CN101232071A - Thermoelectric module and package thereof - Google Patents
Thermoelectric module and package thereof Download PDFInfo
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- CN101232071A CN101232071A CNA2007103057139A CN200710305713A CN101232071A CN 101232071 A CN101232071 A CN 101232071A CN A2007103057139 A CNA2007103057139 A CN A2007103057139A CN 200710305713 A CN200710305713 A CN 200710305713A CN 101232071 A CN101232071 A CN 101232071A
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Abstract
The present invention provides a thermoelectric conversion module and thereof packaging. The thermoelectric conversion module is provided with a support substrate, a plurality of the thermoelectric conversion elements arranged on the support substrate, the wiring conductors which electrically connect the thermoelectric conversion elements, and an external connector electrically connected to the wiring conductors. In the module, a cross section shape of the wiring conductor is made into a rectangle profile or a trapezoidal shape whose upper edge of an element joint surface side is longer than the lower edge of a support substrate side. Thereafter, reliability can be improved.
Description
The application divides an application, the application number of its female case application: the 200410089674.X applying date: 2004.10.29, denomination of invention: thermoelectric inverting model
Technical field
The present invention relates to be suitable for that temperature control, low temperature are heat insulation, the thermoelectric (al) inversion module and the encapsulation thereof of generating.
Background technology
If the PN junction that thermoelectric element utilization current direction is made of P type semiconductor and N type semiconductor, then the peltier effect of end heating and other end heat absorption.Can carry out accurate temperature control, small-sized and simple structure to its modular thermoelectric inverting model.Therefore, wait in expectation to the electronic cooling element of the cooling device of no freon, photodetector, semiconductor-fabricating device etc., the thermoregulator extensive utilization of laser diode.In addition, on the contrary, when the formation temperature difference of the two ends of thermoelectric inverting model, have the feature that flows through electric current, also wait in expectation and utilize on generating etc. is reclaimed in heat extraction.
Being constructed as follows of thermoelectric inverting model is described.Surface 2 support substrates forms the wiring conductor respectively.Clamping has a plurality of thermoelectric elements that P type thermoelectric element and N type thermoelectric element constitute between 2 support substrates, is engaged by solder.The P type of equal number and N type thermoelectric element are paired, are linked in sequence with the wiring conductor, make many electricity to be connected.The end of wiring conductor is connected on the external connection terminals again.On this external connection terminals, connect lead-in wire, from outside supply capability by solder.Below, describe the formation of each one in detail.
At first, be illustrated with regard to the thermoelectric element.Near the cooling of using room temperature has the P type of a plurality of paired equal numbers of electricity series connection and the structure of N type thermoelectric element with thermoelectric inverting model.In the material of thermoelectric element used herein,, generally use A from the viewpoint of cooling characteristics excellence
2B
3Type crystallization (A is Bi and/or Sb, and B is Te and/or Se).Wherein, as P type thermoelectric element, Bi
2Te
3(bismuth telluride) and Sb
2Te
3The excellent especially performance of solid solution performance of (antimony telluride) is as N type thermoelectric element, Bi
2Te
3And Bi
2Se
3The excellent especially performance of solid solution performance of (bismuth selenide).
The pyroelecthc properties do as one likes of these thermoelectric crystallizations can exponential representation.Here, performance index Z be when Seebeck coefficient be S, resistivity is ρ, when pyroconductivity is k, by Z=S
2/ ρ k definition.Be performance and the efficient of performance index Z when representing to use thermoelectric crystalline material as the thermoelectric element.Promptly as N type thermoelectric element and P type thermoelectric element, more the material that the serviceability index is high, can obtain the thermoelectric inverting model of cooling performance, efficient excellence more.
As these A
2B
3Crystallization proposes to use melting material (thermoelectric semiconductor and the application thereof (Nikkan Kogyo Shimbun p.149) of making by based on the unidirectional solidification technology of disclosed single crystals manufacturing technologies such as Bridgman method, crystal pulling method (CZ), zone melting method.In view of the above, obtain by the crystallization of crystal orientation unanimity or near mcl crystalline solid constitutes and performance index Z is high thermoelectric crystallization.
And there is damaged problem easily in the melting material, so viewpoint of the processed finished products rate during from the making that improves thermoelectric inverting model, propose to use: the mixed-powder fusing that makes Bi, Sb, Te, Se etc., the melted alloy of solidifying are pulverized, obtain alloy powder, the agglomerated material (the flat 8-32588 of Japanese patent laid-open publication gazette communique number, open the flat 1-106478 of communique number of Japan Patent) that this alloy powder pressure sintering is formed by hot press etc.
By making up the thermoelectric element of these agglomerated materials of a plurality of uses or melting material, make thermoelectric inverting model.At this moment, from improving performance index, improving the viewpoint of the reliability of processed finished products rate or thermoelectric inverting model, the thermoelectric inverting model (open the flat 8-148725 of communique number of Japan Patent, open the flat 11-26818 of communique number of Japan Patent) of combination melting material and agglomerated material is also proposed.
Also report: N type thermoelectric element is used the single crystals material, P type thermoelectric element is used agglomerated material, ratio resistance by making these thermoelectric elements is identical in fact, and the performance of thermoelectric inverting model further improves (U.S. Patent bulletin 5448109B1 number).
Below, the method for attachment of thermoelectric element and wiring conductor is described.The wiring conductor is used copper electrode.And on the joint face of thermoelectric element, form electrode by nickel plating.For the solder that makes wiring conductor and thermoelectric element engages firmly, improve the soakage of thermoelectric element and solder, prevent of the diffusion of solder composition to thermoelectric inverting element, form electrode based on nickel plating.Particularly, propose to form nickel plating (open the flat 6-21268 of communique number of the practical new case of Japan) by spraying plating in order to improve the intensity of being close to of nickel plating.On the surface of Ni electrode, in order further to improve the soakage of solder, form cover layer by Au etc.
In addition, when engaging wiring conductor and thermoelectric element, because the surface tension of the solder of fusing causes the offset of thermoelectric element, and make the pars intermedia shape narrow (No. 2544221, Japanese patent gazette) of wiring conductor in order to prevent by solder.
In addition, in order to prevent to remain the contacts side surfaces of solder and thermoelectric element, propose on the wiring conductor, to form recess (open the flat 10-303470 of communique number of Japan Patent).
For the space (bubble) of discharging, reducing solder, propose on the wiring conductor, to form ditch (open the flat 9-055541 of communique number of Japan Patent).
Below, thermoelectric inverting model and outside being connected are described.The end of the wiring conductor in the thermoelectric inverting model also is connected on the external connection terminals.On this external connection terminals, connect lead-in wire, from outside supply capability by solder.In the connection of lead-in wire,, the method (No. 2583149, Japanese patent gazette) that engages by LASER HEATING is proposed in order to improve problem of short-circuit and operation.Particularly, the thermoelectric element that is arranged on the support substrates is electrically connected with the wiring conductor, forms external connection electrode in its end.Shine on one side YAG laser, on one side by solder wire-bonded on external connection electrode., in order to connect lead-in wire, except the joining technique based on the special type of YAG laser necessitates, because splicing ear is positioned at the inside of thermoelectric inverting model, so be necessary that operation is connected lead-in wire in the encapsulation by hand.Therefore, take the time, the problem that exists rate of finished products to reduce.
Therefore, the end of the wiring conductor of promotion in thermoelectric inverting model is provided with the thermoelectric inverting model (for example, No. the 3082170th, Japanese patent gazette) that carries out the external connection electrode of wire-bonded from external energy.In view of the above, after the package bottom of semiconductor laser is provided with thermoelectric inverting model, can connect the outer electrode of thermoelectric inverting model and the electrode terminal in the laser module with lead-in wire 28.; in No. the 3082170th, Japanese patent gazette in the method for record; connect the thermoelectric inverting model that is positioned near the position of the inner base plate of semiconductor laser encapsulation, the electrode terminal that is arranged on the position of close top board with elongated lead-in wire; so resistance increases; exist owing to generate heat the problem that power consumption increases.
In addition, propose on electrode pad, to be provided with elongated prolongation electrode, shorten the length of lead-in wire., in order to obtain sufficient height, be necessary to form elongated prolong electrode by prolonging electrode.Become elongatedly if prolong electrode, the intensity that then prolongs electrode becomes insufficient, prolongs electrode fracture, bending so exist when wire-bonded, or prolongs the problem that peel off at the junction surface of electrode and external connection electrode.Particularly when the prolongation electrode is elongated, be difficult to vertical setting, the rate of finished products of wire-bonded usually reduces.
In addition, propose on the upper support substrate of thermoelectric inverting model plane electrode to be set, the electrode terminal and the lead-in wire 28 of the encapsulation by being arranged in semiconductor laser etc. are connected (for example Japan Patent discloses the flat 11-54806 of communique number)., in the method for record, on support substrates, directly carry out wire-bonded in open the flat 11-54806 of communique number of the Japan Patent, thus owing to impact, crisp thermoelectric element breakage, or the support substrates distortion and between element and cloth line electrode crackle.
Performance demands for thermoelectric inverting model further improves, also variation of the characteristic of Yao Qiuing in addition.For example, in purposes such as refrigerator, the temperature difference of the top and bottom when thermoelectric inverting model is switched on is compared, and especially payes attention to caloric receptivity or endothermic character.And in the laser diode temperature adjustment, be necessary temperature is kept certain, so compare more demanding temperature difference with endothermic character.
, for these requirements, in thermoelectric inverting model in the past, in the raising of performance, there is boundary.Be that endothermic character and maximum temperature difference all increase according to the performance index of thermoelectric crystallization, so only be difficult to obtain the performance of improving thermoelectric crystallization by simple, just can only increasing substantially endothermic character or only increase substantially the module that maximum temperature difference etc. respectively requires to have on the characteristic feature.
In addition, to the demanding reliability of thermoelectric inverting model., in thermoelectric inverting model in the past, in reliability tests such as impact, power cycles test, high temperature action, there is inadequate thermoelectric inverting model.Because a variety of causes such as deterioration of the coupling part of deterioration, thermoelectric inverting model and the outside at the junction surface of the deterioration of thermoelectric element self, thermoelectric element and wiring conductor cause the bad of these reliability tests.
At thermoelectric inverting model with in outside the connection, exist by solder connect lead-in wire type, connect the type of lead-in wire by wire-bonded, but at any time, all on reliability, have problems.Promptly by solder to thermoelectric inverting model the time, there is skew in wire-bonded on the bond strength of lead-in wire, wiring sometimes comes off easily.In addition, when the type that thermoelectric inverting model is electrically connected, there is the high problem of the resistance of lead-in wire, by wire-bonded because the problem of the impact thermoelectric element breakage during wire-bonded.
Summary of the invention
The objective of the invention is to: at least more than one of problem that solves described thermoelectric inverting model.
More specifically, first purpose of the present invention is: provide the thermoelectric inverting model of any one particularization of endothermic character or temperature difference characteristic.
In addition, second purpose of the present invention is: provide reliability high thermoelectric inverting model.
One of thermoelectric inverting model of the present invention is characterised in that: N type and P type thermoelectric combination of elements in the thermoelectric inverting model.The present inventor prepares N type thermoelectric element with different pyroelecthc properties and the P type thermoelectric element of being made by the whole bag of tricks in advance, make thermoelectric inverting model by various combinations, found that of investigation endothermic character and temperature difference characteristic: the ratio resistance by making N type, P type thermoelectric element is various combination, and any one party of the endothermic character of thermoelectric inverting model or temperature difference characteristic all improves.
