CN1947461A - Ceramic heater and manufacturing method of same - Google Patents
Ceramic heater and manufacturing method of same Download PDFInfo
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- CN1947461A CN1947461A CN200480034597.6A CN200480034597A CN1947461A CN 1947461 A CN1947461 A CN 1947461A CN 200480034597 A CN200480034597 A CN 200480034597A CN 1947461 A CN1947461 A CN 1947461A
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Abstract
A ceramic heater which has a ceramic body having a resistance heating element in the inside thereof, an electrode pad being formed on the surface of the ceramic body and having a boron-based plating layer, and a brazing material and a lead member being joined to the electrode pad by a baking treatment in a nitrogen reducing gas atmosphere, wherein the surface of the above plating layer contains boron (B) in an amount of 1 wt % or less. In the above ceramic heater, the amount of boron carbide being deposited on the surface of the plating layer is suppressed and thus the satisfactory area for the join with the brazing material can be secured.
Description
Technical field
The present invention relates to a kind of ceramic heater and manufacture method thereof, its be used in the fan-shaped heater of oil etc. various burners igniting with or the gasification heater, the heater of various transducers, measuring instrument, electronic component, industrial machinery, general home electric goods etc., hot-water heater, the heater of the air-fuel ratio detecting sensor that automobile is used, internal combustion engine in the rapid warm subsidiary combustion chamber is with glow plug etc. when the carburetor heater that automobile is used, the starting of diesel engine etc. and during idle running.
Background technology
All the time, promote with the starting that is used for diesel engine headed by the glow plug of usefulness, as various igniting and heater, adopt the various sheathed heaters of in the shell of heating resisting metal system, burying the heating resistor that constitutes by refractory metal line etc. underground and the various igniters of utilizing sparkover more.But they all are difficult to heat up rapidly, and mar proof and poor durability especially in described various igniters, except that being easy to take place radio interference such as noise when the igniting, also have the shortcoming from the reliability shortcoming of the viewpoint of certain igniting etc.
Therefore, as the heat transference efficiency excellence, can heat up rapidly, radio interference can not take place, the mar proof that the fail safe of positively fighting is also high and the heater of excellent in te pins of durability adopt ceramic heater mostly.Ceramic heater headed by the glow plug of internal combustion engine, extensively is utilized as various heaters.
In general, as ceramic heating element, known surface and the inner ceramic heater that is provided with the heat generating part of refractory metal that has at aluminium oxide ceramics.This heater for example, shown in patent documentation 1～4, is being in the ceramic body of principal component with the aluminium oxide, the built-in heating resistor of being made up of refractory metals such as W, Re, Mo.In heating resistor, (pad) engages leaded member by electrode pad.
Columned ceramic heater is made as follows.At first, prepare ceramic core and ceramic sheet material (sheet).Paste (paste) at the refractory metal of the printing of the one side of ceramic sheet material W, Re, Mo etc. forms after heating resistor and the electrode lead-out part, makes the face that has formed these become the inboard, the ceramic sheet material of so reeling around ceramic core.Then, by with the integrated calcining of integral body, thereby obtain ceramic heater.
On ceramic sheet material, be formed with through hole, connect the electrode pad and the electrode lead-out part of the inside that is present in ceramic sheet material.In through hole, inject conductor paste as required.On the electrode pad 4 of the inside that is formed at ceramic sheet material, engage leaded member by solder.Thereby be a kind of by make the structure of heating resistor heating from this lead member making current.
As ceramic heater 1, not soldering lead member is also arranged, in the type that electrode pad is pushed outside terminal, but, if from present market trends, the type of then soldering lead member is becoming main flow.
On the other hand, as the employed aluminium oxide (Al of electrical insulating material
2O
3), because resistance to sudden heating and elevated temperature strength are poor, so the non-oxide system pottery of thermal endurance, resistance to sudden heating, oxidative resistance excellence, especially the silicon nitride pottery also is widely used.The silicon nitride pottery, excellent heat resistance, elevated temperature strength is also high, and thermal capacity is little, and electrical insulating property is good.Therefore, the silicon nitride pottery, the ceramic body of the ceramic heating element of using as the high temperature that can heat up rapidly is widely adopted.
As this silicon nitride ceramic heater, has for example following structure.In the inside of the ceramic body that constitutes by cylindric or columned silicon nitride based sintered material, be embedded with the heat generating part of approximate U word shape, lead-in wire and electrode lead-out part make the end of electrode lead-out part be exposed to the surface of ceramic body, so form.Shown in patent documentation 5, at the electrode lead-out part of the end sides that is exposed to ceramic body, engage the metallic plate that Ni is arranged by metal level, on the metallic plate of this Ni, be welded with lead member.
Also have, when the non-oxide ceramics that uses as silicon nitride, different with the method for attachment of the lead-in wire of the ceramic heater of the oxide ceramics of use aluminium oxide etc.Promptly, in general for jointing metal on pottery, can use following the whole bag of tricks: make ceramic surface metallization (metallize) with the Mo-Mn method, in addition, after having implemented plating Ni, can use method by solder brazing, or the whole bag of tricks such as reactive metal method, shrunk fit method, plunging, autogenous soldering.Particularly, just can access higher bond strength, so adopted (with reference to patent documentation 6～8) widely because Mo-Mn method and reactive metal method do not need the high-precision processed at junction surface.Yet the Mo-Mn method is widely adopted in the oxide ceramics that with aluminium oxide etc. is representative, but is difficult to use in non-oxide ceramics.Therefore, in non-oxide ceramics, in the majority by the situation of joints such as reactive metal method.
Patent documentation 1: the spy opens flat 11-354225 communique
Patent documentation 2: the spy opens flat 11-257659 communique
Patent documentation 3: the spy opens 2001-126852 number
Patent documentation 4: the spy opens 2002-146465 number
Patent documentation 5: the spy opens flat 7-25674 communique
Patent documentation 6: the spy opens flat 4-317473 communique
Patent documentation 7: the spy opens flat 6-1670 communique
Patent documentation 8: the spy opens flat 11-329676 communique
Particularly, in being used in the ceramic heater that automobile uses, need the bonding strength height of lead member., in existing ceramic heater, there is the such problem of tensile strength reduction of lead member owing to the thermal cycle in using.In addition,, be positioned in the high-temperature atmosphere, then also have soldering strength significantly to reduce the situation of generation if after the soldering lead member.In addition, also have if ceramic body is connected with lead-in wire and use the thermal expansion difference of hardware big, then have residual stress to take place in cooling procedure near the junction surface, this residual stress acts on solder or ceramic surface, the situation of the reduction of the bond strength of conjugant.
Therefore, the objective of the invention is to,, and provide a kind of durability good ceramic heater by the bond strength of raising for the lead member of ceramic heater.
Summary of the invention
In order to solve above-mentioned problem, in the ceramic heater of this mode of this invention, built-in heating resistance in ceramic body, has electrode pad to this heating resistor making current on the surface of above-mentioned ceramic body, form coating by electroless plating on the surface of above-mentioned electrode pad, by solder lead member is being installed, wherein, the amount of the boron of the coating surface of above-mentioned electrode pad (B) is below the 1 weight %.In addition, the amount of the lip-deep carbon (C) of preferred coating is below the 10 weight %.
In common ceramic heater, during by solder bonding wire member, in reducing atmosphere, implement to fire processing.At this moment, in order to make the solder fusing, need make the temperature of firing processing is more than 600 ℃.But, if temperature becomes more than 600 ℃, then as shown in Figure 3, being formed at the boron (B) that the coating 5 on the surface of electrode pad 4 is contained, nitrogen (N) reaction with reducing atmosphere gas is contained generates boron nitride (BN) 14 on the surface of coating 5.If the generation quantitative change of this boron nitride 14 is many, then hinder flowing of the solder 6 that is formed on the coating 5.Its result, the formation of the good meniscus (meniscus) of solder 6 is hindered, and is diminished by the bonding area of solder 6.Therefore, if the stress that takes place owing to the thermal expansion difference of ceramic body 2 and solder 6 supports with little bonding area, because the thermal cycle in using, the tensile strength of lead member 7 reduces.Equally, if be contained in the coating 5 organic principle be carbon (C) 15, precipitate into the surface of coating 5, then this carbon 15 also hinders flowing of solder 6.
According to this invention, because the amount of the boron of the coating surface of electrode pad (B) is below the 1 weight %, preferably the amount of the carbon in the surface of coating (C) also is controlled at below the 10 weight %, so at the good fluidity of the pricker amount of coating surface, can improve the bond strength of lead member 7.
The boron in coating surface and the amount of carbon can reduce by the heat treatment in the manufacturing process of ceramic heater.Promptly, the manufacture method of the ceramic heater of this mode of the present invention, be a kind of in ceramic body built-in heating resistance, the surface of above-mentioned ceramic body has in the electrode pad of this heating resistor making current, surface at above-mentioned electrode pad forms coating, the manufacture method of the ceramic heater of lead member is installed by solder, wherein, form electrode pad built-in on the ceramic body of heating resistor, surface at this electrode pad forms coating, implement heat treatment, lead member is installed, handle and the bonding wire member by in reducing atmosphere, firing by solder.
According to this manufacture method,,, can reduce the boron amount in the coating by in advance coating being implemented heat treatment utilizing the firing before the processing of solder bonding wire member.That is, can boron oxide be generated by heat treatment, again along with boron is removed in the rising of temperature.In addition, similarly also can be except that the carbon (organic substance) in the de-plating.Therefore, the boron and the organic substance that can reduce in the coating in advance to be contained carry out the processing of firing of solder again, can suppress to the boron nitride of coating surface and the growing amount of carbon, and the durability of the tensile strength of lead member is improved.This heat treatment is 800～1200 ℃ with temperature preferably, carries out more than the steam partial pressure 900Pa.
In addition, preferably on electrode pad, form 1 coating, by solder anchor leg member on 1 coating, when on solder, implementing 2 coating, the diffusion layer of the solder composition in 2 coating is more than the 1 μ m, and the thickness of the non-diffusion layer of the solder composition in described 2 coating has more than the 1 μ m apart from the surface.
In existing ceramic heater,, the significantly reduced situation of soldering strength is arranged then if after the soldering lead member, be positioned in the high-temperature atmosphere.If observe the significantly reduced situation of this soldering strength, then decidable is confirmed to have to break at 2 coating that are used to protect soldering portion to form.If further analyze these 2 coating, can confirm that then the composition of solder diffuses to superficial layer.
Therefore as can be known from the result of various researchs, diffusion layer at the solder composition in 2 coating is more than the 1 μ m, and, when the thickness of the non-diffusion layer of the solder composition in described 2 coating has 1 μ m above apart from the surface, take place to be suppressed effectively to breaking of 2 coating, the bond strength of lead member improves.
In addition, the particle diameter of preferred 2 coating is below the 5 μ m.Thus, can further improve durability to the thermal cycle in using.
In addition, the ceramic heater of the mode of other of this invention, on the ceramic body that constitutes by non-oxidized substance, connected metallic plate by solder, wherein, described solder is a principal component with the metal ingredient of liquidus temperature below 1200 ℃, contains as reactive metal more than at least a kind with V, Ti, Zr, Hf, the ratio of the oxide of the described reactive metal in the conversion zone of described solder and non-oxide ceramics member is in the scope of 5～90 atom %.
