阅读说明：本技术 半导体封装材料或基板材料的制备方法，由此得到的半导体封装材料或基板材料及其应用 (Preparation method of semiconductor packaging material or substrate material, semiconductor packaging material or substrate material obtained by preparation method and application of semiconductor pac) 是由 王珂 方袁峰 沈海斌 陈树真 于 2021-09-01 设计创作，主要内容包括：本发明提供一种半导体封装材料或基板材料的制备方法,其包括提供球形或不定形聚硅氧烷,在氧化性气体氛围下,在聚硅氧烷粒子中的有机成分实质上被全部氧化完之前将温度升至介于600度-800度之间进行热处理使得粉体表面形成致密的氧化硅层,同时使得热处理粉体内部的有机成分热分解成碳元素；进行煅烧得到黑色球形或不定形氧化硅填料,煅烧温度大于800度且低于1100度,以缩合剩余的硅羟基；将黑色球形或不定形氧化硅填料紧密填充级配在树脂中形成半导体封装材料或基板材料。用这种黑色球形或不定形氧化硅可以直接制成灰色或黑色半导体封装材料或基板材料,从而从根本上解决引入乙炔黑染色带来的导电问题和二氧化硅难激光加工问题。(The invention provides a preparation method of a semiconductor packaging material or a substrate material, which comprises the steps of providing spherical or amorphous polysiloxane, raising the temperature to 600-800 ℃ for heat treatment under an oxidizing gas atmosphere before substantially all organic components in polysiloxane particles are oxidized, so that a compact silicon oxide layer is formed on the surface of powder, and simultaneously, the organic components in the heat-treated powder are thermally decomposed into carbon elements; calcining to obtain black spherical or amorphous silica filler, wherein the calcining temperature is more than 800 ℃ and less than 1100 ℃ to condense the residual silicon hydroxyl; the black spherical or amorphous silica filler is tightly packed and graded in resin to form a semiconductor packaging material or a substrate material. The black spherical or amorphous silicon oxide can be directly made into grey or black semiconductor packaging materials or substrate materials, thereby fundamentally solving the problems of electric conduction and difficult laser processing of silicon dioxide caused by introducing acetylene black dyeing.)

1. A preparation method of a semiconductor packaging material or a substrate material is characterized by comprising the following steps:

s1, providing a spherical or amorphous polysiloxane comprising T units, wherein T units ═ R₁SiO₃-，R₁Is an independently selected hydrocarbyl group of carbon atoms 1 to 16 or a hydrogen atom;

s2, heating to 600-800 ℃ in an oxidizing gas atmosphere before the organic components in the polysiloxane particles are substantially completely oxidized to form a compact silicon oxide layer on the surface of the powder, and simultaneously thermally decomposing organic groups in the heat-treated powder into carbon elements;

s3, calcining to obtain black spherical or amorphous silica filler, wherein the calcining temperature is more than 800 ℃ and less than 1100 ℃ to condense the residual silicon hydroxyl;

and S4, tightly filling and grading the black spherical or amorphous silica filler in resin to form a semiconductor packaging material or a substrate material.

2. The method as set forth in claim 1, wherein in the step S2, in the step S2, a temperature raising rate of raising the temperature from room temperature to 600-800 degrees is 1-10 ℃/min.

3. The method according to claim 1 or 2, wherein the whiteness of the black spherical or amorphous silica filler obtained in step S3 is < 80%.

4. The process according to claim 1 or 2, wherein the polysiloxane further comprises Q units, D units and/or M units, wherein Q units are SiO units₄-, D unit ═ R₂R₃SiO₂-, M units ═ R₄R₅R₆SiO-，R₂，R₃，R₄，R₅，R₆Each hydrogen atom or an independently selected hydrocarbyl group of carbon atoms 1 to 18.

5. The method according to claim 1 or 2, wherein the polysiloxane is prepared by using T unit material selected from the group consisting of alkyl trialkoxysilane and alkyl trichlorosilane, Q unit material selected from the group consisting of tetraalkoxysilane, silicon tetrachloride and silicon dioxide, D unit material selected from the group consisting of dialkyl dialkoxysilane and dialkyl dichlorosilane, and M unit material selected from the group consisting of trialkyl alkoxysilane, trialkyl chlorosilane and hexaalkyl disilazane.

6. The production method according to claim 1 or 2, characterized in that, in step S4, coarse large particles 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, or 75 microns or more in the black spherical or amorphous silica filler are removed using dry or wet sieving or inertial classification.

7. The method of claim 1 or 2, wherein in step S4, the black spherical or amorphous silica filler is treated with a surface treatment agent and then tightly packed in a graded manner in a resin to form a semiconductor encapsulation material or a substrate material.