Be the thermoelectric inverting model of certain form of the present invention have support substrates, at the N type of arranging with equal number on this support substrates and P type thermoelectric element, the interelement wiring conductor of the electricity a plurality of thermoelectrics of series connection, be arranged on the described support substrates and the external connection terminals that is electrically connected with this wiring conductor, it is characterized in that: described N type thermoelectric element is different with the ratio resistance of P type thermoelectric element, described N type thermoelectric element is made of the melting material, and P type thermoelectric element is made of agglomerated material.Have gap by the ratio resistance that makes N type thermoelectric element and P type thermoelectric element, can only improve the endothermic character of thermoelectric inverting model or any one party of temperature difference characteristic.
When wanting to increase the maximum temperature difference of thermoelectric inverting model, can control, make the ratio resistance ratio P type thermoelectric element of N type thermoelectric element also little.At this moment, the ratio (N type/P type) of wishing the ratio resistance of N type thermoelectric element and P type thermoelectric element is more than 0.7, below 0.95.
And when wanting to reduce the caloric receptivity of thermoelectric inverting model, can control, make the ratio resistance ratio P type thermoelectric element of N type thermoelectric element also big.At this moment, the ratio (N type/P type) of wishing the ratio resistance of N type thermoelectric element and P type thermoelectric element is more than 1.05, below 1.30.
In addition, N type thermoelectric element is made of the melting material, and P type thermoelectric element is made of agglomerated material.In view of the above, can increase substantially described effect.
In addition, wish the output factor ((Seebeck coefficient) of N type thermoelectric element and P type thermoelectric element
2/ than resistance) be 4 * 10
-3W/mK
2More than.In view of the above, can find practical cooling characteristics.
Wish that N type inverting element is the bar-shaped crystalline solid of being made by unidirectional solidification.By N type thermoelectric element is suitable for bar-shaped crystalline solid, can further improve the performance of thermoelectric inverting model, can realize low-cost simultaneously.
In addition, P type thermoelectric element wishes it is the following sintered bodies of particle diameter 50 μ m.By P type thermoelectric element is used the thermoelectric element that is made of fine agglomerated material, can obtain endothermic character or the excellent especially thermoelectric inverting model of temperature difference characteristic in cooling performance.
Like this, any one party that can obtain caloric receptivity or maximum temperature difference is significantly high, is suitable for the thermoelectric inverting model of the adjustment or the refrigerator purposes of semiconductor laser., demanding reliability in these purposes, but in thermoelectric inverting model in the past, reliability is insufficient.Promptly in thermoelectric inverting model in the past, exist in the shock test low stress reach destruction, in the power cycles test, in short life, reach destruction.
This patent inventor investigates and analyses found that of this phenomenon with keen determination and becomes in reliability test in the bad thermoelectric inverting model, has to have the gap between wiring conductor and thermoelectric element.Found that when thermoelectric element during from the off-centring of the conductor that connects up of investigation and analysis is easy to generate the gap with keen determination.This offset is because the inverting element permutation produces with the surface tension of the gap of anchor clamps and inverting element, solder.In the past, be displaced to the position of the end-limit of wiring conductor sometimes.In addition, the present inventor finds, owing to the marginal portion on the thermoelectric element composition surface of wiring conductor is reasons such as taper or big thickness circular-arc, uneven or wiring conductor self is not parallel, produces the gap.
Therefore, in the thermoelectric inverting model of certain form of the present invention, on the section shape of wiring conductor, has feature.The section shape of conductor of promptly connecting up is characterised in that: the trapezoidal shape that the top of rectangle or element composition surface one side is also longer than the bottom of support substrates face one side.By the section shape that makes the wiring conductor is the length of side trapezoidal of rectangle or element composition surface one side, even the position of inverting element from the off-centring of wiring conductor, also is difficult to produce the gap between inverting element and wiring conductor.Therefore, can prevent that machinery or thermal stress are concentrated.In view of the above, impacting or during energizing test, do not having low stress or destroy in the short time, reliability height, stable thermoelectric inverting model can be provided.In the section shape that makes the wiring conductor, element composition surface and the side angulation adjacent with it are 45～90 ° scope, can provide reliability higher, stable thermoelectric inverting model.
In addition, the depth of parallelism of bottom and upper segment of wishing the element composition surface of described wiring conductor is below the 0.1mm.In addition, the flatness on the element composition surface of described wiring conductor is below the 0.1mm.In view of the above, can provide reliability height, stable thermoelectric inverting model.
In addition, described wiring conductor with select from Cu, Ag, Al, Ni, Pt, Pd at least a more than element be principal component.The resistance of these materials is low, and the pyroconductivity height is so can suppress heating and thermal diffusivity excellence.
In addition, described wiring surface of conductors wishes that having with at least a above element among Sn, Ni, the Au is the cover layer of principal component.In view of the above, the soakage of solder can be improved, good electrical conductivity, bond strength can be obtained.
In addition, wish to use the making of selecting from coating method, metalikon, DBC (Direct-bonding copper) method, chip join method of method more than a kind.In view of the above, the wiring conductor of energy patterning case precision, current value and cost the best.
Be adapted at utilizing the Bi-Te class thermoelectric element that uses in the thermoelectric inverting model of peltier effect, if use for a long time under the ambient temperature more than 80 ℃, then performance runs down sometimes.The present application person investigates and analyses the result of this phenomenon with keen determination shown in Fig. 5 A and Fig. 5 B, when finding the contacts side surfaces when the solder of bonding wire member 5 (going between or block type electrode) and adjacent thermoelectric element 2, the speed of the mis-behave of thermoelectric inverting model is fast.With keen determination investigation and analysis found that the Te reaction that comprises in the Sn that comprises in the solder and the thermoelectric element, cause volumetric expansion, the result is broken in the thermoelectric element, causes destruction.In addition, the Sn composition in the solder is diffused into found that because the solder of bonding wire flows out in the thermoelectric element, so do not keep electric engagement state, final broken string.
In view of described, in certain form of the present invention, it is characterized in that: externally the Sn that comprises in the solder of bonding wire member on the splicing ear is more than the 12 weight %, below the 40 weight %.In view of the above, suppress reaction, the deterioration of thermoelectric element and solder, therefore, can provide the thermoelectric inverting model that carries out the high electrical connection of long-term reliability.
In addition, the porosity of described thermoelectric element is wished below 10%.In view of the above, the reaction speed with solder can be suppressed, long-term reliability can be improved.
Because when described thermoelectric element comprises among among Bi, the Sb at least a kind and Te, the Se at least a kind, can obtain favorable cooling effect, so wish.
In addition, if having at least a kind the cover layer that comprises among Sn, Ni, Au, Pt and the Co, then when joint is carried in encapsulation, with the soakage excellence of solder, so can obtain good bond strength on the surface of described lead member.
Because the bond strength of described external connection terminals and described lead member can be eliminated the problem that lead member comes off when to be 2N above, so wish.
Can carry out the electric step that engages step, the described external connection terminals of joint and the lead member of a plurality of described thermoelectric element that disposes on the support substrates simultaneously, also can in different steps, carry out.When in different steps, carrying out, carry out second step that electricity engages first step, the described external connection terminals of joint and the lead member of a plurality of described thermoelectric element that disposes on the support substrates successively.In view of the above, can heat the bonding wire member with point, in addition, it is different with the joint solder of thermoelectric element that the joint solder of lead member can use.The solder of the solder by use reducing the lead member junction surface and the reaction of inverting element can improve reliability.
In thermoelectric inverting model in the past, as one of low reason of reliability, when in encapsulation etc. when installing, the problem that exists lead-in wire to come off easily.The result that the present inventor analyzes this problem knows existence skew on the bond strength of lead-in wire and solder, has intensity inadequate.In addition, find from the inner diffusion layer that forms the lead-in wire composition of the solder that goes between, inadequate about intensity, between lead-in wire and solder, do not form sufficient diffusion layer.
Therefore, in other forms of the present invention, it is characterized in that: in the solder on the external connection terminals that lead member is joined to thermoelectric inverting model, form the above lead member composition diffusion layer of thickness 0.1 μ m, and this diffusion layer be engaged area 20% or more in existence.
In addition, wave is wished to be in the interface of the diffusion layer of lead member composition and non-diffusion layer.In view of the above, can further improve bond strength.
In addition, if diffusion layer just can provide the thermoelectric inverting model that can realize stable installation, so wish than non-diffusion layer densification on every side.
In addition, if, just can realize stable installation with 103～130% temperature bonding wire member of solder fusion temperature.
In addition, as lead member, can use lead-in wire or block type electrode.If engage block type electrode as lead member, then wire-bonded becomes possibility, can make the installation exercise automation easily, can shorten the activity duration.
Here, when carrying out wire-bonded as lead-in wire formation joint block type electrode, wire widths is very thin, so the resistance height.Therefore, wish to shorten wire length, the high electrical connection of joint reliability is carried out in power saving.In addition, be necessary to improve the operation of wire-bonded.
Therefore, in other forms of the present invention, it is characterized in that: have: the lower support substrate, be arranged in a plurality of thermoelectric elements on this lower support substrate, be arranged on upper support substrate on a plurality of thermoelectric elements, be electrically connected the interelement wiring conductor of a plurality of thermoelectrics, be arranged on the described upper support substrate and the external connection terminals that is electrically connected with this wiring conductor, this external connection terminals possess plane electrode, with its on contact and the block type electrode that is wholely set.
In view of the above, can shorten the length of lead-in wire, can reduce resistance, realize power saving.In addition, can make the height of block type electrode low,, can improve rate of finished products so fracture can reduce wire-bonded the time or the problem that peels off at bending or junction surface.Because the impact in the time of reducing wire-bonded by block type electrode, rate of finished products can be improved, and can improve reliability.
In addition,, required resistance can be set, the I-E characteristic of thermoelectric inverting model can be set easily by shape, size, the material of arbitrarily selected block type electrode.Therefore, complement each other, can reduce the resistance of wiring, help power saving significantly with the shortening of wire length.
Especially, preferred: described upper support substrate had pore electrod, and described external connection terminals and described wiring conductor are situated between and are electrically connected by the described pore electrod of crossing.In view of the above, can on the upper support substrate, block type electrode be set more easily.
In addition, described cross pore electrod wish to be arranged on described thermoelectric element directly over.In view of the above, reliability can be improved, energy loss can be reduced based on heating about being electrically connected.
Described block type electrode wishes to comprise the metal of at least a kind of element of Zn, Al, Au, Ag, W, Ti, Fe, Cu, Ni and Mg.The block type electrode of low resistance, little power consumption can be set in view of the above.
In addition, the ratio for height of the maximum major diameter of described block type electrode wishes to be 0.2～20.In view of the above, can reduce fractureing when engaging or the problem that peels off at bending or junction surface, and can improve perpendicularity and linearity easily, so can improve rate of finished products.
In addition, the fusion temperature of the solder of hope described plane electrode of joint and block type electrode is different with the fusion temperature of the solder that engages described thermoelectric element and wiring conductor.In view of the above, can utilize the fusion temperature of solder poor, make to install to become easy.
And, it is characterized in that: make described plane electrode and block type electrode integrated by localized heating.In view of the above, block type electrode can be set more easily.
In addition, described block type electrode wishes on its surface at least a thin layer that comprises Ni, Au, Sn, Pt and Co to be set.In view of the above, the soakage of solder can be improved, good engagement state can be obtained.
In addition, the encapsulation of thermoelectric inverting model of the present invention has container, is arranged on the electrode terminal of this internal tank, described thermoelectric inverting model, and the upper surface of described block lead member and described electrode terminal are roughly the same height.In view of the above, can make the length of lead-in wire the shortest, and the operation of wire-bonded become easy.
Description of drawings
Fig. 1 is the stereogram of the example of the thermoelectric inverting model when representing lead member for lead-in wire.
Fig. 2 is the stereogram of the example of the thermoelectric inverting model of expression lead member when being block type electrode.
