WO2023029865A1

WO2023029865A1 - Preparation method for semiconductor packaging material or substrate material, and semiconductor packaging material or substrate material obtained thereby and application thereof

Info

Publication number: WO2023029865A1
Application number: PCT/CN2022/110053
Authority: WO
Inventors: 王珂; 方袁峰; 沈海斌; 陈树真
Original assignee: 浙江三时纪新材科技有限公司
Priority date: 2021-09-01
Filing date: 2022-08-03
Publication date: 2023-03-09
Also published as: CN113736142A; CN113736142B

Abstract

The present invention provides a preparation method for a semiconductor packaging material or a substrate material, comprising: providing spherical or amorphous polysiloxane; rising, in an oxidizing gas atmosphere before organic components in polysiloxane particles are completely oxidized, the temperature to 600-800°C for heat treatment, so that a dense silicon oxide layer is formed on the surface of the powder, and the organic components in the heat-treated powder are thermally decomposed into carbon elements; performing calcination to obtain a black spherical or amorphous silicon oxide filler, wherein the calcination temperature is greater than 800°C and less than 1100°C, so as to condense remaining silicon hydroxyl groups; and tightly filling and grading the black spherical or amorphous silicon oxide filler in a resin to form a semiconductor packaging material or a substrate material. The black spherical or amorphous silicon oxide can be directly made into a gray or black semiconductor packaging material or substrate material, thereby fundamentally solving the electrical conduction problem caused by the introduction of acetylene black staining and the problem of difficulty in laser processing of silicon dioxide.

Description

Preparation method of semiconductor encapsulation material or substrate material, semiconductor encapsulation material or substrate material obtained therefrom and application thereof

technical field

The present invention relates to the field of semiconductors, and more particularly to a method for preparing a semiconductor packaging material or substrate material, the semiconductor packaging material or substrate material obtained therefrom and applications thereof.

Background technique

In the packaging process of the semiconductor back-end process, packaging materials such as plastic encapsulants, patch adhesives, underfill materials, and chip carrier boards are required. In addition, when assembling passive components, semiconductor components, electroacoustic devices, display devices, optical devices, and radio frequency devices into equipment, high-density interconnects (high density inerconnect, HDI), high-frequency high-speed boards, and motherboards must be used. circuit board. These packaging materials and circuit boards are generally composed of organic polymers such as epoxy resin and fillers. The fillers are mainly angular or spherical silica, and their main function is to reduce the thermal expansion coefficient of organic polymers. In order to reduce the filler viscosity and increase the filling rate, the existing fillers use spherical silica for dense packing gradation.

For the above-mentioned semiconductor packaging materials or substrate materials, it is usually necessary to add pigments to dye them gray or black. The reason why semiconductor packaging materials or substrate materials need to be dyed gray or black is 1) to facilitate laser printing on components, 2) to reduce photoaging and improve durability, 3) to facilitate laser drilling, 4) to reduce light reflection, 5) to reduce Color variation between batches, etc. Since the general pigment contains conductive ions, the only suitable pigment is acetylene black. However, acetylene black is an electron conductor, so it is necessary to highly disperse the acetylene black so that its size is smaller than the metal spacer of the semiconductor element to prevent short circuits. However, as the packaging density of semiconductor components is getting higher and higher, the risk of short circuits caused by acetylene black is also increasing.

Contents of the invention

In order to solve the problems that acetylene black dyeing in the above-mentioned prior art is easy to cause short circuit and silicon dioxide is difficult to laser process, the present invention aims to provide a method for preparing a semiconductor packaging material or a substrate material, and the semiconductor packaging material or substrate obtained thereby Materials and their applications.

The present invention provides a method for preparing semiconductor packaging materials or substrate materials, which includes the following steps: S1, providing spherical or amorphous polysiloxane including T units, wherein, T units=R ₁ SiO ₃ -, R ₁ is Hydrocarbon groups or hydrogen atoms with 1 to 16 carbon atoms that can be independently selected; S2, under an oxidizing gas atmosphere, the temperature is raised to between 600 degrees before the organic components in the polysiloxane particles are substantially completely oxidized- Heat treatment between 800 degrees makes the surface of the powder form a dense silicon oxide layer, and at the same time causes the organic components inside the heat-treated powder to thermally decompose into carbon elements; S3, perform calcination to obtain black spherical or amorphous silica fillers, and the calcination temperature is greater than 800 degree and lower than 1100 degree, to condense the remaining silanol; S4, the black spherical or amorphous silicon oxide filler is densely filled and graded in the resin to form a semiconductor packaging material or a substrate material.

The polysiloxane of the present invention can form a dense silicon oxide layer in an oxygen-containing gas atmosphere at 600°C to 800°C so as to prevent the diffusion of oxygen into the interior of the polysiloxane particles. Therefore, spherical silica particles containing carbon elements inside can be obtained.

