CN107910426B - Magnetic fluorescent powder composite material and plane coating method thereof - Google Patents

Magnetic fluorescent powder composite material and plane coating method thereof Download PDF

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Publication number
CN107910426B
CN107910426B CN201711124125.5A CN201711124125A CN107910426B CN 107910426 B CN107910426 B CN 107910426B CN 201711124125 A CN201711124125 A CN 201711124125A CN 107910426 B CN107910426 B CN 107910426B
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fluorescent powder
magnetic
fluorescent
composite material
coating method
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CN107910426A (en
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李立勉
李立群
李妙姿
陈育
黄梓龙
文尚胜
吴露锶
辜月纯
余奕伟
苏彬锋
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Guangdong Jinyuan solar energy Co.,Ltd.
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Guangdong Jin Yuan Lighting Polytron Technologies Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/48Semiconductor 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
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/48Semiconductor 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
    • H01L33/50Wavelength conversion elements
    • H01L33/508Wavelength conversion elements having a non-uniform spatial arrangement or non-uniform concentration, e.g. patterned wavelength conversion layer, wavelength conversion layer with a concentration gradient of the wavelength conversion material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008Processes
    • H01L2933/0033Processes relating to semiconductor body packages
    • H01L2933/0041Processes relating to semiconductor body packages relating to wavelength conversion elements

Abstract

The invention belongs to the technical field of photoelectricity, and particularly relates to a magnetic fluorescent powder composite material and a plane coating method thereof, wherein the method comprises the following steps: preparing a magnetic fluorescent powder composite material, and uniformly mixing the magnetic fluorescent powder composite material with packaging glue according to a certain proportion; fixing the flip LED chip on a packaging substrate to form a communicated circuit; coating the magnetic fluorescent powder glue mixture obtained in the step I on a chip; fluorescent powder particles with different luminescent properties are concentrated on different positions and heights of the silica gel under the action of an external magnetic field, and are solidified after the fluorescent powder particles are stably distributed; peripheral optical components are mounted. The fluorescent powder is positioned at different positions and heights of the packaging adhesive under the action of the magnetic field, so that a remote coating process can be realized, the packaging adhesive at the bottom layer is directly used as the protective adhesive of the LED chip, and the chip and the fluorescent powder layer are separated at the same time, so that the problems of accelerated aging, reduced reliability and the like caused by the fact that the heat of the chip is directly conducted to the fluorescent powder layer are avoided.

