CN109912237B - Surface in-situ metallization method based on cation conductive glass - Google Patents
Surface in-situ metallization method based on cation conductive glass Download PDFInfo
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Abstract
The invention discloses a surface metallization method based on cation migration, reaction and in-situ growth in cation conductive glass under the composite action of a temperature field and an electric field. The method comprises the following steps: the method comprises the steps of butting cation conductive glass and a metal foil between a positive electrode and a negative electrode in a vacuum furnace, applying certain axial pressure and heating, activating cations in the glass at high temperature to generate ionization, loading a direct current electric field, forming directional migration transport by the cations, enriching the cations on the side surface of a glass negative electrode, generating an oxidation reduction reaction with free charges to generate a simple substance, then growing a metal layer in situ in a surface micro-nano structure, generating a diffusion or eutectic reaction with the butted metal foil, avoiding the contact of the metal layer and the electrode, and increasing the metallization thickness. The invention has the advantages that the metal layer is closely attached to the surface of the glass to grow, the connection strength is high, the spreading and wetting performance of the metal layer on the surface of the glass after melting is excellent, and the welding and packaging performance of the glass is obviously improved.
Description
Technical Field
The invention relates to a surface metallization technology of glass before brazing or eutectic bonding, in particular to a surface in-situ metallization method of cation conductive glass under the composite action of a temperature field and a direct current electric field.
Background
The connection of glass and metal (semiconductor) materials is widely used in the fields of integrated circuit manufacturing, multifunctional chip integration and packaging of MEMS sensors, microfluidic chips and semiconductor chips. As packaging technologies are developed towards high power, high integration and 3D vertical interconnects, increasingly stringent high-integration requirements are placed on the ultimate size, integration, heat dissipation and reliability of glass-to-metal or semiconductor material bonding technologies.
Common bonding methods for glass and foreign materials include anodic bonding, direct bonding, and eutectic bonding. One of the anodically bonded substrates to be connected must be provided with O2-The principle of the conductive or non-bridging oxygen migration capacity glass is that a silicon chip and the glass are connected to two electrodes of a high-voltage electrode, and O is migrated under the conditions of high temperature (400-500 ℃), high voltage (800-1500V) and pressure2-Or non-bridging oxygen, to form new chemical bonds of Si-O-Si or O-M (M = Mg, Al, Cu and Ni), so as to realize the bonding of the glass and the silicon or the metal.
Compared with other bonding technologies, anodic bonding has the advantages of simple process, high bonding strength, good sealing performance and the like, but high temperature, high voltage and poor conductive heat dissipation performance of a bonding area are the main problems faced by the technology. Direct bonding is generally limited to the connection between silicon wafers, and the principle is that two silicon wafers with smooth surfaces are connected at a certain temperature and pressure after pretreatment, and bonding is finally realized through high-temperature annealing at the temperature of over 800 ℃. Generally, the roughness of the surface to be bonded of a silicon wafer is required to be less than 10nm, the parallelism is less than 3 μm, the surface warpage is less than 25 μm, and the bonding has high requirements on the surface roughness (less than 10 nm) and the annealing temperature (above 800 ℃) so that the bonding packaging cost is high, and large residual stress is generated between bonding parts due to high temperature. Eutectic bonding is an indirect bonding technology which adopts metal as a transition layer and forms intermetallic compounds through eutectic reaction so as to realize bonding between wafers. The bonding process has the advantages of low temperature, small influence by surface roughness, good heat dissipation, capability of forming ohmic contact between wafers and the like, but still has the problems of poor wettability of eutectic liquid relative to a substrate, complex surface coating process, overlarge wafer spacing caused by a multi-coating structure, difficulty in controlling the types and distribution of intermetallic compounds generated by reaction and the like. According to the characteristics of each bonding mode, the bonding technology of glass and semiconductor or metal materials is divided into two types including anodic bonding without intermediate layer, direct bonding, intermediate layer and eutectic bonding. The bonding without an intermediate layer usually needs higher bonding temperature (anodic bonding is more than 400 ℃, and direct bonding is more than 800 ℃), and the bonding region has poor electric and thermal conductivity, so that the packaging requirements of high-power and high-integration devices are difficult to adapt. Therefore, the technical improvement based on the eutectic bonding with the intermediate layer is an important way for realizing the high-comprehensive-performance packaging.
