阅读说明：本技术 墨水组合物、封装结构及半导体器件 (Ink composition, packaging structure and semiconductor device ) 是由 洪海兵 于 2020-07-29 设计创作，主要内容包括：本发明提供了一种墨水组合物、封装结构及半导体器件。该墨水组合物包括可光固化含硅单体组分、活性稀释剂组分和光引发剂组分,可光固化含硅单体组分为一种可光固化含硅单体或多种可光固化含硅单体的组合,各可光固化含硅单体具有如下结构式I：<Image he="321" wi="700" file="DDA0002608458710000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>该可光固化含硅单体组分中的A<Sub>1</Sub>和A<Sub>2</Sub>中至少有一个由结构式II中的任意一种表示。即本申请将含有烯基醚键的含硅单体与含活性稀释剂组分进行配合使用时,可以形成自由基-阳离子混杂固化体系,该自由基-阳离子混杂固化体系可以减少氧阻聚,提高固化速度,降低固化收缩率,从而可以提高体系的光固化率、降低体系的固化收缩率；进而得到具有较高光固化率、较低固化收缩率的有机阻挡层。(The invention provides an ink composition, a packaging structure and a semiconductor device. The ink composition comprises a photocurable silicon-containing monomer component, an active diluent component and a photoinitiator component, wherein the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, and each photocurable silicon-containing monomer has the following structural formula I: a in the photocurable silicon-containing monomer component 1 And A 2 At least one of which is represented by any one of structural formulas II. When the silicon-containing monomer containing alkenyl ether bonds is matched with the component containing the reactive diluent for use, a free radical-cation hybrid curing system can be formed, and the free radical-cation hybrid curing system can reduce oxygen inhibition, improve the curing speed and reduce the curing shrinkage rate, so that the photocuring rate of the system can be improved and the curing shrinkage rate of the system can be reduced; and then the organic barrier layer with higher photocuring rate and lower curing shrinkage is obtained.)

1. An ink composition, comprising a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, wherein the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, and each of the photocurable silicon-containing monomers has the following structural formula I:

wherein n is any integer of 1-50; r₁And R₂Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C₁～C₅₀Alkylene of (a), substituted or unsubstituted C₃～C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁～C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆～C₅₀Arylene of (a), substituted or unsubstituted C₇～C₅₀An arylalkylene group of,-N-(R₃)-R₄-、-O-R₅-any of; wherein R is₃Is hydrogen, substituted or unsubstituted C₁～C₅₀One of the alkyl groups of (1), R₄Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a); r₅Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a);

X₁、X₂、X₃、X₄、X₅、X₆are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₅₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Cycloalkyl, substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted or unsubstituted C₃～C₅₀Heteroaryl, substituted or unsubstituted C₇～C₅₀Aralkyl, -NR₆R₇Any one of the above; wherein R is₆And R₇Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (a);

A₁and A₂Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted or unsubstituted C₇～C₅₀Aralkyl, -NR₈R₉Substituted or unsubstituted acrylate group, substituted or unsubstituted C₃～C₆₀Epoxyalkyl, substituted or unsubstituted C₂～C₆₀Epoxy group, substituted or unsubstituted C₂～C₆₀Any one of the alkenyl ether groups of (a); wherein R is₈And R₉Are the same or different and are each independently selected from hydrogen, substituted or unsubstitutedSubstituted C₁～C₅₀Any one of the alkyl groups of (a); and in the photocurable silicon-containing monomer component, the A₁And said A₂At least one of which is represented by any one of structural formulas II:

wherein, represents a binding site, R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (1).

2. The ink composition according to claim 1, wherein n is an integer of 1 to 10, preferably R₁And R₂Each independently selected from: substituted or unsubstituted C₁To C₁₀Alkylene of, -O-R₅Any one of-and-O-R₅in-R₅Is substituted or unsubstituted C₁To C₁₀One of alkylene groups of (1), preferably X₁、X₂、X₃、X₄、X₅、X₆Same or different, each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀Alkyl, substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1), and X₁、X₂、X₃、X₄、X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1), preferably the X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1).

