CN109912237A - Surface in situ method for metallising based on cationic electroconductive glass - Google Patents
Surface in situ method for metallising based on cationic electroconductive glass Download PDFInfo
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Abstract
The invention discloses the method for surface metallation under a kind of temperature field-electric field compound action based on cation transport in cationic electroconductive glass, reaction and growth in situ.This method are as follows: cationic electroconductive glass is docked with metal foil and is placed in vacuum drying oven between positive and negative electrode, apply certain axial compressive force and heating, cation is ionized by activation at high temperature in glass, load DC electric field, cation forms directional migration and transports, and in glass negative side surface enrichment, with in free charge and occur redox reaction generate simple substance, then growth in situ forms metal layer in surface micro-nano structure, and diffusion or eutectic reaction occurs with metal foil is docked, it avoids metal layer from contacting with electrode and increases metallization thickness.Using it is an advantage of the present invention that metal layer fits closely glass surface growth, bonding strength is high, after metal layer fusing to glass surface sprawl and wettability is splendid, be obviously improved welding and the encapsulation performance of glass.
Description
Technical field
The present invention relates to surface metalization techniques of the glass before soldering or eutectic bonding, specially a kind of temperature field-is straight
The surface in situ method for metallising of cationic electroconductive glass under the compound action of galvanic electricity field.
Background technique
The connection of glass and metal (semiconductor) material, is widely used in IC manufacturing, multifunction chip it is integrated and
The encapsulation field of MEMS sensor, micro-fluidic chip and semiconductor chip.As encapsulation technology is towards high power, high integration and 3D
The direction of perpendicular interconnection is developed, to the dimension limit of glass and metal or semiconductor material bonding techniques, integrated level, thermal diffusivity and
Reliability proposes increasingly harsh high combination property demand.
Common glass and heterogeneous material bonding method have anode linkage, Direct Bonding and eutectic bonding.Anode linkage
One of matrix to be connected must have O2-Conductive or non-bridging oxygen transfer ability glass, principle are to connect silicon wafer and glass
On high-field electrode the two poles of the earth, under high temperature (400 DEG C ~ 500 DEG C), high voltage (800V ~ 1500V) and pressure condition, make to migrate O2-Or
Non-bridging oxygen is chemically reacted in interface, formed Si-O-Si or O-M(M=Mg, Al, Cu and Ni) etc. new chemical bond, thus
Realize being bonded for glass and silicon or metal.
Compared to other bonding techniques, anode linkage has many advantages, such as that simple process, bond strength are high and leakproofness is good, but
High temperature, the poor conductive radiator performance of high voltage and bond area are the main problem that the technology faces.Direct Bonding is general
The connection being only limited between silicon wafer, principle be by the smooth silicon wafer in two panels surface by pretreatment after in certain temperature and pressure
It is connected under power, and finally realizes bonding by 800 DEG C or more of high annealing.Generally require the surface roughness to be bonded of silicon wafer
Lower than 10nm, for the depth of parallelism less than 3 μm, surface warp is lower than 25 μm, since bonding is to surface roughness (being lower than 10nm) and annealing
(800 DEG C or more) requirements of temperature are very high, cause bonding packaging at high cost, and high temperature is caused to generate biggish remnants between keying element and be answered
Power.Eutectic bonding is using metal as transition zone, intermetallic compound is formed by eutectic reaction, to realize chip linkage
A kind of indirect linkage technology closed.Bonding technology is low, small by surface roughness affect with temperature, thermal diffusivity is good, can be formed
The advantages such as Ohmic contact between chip, but there are still eutectic liquid is poor with respect to the wetability of matrix, Coating complex process plate more
Layer structure also results in the problems such as chip spacing is excessive, and the intermetallic species and distribution for reacting generation are difficult to control.According to
According to each bonding pattern feature, the bonding techniques of glass and semiconductor or metal material be divided into without intermediate interlayer include anode linkage and
Direct Bonding and there are intermediate interlayer and two kinds of eutectic bonding.No intermediate interlayer bonding usually requires higher bonding temperature (sun
Pole is bonded 400 DEG C or more, 800 DEG C of Direct Bonding or more), and the electrical and thermal conductivity of bond area is poor, it is difficult to adapt to it is high-power and
The encapsulation requirement of highly integrated device.Therefore, technological improvement is carried out on the basis of having intermediate interlayer i.e. eutectic bonding, is to realize height
The important way of comprehensive performance encapsulation.
