WO2023011270A1

WO2023011270A1 - Polymer film layer, preparation method therefor, and led product

Info

Publication number: WO2023011270A1
Application number: PCT/CN2022/108070
Authority: WO
Inventors: 宗坚
Original assignee: 江苏菲沃泰纳米科技股份有限公司
Priority date: 2021-08-05
Filing date: 2022-07-27
Publication date: 2023-02-09
Also published as: TW202313343A

Abstract

A polymer film layer, a preparation method therefor, an LED product, a protective LED packaging method, and a protective LED lamp bead. The polymer film layer is formed on the surface of an LED substrate. The polymer film layer is a film layer formed on the surface of the LED substrate by means of a plasma-enhanced chemical vapor deposition method using one or more of a monomer group consisting of an acrylate monomer, a fluorine-containing olefin monomer, an organosilicon monomer, an epoxy monomer and an aromatic ring-containing organic matter monomer as reaction raw materials. The protective LED packaging method comprises the steps of: S110: fixing a light-emitting element to an LED support in a conductive manner; S120: dispensing a glue onto the light-emitting element and the LED support to form a packaging adhesive layer, so as to fabricate an LED semi-finished product; and S130: depositing and forming a polymer film layer on the surface of the LED semi-finished product by means of a plasma-enhanced chemical vapor deposition method to fabricate a protective LED semi-finished product, so as to solve the industry pain point that LED lamp beads are prone to vulcanization, water inflow or oxygen permeation, etc.

Description

A kind of polymer film layer and its preparation method and LED product

This application is required to be submitted to the China Patent Office on August 5, 2021, the application number is 202110895813.1, and the title of the invention is "polymer film layer and its preparation method and LED products", and it is submitted to the China Patent Office on August 5, 2021. The priority of the Chinese patent application with the application number 202110895864.4 and the invention title "Protective LED packaging method and protective LED lamp bead", the entire content of which is incorporated in this application by reference.

technical field

The invention relates to the technical field of LEDs, in particular to a polymer film layer and a preparation method thereof, an LED product, a protective LED packaging method, and a protective LED lamp bead.

Background technique

LED (English: Light Emitting Diode, Chinese: Light Emitting Diode) is a solid-state semiconductor device that can convert electrical energy into visible light, so as to directly convert electricity into light. LEDs are mainly used in LED street lights, LED architectural landscape lighting, traffic signal LED lights, LED display screens, automotive lighting, indoor ordinary white LED lighting, artificial LED light sources for agricultural production, LED light sources for medical use, LED light sources for aviation lighting and other fields. The core of LED is the wafer of a semiconductor, and wafer is attached on the support, and one end of this wafer is negative pole, and the other end connects the positive pole of power supply, and whole wafer is encapsulated by epoxy resin. Compared with incandescent lamps, LED lamps have obvious advantages such as energy saving, long service life, and environmental protection. However, LED lamps are easily invaded by external liquids/gases during use, such as water ingress due to humid air, rain, and heavy snow. It is easy to be damaged by short circuit corrosion, so the sealing of the chip is very important.

However, the traditional epoxy resin does not have a good heat dissipation effect, and it is easy to cause problems such as LED light decay and service life reduction. Therefore, polymer silicone is usually used as the encapsulant to prolong the service life of LED lights. However, due to reasons such as the silica gel itself and poor sealing between the silica gel and the bracket, there are still shortcomings such as moisture permeability, oxygen permeability, sulfur permeability, and bromine permeability.

In addition, the brackets of existing LED lamps are usually made of a metal base, and a silver layer is plated on the base as a light source reflection layer of the LED lamp. However, in actual use scenarios of LED lights, such as sulfur (S), water (H2O) or oxygen (O2) in air, humidity, rainy days, etc., will react with the silver plating layer. In particular, the reaction between S in the air and Ag will form Ag2S, which will lead to blackening of the silver plating layer and darkening of the lamp beads, which will cause serious light decay. Of course, when moisture or oxygen in the air enters the interior of the LED lamp, it is also prone to complex chemical reactions with the metal, resulting in a serious decrease in the luminous flux of the LED lamp, a significant drift in the color temperature, and even a dead light.

At present, in order to solve the above-mentioned problems, the prior art usually utilizes a liquid-phase coating method to coat a curable glue composition on the wafer, such as a silicone rubber composition, a metal-containing silica gel composition, etc., to achieve the required protection. Effect. However, after the liquid-phase coating is cured, the coating often reaches several microns or hundreds of microns. On the one hand, a thicker coating will affect the light transmittance; on the other hand, the bonding force between the liquid-phase cured coating and the chip is relatively weak Poor, especially the surface temperature of the LED lamp will change greatly due to the use time and ambient temperature, resulting in different degrees of thermal expansion and contraction of the coating, causing cracking, aging, and even peeling of the coating. Thus losing the protective effect.

Contents of the invention

An advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, which can solve the industry pain points that LED lamps are prone to vulcanization, bromination, water ingress or oxygen permeability.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the present application, the polymer film layer is suitable for being prepared on the surface of the LED substrate on a large scale, and It has long-term anti-sulfur, waterproof, or oxygen-proof properties.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the application, the polymer film layer itself can be firmly combined with the LED substrate to prevent cracking , aging, and even peeling problems.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the application, the polymer film layer itself has better light transmission performance, so as to prevent the The polymer film affects the luminous flux of the LED lamp.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the application, the polymer film layer is suitable for various types of LED substrates, and when formed When the polymer film layer is placed on the surface of the LED substrate, the structure of the LED substrate itself will not be damaged.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the application, the polymer film layer can be formed on the surface of the LED substrate by plasma chemical vapor deposition .

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein, in an embodiment of the application, the thickness of the polymer film layer can be at the nanometer level, so as to avoid affecting the light of the LED lamp transmittance.

Another advantage of the present invention is to provide a polymer film layer and its preparation method and LED products, wherein in order to achieve the above objects, no expensive materials or complex structures are used in the present invention. Therefore, the present application successfully and effectively provides a solution that not only provides a simple polymer film layer and its preparation method and LED products, but also increases the practicability of the polymer film layer and its preparation method and LED products and reliability.

In order to achieve at least one of the above advantages or other advantages and objectives, the present invention provides a polymer film layer for forming on the surface of the LED substrate, wherein the polymer film layer is made of acrylate monomers, fluorine-containing olefins One or more of the monomer group consisting of monomers, organosilicon monomers, epoxy monomers, and aromatic ring-containing organic monomers is used as the reaction raw material, and the LED base is deposited by plasma-enhanced chemical vapor deposition. The film layer formed on the surface of the material.

According to an embodiment of the present invention, the acrylate monomer includes a long-chain alkyl acrylate compound and/or a fluorine-containing acrylate compound.

According to an embodiment of the present invention, the number of carbon atoms in the alkyl group in the long-chain alkyl acrylate compound is greater than or equal to 6; wherein the fluorine-containing acrylate compound is selected from 2-(perfluorobutyl)ethyl Acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, (perfluorocyclohexyl)methacrylate, 1H,1H,2H, One or more of 2H-perfluorohexyl methacrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate and 1H,1H,2H,2H-perfluorodecyl methacrylate .

According to an embodiment of the present invention, the long-chain alkyl acrylate compound is selected from n-hexyl methacrylate, n-octyl methacrylate, decyl methacrylate, isodecyl methacrylate, methacrylic acid Lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, decaacrylate One or more of tetraester, hexadecyl acrylate and stearyl acrylate.

According to an embodiment of the present invention, the fluorine-containing olefin monomers include tetrafluoroethylene, hexafluoropropylene, octafluorobutene, perfluorononene, and/or 1H,1H,2H-perfluoro-1-deca Diene.

According to an embodiment of the present invention, the organosilicon monomer is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methyl Vinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributanoximinosilane, Tetramethyldivinyldisiloxane, Dimethylethylene Ethylethoxysilane, 1,2,2-trifluorovinyltriphenylsilane, tetramethoxysilane, trimethoxyhydrogensilane, n-octyltriethoxysilane, phenyltriethoxysilane, Vinyltris(2-methoxyethoxy)silane, triethylvinylsilane, hexaethylcyclotrisiloxane, 3-(methacryloxy)propyltrimethoxysilane, phenyltris One or more of (trimethylsiloxane) silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, dimethoxysilane and 3-chloropropyltrimethoxysilane kind.

According to an embodiment of the present invention, the epoxy monomer includes 3-glycidoxypropyltriethoxysilane and/or γ-glycidoxypropyltrimethoxysilane.

According to an embodiment of the present invention, the reaction raw material is a mixture composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative, and the reaction The mass fraction of the at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative in the raw material is 10%-60%.

According to an embodiment of the present invention, the organosilicon monomer containing a double bond structure is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethyl Oxysilane, Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributylketoximosilane, Tetramethyldivinyldisiloxane , dimethylvinylethoxysilane and 1,2,2-trifluorovinyltriphenylsilane, and the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are selected from iso Pentadiene, Ethylene Glycol Diacrylate, 1,3-Butadiene, 1,4-Pentadiene, Ethoxylated Trimethylolpropane Triacrylate, Tripropylene Glycol Diacrylate, Polyethylene Diol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol divinyl ether, neopentyl glycol diacrylate, 1,4-butylene glycol methacrylate, dimethacrylic acid 1,6-hexanediol, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethyl 1,3-butylene glycol acrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, 2-benzylidene propane One or more of diprop-2-enyl ester and diethyl diallyl malonate.

According to an embodiment of the present invention, the static water contact angle of the polymer film layer is greater than 100°.

According to an embodiment of the present invention, the thickness of the polymer film layer is 10 nm-10 μm.

According to another aspect of the present invention, the present invention provides the preparation method of polymer membrane layer, comprises steps:

In the PECVD device, one or more of the monomer groups composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers are used as The reaction raw materials are used to form the polymer film layer on the surface of the LED substrate by plasma enhanced chemical vapor deposition.

According to an embodiment of the present invention, before feeding the reaction materials, the PECVD apparatus is vacuumed and a plasma source gas is fed, wherein the plasma source gas is an inert gas.

According to an embodiment of the present invention, after the polymer film layer is formed, the plasma discharge is stopped and the vacuum is pumped, so as to take out the LED substrate on which the polymer film layer is formed.

According to an embodiment of the present invention, the temperature of the reaction chamber of the PECVD device is controlled at 25-60°C.

According to an embodiment of the present invention, the forming process of the polymer film layer includes a pretreatment stage and a film coating stage. In the pretreatment stage, the discharge power of the plasma is 100-600W, and the discharge time is 60-1800s, and then When entering the coating stage, the discharge power of the plasma is adjusted to 10-200W, and the discharge duration is 600-36000s.

According to an embodiment of the present invention, the formation process of the polymer film layer includes a pretreatment stage and a coating stage, the plasma discharge power of the pretreatment stage is 150-600W, and the discharge time is 60-1800s, and then enters the coating stage , the coating stage is a pulse discharge, the power is 10-300W, the time is 600s-36000s, the frequency of the pulse discharge is 20Hz-20KHz, and the duty ratio of the pulse is 1:1-1:500.