As the reactive metal in the above-mentioned conversion zone, except that above-mentioned non-oxidized substance, preferably contain more than at least a kind of nitride, silicide, carbide.In addition, the principal component of preferred above-mentioned solder is a Ni system, Au-Ni system, Ag-Cu system, Ag-Cu-In system, any one of Au-Cu system.In addition, the ratio of the oxide of the reactive metal of the conversion zone of the joint interface between above-mentioned non-oxide ceramics member and solder to the scope of the degree of depth 0.1 μ m is preferably in the scope of 0.5～90 atom %.
For the joint that carries out being produced by solder, for example, the preferred metal paste that contains above-mentioned reactive metal monomer or hydrogen compound with the scope of particle diameter 0.5～100 μ m that is coated with is 1.33～1.33 * 10 in vacuum values
-5Heating and engaging in the vacuum atmosphere in the scope of Pa.
In addition, be cylindrical shape or cylindrical particularly at ceramic body, when connecting curved metallic plate in its electrode taking-up portion by solder, radius of curvature when the ceramic body of electrode taking-up portion, when satisfying concerning of appointment with the radius of curvature of the inner peripheral surface of metallic plate, can suppress to obtain the high ceramic heater of reliability by the generation of breaking due to the residual stress.
Promptly, in existing ceramic heater, for example, with respect to the temperature by electrode being taken out portion repeatedly in the fatigue test of the temperature heating cooling of 40 ℃ and 45 ℃, the heating that surpasses the chronicity in 500 weeks is cooled off repeatedly, exist the soldering portion periphery of metallic plate to have residual stress to take place, near the ceramic body it has the problem of breaking and growing up.Its result has the lead-in wire metal parts that is engaged in metallic plate to peel off, and oxygen is invaded from breaking and made the heater oxidation, and the durability deterioration of ceramic heater lacks the long-term such problem of reliability.
When the radius of curvature of the ceramic body of electrode taking-up portion as R
1(mm), the radius of curvature of the inner peripheral surface of described metallic plate is as R
2(mm), the average thickness of described metal level is during as t (mm), if-0.1≤(R
1-R
2)＜t then can be according to the stress that thermal expansion difference took place by ceramic body and metallic plate, prevents to contain the reduction of bond strength of the solder of reactive metal, and the generation to ceramic body of preventing to break improves durability.At the periphery of metallic plate, be formed at the thickness of the solder between metallic plate and the ceramic matrix, be preferably 30～150 μ m.
Description of drawings
Figure 1A is the part intercepting stereogram of ceramic heater of the execution mode 1 of expression this invention.
Figure 1B is the expanded view of the ceramic heater shown in Figure 1A.
Fig. 1 C is the part amplification view of ceramic sheet material.
Fig. 2 A is the part amplification stereogram of the lead-in wire connecting portion of the ceramic heater shown in expression Figure 1A.
Fig. 2 B is the part amplification profile of the lead-in wire connecting portion of the ceramic heater shown in expression Figure 1A.
Fig. 3 is the part enlarged drawing profile of the lead-in wire connecting portion of the existing ceramic heater of expression.
Fig. 4 is the part amplification profile of the bonding part of expression solder 6 and 2 coating 8.
Fig. 5 A is the stereogram of ceramic heater that expression relates to the execution mode 3 of this invention.
Fig. 5 B is the profile on the X-X line of the ceramic heater shown in Fig. 5 A.
Fig. 6 is the expanded view that is used for the manufacture method of the ceramic heater shown in key diagram 5A and the B.
Fig. 7 is the part amplification profile of the bonding part of expression ceramic body 22 and metallic plate 25.
Fig. 8 is the profile of ceramic heater, the relation of the radius of curvature of expression ceramic body 22 and metallic plate 25.
Among the figure: 1-ceramic heater, 2-ceramic body, 3-heat unit, the 4-electrode pad, 5-1 coating, 6-solder, the 7-lead member, 8-2 coating, 9-ceramic sheet material, 10-pottery core, 22-ceramic body, 23a-heat unit, 23b-2 level lead-in wire, 23c-lead-in wire, 23d-electrode lead-out part, the 24-solder layer, 25-metallic plate, 27-lead member.
Embodiment
Below, based on the execution mode of description of drawings ceramic heater of the present invention.
Figure 1A and B represent the execution mode of ceramic heater 1 of the present invention.Figure 1A is the part intercepting stereogram of ceramic heater 1, and Figure 1B is the expanded view of the part of ceramic body 2.
Such ceramic body 1 shown in Figure 1B, has the structure of the ceramic sheet material 9 of reeling around ceramic core 10.On the surface of ceramic sheet material 9, be formed with heating resistor 3 and electrode lead-out part 3a, the electrode pad 4 of via through holes and the inside side that is formed at ceramic sheet material 2 engages.Make heating resistor 3 become the inboard, this ceramic sheet material 9 is wound in ceramic core 10, fire by bonding and can access the ceramic body 2 of heating resistor 3 built-in.
Constitute the ceramic sheet material 9 of ceramic body 2, for example, by the aluminum oxide pottery, the silicon nitride pottery, aluminium nitride matter pottery, the various potteries of the siliceous pottery of carbonization etc. constitute.When particularly constituting, preferably adopt for example by Al by aluminium oxide ceramics
2O
3Be 88～95 weight %, SiO
2Be 2～7 weight %, CaO is 0.5～3 weight %, and MgO is 0.5～3 weight %, ZrO
2It is the aluminium oxide ceramics that 1～3 weight % constitutes.If Al
2O
3Amount is lower than 88 weight %, then because the glass qualitative change is many, so move (migration) might switch on the time becomes big.On the other hand, if Al
2O
3Amount surpass 95 weight %, the amount of glass that then might in the metal level of the heating resistor be built in ceramic body 2 in 3, spread minimizing, the durability deterioration of ceramic heater 1.
In above-mentioned ceramic body 2, the refractory metal that is built-in with W, Mo, Re etc. is the heating resistor 3 of principal component.Shown in Fig. 1 C, when the pattern defectiveness b of heating resistor 3 produced, preferably the width t of this defect part was below 1/2 of pattern (pattern) width T.This is because if the width t of above-mentioned defective surpasses 1/2 of pattern width T, then in this part local pyrexia, the resistance value of heating resistor 3 becomes big and the durability deterioration.
The reason that this defective takes place is owing to when printing formation heating resistor 3, be attached with dust on the plate making, or have foreign matter to sneak in the resistance material of printing, or burn when firing.Be with printing and bonding process, handle the operation of unprocessed ceramic sheet material 9.The cleanliness factor of this operation is improved, can prevent the generation of defective, and just in case defectiveness when taking place, to be used to get rid of the defence of inspection operation of the above defective of above-mentioned size very important.
In addition, when using at the heater of using as automobile, the heating length that preferably makes above-mentioned heating resistor 3 is 3～15mm.If this heating length is shorter than 3mm, though the intensification then can accelerate to switch on the time can make the durability reduction of ceramic heater 1.On the other hand, if longer than 15mm, then programming rate slows down, if will accelerate programming rate, then the consumed power of ceramic heater 1 becomes big.
Also have, so-called above-mentioned heating length is illustrated in the length f by the part of the round pattern in the heating resistor shown in Figure 1B 3.This heating length f selects variedly according to purposes.
Be formed with electrode lead-out part 3a at the both ends of heating resistor 3.Be formed at the electrode lead-out part 3a of the end of heating resistor 3, via through holes (not shown) and be connected in electrode pad 4.Electrode pad 4 can be that the metal layer of principal component forms by the refractory metal with W, Mo, Re etc.
Fig. 2 A and B are the part enlarged drawings of structure of the periphery of expression electrode pad 4.Shown in Fig. 2 A and B, on the surface of electrode pad 4, be formed with the thickness of 1～5 μ m, by the coating that constitutes more than a kind 5 among Ni, Cr, Cu, Pt, Au, Co, Sn, the Pd etc., and on coating 5, engage leaded member 7 by solder 6.
In ceramic heater 1, importantly the amount with the boron (B) on the surface of the coating 5 on the above-mentioned electrode pad 4 is controlled at below the 1 weight %.This is because the boron (B) of the trace that coating 5 is contained reduces owing to following reason makes the bonding strength of lead member.That is, on coating 5, when the solder 6 bonding wire members 7, make again in can the oxidation not such reducing atmosphere gas of electrode pad 4, solder 6 and lead member 7 and fire processing.For this reason, the nitrogen (N that is contained in the reducing atmosphere gas
2) with coating 5 in boron reaction, at surfaces nitrided boron (BN) 14, the boron oxide (B of coating 5
2O
3) boride that waits generates.If there is a large amount of boron nitride 14 to generate on the surface of coating 5, then,, hinder the generation of the good meniscus of solder 6 so be used for the mobile variation of bonding wire member 7 used solders 6 because this boron nitride 14 is poor with the wetability of solder 6.Therefore, the bonding area of lead member 7 and solder 6 reduces, and the bond strength of lead member 7 reduces, and the durability of ceramic heater reduces.
Therefore, be controlled at below the 1 weight %, suppress the generation of the boron nitride 14 shown in Fig. 2 B by amount with the boron (B) on the surface of coating 5.Can make thus with coating 5 on the bonding area of solder 6 increase, can firmly connect lead member 7.In addition, hope is preferably 0.3 weight % in the amount of the boron on the surface of coating, more preferably below the 0.1 weight %.
Also have,, can measure by Auger (auger) analysis in the amount of the boron on the surface of coating 5.For example,, analyze the auger electrons that encourages thus, the extremely composition on surface about can quantitative analysis surface number nanometer by electron ray to the surface irradiation 5kV * 10nA of determinand.According to auger analysis, can not destroy ceramic heater and measure.By the amount of the boron of being measured by auger analysis is controlled at below the 1 weight %, also can make the amount of the boron nitride that generates on the surface of coating 5 reach the degree of the joint that does not hinder solder 6.Because the molecular weight (10.82) of B, the molecular weight of BN (24.828) is so if all be boron nitride 14 from the surperficial detected boron of coating 5, then the amount of this boron nitride can calculate according to following formula.
The amount of the amount of BN (weight %)=B * (24.828/10.82)
Therefore, be below the 1 weight % if make the amount of boron on the surface of coating, then the growing amount of the surface boron nitride of being separated out becomes below the 2.3 weight %, can be suppressed at the scope that does not hinder with the bonding area of solder 6.
In addition, similarly, the amount of the carbon (C) on the surface of preferred coating 5 is below the 10 weight %.Thus, can make flowing of the solder on the surface of coating 5 well, the durability of the tensile strength of lead member 7 is improved.Carbon 15 is the same with boron nitride 14, generates on the surface of coating 5.This carbon 15 is considered to be in when forming coating 5, generates by becoming entrained in the organic substance in the coating 5 and being attached to surperficial organic substance by the operation after the plating.Carbon 15 is also same with boron nitride 14, is the material bad with the wetability of solder 6.Therefore, if carbon 15 is present in the surface of coating 5, the mobile variation of solder 6 then becomes the reason that the durability of the tensile strength of lead member 7 reduces.In the amount of the carbon 15 on the surface of coating, more preferably below the 2.5 weight %.Also have,, also can measure by auger analysis in the amount of the carbon 15 on the surface of coating 5.
For the boron on the surface of adjusting coating 12, the amount of carbon, for example, can form coating 5 on the surface of the electrode pad 4 of the ceramic body 2 of built-in heating resistor 3 after, implement heat treatment.That is, can implement heat treatments to coating 5 utilizing the firing before the processing of solder 6 bonding wire members 7, thus the boron in the oxidation removal coating.Specifically, utilize boron and the oxygen in the atmosphere in the coating 5 that boron oxide is generated exactly, temperature is risen remove boron oxide.Meanwhile, also can oxidation removal as the organic substance of the carbon source in the coating 5.So, by removing boron and the organic substance that in coating 5, contains in advance, can be when firing of solder 6 to be handled, the boron nitride 14 that the surface of inhibition coating 5 generates and the amount of carbon 15 improve the durability of the tensile strength of lead member 7.
