CN110246769B - Eutectic bonding method based on in-situ metallization of cation conductive metal and glass surface - Google Patents
Eutectic bonding method based on in-situ metallization of cation conductive metal and glass surface Download PDFInfo
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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Abstract
The invention discloses a metal/glass surface in-situ metallization eutectic bonding method based on cation behavior in cation conductive glass under the action of multi-energy field recombination. The method comprises the following steps: the method comprises the steps of butting cation conductive glass with a metal substrate with a metal film pre-plated on the surface, placing the metal substrate in a vacuum furnace, respectively communicating the metal substrate with a positive electrode and a negative electrode, applying certain axial pressure and heating, activating cations in the glass at high temperature to ionize, loading a direct current electric field, forming directional migration transport by the cations, enriching the cations on the bonding surface of the glass, neutralizing the cations with free charges to generate an oxidation-reduction reaction to generate a simple substance, then growing a metal layer in situ in a surface micro-nano structure, and performing diffusion and eutectic reaction with the metal film to realize eutectic bonding. The invention has the advantages that the in-situ metal layer is closely attached to the surface of the glass to grow, the connection strength is high, the spreading and wetting properties of the glass surface after melting are excellent, and the reliable bonding of the metal and the glass can be realized without plating for many times.
Description
Technical Field
The invention relates to a packaging technology of a metal substrate and a glass wafer in the manufacturing process of an electronic device, in particular to a method for promoting the surface of cation conductive glass to separate out a metal simple substance and grow in situ through the composite action of a temperature field and a direct current electric field, and promoting a nickel-plated layer of the metal substrate and an in-situ metal layer on the surface of the cation conductive glass to generate low-temperature eutectic reaction at low temperature so as to realize reliable bonding of the metal substrate and the cation conductive glass wafer.
Background
The connection of the glass wafer and the metal substrate is widely applied to the fields of integrated circuit manufacturing, multifunctional chip integration and packaging of MEMS sensors, microfluidic chips and semiconductor chips. With the development of packaging technology towards high power, high integration and 3D vertical interconnection, increasingly stringent high-integration performance requirements are placed on the ultimate size, integration, heat dissipation and reliability of the glass wafer and metal substrate bonding technology.
The conventional wafer-level bonding technology for bonding a glass chip and a metal substrate mainly includes two types, namely, an intermediate layer (glass paste and eutectic bonding) and a non-intermediate layer (direct bonding and anodic bonding). 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. Compared with other bonding techniques, anodic bonding has the advantages of simple process, high bonding strength andthe principle of the method is that a silicon chip and glass are connected to two electrodes of a high-voltage electrode, and O is transferred under the conditions of high temperature (400-500 ℃), high voltage (800-1500V) and pressure2-Or non-bridging oxygen chemically reacts at the interface to form new chemical bonds such as Si-O-Si or O-M (M = Mg, Al, Cu and Ni), but high temperature, high voltage and poor conductive heat dissipation performance of the bonding region are the main problems faced by the technology.
It is easy to see that the anodic bonding process is simple and the wafer pitch is small, but it does not have the ohmic contact and excellent heat dissipation characteristic of eutectic bonding. In fact, the two bonding techniques have different connection principles, so that they form a good complementary relationship with each other in terms of advantages and disadvantages.
In view of the above, the invention aims at the connection of glass and silicon chip, takes the transport mechanism of the electro-cation substance as a tie, combines the principles of anodic bonding and eutectic bonding, and transfers carriers which are generated in the anodic bonding and participate in the interface reaction from O2-The method comprises the steps of changing to metal cations, leading out the cations on the surface of the glass based on cation migration and material transport characteristics of the cation conductive glass under certain temperature (lower than 200 ℃) and voltage (lower than 300V) conditions, neutralizing the cations with free electrons to form a metal simple substance, enabling the simple substance layer to grow in situ by clinging to the surface, further enabling the simple substance layer to perform low-temperature eutectic reaction with a coating (such as a tin coating) on the surface of a metal substrate to form a eutectic connection layer, and achieving reliable bonding of a glass wafer and the metal substrate, wherein the low-temperature eutectic connection layer has high heat conduction and electric conduction performance and is fatigue.
