的一侧，例如靠近陶瓷导热基板10的一侧。所述AlN陶瓷颗粒22由于相似相溶原理，在高温下向陶瓷导热基板10侧扩散，紧紧粘贴在陶瓷导热基板10表面；而Al-Me合金21则紧紧粘接金属反射层30，粘接性能优良。所述粘结层20能够改善金属反射层30与陶瓷导热基板10间的粘接情况，提高界面粘接力，防止界面粘接不牢而导致的热量传导困难和热量积聚，避免发生光饱和，甚至荧光淬灭现象，同时粘结层20可以减少金属反射层30与空气接触，防止金属反射层30在热激发时与空气中的氧及硫发生反应而造成反射率的大幅下降。
需要说明的是，Me理论上可以是不同于Al的任意一种金属，例如可以为Al、Ag、Au或Cu等。如前所述，考虑作为本发明发光装置中起反射作用的金属反射层30，其材质可以是对预定波长具有较高反射率的任意金属，例如对400nm-800nm的可见光范围内具有较高反射 率金属Ag，对红外光具有较高反射率的金属Au。因此，金属反射层30的材质可以与Al-Me合金中至少一种金属相同，例如当Me具体为Ag时，金属反射层为Ag反射层，粘结层中的合金为Al-Ag合金；或者金属反射层为Al反射层，粘结层中的合金为Al-Ag合金。当然，金属反射层30的材质也可以与Al-Me合金中的任意金属都不同，例如当Me具体为Ag时，粘结层中的合金为Al-Ag合金，而金属反射层为Au反射层或Cu反射层等。
本发明以金属反射层为Ag反射层，Al-Me合金为Al-Ag合金为例进行说明。
下面介绍一种上述发光装置的制备方法。需要说明的是，本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
S1：清洁陶瓷导热基板。具体来说，可以使用无水乙醇清洗陶瓷导热基板，之后在80℃温度下烘烤2h，从而得到表面清洁无脏污的陶瓷导热基板。
S2：将粘结粉和有机载体均匀混合以制备粘结层浆料。具体来说，可以将粘结粉和有机载体置入行星搅拌装置中混合10min，以实现粘结粉均匀分散在有机载体中。其中粘结粉和有机载体的质量比为1：(0.05-0.2)，优选为1：(0.08-0.12)。所述有机载体为乙基纤维素、松油醇、丁基卡比醇、丁基卡比醇酯中的至少一种。
所述粘结粉可以为Al粉、或者Me粉和Al粉，本发明并不限制Me粉和Al粉的比例，只要可以实现按本发明的制备方法所形成的发光装置中粘结层与导热基板的附着力大于现有技术中不设该粘结层的发光装置的金属反射层与导热基板的附着力即可。
S3：在所述陶瓷导热基板表面涂刷并烘烤所述粘结层浆料。烘烤温度为130℃，烘烤时间为30min-60min。本领域技术人员可以根据试验来选择涂刷粘结层浆料的厚度，从而控制粘结层厚度，粘结层的厚度优选为5μm-20μm，更优选为10μm-15μm。
S4：将金属粉和有机载体均匀混合以制备反射层浆料。具体来说，可以将金属粉和有机载体置入行星搅拌装置中混合10min，以实现金属 粉均匀分散在有机载体中。其中金属粉和有机载体的质量比为1：(0.05-0.2)，优选为1：(0.08-0.12)。所述有机载体为乙基纤维素、松油醇、丁基卡比醇、丁基卡比醇酯中的至少一种。
S5：在烘烤后的粘结层浆料上涂刷所述反射层浆料，并将发光层盖在反射层浆料上后烘烤以得到半成品。烘烤温度为130℃，烘烤时间为30min-60min。本领域技术人员可以根据试验来选择涂刷反射层浆料的厚度，从而控制金属反射层的厚度，所述金属反射层的厚度优选为40μm-120μm，更优选为60μm-100μm。