In addition, preferably in reducing atmosphere, temperature is as 800～1200 ℃ in heat treatment, and steam partial pressure is as more than the 900Pa.If temperature is lower than 800 ℃, then the reaction of boron and oxygen becomes insufficient, has boron residual in coating 5.On the other hand, if heat treatment temperature surpasses 1200 ℃, the then metal ingredient of the metal ingredient of coating 5 and electrode pad 4 reaction might form metallic compound at the periphery of electrode pad 4.In addition, if steam partial pressure is lower than 900Pa, the oxygen quantity not sufficient in the atmosphere then, the oxidation reaction of the boron in the coating 5 becomes insufficient, and boron residues in the coating 5 easily.In addition, if steam partial pressure becomes too high, then electrode pad 4 and coating 5 oxidations.At the material that adopts W as electrode pad 4, when using Ni as coating 5, steam reaches the 6000Pa right and left at least can be used.
The organic substance that contains in the coating 5 if heat-treat in the reducing atmosphere as above-mentioned steam partial pressure, also can be removed.Therefore, can be reduced in the amount of the carbon that the surface of coating 5 generates.
On coating 5, the coating solder 6 for bonding wire member 7.This solder 6 is a principal component with Ag-Cu, Au-Cu, Ag, Cu, Au etc., can be as required, and use and contain as the resin of adhesive with as the material that metal constituted of Ti, the Mo of reactive metal, V etc.
In addition, if solder 6 Au amount when adopting the Au-Cu solder is 25～95 weight %, the Au amount is 50～95 weight % when adopting the Au-Ni solder, then the temperature of firing processing can be set in about 1100 ℃.Therefore, can reduce the residual stress of firing after the processing.Thus, in thermal cycle, even the fatigue that is caused by the thermal expansion difference of solder 6 and ceramic body 2 produces, the tensile strength of lead member 7 also is difficult to reduce.
As lead member 7, can use the material that constitutes by Ni, Fe-Ni-Co alloy, 4-2 alloy, Fe-Ni base alloy, various stainless steels etc.Especially preferably using thermal endurance good Ni system, Fe-Ni is alloy.Thus, by heat transmission from heating resistor 3, the rising of the temperature of lead member 7, deterioration in can preventing from effectively to use.In addition, as lead member 7, can use the wire rod of cross section circle and tabular wire rod, various shapes such as bulk.
When using Ni and Fe-Ni alloy as lead member 7, preferably its average crystallite particle diameter is below the 400 μ m.If its average grain diameter surpasses 400 μ m, vibration and thermal cycle during then owing to use, near lead member 7 fatigues the junction surface, breaking becomes takes place easily.When lead member was other material, if it is big for example to form the thickness of crystallization size ratio lead member 7 of material of lead member 7, then solder 6 had stress to concentrate with the crystal boundary of the boundary vicinity of lead member 7, breaks and also takes place easily.
Also have, when utilizing solder 6 that lead member 7 is connected, implement to be called the processing of firing of soldering.This fires the temperature of processing, and preferably low temperature as far as possible shortens the processing time.Can make the average crystallite particle diameter of lead member 7 little to 400 μ m thus, can prevent further that the intensity of lead member 7 from reducing.
In addition, on the surface of the solder 6 of bonding wire member 7, be preferably formed the 2nd the coating 8 that is used to prevent solder 6 oxidations.When the coating 8 that on solder 6, do not form the 2nd, preferably lead member 7 integral body are carried out plating and handle.
Next, the manufacture method of the ceramic heater 1 that forms above-mentioned structure is described.
At first, be principal component with the aluminium oxide, being shaped with the total amount as sintering aid is that 4～12 weight % contain SiO
2, CaO, MgO, ZrO
2The glutinous slurry of pottery (ceramic slurry), obtain ceramic sheet material 9.Then, the method for utilization printing and manifolding etc. forms heating resistor 3 and electrode lead-out part 3a at a side's of ceramic sheet material 9 interarea, utilizes the method for printing and manifolding etc., forms electrode pad 4 at the interarea relative with the face that forms electrode lead-out part 3a.
Secondly, between electrode lead-out part 3a and electrode pad 4, form through hole (not shown).By at least a kind of filling in this through hole with W, Mo, Re is the electric conducting material of principal component, perhaps coats the medial surface of through hole, thereby electrode lead-out part 3a is electrically connected with electrode pad 4.
After this, on heating resistor 3 and electrode lead-out part 3a, form by with roughly the same the forming after the coating that constitutes of ceramic sheet material 9, circumvolution ceramic sheet material 9 make its be close to ceramic core 10 around, the formed body raw material of shaping tubular.The formed body raw material that so obtain are fired in 1500～1650 ℃ reducing atmosphere becomes ceramic body 2.
After this, by electroless plating, the coating 5 that more than at least a kind of the surface of electrode pad 4 formation, constitutes by the metal of Ni, Cr, Pt, Au, Pd, Cu etc.
Then, in the reducing atmosphere more than steam partial pressure 900Pa,, on coating 5, carry out heat treatment step with 800～1200 ℃ temperature.Can be by this heat treatment except that boron and the organic substance in the de-plating 5.
After the end, lead member 7 is installed on coating 5, in containing the reducing atmosphere of aerobic, fires processing, finish ceramic heater 1 thus by solder 6.Also have, preferably fire the temperature of processing, if the Ag-Cu solder then is 770～870 ℃, if the Au-Cu solder then is 950～1050 ℃, if the Ag solder then is 1000～1100 ℃.
In addition, when in the high atmosphere of humidity, using ceramic heater 1,, can suppress the generation of mobile (migration) by adopting the solder 6 of Au system, Cu system.In addition, shown in Fig. 2 A, preferred being at least more than the 0.2mm from the end of electrode pad 4 to the end of solder 6 apart from k.If this is lower than 0.2mm apart from k, then the end of electrode pad 4 is stretched when the contraction of solder 6 and becomes and be easy to peel off, and the tensile strength of lead-in wire structure 7 reduces.
After so the coating 5 on the surface that is formed at electrode pad 4 being implemented heat treatment in comprising the reducing atmosphere of steam, if fire processing by 6 pairs of lead member 7 of solder, then the flowability of the solder on coating 56 becomes well, and can prevent solder 6 oxidations owing to the thermal cycle in using, the problem that the tensile strength of lead member 7 reduces.
In the present embodiment, to by suppressing the diffusion in 2 coating of solder composition on being implemented on solder, thereby the example that improves the reliability of lead member connecting portion is illustrated.
Circumvolution ceramic sheet material 9 is up to forming ceramic body on ceramic core 10, and is identical with execution mode 1.Secondly, shown in Fig. 2 B, fire the back on the electrode pad 4 of ceramic heater 1, form 1 time coating 5.This 1 coating 5 is to be used for when lead member 7 being brazed in electrode pad 4 surperficial, makes flowing of solder good, increases soldering strength.Usually form 1 coating 5 of 1～5 μ m thickness.As the material of 1 coating 5, can use Ni, Cr, or be the composite material of principal component with it.
When forming this 1 coating 5,, preferably use electroless plating in order to manage plating thickness.When using electroless plating, as the plating pre-treatment,, serve as that nuclear is replaced then with this Pd if impregnated in the active liquid that contains Pd, 1 coating 10 like this is formed on the electrode pad 7.
Then, utilize solder 6 that lead member 7 is fixed on 1 coating 5.If it is the brazing temperature of solder 6 is set in about 1000 ℃, then preferred because can reduce residual stress after the soldering.As solder 6, for example, can use the material of Au, Cu, Au-Cu, Au-Ni, Ag, Ag-Cu system.As the Ag-Cu solder, if the Ag amount is 71～73 weight %, then become the composition of eutectic point, because the generation of the alloy that the xenogenesis the when intensification can prevent soldering time the, cooling is formed, so can reduce residual stress after the soldering.In addition, when in the high atmosphere of humidity, using, because adopt solder 6 one sides of Au system, Cu system to be difficult to be moved (migration), so preferred.
In addition, in order to improve durability,, and form 2 coating 8 that constitute by Ni etc. on the surface of solder 6 from corrosion angle protection solder 8 at high temperature.Fig. 3 is the part amplification profile of the near interface of expression solder 6 and 2 coating 8.As shown in Figure 3, in 2 coating 8, there are the layer 8a of composition diffusion of no solder 6 and the 8b that has spread.In the present embodiment, by controlling the thickness of this diffusion layer 8a and no diffusion layer 8b, thereby suppress the generation of breaking, the reliability of raising ceramic heater to 2 coating.
At first, in 2 coating, from the thickness t on the surface of 2 coating of the no diffusion layer 8a of solder composition
1, be preferably more than the 1 μ m.This is because if the thickness t of no diffusion layer
1Be lower than 1 μ m, then the defencive function of the solder that is produced by 2 coating can not be brought into play fully.For example, adopting the Ag-Cu solder, when adopting plating Ni, be contained in nickel solid solution in Cu composition and 2 coating 8 in the solder 6 and fusing point decline as 2 coating as solder 6.Specifically, under heat treated situation, the Cu that nickel in 2 coating 8 and solder 6 are contained generates the solid solution composition of full rate solid solution, still because this solid solution and pure nickel relatively fusing point is low, so the fusing point of 2 coating integral body reduces.If the fusing point of 2 coating reduces, then when be positioned in the high-temperature atmosphere, on 2 coating 8, the generation of breaking is arranged easily to ceramic heater 1, oxygen is invaded between this breaks, and solder 6 is oxidized, the intensity reduction of soldering portion.Also have, when adopting the Ag-Cu solder, diffuse in 2 coating 8 with respect to Cu as solder 8 because Ag original with the Ni anergy, so can in 2 coating 8, spread hardly.
On the other hand, in 2 coating, the thickness t of the diffusion layer 8b of preferred solder composition
2Be more than the 1 μ m.This is for the caking property that makes solder 6 and 2 coating 8 improves, and prevents plating exfoliation.
The thickness of 2 coating 8 is preferably the scope of 2 μ m～10 μ m.This is because if thickness is lower than 2 μ m, then oxidative resistance is insufficient, on the other hand, if surpass 10 μ m, then because the thermal expansion difference of metal layer and pottery and durability deterioration.
In 2 coating, the no diffusion layer 8a of solder composition and the thickness of diffusion layer 8b can be according to the Auger electron spectroscopy assays.For example, adopt sweep type FE-Auger electron spectroscopy analytical equipment PHI system Model680,, under the condition of test portion electric current 10nA, carry out line analysis with accelerating voltage 5Kv.The position of measuring is the central portion of solder meniscus.
In addition, for durability improves, the particle diameter that preferably makes the crystallization that constitutes 2 coating 8 is below 5 μ m.If this size ratio 5 μ m are big,, take place easily so place breaking under the environment at high temperature then because the weakened of 2 coating 8 becomes fragile.In addition, constitute the little side of particle diameter of the crystallization of 2 coating 8, be considered to filling out of plating and cover well, can prevent small defective.