Fig. 3 A and B are the thermoelectric element of thermoelectric inverting model of expression example of the present invention and the local amplification view of connecting portion of wiring conductor.
Fig. 4 A～C is a local amplification view of representing the connecting portion of the thermoelectric element of thermoelectric inverting model in the past and the conductor that connects up.
Fig. 5 A is near the partial enlarged drawing of the appearance of the external connection terminals of the thermoelectric inverting model when representing lead member for lead-in wire.
Fig. 5 B is near the partial enlarged drawing of the appearance of the external connection terminals of the thermoelectric inverting model when representing lead member for lead-in wire.
Fig. 6 A is near the local amplification view of the appearance of the connecting portion of the lead member when representing lead member for lead-in wire.
Fig. 6 B is near the local amplification view of the appearance the connecting portion of the lead member of expression lead member when being block type electrode.
Fig. 7 A and B are the stereogram and the cutaway views of the thermoelectric inverting model structure in expression the present invention example.
Fig. 7 C is the cutaway view that expression is installed in the thermoelectric inverting model shown in Fig. 7 A and the B appearance in the encapsulation.
Embodiment
Below, describe the invention process form in detail.
Example 1
In this example, the different thermoelectric inverting model of ratio resistance of P type thermoelectric element and N type thermoelectric element is described.Here, as shown in Figure 1, be that example describes when being lead-in wire with the lead member.
Thermoelectric inverting model shown in Figure 1 has support substrates 1a, the 1b that is made of pottery such as aluminium oxide or insulative resin, the N type thermoelectric element 2a that arranges with equal number and P type thermoelectric element 2b, the interelement wiring conductor of the electricity a plurality of thermoelectrics of series connection 3a, 3b, is arranged on described support substrates 1a, the 1b and the external connection terminals 4 that is electrically connected with wiring conductor 3a, 3b on this support substrates 1a, 1b.Externally can connect lead-in wire 5 by solder 6 on the splicing ear 4.Become by being connected lead-in wire 5 on the external connection terminals 4 from the structure of outside supply capability.
N type, P type thermoelectric element can be used and almost same in the past method manufacturing.For example, thermoelectric material section for sandwiching the thickness of the direction in the thermoelectric inverting model, in order to improve the solder zygosity, carry out nickel plating, gold-plated after, be cut to required form, obtain inverting element.
In the thermoelectric inverting model of this example, it is characterized in that: described N type thermoelectric element 2a and P type thermoelectric element 2b than resistance difference.Here, in order to control the ratio resistance of N type and P type thermoelectric element, following method is arranged.Promptly by when making element, pressurization or unijunction crystallization make the crystalline orientation variation, and can control ratio resistance.For example, when the pressure sintering material, pressure high specific resistance more is high more.In addition, little about 1 order of magnitude of the ratio resistance of the perpendicular direction of ratio resistance ratio of the c face parallel direction thermoelectric element and crystallization.For this reason, if make thermoelectric element unijunction crystallization, control makes the c face of crystallization towards the direction parallel with respect to the direction of growth, then than resistance decreasing.In addition, the adding rate of halogens such as iodine, bromine is changed, the adding rate of elements such as Te, Se is changed, compare resistance thereby can adjust.By the adding rate of described interpolation element, when adjusting than resistance, general adding rate is low more, and is higher more than resistance.
By making N type thermoelectric element 2a different with the ratio resistance of P type thermoelectric element 2b, and compare when identical, the caloric receptivity of thermoelectric inverting model or any one party of temperature difference all can increase substantially.Here, be meant with mensuration thermoelectric materials such as four-terminal methods more than the precision of determining instrument, to have poor situation fully than resistance difference than the value of resistance.In the present invention, the difference that refers to the ratio resistance of N type thermoelectric element 2a and P type thermoelectric element 2b is 5% when above.
Poor about forming by such contrast resistance, can improve the essential factor of any one party of the caloric receptivity of thermoelectric inverting model or temperature difference, though indeterminate, consider as follows.
Transmitting the carrier of the heat of thermoelectric semiconductor, is electronics in N type thermoelectric element 2a, is the hole in P type thermoelectric element 2b.Here, move in the hole is moving of outward appearance, and in P type thermoelectric element 2b, electronics is to moving with the mobile opposite direction of heat in fact.Therefore, moving in N type thermoelectric element 2a of the heat when thermoelectric inverting model is switched on carried out along the direction identical with the direction of electronics, but in P type thermoelectric element 2b, carries out in the opposite direction along the side with electronics.Electronics self is as the carrier work of heat, so even the effect of moving about the character heat of the essence of thermoelectric inverting model think that the heat of N type thermoelectric element 2a self moves and be decisive factor.
At this moment, ratio resistance at the ratio resistance ratio P of N type thermoelectric element 2a type thermoelectric element 2b is big, promptly when the conductivity of P type thermoelectric element 2b is bigger than P type thermoelectric element 2b, 2b compares with P type thermoelectric element, and the carrier concn of N type thermoelectric element 2a self is little.Therefore, the thermo-electromotive force of P type thermoelectric element 2b is that Seebeck coefficient increases.The caloric receptivity of thermoelectric inverting model is arranged by Seebeck coefficient, so at this moment, compares when equal with the ratio resistance of N type thermoelectric element 2a with P type thermoelectric element 2b, can improve caloric receptivity.
On the contrary, when the ratio resistance ratio P of N type thermoelectric element 2a type thermoelectric element 2b is also little, think that the carrier concn of N type thermoelectric element 2a is big.Therefore, suppress the joule heating of N type thermoelectric element 2a self, compare when thinking equal with the ratio resistance of N type thermoelectric element 2a, can increase temperature difference with P type thermoelectric element 2b.
Therefore, in this example, when increasing maximum temperature difference, wish that the ratio (N type/P type) of the ratio resistance of N type thermoelectric element 2a and P type thermoelectric element 2b is more than 0.7 and below 0.95.If this scope, just can improve the support density of N type thermoelectric element 2a, increase the temperature difference of thermoelectric inverting model.For improving the temperature difference aspect, hope is below 0.90, more wishes to be below 0.85.At this moment, more excessive when the ratio than resistance is lower than 0.7 than the difference of resistance, so can't bring into play described effect.If bigger than 0.95, the effect that then improves temperature difference is little, so bad.Here, temperature difference refers to that the radiating surface of thermoelectric inverting model is the cooling surface in uniform temperature and when energising and the temperature difference of radiating surface, according to the present invention, compare when being equal with the ratio resistance of N type thermoelectric element 2a and P type thermoelectric element 2b, can increase this temperature difference more than 0.1 ℃.
And when increasing caloric receptivity, wish that the ratio (N type/P type) of the ratio resistance of N type thermoelectric element 2a and P type thermoelectric element 2b is more than 1.05 and below 1.30.If such scope just can reduce the carrier concn of described N type thermoelectric element 2a, can increase the thermoelectric inverting model caloric receptivity.If the ratio than resistance is more than 1.10, and then is more than 1.15, be preferred then increasing on the caloric receptivity.At this moment than resistance such as fruit than 1.30 big, then excessive, so can't bring into play described effect than the difference of resistance.Be lower than at 1.05 o'clock, the effect that increases caloric receptivity is little, so bad.Here, on one side caloric receptivity to refer to make radiating surface be uniform temperature, switch on make temperature difference with cooling surface become maximum after, heat cooling surface, the temperature difference of cooling surface and radiating surface become a timing cooling surface add heat.Can use the heater mensuration caloric receptivity identical shaped with cooling surface.According to the present invention, in identical shaped module, with the ratio resistance of N type thermoelectric element and P type thermoelectric element when equal relatively, can improve caloric receptivity more than 5%.
In addition, N type thermoelectric element 2a is identical with the quantity of P type thermoelectric element 2b, and series connection engages.In the thermoelectric inverting model, N type thermoelectric element 2a and P type thermoelectric element 2b work in pairs.Therefore, the quantity of N type thermoelectric element and P type thermoelectric element is not for not simultaneously, and the remaining inverting element that is helpless to cool off increases a joule heating, and cooling performance is descended.In addition, when P type thermoelectric element and N type thermoelectric element were not connected, the wiring that is used to engage complicated significantly.Therefore, when P type thermoelectric element and N type thermoelectric element were not connected, a joule heating increases, and was bad.
The size of thermoelectric element is according to required cooling performance, size, and varies, but in general cooling purposes, length and width are 0.4～2.0mm, and height 0.3～3.0mm is suitable.When electrode size is 1.5～2.0 times of inverting element length, help improving performance.When thermoelectric inverting model 11 when being small-sized, wish to prepare to be processed as the thermoelectric element of long 0.1～2mm, wide 0.1～2mm, height 0.1～3mm.
In addition, wish the output factor [(Seebeck coefficient) of N type thermoelectric element 2a and P type thermoelectric element 2b
2/ than resistance] be 4 * 10
-3W/mK
2More than.Having the output tendency that the factor is high more, performance index is big more, is more than 4 by making the output factor, and effect of the present invention increases.It should be noted that even the output factor is lower than 4 inverting element, the performance of thermoelectric inverting model descends significantly, but can be practical.
Below, the manufacture method of the thermoelectric inverting model of this example is described.At first, prepare thermoelectric element 2.As mentioned above, in this example, make respectively, so that N type thermoelectric element is different with the ratio resistance of P type thermoelectric element.N type thermoelectric element and P type thermoelectric element 2 can use to be obtained by well-known method.The crystallization that can use any one party by sintering process or smelting process to obtain.
In this example, wish to make up N type thermoelectric element 2a that constitutes by the melting material and the P type thermoelectric element 2b that constitutes by agglomerated material.By making N type thermoelectric element 2a is the melting material, and the influence at random of the electrical conductivity that the intergranular in N type thermoelectric element 2b causes reduces, so described effect increases.It should be noted that in the present invention, the melting material refers to alloy melting, the material that solidifies are also comprised single crystals materials such as unidirectional solidification material certainly in cooling procedure.In addition, agglomerated material refer to the melting material is once pulverized or in cooling procedure, become Powdered after, with many crystalline materials of pressure sinterings such as hot press.
In addition, in the melting material, special hope is made N type thermoelectric material from the bar-shaped crystalline solid that is solidified making by direction.The unidirectional solidification that through performance is high is made N type thermoelectric element 2a, can extremely improve the performance of thermoelectric inverting model, can increase the effect of the cooling performance that improves described thermoelectric inverting model simultaneously.By becoming bar-shaped crystalline solid, can reduce the cut-out machining period significantly, the shortcoming that can suppress is the decline of processed finished products rate.
In addition, wish that P type thermoelectric element 2b is made by the sintered body below the particle diameter 50 μ m.When particle diameter is 50 μ m when following, pyroconductivity sharply reduces.The little P type sintered body of pyroconductivity is when with N type melting combination of materials, because the difference of pyroconductivity, can further improve the difference of electrical conductivity, can further increase based on the effect than the difference of resistance.Wish that P type thermoelectric element 2b is made by the sintered body below the particle diameter 30 μ m.The sintered body intensity height that such particle diameter is little can further improve the reliability of thermoelectric inverting model.
Then, as support substrates 1, prepare the pottery of aluminium oxide, aluminium nitride, silicon nitride, carborundum, diamond etc.After being processed into substrate shape, use Zn, Al, Au, Ag, W, Ti, Fe, Cu, Ni, Pt, conductive materials such as Pd, Mg, form wiring conductor 3 and external connection terminals 4 on the surface.Wiring conductor 3 and external connection terminals 4 can use methods such as coating method, metalikon, DBC (Direct-bonding copper) method, chip join method to form.Surface at wiring conductor 3 comprises at least a kind cover layer 7 among Ni, Au, Sn, Pt and the Co by formation such as plated films, can improve the soakage of solder 6.