Disclosure of Invention
The invention aims to provide an in-situ metallized eutectic bonding method of metal and glass surface based on cation conduction, by preparing glass with cation conductivity and placing the glass under the composite action of a temperature field and an electric field, cations in the glass are subjected to migration, surface enrichment and redox reaction, thereby forming a metal layer grown in situ on the surface of the cation glass, realizing the surface metallization of the glass without coating, sputtering or ion implantation on the surface of the glass, further, the metal layer and the coating film (such as tin coating film) of the metal substrate are subjected to eutectic reaction at a lower temperature, high-reliability eutectic bonding of the cation conductive glass and the metal substrate is realized, and the method is a novel technology for bonding and packaging the glass wafer and the metal substrate, the method can be used in the fields of multifunctional chip integration, MEMS sensors, LEDs, photovoltaic devices, microfluidic chips, semiconductor chip packaging and the like.
In order to realize eutectic bonding of the nickel-plated metal substrate and the surface in-situ metallized cation conductive glass under the action of a composite field, the invention adopts the following technical scheme:
a metal and glass surface in-situ metallization eutectic bonding method based on cationic conduction comprises the following steps:
s1, preparing a to-be-bonded substrate: preparing cation conductive glass containing halide and sulfide of silver or oxide and halide of copper, and preparing a test piece; a metal film (e.g., a nickel plating film) is plated on the surface of the metal substrate.
S2, surface treatment of the substrate to be bonded: and (3) polishing the contact surfaces of the cation conductive glass test piece and the metal substrate surface coating film by using metallographic abrasive paper, and cleaning by using acetone.
S3, placing a substrate to be bonded: the positive ion conductive glass test piece is contacted with the film-coated surface of the metal substrate and is arranged between a positive plate and a negative plate in a vacuum bonding furnace in a butt joint mode, the non-contact surface of the positive ion conductive glass test piece is connected with the positive plate, the non-film-coated surface of the metal substrate is connected with the negative plate, the positive plate is communicated with the positive pole of a direct current power supply, the negative plate is communicated with the negative pole of the direct current power supply, and certain axial pressure is applied to the positive plate and the negative.
S4, in-situ metallization of the surface of the cation conductive glass: maintaining the vacuum environment in the furnace, heating the stacked test pieces in a vacuum bonding furnace to the ionization activation temperature of cations in the cation conductive glass test pieces, loading a direct current electric field between the positive plate and the negative plate to ensure that the ionized cations form directional movement and are enriched at the contact surface of the cation conductive glass, neutralizing free electrons transmitted by the negative plate to form metal simple substance precipitation, and keeping the temperature for t time1The precipitates are grown in situ and thickened at the contact surface of the cation-conducting glass.
S5, surface in situEutectic reaction of the metallization layer and the coating: thermal insulation t1After the time, the temperature is raised to the eutectic reaction temperature of the in-situ growth metal simple substance and the metal substrate coating material, at the moment, the external electric field can be kept unchanged or disconnected, and the temperature t is kept2And (3) fully performing diffusion reaction on the in-situ metal layer and the coated metal to form an eutectic connecting layer, forming physical embedding with the capillary structures on the surface of the cation conductive glass and the surface of the metal substrate, and naturally cooling the cation conductive glass test piece and the metal substrate connector to room temperature and taking out.
Preferably, in step S1, the cation conductive glass is formed by doping a borate, vanadate, phosphate, tellurate, chalcogenide or chalcohalide glass matrix with AgI, AgBr, Ag2S, CuI, 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 method for preparing the cation conductive glass based on the melt quenching method is described by taking a synthesis example of AgI-doped borate glass: preparing chemical pure AgI and Ag2O and B2O3As raw materials, the materials are 10-80 mol% AgI, 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, cooling the melt with two rollers, and reasonably adjusting the pressure of the two rollers to control the cooling rate of the melt to obtain the 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 into 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 during sinteringAt 10-1Pa 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 of AgI-Ag2PO3.5and their silver ion-conducting properties”，“Nonlinearimpedance as possible result of ion–polaron interaction in Cu2O–Al2O3–SiO2glass "and" chromatography and electrochemical cell chromatography of mesoporous synthesized AgI-Ag2O–MoO3amorphous 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 substrate is 0.1 to 5mm, the thickness of the surface coating film is 20 to 100 μm, and the roughness of the surface coating film 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 electrode plate, and a graphite paper is provided between the metal substrate and the negative electrode plate. The cation conductive glass test piece is not in direct contact with the positive plate, and the metal matrix is separated from the negative plate by graphite paper, so that the experimental materials and the electrodes are prevented from being polluted; the axial pressure is set to be 0.1-5 MPa.