8. A semiconductor encapsulating material or substrate material obtained by the production method according to any one of claims 1 to 7.

9. Use of the semiconductor encapsulation material or the substrate material according to claim 8.

Technical Field

The invention relates to the field of semiconductors, in particular to a preparation method of a semiconductor packaging material or a substrate material, the semiconductor packaging material or the substrate material obtained by the preparation method and application of the semiconductor packaging material or the substrate material.

Background

In the packaging process of the semiconductor back-end process, packaging materials such as a plastic packaging material, a surface mount adhesive, a bottom pouring material, a chip carrier and the like are required. In addition, when passive elements, semiconductor elements, electroacoustic devices, display devices, optical devices, radio frequency devices, and the like are assembled into an apparatus, circuit boards such as a High Density Interconnect (HDI), a high frequency high speed board, and a motherboard are used. These sealing materials and circuit boards are generally mainly composed of an organic polymer such as epoxy resin and a filler, wherein the filler is mainly angular or spherical silica, and has a main function of reducing the thermal expansion coefficient of the organic polymer. In order to reduce the viscosity of the filler and improve the filling rate, the existing filler is selected from spherical silica for tight filling grading.

For the above semiconductor encapsulating material or substrate material, it is generally necessary to add a pigment to dye it in gray or black. The reasons why the semiconductor package material or the substrate material needs to be colored gray or black are 1) to facilitate laser printing on the element, 2) to reduce light aging and improve durability, 3) to facilitate laser drilling, 4) to reduce light reflection, 5) to reduce lot-to-lot color variation, and the like. Since a general pigment contains a conductive ion, only acetylene black is suitable as a pigment. However, acetylene black is an electronic conductor, and thus it is necessary to highly disperse acetylene black to have a size smaller than the metal interval of a semiconductor element to prevent short-circuiting. However, as the packing density of semiconductor devices is higher, the risk of short circuit caused by acetylene black is higher.

Disclosure of Invention

In order to solve the problems that acetylene black dyeing in the prior art is easy to cause short circuit and silicon dioxide is difficult to process by laser, the invention aims to provide a preparation method of a semiconductor packaging material or a substrate material, the semiconductor packaging material or the substrate material obtained by the preparation method and application of the semiconductor packaging material or the substrate material.

The invention provides a halfThe preparation method of the conductor packaging material or the substrate material comprises the following steps: s1, providing a spherical or amorphous polysiloxane comprising T units, wherein T units ═ R₁SiO₃-，R₁Is an independently selected hydrocarbyl group of carbon atoms 1 to 16 or a hydrogen atom; s2, heating to 600-800 ℃ in an oxidizing gas atmosphere before the organic components in the polysiloxane particles are substantially completely oxidized to form a compact silicon oxide layer on the surface of the powder, and simultaneously thermally decomposing the organic components in the heat-treated powder into carbon elements; s3, calcining to obtain black spherical or amorphous silica filler, wherein the calcining temperature is more than 800 ℃ and less than 1100 ℃ to condense the residual silicon hydroxyl; and S4, tightly filling and grading the black spherical or amorphous silica filler in resin to form a semiconductor packaging material or a substrate material.

The polysiloxane of the invention can form a compact silicon oxide layer under the atmosphere containing oxygen at 600-800 ℃ so as to prevent the diffusion of oxygen into the polysiloxane particles. Spherical silica particles containing carbon elements inside can be obtained.

Preferably, in step S2, the heat treatment is performed by raising the temperature to between 600 degrees and 800 degrees before the surface silica forming a dense layer is substantially completely oxidized by the organic components in the polysiloxane particles.

Preferably, in step S2, the temperature rising rate for rising the temperature from room temperature to between 600 degrees and 800 degrees is 1 ℃/min to 10 ℃/min. In particular, the temperature increase rate may control the content of carbon element of the black spherical or amorphous silica filler obtained in step S3. Specifically, the faster the temperature increase 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 content of carbon element of the black spherical or amorphous silica filler obtained in step S3 can be characterized by the whiteness of the powder, with the higher the content of carbon element, the lower the whiteness. Specifically, the carbon content of the whiteness of 60-80% is about 0.06% -0.03%, 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 degrees and 800 degrees.

Preferably, in step S3, the calcination gas atmosphere is a non-oxidizing gas atmosphere or an oxidizing gas atmosphere. In a preferred embodiment, the calcination is carried out in air or nitrogen. In a preferred embodiment, the calcination temperature is between 850 degrees and 1100 degrees.