S6：烘干所述半成品。烘干温度为270℃-420℃，烘干时间为120min-240min，以排去粘结层浆料和反射层浆料中的有机载体。
S7：压制烘干后的半成品，以增强各层间的界面粘接力。例如，优选采用冷等静压压制工艺：以1MPa/s-2MPa/s的加压速率增压至压制压力，而后保压一定时间。压制压力优选80MPa-100MPa，保压时间优选30s-60s。
S8：在N 2气氛下烧结压制后的半成品，以形成发光装置。例如，当金属反射层30的材质为Ag时，烧结温度优选800℃-860℃，烧结时间优选10min-60min，更优选15min-30min。本发明并不以此为限，本领域技术人员可以根据金属反射层30的不同材质选取不同的烧结温度。
图3为Ag-Al二元合金相图。如图3所示，纯银的熔点约为962℃，所以只要烧结温度在800℃-900℃范围，Ag金属反射层不会发生融化现象；粘结层采用Al-Ag合金时，在本发明选择的烧结温度范围内，通过限定合金溶度，Al-Ag合金固溶体融化温度也可以保持在800℃-900℃烧结温度不融化；因此，烧结温度优选800℃-860℃。
在烧结过程中反射层浆料中的金属粉实现烧结致密化，粘结层浆料中与反射层浆料接触的Al粉固溶到金属粉中一定厚度，从而在两者界面生成一薄层Al-Me合金，增强两者界面粘结力。
图4为Al粉直接氮化法制备AlN粉末的示意图。如图4所示，粘结层浆料中与陶瓷导热基板接触的Al粉在高温下与氮气化学反应，生成AlN陶瓷颗粒(2Al+N 2→2AlN)，所述AlN陶瓷颗粒向陶瓷导热基 板表面扩散，扎钉陶瓷导热基板，增强两者间的粘结力。
由于本实施例中，所述金属反射层的厚度优选为40μm-120μm，而当金属反射层的厚度为10μm时，便可实现反射受激光的技术效果，即本实施例中，金属反射层除去与粘结层接触的厚度，仍至少有30μm的厚度空余，其能够防止与金属反射层接触的Al-Me合金影响金属反射层的反射效果。
需要补充的是，在烧结过程中，AlN陶瓷颗粒22可能出现在Al-Me合金附近，但是由于金属Me的存在，靠近金属反射层一侧的Al更趋向于形成Al-Me合金，因此尽管粘结层的Al-Me合金部分中会有少量AlN陶瓷颗粒形成，但这种情况的出现并不会对金属反射层30造成影响，反而可以进一步增强各界面之间的粘接力。
需要说明的是，本发明并不限定上述制备工艺的相关工艺参数，本领域技术人员可以根据实际需要进行调整。
图5为现有技术中发光装置经破坏试验后的示意图；图6为本发明发光装置经破坏试验后的示意图。如图5和图6所示，在经过相同条件的破坏试验后，现有技术中通过胶水将陶瓷导热基板和反射金属层粘接的发光装置中的反射金属层发生脱落，而本发明中通过粘结层连接的发光装置中的反射金属层紧密贴至陶瓷导热基板表面。
需要说明的是，通过不同的二元合金相图可以获取其他混合金属的实施方式在本发明所提供的方法中的烧结温度，进而制备出与本案粘结层类似的结构。应当理解，即便没有二元合金相图，基于两种金属的熔融温度，通过实验也可以获得大致的烧结温度范围。
综上所述，本发明通过在金属反射层与陶瓷导热基板之间增设包含陶瓷颗粒和Al合金的粘结层，改善了金属反射层与陶瓷导热基板间的粘接情况，防止界面粘接不牢，提高了界面的粘接力，避免了热量积聚而导致的荧光淬灭现象，延长了发光装置的使用寿命。