According to another aspect of the present invention, the present invention provides an LED product having a polymer film layer, wherein the LED product is obtained by being exposed to an acrylic monomer, a fluorine-containing olefin monomer, a silicone monomer One or more of the monomer group consisting of epoxy monomers and aromatic ring-containing organic monomers are used as reaction raw materials, and are deposited on at least the surface of the LED substrate by plasma enhanced chemical vapor deposition. A part is prepared by forming a polymer film layer.

According to an embodiment of the present invention, the LED substrate is a finished LED or a semi-finished LED.

An advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, which can solve the industry pain points that LED lamp beads are prone to vulcanization, bromination, water ingress or oxygen permeability.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein, in an embodiment of the application, the protective LED packaging method can prepare a film on the surface of the LED substrate on a large scale Layer, and itself has long-term anti-sulfur, waterproof, or oxygen-proof properties.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein, in an embodiment of the application, the film layer itself prepared by the protective LED packaging method can be combined with the LED substrate Strong to prevent cracking, aging, or even peeling problems.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein, in an embodiment of the application, the film layer prepared by the protective LED packaging method itself has better light transmission performance, in case the polymer film affects the luminous flux of the LED lamp.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein, in an embodiment of the application, the protective LED packaging method can be deposited on the surface of the LED substrate Form a film layer to achieve better waterproof, sulfur-proof or oxygen-proof performance.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein, in an embodiment of the application, the protective LED packaging method is applicable to various types of LED substrates, and in During the process of forming the polymer film layer on the surface of the LED substrate, the structure of the LED substrate itself will not be damaged.

Another advantage of the present invention is to provide a protective LED packaging method and a protective LED lamp bead, wherein in order to achieve the above purpose, no expensive materials or complicated structures are used in the present invention. Therefore, the present application successfully and effectively provides a solution, which not only provides a simple protective LED packaging method and protective LED lamp bead, but also increases the practicability of the protective LED packaging method and protective LED lamp bead and reliability.

In order to achieve at least one of the above advantages or other advantages and objectives, the present invention provides a protective LED packaging method, including steps:

S110: Conductively fixing the light-emitting element to the LED bracket;

S120: dispensing glue on the light-emitting element and the LED bracket to form an encapsulation glue layer, so as to make a semi-finished LED product; and

S130: Deposit and form a polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition, so as to manufacture a protective LED semi-finished product.

According to an embodiment of the present application, the polymer film layer is composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers. One or more of the monomer groups are used as reaction raw materials, and the film layer is formed on the surface of the LED semi-finished product by the plasma enhanced chemical vapor deposition method.

According to an embodiment of the present application, the reaction raw material is a mixture composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives, and the reaction raw material The mass fraction of the two kinds of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives is 10%-60%.

According to an embodiment of the present application, the protective LED packaging method further includes the steps of:

S140 : cutting the semi-finished protective LED into single pieces to obtain finished protective LED products.

According to an embodiment of the present application, the step S130 includes the steps of:

S131: pre-treatment, after placing the LED semi-finished product in the coating chamber of the coating equipment for vacuuming, injecting plasma source gas;

S132: Deposition, one of the monomer groups composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers in the coating equipment or more as reaction raw materials, forming the polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition; and

S133: post-processing, stop the plasma discharge and vacuumize, so as to take out the LED semi-finished product formed with the polymer film layer.

According to an embodiment of the present application, the step S130 further includes the steps of:

Before the step S131, the back surface of the LED semi-finished product is shielded; and

After the step S133, the back surface of the protective LED semi-finished product is de-shielded.

According to an embodiment of the present application, first place the shaded LED semi-finished product on the storage tray of the coating equipment, and then dry the placed LED semi-finished product through a drying cabinet, so as to obtain the dried LED The semi-finished product is then placed in the coating chamber of the coating equipment.

According to an embodiment of the present application, the step S110 includes the steps of:

Use a flat solder paste printer and a 3D printing stencil to print solder paste in the bowl of the EMC bracket;

The printed EMC bracket is carried out on the LED crystal bonding machine for solid crystal operation, so that the light-emitting element is fixed on the EMC bracket; and

A reflow soldering operation is performed by a reflow soldering machine, so as to conductively connect the light emitting element and the EMC bracket.

According to another aspect of the present application, the present application further provides a protective LED packaging method, comprising the steps of:

By plasma-enhanced chemical vapor deposition, a polymer film is deposited on the silver-plated surface of the LED bracket;

Conductively fixing the light-emitting element to the LED bracket coated with the polymer film layer;

Dispensing glue on the light-emitting element and the LED bracket to form an encapsulation glue layer to make a protective LED semi-finished product; and

The protected LED semi-finished product is cut into individual pieces to obtain a protected LED finished product.

Conductively fixing the light-emitting element to the LED bracket;

Depositing a polymer film layer on the silver-plated surface of the LED bracket and the surface of the light-emitting element by plasma-enhanced chemical vapor deposition;

Dispensing glue on the polymer film layer to form an encapsulation layer to make a protective LED semi-finished product; and

According to another aspect of the present invention, the present invention provides a protective LED lamp bead, including:

LED brackets, wherein the LED brackets have a silver-plated surface;

a light emitting element, wherein the light emitting element is conductively fixed to the silver-plated surface of the LED bracket;

an encapsulating adhesive layer, wherein the encapsulating adhesive layer encapsulates the light-emitting element; and

A polymer film layer, wherein the polymer film layer is plated on the outer surface of the packaging adhesive layer.

According to an embodiment of the present application, the polymer film layer is composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers One or more of the monomer groups are used as reaction raw materials, and a film layer is formed on the outer surface of the encapsulation adhesive layer by plasma enhanced chemical vapor deposition.

According to an embodiment of the present application, the reaction raw material is a mixture composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative, and the reaction The mass fraction of the polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives in the raw material is 10%-60%.

According to an embodiment of the present application, the organosilicon monomer containing a double bond structure is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethyl Oxysilane, Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributylketoximosilane, Tetramethyldivinyldisiloxane , dimethylvinylethoxysilane and 1,2,2-trifluorovinyltriphenylsilane, and the polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives are selected from iso Pentadiene, Ethylene Glycol Diacrylate, 1,3-Butadiene, 1,4-Pentadiene, Ethoxylated Trimethylolpropane Triacrylate, Tripropylene Glycol Diacrylate, Polyethylene Diol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol divinyl ether, neopentyl glycol diacrylate, 1,4-butylene glycol methacrylate, dimethacrylic acid 1,6-hexanediol, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethyl 1,3-butylene glycol acrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, 2-benzylidene propane One or more of diprop-2-enyl ester and diethyl diallyl malonate.

According to an embodiment of the present application, the static water contact angle of the polymer film layer is greater than 100°.

According to an embodiment of the present application, the thickness of the polymer film layer is 10 nm-10 μm.

According to an embodiment of the present application, the LED bracket is an EMC bracket.

According to another aspect of the application, the application further provides a protective LED lamp bead, including:

LED brackets, wherein the LED brackets have a silver-plated surface;

A polymer film layer, wherein the polymer film layer is plated on the silver-plated surface of the LED bracket, and the polymer film layer is located on the silver-plated surface of the LED bracket and the light-emitting element and between the encapsulation layers.

LED brackets, wherein the LED brackets have a silver-plated surface;

A polymer film layer, wherein the polymer film layer is plated on the silver-plated surface of the LED bracket and the surface of the light-emitting element, and the polymer film layer is located between the encapsulation adhesive layer and the light-emitting component and the silvered surface of the LED holder.

According to another aspect of the present application, the present application further provides a protective LED packaging system, comprising:

A crystal-bonding device, wherein the crystal-bonding device is used to conductively fix the light-emitting element to the LED bracket;

Dispensing equipment, wherein the dispensing equipment is used for dispensing glue on the light-emitting element and the LED bracket to form an encapsulation layer to make LED semi-finished products; and

Coating equipment, wherein the coating equipment is used for depositing and forming a polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition, so as to make a protective LED semi-finished product.

According to an embodiment of the present application, the coating equipment includes a coating chamber, a movable bracket movably arranged in the coating chamber, a storage tray detachably placed in the movable bracket, a supply and discharge Gas system and excitation system, wherein the storage tray is used to place a plurality of LED semi-finished products on a plate, and the movable bracket is used to drive the LED semi-finished products placed on the storage tray in the coating chamber movement, wherein the supply and exhaust system is connected to the coating chamber in a conductive manner, and is used to supply gas inward to the coating chamber while exhausting outward to form a vacuum in the coating chamber The chamber provides reaction raw materials, wherein the excitation system is correspondingly arranged in the coating chamber for generating an excitation electromagnetic field in the coating chamber to ionize the reaction raw materials to form plasma, so that the plasma is in the coating chamber The surface of the LED semi-finished product is deposited to form the polymer film layer.

According to an embodiment of the present application, the movable support includes a revolving support and a plurality of self-rotating supports, wherein the revolving support is rotatably arranged in the coating chamber, and the plurality of self-rotating supports are respectively movably It is rotatably arranged in the coating chamber to form a planetary turret, wherein the plurality of self-rotating supports are used to place the storage tray.

According to an embodiment of the present application, the storage tray has a plurality of storage slots, wherein the plurality of storage slots extend along the radial direction of the storage tray, and are used for inserting the LED semi-finished product.

According to an embodiment of the present application, the storage tray includes a grid plate and a grid plate, wherein the grid plate and the grid plate are stacked at intervals, so that the grid plate and the mesh A plurality of storage slots are formed between the grid plates.

According to an embodiment of the present application, the protective LED packaging system further includes a cutting device, wherein the cutting device is used to cut the semi-finished protective LED into individual pieces to obtain finished protective LED products.

Further objects and advantages of the invention will fully appear from an understanding of the ensuing description.

These and other objects, features and advantages of the present invention are fully realized by the following detailed description and claims.

Description of drawings

FIG. 1 is a schematic flowchart of a protective LED packaging method according to an embodiment of the present application.

Fig. 2 shows a schematic flow chart of one of the steps in the protective LED packaging method according to the above-mentioned embodiment of the present application.

Fig. 3 shows a schematic flowchart of step 2 in the protective LED packaging method according to the above-mentioned embodiment of the present application.

Fig. 4 shows a schematic structural view of a finished protective LED packaged by the protective LED packaging method according to the above-mentioned embodiments of the present application.

Fig. 5 shows a first modified implementation of the protective LED packaging method according to the above-mentioned embodiments of the present application.

Fig. 6 shows a schematic structural view of a finished protective LED packaged by the protective LED packaging method according to the above-mentioned first modified embodiment of the present application.

Fig. 7 shows a second modified implementation of the protective LED packaging method according to the above-mentioned embodiments of the present application.

Fig. 8 shows a schematic structural view of a finished protective LED packaged by the protective LED packaging method according to the above-mentioned second modified embodiment of the present application.

FIG. 9 is a schematic block diagram of a protective LED packaging system according to an embodiment of the present application.