Then, configuration thermoelectric element 2 on wiring conductor 3.This thermoelectric element 2 carries out metallising by Ni etc. to the composition surface in advance in order to improve the soakage of solder 6.Flash coating is joined on the wiring conductor 3 by solder 6.It should be noted that in the thermoelectric element 2, N type thermoelectric element 2a and P type thermoelectric element 2b alternately arrange, and the electricity series connection.
On the external connection terminals 4 of the thermoelectric inverting model of obtaining like this 11, the lead-in wire 5 with soft light line localized heating diameter 0.3mm engages.In addition, can with the YAG laser to go between 5 and external connection terminals 4 carry out means of spot welds.
The different thermoelectric inverting model of ratio resistance of N type thermoelectric element 2a of Zhi Zuoing and P type thermoelectric element 2b like this, thermoelectric inverting model when equal with their ratio resistance is compared, in cooling performance, can increase substantially any one party of temperature difference characteristic or endothermic character.As a result, the thermoelectric inverting model of this example expectation is to the application of the cooling purposes of the laser diode of demanding temperature adjustment, semiconductor wafer coldplate, the domestic refrigerator that requires high endothermic character, air-conditioning etc.
Example 2
The thermoelectric inverting model of this example by making the given shape that is shaped as of wiring conductor, further improves the reliability of thermoelectric inverting model in the thermoelectric inverting model of example 1.Other points are same with example 1.
In technology in the past, the wiring conductor 3 section shape shown in Fig. 4 A, promising semicircle cone.Therefore,, produce the gap, make reliability decrease at the lower surface of thermoelectric element 2 and 13 of the upper surfaces (=element composition surface) of wiring conductor 3 when the position of thermoelectric element 2 during from the off-centring of wiring conductor 3.Therefore, in this example, the section shape that makes wiring conductor 3 is long trapezoidal (trapezoidal) of a side on the limit on rectangle, square or element composition surface.Fig. 3 A represents to connect up the section shape of conductor when being rectangle, and Fig. 3 B represents to connect up the section shape of conductor for falling when trapezoidal.In view of the above, even the position of thermoelectric element 2 from the off-centring of wiring conductor 3, does not produce the gap yet between thermoelectric element 2 and wiring conductor 3, concentrate on the there so prevent machinery or thermal stress.Therefore, impact or energizing test in, not at low stress or destroy in the short time, can obtain reliability height, stable thermoelectric inverting model.
Especially, shown in Fig. 3 B, if the section shape that makes wiring conductor 3 just has following advantage for trapezoidal.If promptly the section shape of wiring conductor 3 is for trapezoidal, then, can also improve the bonding area of wiring conductor 3 and support substrates 1 except increasing the bonding area of wiring conductor 3 and support substrates 2.If increase the bonding area of wiring conductor 3 and support substrates 2,, also can prevent between thermoelectric element 2 and wiring conductor 3, to produce skew even when then the position of thermoelectric element 2 is offset a little.In addition, if the bonding area of wiring conductor 3 and support substrates 1 is little, just can suppress distortion based on the coefficient of thermal expansion differences of wiring conductor 3 and support substrates 1.Therefore, by make the wiring conductor section shape for trapezoidal, can obtain the higher thermoelectric inverting model of reliability.
In addition, wiring conductor 3 wishes that element composition surface 13 and the side angulation adjacent with it are 45～90 ° scope in its section shape.In view of the above, according to described identical reason, can obtain reliability height, stable thermoelectric inverting model.If element composition surface 13 and the side angulation adjacent with it surpass 90 °, then when 2 skews of thermoelectric element, be easy to generate the gap.In addition,, then lack the edge easily, therefore, on thermoelectric element 2 or joint interface, produce sometimes and break if littler than 45 °.Hope is 60～90 °, more wishes to be 70～90 °.It should be noted that: the edge of wiring conductor allows: have the following R of radius of curvature 0.05mm or become the following C face of 0.05mm.
In addition, in technology in the past, shown in Fig. 4 B, on the thickness of wiring conductor 3, exist sometimes to distribute.Therefore, produce the gap, make reliability decrease at the lower surface of thermoelectric element 2 and 13 of the upper surfaces (=element composition surface) of wiring conductor 3.Therefore, in this example, making the element composition surface 13 of wiring conductor 3 and the depth of parallelism on support substrates composition surface 14 is below the 0.1mm.If the depth of parallelism surpasses 0.1mm, then for thermoelectric element 2, the inclination on element composition surface increases, so be easy to generate the gap on the composition surface of thermoelectric element 2 and wiring conductor 3.Therefore, impact or energizing test in, be created in low stress or destroy in the short time.The depth of parallelism is wished for below the 0.05mm, more wishes for below the 0.03mm.Here, the depth of parallelism of wiring conductor 3 is meant: the element composition surface 13 of the section of an end of wiring conductor 3 and the element composition surface 13 of the section of the distance A between the support substrates composition surface and the other end and poor (A-B) apart from B between the support substrates composition surface.
In addition, in technology in the past, shown in Fig. 4 C, on the surface of wiring conductor 3, have concavo-convex sometimes.Therefore, can between thermoelectric element 2 and wiring conductor 3, produce the gap, make reliability decrease.Therefore, in this example, making the flatness on the element composition surface of wiring conductor 3 is below the 0.1mm.If flatness surpasses 0.1mm, then be easy to generate the gap on the composition surface of thermoelectric element 2 and wiring conductor 3.Therefore, impact or energizing test in, be created in low stress or destroy in the short time.Flatness is wished for below the 0.05mm, more wishes for below the 0.03mm.
In addition, described wiring conductor 3 is provided with on its surface and comprises cover layer at least a among Ni, Au, Sn, Pt, the Co 7, can improve the soakage of solder 6, and this cover layer 7 is formed by plated film.Can obtain good electrical conductivity, bond strength.Viewpoint from close property, solder soakage is particularly suitable for using Ni, Au, Sn.
The suitable method of selecting from coating method, metalikon, DBC (Direct-bonding copper) method, chip join method more than a kind that adopts in the formation of wiring conductor 3.If form, with regard to the wiring conductor of energy patterning case precision, current value and cost the best by these methods.Have feature respectively on the manufacture method of wiring conductor, according to purpose, manufacture method can suit to select.For example, the thickness of wiring conductor is 100 μ m when following, uses coating method, metalikon, when being the above thickness of 100 μ m, is fit to use DBC method, chip join method.
For example, can following such wiring conductor that forms.At first, on dielectric substrate, stick the thick copper coin of 0.5～1mm by methods such as joints.Secondly, on copper coin, press the screening agent that pattern form is coated with the phenolic resins class by silk screen print method etc.Then, substrate is immersed in the mixed solution of salpeter solution before and after 5 equivalent concentration or nitric acid and sulfuric acid, with 80～100 ℃, etching copper coin 2～4 hours.Then, remove screening agent, then can form wiring pattern with acetone and other organic solvent.Flatness, the depth of parallelism of wiring conductor are preferably controlled by grind copper coin before etching.But, also can replace it, adjust by punching press copper coin after etching.Here, for the section of the conductor that will connect up forms trapezoidally, and preferably accelerate etching speed to a certain extent.That is, temperature concentration low excessively or etching solution is crossed when hanging down when etching speed, does not rely on etching period and just is difficult to form trapezoidal.In addition, if prolong etching period, can increase down trapezoidal conical surface angle.
By on support substrates 1, forming described wiring conductor 3, impact or energizing test in, be not created in low stress or destroy in the short time.In addition, constitute thermoelectric inverting model 11 by using such support substrates, the reliability of thermoelectric inverting model improves, and is also stable.
According to the thermoelectric inverting model of this example, the shape of control wiring conductor 3, so impact or energizing test in, be not created in low stress or destroy in the short time.Therefore, the thermoelectric inverting model of long-time stability excellence can be provided.
Example 3
In this example, in the thermoelectric inverting model of example 1 or 2,, further improve the thermoelectric inverting model of reliability by controlling the composition that lead member 5 is connected to the solder 10 on the external connection terminals.Other points are same with example 1 or 2.
In this example, it is below the above 40 weight % of 12 weight % that the solder 10 of connection lead member 5 and external connection terminals is controlled at Sn content.If in the scope that should form, then do not contain the restriction of thing about other.If Sn content is below the 12 weight %, then fusing point become too high, so the fusing of generating device or mis-behave can't be realized good binding.In addition, if bigger than 40 weight %, then the ratio at the Sn of the element that constitutes solder increases, so the reaction with the thermoelectric element takes place easily.Sn content wishes to be below the above 30 weight % of 15 weight %, more wishes to be below the above 25 weight % of 18 weight %.As 1 example of the composition that is fit to, the solder of Au80 weight %-Sn20 weight % is arranged.It should be noted that the composition analysis of solder composition can be measured by X ray micro-analysis (EPMA).
In addition, in this example, thermoelectric element 2 is the porosity below 10%, and hope is below 7%, more wishes to be below 5%.If the porosity of thermoelectric element is bigger than 10%, then the diffusion velocity of solder composition improves, and the long-pending increase of reacted surface, so reactive the raising.If be the described porosity, then do not limit the material of thermoelectric element especially, but the cooling capacity excellence of Bi-Te class is fit to use.It should be noted that, can measure with Archimedes's method.The porosity of thermoelectric element 2 is for example controlled by sintering temperature.That is, if reduce the sintering temperature of thermoelectric element 2, then the porosity reduces.
The lead-in wire 5 of Fig. 1 can be replaced by block type electrode 5 as shown in Figure 2.In view of the above, can connect thermoelectric inverting model and outside with wire-bonded, the installation exercise of thermoelectric inverting model can be realized automation easily, can shorten the activity duration.By upper end that makes block type electrode 5 and the electrode terminal that the encapsulation of thermoelectric inverting model will be installed is equal height, the displacement minimum of the lead-in wire in the time of making wire-bonded, and the time of wire-bonded shortens becomes possibility.The shape of block type electrode 5 can be prisms such as triangular prism, quadrangular, six prisms, eight prisms, also can be cylindrical.Wherein, become big viewpoint, wish to be quadrangular from positioning accuracy, sectional area.And on the viewpoint of formability, processability, form accuracy, cost, hope is cylinder.It should be noted that, in Fig. 2, represent with cylindrical shape.
It should be noted that the lead-in wire 5 or the bond strength of block type electrode 5 and external connection terminals 4 be than 2N hour, with encapsulation engage operation the time probability height that comes off.Therefore, bond strength is more than the 2N, wishes for more than the 5N, more wishes for more than the 10N.In view of the above, when thermoelectric inverting model when encapsulation wait to be installed, can eliminate going between or the problem of block type electrode 5 disengagings.In order to improve bond strength, importantly use the soakage of the electrode of scaling powder improvement and solder, cover the bonding part of lead-in wire 5 or block type electrode 5 fully with solder.
If wiring conductor 3, external connection terminals 4, lead-in wire 5, block type electrode 7 have conductivity, electric current is flowed easily, just do not limit especially, but resistance low aspect, wish to constitute by the metal that comprises at least a kind of element among Zn, Al, Au, Ag, W, Ti, Fe, Cu, Ni and the Mg.In addition,, then can improve the soakage of solder 10, obtain good electrical conductivity, bond strength if form at least a cover layer that comprises Ni, Au, Sn, Pt and Co by plated film on the surface of described lead-in wire 5 or block type electrode 5.Therefore, when thermoelectric inverting model when encapsulation carry to engage, can obtain high bond strength.
The joint of block type electrode 5 and external connection terminals 4 uses reflow ovens to carry out with thermoelectric element 2 and engaging simultaneously of conductor 3 of wiring, can shorten, simplify step.In addition, if use the step different to engage the step of external connection terminals 4 and lead member 5, just can in each step, use the different solder of fusion temperature with the step that engages thermoelectric element 2 and wiring conductor 3.