3. According to claim 1 or 2The ink composition is characterized in that the photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, wherein A of one photocurable silicon-containing monomer is₁And said A₂Each independently represented by any one of formula II, preferably R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably, the alkyl group of (a) is hydrogen.

4. The ink composition as claimed in claim 1 or 2, wherein the photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, wherein the A of one of the photocurable silicon-containing monomers₁Or A₂Is a group represented by any one of structural formula III, structural formula IV, structural formula V and structural formula VI, wherein the structural formula III, the structural formula IV, the structural formula V and the structural formula VI are respectively as follows:

Z₁、Z₂、Z₃、Z₄、Z₅、Z₆、Z₇and Z₈Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any of the alkyl groups of (1), preferably Z₄、Z₅、Z₆Each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably hydrogen, preferably Z₈Is hydrogen.

5. The ink composition of claim 1, wherein the reactive diluent component comprises any one or more reactive diluent monomers having the structure VII:

wherein Y is selected from: single bond, substituted or unsubstituted C₁To C₅₀Alkylene of (a), substituted or unsubstituted C₃To C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁To C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆To C₅₀Arylene of (a), substituted or unsubstituted C₇To C₅₀Arylalkylene of-O-R₁₀-、-N(R₁₁)-R₁₂-any of; wherein R is₁₀Selected from substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; r₁₁Is hydrogen, substituted or unsubstituted C₁To C₅₀Any one of alkyl, R₁₂Is substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; z₉、Z₁₀Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted acrylate group, substituted or unsubstituted C₂～C₆₀And Z is any one of the alkenyl ether groups of (A), and₉、Z₁₀is represented by any one of structural formulas II.

6. The ink composition of claim 5, wherein Y is selected from the group consisting of substituted or unsubstituted C₁To C₁₀Alkylene, substituted or unsubstituted C₁To C₁₀Alkylene ether group, substituted or unsubstituted C₆To C₁₀Arylene, substituted or unsubstituted C₇To C₁₁Any one of arylalkylene groups.

7. The ink composition of claim 1, wherein the photoinitiator component is a cationic photoinitiator, preferably the cationic photoinitiator is selected from one or more of the group consisting of diaryliodonium salt cationic photoinitiators, triarylsulfonium salt cationic photoinitiators, diazonium salt cationic photoinitiators, alkylsulfonium salt cationic photoinitiators, iron arene salt cationic photoinitiators, sulfonyloxyketone cationic photoinitiators, and triarylsiloxaneoxide cationic photoinitiators.

8. The ink composition as claimed in claim 1, wherein the ink composition comprises, by weight, 0.01 to 50% of the photocurable silicon-containing monomer component, 30 to 80% of the reactive diluent component, and 0.01 to 20% of the photoinitiator component, preferably, the photocurable silicon-containing monomer component is 15 to 50%, the reactive diluent component is 40 to 80%, and the photoinitiator component is 1 to 10%.

9. The ink composition as claimed in claim 1, wherein the ink composition further comprises an auxiliary component, preferably the auxiliary component is selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and preferably the auxiliary component is contained in an amount of 0.01 to 5 wt%.

10. The ink composition according to claim 1, wherein the viscosity of the ink composition at 25 ℃ is 1 to 50 mPa-s.

11. An encapsulation structure comprising an organic layer, wherein the organic layer is formed by photocuring using the ink composition according to any one of claims 1 to 10.

12. A semiconductor device comprising a functional structure and an encapsulation structure, wherein the encapsulation structure is the encapsulation structure of claim 11, preferably wherein the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor, and a photodetector.

Technical Field

The invention relates to the technical field of packaging materials, in particular to an ink composition, a packaging structure and a semiconductor device.

