CN113372003A - Method for preparing low-melting-point lead-free glass powder by sol-gel method and application - Google Patents
Method for preparing low-melting-point lead-free glass powder by sol-gel method and application Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000003980 solgel method Methods 0.000 title claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 17
- 238000002161 passivation Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 239000011240 wet gel Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000005476 soldering Methods 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 2
- 210000001808 exosome Anatomy 0.000 abstract description 2
- 238000007496 glass forming Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 Barium acetate Zinc acetate Boric acid Tetraethoxysilane Chemical compound 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a method for preparing low-melting-point lead-free glass powder by a sol-gel method2Is a glass network forming body, is a main framework component of glass, and has high melting point, high viscosity, low thermal expansion coefficient and high chemical stability; BaO is an ionic oxide of the outer body of the glass, can effectively reduce the melting point of the glass and mainly plays a role in fluxing; b is2O3Is a commonly-obtained glass network former, and the solution of the glass network former has high viscosity and glass forming tendency; ZnO generally exists as a network exosome oxide, and can reduce the thermal expansion coefficient, softening temperature and viscosity of glass and improve the chemical stability of the glass in the glass; alkali metal oxide (Na)2O、K2O) can effectively lower the melting point of the glass. The low-melting-point glass powder disclosed by the invention is lead-free and environment-friendly, has a lower melting temperature and good cohesiveness, and can form glass with high adhesionThe state compact layer is suitable for passivation protection and surface welding of P-N junctions in integrated circuit chips.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a method for preparing low-melting-point lead-free glass powder by a sol-gel method, which is used for passivation protection and surface welding of a P-N junction in an integrated circuit chip, namely BaO-ZnO-B prepared by the sol-gel method2O3-SiO2Glass powder (BZBS glass powder), and CuO and Na are added2O、K2One or more regulating elements in O regulate the melting point and the quality of the BZBS glass powder so as to realize passivation protection and surface welding of a P-N junction in the integrated circuit chip.
Background
Since the 21 st century, the international manufacturing industry has been increasingly competitive against the background of global economy and social informatization, and the demand for advanced manufacturing techniques is more urgent. The IC is ranked first in the physical economy, and the government has great support in the IC industry. The integrated circuit industry is not only a foundation of the information-oriented society, but also a strategic, fundamental and precedent industry for supporting the development of the economic society and guaranteeing the national security. The high-quality low-melting-point glass powder is a basic material for manufacturing integrated circuit chips and plays an important role in the aspect of semiconductor chip packaging.
With the rapid development of integrated circuits, demands for precision, reliability, miniaturization, and the like of semiconductor chips have been increasing. The exposed surface of the semiconductor is actually the edge from which the semiconductor crystal lattice is arranged to terminate, wherein a plurality of unsaturated bonds exist, the external environment easily influences the surface state of the semiconductor, thereby causing the electrical performance of the semiconductor to be poor, and in order to improve the performance of the semiconductor device, the passivation protection is needed to be carried out on the surface of the semiconductor. The glass passivation technology, i.e. the GP technology, for passivating and protecting P-N of a semiconductor by using fused glass is widely applied to the production and manufacture of mesa-type semiconductor chips with corrosion groove structures. The glass powder which is the basic material of the glass passivation technology has excellent electrical insulation performance and chemical stability, and has certain mechanical strength after sintering, so that the glass powder with low melting point and high adhesive force can play a good role in passivating and protecting the P-N junction of the semiconductor chip. Meanwhile, the sintering temperature of the low-melting-point glass powder is lower, and the high temperature is not needed during sintering, so that the damage of high temperature to a semiconductor device is avoided.
Most of the traditionally used glass powder contains lead, and in recent years, with the improvement of environmental awareness of people, the lead has great toxicity, so that the lead causes great harm to human beings and the environment and is gradually limited or eliminated. BaO-ZnO-B2O3-SiO2The system glass (BZBS glass) as a novel lead-free and bismuth-free glass system enters the visual field of people due to low melting point and stable structure, and is widely developed and applied to electronic paste.