In the thermoelectric inverting model of this example, can suppress the reactivity of thermoelectric element and solder, so the thermoelectric inverting model of long-time stability excellence can be provided.
Example 4
In example, illustrate in the thermoelectric inverting model of example 1～3, with in the solder 10 that connects lead member 5, forming the example of the diffusion layer 8 of lead member 5 for sizing.Other points are same with example 1～3.
In Fig. 1 or thermoelectric inverting model 11 shown in Figure 2, in the past, be used for the lead member 5 that electric power supplies with and contacted with solder 10, thus electric connecting wire member 5 and external connection terminals 4, the formation circuit., engage, a little less than the mechanical strength,, can't realize stable installation sometimes so during the installation exercise of 11 pairs of encapsulation of thermoelectric inverting model, the problem that block type electrode 5 throws off of taking place is arranged even carry out electricity.
Therefore, in this example, shown in Fig. 6 A or Fig. 6 B, externally on the splicing ear 4 on the solder 10 of bonding wire member 5, the thickness of the diffusion layer 16 of lead member composition is that above and this diffusion layer 16 of 0.1 μ m is present in the area of the face of being engaged than the zone more than 20%.It should be noted that the example the when example when Fig. 6 A represents lead member 5 for lead-in wire, Fig. 6 B are represented lead member 5 for block type electrode.In view of the above, between solder 10 and block type electrode 5, produce anchor effect, can improve intensity mechanically.Therefore, in installation exercise, lead member can not take place throw off, can obtain the thermoelectric inverting model that can carry out stable installation exercise.The thickness of the diffusion layer 16 of lead member composition is littler or than 20% hour that is engaged area than 0.1 μ m, can't obtain sufficient anchor effect, can't obtain stable bond strength.Wish that thickness is more than the 0.3 μ m, more wish to be 0.5 μ m.In addition, diffusion layer 16 is more than 30% for the area that is engaged area than wishing, more wishes to be more than 40%.
In addition, being used for the lead member 5 of supply capability and the bond strength of solder 10 is to be important more than the 2N.In view of the above, lead member 5 can not come off in installation exercise, can realize stable installation exercise.Bond strength is wished for more than the 5N, more wishes for more than the 10N.When being lower than 2N, in installation exercise, installation exercise is thrown off sometimes.
In addition, wish that the diffusion layer 16 of lead member composition and the interface 17 of non-diffusion layer 15 are wave.In view of the above, can expect more firm anchor effect, therefore, bond strength is stable.Cut off the junction surface,, can observe the interface 17 of diffusion layer 16 and non-diffusion layer 15 with the composition of analyses such as X ray micro-analysis, mapping lead member.It should be noted that in solder 10, the scope that comprises the composition of the above lead member of 1at% is a diffusion layer 16.
And diffusion layer 16 is wished than non-diffusion layer 15 densifications on every side.In view of the above, compare when finer and close than diffusion layer 16, can obtain the high stable bond strength of intensity with non-diffusion layer 15.By observe the section at junction surface with 100～3000 times multiplying power, observe all or shared ratio near interface space of section, can judge the compactness extent of diffusion layer 16 and non-diffusion layer 15.Be that the shared area in space is more little, just fine and close more in the unit are.
In this example, control the formation of the diffusion layer 8 of solder 10 by the junction temperature of solder 10.Promptly when the time with solder 10 bonding wire members 5, engage by 103～130% temperature in the fusion temperature of solder 10, can in solder 10, form the diffusion layer 16 of lead member composition.With melting, when engaging, do not form the diffusion layer 8 that sufficient electric power is supplied with the wiring composition, can't obtain stable bond strength than 103% of fusion temperature low temperature.And when with than 130% also high temperature fusion bond solder of fusion temperature the time, the viscosity of solder is low, and is mobile too high, so solder flows out to adjacent wiring conductor 3 sometimes, causes short circuit.Therefore, wish 103～130% temperature, more wish temperature, wish temperature joint most with 107～120% with 105～125% with the solder fusion temperature.According to necessity, cooling rate is adjusted to the best.
Like this, at the thermoelectric inverting model 11 of this example during, be used for the lead member 5 that electric power supplies with and can not throw off, so the thermoelectric inverting model of installation exercise excellence can be provided to the installation of encapsulation.
Example 5
In this example, the example that illustrate in the thermoelectric inverting model of example 1～4, employing is suitable for the electrode structure of wire-bonded.Fig. 7 A represents the stereogram of the thermoelectric inverting model of this example, and Fig. 7 B represents cutaway view.In the thermoelectric inverting model of Fig. 7 A and Fig. 7 B, same with the thermoelectric inverting model of example 1～4, as to constitute by N type thermoelectric element 2a and P type thermoelectric element 2b by lower support substrate 1a and upper support substrate 1b clamping a plurality of thermoelectric elements 2.N type thermoelectric element 2a and P type thermoelectric element are arranged on support substrates 1a, the 1b by wiring conductor 3a, 3b, by wiring conductor 3a, 3b series connection.
Shown in Fig. 7 A and B, the upper surface that the external connection terminals 4 of this example is arranged on upper support substrate 1b promptly with the face of the opposite side of face that engages thermoelectric element 2 on.In addition, externally on the splicing ear 4 one connect block type electrode 5.Promptly on upper support substrate 1b plane external connection terminals 4 is set, contact thereon is wholely set block type electrode 5.
Therefore, shown in Fig. 7 B, the wiring conductor 3b that is arranged on the lower surface of upper support substrate 1b is connected by the pore electrod 18 of crossing that is formed in the upper support substrate 1b with plane electrode 4 on being arranged on upper surface.If passed through pore electrod 18 wirings like this, the breach or the wearing and tearing of then crossing pore electrod are few, so can significantly improve connection reliability, particularly long-term reliability.Cross pore electrod 18 be arranged on thermoelectric element 2 directly over, the shortest by making from thermoelectric element 2 to plane electrode 4 distance, can further reduce the resistance in the thermoelectric inverting model, can help power saving.In addition, in the method in the past (for example Japan Patent is open the flat 11-54806 of communique number), substrate deflection when wire-bonded is broken so produce between thermoelectric element 2 and wiring conductor 3a and 3b.If the structure of this example just can suppress this phenomenon, further improve the rate of finished products and the reliability of thermoelectric inverting model.
Upper surface at upper support substrate 1b forms plane electrode 4 like this, with plane electrode 4 integrally formed block type electrodes 5, can make with outside being electrically connected and become easy.For example shown in Fig. 7 C, at the inside installation diagram 7A of the encapsulation 26 of semiconductor laser and the thermoelectric inverting model 11 shown in the B, use is arranged on electrode terminal 29 and the lead-in wire 28 in the encapsulation 26, joint is arranged on the block type electrode 5 in the thermoelectric inverting model 11, can be to thermoelectric inverting model 11 supplying electric currents.
4 pairs of thermoelectric element 2 supply capabilities of plane electrode wish to be made of Cu, Al, the Au constant resistance is low, pyroconductivity is high metal.In view of the above, the heating of thermoelectric inverting model can be suppressed, and thermal diffusivity can be improved.
The shape of block type electrode 5 can be prisms such as triangular prism, quadrangular, six prisms, eight prisms, also can be cylindrical.Wherein, from the viewpoint that positioning accuracy, sectional area broaden, wish to be quadrangular.And on the viewpoint of formability, processability, form accuracy, cost, hope is cylinder.It should be noted that, in Fig. 7, represent with cylindrical shape.
Block type electrode is the metal that comprises at least a kind of element of Zn, Al, Au, Ag, W, Ti, Fe, Cu, Ni and Mg, and resistance is low, so good.In addition, if these metals, the intensity of the impact when just having anti-wire-bonded, absorb the flexibility of the appropriateness of impacting, so be suitable as the material of block type electrode.
The maximum major diameter d of block type electrode wishes to be 0.2～20 with respect to the ratio (d/h) of height h, and special hope is 0.5～15, more wishes to be 1～10.The maximum major diameter d of block type electrode is equivalent to diameter when cylinder, be equivalent to major diameter when ellipse, is equivalent to diagonal the longest in the diagonal when prism.By being such shape, can prevent the block type electrode bending, fracture, it is easy that arranged perpendicular becomes.Therefore, can help to encapsulate and the miniaturization of thermoelectric inverting model and the raising of rate of finished products.
When block type electrode 5 was cylinder, height h wished to be 2～20 for the ratio d/h of diameter d, if quadrangular, height h can be 0.2～20 for the ratio d/h of diagonal d long in two diagonal.Equally, if six prisms, then height h can be 0.2～20 for the ratio d/h of diagonal d the longest in 9 diagonal, and in eight prisms, height h can be 0.2～20 for the ratio d/h of diagonal d the longest in 20 diagonal.
The solder of the solder of composition plane electrode 4 and block type electrode 5, joint thermoelectric element 2 and wiring conductor 3 is the different solder of fusion temperature.At this moment, the step of composition plane electrode 4 and block type electrode 5, joint thermoelectric element 2 carry out in 2 different steps with the step of wiring conductor 3.For example use the Au-Sn solder of 280 ℃ of fusion temperatures to engage thermoelectric element 2 and wiring conductor 3 earlier, carry out modularization, then, with plane electrode 4 and the block type electrode 5 on the Sn-Sb solder joint upper support substrate 1b of 230 ℃ of fusion temperatures.In view of the above, can carry out the making of thermoelectric inverting model easily.Engage thermoelectric element and the solder of the conductor that connects up fusion temperature, engage the temperature difference of fusion temperature of solder of external connecting electrode and lead member preferably for example about 50 ℃.
In addition, block type electrode 5 can improve the soakage of solder by on its surface at least a kind the thin layer that comprises Ni, Au, Sn, Pt and Co being set, and can obtain good electrical conductivity, bond strength.
Like this, if the thermoelectric inverting model of this example 11 just can carry out wire-bonded with high finished product rate when encapsulation is carried.The encapsulation of the thermoelectric inverting model of this example shown in Fig. 7 C, the connection that have container 26, is arranged on these container 26 inside with electrode (not shown), with the electrode terminal 29 of its one, lay thermoelectric inverting model 11 in the bottom surface that encapsulation is inner.In this encapsulation, wish with the upper surface of the block type electrode 5 of thermoelectric inverting model 11 roughly sustained height electrode terminal is set.If the composition surface of block type electrode 5 and the electrode terminal of encapsulation 29 are sustained height roughly, just can make the length of lead-in wire 28 the shortest, therefore can reduce resistance, can reduce power consumption.In addition, do not need wire-bonded, so the advantage of operation excellence is also arranged in narrow encapsulation inside.
Though do not limit the material of packaging container 26 especially, materials such as the Cu-W of suitable use thermal diffusivity excellence, C-C composition.
Below, embodiments of the invention are described.
Embodiment 1
(making of thermoelectric element)
At first, make various N types and P type thermoelectric material.Manufacture method is: prepare Bi, the Te of purity 99.99% or more, Sb, Se metal dust and as the SbI of thermoelectric element usefulness dopant
3Powder and SbBr
3Powder.As N type thermoelectric material, with Bi
2Te
2.85Se
0.15Consist of substantially,, adjust the amount of dopant in order to adjust than resistance.
In addition, the P type uses thermoelectric material with Bi
xSb
2-xTe
3For substantially, x from 0.3 to 0.7 is changed, adjust and compare resistance.
(a) sintered body makes
After raw material weighing is required composition, be filled in the crucible of carbon system, by the lid sealing.Put into quartz ampoule, carry out vacuum displacement, in argon atmospher, made melted alloy at 800 ℃, 5 hours.
Melted alloy is pulverized with bruisher in spherical box, behind the screen pack of the mesh by 2mm, pulverized 1～12 hour with the small vibration flour mill that makes silicon nitride become ball.This alloy powder at 450 ℃, 1 hour, is heated in hydrogen stream, reduce processing, obtain the micropowder alloy.