Description

Magnetic fluorescent powder composite material and plane coating method thereof
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to a magnetic fluorescent powder composite material and a plane coating method thereof.
Background
A Light emitting diode (Light emitting diode) is an electroluminescent device, and the core part of the Light emitting diode is composed of a P-type semiconductor and an N-type semiconductor, so that electric energy can be directly converted into Light energy, and the Light emitting diode has a series of advantages of environmental protection, low cost, high Light emitting brightness, long service life and the like, and is known as a green illumination energy source in the 21 st century.
At present, a mainstream high-power white light LED is manufactured by covering a layer of yellow phosphor powder (YAG or TAG) on a blue light LED chip (GaN), a part of light emitted by the chip excites a phosphor powder layer to generate yellow light, and the other part of blue light and the yellow light are mixed to form white light. The LED obtained by the method becomes a great research hotspot at home and abroad due to the advantages of high luminous efficiency, low price, high reliability and the like.
The traditional phosphor coating method is a dispensing coating method. The coating process adopts a thin needle-head tool to coat the fluorescent powder glue on the surface of the chip, and the chip is sent into curing equipment for heating and curing after the chip is subjected to flow molding, so that a spherical crown-like coating is ideally formed. However, the structural property from the center to the edge of the fluorescent powder layer prepared by the method is non-uniform, so that the spatial uniformity of the LED light-emitting color is poor, and the fluorescent powder density is higher than that of a silica gel material, so that the particle precipitation phenomenon is easily caused, light can be back-scattered, namely, the light energy is absorbed by the chip and the substrate, and the light-emitting efficiency is reduced. Meanwhile, only one layer of fluorescent powder film is arranged, so that the luminous spectrum is monotonous, and the difficulty in adjusting optical parameters such as color temperature of the lamp is high. In addition, since the fluorescent powder is in direct contact with the chip, the chip is in a closed environment, heat generated during light emission is difficult to dissipate timely, junction temperature of the LED is increased, and the temperature of the chip is conducted to the fluorescent powder layer, so that the fluorescent powder is accelerated to age, and light emitting efficiency and reliability are reduced. Ultimately affecting the luminous efficiency and reliability of the lamp.
In order to improve the quality and reliability of the light source, remote coating technology and multi-layer phosphor structure are introduced into the packaging technology of LED chips in recent years. The remote coating technology adopts the design that the fluorescent powder layer is far away from the chip, so that the heat dissipation performance is improved; by utilizing the multilayer fluorescent powder structure, fluorescent powder layers with different emission spectra can be prepared on the chip, so that the spectral distribution of the LED lamp is enriched, and the aim of changing the optical parameters of the lamp is fulfilled. However, the following problems also exist: (1) a method of independently forming a fluorescent powder layer is adopted far away from a coating technology, the fluorescent powder layer after film formation is bonded with a chip through packaging glue, the adhesion degree of the packaging glue and the fluorescent powder layer is difficult to guarantee, and the phenomenon of falling off is easy to occur in the later period; (2) the fluorescent powder layer is prepared by adopting the modes of spraying, spin coating or deposition and the like, although the precipitation phenomenon of fluorescent powder particles can be improved to a certain degree, partial particles still precipitate before the fluorescent powder particles are cured, and the uniform distribution of the particles cannot be realized; (3) at present, the preparation of a multilayer fluorescent powder structure usually adopts a layer-by-layer coating mode, namely, the coating and curing of one layer of fluorescent powder are firstly completed, then the second layer of fluorescent powder is prepared, and the like, the … … film forming period is long, so that the integrated production is not facilitated.
Implementation of the prior art: the fluorescent powder layer and the protective adhesive are coated separately, and are easy to fall off at the later stage; the multilayer fluorescent powder is coated by adopting a layer-by-layer spin coating method, the time consumption is long, and partial particle precipitation phenomenon still occurs in the fluorescent powder layer before the curing is finished; the traditional white light LED is manufactured by covering a layer of yellow fluorescent powder on a blue light LED chip, partial light emitted by the chip excites a fluorescent powder layer to generate yellow light, and the yellow light is mixed with blue light emitted by the chip to generate white light, but the overall luminous efficiency of the white light LED is not high due to energy loss.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a magnetic fluorescent powder composite material and a plane coating method thereof, and aims to provide a magnetic fluorescent powder composite material which comprises the following steps: the fluorescent powder layer is prepared by utilizing the magnetic fluorescent double-function compound, the distribution uniformity of fluorescent powder particles is effectively improved by combining the action of an external magnetic field, the problem of delamination of the fluorescent powder layer and packaging glue is solved, the process of plane coating of multiple layers of fluorescent powder is optimized, and the manufacturing period is shortened.
In order to achieve the above object, the present invention provides an improved method for plane coating of phosphor, comprising the steps of:
a plane coating method of a magnetic fluorescent powder composite material comprises the following steps:
