CN114920469B - Bonding method of borosilicate glass - Google Patents
Bonding method of borosilicate glass Download PDFInfo
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- CN114920469B CN114920469B CN202210618131.0A CN202210618131A CN114920469B CN 114920469 B CN114920469 B CN 114920469B CN 202210618131 A CN202210618131 A CN 202210618131A CN 114920469 B CN114920469 B CN 114920469B
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- bonding
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- cleaning
- ammonia water
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003213 activating effect Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 2
- 229910008051 Si-OH Inorganic materials 0.000 claims 1
- 229910006358 Si—OH Inorganic materials 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 claims 1
- 231100000719 pollutant Toxicity 0.000 claims 1
- 241000252506 Characiformes Species 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910004742 Na2 O Inorganic materials 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
The invention provides a bonding method of borosilicate glass, which comprises the following steps: the method comprises the steps of (1) cleaning a borosilicate glass substrate with a smooth surface after grinding and polishing by using pure water and ethanol respectively to remove dirt (2) cleaning by using pure water and ethanol again after ultrasonic cleaning in piranha solution, drying by using a nitrogen gun, dripping ammonia water activating solution on a bonding surface, putting the bonding surface in an environment with the humidity of 70% -90% for 2 hours after bonding, separating the bonding surface, dripping the ammonia water activating solution again, and bonding again for standby. (4) And placing the substrate subjected to bonding and standing into a vacuum drying box, firstly preserving heat at 100 ℃ for 1h, and then preserving heat at 200 ℃ for 4h. And (5) naturally cooling to room temperature along with the furnace, and finishing bonding. The bonding method is not required to be carried out in a high-clean environment, has low requirements on equipment and environment, and is low in cost and convenient to operate.
Description
Technical Field
The invention relates to a bonding method of borosilicate glass, and belongs to the technical field of device bonding.
Background
Borosilicate glass refers to glass with SiO 2,B2O3,Al2O3,Na2 O as a basic constituent. Borosilicate glass has extremely low thermal expansion coefficient (one third of common glass), is not easy to crack and deform at high temperature, and is widely applied to cinema projectors, inspection window covers of chemical reactors, high-efficiency lamps and other devices needing to work in high-temperature conditions or in environments with severe temperature changes. In addition, borosilicate glass has the advantages of small shape deviation, high visible light transmittance, low dispersion, relatively low refractive index and the like, and is widely applied to optical devices such as telescope, reflector and the like.
The key and technology are widely applied, and can be used for manufacturing chip structures in electronic products, various semiconductor materials and structural devices, and even more complex three-position structure chips. Bonding techniques are also widely used in the field of optical device fabrication, where the quality of glass bonding directly affects the final performance of the optical component, and is important in the overall process flow.
The bonding methods of the glass at present mainly comprise the following steps:
(1) Traditional thermal bonding: bonding is performed by heating at high temperature (typically greater than 800 ℃), and the major disadvantage of this bonding method is that the higher temperature can cause some deformation of the glass substrates during bonding. For optical devices with higher precision, the deformation of the substrate can cause serious decline of the optical precision, and the performance of the device is affected;
(2) Intermediate medium bonding: the low melting point frit is placed at the bonding interface, heated to the softening temperature of the frit, and bonded through the frit. This approach typically suffers from the problem that the adhesive frit used is not consistent with the refractive index and coefficient of thermal expansion of the glass to be bonded, resulting in reduced optical accuracy of the assembly;
(3) Anodic bonding: and applying pressure and voltage to two ends of the bonding glass to enable Na ions in the glass to drift towards the negative electrode direction to form a depletion layer so as to form O-Si-O bonds, so that bonding is realized. The disadvantage of this method is that the Na ion diffusion capability is limited, and Na ions cannot be sufficiently diffused when the glass substrate to be bonded is too thick, resulting in poor bonding effect.
The bonding method mostly needs to carry out activation treatment through plasma surface modification, and the bonding temperature is high, so that the preparation process is complex in operation, the technology is not easy to master, and the mass industrialized production of the bonding method is affected to a certain extent. Bonding techniques generally include four steps of substrate cleaning, surface modification activation, pre-bonding, and bonding. The activation methods can be broadly classified into plasma activation, ultraviolet activation, and chemical solution activation. In this way, the chemical solution activation does not need specific instruments and equipment, and only needs to use the chemical solution, so the method has the advantages of low cost and simple operation compared with other activation modes. The traditional chemical solution activation method needs to heat and boil the activating solution to activate the substrate when activating the substrate, and has strong reaction and high risk. There is therefore still room for further improvement and simplification of the chemical solution activated bonding process.