Preferably, the polysiloxanes further comprise Q units, D units and/or M units, wherein Q units ═ SiO units₄-, D unit ═ R₂R₃SiO₂-, M units ═ R₄R₅R₆SiO-，R₂，R₃，R₄，R₅，R₆Each hydrogen atom or an independently selected hydrocarbyl group of carbon atoms 1 to 18.

Preferably, the unit material T of the polysiloxane is alkyl trialkoxysilane or alkyl trichlorosilane, the unit material Q is at least one selected from the group consisting of tetraalkoxysilane, silicon tetrachloride and silicon dioxide, the unit material D is at least one selected from the group consisting of dihydrocarbyldialkoxysilane and dihydrocarbyldichlorosilane, and the unit material M is at least one selected from the group consisting of trihydrocarbylalkoxysilane, trihydrocarbylchlorosilane and hexahydrocarbyldisilazane.

Preferably, in step S4, coarse large particles 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, or 75 microns or more in the black spherical or amorphous silica filler are removed using dry or wet sieving or inertial classification.

Preferably, in step S4, the black spherical or amorphous silica filler is tightly graded as a main powder, medium powder and/or fine powder in a resin to form a semiconductor package material or a substrate material, respectively. As used herein, the term "main powder" refers to a powder of a large particle segment of the total filler filled in the resin, the term "medium powder" refers to a powder of a medium particle segment of the total filler filled in the resin, and the term "fine powder" refers to a powder of a small particle segment of the total filler filled in the resin. The terms "large particle fraction", "medium particle fraction" and "small particle fraction" are used herein as relative terms, and those skilled in the art know how to select the particle size range of each fraction, and will not be described herein. The respective volume percentages of "primary powder", "secondary powder" and "fine powder" included in the total filler referred to herein are likewise well known to those skilled in the art. In a preferred embodiment, the main powder is 70% by volume of the total filler, the medium powder is 20% by volume of the total filler, and the fine powder is 10% by volume of the total filler. In a preferred grading process, the resin is first filled with "primary powder", then with "secondary powder" and finally with "fine powder". However, the grading process may be completed by filling only the "medium powder" after filling the "main powder". Of course, the grading process may also be completed by filling only the "fines" after filling the "main fines".

Preferably, in step S4, the black spherical or amorphous silica filler is treated with a surface treatment agent to tightly fill the gradation in a resin to form a semiconductor package material or a substrate material. The reason why the surface treatment agent is added is to improve the affinity of the interface between the black spherical or amorphous silica filler and the organic polymer resin. Wherein the treatment with the surface treatment agent may be performed by a dry method or a wet method. Obviously, the surface treatment agent may be a silane coupling agent, disilazane, higher fatty acid, or surfactant, etc. Preferably, the silane coupling agent is selected from silane coupling agents having radical polymerization reaction, such as vinyl silane coupling agents and the like; silane coupling agents such as epoxy silane coupling agents, aminosilane coupling agents, etc. which react with the epoxy resin; hydrocarbyl silane coupling agents having high affinity with hydrophobic resins, such as dimethyldimethoxysilane, diphenyldimethoxysilane, phenylsilane coupling agents, long-chain alkylsilane coupling agents, and the like.

The invention also provides a semiconductor packaging material or a substrate material obtained by the preparation method.

The invention also provides an application of the semiconductor packaging material or the substrate material. Preferably, the semiconductor packaging material or the substrate material can be used for a molding compound, a chip mounting compound, an underfill material, a chip carrier, a circuit board, or an intermediate semi-finished product thereof. The plastic package material is a plastic package material in a DIP packaging form, a plastic package material in an SMT packaging form, a plastic package material in a MUF, FO-WLP or FCBGA form. Preferably, the circuit board is an HDI, high frequency high speed board, or motherboard.

According to the preparation method, carbon elements are contained in the silicon black filler through the heat treatment in the step S2, the carbon elements in the silicon black filler are prevented from being oxidized by the external surface dense layer under the high-temperature calcination in the step S3, silicon hydroxyl is condensed through the high-temperature calcination in the step S3, the content of the silicon hydroxyl is reduced, the dielectric constant and the dielectric loss are reduced, the carbon elements are contained in the black spherical or amorphous silicon oxide filler, and the black spherical or amorphous silicon oxide filler can be directly made into a gray or black semiconductor packaging material or a substrate material, so that the problems of conductivity and difficulty in laser processing of the silicon oxide due to the introduction of acetylene black dyeing are fundamentally solved.

Detailed Description

The following provides a detailed description of the preferred embodiments of the present invention.