Form the particle diameter of the crystallization of 2 coating 8, can measure with SEM.For example, can on 1000～3000 times SEM photo, draw straight line arbitrarily, the particle assay particle more than 50 and this straight line are handed over the length of the part of knot, try to achieve average grain diameter with the flat structure of arithmetic.As these 2 coating 8, preferably adopt the non-electrolysis Ni plating of boron system.In addition, electroless plating also can be phosphorus system except that boron system.But, in the time might under hot environment, using, preferably implement the non-electrolysis Ni plating of boron system.By 2 heat treatment temperatures behind the plating are changed, can regulate the particle diameter of 2 coating 8.If then the particle diameter change is big to promote heat treatment temperature.
Secondly as the material of lead member 7, preferably using thermal endurance good Ni system and Fe-Ni is alloy etc.This is owing to the heat transmission from heating resistor 4, and in use the temperature of lead member 7 rises, thereby might deterioration.
Also have, in order to reduce the deviation between test portion, the heat treatment during soldering is preferably heat-treated having than the more abundant high temperature more than needed of the fusing point of solder 6.
Also have, illustrated in the present embodiment, no matter ceramic kind all can be suitable for.In addition, be not only ceramic heater, and can be applicable to the enforcement of the soldering of whole Au systems.In addition, as the shape of ceramic heater 1, except that cylindric and cylindric, can also be tabular.
The example of the ceramic heater with the ceramic body that is made of non-oxide ceramics has been described in the present embodiment.Fig. 5 A is the stereogram of the ceramic heater 1 of expression present embodiment, and Fig. 5 B is its X-X profile.
Fig. 6 is the expanded view of the manufacture method of expression ceramic body 22.On the surface of ceramic green formed body 22a, set gradually heater 23a; The 2nd leading part 23b; Leading part 23c; Electrode lead-out part 23d, with its 2 ply, overlapping thereon more other ceramic formation body 22a carries out one by the hot pressing calcining and fires.After this, sintered body is processed into cylinder and becomes ceramic body 4.
Also have, in the ceramic body 22 that constitutes ceramic heater, heat generating part 23a is a shape arbitrarily.For example, also heat generating part 23a can be formed the bulk and the stratiform of U word shape and W word shape etc. when overlooking.This heater 23a also can form by the method for printing and manifolding etc. on ceramic body 22.Perhaps, also the heat generating part 23a of wire can be wound into coiled type, or make it crooked and be embedded in the ceramic body 22.
If describe according to Fig. 5 B again, then, connect metallic plate 25 by solder 24 at an end of ceramic body 22.On metal 25, connect lead-in wire hardware 27 then.Connect the solder 24 of metallic plate 25, it forms with the electrode taking-up 23d of portion that exposes from ceramic body 22 and is electrically connected.Here as solder 24, be need can and the ceramic body 22 that constitutes by non-oxide ceramics between realize the material of high bond strength.
Therefore in the present embodiment, adopt the solder 2 that contains regulation reactive metal element so that and ceramic body 22 between form conversion zone.Fig. 7 is near the part amplification profile of linkage interface of expression ceramic body 22 and solder 24.As shown in Figure 7, the surface coated ceramic 22 contains the solder 24 of reactive metal element, makes and forms conversion zone 30 between pottery 22 and the solder 24.Thus, can firmly engage pottery 22 and metallic plate 25 by solder 24.
In order to obtain such connected structure, this invention person etc. have carried out following research.At first, as reactive metal, will contain hydrogen compound 1～30 weight % of V or V, be preferably 2～10 weight %, surplus is equipped with into pasty state by the mixed-powder of Ni powder constituent with the organic bond accent, on the pottery 22 that constitutes by silicon nitride based sintered material, by silk screen printing or infusion process coating.Then, carry out in vacuum atmosphere, being heated to 1050 ℃, after keeping 15 minutes, obtain conversion zone 30 on the surface of pottery 22.Therefore, form solder layer 24 (for example Au-Ni is, Ag-Cu system etc.) between conversion zone 30 and the hardware 25, then can access conjugant as shown in Figure 7 if make.
In the lining, because the firing temperature in the vacuum atmosphere need be suppressed at below 1200 ℃, so as the metal ingredient of the principal component of solder layer 24, preferred liquid phase line temperature is below 1200 ℃.
Also have, the ratio of the oxide of the reactive metal element conversion zone 30 in can be with the reactiveness of the reactive metal element of ESCA method affirmation conversion zone 3, measures according to the ratio of the peak strength of reactant.
Here, in the movement when coating the heat treated surface, in the vacuum atmosphere of Ni and reactive metal V of pottery 22, be estimated to be following content.The hyperergic reactive metal V and the silicon nitride (Si that contact with the surface of pottery 22
3N
4) reaction, become vanadium silicide (V
3Si
5, VSi
3) and vanadium nitride (VN).Free Si and the Ni powdered reaction that takes place when it reacts, low-melting nickle silicide (NiSi etc.) is generated.Then, this low-melting nickle silicide is as liquid phase, above-mentioned reaction is further carried out, as a result of be considered to, reactive metal V is gathered in the surface of pottery 22, the conversion zone of the densification of being made up of vanadium silicide and vanadium nitride is formed thereon, on this conversion zone, is formed with the metal level based on the Ni particle that has been wrapped up by nickle silicide.
In the formation of conversion zone 30, need become vanadium silicide and vanadium nitride at first by the V and the silicon nitride reaction of hyperergic reactive metal.For this sufficient reacting is carried out, heat treatment in a vacuum is effective as can be known.If in atmosphere, heat-treat, then hyperergic reactive metal V take the lead in atmosphere in oxygen react, consequently the quantitative change with the V of the reactive metal of silicon nitride reaction is few, has the unstable such problem points of bond strength is taken place.But, in common creating conditions, prevent by the generation of the oxide due to the reaction of reactive metal and oxygen very difficult fully.Therefore, as above-mentioned, the ratio that preferably makes the oxide that is formed by the reaction of reactive metal in the conversion zone 30 and oxygen is below 5～90%, more preferably below 5～50%.
So, reactive metal element in the conversion zone 30 and ceramic reactant are preferably nitride, silicide, reach more than at least a kind of carbide.At nonnitrogenousization of the reactant thing, silicide of reactive metal element and pottery, and during carbide, the problem points that has bond strength to become unstable such takes place.
In addition, about the principal component of solder,, preferably adopt any one that Ni system, Au-Ni system, Ag-Cu system, Ag-Cu-In are, Au-Cu is from liquidus temperature being suppressed at the viewpoint below 1200 ℃.
In addition, particularly, influential greatly to bond strength at the state of the conversion zone of the scope of distance joint interface 0.1 μ m.Therefore, the ratio of the oxide of the reactive metal in the conversion zone of the scope of distance joint interface 0.1 μ m is preferably in 0.5～90% scope.The ratio of the oxide of the reactive metal of the conversion zone in the scope of distance joint interface 0.1 μ m is 90 atom % when above, from the low outside stress application of the bond strength of conjugant the time, has and peels off such problem from joint interface and take place.In addition, if the ratio that makes above-mentioned oxide below 0.5 atom %, has because the processing method of the powder of reactive metal complicates, the condition of the heat treated in the vacuum atmosphere complicates in addition, very high such problem points thereby manufacturing cost becomes.In addition, the ratio of the oxide by further preferably making above-mentioned conversion zone can reach engagement state more stably in 0.5～30% scope.
According to more than, in the present embodiment, preferred joint method is as follows.That is, on the surface of non-oxide ceramics, be that metal ingredient below 1200 ℃ is a principal component with liquidus temperature, it is the metal paste of reactive metal that coating contains more than at least a kind with V, Ti, Zr, Hf, heats in vacuum atmosphere.Thus, can form conversion zone, metallic plate be engaged with non-oxide ceramics by this conversion zone on the non-oxide ceramics surface.
Reactive metal is preferably metal monomer or the hydrogen compound of V, Ti, Zr, Hf, and particle diameter is the scope of 0.5～100 μ m.Thus, can access the engagement state that is stable, and the high conjugant of bond strength.When adopting particle diameter to be the powder of the reactive metal below the 0.5 μ m, because the activity degree height of powder surface, so the surface oxidation easily of powder, the amount of the reactive metal element that reacts with pottery can tail off.On the other hand, when adopting particle diameter to be the powder of the reactive metal more than the 100 μ m, the dispersity of active metal powder is bad, with the engagement state of pottery under take place easily uneven.
In the ablating work procedure of solder, the vacuum values in the preferred atmosphere is 1.33～1.33 * 10
-5In the scope of Pa.If vacuum values is more than the 1.33Pa, then with atmosphere in the oxygen reaction, the oxidation of reactive metal element, generation can't obtain the such problem of desirable bond strength.On the other hand, if be 1.33 * 10 with vacuum values
-5The following vacuum degree of Pa is carried out ablating work procedure, then when manufacturing cost uprises, because the composition of solder evaporates in high vacuum, the destroyed such problem of composition of solder takes place.The vacuum values of ablating work procedure is preferably 1.33～1.33 * 10 for this reason
-5In the scope of Pa.By further preferred, the vacuum values that makes ablating work procedure is 1.33～1.33 * 10
-4In the scope of Pa, can access more stable conjugant.
Also have, so the solder layer 24 that forms when passing through conversion zone 30 and ceramic body 22 engages, need be electrically connected with the electrode taking-up 23d of portion.In addition, preferably in 20～80% scope of the surface area of solder layer 24, be close to metallic plate 25.
In the explanation of above execution mode, be silicon nitride with pottery 22, the reactive metal element is that the situation of vanadium is main being illustrated, but the combination of other non-oxide ceramics and reactive metal also can obtain same effect.For example, pottery 22 also can be other a non-oxide ceramics of aluminium nitride, carborundum etc.In addition, reactive metal is that Ti, Zr, Hf also can obtain same effect.
In addition, in the structure of ceramic body 22, heat generating part 23a, the 2nd leading part 23b, leading part 23c, the electrode taking-up 23d of portion etc., be not limited to the present embodiment explanation.For example, ceramic body 22 is not limited to column, also can be Any shape such as bulk.
In the present embodiment, to as enforcement mode 3 illustrated, connected in the ceramic heater of metallic plate 25 by the electrode taking-up portion of solder 24 at columned ceramic body 22, by the radius of curvature of control ceramic body 22 and metallic plate 25, be illustrated thereby improve reliability.
Fig. 8 is the key position profile of the cylindric or cylindrical ceramic heater 1 shown in Fig. 5 A and Fig. 5 B.When the radius of curvature of ceramic body as R
1(mm), the radius of curvature of metallic plate 25 is as R
2(mm), the average thickness of solder layer 24 is during as t (mm), preferably satisfies the relation shown in the following formula 1.
-0.1≤(R
1-R
2)＜t (formula 1)
If satisfy this relation, then by solder layer 24 on ceramic body 22 during bonding metal plates 25, the solder layer 24 of fusing pulls to the such power of ceramic body 22 sides with metallic plate 25 and works by its surface tension.For this reason, in the thickness attenuation of the peripheral part solder layer 24 of metallic plate 25, be easy to relax the stress that the thermal expansion difference of solder layer 24 and metallic plate 25 and ceramic body 22 causes.Therefore, demonstrate favorable durability for the thermal cycle in using.
In order to satisfy this relation, need the shape of control ceramic body 22 and metallic plate 25, and will accurately control the amount of solder layer 24.For example, at the represented volume of (average thickness of solder layer 24) * (area of solder layer 24), preferably belonging to ± 15% coating weight with adjustment solder layer 24 in the interior deviation range.Here, the average thickness t of so-called solder layer 24 is on average at the thickness of the central portion of the thickness of the peripheral part of metallic plate 25 and metallic plate 25.Also have, when between solder layer 24 and ceramic body 22, forming conversion zone, comprise the thickness of this conversion zone among the average thickness t of solder layer 24.