Use the carbon punch die of 20mm diameter-10mm thickness that powder is carried out hot pressing, obtain sintered body.
This sintered body part is cut into the rectangular shape of 2 * 3 * 15mm, and to make the direction vertical with compression aspect be length direction.About the sintered body of cuboid,, calculate the output factor (S with the Seebeck coefficient (S) of the Seebeck coefficient determinator of selling on the market (vacuum science and engineering system ZEM device) measured length direction with than resistance (ρ)
2/ ρ).
Remaining partially sliced of sintered body, and make compression aspect become thickness direction with thickness 0.9mm.To this thin plate carry out electroless plating and gold-plated after, slice processing becomes the square shape of length of side 0.65mm, obtains the thermoelectric element.
(b) the melting material make 1: based on the club-shaped material of unidirectional solidification
In addition, as the melting material,, as described below about the making of unidirectional solidification.
Using the alloy powder made from described identical method to be configured in the top of mould frame of the carbon casting mould with space of four prism type.This mould frame is made of 2 Zhang Ping's plates with a plurality of V word shape grooves, to each other relatively during the overlapping 2 Zhang Ping's plates of the mode of subtend, forms the space of four prism type at V word shape groove.The space of four prism type has the square cross-section of length of side 0.65mm, and length is 10mm.Then, with the single crystals generating apparatus (Bridgman method) of longitudinal type quartz ampoule as furnace core tube, make its fusing at 700 ℃, after in the space, filling fusing fluid, use the Bridgman ratio juris, while make mould frame shift moving, cool off, near solidifying point (about 600 ℃), speed with 2～3mm/H makes crystalline growth.Like this, make the N type thermoelectric element 2a that constitutes by the thermoelectric crystalline material of unidirectional solidification and the elongate body of P type thermoelectric element 2b.
The thermoelectric crystalline material of the bar-shaped unidirectional solidification of obtaining is cut to 15mm at length direction, same with sintered body, measure Seebeck coefficient (S) and, calculate the output factor (S than resistance (ρ)
2/ ρ).
Use the thermoelectric crystalline material of this bar-shaped unidirectional solidification, make the thermoelectric element.
At first, after with the plated film resist of selling on the market (acrylic resin) side of unidirectional solidification thermoelectric material being applied, be cut to length 0.9mm, make the cuboid element with wafer dicing saw.The element of obtaining is carried out electroless plating, behind the nickel coating of formation thickness 5～10 μ m, carry out the gold-plated of thickness 0.1 μ m.Then, put into aqueous slkali,, remove, only on section, form coating, make the thermoelectric element attached to the coating on the plated film resist of element by ultrasonic cleansing.
(c) making of melting material: ingot
In addition, as the manufacture method of other melting materials, use the infrared image stove, use zone melting method, crystalline growth is the ingot of diameter 30.Ingot and direction of growth terrace cut slice, same during with sintered body, make the thermoelectric element, calculate pyroelecthc properties in addition.
(making of thermoelectric element)
Each 23 of N type that use is obtained by above manufacture method and P type thermoelectric elements, the carrying out of 6 * 8mm on the aluminium oxide ceramics substrate of copper wiring, by SnSb (95 to 5) solder paste, utilize cancellate arrange fixture to arrange, use ceramic heater, be heated to 250～280 ℃, engage, obtain thermoelectric inverting model.
Engage thermoelectric inverting model by thermal conductive grease on the fin of the adjustment to 27 of cooling surface ℃, energising is with the temperature on the K type thermocouple measurement cooling surface top of diameter 0.1mm.While making power on condition change, measure the temperature of cooling surface, 27 ℃ of differences with cold-boundary temperature are become maximum temperature as maximum temperature difference.
And, obtaining under the state of switching under the condition of maximum temperature difference, use and the identical shaped ceramic heater of cooling surface substrate, the heating cooling surface, the output of the ceramic heater when cold-boundary temperature is become 27 ℃ is obtained as caloric receptivity.
The thermoelectric element of obtaining with the SEM observation from about 300 particles, is obtained average grain diameter with line intercepting method again.
Table 1 ecbatic.
[table 1]
(a) effect of the ratio of the ratio resistance of N type thermoelectric element and P type thermoelectric element
As known from Table 1, in almost equal comparative example No.8～11,28,33,42,45 of the ratio resistance of N type thermoelectric element 2a and P type thermoelectric element 2b, maximum temperature difference is 73.2～73.8 ℃, and caloric receptivity is 3.01～3.06W.And in N type thermoelectric element 2a embodiment No.1～7,13～27,29～32,34～41,43,44,46 different with the ratio resistance of P type thermoelectric element 2b, maximum temperature difference is all more than 74.3 ℃, perhaps caloric receptivity is for more than the 3.10W, and the maximum temperature difference of thermoelectric inverting model, caloric receptivity all improve.
Promptly in fact little No.1～7,29,34～37,43,46 of the ratio resistance of the ratio resistance ratio P of N type thermoelectric element type thermoelectric element, caloric receptivity does not have big different with comparative example, but the maximal degree difference shows than the also high a lot of value of comparative example more than 74.3 ℃.If No.1～10 that raw-material manufacture method of more thermoelectric inverting element or shape are identical, then the ratio resistance ratio of N type thermoelectric element and P type thermoelectric element is more than 0.7 in the scope below 0.95, can obtain bigger maximum temperature difference.
In addition, in in fact also big No.13～27,30～32,38～41,44 of the ratio resistance of the ratio resistance ratio P of N type thermoelectric element type thermoelectric element, maximum temperature difference and comparative example do not have big different, but caloric receptivity shows than the also high a lot of value of comparative example for more than the 3.10W.Especially, if identical No.11～20 of raw-material manufacture method of more thermoelectric inverting element or shape, then the ratio resistance ratio of N type thermoelectric element and P type thermoelectric element is more than 1.05 in the scope below 1.30, can obtain bigger caloric receptivity.
(b) effect of the manufacture method of N type thermoelectric element
No.1～26 are made as ingot to N type thermoelectric element and P type thermoelectric element both sides by sintering, in No.27～29, by melting N type thermoelectric element are made as ingot, by sintering P type thermoelectric element are made as ingot.The manufacture method that is the P type thermoelectric element of No.1～26, No.27～29 is being used sintering, still is being that melting is made on the thermoelectric element different.Therefore, if wherein than the equal No.6 of resistance ratio and 29 or No.16 and 27, the No.29 and the good characteristic of 27 performances of then making N type thermoelectric element of melting.Therefore, know: be not sintering but when making N type thermoelectric element with melting, modular character is good.
In addition, difference is: in No.27～29, generate N type thermoelectric element with melting as ingot; And in No.30～40, make bar-shaped N type thermoelectric element by unidirectional solidification.Therefore, wherein the ratio resistance of the ratio resistance ratio P type thermoelectric element of N type thermoelectric element is big, the equal sample No.27 and 30 of ratio resistance more each other.The caloric receptivity of No.27 is 3.36W, and the caloric receptivity of No.30 is 3.50W.Therefore, when making N type thermoelectric element by unidirectional solidification, characteristic becomes well.
(c) effect of the output factor
In No.15,17～20, the output factor of N type thermoelectric element is 4.1 * 10
-3W/mK
2, the output factor of P type thermoelectric element is 4.4 * 10
-3W/mK
2And in No.21～23, the output factor of P type thermoelectric element also is 4.4 * 10
-3W/mK
2Identical, still, the output factor of N type thermoelectric element drops to 4.0 * 10
-3W/mK
2Below.Therefore, if the caloric receptivity of No.21～23 is compared with the No.17 more equal than the ratio of resistance, No.17 is 3.23W, and No.21～23 drop to 3.11～3.20W.And in No.21～23, the output factor of N type thermoelectric element is low more, caloric receptivity also descends more.
In addition, in No.24～26, the output factor of N type thermoelectric element is 4.1 * 10
-3W/mK
2, with No.15,17～20 identical, but the output factor of P type thermoelectric element drops to 4.0 * 10
-3W/mK
2Below.Therefore, if the caloric receptivity of No.24～26 is compared with the No.15,17 more equal than the ratio of resistance, then No.15 is 3.22W, and No.17 is 3.23W, and No.24～26 drop to 3.10～3.18W.And in No.24～26, exist the output factor of P type thermoelectric element low more, the tendency that caloric receptivity also descends.
(d) effect of particle diameter
In addition, among the No.38,39,40, other conditions are almost certain, and sintered body is the order increase of the particle diameter of P type thermoelectric element by 45 μ m, 70 μ m, 120 μ m.Therefore, if compare their caloric receptivity, then caloric receptivity is 3.40W, 3.37W, 3.36W.Promptly the particle diameter according to sintered body surpasses 50 μ m change greatly, and caloric receptivity reduces in order.Therefore, the particle diameter of P type thermoelectric element wishes to be below the 50 μ m.
[embodiment 2]
Initial feed is prepared by Bi
2Te
2.85Se
0.15The thermoelectric element 2 that the class sintered body constitutes.Be shaped as quadrangular, be of a size of long 0.6mm, wide 0.6mm, height 1mm.In addition, as support substrates 1, prepare the aluminium oxide of size 6mm * 8mm.
On support substrates 1, make the wiring conductor 3 of Cu by plated film-etching method.Form the cover layer 7 of Au on its surface.
Printing is arranged thermoelectric element 2 thereon by the solder paste that the solder 6 of Au-Sn etc. constitutes on the wiring conductor 3a of lower support substrate 1a, from the reverse side heating of lower support substrate 1a, and fixing thermoelectric inverting element 2.The quantity of thermoelectric element 2 is that N type thermoelectric element 2a and P type thermoelectric element 2b use equal number respectively.Equally, fixedly the upper support substrate 1b of another side and thermoelectric element 2 are obtained thermoelectric inverting model 11.
To supplying with solder 10 on the wiring conductor 3 of the thermoelectric inverting model 11 obtained, and, connect lead-in wire 5 by soft light bundle localized heating.
The depth of parallelism of wiring conductor is to measure 4 jiaos of wiring conductor with altimeter, calculates the poor of maximum-minimum.In addition, flatness is to measure 4 jiaos and central part of wiring conductor with altimeter, calculates the poor of maximum-minimum.
The bond strength of cover layer and solder is used solder (Sn-Sb) bonding wire from opening being with of 1mm square hole, and the lead-in wire that stretches is measured peel strength.
The thermoelectric inverting model of obtaining like this 11 behind the illusory joint that carries out 1g weight on the cooling surface, is carried out shock test.Shock test is implemented according to MLT-STD-883, METHOD2002, CONDITION B.In addition, in 30 ℃ oil, carry out making in per 15 seconds electric current+-the power cycles test of putting upside down.By exchanging the resistance before and after the 4 terminal method determination tests, resistance change rate (Δ R) be 5% below for qualified, Δ R above 5% be defective.
[table 2]
The section shape of wiring conductor is that rectangle or top are below 5% than the following also long resistance variations of trapezoidal sample No.1～23,29～32 before and after shock test and power cycles test, and is good.Wherein, the thermoelectric element composition surface of wiring conductor and the scope that the adjacent surface angulation is 45 °～90 °, the depth of parallelism and flatness are following sample No.1～4,6,9～23,29～32nd of 0.1mm, and resistance variations is below 3%, in the error range of measuring, excellent especially in all estimating.
And the No.24 of comparative example～26th, the section shape of wiring conductor is narrow trapezoidal, the semicircle cone in top, hexagon.In reliability test, they all produce underproof, compare with No.1～23,29～32, and are obviously poor.In addition, the No.27 of comparative example is a quadrangle for the section shape of wiring conductor, but the flatness of conductive surface of connecting up poor, reach 0.1mm, so the result of reliability compare with No.1～23,29～32, obviously poor.Equally, the No.28 of comparative example is that the section shape of wiring conductor is a quadrangle, but the depth of parallelism of conductive surface of connecting up poor, reach 0.1mm, so the result of reliability compare with No.1～23,29～32, obviously poor.