Background

Organic Light-Emitting Diodes (OLEDs for short) have the characteristics of all solid-state, active Light emission, high brightness, high contrast, ultra-thin and ultra-Light, low cost, low power consumption, no view angle limitation, wide working temperature range and the like, can be manufactured on a flexible, Light and durable plastic substrate, can realize flexible display in the true sense, and is a technology which can best meet the requirements of people on future displays.

The currently applied various light emitting diodes mainly comprise organic small molecule light emitting diodes (OLEDs), Polymer Organic Light Emitting Diodes (POLED), organic phosphorescent light emitting diodes (PHOLEDs) and organic thermal excitation delay light emitting materials (TADFs). However, the largest problem of the OLED at present is that the lifetime of the OLED is shorter than that of the LCD, and the lifetime of the OLED is only about 5000 hours, which is significantly inferior to that of the LCD. The service life of the OLED device is a key problem which puzzles numerous experts and scholars of the OLED at present and is a bottleneck which restricts the development of the OLED industry. The factors influencing the service life of the OLED device are many, and physical factors such as the structure of the device, the circuit driving mode and the like exist; there are also chemical factors such as oxidation of the metal cathode, crystallization of the organic material, etc. Although the failure mechanism of OLEDs is not completely understood, there are many studies that suggest that the presence of moisture and oxygen inside the OLED device is a major factor affecting the lifetime of OLEDs. According to the research of the Kodak company on the OLED service life improving method, the research on the packaging technology is the most direct and obvious method in terms of solving the service life problem of the device.

For an OLED device, if the service life of the device is longer than 1 ten thousand hours, the Water Vapor Transmission Rate (WVTR) of the device needs to be less than 10-6 g/m²The oxygen permeability (OTR) is less than 10-5 g/(m) for the per day²D), which is a great challenge for the sealing structure of display devices, and therefore suitable OLED encapsulation technologies need to be developed.

The OLED packaging aims to isolate the light-emitting device from the environment, prevent invasion of undesirable substances such as moisture, oxygen and the like, prevent external force damage, stabilize various parameters of the device and further prolong the service life of the OLED. The OLED packaging mainly comprises cover plate packaging, filler packaging, laser packaging, film packaging and the like.

In the traditional cover plate packaging, the prepared substrate and the cover plate are bonded together by using epoxy resin in a glove box filled with inert gas to form a closed space to isolate the device from the external environment, and components such as water and oxygen in the air can only permeate into the device through the epoxy resin, so that the contact of the water and the oxygen in the air of each functional layer of the OLED is effectively prevented. The material of the package cover plate is generally glass or metal, but the light-tight property of the metal cover plate causes the application of the metal cover plate in the device package to be limited. Although the glass cover plate package has no light transmission problem, the toughness is poor and the glass cover plate package is fragile.

The three packaging methods of laser packaging, filler packaging and film packaging do not need to use drying agents, and can be used in top-emitting OLED devices. The film packaging is to grow a single-layer or multi-layer film on the prepared OLED device substrate so as to achieve the effect of blocking water vapor. For the research of the OLED thin film, an organic-inorganic composite thin film method is generally used. The inorganic film can effectively block water vapor and oxygen, but has poor film forming property and interface matching property and is easy to form defects; the organic film has good flexibility, good film forming property and high flatness due to the large free volume and the large average degree of freedom of chain segments, and the defects of the inorganic film can be covered by the organic film. The inorganic film has high water vapor and oxygen barrier property and good surface morphology of the organic film, and the organic film and the inorganic film are alternately formed to be packaged to obtain satisfactory effect.

Thin film encapsulation is represented by a three-layer structure (PECVD-Flatness-PECVD), and the excellent performance of the thin film encapsulation is the mainstream way of flexible OLED encapsulation. The third laminated layer is obtained by using a first inorganic layer (SiNX) as a smooth substrate, printing an organic polymer buffer layer on the substrate by ink jet printing and then curing, and using a third inorganic layer (SiNX) as a last inorganic layer.