In view of the above, aiming at the problems of poor wettability of the intermediate interlayer to the substrate, complex surface coating process, large wafer spacing, difficult control of the kind and distribution of the intermetallic compound generated by the reaction and the like in eutectic bonding, the invention is based on the cation migration and material transport characteristics of the cation conductive glass under the conditions of certain temperature (lower than 200 ℃) and voltage (lower than 300V), the cations are led out from the surface of the glass and neutralized with free electrons to form a metal simple substance, and the simple substance layer grows in situ clinging to the surface, thereby realizing the in-situ metallization of the surface of the cation conductive glass.
Disclosure of Invention
The invention aims to provide an in-situ metallization method for the surface of cation conductive glass, which improves the connection strength between a metal layer on the surface of the cation conductive glass and a substrate and the spreading and wetting effects on the substrate after melting, can realize surface metallization without coating, sputtering or ion injection on the surface of the cation conductive glass, and can be used in the field of brazing and eutectic bonding of the cation conductive glass.
In order to realize the in-situ metallization of the surface of the cation conductive glass, the technical scheme adopted by the invention is as follows:
a surface in-situ metallization method based on cation conductive glass comprises the following steps:
s1, preparing cation conductive glass containing halide and sulfide of silver or oxide and halide of copper, and making a test piece;
s2, polishing the contact surfaces of the cationic conductive glass test piece and the metal foil by using metallographic abrasive paper, and cleaning by using acetone;
s3, butting the cation conductive glass test piece and the metal foil between the positive power supply plate and the negative power supply plate, connecting the cation conductive glass test piece with the positive power supply plate, and connecting the metal foil with the negative power supply plate;
s4, maintaining a vacuum environment in the furnace, setting the axial pressure to be 1-3 MPa, the heating temperature in the furnace to be 150-400 ℃, keeping the temperature for 2-20 min, keeping the direct-current voltage to be 200-400V, and keeping the loading time for 2-10 min; loading axial pressure and heating to the ionization activation temperature of cations in the cation conductive glass test piece, and then loading a direct current electric field to enable ionized ions to form directional migration;
and S5, stopping heating, closing the external electric field, naturally cooling the cationic conductive glass test piece and the metal foil connector to room temperature, and taking out.
Preferably, in step S1, the cation conductive glass is prepared by doping Ag i, AgBr, Ag in a borate, vanadate, phosphate, tellurate, chalcogenide or chalcohalide glass matrix2S, Cu I, CuBr or Cu2O is one or more of. The preparation method of the cation conductive glass comprises a melting quenching method and a mechanochemical synthesis method. The preparation of a cation-conducting glass based on a melt-quenching process is described by way of example of the synthesis of an Ag I-doped borate glass: preparing chemical pure grade Ag I and Ag2O and B2O3As raw materials, the raw materials are 10-80 mol% of Ag I and Ag2O/B2O3Mixing completely at a ratio of =3, placing in a quartz glass tube with an opening at one end, heating to 480-800 ℃ in an electric heating furnace to melt, and meltingCooling with two rollers, and adjusting the pressure between the two rollers to control the cooling rate of the solution to obtain Ag+Conductive glass. Secondly, by containing Ag2Ag of S2S-Sb2S3Synthesis of chalcogenide glass as an example, a method for preparing a cation conductive glass based on a mechanochemical synthesis method is explained: preparing chemical pure grade Ag2S and Sb2S3Mixing according to an equal molar ratio, weighing 5g of mixed powder in a 250mL agate ball mill tank, putting 10 agate grinding balls with the diameter of 10mm, adding 10mL acetone serving as a process control agent, ball-milling for 10h in a planetary ball mill at the rotating speed of 400rpm, pausing for 30min every 3h, putting the ball-milled powder in a vacuum drying oven for drying for 2h, putting the dried powder in a graphite mold, putting the graphite mold into an SPS system for sintering, wherein the sintering temperature is 980-1140 ℃, the axial pressure is 70MPa, and the vacuum degree is kept at 10 in the sintering process-1Pa or so. The preparation principle of different glass substrates and cationic compounds doped with the same is similar, but the process and parameters are different, and reference is made to the published article "mechanical-chemical synthesis of inorganic solids in the system AgI-Ag2PO3.5 and their silver ion-conducting properties”，“Nonlinear impedance as possible result of ion–polaron interaction in Cu2O–Al2O3–SiO2glass "and" chromatography and electrochemical cell chromatography of mesoporous synthesized AgI-Ag2O–MoO3 amorphous superionic system”。
Preferably, in step S2, the thickness of the cationic conductive glass test piece is 0.5 to 5mm, the roughness of the contact surface is Ra =0.5 to 1.2 μm, the thickness of the metal foil is 0.1 to 1mm, and the roughness of the contact surface is Ra =0.1 to 0.3 μm.