At (R
1-R
2) than-0.1 (mm) hour, on whole of metallic plate 25, be difficult to form solder layer 24, pore takes place in solder layer 24, have owing to stress is concentrated such problem of breaking.Not, if (R
1-R
2) become more than the t (mm), then there are the end of metallic plate 25 and the gap of ceramic body 22 to become big, at the thickness thickening of the solder layer 24 of metallic plate 25 ends, the problem that the residual stress that causes owing to the thermal expansion difference of 24 of ceramic body 22 and solder layers is broken such takes place.
Take out the metallic plate 25 of usefulness if engaged the electrode of lead-in wire hardware 27, in cooling procedure after adding thermal bonding by the solder layer 24 that contains reactive metal, relaxed with the thermal expansion difference of the ceramic body 22 that takes place in the heating cooling in when operation, then any material can be suitable for.Preferably be similar to the coefficient of thermal expansion 3.0～5.4 * 10 of ceramic body 22
-6/ ℃ 3.0～7.5 * 10
-6/ ℃ metallic plate 25.
In addition, metallic plate 25, from easy plastic deformation this point, yang type modulus shows 14～15 * 10
3Kg/mm
2The Fe-Ni-Co alloy and basic alloy the best of iron (Fe) of Fe-Ni alloy etc.From plastic deformation by described metallic plate 25 self, to set out and can fully absorb the stress this point that takes place owing to thermal expansion difference, the limit portion of metallic plate 25 concentrates for fear of stress, and preferably implements the Machining of Curved Surface of chamfering and circle.
For fear of concentrating on narrow and small scope, be area bonding metal plates more than 20% preferably with surface area with respect to solder layer 24 by the stress due to the thermal expansion difference.On the other hand, if bonding area surpasses 80%, then the periphery of the periphery on the composition surface of the metallic plate 25 concentrated of stress and solder layer 24 is approaching, and stress is concentrated and broken to become and take place easily.Therefore, the bonding area of metallic plate 25 and solder layer 24, be preferably solder layer 24 surface area 20～80%.In addition, the periphery on the composition surface of metallic plate 25 and solder layer 24, preferably not overlapping with the whichever edge of the periphery of solder layer 24.
On the other hand, electrode lead-out part 23d also can be the state that exposure is appeared of cutting, if but the metal of enforcement Ni etc. covers, form solder layer 24 thereon, and the reliability of connection is improved.In addition, also can use the Ni line etc. of low thermal expansion as the lead-in wire hardware 27 that is connected in metallic plate 25.
In addition, at the peripheral part of metallic plate 25, the thickness of the solder layer 24 between metallic plate 25 and ceramic body 22 is preferably 30～150 μ m.If solder layer 24 surpasses 150 μ m, then break because of the thermal stress that causes by thermal expansion difference to become and take place easily, so be not preferred.In addition, if the thickness of solder layer 24 is lower than 30 μ m, then because the quantitative change of the metal of formation solder layer 24 is few, so pore takes place in solder layer 24 easily.In addition because at the junction surface of lead-in wire hardware 27 when metallic plate 25 floats, have so-called because at the stress of lead-in wire hardware 27, the hardware 27 broken problem that stretches takes place, so be not preferred.
In the present embodiment, as solder layer 24, can enumerate alloy with Au-Cu, or the Au-Cu alloy, the Au-Ni alloy is a principal component, the total amount is 90～99 weight %, surplus is 1～10 weight %, contains any above reactive metal of V, Mo, Ti, Zr, Hf, Mn etc.Reactive metal also can contain with the form of nitride and carbide, hydride etc.Thus, the durability of the ceramic heater 1 that is directed to the thermal cycle in the use is improved.Particularly, preferably contain vanadium (V) or titanium (Ti) as reactive metal.
When the amount of reactive metal was lower than 1 weight %, the raising effect of bond strength did not manifest, if surpass 10 weight %, then the firing temperature of metal level 7 uprises, and produced huge residual stress when cooling, became the reason of breaking.Therefore, the amount of reactive metal is preferably 1～10 weight %, more preferably 1～5 weight %.In addition, from since the short circuit due to move waiting prevent this viewpoint, the principal component as the noble metal of solder layer 24 most preferably contains Au.
In the present embodiment, as the material of ceramic body 22, except that the non-oxide ceramics of the siliceous pottery of nitrogenize, aluminium nitride matter pottery etc., also can be the oxide ceramics of aluminium oxide, mullite or the like.Yet the relation by the curvature of present embodiment explanation particularly betides breaking effectively of ceramic body 22 to being used for being suppressed at non-oxide ceramics.
In the silicon nitride pottery, its crystal boundary mutually in, mostly have the crystalline phase or the glassy phase that contain as periodic table 3a family's element of sintering aid composition and silicon etc.Preferably preferably by monosilicate (RE
2SiO
5) and dislicata (RE
2Si
2O
7) crystalline phase that constitutes is as principal phase, make it to separate out at crystal boundary.This is because separating out of monosilicate (monosilicate) and dislicata (disilicate) can improve ceramic body 22 oxidative resistance at high temperature.In addition, the SiO of the oxygen of the oxide conversion amount of the whole rare earth elements in the ceramic body 22 and impurity
2The mol ratio of conversion amount from the viewpoint of oxidative resistance, is preferably more than 2, and the densification this point from sintered body preferably is controlled at below 5.
Also have, also can be in non-oxide system ceramic sintered bodies as ceramic body 22, a small amount of constituent that adds the inorganic conductive material that constitutes heater 23a is to adjust the thermal expansion difference and the reactivity of heater 23a and ceramic body 22.
In addition, in order to control the crystal grain-growth of inorganic conductive material 23a, preventing breaking due to the thermal expansion difference with ceramic body 22, and impedance is increased, can make inorganic conductive material 23a as heater contain more than one of silicon nitride, boron nitride, aluminium nitride or carborundum yet.Its content is with respect to principal component 100 wt parts, for example is preferably that silicon nitride has 5～30 wt parts, and boron nitride (BN) has 1～20 wt part, and aluminium nitride has 1～15 wt part, and carborundum has the ratio of 3～15 wt parts.
In addition, constitute the inorganic conductive material of heater 23a, preferably with refractory metal and WC, the MoSi of W, Mo, Ti etc.
2, TiN etc. the carbide, silicide, nitride etc. of refractory metal be principal component.From reducing the thermal expansion difference with ceramic body 22, under high-temperature, also be difficult to react this point with it and set out, be principal component preferably with WC or W.
Also have, the ceramic heater 1 of the enforcement of this enforcement is not limited to mode described herein.The shape of solder layer 24 and metallic plate 25 also can be an Any shape if do not break away from purport of the present invention.In addition, according to purposes, the cross sectional shape of ceramic body 22 also can have various variations.In addition, can a plurality ofly abreast set heater 23a, be applied to also can play same effect as in upright arrangement or connect the structure of each heater 23a side by side as sandwich construction.
In the present embodiment, the ceramic heater 1 of making shown in Figure 1A.Preparation is with Al
2O
3Be principal component, adjust SiO
2, CaO, MgO, ZrO
2Make its be aggregated in 10 weight % with interior ceramic sheet material 9 as ceramic body 2.Print heating resistor 3 that constitutes by W-Re and the electrode lead-out part 3a that constitutes by W thereon.In addition, in the inside of ceramic sheet material 9, pad 4 prints electrode.Heating resistor 3, its making are to be made of 5mm heating length to come and go 4 times pattern.
Then,,, inject at this and to stick with paste, realize the conduction between electrode pad 4 and electrode lead-out part 3a by on ceramic body 22, forming through hole in the position of the end of the electrode lead-out part 3a that constitutes by W.The position of through hole, it forms the inboard that enters into the junction surface when handling implementing to fire.
Then, form the coating that is made of ceramic sheet material 9 and essentially identical composition on the surface of heating resistor 3, after the intensive drying, coating makes the adhesive that the pottery of ceramic sheet material 9 and essentially identical composition disperses again.With the ceramic sheet material of preparing like this 9 be close to ceramic core 10 around, with 1500～1600 ℃ of calcinings.
Once more, after electrode pad 4 surfaces formed the coating 5 of the thick 3 μ m that are made up of Ni, with the reducing atmosphere that steam partial pressure changes between 600～6000Pa, changing temperature was implemented heat treatment between 600～1300 ℃.In addition, prepared the sample of not heat-treating as a comparative example.
Thereafter, adopting the solder of being made up of Au-Cu 6, will be the lead member 7 of the diameter 0.8mm of principal component with Ni, in reducing atmosphere, do for 830 ℃ with temperature and to fire processing and engage, and obtain the ceramic heater test portion.Then, observe each test portion, the boron on the surface of investigation coating 5, the adhesion amount of carbon by auger analysis.In addition, the bent moon face from the surface to the solder 6 at the junction surface of the lead member 7 of each test portion is taken pictures, and measures vertical, wide size from photo.
In addition, each test portion is put into 350 ℃ thermostat 5 minutes, force quench cooled behind the temperature stabilization, also implement to put into the thermal cycling test 2000 times of thermostat, in addition, implement to be positioned over thermostat such fatigue test in 500 hours of 500 ℃.Adopt cupping machine, the tensile strength of the lead member 7 of each test portion after the mensuration fatigue test.Tensile strength is measured by the Surface Vertical stretching lead member 7 from ceramic body 2.The accelerated test of the thermal cycle during this test is equivalent to use.
Table 1 ecbatic.
Table 1
| Test portion No. | Heat treatment temperature (℃) | Steam partial pressure Pa | The amount of B (weight %) | The amount of C (weight %) | Solder flows, and cun (mm) n=10 is average for linear foot | N=10 is average for solder flow width size (mm) | The durable evaluation in junction surface n=10 average (N) |
| *1 | No heat treatment | - | 3.4 | 13.2 | 2.41 | 1.31 | 12 |
| *2 | 600 | 800 | 3.1 | 12.1 | 2.42 | 1.32 | 13 |
| *3 | 800 | 800 | 1.4 | 10.8 | 2.45 | 1.39 | 16 |
| 4 | 800 | 900 | 0.9 | 8.8 | 2.51 | 1.42 | 25 |
| 5 | 780 | 1200 | 0.5 | 3.6 | 2.63 | 1.43 | 33 |
| 6 | 800 | 2000 | 0.35 | 2.7 | 2.71 | 1.45 | 38 |
| 7 | 800 | 3200 | 0.28 | 0.8 | 2.82 | 1.50 | 44 |
| 8 | 800 | 6000 | 0.13 | 0.12 | 2.88 | 1.53 | 52 |
| 9 | 900 | 900 | 0.42 | 6.8 | 2.68 | 1.44 | 36 |
| 10 | 1000 | 900 | 0.12 | 2.3 | 2.88 | 1.53 | 48 |
| 11 | 1000 | 2000 | 0.08 | 0.4 | 2.90 | 1.55 | 52 |
| 12 | 1050 | 2000 | 0 | 0.2 | 2.91 | 1.55 | 55 |
| 13 | 1050 | 3200 | 0 | 0.11 | 2.92 | 1.55 | 54 |
| 14 | 1200 | 2000 | 0 | 0.05 below | 2.92 | 1.55 | 54 |
| 15 | 1300 | 2000 | 0 | 0.05 below | 2.51 | 1.45 | 34 |
The test portion that has * is outside the claimed range of the present invention.