Disclosure of Invention
The invention aims to overcome the defects and provide a borosilicate glass bonding method which can be completed in a general laboratory. The bonding method adopts a chemical solution ultrasonic cleaning method to perform activation treatment on the substrate, does not need special treatment equipment, has low cost, does not need to boil an activating solution in the activation process, is safe and reliable, and is easy to operate. The bonding technology has high bonding power, the strength can meet the preparation requirement of a common optical component, and the optical component obtained by bonding has excellent performance.
The borosilicate glass bonding method comprises the following specific steps:
1. polishing the glass surface by using an optical polishing instrument, and then ultrasonically cleaning the glass surface in pure water, ethanol and acetone for 5min.
2. And (3) placing the glass substrate in a washing liquid of 98% concentrated sulfuric acid and 30% hydrogen peroxide mixed solution in a volume ratio of 7:3 in a fume hood, ultrasonically cleaning for 5min, sequentially using pure water and ethanol, ultrasonically cleaning for 3min, taking out, and drying by a nitrogen gun for later use.
3. Sucking (NH 4)OH:H2O2:H2 0 volume ratio of 6:2:2) ammonia water activating solution by a needle cylinder, dripping the ammonia water activating solution on the surface to be bonded of one substrate, bonding the surface to be bonded of the other substrate, standing for 2h in an environment with the humidity of 70% -90%, separating the substrates, repeatedly dripping ammonia water activating solution, bonding again, and standing for later use.
4. And (3) placing the bonded substrate into a vacuum drying oven, vacuumizing to 100Mbar-200Mbar, heating to 100 ℃ at a speed of 2-3 ℃/min, preserving heat for 2h, and heating to 200 ℃ at the same heating speed, and preserving heat for 4h. And then naturally cooling to room temperature along with the furnace, and finishing bonding.
The mechanism and the beneficial effects of the invention are as follows:
the invention has the advantages of simple equipment and lower cost, does not need to use plasma or ultraviolet light and other methods for surface modification, and does not need to be carried out in a high-cleanliness environment. The method does not need to boil the activating liquid when activating the substrate, and is safer and more convenient to operate compared with the traditional chemical activation. Bubbles are not easy to generate in the bonded glass substrates, the glass substrates cannot deform in the bonding process, and the bonded glass assembly has good light transmittance. The formation of Si-O-Si bonds after annealing results in a glass substrate having a greater bonding force without the surface micro-nano structure being destroyed. The whole bonding process is simple to operate, the technology is easy to master, and the method is suitable for mass industrial production. ,
Drawings
FIG. 1 is a bonding flow chart of borosilicate glass according to the present invention.
Detailed Description
The invention provides a bonding method of borosilicate glass, and in order to make the purpose and advantages of the invention more clear, the invention will be further described with reference to examples.
Example 1
Placing the polished two pieces of borosilicate glass into a beaker filled with pure water for ultrasonic cleaning for 5min, pouring out the pure water, pouring absolute ethyl alcohol, ultrasonic cleaning for 5min again, pouring out the ethyl alcohol, adding acetone, ultrasonic cleaning for 5min, and taking out the two pieces of borosilicate glass.
The cleaned glass substrate is put into a mixed solution (piranha solution, commonly called piranha solution) of 98 percent concentrated sulfuric acid and 30 percent hydrogen peroxide in a volume ratio of 7:3, and is ultrasonically cleaned for 5 minutes under the power of 50W. And pouring out the mixed solution, adding a large amount of pure water, ultrasonically cleaning for 3min, pouring out the pure water, adding a large amount of ethanol, ultrasonically cleaning for 3min, taking out, and drying by using a nitrogen gun.
Placing a substrate to be bonded with the bonding surface facing upwards, sucking 10mL of activating solution of 25% -28% concentrated ammonia water, 30% hydrogen peroxide and pure water with the volume ratio of 6:2:2 by using a syringe, and slowly and uniformly dripping the activating solution on the whole surface to be bonded. And (3) attaching the surface to be bonded of the other substrate, and then placing the substrate into a constant-humidity box with the humidity set to 75% for standing for 2 hours. Then the substrate is taken out, and after the substrate is separated, the activating solution is dripped again, and the substrate is attached again and put back into a constant humidity box.
And taking the substrate out of the constant-humidity box, placing the substrate into a vacuum drying box, vacuumizing to 1500Mbar, setting the heating rate to be 2 ℃/min, heating, keeping the temperature for 2 hours after heating to 100 ℃, and keeping the temperature for 4 hours after continuously heating to 200 ℃ at the rate of 2 ℃/min. And naturally cooling to room temperature, and taking out the bonded substrate. The bonded substrate has good light transmittance and high bonding strength.