In view of this, poor to the wetability of matrix for intermediate interlayer existing for eutectic bonding, Coating technique is multiple
The problems such as miscellaneous, chip spacing is big, and the intermetallic species and distribution for reacting generation are difficult to control, the present invention is based on cations
The cation transport and transport of substances that electro-conductive glass has under the conditions of certain temperature (being lower than 200 DEG C) and voltage (being lower than 300V)
Characteristic, by cation in glass surface export and in free electron and form metal simple-substance, and simple substance layer urged against surface original position
The metallization in situ of cationic electroconductive glass surface is realized in growth.
Summary of the invention
Object of the present invention is to propose a kind of cationic electroconductive glass surface original position method for metallising, cationic electroconductive glass is promoted
After the bonding strength of glass surface metal-layer and matrix, and fusing to matrix sprawl and wetting effect, and without to cation
Conductive glass surface, which carries out coating, sputtering or ion implanting, can be realized its surface metalation, can be used for cationic electroconductive glass
Soldering and eutectic bonding field.
To realize that cationic electroconductive glass surface metallizes in situ, The technical solution adopted by the invention is as follows:
A kind of surface in situ method for metallising based on cationic electroconductive glass, includes the following steps:
The halide of S1, preparation containing silver, sulfide, or the cationic electroconductive glass of the oxide containing copper, halide, and make
Make test piece;
S2, cationic electroconductive glass coupon and the metal foil contact surface of being polished using abrasive paper for metallograph are simultaneously cleaned with acetone;
S3, it cationic electroconductive glass coupon is docked with metal foil is placed between positive pole plate and power cathode plate, cation
Electro-conductive glass test piece is connected with positive pole plate, and metal foil is connected with power cathode plate;
S4, keep vacuum environment in furnace, setting axial compressive force is 1 ~ 3MPa, in furnace heating temperature be 150 ~ 400 DEG C, keep the temperature 2 ~
20min, DC voltage are 200 ~ 400V, 2 ~ 10min of load time;Load axial compressive force is simultaneously warming up to the examination of cationic electroconductive glass
Cationic ionization activationary temperature, then loads DC electric field in piece, makes to ionize ion formation directional migration;
S5, stop heating and simultaneously close external electric field, then allow cationic electroconductive glass coupon and metal foil connector natural cooling
To room temperature and take out.
Preferably, in step S1, cationic electroconductive glass passes through in borate, vanadate, phosphate, tellurate, sulphur system
Or Ag I, AgBr, Ag are adulterated in sulphur halogen system glass matrix2S, Cu I, CuBr or Cu2One of O or a variety of is made.The cation
The preparation method of electro-conductive glass includes melt quenching method and mechanochemical synthesis.One, to adulterate the conjunction of the borate glass of Ag I
As example, the method that cationic electroconductive glass is prepared based on melt quenching method is illustrated: preparing the pure grade Ag I of chemistry, Ag2O and B2O3Make
For raw material, material presses 10 ~ 80mol%Ag I, Ag2O/B2O3=3 proportion is sufficiently mixed, and is placed in quartz glass tube open at one end
It is interior, it is heated to 480 ~ 800 DEG C in electrothermal furnace and causes its fusing, subsequent melt is cooling through double roller, reasonably adjusts double roller pressure therebetween
To control solution cooling rate, Ag is finally obtained+Electro-conductive glass.Two, to contain Ag2The Ag of S2S-Sb2S3The synthesis of chalcogenide glass
For, it illustrates the method that cationic electroconductive glass is prepared based on mechanochemical synthesis: preparing the pure grade Ag of chemistry2S and Sb2S3, press
Equimolar weighs 5g mixed-powder in 250mL agate jar than mixing, is put into the agate that 10 diameters are 10mm and grinds
Ball, and 10mL acetone is added as process control agent, with the revolving speed of 400rpm in planetary ball mill ball milling 10h, it is temporary every 3h
Stop 30min, and powder after ball milling is placed in a vacuum drying oven dry 2h, the powder after drying is fitted into graphite jig, is put
Enter SPS system to be sintered, sintering temperature is 980 ~ 1140 DEG C, axial compressive force 70MPa, and vacuum degree is maintained in sintering process
10-1Pa or so.It is similar that different glass matrix and cationic compound adulterate its preparation principle, but process and parameter are not
Together, it can refer to " the Mechano-chemical synthesis of amorphous solids in that published thesis
system AgI–Ag2PO3.5And their silver ion-conducting properties ", " Nonlinear
impedance as possible result of ion–polaron interaction in Cu2O–Al2O3–SiO2
Glass " and " Characterization and electrochemical cell characteristics of
mechanochemically synthesized AgI–Ag2O–MoO3 amorphous superionic system”。
Preferably, in step S2, the roughness with a thickness of 0.5 ~ 5mm, contact surface of cationic electroconductive glass coupon is
Ra=0.5 ~ 1.2 μm, the roughness with a thickness of 0.1 ~ 1mm, contact surface of metal foil are Ra=0.1 ~ 0.3 μm.