The existing packaging material systems are divided into two categories of epoxy and acrylate. The acrylate system generally has higher photocuring rate, but has extremely high requirement on the oxygen content in the curing environment, a small amount of oxygen can greatly reduce the curing rate, and meanwhile, the volume shrinkage is larger, and the adhesive force is poorer; the epoxy system is insensitive to oxygen content, has a slow curing speed, good adhesion and low curing shrinkage, needs high-temperature curing and has high hardness after curing, and is difficult to meet the increasingly developed flexible packaging requirements.

For example, Sanxing SDI corporation proposed an ink composition of silicone modified acrylates. The silicone-modified acrylate ink composition exhibits a higher photo-curing rate, a high light transmittance, and a low etching rate, compared to the acrylate ink composition without the silicone. However, it is difficult for the current ink compositions to satisfy the performance indexes such as high light curing rate and low curing shrinkage rate required for the increasing film packaging.

Compared with the common acrylate resin system packaging material, the epoxy resin system packaging material has good adhesive force, chemical resistance and strength. But in the actual course of operation it was found that: the photocuring performance of the epoxy system is greatly influenced by humidity and impurities in the system, and secondly, the viscosity of the epoxy monomer is too high, which is not favorable for ink jetting, and moreover, the cationic curing rate of the epoxy monomer is slow, which is not favorable for improving the production efficiency.

Disclosure of Invention

The invention mainly aims to provide an ink composition, a packaging structure and a semiconductor device, and aims to solve the problem that a film packaging material in the prior art cannot give consideration to high light curing rate and low curing shrinkage rate.

In order to achieve the above objects, according to one aspect of the present invention, there is provided an ink composition comprising a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, the photocurable silicon-containing monomer component being a photocurable silicon-containing monomer or a combination of photocurable silicon-containing monomers, each photocurable silicon-containing monomer having the following structural formula I:

wherein n is any integer of 1-50; r₁And R₂Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C₁～C₅₀Alkylene of (a), substituted or unsubstituted C₃～C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁～C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆～C₅₀Arylene of (a), substituted or unsubstituted C₇～C₅₀Arylalkylene of (A), N- (R)₃)-R₄-、-O-R₅-any of; wherein R is₃Is hydrogen, substituted or unsubstituted C₁～C₅₀One of the alkyl groups of (1), R₄Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a); r₅Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a); x₁、X₂、X₃、X₄、X₅、X₆Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₅₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Cycloalkyl, substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted or unsubstituted C₃～C₅₀Heteroaryl, substituted or unsubstituted C₇～C₅₀Aralkyl, -NR₆R₇Any one of the above; wherein R is₆And R₇Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (a); a. the₁And A₂Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted orUnsubstituted C₇～C₅₀Aralkyl, -NR₈R₉Substituted or unsubstituted acrylate group, substituted or unsubstituted C₃～C₆₀Epoxyalkyl, substituted or unsubstituted C₂～C₆₀Epoxy group, substituted or unsubstituted C₂～C₆₀Any one of the alkenyl ether groups of (a); wherein R is₈And R₉Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (a); and in the photocurable silicon-containing monomer component, A₁And A₂At least one of which is represented by any one of structural formulas II:

wherein, represents a binding site, R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (1).

Further, n is an integer of 1 to 10, preferably R₁And R₂Each independently selected from: substituted or unsubstituted C₁To C₁₀Alkylene of, -O-R₅Any one of-and-O-R₅in-R₅Is substituted or unsubstituted C₁To C₁₀One of alkylene groups of (1), preferably X₁、X₂、X₃、X₄、X₅、X₆Same or different, each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀Alkyl, substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1), and X₁、X₂、X₃、X₄、X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any of the aralkyl groups of (1), preferably X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1).

Further, the above-mentioned photocurable silicon-containing monomer component is a combination of several photocurable silicon-containing monomers, in which A of one photocurable silicon-containing monomer is₁And A₂Each independently represented by any one of formula II, preferably R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably, the alkyl group of (a) is hydrogen.