Preferably, in step S4, the vacuum degree of the vacuum environment is 10-35Pa, the ionization activation temperature is changed according to the iodide, bromide, sulfide or oxide of different Ag or Cu doped in the step S1, and AgI-doped borate glass AgI-Ag2O-B2O3For example, Ag+The ionization activation temperature is 150 ℃ or above, the ionization activation temperature is lower than the temperature (the temperature ranges from 220 ℃ to 900 ℃) of eutectic reaction between the in-situ growth metal simple substance and the coating metal, the direct current field strength is 220V at the lowest, and the heat preservation time t is1Is 2-15 min.
Preferably, in step S5, AgI-Ag is used2O-B2O3For example, the eutectic reaction temperature is 230 ℃ and is higher than that of Ag/Sn, and the heat preservation time t is2Is 5-20 min.
The method of the invention integrates the anodic bonding and eutectic bonding processes of glass and metal, and can share the same device with the anodic bonding, step S4 is to realize the in-situ metallization of the bonding surface of the cation conductive glass by utilizing the cation migration performance of the cation conductive glass, while the traditional anodic bonding is realized by O2-Or migration of non-bridge oxygen and interface reaction to realize bonding between glass and metal. Step S5 is to form a eutectic connection layer by using a low-temperature eutectic reaction between the in-situ metallization layer and the metal substrate coating after the in-situ metallization of the surface of S4, thereby achieving bonding between the cation conductive glass and the metal substrate, whereas in the conventional eutectic bonding, a metal film is coated on the surface of the glass in advance by means of magnetron sputtering or plasma spraying, and the like, and step S5 uses the in-situ metal layer of the cation conductive glass as a eutectic reaction substance, so that the spreading wetting effect of the formed eutectic liquid with respect to the surface of the glass is excellent, the connection strength is remarkably improved, and the connection condition is reduced.
The invention has the following beneficial effects:
1. the metallized material on the surface of the glass is derived from material transportation generated by cation migration in the glass, cations are enriched on a cation bonding surface and undergo an oxidation-reduction reaction to form a metal simple substance corresponding to the cations, and the metal simple substance is attached to a rough fine structure of the surface and grows in situ after being precipitated on the surface, so that the connection strength of a coating film and the glass is greatly improved, the spreading, wetting and filling performances of the surface of the glass after a surface metal layer is melted can be remarkably 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 generally lower than the treatment temperature of metal or alloy by surface metallization methods such as laser coating and plasma spraying, so that the residual thermal stress caused by the mismatch of the thermal expansion coefficients of a coating film and the glass is remarkably reduced. No extra coating equipment is needed, the process is simple and the cost is low.
3. The in-situ metal layer on the surface of the cation conductive glass and the metal substrate coating film are subjected to eutectic reaction, so that on one hand, a eutectic liquid phase can be formed to fill the surface of the bonding material, on the other hand, the eutectic reaction temperature is low, the low-temperature connection between the cation conductive glass and the metal polar plate can be realized, and the eutectic connection layer has good conductive and heat-conducting properties and has application potential in the aspects of high-power device packaging and three-dimensional integrated packaging.
The invention has reasonable design and good popularization and application value.
Drawings
FIG. 1 is a schematic diagram of a eutectic bonding device based on in-situ metallization of metal and glass surfaces with cationic conduction.
FIG. 2 is a schematic diagram of the eutectic bonding process of the metal based on cationic conduction and the in-situ metallization of the glass surface.
FIG. 3 shows a tin-plated Cu substrate and AgI-Ag prepared by the method described in example 12O-MoO3The method comprises the steps of carrying out in-situ metallization on a eutectic bonding sample on the surface of conductive glass, carrying out tensile failure to expose a eutectic bonding structure photo, and carrying out an X-ray diffraction pattern of the eutectic bonding layer.
In the figure: 1-furnace body, 2-power line, 3-direct current power supply, 4-current recording device, 5-resistor, 6-vacuum pump, 7-heating device, 8-control panel, 9-support plate, 10-pressing plate, 11-positive plate, 12-negative plate, 13-cation conductive glass test piece, 14-metal substrate, 15-metal coating film, 16-surface in-situ metal layer, 17-eutectic reaction liquid phase and 18-eutectic connecting layer.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
The glass and metal surface in-situ metallization eutectic bonding method based on cation conduction is used for a bonding packaging process of cation conduction glass and a metal substrate, a bonding intermediate layer is formed by cation reaction in the cation conduction glass after being activated by a composite field and grows in situ at a bonding surface of the cation conduction glass, and surface coating, sputtering or ion implantation is not needed. Specific examples are as follows.
