CN114426399A - Glass powder for semiconductor surface passivation and preparation method thereof - Google Patents
Glass powder for semiconductor surface passivation and preparation method thereof Download PDFInfo
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- CN114426399A CN114426399A CN202111495878.3A CN202111495878A CN114426399A CN 114426399 A CN114426399 A CN 114426399A CN 202111495878 A CN202111495878 A CN 202111495878A CN 114426399 A CN114426399 A CN 114426399A
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- glass powder
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
Abstract
The invention discloses glass powder for semiconductor surface passivation and a preparation method thereof, relating to the technical field of semiconductor surface passivation materials, and the glass powder comprises the following components: ZnO, B2O3、SiO2、RxOy，RxOyIs MgO, K2O、Al2O3One or more of (a); wherein, the mol percentages of Zn, B, Si and R elements are as follows: 48-50% of Zn, 25-28% of B, 20-21% of Si and 3-5% of R; the preparation method comprises the following steps: dissolving tetraethyl orthosilicate in ethanol, then adding acetic acid to adjust the pH, heating and stirring for hydrolysis; then adding boric acid for continuous hydrolysis; adding zinc salt to continue hydrolysis; adding R salt, then adding water to adjust the pH value to 4-6, stirring to form transparent wet gel, drying, calcining, grinding to obtain the glassAnd (3) pulverizing. The glass powder disclosed by the invention has the advantages of high adhesion property, low expansion coefficient, good electrical insulation property and chemical stability, low glass transition temperature, strong mechanical property and the like, and the preparation method is low in energy consumption, easy to obtain raw materials and environment-friendly.
Description
Technical Field
The invention relates to the technical field of semiconductor surface passivation materials, in particular to glass powder for semiconductor surface passivation and a preparation method thereof.
Background
With the rapid development of electronic technology, demands for electrical characteristics, reliability, miniaturization, and the like of semiconductors have been increasing. The exposed surface of the semiconductor is actually the edge where the semiconductor lattice is arranged to terminate, unsaturated bonds exist on the terminated edge, the state of the semiconductor surface is changed, and impurity ions (such as Na) on the surface of a p-n junction of the semiconductor are generated+) Can shift under the action of an electric field, increase leakage current, reduce reverse breakdown voltage and reduce the performance of a semiconductor device. In order to reduce leakage current, increase reverse breakdown voltage, and improve the performance of semiconductor devices, passivation protection is required on the semiconductor surface.
Fused glass is used as a p-n junction protective layer, called Glass Passivation (GP). The whole process of fused glass protection is to melt various prepared glass component materials under certain high temperature conditions to form glass, to be cooled, to be crushed and to be ground into uniform powder, to be coated on the position to be protected by different methods when in use, to be sintered at high temperature (lower than the melting temperature), to be cooled and to be solidified to form the microcrystalline glass body meeting the requirements.
However, most of the glass frits developed at present have a glass transition temperature of over 1100 ℃, and a semiconductor chip is easily damaged due to an excessively high sintering temperature, and thus the glass frits cannot protect the semiconductor chip. Therefore, the development of low glass transition temperature glass frits for passivation protection of semiconductor chips and other materials is not feasible.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides glass powder for semiconductor surface passivation and a preparation method thereof.
The invention provides glass powder for semiconductor surface passivation, which comprises the following components:ZnO、B2O3、SiO2、RxOy，RxOyis MgO, K2O、Al2O3One or more of (a); wherein, the mol percentages of Zn, B, Si and R elements are as follows: 48-50% of Zn, 25-28% of B, 20-21% of Si and 3-5% of R.
The invention also discloses a preparation method of the glass powder for semiconductor surface passivation, which comprises the following steps:
1) dissolving tetraethyl orthosilicate in ethanol, then adding acetic acid to adjust the pH, heating and stirring for hydrolysis;
2) adding boric acid into the reaction system in the step 1), and continuing to hydrolyze;
3) adding zinc salt into the reaction system in the step 2), and continuing hydrolysis;
4) adding the R salt into the reaction system in the step 3), adding water to adjust the pH value to 4-6, and stirring to form transparent wet gel;
5) and drying, calcining and grinding the wet gel to obtain the glass powder.
Preferably, in the step 1), the mixture is heated to 80-95 ℃ and stirred for 30-60 min; the mol ratio of tetraethyl orthosilicate, ethanol and acetic acid is 1: 6-8: 0.6 to 0.8.
Preferably, in the step 2), the hydrolysis is continued for 0-5 min.
Preferably, in the step 3), the hydrolysis is continued for 0-5 min.