firstly, preparing a magnetic fluorescent powder composite material, and uniformly mixing the magnetic fluorescent powder composite material with packaging adhesive according to a certain proportion;
fixing the flip LED chip on a packaging substrate to form a communicated circuit;
thirdly, coating the magnetic fluorescent powder glue mixture obtained in the step one on a chip;
fourthly, fluorescent powder particles with different luminescence properties are concentrated on different positions and heights of the silica gel under the action of an external magnetic field, and are solidified after the fluorescent powder particles are stably distributed;
installing peripheral optical components;
and (c) adsorbing the magnetic fluorescent particles with different magnetic sizes to different positions in the colloid under the action of the external magnetic field in the step (d), and synchronously performing thermocuring after the magnetic fluorescent particles are stably distributed to realize the layered arrangement of the fluorescent powder with different luminescent properties.
Further, the packaging adhesive is epoxy colloid or silica gel colloid, and can be directly mixed with the magnetic fluorescent powder composite material; or adding powdery filler to obtain colloid with improved refractive index, and mixing with the magnetic fluorescent powder composite material; the powder filler is one or more of fused quartz, fluorite and glass beads.
Further, the LED chip is one or more of a blue LED chip, a red LED chip, a yellow LED chip, a green LED chip and a purple LED chip; it may be a single LED chip, or a combination of a group of LED chips.
Furthermore, the material of the substrate in the second step may be aluminum, copper, alloy, silicon carbide, aluminum nitride, or epoxy resin.
Furthermore, the coating mode in the third step can be spin coating, spray coating, deposition and printing.
Furthermore, the external magnetic field in the step (iv) is provided by a magnet with a certain shape, and the shape is one or more of horseshoe shape, spherical shape, circular shape and planar shape.
Furthermore, the peripheral optical component is a lens with a free-form surface on the outer surface and is used for controlling light rays and realizing the requirement of uniform illumination; the inner surface of the inner ring can be rectangular, hemispherical or cylindrical; the lens is made of one or more of polycarbonate, silica gel or glass.
The magnetic fluorescent powder composite material is a magnetic fluorescent double-function composite with ferroferric oxide as a magnetic core, silicon dioxide as a coupling agent and an inorganic fluorescent material doped with rare earth as a shell, wherein the particle size of the magnetic core is 50 ~ 200nm, the coupling agent has good biocompatibility, can reduce the quenching effect of the ferroferric oxide on fluorescent powder, and the thickness of the coupling agent is 10 ~ 20 nm;
further, the fluorescent material is a plurality of red fluorescent powder, green fluorescent powder, yellow fluorescent powder and blue fluorescent powder, and the thickness of the fluorescent material is 20 ~ 40 nm;
for the magnetic fluorescent powder composite material, the rare earth-doped inorganic fluorescent materials with different luminescent properties are coated with magnetic cores with different particle sizes or coated with different numbers of magnetic cores to obtain the magnetic fluorescent dual-function composite with different magnetic sizes;
further, the magnetic cores with different particle sizes are obtained by adding a surface modifier in the preparation process of ferroferric oxide; the surface modifier is hydrochloric acid, hydrogen peroxide, ferric chloride or oleic acid.
Further, the red phosphor is a phosphor material mainly composed of a sulfide system, a nitride system, or a tungsten/molybdate system; the green fluorescent powder is a fluorescent material taking a thiogallate system, a nitrogen oxide system or a silicate system as a main body; the blue fluorescent powder is a fluorescent material which takes YAG, TAG, nitrogen oxide system, halogen phosphate system or silicate system as a main body.
Furthermore, the magnetic fluorescent bifunctional complex can be prepared by a sol-gel method, a micro-emulsion thermal method, a coprecipitation method or a solvothermal method.
The invention provides an improved method for plane coating of fluorescent powder, which has the following advantages:
1. the LED light source excites various fluorescent powders with different luminescence properties to emit light with different wavelengths, and the spectral distribution is wider;
2. the magnetic fluorescent composite material is adopted, the controllable effects of uniform distribution of the same type of fluorescent powder and layered arrangement of different types of fluorescent powder are realized by utilizing the action of an external magnetic field, the preparation of the multilayer fluorescent powder is completed at one time, the production efficiency is improved, and the problem of fluorescent powder precipitation is solved;
3. the preparation of the magnetic fluorescent powder with different magnetic sizes is realized by a method of surface modification or coating of different numbers of magnetic cores;
4. the fluorescent powder is positioned at different positions and heights of the packaging adhesive under the action of the magnetic field, so that a remote coating process can be realized, the packaging adhesive at the bottom layer is directly used as the protective adhesive of the LED chip, and the chip and the fluorescent powder layer are separated at the same time, so that the problems of accelerated aging and reduced reliability caused by the fact that the heat of the chip is directly conducted to the fluorescent powder layer are avoided.
5. The preparation of the protective glue and the fluorescent powder layer is realized by one-time coating by utilizing the matching of the magnetic fluorescent powder and an external magnetic field, so that the adhesion between the fluorescent powder layer and the protective glue is better and superior, and the fluorescent powder layer is not easy to fall off in the later period; the cooperation of the magnetic fluorescent powder and an external magnetic field is utilized, and the magnetic sizes of different fluorescent powders are changed, so that the one-time coating of the multiple layers of fluorescent powders is realized, and the light emitting performance is improved.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a second embodiment of the present invention.