Fig. 10 shows a schematic structural view of the coating equipment in the protective LED packaging system according to the above-mentioned embodiments of the present application.

Fig. 11 shows a schematic structural view of the storage tray in the coating device according to the above-mentioned embodiment of the present application.

Fig. 12 is a schematic diagram showing the comparison of the test results of the coated LED substrate according to the present application, the untreated LED substrate and the LED substrate sprayed on the surface.

Fig. 13A is a schematic table showing the light attenuation data of LED lamp beads before and after the coating of 200nm.

FIG. 13B is a schematic table showing the light attenuation data of the LED lamp bead before and after coating of 800nm.

FIG. 14A shows a schematic table of vulcanization decay data of uncoated hard rubber blanking type LED lamp beads.

FIG. 14B is a schematic table showing the vulcanization attenuation data of the hard rubber blanking type LED lamp bead after coating with 200nm.

FIG. 14C is a schematic table showing the vulcanization attenuation data of hard rubber blanking LED lamp beads before and after coating with a film thickness of 800 nm.

Fig. 15A shows a table schematic diagram of vulcanization decay data of uncoated hard rubber cut LED lamp beads.

FIG. 15B is a schematic table showing the vulcanization attenuation data of hard rubber cut LED lamp beads after coating with 200nm.

FIG. 15C is a schematic table showing the vulcanization attenuation data of the hard rubber cut LED lamp bead before and after coating with a film thickness of 800 nm.

Fig. 16 shows a table schematic diagram of the vulcanization attenuation data of the soft rubber-cut LED lamp bead after coating 200nm.

Detailed ways

The following description serves to disclose the present invention to enable those skilled in the art to carry out the present invention. The preferred embodiments described below are only examples, and those skilled in the art can devise other obvious variations. The basic principles of the present invention defined in the following description can be applied to other embodiments, variations, improvements, equivalents and other technical solutions without departing from the spirit and scope of the present invention.

It can be understood that the term "a" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element can be one, while in another embodiment, the number of the element The quantity can be multiple, and the term "a" cannot be understood as a limitation on the quantity.

In the present invention, the term "a" in the claims and the specification should be understood as "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element Can be multiple. Unless it is clearly indicated in the disclosure of the present invention that there is only one element, the term "a" cannot be understood as unique or single, and the term "a" cannot be understood as a limitation on the number.

In the description of the present invention, it should be understood that belonging to "first", "second" and so on are only for descriptive purposes, and should not be understood as indicating or implying relative importance. In the description of the present invention, it should be noted that, unless otherwise specified and limited, "connected" and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection or an integral connection ; It can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through a medium. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

The invention provides a polymer film layer and its preparation method and LED products, wherein the polymer film layer has good sealing performance, so that when the polymer film layer is attached to the surface of an LED substrate, it can Therefore, the surface of the LED base material has better waterproof, sulfur-proof and oxygen-proof properties. At the same time, the polymer film layer itself has good light transmission performance, which enables the polymer film layer to be applied to products without too much impact on the light transmission performance of the product.

In some embodiments of the present invention, the type of the LED substrate can be, but is not limited to, materials such as glass, metal, ceramic, plastic, semiconductor or polymer. In detail, the LED base material can be, but not limited to, LED finished products such as LED display screens or LED lamps, and can also be implemented as LED semi-finished products such as LED brackets or light-emitting elements.

The polymer film layer can be prepared to have a small thickness, and its thickness range is for example but not limited to 10nm-20um. Preferably, the thickness of the polymer film layer is implemented to be 10nm˜10um.

Specifically, according to an embodiment of the present invention, the polymer film layer is formed on the surface of the LED substrate through a plasma enhanced chemical vapor deposition (PECVD) process. That is to say, during the preparation process, the surface of the LED substrate is exposed to the chamber of the plasma-enhanced chemical vapor deposition reaction device, a plasma is formed in the chamber, and the reaction raw material deposition reaction forms the The polymer film layer is on the surface of the LED substrate.

Compared with other existing deposition processes, the plasma enhanced chemical vapor deposition (PECVD) process has many advantages: (1) dry film formation does not require the use of organic solvents; (2) the etching effect of plasma on the surface of the LED substrate , so that the deposited film has good adhesion to the LED substrate; (3) the coating can be uniformly deposited on the surface of the irregular LED substrate, and the gas phase permeability is extremely strong; (4) the film layer can be designed well, compared with The micron-level control accuracy of the liquid phase method, the chemical vapor phase method can control the coating thickness at the nanoscale scale; (5) The film structure design is easy, the chemical vapor phase method uses plasma activation, and does not need to be designed for composite coatings of different materials Specific initiators are used to initiate, and various raw materials can be combined through the regulation of input energy; (6) The compactness is good, and the chemical vapor deposition method often activates multiple active sites during the plasma initiation process. Similar to a solution reaction in which there are multiple functional groups on one molecule, a cross-linking structure is formed between the molecular chains through multiple functional groups; (7) As a coating treatment technology, it has excellent universality, and the coating object and coating use The selection of raw materials is very wide.

In addition, the plasma-enhanced chemical vapor deposition (PECVD) process can generate plasma through glow discharge, and the methods of discharge include radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electric spark discharge. The high frequency discharge and The waveform of intermediate frequency discharge is sinusoidal or bipolar pulse. Certainly, the discharge type in the plasma enhanced chemical vapor deposition (PECVD) process may be continuous discharge or pulse discharge.

According to the above embodiments of the present application, the polymer film layer may be composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers, and aromatic ring-containing organic monomers One or more of the monomer groups are used as reaction raw materials and formed on the surface of the LED substrate by plasma-enhanced chemical vapor deposition.

It is worth noting that the acrylate monomer has a double bond that is easily activated by plasma, so that the deposition speed is accelerated. Exemplarily, the acrylate monomer may include, but is not limited to, long-chain alkyl acrylate compounds and/or fluorine-containing acrylate compounds.

Preferably, the number of carbon atoms of the alkyl group in the long-chain alkyl acrylate compounds is generally greater than or equal to 6, such as n-hexyl methacrylate, n-octyl methacrylate, decyl methacrylate, isodecyl methacrylate ester, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, isodecyl acrylate, decaacrylate Diester, tetradecyl acrylate, cetyl acrylate or octadecyl acrylate, etc.

The fluorine-containing acrylate compounds can be implemented as, but not limited to, 2-(perfluorobutyl)ethyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,1H,2H,2H - Perfluorooctyl Acrylate, (Perfluorocyclohexyl) Methacrylate, 1H,1H,2H,2H-Perfluorohexyl Methacrylate, 1H,1H,2H,2H-Perfluorooctyl Methacrylate ester or 1H,1H,2H,2H-perfluorodecyl methacrylate, etc.

The fluorine-containing olefin monomer may include, but is not limited to, tetrafluoroethylene, hexafluoropropylene, octafluorobutene, perfluorononene, or 1H,1H,2H-perfluoro-1-dodecene and the like.

The organosilicon-based monomers may include, but are not limited to, vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methylvinyldiethyl Oxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributanoximinosilane, Tetramethyldivinyldisiloxane, Dimethylvinylethoxysilane , 1,2,2-trifluorovinyltriphenylsilane, tetramethoxysilane, trimethoxyhydrogensilane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyl tri(2 -methoxyethoxy)silane, triethylvinylsilane, hexaethylcyclotrisiloxane, 3-(methacryloxy)propyltrimethoxysilane, phenyltris(trimethylsilane oxyalkyl)silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, dimethoxysilane or 3-chloropropyltrimethoxysilane and the like.

The epoxy monomer may include, but is not limited to, 3-glycidyloxypropyltriethoxysilane or γ-glycidyloxypropyltrimethoxysilane and the like.

It should be noted that one layer of the polymer film layer or multiple layers of the polymer film layer may be deposited on the surface of the LED substrate. In particular, when only one layer of the polymer film layer is deposited on the surface of the LED substrate, the static water contact angle of the polymer film layer can reach more than 100°.

In addition, the reaction raw materials for preparing the polymer film layer are introduced into the reaction chamber of the preparation equipment in the form of monomer vapor.

Exemplarily, the reaction raw material for preparing the polymer film layer can be implemented, but not limited to, by at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon mixture of derivatives. Preferably, the mass fraction of the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the reaction raw materials is 10%-60%.

More preferably, the organosilicon monomer containing a double bond structure can be selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane , Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributanoneximosilane, Tetramethyldivinyldisiloxane, Dimethicone One or more of vinylethoxysilane and 1,2,2-trifluorovinyltriphenylsilane.

The polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives can be selected from isoprene, ethylene glycol diacrylate, 1,3-butadiene, 1,4-pentadiene, ethoxylated trihydroxy Methylpropane Triacrylate, Tripropylene Glycol Diacrylate, Polyethylene Glycol Diacrylate, 1,6-Hexanediol Diacrylate, Diethylene Glycol Divinyl Ether, Neopentyl Glycol Diacrylate , 1,4-butylene glycol methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethacrylate Ethylene glycol ester, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl One or more of 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, and diethyl diallyl malonate.

According to another aspect of the present application, an embodiment of the present application provides a method for preparing the polymer film layer, which may include steps:

(1) Pre-treatment: After placing the LED base material in the reaction chamber of the PECVD device for vacuuming, the plasma source gas is introduced, and the movement mechanism is turned on so that the LED base material moves in the reaction chamber;

(2) Deposition: In the PECVD device, a monomer group consisting of acrylate monomers, fluorine-containing olefin monomers, organosilicon monomers, epoxy monomers, and aromatic ring-containing organic monomers is used One or more of them are reaction raw materials, and the polymer film layer is formed on the surface of the LED substrate by plasma-enhanced chemical vapor deposition; and

(3) Post-processing: stop the plasma discharge, stop the vacuuming, and ventilate the atmosphere to an atmospheric pressure, stop the movement of the LED base material, and then take out the LED base material formed with the polymer film layer.

It can be understood that the plasma source gas may be an inert gas, nitrogen or oxygen, or the like. The plasma source gas may be a single gas or a mixed gas of the above single gas, such as a mixed gas of He and Ar in an inert gas.

It is worth mentioning that the polymer film layer can be prepared in large quantities, and the preparation steps are simple. The method, the prepared polymer film layer has long-term waterproof, sulfur-proof and oxygen-proof properties, suitable for industrial applications.

According to the above-mentioned embodiments of the present invention, in the step (1) of the overall preparation method of the polymer film layer: the reaction chamber is continuously evacuated, so that the vacuum degree in the reaction chamber is evacuated to 10-5000 mTorr.

Preferably, when the vacuum degree in the reaction chamber reaches 10-200 mTorr, an inert gas, such as He, Ar or a mixed gas thereof, is started to be introduced, and the movement mechanism is turned on, so that the LED substrate is Motion is generated within the reaction chamber.