Further, the above-mentioned photocurable silicon-containing monomer component is a combination of several photocurable silicon-containing monomers, in which A of one photocurable silicon-containing monomer is₁Or A₂Is a group represented by any one of a structural formula III, a structural formula IV, a structural formula V and a structural formula VI, wherein the structural formula III, the structural formula IV, the structural formula V and the structural formula VI are respectively as follows:

Z₁、Z₂、Z₃、Z₄、Z₅、Z₆、Z₇and Z₈Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any of the alkyl groups of (1), preferably Z₄、Z₅、Z₆Each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably hydrogen, preferably Z₈Is hydrogen.

Further, the reactive diluent component includes any one or more reactive diluent monomers having the structure of formula VII:

wherein Y is selected from: single bond, substituted or notSubstituted C₁To C₅₀Alkylene of (a), substituted or unsubstituted C₃To C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁To C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆To C₅₀Arylene of (a), substituted or unsubstituted C₇To C₅₀Arylalkylene of-O-R₁₀-、-N(R₁₁)-R₁₂-any of; wherein R is₁₀Selected from substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; r₁₁Is hydrogen, substituted or unsubstituted C₁To C₅₀Any one of alkyl, R₁₂Is substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; z₉、Z₁₀Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted acrylate group, substituted or unsubstituted C₂～C₆₀And Z is any one of the alkenyl ether groups of (A), and₉、Z₁₀is represented by any one of structural formulas II.

Further, the above Y is selected from substituted or unsubstituted C₁To C₁₀Alkylene, substituted or unsubstituted C₁To C₁₀Alkylene ether group, substituted or unsubstituted C₆To C₁₀Arylene, substituted or unsubstituted C₇To C₁₁Any one of arylalkylene groups.

Further, the photoinitiator component is a cationic photoinitiator, and preferably the cationic photoinitiator is one or more selected from the group consisting of diaryliodonium salt cationic photoinitiators, triarylsulfonium salt cationic photoinitiators, diazonium salt cationic photoinitiators, alkylsulfonium salt cationic photoinitiators, iron arene salt cationic photoinitiators, sulfonyloxy ketone cationic photoinitiators, and triarylsiloxy ether cationic photoinitiators.

Further, the ink composition comprises, by weight, 0.01-50% of a photo-curable silicon-containing monomer component, 30-80% of a reactive diluent component and 0.01-20% of a photoinitiator component, and preferably, the content of the photo-curable silicon-containing monomer component is 15-50%, the content of the reactive diluent component is 40-80%, and the content of the photoinitiator component is 1-10%.

Further, the ink composition further comprises an auxiliary component, preferably the auxiliary component is selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and preferably the content of the auxiliary component is 0.01-5 wt%.

Further, the viscosity of the ink composition at 25 ℃ is 1 to 50 mPas.

According to another aspect of the present invention, there is provided an encapsulation structure comprising an organic layer formed by photo-curing using the ink composition described above.

According to a further aspect of the present invention, there is provided a semiconductor device comprising a functional structure and an encapsulation structure, the encapsulation structure being the aforementioned encapsulation structure, preferably the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor and a photodetector.

By applying the technical scheme of the invention, the silicon-containing photocurable monomer component is a silicon-containing photocurable monomer or a combination of multiple silicon-containing photocurable monomers, and the silicon-containing photocurable monomer with the structural formula I is adopted as a polymerized monomer, wherein in the silicon-containing photocurable monomer component A₁And A₂At least one of which is represented by any one of structural formulas II. When the silicon-containing monomer containing alkenyl ether bonds is matched with the component containing the reactive diluent for use, a free radical-cation hybrid curing system can be formed, the free radical-cation hybrid curing system can reduce oxygen inhibition, improve the curing speed and reduce the curing shrinkage, and the silicon-containing monomer containing alkenyl ether bonds has no induction period, so that the photocuring rate of the system can be improved and the curing shrinkage of the system can be reduced; and then the organic barrier layer with higher photocuring rate and lower curing shrinkage is obtained. And the organic barrier layer is subjected to temperatureAnd the influence of humidity is small, and the requirements of the prior art on ink-jet printing can be better met.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As analyzed by the background art, the problem that the film encapsulation material cannot give consideration to both high light curing rate and low curing shrinkage rate exists in the prior art, and in order to solve the problem, the invention provides an ink composition, an encapsulation structure and a semiconductor device.