As shown in Table 1, the amount of the boron on the surface of coating is following test portion No.4～14 of 1.0 weight %, and the linear foot of the bent moon face of solder is very little can be more than 2.51mm, and crossfoot is very little can be more than 1.42mm.In addition, the bond strength of the lead member after the fatigue test demonstrates above this favorable durability of 20N.In addition, make the test portion No.7,8,10～14 of amount below 0.3 weight % of above-mentioned boron, the linear foot of the bent moon face of solder is very little can be further greatly to more than the 2.82mm, and crossfoot is very little further greatly to more than the 1.5mm, and the bond strength after the fatigue test also can be greatly to more than the 40N.Have again, make the test portion No.8,11～14 of the amount of boron, bond strength is further increased to more than the 50N at 0.1 weight %.
In addition, can further increase the size of the bent moon face of solder, also can increase the heat-treat condition of the bond strength of the lead member after the fatigue test, be judged to be 800～1200 ℃ of temperature, more than its steam partial pressure 900Pa.
With respect to this, the amount of the boron in the surface of coating surpasses test portion No.1～3 of 1.0 weight %, the mean value 100N of the bond strength at relative initial stage, and the bond strength after the fatigue test is lower than 20N, and bond strength reduces greatly.In addition, heat treatment temperature is as 1300 ℃ test portion No.15, electrode pad that constitutes by W and the coating reaction that constitutes by Ni, because coating color, so stopped test after this.
In addition, make following test portion No.4～14 of amount city 10 weight % of the carbon in the surface of coating, judge that the bond strength after the fatigue test surpasses 20N, demonstrate favorable durability.In addition, the test portion No.7,8,11～14 below 2.5 weight % judges that the bond strength after the fatigue test surpasses 40N.With respect to this, the amount of carbon surpasses test portion No.1～3 of 10 weight %, and the bond strength after the judgement fatigue test is reduced to and is lower than below the 20N.
In the present embodiment, making is as the ceramic heater of Figure 1A.Preparation is with Al
2O
3Be principal component, adjust SiO
2, CaO, MgO, ZrO
2Make it be aggregated in 10 weight %,, print heating resistor 3 that constitutes by W-Re and the lead-in wire lead division 3a that constitutes by W on its surface with interior ceramic sheet material 9.In addition, the pad 4 that inside prints electrode.Heating resistor 3, its making are to be made of 5mm heating length to come and go 4 times pattern.
Then,, form the through hole that connects ceramic sheet material 9, inject the work of sticking with paste, realize the conduction of lead-in wire lead division 3a and electrode pad 4 at this by end at the lead-in wire lead division 3a that constitutes by W.The position of through hole, it forms the inboard that enters into the junction surface when implementing soldering.By the ceramic sheet material 9 that will prepare like this be close to ceramic core 10 around, with 1500～1600 ℃ of calcinings, become ceramic heater 1.
After this, implement to adopt the activate of the active liquid that contains Pd to handle, form 1 coating 4 that the non-electrolysis Ni plating by thick 3 μ m constitutes, adopt the Au-Cu solder, the lead member 7 that constitutes by the Fe-Ni-Co alloy with 1020 ℃ of solderings on the surface of electrode pad 4.Implement non-electrolysis Ni plating that 2 time coating 8 be thick 6 μ ms thereafter.Then, will be at H
2-N
2Heat treatment temperature variable in the air-flow is 600 ℃, 700 ℃, 800 ℃, 900 ℃, makes 50 sample respectively.With the goods after the transverse direction grinding heat treatment, make assay sample.
Also have, (determinator: sweep type FE-Auger electron spectroscopy analytical equipment PHI makes Model680 with the Auger electron spectroscopy analytic approach, condition determination: accelerating voltage 5Kv, test portion electric current 10nA) thickness of 2 coating 8 of mensuration, and, in 2 coating 8, measure the 8b that solder 6 compositions have spread according to the line analysis result.
These results of table 2 expression.
Table 2
** * * *
| Sample NO. | Heat treatment temperature (℃) | The non-thickness of diffusion layer t1 of solder (μ m) | Solder thickness of diffusion layer t2 (μ m) |
| 1 | Do not have | 5 | 0 |
| 2 | 500 | 4.9 | 0.1 |
| 3 | 600 | 4 | 1.0 |
| 4 | 650 | 2.6 | 1.4 |
| 5 | 700 | 2.9 | 2.1 |
| 6 | 750 | 2 | 3 |
| 7 | 800 | 1.5 | 3.5 |
| 8 | 850 | 0.5 | 4.5 |
| 9 | 900 | 0.1 | 4.9 |
| 10 | 950 | 0 | 5 |
*Be outside the scope of the invention.
As shown in Table 2, in the low zone of heat treatment temperature, the diffusion of the composition that the solder 6 in 2 coating 8 is contained fails to confirm.But,, then can confirm in 2 coating 8, as the element Cu diffusion that is contained in the solder 6 if heat treatment temperature uprises.
In addition, the heat treatment behind 2 platings, its enforcement are the close-burning raisings for 2 coating 8 and solder 6.In order to confirm this effect, carry out the bend test of each sample, lead member 7, to carry out the affirmation that whether takes place of peeling off of 2 coating 8.The evaluation method of this test is, lead member 7 is carried out 3 bendings back and forth in 90 ° of directions, is amplified to 10 times of eyes, carries out the judgement that whether takes place of peeling off of 2 coating 11.
Its result of table 3 expression.
Table 3
| Sample No. | Heat treatment temperature (℃) | Have or not peeling off of coating after the bending |
| 1 | Do not have | |
| 2 | 500 | Have |
| 3 | 600 | Do not have |
| 4 | 650 | Do not have |
| 5 | 700 | Do not have |
| 6 | 750 | Do not have |
| 7 | 800 | Do not have |
| 8 | 850 | Do not have |
| 9 | 900 | Do not have |
| 10 | 950 | Do not have |
Judge according to table 3, in the low temperature of heat treatment, can confirm lead member 7 after bending, put on the generation of peeling off of 2 coating 8 on the lead member 7.With the No.1,2 of the Low Temperature Heat Treatment below 500 ℃, what can confirm is because the diffusion layer of the solder 6 in 2 coating 8 does not form, so thermal effectiveness fully do not manifest, thereby can't improve the caking property of 2 coating 8 and solder 6.With respect to this, heat treatment temperature as the No.3 more than 600 ℃～10 in, judge that not peeling off of Ni plating take place.This is considered to because the diffusion layer that is used to make caking property to improve forms.
In order to confirm the influence of the diffusing capacity of composition in the Ni plating that solder 6 contained, and each sample is implemented cyclic test in the 400 ℃-R.T atmosphere to quality, the surface after confirming break have or not and the tensile strength of lead member 9.
Its result of table 4 expression.
Table 4
| Sample No. | Heat treatment temperature (℃) | After 400 ℃-3000 circulations | |
| Crack-free is arranged | Soldering | ||
| 1 | Do not have | Do not have | 2.0 |
| 2 | 500 | Do not have | 2.5 |
| 3 | 600 | Do not have | 4.0 |
| 4 | 650 | Do not have | 4.3 |
| 5 | 700 | Do not have | 4.7 |
| 6 | 750 | Do not have | 5.1 |
| 7 | 800 | Do not have | 5.0 |
| 8 | 850 | Have | 2.0Kgf |
| 9 | 900 | Have | 1.8Kgf |
| 10 | 950 | Have | 2.0Kgf |
Judge according to table 4, the thickness of the layer that the composition that the solder 6 in 2 coating 8 is contained does not spread, apart from the surface is among the following No.8,9,10 of 1 μ m, situation about can confirm is, because solder 6 contains the composition excess diffusion in the plating tunicle, so the tensile strength of the lead member 7 after the fatique testing at elevated temperature reduces.If observe this test portion, then can confirm has the generation of breaking on the surface of 2 coating 8.
In the present embodiment, about by the non-oxide ceramics body of execution mode 3 explanation and the joint method of metallic plate, carried out the evaluation of bond strength etc.
(experimental example 1)
The test sample that is produced as follows.
Preparation is the columned ceramic body of principal component and the columned hardware that is made of the Fe-Ni-Co alloy with the silicon nitride, with #600 number grinding stone separately jointing end face is carried out fine gtinding.Afterwards, prepare the Ni powder 96 weight % of particle diameter 1 μ m respectively, the mixed-powder as the powder 4 weight % of V, the Ti of reactive metal particle diameter 1 μ m, Zr, Hf adopts some organic system adhesive and solvent, makes this mixed-powder become pasty state.This muddle is distributed in the joint interface of pottery with the thickness of 0.2mm.After the drying, be coated with solder on the metal level that obtains, the overlapped metal member is fixed, after the intensive drying with the vacuum furnace soldering.
For the test sample that obtains, carry out the mensuration of bond strength, and according to the state confirmation of the reactive metal element in the conversion zone of ESCA.Whether the evaluation of bond strength is by to each layer suspended load, confirm to peel off and judge.Its result is represented by table 5.
Table 5
| The test portion numbering | Impose a condition | Effect | ||||||||
| * be outside the scope of the invention | Reactive metal | Reactive metal adds to be formed | The ratio of the oxide of the reactive metal element of conversion zone (atom %) | The reactiveness of the reactive metal element of joint interface | Particle diameter (μ m) | Vacuum degree (Pa) | Bond strength | |||
| 1 | * | Do not have | - | - | - | - | - | 1.33×10 -1 | × | |
| 2 | * | V | V (metal) | 95 | Oxide | Nitride | Silicide | 1 | 1.33×10 1 | × |
| 3 | V | V (metal) | 60 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | ○ | |
| 4 | V | V (metal) | 30 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | |
| 5 | * | V | VHx (hydrogen compound) | 92 | Oxide | Nitride | Silicide | 1 | 1.33×10 1 | × |
| 6 | V | VHx (hydrogen compound) | 58 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | ○ | |
| 7 | V | VHx (hydrogen compound) | 30 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | |
| 8 | V | VHx (hydrogen compound) | 2 | Oxide | Nitride | Silicide | 1 | 1.33×10 -6 | △ | |
| 9 | * | V | VOx (oxide) | 98 | Oxide | Nitride | Silicide | 1 | 1.33×10 1 | × |
| 10 | * | V | VOx (oxide) | 93 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | × |
| 11 | V | VOx (oxide) | 87 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ○ | |
| 12 | Ti | TiHx (hydrogen compound) | 43 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | |
| 13 | Zr | ZrHx (hydrogen compound) | 38 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | |
| 14 | Hf | HfHx (hydrogen compound) | 40 | Oxide | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | |
More than ◎-50N
Be lower than 50N more than zero-30N
Be lower than 30N more than △-20N
*-be lower than 20N
According to table 5 as can be known, in conversion zone, in the test portion (No.3,4,6,7,11～14) of the ratio of the oxide of reactive metal element in the scope of 5～90 atom %, can access the good test portion of the abundant this engagement state of intensity of conjugant.On the other hand, surpass in the test portion (No.2,5,9,10) of 90 atom %, can not obtain sufficient joint strength at the ratio of the oxide of reactive metal element.In addition, in the ratio of the oxide of reactive metal element is test portion (No.8) below the 5 atom %, in the processing of powder and fire in the processing, must under the condition of high vacuum, engage, aspect manufacture method, stay problem.In addition, in the test portion that does not adopt reactive metal (No.1), also can not get full intensity.
(experimental example 2)
As experimental example 2, make the test sample identical with experimental example 1.Carry out the mensuration of bond strength by ESCA, and from the affirmation of the state of the reactive metal element of the joint interface of the ceramic body conversion zone 3 in the distance of depth direction 1 μ m.
Its result is represented by table 6.