[embodiment 3]
Except the composition that makes the solder that connects lead-in wire changes, make thermoelectric inverting model similarly to Example 2.
The thermoelectric inverting model of obtaining is placed in 170 ℃ the high-temperature atmosphere, by exchanging the resistance variations (Δ R) after 4 terminal methods are measured 100 hours, Δ R surpass 5% be defective promptly *, below 5% be qualified be zero.
[table 3]
| Sample No. | The lead-in wire solder is formed | The porosity of element (%) | The thermoelectric element | ΔR(％) | Judge | ||||||
| Sn (weight %) | Other constituents (weight %) | The P type | The N type | ||||||||
| 1 | 20 | Au | 80 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 0.2 | ◎ | |||
| 2 | 12 | Au | 88 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 0.3 | ◎ | |||
| 3 | 30 | Au | 70 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 1 | ◎ | |||
| 4 | 40 | Au | 60 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 3 | ◎ | |||
| * | 5 | 5 | Au | 95 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | Can't engage | × | ||
| * | 6 | 50 | Au | 50 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 20 | × | ||
| * | 7 | 95 | Sb | 5 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | ∞ | × | ||
| * | 8 | 60 | Pb | 40 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | ∞ | × | ||
| * | 9 | 96.5 | Ag | 3 | Cu | 0.5 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | ∞ | × |
| 10 | 20 | Au | 80 | 1 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 0.2 | ◎ | |||
| 11 | 20 | Au | 80 | 5 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 1 | ◎ | |||
| 12 | 20 | Au | 80 | 10 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 3 | ◎ | |||
| 13 | 20 | Au | 80 | 15 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 4 | ○ | |||
| 14 | 20 | Au | 80 | 2 | Bi 0.4Sb 1.5Te 2 | Bi 2Te 2.85Se 0.15 | 0.1 | ◎ | |||
| 15 | 20 | Au | 80 | 2 | Bi 0.6Sb 1.5Te 2 | Bi 2Te 2.9Se 0.1 | 0.3 | ◎ | |||
| 16 | 20 | Au | 80 | 2 | Bi 0.5Sb 1.5Te 2 | Bi 2Te 2.8Se 0.1 | 0.2 | ◎ | |||
* be outside the scope of the present invention
The scope of Sn content is that following sample No.1～4 of the above 40 weight % of 12 weight %, 10～16 resistance variations are, well 5% below.Wherein the porosity of thermoelectric element is that sample No.1～4,10～12 below 10%, 14～16 resistance variations are below 3%, and is in the error range of measuring, excellent especially in all estimating.
And the scope of Sn content is lower than 12 weight % or it is big to be higher than the resistance of sample No.5～9 of 40 weight %, or broken string fully after the test, compares with other test, obviously worsens.
It should be noted that the scope of Sn content is in the following sample of the above 40 weight % of 12 weight %, it is acceptable ranges that the porosity surpasses 10% sample No.13, but is that sample No.10～12 below 10% are compared with the porosity, shows big Δ R.Therefore, the porosity of wishing solder is below 10%.
[embodiment 4]
Except the condition that makes the solder joint that connects lead member changes, make thermoelectric inverting model similarly to Example 2.
The lead member 5 of the thermoelectric inverting model of obtaining 11 is stretched to the direction of bending for the right angle, measure peel strength.Rate of finished products when in addition, measuring to the encapsulation installation.
[table 4]
| Test portion No. | Thickness of diffusion layer (μ m) | The composition surface ratio (%) of diffusion layer | The diffusion layer interface shape | Density | Electric power is supplied with wiring shape | Solder | Peel strength (N) | Short circuit | Mounting finished product rate (%) | |||||
| Diffusion layer voidage (%) | Non-diffusion layer voidage (%) | Kind | Fusing point (℃) (=A) | Junction temperature (℃) (=B) | B/A×1 00(％) | |||||||||
| * | 1 | 0 | 0 | - | - | 30 | Lead-in wire | Au-Sn | 280 | 280 | 100 | 0.5 | ○ | 90 |
| 2 | 0.1 | 70 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 288 | 103 | 2.0 | ○ | 100 | |
| 3 | 0.3 | 70 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 295 | 105 | 7.0 | ○ | 100 | |
| 4 | 0.5 | 70 | Wavy | 5 | 25 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 12.0 | ○ | 100 | |
| 5 | 1 | 70 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 310 | 111 | 15.0 | ○ | 100 | |
| 6 | 1.5 | 80 | Wavy | 5 | 25 | Lead-in wire | Au-Sn | 281 | 340 | 121 | 16.0 | ○ | 100 | |
| 7 | 2 | 95 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 281 | 370 | 132 | 16.0 | △ | 100 | |
| * | 8 | 0.3 | 10 | Wavy | 5 | 25 | Lead-in wire | Au-Sn | 280 | 285 | 102 | 1.0 | ○ | 90 |
| 9 | 0.5 | 20 | Wavy | 10 | 30 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 3.0 | ○ | 100 | |
| 10 | 0.5 | 50 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 8.0 | ○ | 100 | |
| 11 | 0.5 | 90 | Wavy | 5 | 30 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 15.0 | ○ | 100 | |
| 12 | 0.2 | 50 | Wavy | 10 | 30 | Lead-in wire | Au-Sn | 280 | 290 | 104 | 2.0 | ○ | 100 | |
| 13 | 0.4 | 50 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 295 | 105 | 5.0 | ○ | 100 | |
| 14 | 0.5 | 50 | Wavy | 5 | 25 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 10.0 | ○ | 100 | |
| 15 | 1 | 50 | Wavy | 5 | 20 | Lead-in wire | Au-Sn | 280 | 320 | 114 | 13.0 | ○ | 100 | |
| 16 | 0.5 | 70 | Smooth | 5 | 25 | Lead-in wire | Au-Sn | 280 | 290 | 104 | 8.0 | ○ | 100 | |
| 17 | 0.5 | 70 | Wavy | 5 | 25 | Lead-in wire | Au-Sn | 280 | 310 | 111 | 12.0 | ○ | 100 | |
| 18 | 0.5 | 70 | Wavy | 10 | 30 | Lead-in wire | Sn-Sb | 240 | 260 | 108 | 13.0 | ○ | 100 | |
| 19 | 0.5 | 70 | Wavy | 5 | 20 | Lead-in wire | Sn-Pb | 180 | 195 | 108 | 15.0 | ○ | 100 | |
| 20 | 0.5 | 70 | Wavy | 10 | 30 | Lead-in wire | Sn-Ag-Cu | 220 | 235 | 107 | 13.0 | ○ | 100 | |
| 21 | 0.5 | 70 | Wavy | 5 | 20 | Cylinder | Au-Sn | 280 | 300 | 107 | 12.0 | ○ | 100 | |
| 22 | 0.5 | 70 | Wavy | 5 | 25 | Prismatic | Au-Sn | 280 | 300 | 107 | 12.0 | ○ | 100 | |
| 23 | 0.5 | 70 | Wavy | 20 | 20 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 10.0 | ○ | 100 | |
| 24 | 0.5 | 70 | Wavy | 15 | 20 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 11.0 | ○ | 100 | |
| 25 | 0.5 | 70 | Wavy | 10 | 20 | Lead-in wire | Au-Sn | 280 | 300 | 107 | 12.0 | ○ | 100 | |
Diffusion layer is more than 20% to the area ratio on composition surface, and the thickness of diffusion layer is that above sample No.2～7 of 0.1 μ m, 9～20 peel strength are more than the 2N, and the mounting finished product rate is 100%, and is good.And do not have only in 10% the comparative example forming the sample No.1 of diffusion layer, the diffusion layer area ratio to the composition surface, peel strength is low, takes place badly in installation test, compares with other sample, obviously worsens.
It should be noted that, below the results of indivedual each sample of explanation.
Among the sample No.7, the temperature of solder heating is too high, and solder drips, and causes short circuit.
In sample No.16, the diffusion layer interface shape is smooth, so anchor effect is inoperative, peel strength descends a little, but be to use no problem.The peel strength of sample No.16 is compared than identical sample No.4 with the thickness of diffusion layer and bonding area, and the peel strength of No.16 is 8N, and the peel strength of No.4 is 12N.Therefore, be waveform by the interface shape that makes diffusion layer, the bond strength of solder and lead-in wire increases substantially.
In sample No.21,22, replace lead-in wire, engage cylinder or prismatic block type electrode.In these embodiments, by form thickness 0.5 μ m, to the area on composition surface than the diffusion layer that is 70%, show high peel strength and mounting finished product rate.In No.21,22,, all be not short-circuited with solder, wire-bonded.
In sample No.23～25, the voidage that is accompanied by diffusion layer reduces, and peel strength improves.Therefore, the voidage of preferred diffusion layer is little.The voidage Vd that wishes diffusion layer with respect to the voidage Vn of non-diffusion layer than Vd/Vn less than 1, preferred below 0.8, more preferably below 0.5.
Can still as required,, also can implement with the such control of solder fusion temperature management by management programming rate or solder atmosphere or fin.
[embodiment 5]
In initial feed, prepare by Bi
2Te
2.85Se
0.15The thermoelectric element that the class sintered body constitutes.Be shaped as quadrangular, be of a size of long 0.6mm, wide 0.6mm, high 1mm.In addition, as the upper and lower support substrates, prepare the aluminium oxide of big or small 6mm * 8mm.
On the wiring conductor of lower support substrate, printing is arranged element thereon by the solder paste that the solder 1 of Au-Sn etc. constitutes, from the opposing face heating of dielectric substrate, and fixing thermoelectric inverting element.The quantity of element is that N type thermoelectric element and P type thermoelectric element use equal number.Equally another side dielectric substrate and thermoelectric element are fixed, obtain thermoelectric inverting model.The fusion temperature of table 5 expression solder 1.
In sample No.3～51, by the thermoelectric inverting model of the structure shown in following construction drawing 7A and Fig. 7 B.Promptly printing is arranged the cylindricality block type electrode thereon, from the heating of lower support substrate one side, fixedly block type electrode by the solder paste that the solder 2 of Sn-Sb etc. constitutes on the upper support substrate of the thermoelectric inverting model of obtaining.The fusion temperature of table 5 expression solder and the shape of block type electrode.And in sample 1 and 2, block type electrode is not set, make the thermoelectric inverting model that No. the 3082170th, Japan Patent or Japan Patent disclose the structure of expression in the flat 11-54806 of communique number.Promptly in sample No.1, on lower support substrate 1a, form the planar electrode of the 20 μ m thickness that constitute by NiAu, it as the wire-bonded pad.In sample 2, after forming pore electrod on the upper support substrate, form the planar electrode of the 20 μ m thickness that constitute by NiAu at the upper surface of upper support substrate, as the wire-bonded pad.
The thermoelectric inverting model of obtaining is like this installed to encapsulation, carried out following evaluation.
About rate of finished products, measure resistance variations (Δ R) before and after encapsulation installed by exchanging 4 terminal methods, Δ R surpass 5% be defective i.e. " * ", below 5% is qualified be " zero ".
About operation, measure lead-in wire wiring required time, time-consuming 20 seconds/bar is above is judged as defective " * ".
About power consumption, measure power consumption required when LD remained on 25 ℃.
About reliability test, carry out the power cycles test.After carrying out power cycles test and in 1.5 minutes, adding (ON) electric current, stop impressed current (OFF), keeps the power cycles test (5000 circulation) of 4.5 minutes ON-OFF after, carry out visual examination and by exchanging 4 terminal methods mensuration resistance variations (Δ R).To each test piece number (Test pc No.), each implements 22 this test, even when 1 NG wherein takes place, also is judged to be defective i.e. " * ".Table 5 ecbatic.