In one exemplary embodiment of the present application, an ink composition is provided that includes a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, the photocurable silicon-containing monomer component being a photocurable silicon-containing monomer or a combination of photocurable silicon-containing monomers, each photocurable silicon-containing monomer having the following structural formula I:

wherein n is any integer of 1-50; r₁And R₂Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C₁～C₅₀Alkylene of (a), substituted or unsubstituted C₃～C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁～C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆～C₅₀Arylene of (a), substituted or unsubstituted C₇～C₅₀Arylalkylene of (A), N- (R)₃)-R₄-、-O-R₅-any of; wherein R is₃Is hydrogen, substituted or unsubstituted C₁～C₅₀One of the alkyl groups of (1), R₄Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a); r₅Is substituted or unsubstituted C₁～C₅₀An alkylene group of (a); x₁、X₂、X₃、X₄、X₅、X₆Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₅₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Cycloalkyl, substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted or unsubstituted C₃～C₅₀Heteroaryl, substituted or unsubstituted C₇～C₅₀Aralkyl, -NR₆R₇Any one of the above; wherein R is₆And R₇Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (a); a. the₁And A₂Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted C₁～C₅₀Alkyl sulfide group of (a), substituted or unsubstituted C₆～C₅₀Aryl, substituted or unsubstituted C₇～C₅₀Aralkyl, -NR₈R₉Substituted or unsubstituted acrylate group, substituted or unsubstituted C₃～C₆₀Epoxyalkyl, substituted or unsubstituted C₂～C₆₀Epoxy group, substituted or unsubstituted C₂～C₆₀Any one of the alkenyl ether groups of (a); wherein R is₈And R₉Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (a); and in the photocurable silicon-containing monomer component, A₁And A₂At least one of which is represented by any one of structural formulas II:

wherein, represents a binding site, R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any one of the alkyl groups of (1).

As the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, and the curable silicon-containing monomer with the structural formula I is adopted as a polymerized monomer, in the photocurable silicon-containing monomer component, A₁And A₂At least one of which is represented by any one of structural formulas II. When the silicon-containing monomer containing alkenyl ether bonds is matched with the component containing the reactive diluent for use, a free radical-cation hybrid curing system can be formed, the free radical-cation hybrid curing system can reduce oxygen inhibition, improve the curing speed and reduce the curing shrinkage, and the silicon-containing monomer containing alkenyl ether bonds has no induction period, so that the photocuring rate of the system can be improved and the curing shrinkage of the system can be reduced; and then the organic barrier layer with higher photocuring rate and lower curing shrinkage is obtained. And the organic barrier layer is less affected by temperature and humidity, and can better meet the requirements of the prior art on ink-jet printing.

In order to further improve the photocurability while reducing the curing shrinkage, it is preferable that n is an integer of 1 to 10, and R is preferably₁And R₂Each independently selected from: substituted or unsubstituted C₁To C₁₀Alkylene of, -O-R₅Any one of-and-O-R₅in-R₅Is substituted or unsubstituted C₁To C₁₀One of alkylene groups of (1), preferably X₁、X₂、X₃、X₄、X₅、X₆Same or different, each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀Alkyl, substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1), and X₁、X₂、X₃、X₄、X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl of (a),Substituted or unsubstituted C₇To C₁₁Any of the aralkyl groups of (1), preferably X₅、X₆Is substituted or unsubstituted C₆To C₁₀Aryl, substituted or unsubstituted C₇To C₁₁Any one of the aralkyl groups of (1). Such as X₁、X₂、X₃、X₄、X₅、X₆The same or different, and each is independently selected from any one of methyl, ethyl, propyl, butyl and hexyl, such as X₅、X₆At least one of which is phenyl, 1-methylnaphthyl, naphthyl or benzyl.