Claims (7)
1. A bonding method of borosilicate glass, comprising the steps of:
step 1, polishing a glass sample by using an optical polishing instrument, and cleaning by using pure water, ethanol and acetone respectively to obtain a cleaned glass substrate;
Step 2, placing the glass substrate into a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3 in a fume hood for ultrasonic cleaning, placing the substrate cleaned in the step 1 into a medium ultrasonic treatment device for a period of time, further removing pollutants on the surface of the glass substrate, generating Si-OH bonds to make the surface hydrophilic, ultrasonically cleaning the surface for a period of time again by using pure water and ethanol, and drying the surface for later use by using a nitrogen gun;
Preparing ammonia water activating solution according to the volume ratio of NH 4OH:H2O2:H2 O=6:2:2, dripping the ammonia water activating solution on the surface of one substrate to be bonded by using a needle cylinder, attaching the other substrate to the ammonia water activating solution, standing for a period of time in a wet environment with the humidity of 70% -90%, repeating the steps, and continuing standing for standby;
Step 4, separating the substrate after standing, repeating the step 3, dripping ammonia water activating solution, then re-attaching and putting the substrate back into a constant humidity box, and continuously standing for 2 hours;
step 5, placing the substrate into a vacuum drying box, heating to 100 ℃ for heat preservation for a period of time, and then continuously heating to 200 ℃ for heat preservation for a period of time;
and 6, cooling to room temperature along with the furnace, and finishing bonding.
2. The bonding method according to claim 1, wherein:
In the step 1, the ultrasonic power of the ultrasonic cleaning is 40-60W, and the cleaning time is 5min.
3. The bonding method according to claim 1, wherein:
In step 2, the ultrasonic treatment is performed for more than 5 minutes.
4. The bonding method according to claim 1, wherein:
in the step 2, the ultrasonic cleaning is performed for more than 3 minutes by using pure water and ethanol again.
5. The bonding method according to claim 1, wherein:
In the step 2, the other piece is attached to the plate and then is kept stand for more than 2 hours in a wet environment with the humidity of 70% -90%.
6. The bonding method according to any one of claims 1 to 5, wherein:
in step 5, the substrate is placed in a vacuum oven with the vacuum degree of 100Mbar-200Mbar, and is heated to 100 ℃ at the speed of 2-3 ℃/min and then is kept for more than 2 hours.
7. The bonding method according to claim 6, wherein the temperature is kept for 4 hours or more after the temperature is further raised to 200 ℃ at the same temperature raising rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210618131.0A CN114920469B (en) | 2022-06-01 | 2022-06-01 | Bonding method of borosilicate glass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210618131.0A CN114920469B (en) | 2022-06-01 | 2022-06-01 | Bonding method of borosilicate glass |
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| Publication Number | Publication Date |
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| CN114920469A CN114920469A (en) | 2022-08-19 |
| CN114920469B true CN114920469B (en) | 2024-04-30 |
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| CN202210618131.0A Active CN114920469B (en) | 2022-06-01 | 2022-06-01 | Bonding method of borosilicate glass |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050066A (en) * | 2007-05-11 | 2007-10-10 | 华中科技大学 | Method for local bonding silicon / glass by laser |
| CN109721257A (en) * | 2018-08-02 | 2019-05-07 | 比亚迪股份有限公司 | Glass composite, shell, display device and terminal device |
| CN112851145A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Chemical activation based low-temperature direct bonding method for quartz glass |
| CN112897899A (en) * | 2021-01-21 | 2021-06-04 | 中国科学院电工研究所 | Glass assembly bonding method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6902987B1 (en) * | 2000-02-16 | 2005-06-07 | Ziptronix, Inc. | Method for low temperature bonding and bonded structure |
| US6814833B2 (en) * | 2001-10-26 | 2004-11-09 | Corning Incorporated | Direct bonding of articles containing silicon |
| US10086584B2 (en) * | 2012-12-13 | 2018-10-02 | Corning Incorporated | Glass articles and methods for controlled bonding of glass sheets with carriers |
-
2022
- 2022-06-01 CN CN202210618131.0A patent/CN114920469B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050066A (en) * | 2007-05-11 | 2007-10-10 | 华中科技大学 | Method for local bonding silicon / glass by laser |
| CN109721257A (en) * | 2018-08-02 | 2019-05-07 | 比亚迪股份有限公司 | Glass composite, shell, display device and terminal device |
| CN112851145A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Chemical activation based low-temperature direct bonding method for quartz glass |
| CN112897899A (en) * | 2021-01-21 | 2021-06-04 | 中国科学院电工研究所 | Glass assembly bonding method |
Non-Patent Citations (1)
| Title |
|---|
| 张克立等.无机合成化学 第2版.武汉大学出版社,2012,第49页. * |
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| CN114920469A (en) | 2022-08-19 |
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