Preferably, in step S3, a graphite paper is provided between the cation conductive glass test piece and the positive power supply plate, and a graphite paper is provided between the metal foil and the negative power supply plate. The cation conductive glass test piece is not in direct contact with the positive plate, and the metal foil is separated from the negative plate by graphite paper, so that the experimental materials and the electrodes are prevented from being polluted mutually.
The invention isThe method is similar to the anodic bonding process of glass and metal, and can share the same device with anodic bonding, but is different from the traditional anodic bonding in that: the method aims at carrying out metallization treatment on the surface of the cation conductive glass, and the connection with the metal foil is that after the cation leading-out surface is considered, the metal foil has stronger oxidability, and strong oxidability ions react with electrode materials at high temperature to cause mutual pollution, so that the glass and the electrode are separated by the metal foil with relatively stable performance, the mutual pollution of the electrode and the glass surface is avoided, and the metallization thickness of the surface of the cation conductive glass is increased; II, anodic bonding through O2-Or the migration of non-bridge oxygen and the interface reaction realize the bonding of glass and metal, and the method realizes the metallization of the surface of the glass based on the migration of cations and the interface reaction.
The invention has the following beneficial effects:
1. the coating material on the surface of the glass is transported by substances generated by cation migration in the glass, and the coating material is precipitated on the surface and then grows in situ by attaching to a rough fine structure on the surface, so that the connection strength of the coating and the glass is greatly improved, the spreading, wetting and filling performances of a surface metal layer melted on the surface of the glass are obviously improved, and the difficulty in welding or bonding the glass and a heterogeneous material is reduced.
2. The surface in-situ metallization temperature is related to the ionization activation energy and the conductivity of cations in the cation conductive glass, and the required temperature is usually lower than the treatment temperature of metal or alloy by surface metallization methods such as laser coating, plasma spraying and the like, so that the residual thermal stress caused by the mismatch of the thermal expansion coefficients of the coating and the glass is remarkably reduced, and the coating is further in diffusion connection with metal foil to form a metal coating with adjustable thickness and high reliability.
3. The surface in-situ metallization method has low requirement on equipment, does not need additional coating equipment, and has simple process and low cost.
The invention has reasonable design and good popularization and application value.
Drawings
FIG. 1 is a schematic view of the surface in-situ metallization device based on the cation conductive glass.
FIG. 2 is a schematic view showing the surface in-situ metallization process of the cation-conducting glass of the present invention.
FIG. 3 shows Ag prepared by the method described in example 1+In-situ metalizing sample on the surface of conductive glass, and testing Ag based on Atomic Force Microscope (AFM) and X-ray diffractometer+The micro-morphology, the roughness and the phase composition of the in-situ metal layer on the surface of the ion conductive glass are obtained to obtain Ag+Atomic force micrographs and X-ray diffraction patterns of the in-situ metal layer on the surface of the ion-conducting glass.
In the figure: 1-furnace body, 2-vacuum device, 3-electrode lead, 4-direct current power supply, 5-resistor, 6-current recording device, 7-heating device, 8-control panel, 9-support plate, 10-pressing plate, 11-power negative plate, 12-power positive plate, 13-metal foil, 14-cation conductive glass test piece, 15-cation glass surface rough structure, 16-surface in-situ metal layer and 17-eutectic connection layer.