More preferably, the reaction chamber of the PECVD device is implemented as a rotating body-shaped chamber or a cube-shaped chamber with a volume of 50-1000 L, and the temperature of the reaction chamber is controlled at 25-60°C. The inert gas The flow rate is 5-300 sccm. For example, the volume of the reaction chamber is 100 L, the temperature of the reaction chamber is controlled at 30° C., and the flow rate of the inert gas is 15 sccm.

It is worth noting that, in the step (1), the movement form of the LED base material in the reaction chamber can be that the LED base material performs linear reciprocating motion or curvilinear motion relative to the reaction chamber, wherein the The curved motion may include circular motion, elliptical circular motion, planetary motion, spherical motion or other irregularly routed curved motion. For example, when the LED base material performs circular motion relative to the reaction chamber, the rotational speed of the LED base material can be implemented as, but not limited to, 1˜10 revolutions/min.

In addition, the LED base material can be implemented, but not limited to, as finished LED products such as LED display screens or LED lamps. Of course, in other examples of the present application, the LED base material can also be implemented as an LED bracket or an LED semi-finished product before packaging, and the like.

According to the above-mentioned embodiment of the present invention, in the step (2) of the preparation method of the polymer film layer: feed monomer vapor into the reaction chamber until the vacuum degree is 30-300 mTorr, open Plasma discharge and chemical vapor deposition are performed to form the polymer film on the surface of the substrate. For example, when the vacuum degree in the reaction chamber reaches 50-200 mTorr, the plasma discharge is turned on to perform chemical vapor deposition.

It is worth noting that the composition of the monomer vapor may include one of acrylate monomers, fluorine-containing olefin monomers, organosilicon monomers, epoxy monomers, and aromatic ring-containing organic monomers or multiple monomers.

Preferably, the composition of the monomer vapor is implemented as a mixture of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative, wherein the monomer The mass fraction of the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the steam is 10%-60%.

In addition, in the step (2): when the plasma discharge is turned on for chemical vapor deposition, the plasma discharge process during the deposition process is a low-power continuous discharge, which specifically includes the following deposition process at least once: wherein the deposition process Including the pretreatment stage and the coating stage, firstly, the plasma discharge power in the pretreatment stage is 100-600W, and the continuous discharge time is 60-1800s. Then, when entering the coating stage, adjust the plasma discharge power to 10-200W, and last The discharge time is 600~36000s.

Preferably, in the pretreatment stage, the plasma discharge power is 150W, and the discharge time is 600s; and in the coating stage, the plasma discharge power is adjusted to 60W, and the discharge time is 800s.

Optionally, in some embodiments of the present invention, in the step (2): when the plasma discharge is turned on for chemical vapor deposition, the plasma discharge process in the deposition process is a pulse discharge, specifically including the following deposition Process at least once: The formation process of the polymer film layer includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600W, and the continuous discharge time is 60-1800s, and then enters the coating stage. The coating stage is pulse discharge. The power is 10~300W, the time is 600s~36000s, the frequency of pulse discharge is 20Hz-20KHz, and the duty ratio of pulse is 1:1~1:500.

Further, in the step (2): the monomer is atomized and volatilized by the feed pump to form the monomer vapor, and introduced into the reaction chamber at a low pressure of 100-300 mTorr, wherein the The flow rate of the monomer steam can be 10-1000 μL/min. For example, the flow rate of the monomer vapor can be 500 uL/min.

Preferably, in the step (2), the plasma discharge method is implemented as radio frequency discharge.

More preferably, the total thickness of the polymer film layer is 10 nm-10 μm.

According to the above-mentioned embodiments of the present application, in the step (3) of the preparation method of the polymer film layer: while stopping the introduction of the monomer vapor, stop the plasma discharge, and continue vacuuming to maintain The vacuum degree of the reaction chamber is 10-200 mTorr; then after 1-5 minutes, the atmosphere is vented to an atmospheric pressure, the movement of the LED base material is stopped, and then the LED base material is taken out. Of course, in other examples of the present application, the plasma discharge is stopped, and the reaction chamber is filled with air or an inert gas to a pressure of 2000-5000 millitorr, and then vacuumed to 10-200 millitorr to carry out the above-mentioned inflation and pumping. The vacuum step is at least once, the air is introduced to an atmospheric pressure, the movement of the LED base material is stopped, and then the LED base material is taken out.

It is worth noting that the polymer film layer can be formed on the surface of the LED substrate (such as LED lamp beads or LED display screens, etc.) to form an LED product with a polymer film layer, which helps to improve the performance of the LED. Waterproof, sulfur-proof and oxygen-proof performance of the product. Specifically, the LED product with a polymer film layer can expose the LED substrate to an environment in which the monomer vapor is used as a reaction raw material, so that at least A part of the polymer film layer is formed, wherein the monomer vapor can be composed of acrylate monomers, fluorine-containing olefin monomers, organosilicon monomers, epoxy monomers, and organic compounds containing aromatic rings One or more of the group of monomers composed of monomers.

Preferably, the LED base material is a finished LED product or a semi-finished LED product.

At present, although the existing LED lights usually use polymer silicone as the encapsulant to prolong the service life, the silica gel itself and the poor sealing between the silica gel and the bracket still have disadvantages such as moisture permeability, oxygen permeability, sulfur permeability, and bromine permeability. . In fact, the brackets of most LED lamps are usually made of a metal base, and a silver layer is plated on the base as the light source reflection layer of the LED lamp. However, in actual use scenarios of LED lights, such as sulfur (S), water (H2O) or oxygen (O2) in air, humidity, rainy days, etc., will react with the silver plating layer. In particular, the reaction between S in the air and Ag will form Ag2S, which will lead to blackening of the silver plating layer and darkening of the lamp beads, which will cause serious light decay. Of course, when moisture or oxygen in the air enters the interior of the LED lamp, it is also prone to complex chemical reactions with the metal, resulting in a serious decrease in the luminous flux of the LED lamp, a significant drift in the color temperature, and even a dead light. In order to solve the above problems, this application provides a protective LED packaging method and protective LED lamp beads, which can prepare LED lamps with properties such as sulfur resistance, water resistance, or oxygen resistance, so as to solve the problem that LED lamps are prone to vulcanization, further damage Industry pain points such as water or oxygen permeability.

Referring to FIG. 1 to FIG. 4 of the accompanying drawings of the present application, a protective LED packaging method according to an embodiment of the present application is illustrated. Specifically, as shown in Figure 1, the protective LED packaging method may include steps:

S110: Conductively fixing the light-emitting element to the LED bracket;

It is worth noting that since the polymer film layer has good sealing performance, when the polymer film layer is attached to the surface of the LED semi-finished product, the surface of the LED semi-finished product can have better waterproof , Anti-sulfur, anti-oxidation properties. At the same time, the polymer film layer itself has better light transmission performance, which makes the polymer film layer provide protective functions such as waterproof, sulfur-proof, oxygen-proof, etc., without affecting the performance of the LED. Surface light transmission properties of semi-finished products.

It can be understood that the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages compared with other existing deposition processes: (1) dry film formation does not require the use of organic solvents; The etching effect makes the deposited film and the substrate have good adhesion; (3) the coating can be uniformly deposited on the surface of the irregular substrate, and the gas phase permeability is extremely strong; (4) the film layer can be designed well, and the phase Compared with the micron-level control accuracy of the liquid-phase method, the chemical vapor-phase method can control the coating thickness at the nano-scale; (5) The film structure is easy to design, and the chemical vapor-phase method uses plasma activation, which is not suitable for composite coatings of different materials. It is necessary to design a specific initiator for initiation, and a variety of raw materials can be compounded together through the regulation of input energy; (6) The compactness is good, and the chemical vapor deposition method often destroys multiple active sites during the plasma initiation process. Activation, similar to the solution reaction in which there are multiple functional groups on a molecule, the cross-linking structure is formed between the molecular chains through multiple functional groups; (7) As a coating treatment technology, it has excellent universality, and the coating object , The range of raw materials used for coating is very wide.

More specifically, in the step S130 of the protective LED encapsulation method in the above embodiment of the present application, the polymer film layer is made of acrylate monomer, fluorine-containing olefin monomer, silicone One or more of the monomer group composed of monomers, epoxy monomers and aromatic ring-containing organic monomers are used as reaction raw materials, and are deposited on the surface of the LED semi-finished product by the plasma-enhanced chemical vapor deposition method. formed film layer.

Preferably, the polymer film layer can be prepared to have a small thickness, and its thickness range is for example but not limited to 10nm-20um. More preferably, the thickness of the polymer film layer is implemented to be 10nm-10um. It should be noted that one layer of the polymer film layer or multiple layers of the polymer film layer may be deposited on the surface of the LED semi-finished product. Especially, when only one layer of the polymer film layer is deposited on the surface of the LED semi-finished product, the hydrophobic angle of the polymer film layer can reach more than 100°.

Exemplarily, the acrylate monomer may include, but is not limited to, acrylate and its derivatives, long-chain alkyl acrylate compounds, or fluorine-containing acrylate compounds.

Preferably, the number of carbon atoms of the alkyl group in the long-chain alkyl acrylate compounds is generally greater than or equal to 6, such as n-hexyl methacrylate, n-octyl methacrylate, decyl methacrylate, isodecyl methacrylate ester, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, isodecyl acrylate, decaacrylate Diesters, myristyl acrylate, cetyl acrylate and/or octadecyl acrylate, etc.

The fluorine-containing acrylate compounds can be implemented as, but not limited to, 2-(perfluorobutyl)ethyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,1H,2H,2H - Perfluorooctyl Acrylate, (Perfluorocyclohexyl) Methacrylate, 1H,1H,2H,2H-Perfluorohexyl Methacrylate, 1H,1H,2H,2H-Perfluorooctyl Methacrylate esters and/or 1H,1H,2H,2H-perfluorodecyl methacrylate.

The fluorine-containing olefin monomer may include, but is not limited to, tetrafluoroethylene, hexafluoropropylene, octafluorobutene, perfluorononene and/or 1H,1H,2H-perfluoro-1-dodecene.

The organosilicon-based monomers may include, but are not limited to, vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methylvinyldiethyl Oxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributanoximinosilane, Tetramethyldivinyldisiloxane, Dimethylvinylethoxysilane , 1,2,2-trifluorovinyltriphenylsilane, tetramethoxysilane, trimethoxyhydrogensilane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyl tri(2 -methoxyethoxy)silane, triethylvinylsilane, hexaethylcyclotrisiloxane, 3-(methacryloxy)propyltrimethoxysilane, phenyltris(trimethylsilane oxyalkyl)silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, dimethoxysilane and/or 3-chloropropyltrimethoxysilane and the like.

The epoxy monomer may include, but is not limited to, 3-glycidoxypropyltriethoxysilane and/or γ-glycidoxypropyltrimethoxysilane.

It is worth noting that the LED bracket can be implemented as an EMC bracket, but not limited to, wherein the EMC (Epoxy Molding Compound in English) bracket is a new epoxy resin material and etching technology under the package of the molding device. A highly integrated framework form. Of course, in other examples of the present application, the LED bracket can also be implemented as other types of brackets, which will not be described in detail in this application.