Preferably, in the step 5), the wet gel is dried at 90-150 ℃, and then is calcined at 400-550 ℃ for 30-60 min in a protective atmosphere.
Preferably, the molar ratio of Zn, B, Si and R elements in the zinc salt, boric acid, tetraethyl orthosilicate and R salt is 48-50: 25-28: 20-21: 3 to 5.
Preferably, the zinc salt is one or two of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate.
Preferably, the R salt is one or more of magnesium salt, aluminum salt and potassium salt; wherein the magnesium salt is one or two of magnesium nitrate, magnesium sulfate and magnesium acetate, the aluminum salt is one or two of aluminum nitrate, aluminum sulfate and aluminum acetate, and the potassium salt is one or two of potassium nitrate, potassium sulfate and potassium acetate.
Has the advantages that: the components in the glass powder of the invention have mutual synergistic effect, wherein ZnO and B2O3、SiO2Is the main component of it, B2O3、SiO2The glass network forming agent has the advantages of high adhesion performance, low expansion coefficient, electric insulation performance, chemical stability and the like; ZnO is used as an intermediate oxide of glass and has high stability; rxOyIs MgO, K2O、Al2O3The one or more than one of the above components are added into the glass to play a role of a network regulator, so that the glass transition temperature of the glass powder can be reduced, the adhesive capacity of the glass is further increased, and the mechanical property of the glass is improved.
The method for preparing the glass powder has low energy consumption, easily obtained raw materials, low price and environmental friendliness; the prepared glass powder is nontoxic and tasteless, has the advantages of high adhesion performance, low expansion coefficient, good electrical insulation performance and chemical stability, low glass transition temperature, strong mechanical property and the like, and can be used for passivating and protecting semiconductor chip materials.
Drawings
FIG. 1 is an XRD pattern of a glass frit produced in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The glass powder comprises the following components (the mol content is calculated by mol percent of Zn, B, Si and R elements):
| composition of | ZnO | SiO2 | B2O3 | MgO |
| Molar content | 49％ | 20％ | 28％ | 3％ |
Weighing or measuring salt raw materials corresponding to the oxides according to the composition of the glass powder, firstly dissolving tetraethyl orthosilicate (TEOS), ethanol and acetic acid in a beaker after weighing, and stirring for 30min at 80 ℃, wherein the molar ratio of the tetraethyl orthosilicate to the ethanol to the acetic acid is 1: 8: 0.7; secondly, adding boric acid into the mixture to be continuously hydrolyzed for 2 min; adding zinc acetate into the beaker, hydrolyzing for 1min, adding magnesium acetate into the beaker, hydrolyzing for 2min, adding water into the beaker, adjusting the pH value to be 4, and continuously stirring to form transparent wet gel; drying the obtained transparent gel at 100 ℃ for 12h to obtain xerogel; and (3) preserving the obtained dried gel in a muffle furnace in air atmosphere for 30min, setting the temperature to be 400 ℃, grinding the dried gel after heat treatment to obtain glass powder, and then grinding the glass powder into fine powder in a grinding bowl. The prepared glass frit was characterized by XRD, as shown in FIG. 1, and it was seen to be amorphous.
Weighing a certain amount of glass powder, putting the glass powder into a quartz boat, heating the quartz boat to 900 ℃ in a muffle furnace at the heating rate of 8 ℃/min, and naturally cooling the quartz boat to room temperature in the muffle furnace to obtain amorphous glass.
Example 2
The glass powder comprises the following components (the mol content is calculated by mol percent of Zn, B, Si and R elements):
| make up of | ZnO | SiO2 | B2O3 | Al2O3 |
| Molar |
50％ | 21％ | 25％ | 4％ |
Weighing or measuring salt raw materials corresponding to the oxides according to the composition of the glass powder, firstly dissolving tetraethyl orthosilicate (TEOS), ethanol and acetic acid in a beaker after weighing, and stirring for 35min at 85 ℃, wherein the molar ratio of the tetraethyl orthosilicate to the ethanol to the acetic acid is 1: 8: 0.8; secondly, adding boric acid for continuous hydrolysis for 3 min; adding zinc nitrate into the beaker, hydrolyzing for 2min, adding aluminum nitrate into the beaker, hydrolyzing for 2min, adding water into the beaker, adjusting the pH value to 4.5, and continuously stirring to form transparent wet gel; drying the obtained transparent gel at 120 ℃ to obtain dry gel; and (3) preserving the obtained dried gel in a muffle furnace in a nitrogen atmosphere for 35min, setting the temperature to 410 ℃, grinding the dried gel after heat treatment to obtain glass powder, and then grinding the glass powder into fine powder in a grinding bowl.