Preferably, in step S2, heat treatment is performed by raising the temperature to between 600°C and 800°C before forming a dense layer of silicon oxide on the surface and before the organic components in the polysiloxane particles are substantially completely oxidized.

Preferably, in step S2, the rate of temperature increase from room temperature to 600°C-800°C is 1°C/min-10°C/min. In particular, the heating rate can control the carbon content of the black spherical or amorphous silica filler obtained in step S3. Specifically, the faster the heating rate in step S2, the lower the whiteness of the black spherical or amorphous silica filler obtained in step S3.

Preferably, the whiteness of the black spherical or amorphous silica filler obtained in step S3 is <80%. In particular, the carbon content of the black spherical or amorphous silica filler obtained in step S3 can be characterized by the whiteness of the powder, and the higher the carbon content, the lower the whiteness. Specifically, the carbon content is about 0.06%-0.03% when the whiteness is 60-80%, and the carbon content is about more than 1% when the whiteness is less than 20%.

Preferably, in step S2, the oxidizing gas atmosphere is air.

Preferably, in step S2, the heat treatment temperature is between 650°C and 800°C.

Preferably, in step S3, the calcining gas atmosphere is a non-oxidizing gas atmosphere or an oxidizing gas atmosphere. In preferred embodiments, calcination is performed in air or nitrogen. In a preferred embodiment, the calcination temperature is between 850°C and 1100°C.

Preferably, the polysiloxane further includes Q units, D units and/or M units, wherein, Q units=SiO ₄ -, D units=R ₂ R ₃ SiO ₂ -, M units=R ₄ R ₅ R ₆ SiO -, R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each a hydrogen atom or an independently selected hydrocarbon group with 1 to 18 carbon atoms.

Preferably, the T unit raw material of the polysiloxane is hydrocarbyl trialkoxysilane or hydrocarbyl trichlorosilane, and the Q unit raw material is at least one selected from the group consisting of tetraalkoxysilane, silicon tetrachloride and silicon dioxide. kind, the D unit raw material is selected from at least one of the group consisting of dihydrocarbyldialkoxysilane and dihydrocarbyl dichlorosilane, and the M unit raw material is selected from trihydrocarbyl alkoxysilane, trihydrocarbyl chlorosilane and hexahydrocarbyl disilane At least one of the group consisting of azanes.

Preferably, in step S4, use dry or wet sieving or inertial classification to remove 1 micron or more, 3 microns or more, 5 microns or more, 10 microns or more, and 20 microns in the black spherical or amorphous silica filler. Coarse particles above, above 45 microns, above 55 microns or above 75 microns.

Preferably, in step S4, black spherical or amorphous silica fillers are respectively used as main powder, medium powder and/or fine powder to closely fill and grade in the resin to form semiconductor packaging materials or substrate materials. The "main powder" mentioned here refers to the powder of the large particle section of the total filler filled in the resin, the "medium powder" refers to the powder of the medium particle section of the total filler filled in the resin, and the "fine powder" refers to the powder of the medium particle section of the total filler filled in the resin. "Powder" refers to the powder of the small particle segment of the total filler filled in the resin. The "large particle segment", "medium particle segment" and "small particle segment" mentioned here are relative concepts, and those skilled in the art are familiar with how to select the particle size range of each segment, and will not repeat them here. The respective volume percentages of the "main powder", "medium powder" and "fine powder" included in the total filler mentioned here are also well known to those skilled in the art. In a preferred embodiment, the main powder accounts for 70% of the total filler volume percentage, the medium powder accounts for 20% of the total filler volume percentage, and the fine powder accounts for 10% of the total filler volume percentage. In the preferred grading process, the resin is first filled with "main powder", then filled with "medium powder", and finally filled with "fine powder". However, it is also possible to complete the grading process by filling only the "intermediate powder" after filling the "main powder". Of course, it is also possible to complete the grading process by filling only the "fine powder" after filling the "main powder".

Preferably, in step S4, the black spherical or amorphous silica filler is treated with a surface treatment agent and then closely packed and graded in the resin to form a semiconductor packaging material or a substrate material. The reason for adding the surface treatment agent is to improve the affinity between the black spherical or amorphous silica filler and the interface of the organic polymer resin. Among them, the treatment of the surface treatment agent can be performed by a dry method or a wet method. Obviously, the surface treatment agent can be silane coupling agent, disilazane, higher fatty acid, or surfactant, etc. Preferably, the silane coupling agent is selected from a silane coupling agent with free radical polymerization, such as vinyl silane coupling agent, etc.; a silane coupling agent that reacts with epoxy resin, such as epoxy silane coupling agent, aminosilane Coupling agent, etc.; Hydrocarbyl silane coupling agent with high affinity to hydrophobic resin, such as dimethyldimethoxysilane, diphenyldimethoxysilane, phenylsilane coupling agent, long chain alkyl Silane coupling agent, etc.