Preferably, in step S3, between cationic electroconductive glass coupon and positive pole plate be equipped with graphite paper, metal foil with
Graphite paper is equipped between power cathode plate.Cationic electroconductive glass coupon is not direct with positive plate, metal foil and negative plate
Contact, but separated with graphite paper, prevent experimental material from mutually polluting with electrode.
The method of the invention is similar to the anodic bonding process of glass and metal, and this method can share same with anode linkage
Kind of device, but be bonded with conventional anode the difference is that: I, this method purpose is to the progress of cationic electroconductive glass surface
Metalized connect after allowing for cation export surface with metal foil, has stronger oxidisability, Strong oxdiative under high temperature
Property ion reacted with electrode material, cause mutually to pollute, therefore, glass and electrode separated with the metastable metal foil of performance,
The mutual pollution for not only avoiding electrode and glass surface further increases the thickness of cationic electroconductive glass surface metallization;Ⅱ,
Anode linkage passes through O2-Or non-bridging oxygen migration and interfacial reaction realize being bonded for glass and metal, our rule is based on cation
Migration and interfacial reaction realize glass surface metallization.
The invention has the following advantages:
1, the coating material of glass surface is derived from the transport of substances that inside glass cation transport generates, and coating material is analysed on surface
The coarse fine structure growth in situ of coating surface after out, to greatly improve the bonding strength of coating and glass, and aobvious
It writes after improving surface metal-layer fusing to the sprawling of glass surface, soak and filling capacity, reduce glass and dissimilar materials welds
Or the difficulty of bonding.
2, surface in situ metallizing temperature is related with ionization activation energy cationic in cationic electroconductive glass and conductivity,
Required temperature is usually less than the method for surface metallation such as coating produced by laser cladding and plasma spraying to the treatment temperature of metal or alloy, from
And the residual thermal stress due to caused by coating and thermal expansion coefficient of glass mismatch is significantly reduced, and further spread with metal foil
Connection forms that thickness is adjustable and the coat of metal of high reliablity.
3, surface in situ method for metallising is low for equipment requirements, without using additional coater, simple process and cost
It is low.
The present invention has rational design, has good application value.
Detailed description of the invention
Fig. 1 shows the present invention is based on the surface in situ metallization apparatus schematic diagrames of cationic electroconductive glass.
The surface in situ metallization processes schematic diagram of Fig. 2 expression subject cationic electro-conductive glass.
Fig. 3 indicates to prepare Ag by 1 the method for embodiment+Conductive glass surface original position metallization sample, is based on atom
Force microscope (AFM) and X-ray diffractometer test Ag+The microscopic appearance of ionic conducting glass surface in situ metal layer, roughness
And object phase composition, obtain Ag+The atomic force micrograph and X-ray diffractogram of ionic conducting glass surface in situ metal layer.
In figure: 1- furnace body, 2- vacuum plant, 3- contact conductor, 4- DC power supply, 5- resistance, 6- electric current recording device, 7-
Heating device, 8- control panel, 9- support plate, 10- pressing plate, 11- power cathode plate, 12- positive pole plate, 13- metal foil,
14- cationic electroconductive glass coupon, 15- cation glass surface coarse structure, 16- surface in situ metal layer, the connection of 17- eutectic
Layer.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing, it should be apparent that, for these realities
The explanation for applying mode is used to help understand the present invention, but and does not constitute a limitation of the invention.Implement in addition, following present invention are each
Involved technical characteristic can be combined with each other as long as they do not conflict with each other in mode.