The glass powder prepared by the sol-gel method not only can greatly reduce the calcining temperature, but also has the advantages of low preparation temperature, low energy consumption, uniform components and the like. Meanwhile, the prepared glass powder has the excellent performances of low melting point and high adhesion, and is suitable for passivation protection and surface welding of P-N junctions in integrated circuit chips. Therefore, the invention has very important significance.
Disclosure of Invention
The invention aims to provide a method for preparing low-melting-point lead-free glass powder, which is used for preparing BaO-ZnO-B by a sol-gel method2O3-SiO2Glass powder (BZBS glass powder), and CuO and Na are added2O、K2One or more regulating elements in O regulate the melting point and the quality of the BZBS glass powder so as to realize passivation protection and surface welding of a P-N junction in the integrated circuit chip.
In order to achieve the above object, the invention adopts the technical scheme that:
a method for preparing low-melting-point lead-free glass powder by a sol-gel method comprises the following steps:
(1) preparing a solution: dissolving ethyl orthosilicate in alcohol under an acidic condition, and vigorously stirring for 0.5-1 hour at room temperature to fully hydrolyze the ethyl orthosilicate, wherein the molar ratio of the alcohol to the ethyl orthosilicate is controlled to be 5-9, and the molar ratio of the acid to the ethyl orthosilicate is controlled to be 0.05-0.1;
(2) dissolving boric acid, a barium salt raw material, a zinc salt raw material and an adjusting raw material in deionized water, then adding an aqueous solution into the alcoholic solution of ethyl orthosilicate in the step (1), and uniformly stirring;
(3) adjusting the pH: adjusting the pH value of the mixed solution in the step (2) to 4-6 by using acid, and uniformly stirring;
(4) aging and drying: stirring the mixed solution at 60-100 ℃ for 12-15 hours until the mixed solution becomes soft wet gel, transferring the wet gel into a quartz boat, and drying at 100-120 ℃ for 16-24 hours to obtain solid particles or powder;
(5) calcining and grinding: calcining the solid particles or powder obtained in the step (3) at the temperature of 500-900 ℃ for 1-3 hours, and then grinding into powder to obtain the lead-free glass powder with low melting point.
The barium salt raw material is one or more than two of barium acetate, barium nitrate, barium chloride and barium sulfate.
The zinc salt raw material is one or more than two of zinc acetate, zinc nitrate, zinc chloride and zinc sulfate.
The adjusting raw material is one or more of a copper salt raw material, a sodium salt raw material and a potassium salt raw material.
The copper salt raw material is one or more than two of copper acetate, copper nitrate, copper chloride and copper sulfate.
The sodium salt raw material is one or more than two of sodium acetate, sodium nitrate, sodium chloride and sodium sulfate.
The potassium salt raw material is one or more than two of potassium acetate, potassium nitrate, potassium chloride and potassium sulfate.
The acid in the step (1) is one or more than two of acetic acid, nitric acid, hydrochloric acid and oxalic acid.
The application of low-melting point lead-free glass powder in passivation protection and surface welding of P-N junctions in integrated circuit chips.
The components in the glass powder provided by the invention act together, so that the glass powder can achieve the effects of well reducing the melting point and improving the adhesion, wherein SiO is used for preparing the glass powder2Is in the form of a glass networkAn adult body, which is a main framework component of glass, having a high melting point, a high viscosity, a low thermal expansion coefficient, and a high chemical stability; BaO is an ionic oxide of the outer body of the glass, can effectively reduce the melting point of the glass and mainly plays a role in fluxing; b is2O3Is a commonly-obtained glass network former, and the solution of the glass network former has high viscosity and glass forming tendency; ZnO generally exists as a network exosome oxide, and can reduce the thermal expansion coefficient, softening temperature and viscosity of glass and improve the chemical stability of the glass in the glass; alkali metal oxide (Na)2O、K2O) can effectively lower the melting point of the glass.