Claims (11)

  1. 一种发光装置，所述发光装置包含依次层叠的发光层(40)、金属反射层(30)以及陶瓷导热基板(10)，其特征在于，所述金属反射层(30)与陶瓷导热基板(10)之间设有粘结层(20)，所述粘结层(20)包含AlN陶瓷颗粒(22)，所述粘结层(20)还包含金属Al或者Al-Me合金(21)，其中，所述Me为不同于Al的金属材料。
  2. 如权利要求1所述的发光装置，其特征在于，所述Me为Ag、Au或Cu，所述金属反射层(30)的材质为Al、Ag、Au或Cu。
  3. 如权利要求1所述的发光装置，其特征在于，所述发光层(40)的材质为Ce 3+掺杂的YAG陶瓷、YAG相和Al 2O 3相复合的黄光陶瓷以及(Sr,Ca)AlSiN 3:Eu 2+、(Sr,Ca) 2Si 5N 8：Eu 2+红光陶瓷中的一种；所述陶瓷导热基板(10)的材质为AlN。
  4. 如权利要求1所述的发光装置，其特征在于，所述Al-Me合金(21)设置在所述粘结层(20)朝向金属反射层(30)的一侧，所述AlN陶瓷颗粒(22)设置在粘结层(20)远离金属反射层(30)的一侧。
  5. 如权利要求1所述的发光装置，其特征在于，所述粘结层(20)的厚度为5μm-20μm；所述金属反射层(30)的厚度为40μm-120μm。
  6. 如权利要求5所述的发光装置，其特征在于，所述粘结层(20)的厚度为10μm-15μm；所述金属反射层(30)的厚度为60μm-100μm。
  7. 一种发光装置的制备方法，其特征在于，所述制备方法包含：
    S1：清洁陶瓷导热基板；
    S2：将粘结粉和有机载体均匀混合以制备粘结层浆料；
    S3：在所述陶瓷导热基板表面涂刷并烘烤所述粘结层浆料；
    S4：将金属粉和有机载体均匀混合以制备反射层浆料；
    S5：在烘烤后的粘结层浆料上涂刷所述反射层浆料，并将发光层盖在反射层浆料上后烘烤以得到半成品；
    S6：烘干所述半成品；
    S7：压制烘干后的半成品；
    S8：在N 2气氛下烧结压制后的半成品，以形成发光装置；
    其中，所述金属粉的材质为Al、Ag、Au或Cu，所述粘结粉为Al粉、或者Me粉和Al粉，所述Me为不同于Al的金属材料。
  8. 如权利要求7所述的制备方法，其特征在于，在S2中，所述粘结粉和有机载体的质量比为1：(0.05-0.2)；在S4中，所述金属粉和有机载体的质量比为1：(0.05-0.2)。
  9. 如权利要求8所述的制备方法，其特征在于，在S2中，所述粘结粉和有机载体的质量比为1：(0.08-0.12)；在S4中，所述金属粉和有机载体的质量比为1：(0.08-0.12)。
  10. 如权利要求7所述的制备方法，其特征在于，在S3和S5中，所述烘烤的烘烤温度为130℃，烘烤时间为30min-60min；在S6中，所述烘干的烘干温度为270℃-420℃，烘干时间为120min-240min；在S7中，所述压制采用冷等静压压制工艺，压制压力为80MPa-100MPa，保压时间为30s-60s。
  11. 如权利要求7所述的制备方法，其特征在于，所述金属粉的材质为Ag，在S8中，所述烧结的烧结温度为800℃-860℃，烧结时间为10min-60min。
PCT/CN2019/086932 2018-10-16 2019-05-15 发光装置及其制备方法 Ceased WO2020077992A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811201713.9 2018-10-16
CN201811201713.9A CN111063810B (zh) 2018-10-16 2018-10-16 发光装置及其制备方法

Publications (1)

Publication Number Publication Date
WO2020077992A1 true WO2020077992A1 (zh) 2020-04-23

Family

ID=70283353

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/086932 Ceased WO2020077992A1 (zh) 2018-10-16 2019-05-15 发光装置及其制备方法

Country Status (2)

Country Link
CN (1) CN111063810B (zh)
WO (1) WO2020077992A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115702229A (zh) * 2020-06-16 2023-02-14 昕诺飞控股有限公司 嵌入式荧光体瓷砖

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4286901A4 (en) * 2021-01-28 2025-01-01 Niterra Co., Ltd. WAVELENGTH CONVERSION ELEMENT AND LIGHT SOURCE DEVICE PROVIDED WITH SAME

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212008A (zh) * 2006-12-29 2008-07-02 台达电子工业股份有限公司 电致发光装置及其制造方法
CN106287580A (zh) * 2015-06-02 2017-01-04 深圳市光峰光电技术有限公司 波长转换装置及其制备方法、相关发光装置和投影系统