Detailed Description
The following further description of the embodiments of the present invention will be made with reference to the accompanying drawings, and it should be understood that the description of the embodiments is provided for the purpose of facilitating understanding of the present invention, and is not intended to limit the present invention. The technical features of the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A surface in-situ metallization method based on cation conductive glass is used for assisting the surface metal layer of the cation conductive glass in soldering or bonding, is formed by the cation reaction in the cation conductive glass after being activated by a composite field, does not need surface coating, sputtering or ion implantation, and is carried out according to the following steps:
the first step is as follows: selection of Ag I-Ag with high conductivity and low ionization activation energy2O-B2O3The silver ion conductive glass is used as a surface in-situ metallization sample piece, and the preparation process comprises the following steps: preparing chemical pure grade Ag I and Ag2O and B2O3As raw materials, 60mol percent of Ag I and Ag2O/B2O3Mixing completely in proportion of =3, placing in a quartz glass tube with an opening at one end, heating to 480-800 ℃ in an electric heating furnace to melt, cooling the melt by double rollers, reasonably adjusting the pressure of the double rollers to control the cooling rate of the melt, and processing the glass into a test piece 14 with the thickness of 2mm and 15mm multiplied by 15 mm; selecting tin (Sn) foil as the Ag I-Ag2O-B2O3A separating layer between the silver ion conductive glass and the negative electrode, the thickness is 50 μm and the silver ion conductive glass is cut into test pieces 13 with the thickness of 15mm multiplied by 15 mm.
The second step is that: the bonding surfaces of the positive ion conductive glass test piece 14 and the Sn foil 13 are polished by using metallographic abrasive paper so that the surface roughness Ra = 0.5-1.2 μm of the positive ion conductive glass test piece 14 and the surface roughness Ra = 0.1-0.3 μm of the Sn foil 13. And cleaning the surface to be bonded by using acetone after polishing.
The third step: as shown in fig. 1, a cation conductive glass test piece 14 and a Sn foil 13 are combined in a butt joint manner and placed between a positive power supply plate 12 and a negative power supply plate 11, a graphite paper is arranged between the cation conductive glass test piece 14 and the positive power supply plate 12, and a graphite paper is arranged between the metal foil 13 and the negative power supply plate 11.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-4~10-2Pa, setting the axial pressure to be 2MPa, applying a 230V direct current electric field between the positive and negative plates after the temperature is raised to 150 ℃, loading for 10min, preserving the heat for 10min, activating the ionization of Ag + in the cationic conductive glass test piece 14, so that the Ag + is migrated and transported and is separated out at the contact surface of the glass and the Sn foil 13 to form an Ag single substance layer 16 as shown in figure 2, and the single substance layer grows in situ by clinging to the surface of the cationic conductive glass test piece 14.
The fifth step: after the heat preservation is finished, the temperature is further raised to 230 ℃ (higher than the Ag/Sn eutectic reaction temperature), the voltage is kept unchanged, the heat preservation is carried out for 10min to enable the surface in-situ Ag layer 16 of the cation conductive glass test piece 14 to carry out eutectic reaction with the Sn foil 13 to form a liquid phase, and the high-melting-point Ag is generated3Sn phase andβand (4) precipitating a Sn phase from the liquid phase to form a eutectic connecting layer 17, cooling to room temperature along with the furnace after heat preservation is finished, and taking out the sample wafer. FIG. 3 is an Atomic Force Microscope (AFM) photograph of in-situ grown Ag layer on the surface of a cationic conductive glass test pieceAnd an X-ray diffraction pattern of the in-situ grown Ag layer, wherein the characterization result shows that: the in-situ grown Ag layer contains a polycrystalline face-centered cubic (fcc) structure Ag simple substance, diffraction peaks of (111) and (200) crystal faces appear in the X-ray diffraction pattern, and the surface roughness of the in-situ grown Ag layer is 3.98 nm.