The invention has the advantages that:
the lead-free glass powder provided by the invention does not contain components which are easy to pollute the environment, can be prepared at a lower temperature, has a lower melting point and good cohesiveness, can form a glassy state compact layer with high adhesive force, and is suitable for passivation protection and surface welding of P-N junctions in integrated circuit chips.
Drawings
FIG. 1 shows BaO-ZnO-B prepared by the present invention2O3-SiO2-X-ray diffraction pattern of CuO glass frit;
FIG. 2 shows BaO-ZnO-B prepared by the present invention2O3-SiO2-CuO-Na2Sintering pictures of O glass powder;
FIG. 3 shows BaO-ZnO-B prepared by the present invention2O3-SiO2-CuO-K2Sintering picture of O glass powder.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
In one embodiment of the glass powder of the present invention, the components, contents and raw materials of the glass powder are shown in Table 1, the composition, contents and raw materials of the glass powder in example 1 of Table 1
| Composition of | BaO | ZnO | B2O3 | SiO2 | CuO |
| Content (mol%) | 15 | 30 | 40 | 10 | 5 |
| Raw materials | Barium acetate | Zinc acetate | Boric acid | Tetraethoxysilane | Cupric acetate |
Preparing glass powder: weighing corresponding raw materials according to the components and the molar ratio of the glass powder in the table 1, mixing ethyl orthosilicate, ethanol and acetic acid according to the molar ratio of 1:7:0.07, and violently stirring for 0.5 hour at room temperature to fully hydrolyze tetraethyl silicate, wherein the mark is A; meanwhile, barium acetate, zinc acetate, boric acid and copper acetate are dissolved in a certain amount of deionized water and are marked as B; dropwise adding the solution A into the solution B, uniformly stirring by magnetic force, and adjusting the pH value of the mixed solution to 5 by using acetic acid to obtain a transparent solution; aging the transparent solution in a water bath kettle at 80 ℃ for 12 hours to obtain soft wet gel; drying the wet gel in an oven at 100 ℃ for 24 hours to obtain a blue solid; and taking out the dried powder, grinding the powder in a mortar, putting the powder into a quartz boat, heating the quartz boat to 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, naturally cooling the quartz boat to room temperature, and grinding the obtained glass material to obtain the glass powder. Putting the glass powder into a quartz boat, heating to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, and naturally cooling to room temperature to form a glassy state compact layer with high adhesion.
The X-ray diffraction pattern of the glass frit is shown in fig. 1, and it can be seen from fig. 1 that no sharp peak is formed, and the glass frit is obtained in a glassy state.
Example 2
In one embodiment of the glass powder of the present invention, the components, contents and raw materials of the glass powder are shown in Table 2, and the composition, contents and raw materials of the glass powder in example 2
Preparing glass powder: weighing corresponding raw materials according to the components and the molar ratio of the glass powder in the table 2, mixing ethyl orthosilicate, ethanol and acetic acid according to the molar ratio of 1:7:0.07, and violently stirring for 0.5 hour at room temperature to fully hydrolyze tetraethyl silicate, wherein the mark is A; meanwhile, barium acetate, zinc acetate, boric acid, copper acetate and sodium acetate are dissolved in 200mL of deionized water and are marked as B; dropwise adding the solution A into the solution B, uniformly stirring by magnetic force, and adjusting the pH value of the mixed solution to 5 by using acetic acid to obtain a transparent solution; aging the transparent solution in a water bath kettle at 80 ℃ for 12 hours to obtain soft wet gel; drying the wet gel in an oven at 100 ℃ for 24 hours to obtain a blue solid; and taking out the dried powder, grinding in a mortar, putting into a quartz boat, heating to 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, naturally cooling to room temperature, and grinding the obtained glass material to obtain the glass powder. Putting the glass powder into a quartz boat, heating to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, and naturally cooling to room temperature.
The product obtained after the glass powder is calcined at 800 ℃ is shown in FIG. 2, and it can be seen from FIG. 2 that the glass powder can form a glassy compact layer with high adhesion.