Embodiment 1
A kind of surface in situ method for metallising based on cationic electroconductive glass, for assisting cationic electroconductive glass to be brazed or key
The surface metal-layer of conjunction is formed by the cationoid reaction in cationic electroconductive glass after by compound field activation, is applied without surface
Plating, sputtering or ion implanting, and carry out in accordance with the following steps:
Step 1: selection has the I-Ag of Ag of high conductivity and low ionization activation energy2O-B2O3Silver ion electro-conductive glass is as surface
Metallization exemplar in situ, preparation process are as follows: prepare the pure grade Ag I of chemistry, Ag2O and B2O3As raw material, material presses 60mol%Ag
I, Ag2O/B2O3=3 proportion is sufficiently mixed, and is placed in quartz glass tube open at one end, 480 ~ 800 are heated in electrothermal furnace
DEG C cause its fusing, subsequent melt is cooling through double roller, reasonably adjust double roller pressure therebetween to control solution cooling rate, by glass plus
Work is the test piece 14 of thickness 2mm and 15mm × 15mm;Select tin (Sn) foil as the I-Ag of Ag2O-B2O3Silver ion conduction glass
Interlayer between glass and cathode with a thickness of 50 μm and is cut into the test piece 13 of 15mm × 15mm.
Step 2: polished the bonding surface of cationic electroconductive glass coupon 14 and Sn foil 13 using abrasive paper for metallograph, make sun from
Surface roughness Ra=0.5 ~ 1.2 μm of subconductive glass test piece 14, surface roughness Ra=0.1 ~ 0.3 μm of Sn foil 13.Polishing
Surface to be bonded is cleaned using acetone afterwards.
Step 3: as shown in Figure 1, cationic electroconductive glass coupon 14 combining juxtaposition by the way of docking with Sn foil 13
Between positive pole plate 12 and power cathode plate 11, stone is equipped between cationic electroconductive glass coupon 14 and positive pole plate 12
Black paper is equipped with graphite paper between metal foil 13 and power cathode plate 11.
Step 4: vacuumizing makes vacuum degree in furnace be maintained at 10-4~10-2Pa, setting axial compressive force are 2MPa, and temperature rises to
After 150 DEG C, apply 230V DC electric field between positive/negative plate, load time 10min keeps the temperature 10min, activatable cationic conduction glass
The ionization of Ag+ in glass test piece 14 brings it about migration and transport of substances and is precipitated at the contact surface of glass and Sn foil 13, formed
Ag simple substance layer 16 as shown in Figure 2, the simple substance layer are close to the surface in situ growth of cationic electroconductive glass coupon 14.
Step 5: temperature to be further promoted to 230 DEG C (being higher than Ag/Sn eutectic reaction temperature), voltage after heat preservation
It remains unchanged, heat preservation 10min makes the surface in situ Ag layer 16 of cationic electroconductive glass coupon 14 and Sn foil 13 that eutectic reaction occur
Liquid phase is formed, high-melting-point Ag is generated3Sn phase andβ- Sn is mutually precipitated from liquid phase and forms eutectic articulamentum 17, with furnace after heat preservation
It is cooled to room temperature, and takes out print.Fig. 3 is the atomic force microscopy that cationic electroconductive glass coupon surface in situ grows Ag layers
(AFM) photo and Ag layers of growth in situ of X-ray diffractogram, characterization result show: the ingredient that Ag layers of growth in situ is polycrystalline face
There is the diffraction maximum of (111) and (200) crystal face in the X-ray diffractogram in the heart cube (fcc) structure Ag simple substance, in situ raw
Long Ag layers of surface roughness is 3.98nm.
Embodiment 2
A kind of surface in situ method for metallising based on cationic electroconductive glass, for assisting cationic electroconductive glass to be brazed or key
The surface metal-layer of conjunction is formed by the cationoid reaction in cationic electroconductive glass after by compound field activation, is applied without surface
Plating, sputtering or ion implanting, and carry out in accordance with the following steps:
Step 1: selection has the I-Ag of Ag of high conductivity and low ionization activation energy2O-B2O3Silver ion electro-conductive glass is as surface
Metallization exemplar in situ, preparation process are as follows: prepare the pure grade Ag I of chemistry, Ag2O and V2O5As raw material, material presses 50mol%Ag
I, Ag2O/ V2O5The proportion of=0.67:0.33 is sufficiently mixed, and is weighed 5g mixed-powder in 250mL agate jar, is put into 10
Diameter is the agate mill ball of 10mm, and 10mL acetone is added as process control agent, is expert at celestial body with the revolving speed of 400rpm
Ball milling 10h in grinding machine suspends 30min every 3h, and powder after ball milling is placed in a vacuum drying oven dry 2h, after drying
Powder is fitted into graphite jig, is put into SPS system and is sintered, and sintering temperature is 900 ~ 1200 DEG C, and axial compressive force is
70MPa, vacuum degree is maintained at 10 in sintering process-1Pa or so.It is the test piece of thickness 2mm and 15mm × 15mm by glass processing
14, select aluminium (Al) foil as the I-Ag of Ag2O-B2O3Interlayer between silver ion electro-conductive glass and cathode, simultaneously with a thickness of 50 μm
It is cut into the test piece 13 of 15mm × 15mm.