Table 6
| The test portion numbering | Impose a condition | Effect | |||||||||
| * be outside the scope of the invention | Reactive metal | Reactive metal adds to be formed | Ratio (atom %) from the oxide of the reactive metal element of the joint interface degree of | The reactiveness of the reactive metal element of conversion zone | Particle diameter (μ m) | Vacuum degree (Pa) | Bond strength | ||||
| 15 | V | V (metal) | 92 | Oxide | Nitride | Silicide | - | 1.33×10 1 | ○ | ||
| 16 | V | V (metal) | 40 | | Nitride | Silicide | 1 | 1.33×10 -1 | ◎ | ||
| 17 | V | V (metal) | 10 | | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | ||
| 18 | V | VHx (hydrogen compound) | 92 | | Nitride | Silicide | 1 | 1.33×10 1 | ○ | ||
| 19 | V | VHx (hydrogen compound) | 30 | | Nitride | Silicide | 1 | 1.33×10 -1 | ◎ | ||
| 20 | V | VHx (hydrogen compound) | 13 | | Nitride | Silicide | 1 | 1.33×10 -3 | ◎ | ||
| 21 | V | VHx (hydrogen compound) | 0.2 | | Nitride | Silicide | 1 | 1.33×10 -6 | ◎ | ||
| 22 | V | VOx (oxide) | 94 | | Nitride | Silicide | 1 | 1.33×10 1 | ◎ | ||
| 23 | V | VOx (oxide) | 91 | | Nitride | Silicide | 1 | 1.33×10 -1 | ◎ | ||
| 24 | V | VOx (oxide) | 60 | | Nitride | Silicide | 1 | 1.33×10 -3 | ○ | ||
More than ◎-50N
Be lower than 50N more than zero-30N
Be lower than 30N more than △-20N
*-be lower than 20N
According to table 6 as can be known, in conversion zone, in the test portion (No.16,17,19～21,24) of the ratio of the oxide of reactive metal element in the scope of 0.5～90 atom %, can access the good test portion of the abundant this engagement state of intensity of conjugant.
On the other hand, surpass in the test portion (No.15,18,22,23) of 90 atom % at the ratio of the oxide of reactive metal element, intensity slightly reduces, and is no problem scope in the actual use.In addition, in the ratio of the oxide of reactive metal element is test portion (No.21) below the 0.5 atom %, in the processing of powder and fire in the processing, must under the condition of high vacuum, engage.
(experimental example 3)
As experimental example 3,,, estimate Yi Bian make the test sample identical with experimental example 1 Yi Bian change the reactiveness and the particle diameter of reactive metal element.About estimating, carried out the mensuration of bond strength, carry out with ESCA the conversion zone in the joint interface the reactive metal element state and carry out affirmation with EPMA at the state of the distribution of the reactive metal element on composition surface.
Its result is represented by table 7.
Table 7
| Test number | Impose a condition | Effect | ||||||||||
| * be outside the scope of the invention | Reactive metal | Reactive metal adds to be formed | The ratio of the oxide of the reactive metal element of conversion zone (atom %) | The reactiveness of the reactive metal element of conversion zone | Particle diameter (μ m) | Vacuum degree (Pa) | Solder | Brazing temperature | Engage the Strong degree | |||
| 25 | V | V (metal) | 60 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 26 | V | V (metal) | 58 | Oxide | Nitride | Silicide | 5 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 27 | V | V (metal) | 56 | Oxide | Nitride | Silicide | 10 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 28 | * | V | VHx (hydrogen compound) | 94 | Oxide | Nitride | Silicide | 0.1 | 1.33×10 -1 | Ag-Cu | 1000 | × |
| 29 | * | V | VHx (hydrogen compound) | 94 | Oxide | Nitride | Silicide | 02 | 1.33×10 -1 | Ag-Cu | 1000 | × |
| 30 | * | V | VHx (hydrogen compound) | 92 | Oxide | Nitride | Silicide | 0.3 | 1.33×10 -1 | Ag-Cu | 1000 | × |
| 31 | V | VHx (hydrogen compound) | 73 | Oxide | Nitride | Silicide | 0.6 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 32 | V | VHx (hydrogen compound) | 58 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 33 | V | VHx (hydrogen compound) | 57 | Oxide | Nitride | Silicide | 5 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 34 | V | VHx (hydrogen compound) | 57 | Oxide | Nitride | Silicide | 10 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 35 | V | VHx (hydrogen compound) | 58 | Oxide | Nitride | Silicide | 20 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 36 | V | VHx (hydrogen compound) | 55 | Oxide | Nitride | Silicide | 50 | 1.33×10 -1 | Ag-Cu | 1000 | ○ | |
| 37 | V | VHx (hydrogen compound) | 54 | Oxide | Nitride | Silicide | 100 | 1.33×10 -1 | Ag-Cu | 1000 | △ | |
| 38 | V | VHx (hydrogen compound) | 50 | Oxide | Nitride | Silicide | 200 | 1.33×10 -1 | Ag-Cu | 1000 | △ | |
| 39 | V | VHx (hydrogen compound) | 46 | Oxide | Nitride | Silicide | 500 | 1.33×10 -1 | Ag-Cu | 1000 | △ | |
| 40 | V | VHx (hydrogen compound) | 58 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | Ag-Ni | 1300 | △ | |
| 41 | * | V | VOx (oxide) | 93 | Oxide | Nitride | Silicide | 1 | 1.33×10 -1 | Ag-Cu | 1000 | × |
| 42 | * | V | VOx (oxide) | 94 | Oxide | Nitride | Silicide | 5 | 1.33×10 -1 | Ag-Cu | 1000 | × |
| 43 | * | V | VOx (oxide) | 94 | Oxide | Nitride | Silicide | 10 | 1.33×10 -1 | Ag-Cu | 1000 | × |
More than ◎-50N
Be lower than 50N more than zero-30N
Be lower than 30N more than △-20N
*-be lower than 20N
Adopting reactive metal is V, Ti, Zr, Hf or their hydrogen compound, and particle diameter is in the test portion (No.25～27,31～40) of the scope of 0.5～100 μ m, can access to have stable engagement state, and the high ceramic joined article of bond strength.On the other hand, be that it is unstable that bond strength becomes in the test portion (No.41～43) of metal or hydrogen compound powder in addition adopting reactive metal, there is the such problem points of the sufficient joint strength of can not get to take place.
In addition, be in the test portion (No.28,29,30) of the powder of the reactive metal below the 0.5 μ m at same employing particle diameter, it is unstable that bond strength becomes equally, has the such problem points of the sufficient joint strength of can not get to take place.On the other hand, be that the dispersity of active metal powder is bad in the test portion (No.38,39) of the powder of the reactive metal more than the 100 μ m adopting particle diameter, inhomogeneous with the engagement state generation of pottery 40, bond strength is impacted.
In addition, being in the test portion of making more than 1200 ℃ (No.40) with brazing temperature, because be the state of vacuum high-temperature, so the composition evaporation of solder is also arranged, the composition of solder is destroyed, can not get the such problem points of stable engagement state and takes place.
(experimental example 4)
As experimental example 4, on one side the vacuum degree of change in ablating work procedure, make the test sample identical on one side with experimental example 1, carry out this evaluation.About estimating, carry out the mensuration of bond strength, undertaken by ESCA conversion zone the reactive metal element state and carry out affirmation by EPMA in the distribution of the reactive metal element on composition surface.
Its result is represented by table 8.
Table 8
| The test portion numbering | Impose a condition | Effect | |||||||||
| * be outside the scope of the invention | Reactive metal | Reactive metal adds to be formed | The ratio of the oxide of the reactive metal element of conversion zone (atom %) | The reactiveness of the reactive metal element of conversion zone | Particle diameter (μ m) | Vacuum degree (Pa) | Bond strength | ||||
| 44 | * | V | VHx (hydrogen compound) | 94 | | Nitride | Silicide | 1 | 1.33×10 1 | × | |
| 45 | V | VHx (hydrogen compound) | 94 | | Nitride | Silicide | 1 | 1.33 | ○ | ||
| 46 | V | VHx (hydrogen compound) | 58 | | Nitride | Silicide | 1 | 1.33×10 -1 | ○ | ||
| 47 | V | VHx (hydrogen compound) | 30 | | Nitride | Silicide | 1 | 1.33×10 -3 | ○ | ||
| 48 | V | VHx (hydrogen compound) | 10 | | Nitride | Silicide | 1 | 1.33×10 -5 | ○ | ||
| 49 | * | V | VHx (hydrogen compound) | 2 | | Nitride | Silicide | 1 | 1.33×10 -6 | △ | |
More than ◎-50N
Be lower than 50N more than zero-30N
Be lower than 30N more than △-20N
*-be lower than 20N
Be 1.33～1.33 * 10 with the vacuum values in the atmosphere of ablating work procedure
-5In the test portion of making in the scope of Pa (No.46～48), can access and have stable engagement state, and the high ceramic joined article of bond strength.Be that state more than the 1.33Pa has carried out in the test portion (No.44) of ablating work procedure with the vacuum values,, having to can not get the such problem points of desirable bond strength and take place with the oxygen reaction in the atmosphere, the oxidation of reactive metal element.On the other hand, be lower than 1.33 * 10 with vacuum values
-5The vacuum values of Pa has been carried out in the test portion (No.49) of ablating work procedure, when manufacturing cost uprises, because the evaporation of the composition of the solder in the high vacuum is destroyed by forming of solder, can not get the such problem points of stable engagement state and takes place.
In the present embodiment, the ceramic heater 1 shown in construction drawing 5A and Fig. 5 B.
At first, will be as the Yb of the oxide of rare earth element
2O
3Be 10～15 weight %, and MoSi
2Be lower than 5 weight % and an amount of Al
2O
3As sintering aid, making an addition to specific area is 7～15m respectively
2The Si of/g
3N
4In the powder.In addition, suitably make MoSi as required
2, Mo
2C, WSi
2, WO
3Deng containing, adjust agent as colouring agent and coefficient of thermal expansion.This mixed-powder is carried out wet mixing in 24 hours with ball mill to be closed.Afterwards, with the described mud spray-dried separately granulating that obtains, adopt this one-tenth plastochondria to make flat formed body raw material 22a by extrusion.
Then, at micropowder 80 weight % and the Si of WC
3N
4The mixed-powder of micropowder 20 weight % in add solvent, use the paste of modulation, by silk screen print method etc. heater 23a is formed at the surface that generates body 22a.Heater 23a is the pattern of U word shape, finally is positioned in about 5mm compared with the tip of sintered body, so forms.
Then, use the paste of forming by each micropowder of the BN of the WC of 92 weight % and 8 weight %, make the two ends of heater 23a overlapping, 2 the 2nd 23b that go between are formed at appointed positions with a part.Meanwhile, by with the paste of the 2nd lead-in wire 23b same composition, form 2 electrode lead-out part 23d.Electrode lead-out part 23d, rectangular pattern is formed into the side of formed body raw material 22a abreast.
Printing respectively formed described heater 23a, the 2nd lead-in wire 23b, and electrode get on each formed body raw material 22a of lead division 23d, load the W line of diameter 0.3mm, make it to be electrically connected respectively with the pattern of the 2nd lead-in wire 23b and the electrode taking-up 23d of portion.Behind overlapping other the formed body raw material 22a, more than 1 hour, obtaining the roughly ceramic body 22 of rectangular shape with 1780 ℃ temperature hot pressing calcining under the atmosphere of reproducibility thereon.Then, with centerless lapping machine (centerless) nearly the ceramic body 22 of rectangular shape be processed into cylindric.