Example 2
A surface in-situ metallization method based on cation conductive glass is used for assisting the surface metal layer of the cation conductive glass in soldering or bonding, is formed by the cation reaction in the cation conductive glass after being activated by a composite field, does not need surface coating, sputtering or ion implantation, and is carried out according to the following steps:
the first step is as follows: selection of Ag I-Ag with high conductivity and low ionization activation energy2O-B2O3The silver ion conductive glass is used as a surface in-situ metallization sample piece, and the preparation process comprises the following steps: preparing chemical pure grade Ag I and Ag2O and V2O5As raw materials, 50mol% of Ag I and Ag2O/ V2O5Mixing sufficiently in a ratio of =0.67:0.33, weighing 5g of mixed powder in a 250mL agate ball milling tank, putting 10 agate grinding balls with the diameter of 10mm, adding 10mL acetone serving as a process control agent, ball milling for 10h in a planetary ball mill at the rotation speed of 400rpm, pausing for 30min every 3h, putting the ball-milled powder in a vacuum drying oven for drying for 2h, putting the dried powder in a graphite mold, putting the graphite mold into an SPS system for sintering, wherein the sintering temperature is 900-1200 ℃, the axial pressure is 70MPa, and the vacuum degree is kept at 10 in the sintering process-1Pa or so. Processing glass into test piece 14 with thickness of 2mm and 15mm × 15mm, and selecting aluminum (Al) foil as the Ag I-Ag2O-B2O3A separating layer between the silver ion conductive glass and the negative electrode, the thickness is 50 μm and the silver ion conductive glass is cut into test pieces 13 with the thickness of 15mm multiplied by 15 mm.
The second step is that: polishing the bonding surfaces of the cation conductive glass test piece 14 and the Al foil 13 by using metallographic abrasive paper so that the surface roughness Ra = 0.5-1.2 μm of the cation conductive glass test piece 14 and the surface roughness Ra = 0.1-0.3 μm of the Al foil 13. And cleaning the surface to be bonded by using acetone after polishing.
The third step: as shown in fig. 1, a cation conductive glass test piece 14 and an Al foil 13 are combined in a butt joint manner and are placed between a power positive plate 12 and a power negative plate 11, a graphite paper is arranged between the cation conductive glass test piece 14 and the power positive plate 12, and a graphite paper is arranged between the metal foil 13 and the power negative plate 11.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-4~10-2Pa, setting the axial pressure to be 1-2 MPa, applying a 230V direct current electric field between a positive plate and a negative plate after the temperature is raised to 150 ℃, loading for 10min, preserving the temperature for 10min, activating the ionization of Ag + in the cationic conductive glass test piece 14, so that the Ag + is migrated and transported and is separated out at the contact surface of the glass and the Al foil 13 to form an Ag single substance layer 16 shown in figure 2, and the single substance layer clings to the surface of the cationic conductive glass test piece 14 to grow in situ.
The fifth step: after the heat preservation is finished, the temperature is further raised to 490 ℃ (higher than the Ag/Al eutectic reaction temperature), the voltage is kept unchanged, and the heat preservation is carried out for 10min to ensure that the surface in-situ Ag layer 16 of the cation conductive glass test piece 14 and the Al foil 13 have eutectic reaction to form a liquid phase, so that a high melting point is generatedμ-Ag3And precipitating the eutectic connecting layer 17 of the Al phase and the Al matrix phase from the liquid phase, cooling to room temperature along with the furnace after heat preservation is finished, and taking out the sample wafer.
Example 3
A surface in-situ metallization method based on cation conductive glass is used for assisting the surface metal layer of the cation conductive glass in soldering or bonding, is formed by the cation reaction in the cation conductive glass after being activated by a composite field, does not need surface coating, sputtering or ion implantation, and is carried out according to the following steps:
the first step is as follows: selection of Cu with high conductivity and low ionization activation energy2O-Al2O3-SiO2The copper ion conductive glass is used as a surface in-situ metallization sample piece, and the preparation process comprises the following steps: according to the proportion of 12.5 percent of CuO to 12.5 percent of Al2O3-75%SiO2Is ground for 2 hours at a rotating speed of 400rpm, and Al is added2O3Heating the crucible to 1550 ℃ for melting, then cooling the melt by two rollers, reasonably adjusting the pressure of the two rollers to control the cooling rate of the melt,obtaining the flake glass, processing the flake glass into a test piece 14 with the thickness of 2mm and the area of 15mm multiplied by 15 mm; selecting Sn foil as the Cu2O-Al2O3-SiO2A spacer layer between the copper ion conductive glass and the negative electrode, the thickness is 50 μm and the copper ion conductive glass is cut into 15mm test pieces 13.