Step 2: polished the bonding surface of cationic electroconductive glass coupon 14 and Al foil 13 using abrasive paper for metallograph, make sun from
Surface roughness Ra=0.5 ~ 1.2 μm of subconductive glass test piece 14, surface roughness Ra=0.1 ~ 0.3 μm of Al foil 13.Polishing
Surface to be bonded is cleaned using acetone afterwards.
Step 3: as shown in Figure 1, cationic electroconductive glass coupon 14 combining juxtaposition by the way of docking with Al foil 13
Between positive pole plate 12 and power cathode plate 11, stone is equipped between cationic electroconductive glass coupon 14 and positive pole plate 12
Black paper is equipped with graphite paper between metal foil 13 and power cathode plate 11.
Step 4: vacuumizing makes vacuum degree in furnace be maintained at 10-4~10-2Pa, setting axial compressive force are 1 ~ 2MPa, temperature liter
To after 150 DEG C, apply 230V DC electric field between positive/negative plate, load time 10min keeps the temperature 10min, and activatable cationic is conductive
The ionization of Ag+ in glass coupon 14 brings it about migration and transport of substances and is precipitated at the contact surface of glass and Al foil 13, shape
At Ag simple substance layer 16 as shown in Figure 2, which is close to the surface in situ growth of cationic electroconductive glass coupon 14.
Step 5: temperature to be further promoted to 490 DEG C (being higher than Ag/Al eutectic reaction temperature), voltage after heat preservation
It remains unchanged, heat preservation 10min makes the surface in situ Ag layer 16 of cationic electroconductive glass coupon 14 and Al foil 13 that eutectic reaction occur
Liquid phase is formed, high-melting-point is generatedμ-Ag3The eutectic articulamentum 17 of Al phase and Al matrix phase is precipitated from liquid phase, after heat preservation
It cools to room temperature with the furnace, and takes out print.
Embodiment 3
A kind of surface in situ method for metallising based on cationic electroconductive glass, for assisting cationic electroconductive glass to be brazed or key
The surface metal-layer of conjunction is formed by the cationoid reaction in cationic electroconductive glass after by compound field activation, is applied without surface
Plating, sputtering or ion implanting, and carry out in accordance with the following steps:
Step 1: selection has the Cu of high conductivity and low ionization activation energy2O-Al2O3-SiO2Copper ion electro-conductive glass is as table
Metallize exemplar in situ in face, preparation process are as follows: press 12.5%CuO-12.5%Al2O3-75%SiO2Molar ratio through 400rpm turn
Fast abrading-ball 2h, and it is put into Al2O31550 DEG C of meltings are heated in crucible, subsequent melt is cooling through double roller, reasonably adjusts double roller therebetween
Pressure obtains flake glass to control solution cooling rate, is processed into the test piece for being 15mm × 15mm with a thickness of 2mm area
14;Select Sn foil as the Cu2O-Al2O3-SiO2Interlayer between copper ion electro-conductive glass and cathode with a thickness of 50 μm and is cut
It is cut into the test piece 13 of 15mm × 15mm.
Step 2: polished the bonding surface of cationic electroconductive glass coupon 14 and Sn foil 13 using abrasive paper for metallograph, make sun from
Surface roughness Ra=0.5 ~ 1.2 μm of subconductive glass test piece 14, surface roughness Ra=0.1 ~ 0.3 μm of Sn foil 13.Polishing
Surface to be bonded is cleaned using acetone afterwards.
Step 3: as shown in Figure 1, cationic electroconductive glass coupon 14 combining juxtaposition by the way of docking with Sn foil 13
Between positive plate 12 and negative plate 11, graphite paper, gold are equipped between cationic electroconductive glass coupon 14 and positive pole plate 12
Belong to and is equipped with graphite paper between foil 13 and power cathode plate 11.