Weighing a certain amount of glass powder, placing the glass powder in a quartz boat, heating the quartz boat to 950 ℃ in a muffle furnace at the heating rate of 7 ℃/min, and naturally cooling the quartz boat to room temperature in the muffle furnace to obtain amorphous glass.
Example 3
The glass powder comprises the following components (the mol content is calculated by mol percent of Zn, B, Si and R elements):
| composition of | ZnO | SiO2 | B2O3 | K2O |
| Molar content | 48％ | 20％ | 27％ | 5％ |
Weighing or measuring salt raw materials corresponding to the oxides according to the composition of the glass powder, firstly dissolving tetraethyl orthosilicate (TEOS), ethanol and acetic acid in a beaker after weighing, and stirring for 40min at 86 ℃, wherein the molar ratio of the tetraethyl orthosilicate to the ethanol to the acetic acid is 1: 6: 0.6; secondly, adding boric acid into the mixture to be continuously hydrolyzed for 5 min; adding zinc sulfate into the beaker, hydrolyzing for 3min, adding potassium sulfate into the beaker, hydrolyzing for 3min, adding water into the beaker, adjusting the pH value to be 5, and continuously stirring to form transparent wet gel; drying the obtained transparent gel at 140 ℃ to obtain dry gel; and (3) preserving the obtained dried gel in a muffle furnace in an argon atmosphere for 40min, setting the temperature to be 450 ℃, grinding the dried gel after heat treatment to obtain glass powder, and then grinding the glass powder into fine powder in a grinding bowl.
Weighing a certain amount of glass powder, putting the glass powder into a quartz boat, heating the quartz boat to 920 ℃ in a muffle furnace at the heating rate of 5 ℃/min, and naturally cooling the quartz boat to room temperature in the muffle furnace to obtain amorphous glass.
Comparative example 1
Compared with the example 1, the difference is that no MgO is contained in the composition, and magnesium acetate is not added in the preparation process; the amounts of other raw materials and the preparation process were the same as in example 1.
The glass powder obtained is placed in a quartz boat and heated in a muffle furnace to 1000 ℃ at a heating rate of 5 ℃/min, and the glass powder is not converted into amorphous glass, which indicates that the glass transition temperature is more than 1000 ℃.
Comparative example 2
Compared with example 2, the difference is only that Al is not contained in the composition2O3Aluminum nitrate is not added in the preparation process; the amounts of other raw materials and the preparation process were the same as in example 1.
The glass powder obtained is placed in a quartz boat and heated in a muffle furnace to 1000 ℃ at a heating rate of 7 ℃/min, and the glass powder is not converted into amorphous glass, which indicates that the glass transition temperature is more than 1000 ℃.
Comparative example 3
Compared with example 3, the only difference is that K is not contained in the composition2O, potassium sulfate is not added in the preparation process; the amounts of other raw materials and the preparation process were the same as in example 1.
The glass powder obtained is placed in a quartz boat and heated in a muffle furnace to 1000 ℃ at a heating rate of 5 ℃/min, and the glass powder is not converted into amorphous glass, which indicates that the glass transition temperature is more than 1000 ℃.
The glass powder for passivating and protecting the semiconductor is environment-friendly lead-free glass powder, is non-toxic, tasteless and good in barrier property, can form glass by calcination, and has strong adhesion, low expansion coefficient, high chemical stability, strong mechanical property and sealing property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. The glass powder for passivating the surface of a semiconductor is characterized by comprising the following components: ZnO, B2O3、SiO2、RxOy，RxOyIs MgO, K2O、Al2O3One or more of (a); wherein, the mol percentages of Zn, B, Si and R elements are as follows: 48-50% of Zn, 25-28% of B, 20-21% of Si and 3-5% of R.
2. The method for preparing the glass frit for semiconductor surface passivation according to claim 1, comprising the steps of:
1) dissolving tetraethyl orthosilicate in ethanol, then adding acetic acid to adjust the pH, heating and stirring for hydrolysis;
2) adding boric acid into the reaction system in the step 1), and continuing to hydrolyze;
3) adding zinc salt into the reaction system in the step 2), and continuing hydrolysis;
4) adding the R salt into the reaction system in the step 3), adding water to adjust the pH value to 4-6, and stirring to form transparent wet gel;
5) and drying, calcining and grinding the wet gel to obtain the glass powder.