FIG. 3 is a schematic structural diagram of a second embodiment of the present invention.
FIG. 4 is a schematic diagram of a third structure of the embodiment of the present invention.
FIG. 5 is a schematic diagram of a third structure of the embodiment of the present invention.
Fig. 6 is a schematic structural diagram of a fourth embodiment of the present invention.
Fig. 7 is a schematic structural diagram of a fifth embodiment of the present invention.
Fig. 8 is a schematic structural diagram of a fifth embodiment of the present invention.
Fig. 9 is a schematic structural diagram of a fifth embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail.
Example 1: as shown in FIG. 1, the present invention provides an improved method for planar coating of phosphors, comprising a total of 5 parts. The substrate 1 is used for supporting the whole LED packaging structure; the flip LED chip 2 is fixed on the substrate 1 in a die bonding or eutectic welding mode; the packaging glue 3 is mixed with a plurality of different types of magnetic fluorescent bifunctional compounds 4; the magnet 5 provides an external magnetic field to attract the different fluorescent bifunctional compounds 4 to different positions in the packaging glue 3.
The magnetic size of the material is measured by the magnetic permeability, and the magnetic permeability of ferroferric oxide is influenced by the particle size. The magnetic size of the magnetic core can be adjusted in the following manner. Mode 1: ferroferric oxide particles with different particle sizes can be obtained by performing surface treatment on hydrochloric acid, hydrogen peroxide, ferric chloride or oleic acid and the like, and a coupling agent such as silicon dioxide is added to prevent the quenching effect of the ferroferric oxide on the fluorescent powder; mode 2: the couplant coats one, two or three ferroferric oxide particles with different numbers to obtain cores with different magnetic sizes.
Example 2: as shown in fig. 2 and 3, different types of fluorescent powder are used as shells to coat the ferroferric oxide with different magnetism obtained in the method 1 or 2, so as to obtain the magnetic fluorescent dual-function compound 4 with different magnetism.
The packaging adhesive can be added with powdery fillers such as glass beads to obtain colloid with improved refractive index, and then the colloid is mixed with the magnetic fluorescent powder composite material. After the magnetic fluorescent dual-function compound 4 with different excitation wavelengths is excited by the light emitted by the LED chip 2, the light with different wavelengths is generated and mixed to generate white light for emitting; the type of the magnetic fluorescent double-function compound 4 and the proportion of the compound to the packaging adhesive 3 can be adjusted according to the requirement of the lamp on spectral energy distribution, and the effective control of optical parameters such as color temperature, color rendering index and the like is realized.
Example 3: as shown in fig. 4, different magnetic fluorescent dual-function compounds are adsorbed to different positions of the encapsulating adhesive layer by the action of the external magnetic field, so that the layered arrangement of the fluorescent powder is realized: the yellow fluorescent powder is positioned at the bottom layer, the green fluorescent powder is positioned at the middle layer, and the red fluorescent powder is positioned at the top layer or other arrangement modes. And after the positions of the fluorescent powder particles are fixed, synchronously carrying out thermocuring to realize the coating of the fluorescent powder layer. The position of the bottom layer fluorescent powder can be fixed in the middle of the packaging adhesive layer by the action of an external magnetic field, and no fluorescent powder is distributed at the lower part of the packaging adhesive, so that the fluorescent powder layer is isolated from the chip, and the performance attenuation of the fluorescent powder caused by the temperature of the chip is effectively avoided. Meanwhile, the fluorescent powder layer prepared by the method can directly use the packaging adhesive at the bottom as the protective adhesive of the chip, so that the link of protective adhesive injection in the traditional coating process is omitted, and the problem of later falling off is avoided due to synchronous spraying and curing of the protective adhesive and the fluorescent powder layer. Finally, as shown in fig. 5, the peripheral optical member 7 is mounted, completing the packaging of the LED chip.
Example 4: as shown in fig. 6, the arrangement shape of the phosphor layer can be changed by changing the shape of the magnet, and the shape of the magnet is not limited to the planar shape and the curved surface shape shown in the drawing, and may be other horseshoe-shaped or conical shapes, and the number of the magnets is not limited to a single one, and may be a group of magnets to realize the periodic arrangement distribution of the magnetic phosphor particles.
Example 5: as shown in fig. 7 and 8, the method is suitable for integrally packaging a multi-chip LED. The multiple chips are fixed on the substrate by eutectic soldering or the like to form a connected circuit. The magnetic fluorescent particle/packaging adhesive composite material is directly coated on the surface of a chip by adopting a spraying method, different magnetic fluorescent double-function compounds are adsorbed to different positions of a packaging adhesive layer by utilizing the action of an external magnetic field, the layered arrangement of fluorescent powder is realized, and after the positions of fluorescent powder particles are fixed, the thermal curing is synchronously carried out, so that the coating of a fluorescent powder layer is completed. Finally, the peripheral optical member 7 is mounted to complete the multi-chip LED package, as shown in fig. 9.
It should be understood that the above-mentioned drawings are merely illustrative of the preferred embodiments of the present invention, and that the scope of the invention is not limited thereto.