The detection methods referred to in the following examples include:

the average particle size is measured by a laser particle size distribution instrument LA-700 of HORIBA;

the specific surface area was determined using FlowSorbIII2305 from SHIMADZU;

the true specific gravity was measured using BELPycocno from MicrotracBEL;

the uranium and thorium contents are measured by Agilent's 7700X type ICP-MS, and the sample preparation method is to use hydrofluoric acid to fully dissolve the sample after burning at 800 ℃;

the carbon content is measured by a CS-8810C carbon-sulfur analyzer of Sichuan Saiensi;

measuring whiteness by using a whiteness meter;

herein, "degree" refers to "degrees celsius," i.e., the temperature of the sample;

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

Example 1

At room temperature, a certain weight part of deionized water is put into a reaction kettle with a stirrer, the stirring is started, and 80 weight parts of methyltrimethoxysilane and a small amount of acetic acid are added to adjust the pH to about 5. After the methyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added thereto, and the mixture was stirred for 10 seconds, and then the stirring was stopped. Standing for 1 hour, filtering, and drying to obtain the spherical polysiloxane. And putting the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 1 below.

TABLE 1

Example 2

At room temperature, 1100 parts by weight of deionized water is put into a reaction kettle with a stirrer, and 80 parts by weight of propyl trimethoxy silane and a small amount of acetic acid are added with stirring to adjust the pH to about 5. After the propyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added thereto and stirred for 10 seconds, and then the stirring was stopped. Standing for 1 hour, filtering, and drying to obtain the spherical polysiloxane. And putting the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 2 below.

TABLE 2

Example 3

Placing 2500 parts by weight of 40 ℃ deionized water into a reaction kettle with a stirrer, starting stirring, adding 80 parts by weight of methyltrimethoxysilane and a small amount of acetic acid, and adjusting the pH to about 5. After the methyltrimethoxysilane was dissolved, 60 parts by weight of 5% ammonia water was added thereto, and the mixture was stirred for 10 seconds, and then the stirring was stopped. Standing for 1 hour, filtering, and drying to obtain the spherical polysiloxane. And putting 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 shown in Table 3 below.

TABLE 3

Example 4

At room temperature, 1500 parts by weight of deionized water is put into a reaction kettle with a stirrer, the stirring is started, and 75 parts by weight of methyltrimethoxysilane and 25 parts by weight of tetraethoxysilane are added and stirred for 1 hour. The T unit content is 82.1%. After the methyltrimethoxysilane and the tetraethoxysilane are dissolved, 25 parts by weight of 5 percent ammonia water is added, the stirring is stopped after 10 seconds, and the spherical polysiloxane is obtained. Drying to obtain spherical powder. And putting the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 4 below.

TABLE 4

Example 5

600 parts by weight of deionized water were taken at room temperature and placed in a reaction vessel equipped with a stirrer, and the stirring was started, and 78 parts by weight of methyltrimethoxysilane and 2 parts by weight of dimethyldimethoxysilane were added and stirred for 1 hour. The T unit content is 97.2%. After methyltrimethoxysilane and dimethyldimethoxysilane were dissolved, 5 parts by weight of 5% ammonia water was added thereto, and stirring was stopped after 10 seconds to obtain a spherical polysiloxane. Drying to obtain spherical powder. And putting the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 5 below.

TABLE 5

Example 6

Taking a certain weight part of deionized water at room temperature, putting the deionized water into a reaction kettle with a stirrer, starting stirring, adding 78 weight parts of methyltrimethoxysilane and 2 weight parts of propyltrimethoxysilane, and stirring for 1 hour. After methyltrimethoxysilane and propyltrimethoxysilane were dissolved, 25 parts by weight of 5% ammonia water was added thereto, and stirring was stopped after 10 seconds to obtain a spherical polysiloxane. Drying to obtain spherical powder. And putting the polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 6 below.

TABLE 6

Example 7

The methyltrichlorosilane is added to water to produce amorphous polymethylsiloxane. Filtering and drying after sanding to obtain the amorphous powder. And putting the amorphous polysiloxane powder into a muffle furnace for heat treatment and calcination. The results of the analysis of the samples are shown in Table 7 below.

TABLE 7

All of the examples 1 to 10 had uranium, thorium contents of less than 1 ppb. It should be understood that the example samples obtained in examples 1 to 10 described above may be surface-treated. Specifically, a vinyl silane coupling agent, epoxy silane coupling, disilazane, or the like may be treated as necessary. More than one treatment may be performed as necessary.

It is to be understood that the preparation method includes the use of dry or wet screening or inertial classification to remove coarse large particles 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, or 75 microns or more in the filler.

It should be understood that the closely packed grading of spherical silica fillers of different particle sizes forms a composite in the resin.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.