In an example of the present application, the EMC bracket is a whole piece of bracket, so when a single LED lamp bead needs to be obtained, the EMC bracket needs to be cut.

Exemplarily, as shown in Figure 1, the protective LED packaging method may further include the steps of:

S140: Cut the semi-finished protective LED into single pieces to obtain finished protective LED.

As shown in Figure 4, the protective LED finished product 50 includes an LED bracket 51, a light emitting element 52, an encapsulation adhesive layer 53 and a polymer film layer 54, wherein the light emitting element 52 is conductively fixed to the LED bracket 51 of the silver-plated surface 510 , and the encapsulation adhesive layer 53 encapsulates the light-emitting element 52 , wherein the polymer film layer 54 is plated on the outer surface of the encapsulation adhesive layer 53 .

It is worth mentioning that, as shown in FIG. 2, the step S130 of the protective LED packaging method may include the steps of:

S131: Pre-processing: After placing the LED semi-finished product in the coating chamber of the coating equipment for vacuuming, inject plasma source gas, and turn on the movement mechanism to make the LED semi-finished product move in the coating chamber;

S132: Deposition: In the coating equipment, in the monomer group consisting of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers, and aromatic ring-containing organic monomers One or more of them are reaction raw materials, and the polymer film layer is formed on the surface of the LED semi-finished product by plasma-enhanced chemical vapor deposition; and

S133: post-processing: stop the plasma discharge, stop vacuuming and then ventilate the atmosphere to an atmospheric pressure, stop the movement of the LED semi-finished product, and then take out the LED semi-finished product formed with the polymer film layer.

According to the above-mentioned embodiment of the present invention, in the step S131 : continuously evacuate the coating chamber, so as to evacuate the vacuum degree in the coating chamber to 10-5000 mTorr.

Preferably, when the vacuum in the coating chamber reaches 10-200 mTorr, an inert gas, such as He and/or Ar, is started to be introduced, and the movement mechanism is turned on, so that the LED semi-finished product is in the coating chamber Motion is generated indoors.

More preferably, the coating chamber of the coating equipment is implemented as a rotating body-shaped chamber or a cube-shaped chamber with a volume of 50-1000L, the temperature of the coating chamber is controlled at 25-60°C, and the inert gas The flow rate is 5-300 sccm. For example, the volume of the coating chamber is 100 L, the temperature of the coating chamber is controlled at 30° C., and the flow rate of the inert gas is 15 sccm.

It is worth noting that, in the step S131, the movement form of the LED semi-finished product in the coating chamber may be that the LED semi-finished product performs a linear reciprocating motion or a curved motion relative to the coating chamber, wherein the curved motion may include Circular motion, elliptical circular motion, planetary motion, spherical motion or curve motion of other irregular routes. For example, when the LED semi-finished product performs circular motion relative to the coating chamber, the rotational speed of the LED semi-finished product may be, but not limited to, implemented as 1-10 revolutions/min.

According to the above-mentioned embodiment of the present invention, in the step S132: feed the monomer vapor into the coating chamber until the vacuum degree is 30-300 mTorr, turn on the plasma discharge, and perform chemical vapor deposition in the coating chamber. The polymer film layer is formed on the surface of the LED semi-finished product. For example, when the vacuum in the coating chamber reaches 50-200 mTorr, the plasma discharge is turned on to perform chemical vapor deposition.

In addition, in the step S132: when the plasma discharge is turned on for chemical vapor deposition, the plasma discharge process during the deposition process is a low-power continuous discharge, which specifically includes the following deposition process at least once: wherein the deposition process includes pre- In the treatment stage and the coating stage, firstly, the plasma discharge power in the pretreatment stage is 100-600W, and the continuous discharge time is 60-1800s. Then, when entering the coating stage, adjust the plasma discharge power to 10-200W, and the continuous discharge time 600～36000s.

Optionally, in some embodiments of the present invention, in the step S132: when the plasma discharge is turned on for chemical vapor deposition, the plasma discharge process during the deposition process is a pulse discharge, specifically including the following deposition process at least One time: The formation process of the polymer film layer includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600W, and the continuous discharge time is 60-1800s, and then enters the coating stage. The coating stage is a pulse discharge with a power of 10 ～300W, time 600s～36000s, pulse discharge frequency 20Hz-20KHz, pulse duty ratio 1:1～1:500.

Further, in the step S132: the monomer is atomized and volatilized by the feed pump to form the monomer vapor, and introduced into the coating chamber by a low pressure of 100-300 mTorr, wherein the monomer The flow rate of the steam can be 10-1000 μL/min. For example, the flow rate of the monomer vapor can be 500 uL/min.

Preferably, in the step S132, the plasma discharge method is implemented as radio frequency discharge.

According to the above-mentioned embodiment of the present application, in the step S133: stop the plasma discharge while stopping the introduction of the monomer vapor, and continue vacuuming to keep the vacuum degree of the coating chamber at 10-200 millitorr; then after 1 to 5 minutes, the atmosphere is vented to an atmospheric pressure, the movement of the LED semi-finished product is stopped, and then the LED semi-finished product is taken out. Of course, in other examples of the present application, the plasma discharge is stopped, and the coating chamber is filled with air or an inert gas to a pressure of 2000-5000 millitorr, and then vacuumed to 10-200 millitorr to carry out the above-mentioned inflation and pumping. The vacuum step is at least once, the air is introduced to an atmospheric pressure, the movement of the LED semi-finished product is stopped, and then the LED semi-finished product is taken out.

It is worth noting that since the front side of the LED bracket of the LED semi-finished product is usually used for die bonding and dispensing, the back side of the LED bracket needs to be exposed to be electrically connected to the power supply and to ensure better heat dissipation Therefore, before coating the LED semi-finished product, it is necessary to shield the back surface of the LED semi-finished product so that the polymer film layer is only formed on the front surface of the LED semi-finished product. It can be understood that the front surface of the LED semi-finished product refers to the surface corresponding to the front surface of the LED bracket as the light-emitting surface of the LED semi-finished product, and the back surface of the LED semi-finished product refers to the surface corresponding to the LED bracket. The surface of the back of the LED bracket is used as the backlight surface of the LED semi-finished product.

Specifically, the step S130 of the protective LED packaging method may further include the steps of:

Before the step S131, performing shielding treatment on the back surface of the LED semi-finished product; and

After the step S133, de-shielding treatment is performed on the back surface of the protective LED semi-finished product.

Preferably, the present application may perform shielding treatment on the back surface of the LED semi-finished product by bonding a shielding film to the back surface of the LED semi-finished product. Certainly, in other examples of the present application, the present application may also use other types of shielding fixtures to perform shielding treatment on the back surface of the LED semi-finished product.

It is worth noting that, in order to ensure the deposition effect, the LED semi-finished product after shading needs to be dried. That is to say, the step S130 of the protective LED packaging method may further include the steps of:

The placed LED semi-finished products are dried in a drying cabinet, so that after the dried LED semi-finished products are obtained, they are placed in the coating chamber of the coating equipment for subsequent coating operations.

Exemplarily, the drying cabinet can use gas, such as air, with a relative humidity of less than 3%, a temperature of 20-30° C., and a flow rate of 15-18 m3/h.

According to the above-mentioned embodiment of the present application, as shown in FIG. 3, the step S110 of the protective LED packaging method may include the steps of:

S111: Use a flat solder paste printing machine and a 3D printing stencil to print solder paste in the cup of the EMC bracket;

S112: Carry out die-bonding operation on the printed EMC bracket on an LED die-bonding machine, so as to fix the light-emitting element on the EMC bracket; and

S113: Perform reflow soldering operation by using a reflow soldering machine to conductively connect the light emitting element and the EMC bracket.

It is worth noting that although in the above-mentioned embodiments of the present application, the polymer film layer is formed after solid crystal, wire bonding and glue dispensing, in order to improve the LED products (such as LED lamp beads or LED display screens, etc.) ) waterproof, anti-sulfur and anti-oxidation properties. However, in other examples of the present application, the polymer film layer may also be formed before die bonding, or may also be formed before glue dispensing and after wire bonding.

Fig. 5 shows a first modified implementation of the protective LED packaging method according to the above-mentioned embodiments of the present application. Specifically, compared with the above-mentioned embodiment according to the present application, the difference of the first variant implementation according to the present application is that: the protective LED packaging method may include the steps of:

S210: Depositing a polymer film layer on the silver-plated surface of the LED bracket by a plasma-enhanced chemical vapor deposition method;

S220: Conductively fixing the light-emitting element to the LED bracket coated with the polymer film layer;

S230: dispensing glue on the light-emitting element and the LED bracket to form an encapsulating glue layer, so as to make the semi-finished protective LED; and

S240: Cut the protective LED semi-finished product into individual pieces to obtain a protective LED finished product.

As shown in FIG. 6, the protective LED finished product 50 includes an LED bracket 51, a light emitting element 52, a packaging adhesive layer 53 and a polymer film layer 54, wherein the light emitting element 52 is conductively fixed to the LED bracket 51 of the silver-plated surface 510, and the encapsulation adhesive layer 53 encapsulates the light-emitting element 52, wherein the polymer film layer 54 is plated on the silver-plated surface 510 of the LED bracket 51, and the The polymer film layer 54 is located between the silver-plated surface 510 of the LED bracket 51 and the light-emitting element 52 and the encapsulation adhesive layer 53, so that the LED bracket 51 is sealed by the polymer film layer 54. The silver-plated surface 510 is separated from the light-emitting element 52 and the packaging adhesive layer 53 .

FIG. 7 shows a second modified implementation of the protective LED packaging method according to the above-mentioned embodiments of the present application. Specifically, compared with the above-mentioned embodiment according to the present application, the difference of the second variant implementation according to the present application is that: the protective LED packaging method may include the steps of:

S310: Conductively fixing the light-emitting element to the LED bracket;

S320: Deposit and form a polymer film layer on the silver-plated surface of the LED bracket and the surface of the light-emitting element by plasma-enhanced chemical vapor deposition;

S330: dispensing glue on the polymer film layer to form an encapsulation glue layer, so as to make the protective LED semi-finished product; and

S340: Cut the semi-finished protective LED into single pieces to obtain finished protective LED.

As shown in Figure 8, the protective LED finished product 50 includes an LED bracket 51, a light emitting element 52, an encapsulation layer 53 and a polymer film layer 54, wherein the light emitting element 52 is conductively fixed to the LED bracket 51 of the silver-plated surface 510, and the encapsulation adhesive layer 53 encapsulates the light-emitting element 52, wherein the polymer film layer 54 is plated on the silver-plated surface 510 of the LED bracket 51 and the The surface of the light-emitting element 52, and the polymer film layer 54 is located between the encapsulation adhesive layer 53 and the silver-plated surface 510 of the light-emitting element 52 and the LED bracket 52, so as to pass through the polymer film The layer 54 separates the packaging adhesive layer 53 from the light emitting element 52 and the silver-plated surface 510 of the LED bracket 52 .