3. The method for preparing the glass powder for semiconductor surface passivation according to claim 2, wherein in the step 1), the glass powder is heated to 80-95 ℃ and stirred for 30-60 min; the mol ratio of tetraethyl orthosilicate, ethanol and acetic acid is 1: 6-8: 0.6 to 0.8.
4. The method for preparing the glass powder for semiconductor surface passivation according to claim 2, wherein in the step 2), the hydrolysis is continued for 0-5 min.
5. The method for preparing the glass powder for semiconductor surface passivation according to claim 2, characterized in that in the step 3), the hydrolysis is continued for 0-5 min.
6. The method for preparing the glass powder for semiconductor surface passivation according to claim 2, wherein in the step 5), the wet gel is dried at 90-150 ℃, and then is subjected to heat preservation calcination at 400-550 ℃ for 30-60 min in a protective atmosphere.
7. The method for preparing the glass powder for passivating the surface of the semiconductor according to claim 2, wherein the molar ratio of Zn, B, Si and R elements in the zinc salt, the boric acid, the tetraethyl orthosilicate and the R salt is 48-50: 25-28: 20-21: 3 to 5.
8. The method for preparing glass powder for semiconductor surface passivation according to claim 2, wherein the zinc salt is one or two of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate.
9. The method according to claim 2, wherein the R salt is one or more of a magnesium salt, an aluminum salt, and a potassium salt; wherein the magnesium salt is one or two of magnesium nitrate, magnesium sulfate and magnesium acetate, the aluminum salt is one or two of aluminum nitrate, aluminum sulfate and aluminum acetate, and the potassium salt is one or two of potassium nitrate, potassium sulfate and potassium acetate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111495878.3A CN114426399A (en) | 2021-12-08 | 2021-12-08 | Glass powder for semiconductor surface passivation and preparation method thereof |
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| CN202111495878.3A CN114426399A (en) | 2021-12-08 | 2021-12-08 | Glass powder for semiconductor surface passivation and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20080024086A (en) * | 2006-09-12 | 2008-03-17 | 주식회사 휘닉스피디이 | Glass powder for covering electrode of display device |
| CN101298365A (en) * | 2008-04-17 | 2008-11-05 | 东华大学 | Preparation and use of electronic device passivation encapsulation modified zinc-boron-silicon-lead glass frit |
| CN101648816A (en) * | 2009-09-18 | 2010-02-17 | 西北大学 | Method for preparing monodisperse nano zinc-boron-silicon oxide powder body |
| CN102643025A (en) * | 2012-05-09 | 2012-08-22 | 东莞彩显有机发光科技有限公司 | Nanometer zinc borosilicate oxide glass powder and preparation method thereof |
| CN105439419A (en) * | 2015-11-16 | 2016-03-30 | 徐州中韵新材料科技有限公司 | Method for preparing low-melting-point quarternary BZBS (BaO-ZnO-B2O3-SiO2) glass by virtue of sol-gel method |
| CN113372003A (en) * | 2021-07-22 | 2021-09-10 | 安徽大学 | Method for preparing low-melting-point lead-free glass powder by sol-gel method and application |
| CN113387583A (en) * | 2020-03-13 | 2021-09-14 | 肖特股份有限公司 | Glass and molten solder for passivating semiconductor components |
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2021
- 2021-12-08 CN CN202111495878.3A patent/CN114426399A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080024086A (en) * | 2006-09-12 | 2008-03-17 | 주식회사 휘닉스피디이 | Glass powder for covering electrode of display device |
| CN101298365A (en) * | 2008-04-17 | 2008-11-05 | 东华大学 | Preparation and use of electronic device passivation encapsulation modified zinc-boron-silicon-lead glass frit |
| CN101648816A (en) * | 2009-09-18 | 2010-02-17 | 西北大学 | Method for preparing monodisperse nano zinc-boron-silicon oxide powder body |
| CN102643025A (en) * | 2012-05-09 | 2012-08-22 | 东莞彩显有机发光科技有限公司 | Nanometer zinc borosilicate oxide glass powder and preparation method thereof |
| CN105439419A (en) * | 2015-11-16 | 2016-03-30 | 徐州中韵新材料科技有限公司 | Method for preparing low-melting-point quarternary BZBS (BaO-ZnO-B2O3-SiO2) glass by virtue of sol-gel method |
| CN113387583A (en) * | 2020-03-13 | 2021-09-14 | 肖特股份有限公司 | Glass and molten solder for passivating semiconductor components |
| CN113372003A (en) * | 2021-07-22 | 2021-09-10 | 安徽大学 | Method for preparing low-melting-point lead-free glass powder by sol-gel method and application |
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