Example 3
In one embodiment of the glass frit of the present invention, the components, contents and raw materials of the glass frit are shown in Table 3, and the composition, contents and raw materials of the glass frit in example 3 of Table 3
Preparing glass powder: weighing corresponding raw materials according to the components and the molar ratio of the glass powder in the table 3, mixing ethyl orthosilicate, ethanol and acetic acid according to the molar ratio of 1:7:0.07, and violently stirring for 0.5 hour at room temperature to fully hydrolyze tetraethyl silicate, wherein the mark is A; meanwhile, barium acetate, zinc acetate, boric acid, copper acetate and potassium acetate are dissolved in 200mL of deionized water and are marked as B; dropwise adding the solution A into the solution B, uniformly stirring by magnetic force, and adjusting the pH value of the mixed solution to 5 by using acetic acid to obtain a transparent solution; aging the transparent solution in a water bath kettle at 80 ℃ for 12 hours to obtain soft wet gel; drying the wet gel in an oven at 100 ℃ for 24 hours to obtain a blue solid; and taking out the dried powder, grinding in a mortar, putting into a quartz boat, heating to 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, naturally cooling to room temperature, and grinding the obtained glass material to obtain the glass powder. Putting the glass powder into a quartz boat, heating to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 2 hours, and naturally cooling to room temperature.
The product obtained after the glass powder is calcined at 800 ℃ is shown in FIG. 3, and it can be seen from FIG. 3 that the glass powder can form a glassy compact layer with high adhesion.
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 to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing low-melting-point lead-free glass powder by a sol-gel method is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a solution: dissolving ethyl orthosilicate in alcohol under an acidic condition, and vigorously stirring for 0.5-1 hour at room temperature to fully hydrolyze the ethyl orthosilicate, wherein the molar ratio of the alcohol to the ethyl orthosilicate is controlled to be 5-9, and the molar ratio of the acid to the ethyl orthosilicate is controlled to be 0.05-0.1;
(2) dissolving boric acid, a barium salt raw material, a zinc salt raw material and an adjusting raw material in deionized water, then adding an aqueous solution into the alcoholic solution of ethyl orthosilicate in the step (1), and uniformly stirring;
(3) adjusting the pH: adjusting the pH value of the mixed solution in the step (2) to 4-6 by using acid, and uniformly stirring;
(4) aging and drying: stirring the mixed solution at 60-100 ℃ for 12-15 hours until the mixed solution becomes soft wet gel, transferring the wet gel into a quartz boat, and drying at 100-120 ℃ for 16-24 hours to obtain solid particles or powder;
(5) calcining and grinding: calcining the solid particles or powder obtained in the step (3) at the temperature of 500-900 ℃ for 1-3 hours, and then grinding into powder to obtain the lead-free glass powder with low melting point.
2. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the barium salt raw material is one or more than two of barium acetate, barium nitrate, barium chloride and barium sulfate.
3. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the zinc salt raw material is one or more than two of zinc acetate, zinc nitrate, zinc chloride and zinc sulfate.
4. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the adjusting raw material is one or more of a copper salt raw material, a sodium salt raw material and a potassium salt raw material.
5. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the copper salt raw material is one or more than two of copper acetate, copper nitrate, copper chloride and copper sulfate.
6. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the sodium salt raw material is one or more than two of sodium acetate, sodium nitrate, sodium chloride and sodium sulfate.
7. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the potassium salt raw material is one or more than two of potassium acetate, potassium nitrate, potassium chloride and potassium sulfate.
8. The method for preparing the low-melting-point lead-free glass powder by the sol-gel method according to claim 1, which is characterized in that: the acid in the step (1) is one or more than two of acetic acid, nitric acid, hydrochloric acid and oxalic acid.
9. A low-melting-point lead-free glass powder is characterized in that: the glass frit is produced by the production method according to any one of claims 1 to 8.
10. Use of the low melting point lead-free glass frit according to claim 9 for passivation protection of P-N junctions and surface soldering in integrated circuit chips.
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| CN114426399A (en) * | 2021-12-08 | 2022-05-03 | 安徽大学 | Glass powder for semiconductor surface passivation and preparation method thereof |
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