Step 4: vacuumizing makes vacuum degree in furnace be maintained at 10-4~10-2Pa, setting axial compressive force are 1 ~ 2MPa, temperature liter
To after 200 DEG C, apply 280V DC electric field between positive/negative plate, load time 10min keeps the temperature 10min, and activatable cationic is conductive
Cu in glass coupon 14+Ionization, bring it about migration and transport of substances and be precipitated at the contact surface of glass and Sn foil 13, shape
At Cu simple substance layer 16 as shown in Figure 2, which is close to the surface in situ growth of cationic electroconductive glass coupon 14.
Step 5: temperature to be further promoted to 240 DEG C (being higher than Cu/Sn eutectic reaction temperature), voltage after heat preservation
It remains unchanged, heat preservation 10min makes the surface in situ Cu layer 16 of cationic electroconductive glass coupon 14 and Sn foil 13 that eutectic reaction occur
Liquid phase is formed, high-melting-point Cu is generated6Sn5Mutually it is precipitated from liquid phase with the Eutectic Layer 17 of Sn matrix phase, it is cold with furnace after heat preservation
But to room temperature, and print is taken out.
It is placed in vacuum drying oven between positive and negative electrode in short, the method for the present invention docks cationic electroconductive glass with metal foil,
Apply certain axial compressive force and heating, cation is ionized by activation at high temperature in glass, loads DC electric field, it is positive from
Son forms directional migration and transports, and in glass negative side surface enrichment, generates with free charge with generation redox reaction
Simple substance, then growth in situ forms metal layer in surface micro-nano structure, and diffusion or eutectic reaction occurs with metal foil is docked,
It avoids metal layer from contacting with electrode and increases metallization thickness.Using it is an advantage of the present invention that metal layer fits closely glass
Surface growth, bonding strength is high, after metal layer fusing to glass surface sprawl and wettability is splendid, be obviously improved glass
Welding and encapsulation performance.
Embodiments above only does illustrative explanation to the present invention, and the case study on implementation detail is merely to explanation
The present invention does not represent whole technical solutions under present inventive concept, any that essentially identical technology is solved based on the present invention
Problem, or realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. belong to this hair
In bright protection scope.
Claims (5)
1. a kind of surface in situ method for metallising based on cationic electroconductive glass, characterized by the following steps:
The cationic electroconductive glass of the halide of S1, selection containing silver, copper or lithium, sulfide or oxide;
S2, cationic electroconductive glass coupon and the metal foil contact surface of being polished using abrasive paper for metallograph are simultaneously cleaned with acetone;
S3, it cationic electroconductive glass coupon is docked with metal foil is placed between positive pole plate and power cathode plate, cation
Electro-conductive glass test piece is connected with positive pole plate, and metal foil is connected with power cathode plate;
S4, keep vacuum environment in furnace, setting axial compressive force is 1 ~ 3MPa, in furnace heating temperature be 150 ~ 400 DEG C, keep the temperature 2 ~
20min, DC voltage are 200 ~ 400V, 2 ~ 10min of load time;Load axial compressive force is simultaneously warming up to the examination of cationic electroconductive glass
Cationic ionization activationary temperature, then loads DC electric field in piece, makes to ionize ion formation directional migration;
S5, stop heating and simultaneously close external electric field, then allow cationic electroconductive glass coupon and metal foil connector natural cooling
To room temperature and take out.
2. the surface in situ method for metallising according to claim 1 based on cationic electroconductive glass, it is characterised in that: step
In rapid S2, the roughness of the contact surface of cationic electroconductive glass coupon is Ra=0.5 ~ 1.2 μm, the contact surface of metal foil it is coarse
Degree is Ra=0.1 ~ 0.3 μm.
3. the surface in situ method for metallising according to claim 1 or 2 based on cationic electroconductive glass, feature exist
In: in step S3, be equipped with graphite paper between cationic electroconductive glass coupon and positive pole plate, metal foil and power cathode plate it
Between be equipped with graphite paper.
4. the surface in situ method for metallising according to claim 1 based on cationic electroconductive glass, it is characterised in that: step
In rapid S1, the cationic electroconductive glass passes through in silicate, borate, vanadate, phosphate, tellurate, sulphur system or sulphur halogen
It is doping Ag I, AgBr, Ag in glass matrix2S, Cu I, CuBr or Cu2One of O or a variety of is made.
5. the surface in situ method for metallising according to claim 4 based on cationic electroconductive glass, it is characterised in that: institute
Cationic electroconductive glass is stated to prepare by melt quenching method or mechanochemical synthesis.
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