In order to further promote the performance of the photocurable silicon-containing monomer in terms of reducing the curing shrinkage of the system and improving the photocuring rate, and obtain a better ink composition, the photocurable silicon-containing monomer component is preferably a combination of a plurality of photocurable silicon-containing monomers, wherein A of one photocurable silicon-containing monomer is₁And A₂Each independently represented by any one of formula II, preferably R₁′、R₂′、R₃' each is independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably, the alkyl group of (a) is hydrogen.

In one embodiment of the present application, the silicon-containing photocurable monomer component is a combination of a plurality of silicon-containing photocurable monomers, wherein A is the number of silicon atoms in the silicon-containing photocurable monomer component₁Or A₂Is a group represented by any one of a structural formula III, a structural formula IV, a structural formula V and a structural formula VI, wherein the structural formula III, the structural formula IV, the structural formula V and the structural formula VI are respectively as follows:

Z₁、Z₂、Z₃、Z₄、Z₅、Z₆、Z₇and Z₈Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Any of the alkyl groups of (1), preferably Z₄、Z₅、Z₆Each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably hydrogen, preferably Z₈Is hydrogen.

The photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, and adopts A₁And A₂At least one of which is a photocurable silicon-containing monomer represented by any one of the structural formulas II, can greatly reduce the curing shrinkage rate and improve the photocuring rate, and preferably A of one photocurable silicon-containing monomer in the photocurable silicon-containing monomer component₁Or A₂Is a group represented by any one of structural formula III, structural formula IV, structural formula V, structural formula VI, and preferably Z₄、Z₅、Z₆Each independently selected from hydrogen, substituted or unsubstituted C₁To C₁₀More preferably hydrogen, preferably Z₈Is hydrogen. The curing quality can be further optimized and the cost can be reduced on the basis of considering both high light curing rate and low curing shrinkage.

In order to make the reactive diluent component more fully dilute the photocurable silicon-containing monomer component, so as to fully exert the performance of each monomer in the photocurable silicon-containing monomer component, thereby obtaining an ink composition with better performance, it is preferable that the reactive diluent component comprises any one or more reactive diluent monomers shown in a structural formula VII:

wherein Y is selected from: single bond, substituted or unsubstituted C₁To C₅₀Alkylene of (a), substituted or unsubstituted C₃To C₅₀Cycloalkylene group of (1), substituted or unsubstituted C₁To C₅₀Alkylene ether group of (A), substituted or unsubstituted C₆To C₅₀Arylene of (a), substituted or unsubstituted C₇To C₅₀Arylalkylene of-O-R₁₀-、-N(R₁₁)-R₁₂-any of; wherein R is₁₀Selected from substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; r₁₁Is hydrogen, substituted or unsubstituted C₁To C₅₀Any one of alkyl, R₁₂Is substituted or unsubstituted C₁To C₅₀Any one of alkylene groups; z₉、Z₁₀Each independently selected from hydrogen, substituted or unsubstituted C₁～C₅₀Alkyl, substituted or unsubstituted C₁～C₆₀Alkyl ether group of (A), substituted or unsubstituted acrylate group, substituted or unsubstituted C₂～C₆₀And Z is any one of the alkenyl ether groups of (A), and₉、Z₁₀is represented by any one of structural formulas II. Preferably Z₉、Z₁₀At least one reactive diluent monomer represented by any of structural formulas II can further contribute to the dispersion of the alkenyl ether group-containing photocurable silicon-containing monomer component herein, thereby facilitating the exertion of its properties.

In order to further enhance the diluting effect of the reactive diluent and the complexing effect with the photocurable silicon-containing monomer component, it is preferable that Y is selected from the group consisting of substituted or unsubstituted C₁To C₁₀Alkylene, substituted or unsubstituted C₁To C₁₀Alkylene ether group, substituted or unsubstituted C₆To C₁₀Arylene, substituted or unsubstituted C₇To C₁₁Any one of arylalkylene groups.