Afterwards, with the exposed division ways of connecting of the electrode lead-out part 23d of ceramic body 22, with silk screen print method solder layer 24 is piled into the square shape on 3mm limit respectively, in vacuum furnace, fire solder layer 24 with 1000 ℃ temperature.
Next, on solder layer 23, load the Ni system welded diameter 0.6mm lead-in wire hardware 27, by the described metallic plate 25 that the Fe-Ni-Co alloy constitutes, the temperature with 900～1200 ℃ in vacuum furnace connects.With the radius of curvature of ceramic body 22 as R
1, the radius of curvature of the inner peripheral surface of metallic plate 25 is as R
2, the thickness of metallic plate 25 is set (R as 0.20mm multiplely
1-R
2), carry out the making of sample.
In addition, as the ceramic heater that constitutes by aluminium oxide, make the built-in heater that constitutes by W, has the electrode pad that constitutes by W at electrode lead-out part, metal level that constitutes with Au-Cu solder and the metallic plate that constitutes by the Fe-Ni-Co alloy of thick 200 μ m by average thick 50 μ m, (R
1-R
2) be the ceramic heater of 0mm.
Adopt the ceramic heater 1 of the evaluation usefulness that so obtains, carry out fatigue test with 600 ℃ 1000 hours continuous placement of temperature exposure, with being exposed to 40 ℃ of operations with two kinds of temperature of 450 ℃ as 1 circulation, this cold cycling is implemented the fatigue experiment of 10000 cycles.With following method, each electrode behind the evaluation experimental takes out the connection status of the metallic plate 25 of usefulness.
At first, measure the resistance value of the fatigue test front and back of ceramic heater 1, try to achieve the maximum of impedance rate of change, and, utilization liquid penetrant test method and microscope take out the connecting portion periphery of the metallic plate 25 of usefulness and check that what affirmation was broken has or not to the electrode after the cold cycling fatigue test.
Table 9
| The test portion numbering | R1-R2 (mm) | Metal layer thickness ↑ (mm) | Electrode takes out metallic plate | Long duration test | Reference | ||
| Material | Bonding area is than (%) | Resistance change rate (%) | Crack-free is arranged | ||||
| *1 *2 3 4 5 6 7 *8 *9 10 11 12 13 *14 *15 | -0.14 -0.12 -0.10 -0.08 -0.04 0.00 0.15 0.17 0.19 0.00 0.00 0.00 0.00 0.00 0.00 | 0.100 0.100 0.030 0.100 0.100 0.100 0.100 0.100 0.100 0.120 0.140 0.150 0.100 0.160 0.170 | Fe-Ni-Co ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ | 60 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ | 12.9 11.5 5.1 3.2 1.1 2.9 5 10.9 12.7 6.3 7.4 8.3 1.2 10.5 12.1 | Have ↑ do not have ↑ ↑ ↑ ↑ have ↑ do not have ↑ ↑ do not have have ↑ | Aluminium oxide |
The test portion numbering that has * is outside the claimed range of the present invention.
According to table 9 as can be known, (R
1-R
2) be the extraneous test portion numbering 1,2,8,9,14,15 of above-mentioned (formula 1), the impedance rate of change before and after the fatigue test is greatly to more than 13.3%, and all confirms to have to break on the ceramic body after the fatigue test 22.
With respect to this, (R
1-R
2) ceramic heater 1 in the scope of above-mentioned (formula 1), impedance rate of change is all little of below 6.0%, the generation of also not breaking on ceramic body 22.Impedance rate of change is below 6.0%, and breaking after the durable evaluation do not take place, if the radius R of ceramic body 22
1, with the radius of curvature R of the inner peripheral surface of metallic plate 25
2Difference in the scope of formula 1, then avoided concentrating of stress, its result can confirm as, the bonding strength that electrode takes out the metallic plate 25 of usefulness is improved significantly.
Claims (14)
1, a kind of ceramic heater has: ceramic body; Be built in the heating resistor of described ceramic body; Electrode pad, it is formed at the surface of described ceramic body, to described heating resistor energising; Be formed at the coating on the surface of described electrode pad; Be engaged in the lead member of described coating by solder, it is characterized in that,
The amount of the boron in the surface of described coating is below the 1 weight %.
2, according to the ceramic heater of claim 1 record, it is characterized in that,
The amount of the carbon in the surface of described coating is below the 10 weight %.
3, according to the ceramic heater of claim 1 or 2 records, it is characterized in that described coating forms by electroless plating.
4, a kind of manufacture method of ceramic heater, this ceramic heater has: ceramic body; Be built in the heating resistor of described ceramic body; Electrode pad, it is formed at the surface of described ceramic body, to described heating resistor energising; Be formed at the coating on the surface of described electrode pad; Be engaged in the lead member of described coating by solder, this manufacture method is characterised in that,
Inside at ceramic body forms heating resistor,
On the surface of described ceramic body, the electrode pad of formation and described heating resistor conducting,
Surface at described electrode pad forms coating,
Implement heat treatment,
By in reducing atmosphere, firing processing, through solder bonding wire member on described coating.
5, according to the manufacture method of the ceramic heater of claim 4 record, it is characterized in that,
Described heat treatment, temperature are 800～1200 ℃, and steam partial pressure is more than the 900Pa.
6, a kind of ceramic heater has: ceramic body; Be built in the heating resistor of described ceramic body; Electrode pad, it is formed at the surface of described ceramic body, to described heating resistor energising; Be formed at the coating on the surface of described electrode pad; Be engaged in the lead member of described coating by solder; Cover 2 coating of described solder, it is characterized in that,
The diffusion layer of the solder composition in described 2 coating is more than the 1 μ m, and the thickness on the surface of the no diffusion layer of the solder composition from described 2 coating is more than the 1 μ m.
7, according to the ceramic heater of claim 6 record, it is characterized in that the particle of described 2 coating directly is below the 5 μ m.
8, a kind of ceramic heater on the ceramic body that is made of non-oxidized substance, is connected with metallic plate by solder, it is characterized in that,
Described solder is a principal component with the metal ingredient of liquidus temperature below 1200 ℃, as reactive metal contain among V, Ti, Zr, the Hf more than at least a kind,
Between described solder and described ceramic body, be formed with the conversion zone of described reactive metal and described ceramic body reaction,
The ratio of the oxide of the described reactive metal in the described conversion zone is in the scope of 5～90 atom %.
9, the ceramic heater of putting down in writing according to Claim 8 is characterized in that,
In described conversion zone, except that the oxide of described reactive metal, also comprise more than at least a kind of nitride, silicide or carbide of described active layer.
10, according to Claim 8 or 9 the record ceramic heaters, it is characterized in that,
The principal component of described solder, be from by Ni system, Au-Ni system, Ag-Cu system, Ag-Cu-In system, and the group that constitutes of Au-Cu system optional a kind.
11, the ceramic heater of each record in 10 according to Claim 8 is characterized in that,
From with the scope of the joint interface 0.1 μ m of described ceramic body described conversion zone in the ratio of oxide of reactive metal, in the scope of 0.5～90 atom %.
12, the manufacture method of the ceramic heater of each record in 11 according to Claim 8 is characterized in that,
On described ceramic body, coating contains the monomer of described reactive metal or the metal paste of hydrogen compound with the scope of particle diameter 0.5～100 μ m,
In vacuum values is 1.33～1.33 * 10
-5Heat in the vacuum atmosphere in the scope of Pa.
13, the ceramic heater of each record in 11 according to Claim 8 is characterized in that,
Described ceramic body is cylindric or cylindric, and described metallic plate is the curved surface shape,
When with the junction surface of described metallic plate on the radius of curvature of described ceramic body as R
1, the radius of curvature of the inner peripheral surface of described metallic plate is as R
2, the average thickness of described solder layer satisfies during as t
-0.1≤(R
1-R
2)＜t
Relation, wherein, R
1, R
2, t unit be mm.
14, according to the ceramic heater of claim 13 record, it is characterized in that,
At the periphery of described metallic plate, the thickness of filler that is formed between described metallic plate and the ceramic body is 30～150 μ m.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003394820A JP2005158471A (en) | 2003-11-25 | 2003-11-25 | Ceramic heater and manufacturing method of same |
| JP394820/2003 | 2003-11-25 | ||
| JP428254/2003 | 2003-12-24 | ||
| JP2003428254A JP4295607B2 (en) | 2003-12-24 | 2003-12-24 | Ceramic heater |
| JP019876/2004 | 2004-01-28 | ||
| JP2004019876A JP4562400B2 (en) | 2004-01-28 | 2004-01-28 | Bonded body using brazing material containing active metal and method for manufacturing the same |
| PCT/JP2004/017404 WO2005060311A1 (en) | 2003-11-25 | 2004-11-24 | Ceramic heater and method for manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1947461A true CN1947461A (en) | 2007-04-11 |
| CN100596248C CN100596248C (en) | 2010-03-24 |
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ID=34720741
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480034597A Active CN100596248C (en) | 2003-11-25 | 2004-11-24 | Ceramic heater and manufacturing method of same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2005158471A (en) |
| CN (1) | CN100596248C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103139948A (en) * | 2011-11-29 | 2013-06-05 | 中国科学院地质与地球物理研究所 | Electrothermal furnace wire and electric heating device provided with the same |
| CN103717552A (en) * | 2011-07-28 | 2014-04-09 | 株式会社东芝 | Method of manufacturing oxide ceramic circuit board, and oxide ceramic circuit board |
| CN114180943A (en) * | 2020-09-15 | 2022-03-15 | 日本碍子株式会社 | Composite sintered body, semiconductor manufacturing apparatus member, and method for manufacturing composite sintered body |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4769136B2 (en) * | 2006-07-21 | 2011-09-07 | 日本特殊陶業株式会社 | Manufacturing method of ceramic joined body and ceramic heater |
| US8058592B2 (en) | 2007-03-27 | 2011-11-15 | Denso Corporation | Ceramic heater, gas sensor, and method of producing ceramic heater |
| JP5336426B2 (en) * | 2010-05-25 | 2013-11-06 | 日本特殊陶業株式会社 | Gas sensor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0648408Y2 (en) * | 1986-03-05 | 1994-12-12 | 日本碍子株式会社 | Oxygen sensor with heater |
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2003
- 2003-11-25 JP JP2003394820A patent/JP2005158471A/en active Pending
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2004
- 2004-11-24 CN CN200480034597A patent/CN100596248C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103717552A (en) * | 2011-07-28 | 2014-04-09 | 株式会社东芝 | Method of manufacturing oxide ceramic circuit board, and oxide ceramic circuit board |
| CN103717552B (en) * | 2011-07-28 | 2016-01-06 | 株式会社东芝 | The manufacture method of oxide based ceramic circuit board and oxide based ceramic circuit board |
| CN103139948A (en) * | 2011-11-29 | 2013-06-05 | 中国科学院地质与地球物理研究所 | Electrothermal furnace wire and electric heating device provided with the same |
| CN103139948B (en) * | 2011-11-29 | 2015-09-09 | 中国科学院地质与地球物理研究所 | Electrothermal furnace silk and there is the electric heater unit of this electrothermal furnace silk |
| CN114180943A (en) * | 2020-09-15 | 2022-03-15 | 日本碍子株式会社 | Composite sintered body, semiconductor manufacturing apparatus member, and method for manufacturing composite sintered body |
| CN114180943B (en) * | 2020-09-15 | 2023-06-27 | 日本碍子株式会社 | Composite sintered body, semiconductor manufacturing device member, and method for manufacturing composite sintered body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005158471A (en) | 2005-06-16 |
| CN100596248C (en) | 2010-03-24 |
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