The present invention also provides a semiconductor packaging material or substrate material obtained according to the above-mentioned preparation method.

The present invention further provides an application of the above-mentioned semiconductor packaging material or substrate material. Preferably, the semiconductor encapsulation material or substrate material can be used for molding compound, patch adhesive, underfill material, chip carrier, circuit board, or intermediate semi-finished products thereof. The molding compound is a molding compound in the form of DIP packaging, a molding compound in the form of SMT packaging, and a molding compound of MUF, FO-WLP, and FCBGA. Preferably, the circuit board is HDI, high-frequency high-speed board, or motherboard.

In the preparation method of the present invention, the carbon element is contained inside through the heat treatment in step S2, and the outer surface dense layer can prevent the internal carbon element from being oxidized under the high-temperature calcination in step S3, and the high-temperature calcination in step S3 makes the silicon hydroxyl group condense, reducing The content of silicon hydroxyl group is used to reduce the dielectric constant and dielectric loss. The black spherical or amorphous silicon oxide filler contains carbon elements, and the black spherical or amorphous silicon oxide can be used to directly make gray or black semiconductors. Encapsulation materials or substrate materials, so as to fundamentally solve the conductive problems caused by the introduction of acetylene black dyeing and the difficult laser processing of silicon dioxide.

Detailed ways

The preferred embodiments of the present invention are given below and described in detail.

The detection methods involved in the following examples include:

The average particle size is measured by HORIBA laser particle size distribution analyzer LA-700;

The specific surface area is determined by FlowSorbIII2305 of SHIMADZU;

The true specific gravity is determined by MicrotracBEL's BELPycno;

The content of uranium and thorium was measured by Agilent's 7700X ICP-MS, and the sample preparation method was to burn at 800 degrees and then fully dissolve the sample with hydrofluoric acid;

The carbon content is measured by the CS-8810C carbon and sulfur analyzer of Sichuan Sains;

The whiteness is measured with a whiteness meter;

As used herein, "degrees" means "degrees Celsius", i.e. °C;

Herein, the average particle diameter refers to the volume average diameter of the particles.

example 1

At room temperature, take a certain weight part of deionized water into a reactor with a stirrer, start stirring, add 80 parts by weight of methyltrimethoxysilane and a small amount of acetic acid to adjust the pH to about 5. After methyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added and stirred for 10 seconds, then the stirring was stopped. After standing still for 1 hour, filter and dry to obtain spherical polysiloxane. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 1 below.

Table 1

Example 2

At room temperature, take 1100 parts by weight of deionized water and put it into a reactor with a stirrer, start stirring and add 80 parts by weight of propyltrimethoxysilane and a small amount of acetic acid to adjust the pH to about 5. After the propyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added and stirred for 10 seconds, then the stirring was stopped. After standing still for 1 hour, filter and dry to obtain spherical polysiloxane. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 2 below.

Table 2

Example 3

Take 2500 parts by weight of deionized water at 40 degrees and put it into a reactor with a stirrer, start stirring and add 80 parts by weight of methyltrimethoxysilane and a small amount of acetic acid to adjust the pH to about 5. After methyltrimethoxysilane was dissolved, 60 parts by weight of 5% ammonia water was added and stirred for 10 seconds, then the stirring was stopped. After standing still for 1 hour, filter and dry to obtain spherical polysiloxane. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The heat treatment atmosphere is a mixed gas of air and nitrogen at a volume ratio of 1/1. The results of the analysis of the samples are listed in Table 3 below.

table 3

Example 4

Take 1500 parts by weight of deionized water at room temperature, put it into a reaction kettle with a stirrer, start stirring, add 75 parts by weight of methyltrimethoxysilane and 25 parts by weight of tetraethoxysilane and stir for 1 hour. The T unit content is 82.1%. After dissolving methyltrimethoxysilane and tetraethoxysilane, add 25 parts by weight of 5% ammonia water and stir for 10 seconds, then stop stirring to obtain spherical polysiloxane. Spherical powder was obtained after drying. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 4 below.