The second step is that: the bonding surfaces of the positive ion conductive glass test piece 14 and the Sn foil 13 are polished by using metallographic abrasive paper so that the surface roughness Ra = 0.5-1.2 μm of the positive ion conductive glass test piece 14 and the surface roughness Ra = 0.1-0.3 μm of the Sn foil 13. And cleaning the surface to be bonded by using acetone after polishing.
The third step: as shown in fig. 1, a cation conductive glass test piece 14 and a Sn foil 13 are combined in a butt joint manner and placed between a positive electrode plate 12 and a negative electrode plate 11, a graphite paper is arranged between the cation conductive glass test piece 14 and the positive power supply plate 12, and a graphite paper is arranged between the metal foil 13 and the negative power supply plate 11.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-4~10-2Pa, setting the axial pressure to be 1-2 MPa, applying a 280V direct current electric field between a positive plate and a negative plate after the temperature is raised to 200 ℃, loading for 10min, preserving the heat for 10min, and activating Cu in the cation conductive glass test piece 14+So that the ions are transferred and transported to be precipitated at the contact surface of the glass and the Sn foil 13, and a Cu single substance layer 16 as shown in figure 2 is formed, and the single substance layer grows in situ by clinging to the surface of the cation conductive glass test piece 14.
The fifth step: after the heat preservation is finished, the temperature is further raised to 240 ℃ (higher than the Cu/Sn eutectic reaction temperature), the voltage is kept unchanged, the heat preservation is carried out for 10min, so that the surface in-situ Cu layer 16 of the cation conductive glass test piece 14 and the Sn foil 13 are subjected to eutectic reaction to form a liquid phase, and the high-melting-point Cu is generated6Sn5And precipitating the eutectic layer 17 of the phase and the Sn matrix phase from the liquid phase, cooling to room temperature along with the furnace after heat preservation is finished, and taking out the sample wafer.
In a word, the method of the invention is that cation conductive glass and metal foil are butted between a positive electrode and a negative electrode in a vacuum furnace, certain axial pressure is applied and heating is carried out, cations in the glass are activated at high temperature to generate ionization, a direct current electric field is loaded, the cations form directional migration transport and are enriched on the side surface of a glass negative electrode, and generate oxidation reduction reaction with free charges to generate simple substances, and then a metal layer is formed by in-situ growth in a surface micro-nano structure and generates diffusion or eutectic reaction with the butted metal foil, thereby avoiding the contact of the metal layer and the electrode and increasing the metallization thickness. The invention has the advantages that the metal layer is closely attached to the surface of the glass to grow, the connection strength is high, the spreading and wetting performance of the metal layer on the surface of the glass after melting is excellent, and the welding and packaging performance of the glass is obviously improved.
The above embodiments are merely exemplary to illustrate the present invention, and the specific details of the embodiments are only for illustrating the present invention and do not represent all technical solutions under the conception of the present invention, and any simple changes, equivalent substitutions or modifications which are based on the present invention to solve substantially the same technical problems or achieve substantially the same technical effects are all within the scope of the present invention.
Claims (4)
1. A surface in-situ metallization method based on cation conductive glass is characterized in that: the method comprises the following steps:
s1, selecting the cation conductive glass, and doping Ag I, AgBr, Ag in the silicate, borate, vanadate, phosphate, tellurate, sulfur system or sulfur halide system glass matrix2S, Cu I, CuBr or Cu2One or more of O;
s2, polishing the contact surfaces of the cationic conductive glass test piece and the metal foil by using metallographic abrasive paper, and cleaning by using acetone;
s3, butting the cation conductive glass test piece and the metal foil between the positive power supply plate and the negative power supply plate, connecting the cation conductive glass test piece with the positive power supply plate, and connecting the metal foil with the negative power supply plate;
s4, maintaining a vacuum environment in the furnace, setting the axial pressure to be 1-3 MPa, the heating temperature in the furnace to be 150-400 ℃, keeping the temperature for 2-20 min, keeping the direct-current voltage to be 200-400V, and keeping the loading time for 2-10 min; loading axial pressure and heating to the ionization activation temperature of cations in the cation conductive glass test piece, and then loading a direct current electric field to enable ionized ions to form directional migration;
and S5, stopping heating, closing the external electric field, naturally cooling the cationic conductive glass test piece and the metal foil connector to room temperature, and taking out.