Claims (9)

1. A plane coating method of a magnetic fluorescent powder composite material is characterized by comprising the following steps:
firstly, preparing a magnetic fluorescent powder composite material, and uniformly mixing the magnetic fluorescent powder composite material with packaging adhesive according to a certain proportion;
fixing the flip LED chip on a packaging substrate to form a communicated circuit;
thirdly, coating the magnetic fluorescent powder glue mixture obtained in the step one on a chip;
fourthly, fluorescent powder particles with different luminescence properties are concentrated on different positions and heights of the silica gel under the action of an external magnetic field, and are solidified after the fluorescent powder particles are stably distributed;
installing peripheral optical components;
and (c) adsorbing the magnetic fluorescent particles with different magnetic sizes to different positions in the colloid under the action of the external magnetic field in the step (d), and synchronously performing thermocuring after the magnetic fluorescent particles are stably distributed to realize the layered arrangement of the fluorescent powder with different luminescent properties.
2. Flat coating method according to claim 1, characterized in that: the packaging adhesive is epoxy colloid or silica gel colloid, and is directly mixed with the magnetic fluorescent powder composite material or mixed with the magnetic fluorescent powder composite material after a powdery filler is added to obtain colloid with improved refractive index; the powder filler is one or more of fused quartz, fluorite and glass beads.
3. Flat coating method according to claim 1, characterized in that: and step two, the LED chip is one or more of a blue LED chip, a red LED chip, a yellow LED chip, a green LED chip and a purple LED chip.
4. Flat coating method according to claim 1, characterized in that: and the substrate is made of aluminum, copper, alloy, silicon carbide, aluminum nitride and epoxy resin.
5. Flat coating method according to claim 1, characterized in that: the coating mode is spin coating, spray coating, deposition and printing.
6. Flat coating method according to claim 1, characterized in that: the external magnetic field is provided by a magnet with a certain shape, and the shape is one or more of horseshoe shape, spherical shape, circular shape and planar shape.
7. Flat coating method according to claim 1, characterized in that: the peripheral optical component is a lens with a free-form surface on the outer surface and is used for controlling light and realizing the requirement of uniform illumination; the inner surface of the inner ring is rectangular, hemispherical or cylindrical; the lens is made of one or more of polycarbonate, silica gel or glass.
8. The planar coating method of claim 1, wherein the magnetic fluorescent powder composite material is a magnetic fluorescent bifunctional compound which takes ferroferric oxide as a magnetic core, silicon dioxide as a coupling agent and rare earth-doped inorganic fluorescent material as a shell, the particle size of the magnetic core is 50 ~ 200nm, the coupling agent has good biocompatibility and can reduce the quenching effect of the ferroferric oxide on the fluorescent powder, and the thickness of the coupling agent is 10 ~ 20 nm;
the fluorescent material is a plurality of red fluorescent powder, green fluorescent powder, yellow fluorescent powder and blue fluorescent powder, and the thickness of the fluorescent material is 20 ~ 40 nm;
for the magnetic fluorescent powder composite material, the rare earth-doped inorganic fluorescent materials with different luminescent properties are coated with magnetic cores with different particle sizes or coated with different numbers of magnetic cores to obtain the magnetic fluorescent dual-function composite with different magnetic sizes;
the magnetic cores with different particle sizes are obtained by adding a surface modifier in the preparation process of ferroferric oxide; the surface modifier is hydrochloric acid, hydrogen peroxide, ferric chloride or oleic acid.
9. The flat coating method according to claim 8, characterized in that: the red fluorescent powder is a fluorescent material taking a sulfide system, a nitride system or a tungsten/molybdate system as a main body; the green fluorescent powder is a fluorescent material taking a thiogallate system, a nitrogen oxide system or a silicate system as a main body; the blue fluorescent powder is a fluorescent material taking YAG, TAG, a nitrogen oxide system, a halogen phosphate system or a silicate system as a main body;
the magnetic fluorescent bifunctional complex is prepared by a sol-gel method, a microemulsion thermal method, a coprecipitation method or a solvothermal method.
CN201711124125.5A 2017-11-14 2017-11-14 Magnetic fluorescent powder composite material and plane coating method thereof Active CN107910426B (en)

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CN109659298A (en) * 2018-12-21 2019-04-19 鸿利智汇集团股份有限公司 A kind of heavy powder magnetism light source and its technique
CN110797449A (en) * 2019-11-05 2020-02-14 鸿利智汇集团股份有限公司 LED package and packaging method thereof
CN110964470A (en) * 2019-11-20 2020-04-07 东莞市银亮电子科技有限公司 Packaging adhesive for improving UV light efficiency and process thereof

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Patentee before: GUANGDONG JINYUAN LIGHTING TECHNOLOGY Co.,Ltd.

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PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A kind of magnetic phosphor composite material and plane coating method thereof

Effective date of registration: 20220810

Granted publication date: 20200103

Pledgee: China Co. truction Bank Corp Chaozhou branch

Pledgor: Guangdong Jinyuan solar energy Co.,Ltd.

Registration number: Y2022980012264