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100505352C (zh) * 2007-12-10 2009-06-24 华中科技大学 一种led芯片及其制备方法
DE202012102188U1 (de) * 2012-06-14 2013-09-26 Polifilm Protection Gmbh Partikelhaltige Klebefolie zum temporären Schutz einer Werkstückoberfläche, insbesondere bei Laserbearbeitung, und Verbund mit einer derartigen Folie
CN104566229B (zh) * 2013-10-15 2016-06-08 深圳市光峰光电技术有限公司 波长转换装置的制造方法
WO2017039200A1 (ko) * 2015-08-28 2017-03-09 부경대학교 산학협력단 에너지변환 경사기능복합체 및 그의 제조방법 및 이를 이용한 센서
CN106931331A (zh) * 2015-12-31 2017-07-07 深圳市光峰光电技术有限公司 一种散热基座及其制备方法、相关发光模块及制备方法
CN105762239B (zh) * 2016-04-12 2018-11-06 杨阳 光转换装置及其制备方法和应用
DE102016114463B4 (de) * 2016-08-04 2019-10-17 Infineon Technologies Ag Die-befestigungsverfahren und halbleiterbauelemente, die auf der grundlage solcher verfahren hergestellt werden
CN106299084B (zh) * 2016-08-30 2018-10-16 开发晶照明（厦门）有限公司 Led封装结构
CN206929725U (zh) * 2017-05-12 2018-01-26 深圳市光峰光电技术有限公司 波长转换装置和激光荧光转换型光源
CN107246596B (zh) * 2017-06-20 2019-12-06 哈尔滨工业大学（威海） 用于led芯片的散热装置以及使用该装置的led光源

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212008A (zh) * 2006-12-29 2008-07-02 台达电子工业股份有限公司 电致发光装置及其制造方法
CN106287580A (zh) * 2015-06-02 2017-01-04 深圳市光峰光电技术有限公司 波长转换装置及其制备方法、相关发光装置和投影系统

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115702229A (zh) * 2020-06-16 2023-02-14 昕诺飞控股有限公司 嵌入式荧光体瓷砖

Also Published As

Publication number Publication date
CN111063810A (zh) 2020-04-24
CN111063810B (zh) 2021-11-12

Similar Documents

Publication Publication Date Title
CN101006031B (zh) 用于安装发光元件的副安装件用陶瓷基板及其制造方法
TWI546267B (zh) 一種具有多層結構的螢光玻璃片及其製作方法及發光裝置
TWI632323B (zh) 波長轉換裝置及其製備方法
CN108930919B (zh) 一种波长转换装置及其制备方法、光源
CN105762239B (zh) 光转换装置及其制备方法和应用
EP2712908A2 (en) Phosphor adhesive sheet, optical semiconductor element-phosphor layer pressure-sensitive adhesive body, and optical semiconductor device
CN204829755U (zh) 波长转换装置、相关发光装置和投影系统
TW201242108A (en) Producing method of light emitting element transfer sheet, producing method of light emitting device, light emitting element transfer sheet, and light emitting device
CN100536130C (zh) 高散热多芯片集成大功率白光发光二极管模块及其制备方法
CN106195924A (zh) 一种波长转换装置及其制作方法、相关发光装置
WO2018205694A1 (zh) 波长转换装置和激光荧光转换型光源
CN103258938B (zh) 一种含荧光粉的导热led灯条封装基板的制作方法
WO2020077992A1 (zh) 发光装置及其制备方法
CN108954039B (zh) 波长转换装置及其制备方法
WO2019136831A1 (zh) 波长转换装置及其光源
CN109681846B (zh) 波长转换装置及其制备方法
JP2010010469A (ja) 発光素子搭載用窒化アルミニウム基板および発光デバイス
WO2019010910A1 (zh) 一种波长转换装置及光源
CN110118312A (zh) 波长转换装置
CN111365685B (zh) 一种具有高的红光亮度和高的可靠性的发光装置
CN105084760A (zh) 一种超薄发光玻璃的制备方法及相关发光装置
CN111129261A (zh) 一种白光led的制备工艺方法及白光led
CN212060849U (zh) 波长转换装置、发光装置和投影装置
JP2011155127A (ja) 発光装置
CN116410003A (zh) 一种基板、制备方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19872595

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19872595

Country of ref document: EP

Kind code of ref document: A1