In order to more efficiently mix the photo-curable silicon-containing monomer with the monomer and the diluent and to improve the polymerization efficiency of the photo-curable silicon-containing monomer and to achieve both the photo-curing rate and the curing shrinkage rate of the ink composition, the photo-initiator component is preferably a cationic photo-initiator, and the cationic photo-initiator is preferably one or more selected from the group consisting of diaryliodonium salt cationic photo-initiators, triarylsulfonium salt cationic photo-initiators, diazonium salt cationic photo-initiators, alkylsulfonium salt cationic photo-initiators, iron arene salt cationic photo-initiators, sulfonyloxy ketone cationic photo-initiators, and triarylsiloxy ether cationic photo-initiators.

In one embodiment of the present application, the ink composition includes, by weight, 0.01 to 50% of a photo-curable silicon-containing monomer component, 30 to 80% of a reactive diluent component, and 0.01 to 20% of a photoinitiator component, and preferably, the content of the photo-curable silicon-containing monomer component is 15 to 50%, the content of the reactive diluent component is 40 to 80%, and the content of the photoinitiator component is 1 to 10%.

The curable silicon-containing monomer component, reactive diluent component, and photoinitiator component described above may be used in amounts conventionally used in the art for each type of material. In order to improve the polymerization effect of the photocurable silicon-containing monomer and obtain the ink composition with better comprehensive performance, the use amount of each component is preferably selected.

In order to further improve the film forming performance of the ink composition, the ink composition preferably further comprises an auxiliary component, the auxiliary component is preferably selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and the content of the auxiliary component is preferably 0.01 to 5 wt%. The above-mentioned additives can be selected from the corresponding additives commonly used in the packaging film in the prior art, and are not listed here.

Each of the above components can be obtained from commercially available products or prepared by typical methods. The components are uniformly mixed at 25-40 ℃ for use.

The proper viscosity environment is favorable for the polymerization of the light-curable silicon-containing monomer in the ink composition, and in order to obtain the ink composition with excellent performance and meet the requirement of ink jet printing, the viscosity of the ink composition at 25 ℃ is preferably 1-50 mPa & s.

In another exemplary embodiment of the present application, there is provided an encapsulation structure including an organic layer formed by photo-curing using the above-described ink composition.

The polymer film formed by the ink composition has higher photocuring rate and lower curing shrinkage, so that the optical requirement and curing speed requirement of a packaging structure are met, the polymer film has more proper viscosity, bonding strength, adhesive force and flexibility, and the packaging requirement of the mainstream inkjet printing mode at present is better met, and a better packaging effect is maintained.

The package structure may further include other functional material layers for achieving better package effect, and the present invention is not limited to this, and a person skilled in the art may choose according to common knowledge or common technical means, for example, add an inorganic insulating material layer, i.e. a layer structure of a package layer formed by an inorganic insulating material, including but not limited to inorganic insulating materials such as metal oxide, metal nitride or metal sulfide. The inorganic insulating material may be formed into the inorganic insulating material layer by a variety of means including, but not limited to, vacuum evaporation, dc sputtering, ion beam deposition, and the like.

The photocurable encapsulating composition described above herein is disposed on a surface of a semiconductor device to be encapsulated and cured using UV radiation to form an encapsulating structure. Methods of disposing the photocurable encapsulating composition include, but are not limited to, ink jet printing.

In yet another exemplary embodiment of the present application, a semiconductor device is provided, which includes a functional structure and an encapsulation structure, the encapsulation structure is the above-mentioned encapsulation structure, and preferably the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor, and a photodetector.

The functional structure may be a member that may cause quality degradation or deterioration due to gas or liquid permeation in the environment, including but not limited to: electroluminescent devices, photoluminescent devices, lighting devices, light emitting diodes, solar cells, thin film transistors, and photodetectors.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the invention in any way. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The following description will explain advantageous effects of the present application with reference to specific examples.

The following are examples of the preparation of each A (silicon-containing monomer):