2. The method according to claim 1, wherein the method comprises: in step S2, the roughness of the contact surface of the cationic conductive glass test piece is Ra =0.5 to 1.2 μm, and the roughness of the contact surface of the metal foil is Ra =0.1 to 0.3 μm.
3. The method for the in-situ metallization of a surface based on a cationically conductive glass according to claim 1 or 2, characterized in that: in step S3, graphite paper is disposed between the positive ion conductive glass test piece and the positive power plate, and graphite paper is disposed between the metal foil and the negative power plate.
4. The method according to claim 3, wherein the method comprises: the cation conductive glass is prepared by a melt quenching method or a mechanochemical synthesis method.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489795A (en) * | 2000-12-21 | 2004-04-14 | 分子技术股份有限公司 | Lithum anodes for electrochemical cells |
| US20050058841A1 (en) * | 2003-01-24 | 2005-03-17 | Baney William J. | Glass frit bond and process therefor |
| CN1679185A (en) * | 2002-08-27 | 2005-10-05 | 德古萨公司 | Ion conducting battery separator for lithium batteries, method for the production and use thereof |
| CN1894821A (en) * | 2003-10-14 | 2007-01-10 | 波利普拉斯电池有限公司 | Active metal/aqueous electrochemical cells and systems |
| CN1942732A (en) * | 2004-04-13 | 2007-04-04 | 索尼株式会社 | Heat transport apparatus, method of manufacturing heat transport apparatus, and electronic equipment |
| US20120145308A1 (en) * | 2010-12-08 | 2012-06-14 | Jiangwei Feng | Methods for anodic bonding material layers to one another and resultant apparatus |
| CN104692676A (en) * | 2015-02-15 | 2015-06-10 | 太原理工大学 | Electric-field-assisted diffusion bonding device and method for glass tubes and metal plates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10259039A (en) * | 1997-03-18 | 1998-09-29 | Fujitsu Ltd | Anodic bonding and device therefor |
| JP6499234B2 (en) * | 2017-07-24 | 2019-04-10 | カルソニックカンセイ株式会社 | Joining method |
-
2019
- 2019-04-09 CN CN201910279523.7A patent/CN109912237B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489795A (en) * | 2000-12-21 | 2004-04-14 | 分子技术股份有限公司 | Lithum anodes for electrochemical cells |
| CN1679185A (en) * | 2002-08-27 | 2005-10-05 | 德古萨公司 | Ion conducting battery separator for lithium batteries, method for the production and use thereof |
| US20050058841A1 (en) * | 2003-01-24 | 2005-03-17 | Baney William J. | Glass frit bond and process therefor |
| CN1894821A (en) * | 2003-10-14 | 2007-01-10 | 波利普拉斯电池有限公司 | Active metal/aqueous electrochemical cells and systems |
| CN1942732A (en) * | 2004-04-13 | 2007-04-04 | 索尼株式会社 | Heat transport apparatus, method of manufacturing heat transport apparatus, and electronic equipment |
| US20120145308A1 (en) * | 2010-12-08 | 2012-06-14 | Jiangwei Feng | Methods for anodic bonding material layers to one another and resultant apparatus |
| CN104692676A (en) * | 2015-02-15 | 2015-06-10 | 太原理工大学 | Electric-field-assisted diffusion bonding device and method for glass tubes and metal plates |
Non-Patent Citations (2)
| Title |
|---|
| "Al-glass-Al阳极键合界面及力学性能的分析";胡利方等;《焊接学报》;20180930;第39卷(第9期);第71-75页 * |
| "Synthesis and Bonding Performance of Conductive Polymer Containing Rare Earth Oxides";Chao Du et al.;《Journal of Inorganic and Organometallic Polymers and Materials》;20171101;第28卷;第746-750页 * |
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