Example 1
An in-situ metallized eutectic bonding method for glass and metal surfaces based on cationic conduction comprises the following steps:
the first step is as follows: selection of AgI-Ag with high conductivity and low ionization activation energy2O-MoO3The 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 AgI, Ag2O and MoO3As raw materials, the materials are 60mol percent AgI and Ag2O and MoO3The preparation method comprises the steps of mixing the components in an equimolar ratio, mixing the components fully, placing the mixture in a quartz glass tube with an opening at one end, heating the mixture in an electric heating furnace to 480-800 ℃ to melt the mixture, cooling the melt through a double roller, reasonably adjusting the pressure of the double roller to control the cooling rate of the melt, processing the glass into a cationic conductive glass test piece 13 with the thickness of 2mm and 15mm × 15mm, selecting a copper (Cu) substrate with the thickness of 1mm as a metal substrate 14 to be connected, plating an Sn layer (a metal plating film 15) on the surface in a plasma spraying or magnetron sputtering mode, wherein the thickness of the Sn film is 50 mu m, and cutting the Sn-plated metal substrate into test pieces with the thickness of 15mm × 15 mm.
The second step is that: polishing cation (Ag) using metallographic abrasive paper+) The bonding surfaces of the conductive glass test piece 13 and the Sn plating film 15 are set such that the surface roughness Ra = 0.5-1.2 μm of the cationic conductive glass test piece 13 and the surface roughness Ra = 0.1-0.3 μm of the Sn plating film 15. And cleaning the surface to be bonded by using acetone after polishing.
The third step: as shown in FIG. 1, Ag is added+The conductive glass test piece 13 is contacted with one side of the Sn-plated layer of the Cu substrate, is combined in a butt joint mode and is arranged between the positive plate 11 and the negative plate 12 of the vacuum bonding furnace, and Ag+Graphite paper is arranged between the non-bonding surface of the conductive glass test piece 13 and the positive plate 11, and graphite paper is arranged between the non-film-coated surface of the Cu substrate 14 and the negative plate 12. The axial pressure between the positive electrode plate 11 and the negative electrode plate 12 was set to 2 MPa.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-3~10-5Pa, after the temperature is raised to 150 ℃, applying a 260V direct current electric field between the positive plate and the negative plate, loading for 10min, preserving the heat for 10min, and activating AgI-Ag2O-MoO3Ag in silver ion conductive glass 13+To make it generate migration and material transport and combine in Ag+The contact surface of the conductive glass 13 and the Sn-plated layer is separated out to form a surface in-situ metallized Ag layer 16 shown in figure 2 (b), and the simple substance Ag layer is tightly attached to Ag+The surface of the conductive glass test piece 13 grows in situ.
The fifth step: after the heat preservation is finished, the temperature in the furnace is increased to 230 ℃ (higher than the Ag/Sn eutectic reaction temperature), the voltage is kept unchanged, and the heat preservation is carried out for 10min to ensure that the Ag is contained+Eutectic reaction occurs between the surface in-situ Ag layer of the conductive glass test piece 13 and the Sn coating film to form a liquid phase 17 until the surface in-situ Ag layer is completely consumed and part of the Sn coating film is still not melted, and thenβ-Sn phase and high melting point Ag3And precipitating the Sn phase from the liquid phase to form an eutectic connecting layer 18, cooling to room temperature along with the furnace after heat preservation is finished, and taking out the sample wafer.
FIG. 3 is Ag+After the conductive glass test piece 13 and the tinned Cu substrate are connected by the method, a digital photo of a joint after tensile fracture and an X-ray diffraction pattern of an Ag/Sn eutectic reaction product show that: the eutectic reaction product is mainly composed ofβ-Sn，Cu6Sn5And Ag3Sn composition, wherein Cu6Sn5Is an intermetallic compound generated by the reaction of the Cu substrate and the Sn plating film.
Example 2
An in-situ metallized eutectic bonding method for glass and metal surfaces based on cationic conduction comprises the following steps:
the first step is as follows: selection of AgI-Ag with high conductivity and low ionization activation energy2O-V2O5The 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 AgI, Ag2O and V2O5As raw materials, the materials are 50mol percent AgI and Ag2O/ V2O5Mixing completely in a molar ratio of =0.67:0.33, weighing 5g of mixed powder in a 250mL agate ball mill tank, putting agate grinding balls with the diameter of 10mm, the ball-to-material ratio is 10:1, adding 10mL acetone 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 SPS in the graphite moldSintering the system at 900-1200 ℃ under 70MPa of axial pressure and 10 of vacuum degree in the sintering process-1Pa, processing glass into a test piece 14 with the thickness of 2mm and 15mm × 15mm, selecting an aluminum (Al) substrate with the thickness of 1mm as a metal substrate to be connected, plating an Sn film 15 on the surface by a plasma spraying or magnetron sputtering mode, wherein the thickness of the Sn film 15 is 50 μm, and cutting the Sn-plated metal substrate into test pieces with the thickness of 15mm × 15 mm.