According to another aspect of the present application, as shown in FIG. 9 , the present application further provides a protective LED packaging system 1, wherein the protective LED packaging system 1 may include a die-bonding device 10, wherein the die-bonding device 10 is used to light-emitting The component can be conductively fixed to the LED bracket; the dispensing equipment 20, wherein the dispensing equipment 20 is used for dispensing glue on the light-emitting element and the LED bracket to form an encapsulation layer to make an LED semi-finished product; and a coating equipment 30 , wherein the coating device 30 is used for depositing and forming a polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition, so as to make a protective LED semi-finished product.

It should be noted that, in an example of the present application, as shown in FIG. 9 and FIG. 10 , the coating device 30 may include a coating chamber 31 , a movable The movable bracket 32 , the storage tray 33 detachably placed on the movable bracket 32 , the air supply and exhaust system 34 and the excitation system 35 . The storage tray 33 is used to place a plurality of LED semi-finished products on a plate, and the movable bracket 32 is used to drive the LED semi-finished products placed on the storage tray 33 in the coating chamber 31 sports. The air supply and exhaust system 34 is conductively connected with the coating chamber 31, and is used to supply gas inward to the coating chamber 31 while exhausting the gas outward to form a vacuum in the coating chamber 31. The coating chamber 31 provides the reaction raw materials. The excitation system 35 is correspondingly arranged in the coating chamber 31, and is used to generate an excitation electromagnetic field in the coating chamber 31 to ionize the reaction material to form a plasma, so that the plasma is formed in the LED semi-finished product. surface deposition to form the polymer film layer.

Specifically, the movable support 32 may include a revolving support 321 and a plurality of self-rotating supports 322, wherein the revolving support 321 is rotatably arranged in the coating chamber 31, and the plurality of self-rotating supports 322 are respectively It is rotatably arranged on the revolving support 321 to form a planetary turret, wherein the plurality of self-rotating supports 322 are used to place the storage tray 33, so that the LED semi-finished product placed on the storage tray 33 is placed on the storage tray 33. Driven by the rotation bracket 322, while rotating around the rotation axis of the rotation bracket 322, it is also driven by the revolution bracket 321 to rotate around the revolution axis of the revolution bracket 321. That is to say, the LED semi-finished products placed on the storage tray 33 both rotate and revolve in the coating chamber 31, so that all the LED semi-finished products regardless of their initial position in the coating chamber 31 Whether the position is in the edge part or the central part, it can be rotated to the edge part of the coating chamber 31, so as to provide more consistent coating conditions for all the LED semi-finished products, thereby ensuring that all the LED semi-finished products obtain uniformity Consistent film layer in order to meet the requirements of industrial mass production.

Preferably, as shown in FIG. 11 , the storage tray 33 has a plurality of storage slots 330, wherein the plurality of storage slots 330 extend along the radial direction of the storage tray, so as to insert the LED semi-finished products in The storage slot 330 of the storage tray 33 is used to place more LED semi-finished products in a limited space, and at the same time prevent a plurality of LED semi-finished products from blocking each other and affect the coating effect.

More preferably, as shown in FIG. 11 , the storage tray 33 includes a grid plate 331 and a grid plate 332, wherein the grid plate 331 and the grid plate 332 are stacked at intervals, so that The plurality of storage slots 330 are formed between the grid plate 331 and the grid plate 332 , so as to ensure the insertion of the LED semi-finished products while minimizing the shielding of the LED semi-finished products by the storage tray 33 .

In an example of the present application, the polymer film layer is composed of acrylate monomers, fluorine-containing olefin monomers, silicone-based monomers, epoxy-based monomers and aromatic ring-containing organic monomers One or more of the monomer groups are used as reaction raw materials, and the film layer is formed on the surface of the LED semi-finished product by the plasma enhanced chemical vapor deposition method.

According to the above-mentioned embodiment of the present application, as shown in FIG. 9, the protective LED packaging system may further include a cutting device 40, wherein the cutting device 40 is used to cut the protective LED semi-finished products into individual pieces to obtain Protected LED finished product.

It is worth mentioning that, whether the LED semi-finished product is used as the LED base material, or the LED bracket or the LED bracket after solid crystal is used as the LED base material for coating, the protective LED packaging method of the application can prepare the above-mentioned Protected LED finished product. In addition, although the protective LED packaging system according to the above embodiments of the present application is described as an example of implementing the protective LED packaging method according to the above embodiments of the present application, it can also be used to implement the The protective LED packaging method of the above-mentioned first or second variant implementation of the present application will not be described in detail here.

The present invention will be further described in detail through specific examples below. It should be pointed out that the following examples are intended to facilitate the understanding of the present invention, but do not limit it in any way.

Example 1

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 200 nm.

The polymer film layer can be prepared according to the following steps:

(1) Pre-treatment: the substrate is placed in the reaction chamber of the PECVD device, the reaction chamber is closed and the reaction chamber is continuously evacuated, and the vacuum degree in the reaction chamber is evacuated to 20 millitorr, The inert gas Ar is introduced, and the movement mechanism is turned on, so that the substrate moves in the reaction chamber.

In the step (1), the reaction chamber is a rotating body chamber, and the volume of the reaction chamber is 100L, the temperature of the reaction chamber is controlled at 30° C., and the flow rate of the inert gas is: 15 sccm. The substrate moves in a circular motion in the reaction chamber at a speed of 2 revolutions/min.

(2) Film layer preparation: feed monomer vapor into the reaction chamber of the PECVD device, evacuate to a vacuum of 120 mTorr, turn on the plasma discharge, and perform chemical vapor deposition on the surface of the substrate The polymer film layer is formed. The monomer vapor component is a mixture of an organosilicon monomer containing a double bond structure and two multifunctional unsaturated hydrocarbons and hydrocarbon derivatives, and the multifunctional unsaturated hydrocarbon and hydrocarbon derivatives in the monomer vapor The mass fraction of quasi-derivatives is 29%.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, the pretreatment In the first stage, the plasma discharge power is 150W, and the continuous discharge time is 600s, and then enters the coating stage, and the plasma discharge power is adjusted to 60W, and the continuous discharge time is 800s.

In the step (2): the monomer steam is introduced into the reaction chamber by a low pressure of 150 mTorr to atomize and volatilize the monomer through the feeding pump, and the flow rate of the monomer steam is 500 μL /min; wherein said one type of organosilicon monomer containing a double bond structure is vinyltriethoxysilane; and said two kinds of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene and di Ethylene glycol acrylate.

In the step (2): the plasma discharge method is radio frequency discharge.

(3) Post-treatment: Stop feeding the monomer steam, stop the plasma discharge at the same time, continue vacuuming, keep the vacuum degree of the reaction chamber at 40 millitorr for 1 min, then feed the atmosphere to an atmospheric pressure, and stop the vacuuming of the substrate. Motion, then remove the substrate.

Example 2

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 800 nm.

The polymer film layer can be prepared according to the following steps:

(2) Film layer preparation: feed monomer vapor into the reaction chamber of the PECVD device, evacuate to a vacuum degree of 120 mTorr, turn on the plasma discharge, and perform chemical vapor deposition on the substrate. The polymer film layer is formed on the surface. The monomer vapor component is a mixture of an organosilicon monomer containing a double bond structure and two multifunctional unsaturated hydrocarbons and hydrocarbon derivatives, and the multifunctional unsaturated hydrocarbon and hydrocarbon derivatives in the monomer vapor The mass fraction of quasi-derivatives is 29%.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, the pretreatment In the first stage, the plasma discharge power is 150W, and the continuous discharge time is 600s, and then enters the coating stage, and the plasma discharge power is adjusted to 60W, and the continuous discharge time is 3200s.

In the step (2): the plasma discharge method is radio frequency discharge.

Example 3

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 10 nm.

The polymer film layer can be prepared according to the following steps:

(1) Pretreatment: the base material is placed in the reaction chamber of the nano film layer preparation equipment, the reaction chamber is closed and the reaction chamber is continuously evacuated, and the vacuum degree in the reaction chamber is evacuated to 10 mTorr, the inert gas Ar is introduced, and the movement mechanism is turned on, so that the substrate moves in the reaction chamber.

In the step (1), the reaction chamber is a rotating body-shaped chamber, and the volume of the reaction chamber is 50L, the temperature of the reaction chamber is controlled at 25° C., and the flow rate of the inert gas is: 5 sccm. The substrate moves in a circular motion in the reaction chamber at a speed of 1 revolution/min.

(2) Film layer preparation: feed monomer vapor into the reaction chamber, evacuate to a vacuum of 30 mTorr, turn on the plasma discharge, perform chemical vapor deposition, and form the polymer on the surface of the substrate. film layer. The monomer vapor component is a long-chain alkyl acrylate compound.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a pulse discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, and the pretreatment stage plasma The bulk discharge power is 150W, the continuous discharge time is 450s, and then enters the coating stage. The coating stage is pulse discharge, the power is 30W, the time is 600s, the frequency of pulse discharge is 10HZ, and the pulse duty ratio is 1:1.

In the step (2): the monomer steam is introduced into the reaction chamber by a low pressure of 100 mTorr to atomize and volatilize the monomer through the feed pump, and the flow rate of the monomer steam is 30 μL /min; wherein the long-chain alkyl acrylate compound is n-hexyl methacrylate.

In the step (2): the plasma discharge method is radio frequency discharge.

(3) Post-treatment: Stop feeding the monomer steam, stop the plasma discharge at the same time, continue vacuuming, keep the vacuum degree of the reaction chamber at 10 mTorr for 1 min, feed the atmosphere to an atmospheric pressure, and stop the vacuuming of the substrate. Motion, then remove the substrate.

Example 4

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 10 um.

The polymer film layer can be prepared according to the following steps:

(1) Pre-treatment: place the base material in the reaction chamber of the nano film layer preparation equipment, close the reaction chamber and continuously evacuate the reaction chamber, and evacuate the vacuum degree in the reaction chamber to 200 mTorr, the inert gas Ar is introduced, and the movement mechanism is turned on, so that the substrate moves in the reaction chamber.

In the step (1), the reaction chamber is a rotating body-shaped chamber, and the volume of the reaction chamber is 1000L, the temperature of the reaction chamber is controlled at 60 ° C, and the flow rate of the inert gas is 300 sccm. The substrate moves in a circular motion in the reaction chamber at a speed of 3 revolutions/min.

(2) Film layer preparation: feed monomer vapor into the reaction chamber, evacuate to a vacuum of 300 mTorr, turn on the plasma discharge, perform chemical vapor deposition, and form the polymer on the surface of the substrate. film layer. The monomer vapor component is a fluorine-containing acrylate compound.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, the pretreatment In the first stage, the plasma discharge power is 600W, and the continuous discharge time is 450s, and then enters the coating stage, and the plasma discharge power is adjusted to 200W, and the continuous discharge time is 14400s.

In the step (2): the monomer steam is introduced into the reaction chamber by a low pressure of 300 mTorr to atomize and volatilize the monomer through the feed pump, and the flow rate of the monomer steam is 1000 μL /min; wherein the fluorine-containing acrylate compound is 1H, 1H, 2H, 2H-perfluorodecyl acrylate.

In the step (2): the plasma discharge mode is microwave discharge.