Table 4

Example 5

Take 600 parts by weight of deionized water at room temperature, put it into a reaction kettle with a stirrer, start stirring, add 78 parts by weight of methyltrimethoxysilane and 2 parts by weight of dimethyldimethoxysilane and stir 1 hour. The T unit content is 97.2%. After methyltrimethoxysilane and dimethyldimethoxysilane were dissolved, 5% by weight of ammonia water was added and stirred for 10 seconds, then the stirring was stopped to obtain spherical polysiloxane. Spherical powder was obtained after drying. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 5 below.

table 5

Example 6

Take a certain weight part of deionized water at room temperature, put it into a reactor with a stirrer, start stirring, add 78 parts by weight of methyltrimethoxysilane and 2 parts by weight of propyltrimethoxysilane and stir for 1 hour . After methyltrimethoxysilane and propyltrimethoxysilane were dissolved, 25 parts by weight of 5% ammonia water was added and stirred for 10 seconds, then the stirring was stopped to obtain spherical polysiloxane. Spherical powder was obtained after drying. Put the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 6 below.

Table 6

Example 7

Put methyltrichlorosilane into water to generate amorphous polymethylsiloxane. After sand grinding, it was filtered and dried to obtain an amorphous powder. Put the amorphous polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are listed in Table 7 below.

Table 7

The content of uranium and thorium in all samples of examples 1 to 10 is lower than 1 ppb. It should be understood that the example samples obtained in the above examples 1 to 10 may be subjected to surface treatment. Specifically, vinyl silane coupling agent, epoxy silane coupling, disilazane, etc. can be used for treatment as required. More than one treatment can be performed as needed.

It should be understood that the preparation method includes using dry or wet sieving or inertial classification to remove fillers of 1 micron or more, 3 microns or more, 5 microns or more, 10 microns or more, 20 microns or more, 45 microns or more, 55 microns or more Coarse particles above or above 75 microns.

It should be understood that spherical silica fillers of different particle sizes are tightly packed and graded in the resin to form a composite.

What is described above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Various changes can also be made to the above embodiments of the present invention. That is to say, all simple and equivalent changes and modifications made according to the claims and description of the application for the present invention fall within the protection scope of the claims of the patent of the present invention. What is not described in detail in the present invention is conventional technical content.

Claims

A method for preparing a semiconductor packaging material or a substrate material, characterized in that the method comprises the following steps:

S1, providing spherical or amorphous polysiloxane including T units, wherein, T units=R 1 SiO 3 -, R 1 is an independently selected hydrocarbon group with 1 to 16 carbon atoms or a hydrogen atom;

S2, in an oxidizing gas atmosphere, before the organic components in the polysiloxane particles are substantially completely oxidized, the temperature is raised to between 600°C and 800°C for heat treatment to form dense silicon oxide on the surface of the powder At the same time, the organic base inside the heat-treated powder is thermally decomposed into carbon elements;

S3, performing calcination to obtain black spherical or amorphous silica filler, the calcination temperature is greater than 800 degrees and lower than 1100 degrees, so as to condense the remaining silanol;

S4, densely filling and grading the black spherical or amorphous silicon oxide filler in a resin to form a semiconductor packaging material or a substrate material.
The preparation method according to claim 1, characterized in that, in the step S2, in the step S2, the temperature rise rate from room temperature to 600-800 degrees is 1°C/min-10°C /point.
The preparation method according to claim 1 or 2, characterized in that the whiteness of the black spherical or amorphous silica filler obtained in step S3 is <80%.
The preparation method according to claim 1 or 2, characterized in that the polysiloxane further includes Q units, D units and/or M units, wherein Q units=SiO 4 -, D units=R 2 R 3 SiO 2 -, M unit = R 4 R 5 R 6 SiO-, R 2 , R 3 , R 4 , R 5 , R 6 are hydrogen atoms or independently selected hydrocarbon groups with 1 to 18 carbon atoms.
According to the preparation method described in claim 1 or 2, it is characterized in that the T unit raw material of polysiloxane is hydrocarbyl trialkoxysilane or hydrocarbyl trichlorosilane, and the Q unit raw material is selected from tetraalkoxysilane, tetrachlorosilane At least one of the group consisting of silicon oxide and silicon dioxide, the D unit raw material is selected from at least one of the group consisting of dihydrocarbyl dialkoxysilane and dihydrocarbyl dichlorosilane, and the M unit raw material is selected from trihydrocarbyl alkane At least one selected from the group consisting of oxysilane, trihydrocarbylchlorosilane and hexahydrocarbyldisilazane.
The preparation method according to claim 1 or 2, characterized in that, in step S4, dry or wet sieving or inertial classification is used to remove black spherical or amorphous silica fillers of more than 1 micron, 3 Coarse particles above microns, above 5 microns, above 10 microns, above 20 microns, above 45 microns, above 55 microns or above 75 microns.
The preparation method according to claim 1 or 2, characterized in that, in step S4, the black spherical or amorphous silica filler is treated with a surface treatment agent and then closely filled and graded in the resin to form a semiconductor packaging material or substrate Material.
A semiconductor encapsulation material or substrate material obtained by the preparation method according to any one of claims 1-7.
An application of the semiconductor packaging material or substrate material according to claim 8.