The second step is that: polishing the bonding surfaces of the cation conductive glass test piece 14 and the Sn plating film 15 by using metallographic abrasive paper to ensure that the surface roughness Ra = 0.5-1.2 μm of the cation conductive glass test piece 13 and the surface roughness Ra = 0.1-0.3 μm of the Al substrate 14. 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 13 is brought into contact with one side of an Sn plating film 15 of an Al substrate 14 and is combined in a butt joint manner and placed between a positive electrode plate 11 and a negative electrode plate 12, graphite paper is provided between a non-bonding surface of the cation conductive glass test piece 13 and the positive electrode plate 11, and graphite paper is provided between a non-bonding surface of the Al substrate 14 and the negative electrode plate 12. The axial pressure between the positive plate 11 and the negative plate 12 is 1-2 MPa.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-3~10-5Pa, after the temperature is raised to 150 ℃, applying a 260V direct current electric field between the positive and negative plates, loading for 10min, keeping the temperature for 10min, activating the ionization of Ag + in the cationic conductive glass test piece 13, so that the Ag + is migrated and transported and is separated out at the contact surface of the cationic conductive glass and the Al substrate 14 to form an Ag single substance layer 16 shown in figure 2 (b), and the single substance layer grows in situ by clinging to the surface of the cationic conductive glass test piece 13.
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, 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 13 and the Sn plating film 15 have eutectic reaction to form a liquid phase to generateβ-Sn phase and high melting point Ag3And precipitating the Sn phase from the liquid phase to form an eutectic connecting layer 18, cooling to room temperature along with the furnace after heat preservation is finished, and taking out the sample wafer.
Example 3
An in-situ metallized eutectic bonding method for glass and metal surfaces based on cationic conduction comprises 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 carrying out double-roll cooling on the melt, reasonably adjusting the pressure of the double rolls 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 × 15mm, selecting a Cu substrate with the thickness of 1mm as a metal substrate to be connected, plating an Sn film 15 on the surface of the Cu substrate by means of plasma spraying or magnetron sputtering, wherein the thickness of the Sn film 15 is 50 mu m, and cutting the Sn-plated metal substrate into a test piece with the thickness of 15mm × 15 mm.
The second step is that: polishing the bonding surfaces of the cation conductive glass test piece 13 and the Sn plating film 15 by using metallographic abrasive paper to ensure that the surface roughness Ra = 0.5-1.2 μm of the cation conductive glass test piece 13 and the surface roughness Ra = 0.1-0.3 μm of the Sn plating film 15. And cleaning the surface to be bonded by using acetone after polishing.
The third step: as shown in FIG. 1, a cationic conductive glass test piece 13 is contacted with the Sn layer plated side of a Cu substrate, and is combined in a butt joint mode and placed between a positive plate 11 and a negative plate 12 of a vacuum bonding furnace, graphite paper is arranged between the non-bonding surface of the conductive glass test piece 13 and the positive plate 11, and graphite paper is arranged between the non-coating surface of the Cu substrate 14 and the negative plate 12. The axial pressure between the positive plate 11 and the negative plate 12 is 1-2 MPa.
The fourth step: vacuumizing to maintain the vacuum degree in the furnace at 10-4~10-2Pa, after the temperature rises to 200 ℃, applying a 280V direct current electric field between the positive plate and the negative plate, loading for 10min, preserving the heat for 10min, and activating Cu in the cation conductive glass test piece 13+Is ionized to generate migration and material transportation and is precipitated at the contact surface of the glass and the Sn plating film 15 to form a Cu sheet as shown in figure 2 (b)And a substance layer 16, wherein the simple substance layer grows in situ by clinging to the surface of the cationic conductive glass test piece 13.