(3) Post-processing: stop feeding monomer steam, stop plasma discharge at the same time, continue vacuuming, keep the vacuum degree of the reaction chamber at 200 millitorr for 5 minutes, feed the atmosphere to an atmospheric pressure, and stop the vacuuming of the substrate. Motion, then remove the substrate.

Example 5

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 20 nm.

The polymer film layer can be prepared according to the following steps:

(1) Pretreatment: place the base material in the reaction chamber of the nano film layer preparation equipment, close the reaction chamber and continuously evacuate the reaction chamber, and evacuate the vacuum degree in the reaction chamber to 20 In mTorr, the inert gas He is fed, and the motion mechanism is turned on, so that the substrate moves in the reaction chamber.

In the step (1), the reaction chamber is a rotating body-shaped chamber, and the volume of the reaction chamber is 200L, the temperature of the reaction chamber is controlled at 40 ° C, and the flow rate of the inert gas is 20 sccm. The substrate moves in a circular motion in the reaction chamber at a speed of 2 revolutions/min.

(2) Film layer preparation: feed monomer vapor into the reaction chamber, evacuate to a vacuum of 150 mTorr, turn on the plasma discharge, perform chemical vapor deposition, and form the polymer on the surface of the substrate. film layer. The monomer vapor component is an epoxy monomer.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a pulse discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, and the pretreatment stage plasma The body discharge power is 200W, the continuous discharge time is 100s, and then enters the coating stage, the coating stage is pulse discharge, the power is 100W, the time is 600s, the frequency of pulse discharge is 500HZ, and the pulse duty ratio is 1:10.

In the step (2): the monomer steam is introduced into the reaction chamber by a low pressure of 150 mTorr to atomize and volatilize the monomer through the feed pump, and the flow rate of the monomer steam is 100 μL /min; wherein the epoxy monomer is 3-glycidyl etheroxypropyl triethoxysilane.

In the step (2): the plasma discharge method is radio frequency discharge.

(3) Post-processing: stop feeding monomer steam, stop plasma discharge at the same time, continue vacuuming, keep the vacuum degree of the reaction chamber at 50 mTorr for 1 min, feed the atmosphere to an atmospheric pressure, and stop the vacuuming of the substrate. Motion, then remove the substrate.

Example 6

In this embodiment, the total thickness of the polymer film layer prepared by the plasma enhanced chemical vapor deposition method is about 2 μm.

The polymer film layer can be prepared according to the following steps:

(2) Film layer preparation: feed monomer vapor into the reaction chamber, evacuate to a vacuum of 150 mTorr, turn on the plasma discharge, perform chemical vapor deposition, and form the polymer on the surface of the substrate. film layer. The monomer vapor component is a fluorine-containing olefin monomer.

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process once: the deposition process includes a pretreatment stage and a coating stage, the pretreatment In the first stage, the plasma discharge power is 200W, and the continuous discharge time is 100s, and then enters the coating stage, and the plasma discharge power is adjusted to 100W, and the continuous discharge time is 7200s.

In the step (2): the monomer steam is introduced into the reaction chamber by a low pressure of 150 mTorr to atomize and volatilize the monomer through the feeding pump, and the flow rate of the monomer steam is 600 μL /min; wherein the fluorine-containing olefin monomer is 1H, 1H, 2H-perfluoro-1-dodecene.

In the step (2): the plasma discharge method is radio frequency discharge.

It is worth mentioning that, for the substrates (such as LED semi-finished products, LED lamp beads, LED displays or LED lamp panels, etc.) after plating in the above-mentioned embodiments, high-temperature aging tests, high-temperature and high-humidity tests, red ink tests, and vulcanization tests were carried out. Various types of tests such as test and thermal shock test are compared with the test results of the untreated substrate and the substrate after surface spraying, and the comparison results are shown in Figure 12.

It is worth noting that the high-temperature aging test mentioned in this application: first place the LED lamp bead sample in a high-temperature box at 85°C for 48 hours, and then light it up to observe whether the LED lamp bead has dead light.

High temperature and high humidity test: Place the LED lamp bead sample without power in the high temperature and humidity test chamber, where the temperature and humidity of the test chamber are set to 50°C and 90% RH respectively, so that the LED lamp bead sample can be tested under high temperature and high humidity. Place it in the environment for 216 hours; during this period, turn on the lamp beads at intervals of 72 hours, observe the electrical performance of the lamp bead module, and observe whether the display of the lamp board is normal (such as whether there is a large area of dead lights/lack of color).

Red ink test: First configure the red ink alcohol mixture, the ratio of the two is 1:1; then place the LED lamp bead sample in the red ink alcohol mixture, boil it at 95°C for 4 hours, and then observe whether there is red ink inside the lamp bead. Ink seeps in.

Vulcanization test: First take 1g of sulfur powder and place it in a 25mL beaker, then put the 25mL beaker into the center of a 500mL U-shaped bottle; then put the LED lamp bead sample into the U-shaped cup, with the front of the lamp bead facing up, and wrap the lamp with label paper The beads are placed evenly in the center of the U-shaped cup lid; finally, the 500mL U-shaped bottle is sealed and baked in an oven at 105°C for 4 hours to observe whether the lamp beads appear black, glue cracked, or fall off.

Thermal shock test: first place the LED lamp bead sample in a thermal shock box at -40°C to 100°C; Whether there is a large area of dead lights or lack of color), whether the appearance of the light board is normal (such as whether there are abnormalities such as whitening and delamination).

According to another aspect of the present application, in order to further verify the effect of the protective LED packaging method, it is necessary to carry out light decay experiments, vulcanization experiments, and weldability tests on the protective LED finished products (such as coated LED lamp beads, etc.). Experiments, spectroscopic probe conduction experiments, thermal shock experiments, and high-temperature and high-humidity aging experiments.

Specifically, the light attenuation experiment is to confirm the brightness attenuation of the LED lamp bead after coating, and the requirement of the light attenuation experiment is that the photoelectric parameter test LM light attenuation is less than or equal to 5%, and the xy offset is less than or equal to 0.008. Exemplarily, light attenuation experiments are carried out on the LED lamp beads before and after coating, wherein the light attenuation data of the LED lamp beads coated with 200nm are shown in Figure 13A, and the light decay data of the LED lamp beads coated with 800nm are shown in Figure 13B. It is easy to know from the light decay data: the average brightness decay of the LED lamp beads before and after coating is less than 1.1%, and the average xy shift is less than 0.0011, which meets the requirements of the light decay experiment.

The vulcanization experiment can be carried out according to different types of LED brackets, wherein the LED brackets are usually divided into hard rubber blanking type LED brackets, hard rubber cutting type LED brackets and soft rubber cutting type LED brackets, and the vulcanization experiment The conditions include: 1) the number of experimental samples is 10pcs; 2) the amount of sulfur powder added is 1.3mg/ml; 3) the experimental temperature is 75°C ± 2%; the high temperature storage experiment is 8H. The requirement of the vulcanization experiment is that the appearance of the LED lamp bead is inspected after the above conditions, and the inside and outside of the lamp bead are not allowed to have black, glue cracking, degumming and other bad phenomena. Exemplarily, vulcanization experiments were carried out on uncoated LED lamp beads with various bracket types, LED lamp beads with 200nm coating and LED lamp beads with 800nm coating, wherein when the bracket type is hard rubber blanking type, the uncoated Figure 14A, 14B and 14C show the vulcanization attenuation data of the LED lamp bead with 200nm coating, and the LED lamp bead with 800nm coating; The vulcanization attenuation data of 200nm-coated LED lamp beads and 800nm-coated LED lamp beads are shown in Figure 15A, 15B, and 15C in sequence; Figure 16 shows. It is easy to know from the vulcanization attenuation data: Under the test conditions, the hard rubber blanking type, hard rubber cutting type and soft rubber cutting type coated LED lamp beads did not appear black.

The solderability test can be performed on the 360 omni-directional coated LED lamp beads and the LED lamp beads coated after covering the back, so as to observe whether there is cracking and discoloration in the appearance after three reflow soldering at 270°C and 10S. The results of the weldability experiment show that the weldability of the coated LED lamp beads meets the requirements, and the lighting rate is 100%.

The conduction experiment of the spectroscopic probe is to test the conductivity of the blanking type pinch test and the conductivity of the blanking type bottom test. The experimental results prove that the lighting rate of the LED lamp beads corresponding to the conductivity of the blanking type bottom test is 100%. .

The thermal shock test includes cold punch + red ink test and cold punch + vulcanization test, wherein the conditions of the thermal shock test are between -40°C, 15min and 100°C, 15min, and 600 cycles; The condition of the red ink test is 150°C, 4h, to observe whether there is penetration in the appearance. It is determined by experiments that the coated LED lamp beads all meet the requirements.

It should be understood by those skilled in the art that the embodiments of the present invention shown in the foregoing description are given by way of example only and do not limit the present invention. The objects of the present invention have been fully and effectively accomplished. The functions and structural principles of the present invention have been shown and described in the embodiments, and the embodiments of the present invention may have any deformation or modification without departing from the principles.

Claims

The polymer film layer is used to form on the surface of the LED substrate, wherein the polymer film layer is made of acrylic ester monomers, fluorine-containing olefin monomers, organosilicon monomers, epoxy One or more of the monomer group consisting of monomers and aromatic ring-containing organic monomers are used as reaction raw materials, and a film layer is formed on the surface of the LED substrate by plasma enhanced chemical vapor deposition.
The polymer film layer according to claim 1, wherein the acrylate monomer comprises a long-chain alkyl acrylate compound and/or a fluorine-containing acrylate compound.
The polymer group according to claim 2, wherein the number of carbon atoms of the alkyl group in the long-chain alkyl acrylate compound is greater than or equal to 6; wherein the fluorine-containing acrylate compound is selected from 2-(all Fluorobutyl) ethyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, (perfluorocyclohexyl)methacrylate, 1H,1H,2H,2H-perfluorohexyl methacrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate and 1H,1H,2H,2H-perfluorodecyl methacrylate one or more of .
The polymer film layer according to claim 3, wherein, the long-chain alkyl acrylate compound is selected from n-hexyl methacrylate, n-octyl methacrylate, decyl methacrylate, isodecyl methacrylate ester, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, isodecyl acrylate, decaacrylate One or more of diester, myristyl acrylate, cetyl acrylate and stearyl acrylate.
The polymer film layer according to claim 1, wherein the fluorine-containing olefin monomer is selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, octafluorobutene, perfluorononene and 1H, 1H, 2H-perfluoro - One or more of 1-dodecene.
The polymer film layer according to claim 1, wherein the organosilicon monomer is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltrimethoxysilane, and allyltrimethoxysilane Ethoxysilane, Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributylketoximosilane, Tetramethyldivinyldisiloxane alkane, dimethylvinylethoxysilane, 1,2,2-trifluorovinyltriphenylsilane, tetramethoxysilane, trimethoxyhydrogensilane, n-octyltriethoxysilane, phenyl Triethoxysilane, Vinyltris(2-methoxyethoxy)silane, Triethylvinylsilane, Hexaethylcyclotrisiloxane, 3-(Methacryloyloxy)propyltrimethoxy phenylsilane, phenyltris(trimethylsiloxy)silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, dimethoxysilane and 3-chloropropyltrimethoxysilane one or more of.
The polymer film layer according to claim 1, wherein the epoxy monomer comprises 3-glycidyl ether oxypropyl triethoxysilane and/or γ-glycidyl ether oxypropyl trimethoxy silane.
The polymer film layer according to claim 1, wherein the reaction raw material is composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives The mixture, and the mass fraction of the polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives in the reaction raw material is 10%-60%.
The polymer film layer according to claim 8, wherein the organosilicon monomer containing a double bond structure is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane , Allyltriethoxysilane, Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-Butenyltrimethylsilane, Vinyltributanoximinosilane, Tetramethyldi One or more of vinyldisiloxane, dimethylvinylethoxysilane and 1,2,2-trifluorovinyltriphenylsilane, and the polyfunctional unsaturated hydrocarbon and hydrocarbon Derivatives selected from isoprene, ethylene glycol diacrylate, 1,3-butadiene, 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, tripropylene glycol Diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol divinyl ether, neopentyl glycol diacrylate, 1,4-butylene glycol methacrylate ester, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate Diol ester, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, 2 - one or more of diprop-2-enyl benzylidene malonate and diethyl diallyl malonate.
The polymer film layer according to any one of claims 1 to 9, wherein the static water contact angle of the polymer film layer is greater than 100°.
The polymer film layer according to any one of claims 1 to 9, wherein the thickness of the polymer film layer is 10 nm-10 μm.
The preparation method of polymer film layer is characterized in that, comprises the steps:

In the PECVD device, one or more of the monomer groups composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers are used as The reaction raw materials are used to form the polymer film layer on the surface of the LED substrate by plasma enhanced chemical vapor deposition.
The preparation method according to claim 12, wherein, before feeding the reaction raw materials, the PECVD device is evacuated, and a plasma source gas is fed, wherein the plasma source gas is an inert gas.
The preparation method according to claim 12, wherein, after forming the polymer film layer, stopping plasma discharge and vacuuming, so as to take out the LED substrate formed with the polymer film layer.
The preparation method according to any one of claims 12-14, wherein the temperature of the reaction chamber of the PECVD device is controlled at 25-60°C.
The preparation method according to any one of claims 12 to 14, wherein the forming process of the polymer film layer includes a pretreatment stage and a film coating stage, and in the pretreatment stage, the discharge power of the plasma is 100-600W, The continuous discharge time is 60-1800s, and then when entering the coating stage, the discharge power of the plasma is adjusted to 10-200W, and the continuous discharge time is 600-36000s.
The preparation method according to any one of claims 12 to 14, wherein the formation process of the polymer film layer includes a pretreatment stage and a film coating stage, the plasma discharge power of the pretreatment stage is 150-600W, and the continuous discharge time is 60~1800s, then enter the coating stage, the coating stage is pulse discharge, the power is 10~300W, the time is 600s~36000s, the frequency of pulse discharge is 20Hz-20KHz, and the pulse duty ratio is 1:1~1: 500.
The LED product with a polymer film layer is characterized in that at least a part of the surface of the LED substrate has the polymer film layer according to any one of claims 1-11.
The LED product according to claim 18, wherein the LED substrate is a finished LED product or a semi-finished LED product.
The LED product according to claim 18 or 19, wherein said LED product does not appear blackened in the anti-sulfurization test.
The protective LED packaging method is characterized in that it comprises the steps of:

S110: Conductively fixing the light-emitting element to the LED bracket;

S120: dispensing glue on the light-emitting element and the LED bracket to form an encapsulation glue layer, so as to make a semi-finished LED product; and

S130: Deposit and form a polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition, so as to manufacture a protective LED semi-finished product.
The protective LED packaging method according to claim 21, wherein the polymer film layer is made of acrylic monomers, fluorine-containing olefin monomers, silicone-based monomers, epoxy-based monomers, and aromatic One or more of the monomer groups composed of ring organic monomers are used as reaction raw materials, and the film layer is formed on the surface of the LED semi-finished product by the plasma enhanced chemical vapor deposition method.
The protective LED packaging method according to claim 22, wherein the reaction raw material is composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives The mixture, and the mass fraction of the multifunctional unsaturated hydrocarbon and hydrocarbon derivatives in the reaction raw material is 10%-60%.
The protective LED packaging method according to any one of claims 21 to 23, further comprising the steps of:

S140 : cutting the semi-finished protective LED into single pieces to obtain finished protective LED products.
The protective LED packaging method according to claim 21, wherein said step S130 includes the steps of:

S131: pre-treatment, after placing the LED semi-finished product in the coating chamber of the coating equipment for vacuuming, injecting plasma source gas;

S132: Deposition, one of the monomer groups composed of acrylate monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and aromatic ring-containing organic monomers in the coating equipment or more as reaction raw materials, forming the polymer film layer on the surface of the LED semi-finished product by plasma enhanced chemical vapor deposition; and

S133: post-processing, stop the plasma discharge and vacuumize, so as to take out the LED semi-finished product formed with the polymer film layer.
The protective LED packaging method according to claim 25, wherein said step S130 further comprises the steps of:

Before the step S131, the back surface of the LED semi-finished product is shielded; and

After the step S133, the back surface of the protective LED semi-finished product is de-shielded.
The protective LED packaging method as claimed in claim 26, wherein, first place the shaded LED semi-finished product on the storage tray of the coating equipment, and then dry the placed LED semi-finished product through a drying cabinet, so that After the dried LED semi-finished product is obtained, it is placed in the coating chamber of the coating equipment.
The protective LED packaging method according to any one of claims 21 to 23, 25 to 27, wherein the step S110 includes the steps of:

Use a flat solder paste printer and a 3D printing stencil to print solder paste in the bowl of the EMC bracket;

The printed EMC bracket is carried out on the LED crystal bonding machine for solid crystal operation, so that the light-emitting element is fixed on the EMC bracket; and

A reflow soldering operation is performed by a reflow soldering machine, so as to conductively connect the light emitting element and the EMC bracket.
The protective LED packaging method is characterized in that it comprises the steps of:

By plasma-enhanced chemical vapor deposition, a polymer film is deposited on the silver-plated surface of the LED bracket;

Conductively fixing the light-emitting element to the LED bracket coated with the polymer film layer;

Dispensing glue on the light-emitting element and the LED bracket to form an encapsulation glue layer to make a protective LED semi-finished product; and

The protected LED semi-finished product is cut into individual pieces to obtain a protected LED finished product.
The protective LED packaging method is characterized in that it comprises the steps of:

Conductively fixing the light-emitting element to the LED bracket;

Depositing a polymer film layer on the silver-plated surface of the LED bracket and the surface of the light-emitting element by plasma-enhanced chemical vapor deposition;

Dispensing glue on the polymer film layer to form an encapsulation layer to make a protective LED semi-finished product; and

The protected LED semi-finished product is cut into individual pieces to obtain a protected LED finished product.
The protective LED lamp bead is characterized in that it includes:

LED brackets, wherein the LED brackets have a silver-plated surface;

a light emitting element, wherein the light emitting element is conductively fixed to the silver-plated surface of the LED bracket;

an encapsulating adhesive layer, wherein the encapsulating adhesive layer encapsulates the light-emitting element; and

A polymer film layer, wherein the polymer film layer is plated on the outer surface of the packaging adhesive layer.
The protective LED lamp bead according to claim 31, wherein the polymer film layer is made of acrylic monomers, fluorine-containing olefin monomers, silicone-based monomers, epoxy-based monomers, and One or more of the monomer groups composed of aromatic ring organic monomers are used as reaction raw materials, and a film layer is formed on the outer surface of the packaging adhesive layer by plasma enhanced chemical vapor deposition.
The protective LED lamp bead according to claim 32, wherein the reaction raw material is composed of at least one organosilicon monomer containing a double bond structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivatives and the mass fraction of the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the reaction raw materials is 10% to 60%.
The protective LED lamp bead according to claim 33, wherein, the organosilicon monomer containing a double bond structure is selected from vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxy Silane, Allyltriethoxysilane, Methylvinyldiethoxysilane, Vinyltrimethylsilane, 3-butenyltrimethylsilane, Vinyltributylketoximosilane, Tetramethyl One or more of divinyldisiloxane, dimethylvinylethoxysilane and 1,2,2-trifluorovinyltriphenylsilane, and the polyfunctional unsaturated hydrocarbon and Hydrocarbon derivatives selected from isoprene, ethylene glycol diacrylate, 1,3-butadiene, 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, trimethylolpropane Propylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol divinyl ether, neopentyl glycol diacrylate, 1,4-butylene methacrylate Alcohol ester, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate Ethylene glycol ester, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, One or more of diprop-2-enyl 2-benzylidene malonate and diethyl diallyl malonate.
The protective LED lamp bead according to any one of claims 31 to 34, wherein the static water contact angle of the polymer film layer is greater than 100°.
The protective LED lamp bead according to any one of claims 31 to 34, wherein the thickness of the polymer film layer is 10 nm-10 μm.
The protective LED lamp bead according to any one of claims 31 to 34, wherein the LED bracket is an EMC bracket.
The protective LED lamp bead is characterized in that it includes:

LED brackets, wherein the LED brackets have a silver-plated surface;

a light emitting element, wherein the light emitting element is conductively fixed to the silver-plated surface of the LED bracket;

an encapsulating adhesive layer, wherein the encapsulating adhesive layer encapsulates the light-emitting element; and

A polymer film layer, wherein the polymer film layer is plated on the silver-plated surface of the LED bracket, and the polymer film layer is located on the silver-plated surface of the LED bracket and the light-emitting element and between the encapsulation layers.
The protective LED lamp bead according to claim 38, wherein the polymer film layer is made of acrylic monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and One or more of the monomer groups composed of aromatic ring organic monomers are used as reaction raw materials, and a film layer is formed on the outer surface of the packaging adhesive layer by plasma enhanced chemical vapor deposition.
The protective LED lamp bead is characterized in that it includes:

LED brackets, wherein the LED brackets have a silver-plated surface;

a light emitting element, wherein the light emitting element is conductively fixed to the silver-plated surface of the LED bracket;

an encapsulating adhesive layer, wherein the encapsulating adhesive layer encapsulates the light-emitting element; and

A polymer film layer, wherein the polymer film layer is plated on the silver-plated surface of the LED bracket and the surface of the light-emitting element, and the polymer film layer is located between the encapsulation adhesive layer and the light-emitting component and the silvered surface of the LED holder.
The protective LED lamp bead according to claim 40, wherein the polymer film layer is made of acrylic monomers, fluorine-containing olefin monomers, silicone monomers, epoxy monomers and One or more of the monomer groups composed of aromatic ring organic monomers are used as reaction raw materials, and a film layer is formed on the outer surface of the packaging adhesive layer by plasma enhanced chemical vapor deposition.