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 13 and the Sn plating film 15 are subjected to eutectic reaction to form a liquid phase, and the high-melting-point Cu is generated6Sn5And precipitating the eutectic structure connecting layer 18 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 short, the method of the invention contacts the cation conductive glass with the coating side of the metal substrate, and is butt-jointed between a positive electrode and a negative electrode in a vacuum furnace, a certain axial pressure is applied and the glass is heated, 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 the glass negative electrode, the cations neutralize free charges to generate redox reaction to generate simple substances, then a metal layer is formed by in-situ growth in a surface micro-nano structure, and diffusion or eutectic reaction is carried out with the contact coating, thereby realizing eutectic bonding of the cation conductive glass and the metal substrate. 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, the welding and packaging performance of the glass is obviously improved, the eutectic bonding temperature is low, the connection strength is high, the bonding layer has excellent electric conduction and heat conduction performance, and the invention is suitable for the high-integration vertical interconnection between wafers.
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 (8)
1. An in-situ metallization eutectic bonding method based on cation conductive metal and glass surface is characterized in that: the method comprises the following steps:
s1, preparing cation conductive glass containing halide and sulfide of silver or oxide and halide of copper, plating a metal film on the surface of the metal substrate, and preparing test pieces;
s2, polishing the contact surfaces of the cation conductive glass test piece and the metal substrate coating film by using metallographic abrasive paper and cleaning by using acetone;
s3, contacting the cationic conductive glass test piece with the coated surface of the metal substrate, and butting the cationic conductive glass test piece and the coated surface of the metal substrate between a positive plate and a negative plate in a vacuum bonding furnace, wherein the non-bonding surface of the cationic conductive glass test piece is connected with the positive plate, and the non-coated surface of the metal substrate is connected with the negative plate; the positive plate is communicated with the positive pole of the direct current power supply, the negative plate is communicated with the negative pole of the direct current power supply, and axial pressure is applied to the positive plate and the negative plate;
s4, maintaining the vacuum environment in the furnace, heating the stacked test pieces in a vacuum bonding furnace to the ionization activation temperature of cations in the cation conductive glass test pieces, loading a direct current electric field between the positive and negative plates to make the ionized cations move directionally and be enriched at the contact surface of the cation conductive glass, neutralizing free electrons transmitted by the negative plate to form metal simple substance precipitation, and keeping the temperature for t time1Enabling the precipitate to grow in situ and thicken at the contact surface of the cation conductive glass;
s5, carrying out eutectic reaction between the surface in-situ metallization layer and the coating film: thermal insulation t1After the time, the temperature is raised to the eutectic reaction temperature of the in-situ growth metal simple substance and the metal substrate coating material, at the moment, the external electric field is kept unchanged or disconnected, and the temperature is kept t2And (3) fully performing diffusion reaction on the in-situ metallization layer and the metal coating to form an eutectic connection layer, forming physical embedding with the capillary structures on the surface of the cation conductive glass and the surface of the metal substrate, and naturally cooling the cation conductive glass test piece and the metal substrate connector to room temperature and taking out.
2. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 1, characterized in that: in step S1, the cation conductive glass is prepared by adding borate or vanadateAgI, AgBr, Ag are doped in phosphate, tellurate, sulfur series or sulfur halide series glass matrix2S, CuI, CuBr or Cu2O is one or more of.
3. The eutectic bonding method based on the in-situ metallization of a cationic conductive metal and a glass surface according to claim 1 or 2, characterized in that: in step S2, the thickness of the cationic conductive glass test piece is 0.5-5 mm, and the roughness of the contact surface is Ra = 0.5-1.2 μm; the thickness of the metal substrate is 0.1-5 mm, the thickness of the surface coating film is 20-100 μm, and the roughness of the coating film surface is Ra = 0.1-0.3 μm.
4. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 3, characterized in that: in step S3, graphite paper is provided between the positive electrode plate and the positive ion conductive glass test piece, and graphite paper is provided between the metal substrate and the negative electrode plate.
5. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 4, characterized in that: in step S3, the axial pressure is set to 0.1-5 MPa.
6. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 5, characterized in that: in step S4, the vacuum degree of the vacuum environment is 10-3~10-5Pa, the ionization activation temperature is lower than the temperature of eutectic reaction between the in-situ growth metal simple substance and the coating metal, the DC electric field strength is 220V at the lowest, and the heat preservation time t1Is 2-15 min.
7. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 6, characterized in that: in step S5, the heat retention time t2Is 5-20 min.
8. The eutectic bonding method based on in-situ metallization of a cationic conductive metal and a glass surface according to claim 2, characterized in that: in step S1, the method for preparing the cationic conductive glass includes a melt quenching method and a mechanochemical synthesis method.
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