[table 5]
| Sample No. | Block type electrode | Thin layer | Cross pore electrod | Fusion temperature | Engage | Characteristic | ||||||||||||
| Material | Shape | The position | L | h | L/h | Material | Thickness | Have or not | The position | Solder 1 | Solder 2 | Difference of height | Wire length | Rate of finished products | Operation | Power consumption | Reliability | |
| mm | mm | μm | ℃ | ℃ | mm | mm | ％ | W | ||||||||||
| 1 | - | - | The bottom | - | - | - | Ni-Au | 20 | Do not have | - | 280 | - | 6 | 10 | 70 | × | 3 | ○ |
| 2 | - | - | Top | - | - | - | Ni-Au | 20 | Have | Laterally | 280 | - | 5 | 9 | 80 | × | 2.5 | × |
| 3 4 5 6 7 | Cu cu Cu Cu Cu | Cylinder cylinder cylinder cylinder cylinder | Top, top, top, top, top | 1 1 1 1 1 | 0.2 0.5 1 2 5 | 5 2 1 0.5 0.2 | Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au | 20 20 20 20 20 | Have | Directly over directly over directly over directly over directly over | 280 280 280 280 280 | 230 230 230 230 230 | 0 0 0 0 0 | 4 4 4 4 4 | 92 95 100 99 93 | ○ ○ ◎ ◎ ◎ | 1.6 1.6 1.5 1.6 1.6 | ○ ○ ○ ○ ○ |
| 8 9 10 | Cu Cu Cu | Cylinder cylinder cylinder | Top, top, top | 4 0.5 2 | 0.2 0.5 2 | 20 1 1 | Ni-Au Ni-Au Ni-Au | 20 20 20 | Have | Directly over directly over directly over | 280 280 280 | 230 230 230 | 0 0 0 | 4 4 4 | 91 100 100 | ○ ◎ ◎ | 1.6 1.6 1.6 | ○ ○ ○ |
| 13 14 15 16 17 | Cu Cu Cu Cu Cu | Quadrangular quadrangular quadrangular quadrangular quadrangular | Top, top, top, top, top | 1 1 1 1 1 | 0.2 0.5 1 2 5 | 5 2 1 0.5 0.2 | Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au | 20 20 20 20 20 | Have | Directly over directly over directly over directly over directly over | 280 280 280 280 280 | 230 230 230 230 230 | 0 0 0 0 0 | 4 4 4 4 4 | 93 94 100 99 94 | ○ ○ ◎ ◎ ◎ | 1.6 1.6 1.5 1.6 1.6 | ○ ○ ○ ○ ○ |
| 18 19 20 | Cu Cu Cu | Quadrangular quadrangular quadrangular | Top, top, top | 4 0.5 2 | 0.2 0.5 2 | 20 1 1 | Ni-Au Ni-Au Ni-Au | 20 20 20 | Have | Directly over directly over directly over | 280 280 280 | 230 230 230 | 0 0 0 | 4 4 4 | 92 100 100 | ○ ◎ ◎ | 1.6 1.6 1.6 | ○ ○ ○ |
| 21 22 23 24 25 | Cu Cu Cu Cu Cu | Six prismatic six prismatic six prismatic six prismatic six prisms | Top, top, top, top, top | 1 1 1 1 1 | 0.2 0.5 1 2 5 | 5 2 1 0.5 0.2 | Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au | 20 20 20 20 20 | Have | Directly over directly over directly over directly over directly over | 280 280 280 280 280 | 230 230 230 230 230 | 0 0 0 0 0 | 4 4 4 4 4 | 92 94 100 100 95 | ○ ○ ◎ ◎ ◎ | 1.8 1.8 1.5 1.6 1.6 | ○ ○ ○ ○ ○ |
| 26 27 28 | Cu Cu Cu | Eight prismatic eight prismatic eight prisms | Top, top, top | 4 0.5 2 | 0.5 1 2 | 8 0.5 1 | Ni-Au Ni-Au Ni-Au | 20 20 20 | Have | Directly over directly over directly over | 280 280 280 | 230 230 230 | 0 0 0 | 4 4 4 | 94 100 100 | ○ ◎ ◎ | 1.6 1.6 1.6 | ○ ○ ○ |
| 29 | Cu | Quadrangular | Top | 1 | 1 | 1 | Ni-Au | 20 | Have | Laterally | 280 | 230 | 0 | 4 | 91 | ◎ | 1.6 | ○ |
| 30 | Cu | Quadrangular | Top | 1 | 1 | 1 | Ni-Au | 20 | Do not have | Directly over | 280 | 230 | 0 | 4 | 100 | ◎ | 1.6 | ○ |
| 31 32 33 34 35 36 37 38 | Al Ag W Ti Fe Zn Ni Mg | Quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular | Top, top, top, top, top, top, top, top | 1 1 1 1 1 1 1 1 | 1 1 1 1 1 1 1 1 | 1 1 1 1 1 1 1 1 | Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au | 20 20 20 20 20 20 20 20 | Have | Directly over directly over directly over directly over directly over directly over directly over directly over | 280 280 280 280 280 280 280 280 | 230 230 230 230 230 230 230 230 | 0 0 0 0 0 0 0 0 | 4 4 4 4 4 4 4 4 | 100 100 100 100 100 100 100 100 | ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ | 1.6 1.6 1.6 1.6 1.6 1.6 1.8 1.6 | ○ ○ ○ ○ ○ ○ ○ ○ |
| 39 40 41 | Cu Cu Cu | Quadrangular quadrangular quadrangular | Top, top, top | 1 1 1 | 1 1 1 | 1 1 1 | Sn Pt Co | 20 20 20 | Have | Directly over directly over directly over | 280 280 280 | 230 230 230 | 0 0 0 | 4 4 4 | 100 100 100 | ◎ ◎ ◎ | 1.6 1.6 1.6 | ○ ○ ○ |
| 42 43 44 45 46 47 48 49 | Cu Cu Cu Cu Cu Cu Cu Cu | Quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular quadrangular | Top, top, top, top, top, top, top, top | 1 1 1 1 1 1 1 1 | 1 1 1 1 1 1 1 1 | 1 1 1 1 1 1 1 1 | Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au Ni-Au | 20 20 20 20 20 20 20 20 | Have | Directly over directly over directly over directly over directly over directly over directly over directly over | 280 230 230 180 180 280 230 180 | 180 180 280 280 230 280 230 180 | 0 0 0 0 0 0 0 0 | 4 4 4 4 4 4 4 4 | 100 100 100 100 100 100 100 100 | ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ | 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 | ○ ○ ○ ○ ○ ○ ○ ○ |
| 50 51 | Cu Cu | The quadrangular quadrangular | Top, top | 1 1 | 1 1 | 1 1 | Ni-Au Ni-Au | 20 20 | Have | Directly over directly over | 280 280 | 230 230 | 1 3 | 5 7 | 97 95 | ○ ○ | 1.8 2.0 | ○ ○ |
* mark is represented extraneous sample of the present invention [operation] [power cycles test]
Bottom: directly over the following substrate plane electrode: zero: 11～19 seconds/bar zero directly over the thermoelectric element: Δ R is below 5%
Top: it is horizontal to go up the substrate plane electrode: ◎ directly over the thermoelectric element not: 10 seconds/bar below *: Δ R is above 5%
*: 20 seconds/more than the bar
In the sample 3～51 of the structure shown in Fig. 7 A and the B, rate of finished products is more than 90%, and power consumption is below the 2W, and operation, reliability test are all good.Wherein, among the sample No.5,6,9,10,15,16,19,20,23,24,27,28,30～49, rate of finished products is more than 99%, and power consumption is below the 1.6W, and operation, reliability test are all good, and is excellent especially in all estimating.
And in the sample No.1 of the plane electrode bonding wire of using the lower support substrate, rate of finished products is low to 70%, and power consumption is high, and operation is compared with sample of the present invention to 3W, worsens.In addition, form on the upper support substrate in the sample 2 of plane electrode, rate of finished products is low to 80%, and power consumption is high, and operation is compared with sample of the present invention to 2.5W, worsens.
Claims (16)
1. thermoelectric inverting model, have support substrates, be arranged in a plurality of thermoelectric elements on this support substrates, be electrically connected the interelement wiring conductor of this thermoelectric, with the external connection terminals that this wiring conductor is electrically connected, it is characterized in that:
The section shape of described wiring conductor is rectangle or the top of the element composition surface one side trapezoidal shape than the following length of side of support substrates face one side.
2. thermoelectric inverting model according to claim 1 is characterized in that:
The interior angle that the element composition surface of described wiring conductor is become with the side is 45～90 ° a scope.
3. thermoelectric inverting model according to claim 1 is characterized in that:
The depth of parallelism of the bottom and upper segment on the element composition surface of described wiring conductor is below the 0.1mm.
4. thermoelectric inverting model according to claim 1 is characterized in that:
The flatness on the element composition surface of described wiring conductor is below the 0.1mm.
5. thermoelectric inverting model according to claim 1 is characterized in that:
Also have the lead member that is connected electrically on the described external connection terminals, it is more than the 12 weight %, below the 40 weight % that lead member is bonded on the Sn that comprises in the solder on the described external connection terminals.
6. thermoelectric inverting model according to claim 5 is characterized in that:
The porosity of described thermoelectric element is below 10%.
7. thermoelectric inverting model according to claim 5 is characterized in that:
The bond strength of described external connection terminals and described lead member is more than the 2N.
8. thermoelectric inverting model according to claim 5 is characterized in that:
In described solder, be formed with the diffusion layer of the lead member composition more than the thickness 0.1 μ m, and this diffusion layer exist for lead member be engaged more than 20% of area.
9. thermoelectric inverting model according to claim 8 is characterized in that:
The bond strength of described solder and described lead member is more than the 2N.
10. thermoelectric inverting model according to claim 8 is characterized in that:
With at least one of the section of described support substrates quadrature in, the diffusion layer of described lead member composition and the interface of non-diffusion layer are wave.
11. thermoelectric inverting model according to claim 8 is characterized in that:
The diffusion layer of described lead member composition is than non-diffusion layer densification on every side.
12. thermoelectric inverting model according to claim 5 is characterized in that:
Described support substrates comprise clip described thermoelectric element and relatively to upper support substrate and lower support substrate;
Described external connection terminals is plane, is formed on the face opposite with the face with thermoelectric element joint of described support substrates;
Described lead member is block, is wholely set with described external connection terminals.
13. thermoelectric inverting model according to claim 12 is characterized in that:
Described upper support substrate had pore electrod, and described external connection terminals and described wiring conductor are situated between and are electrically connected by crossing pore electrod.
14. thermoelectric inverting model according to claim 13 is characterized in that:
Described cross pore electrod be arranged on described thermoelectric element directly over.
15. thermoelectric inverting model according to claim 12 is characterized in that:
The maximum major diameter of described lead member is 0.2～20 with respect to the ratio of height.
16. the encapsulation of a thermoelectric inverting model, it is characterized in that: the connection that have container, is arranged on this internal tank is with electrode, the described thermoelectric inverting model of claim 12, described block lead member upper surface and the described very roughly the same height of electricity consumption that is connected.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003369113 | 2003-10-29 | ||
| JP2003369113A JP4363958B2 (en) | 2003-10-29 | 2003-10-29 | Thermoelectric conversion module and manufacturing method thereof |
| JP2003395650A JP2005159019A (en) | 2003-11-26 | 2003-11-26 | Thermoelectric module |
| JP2003395650 | 2003-11-26 | ||
| JP2004019874A JP2005217028A (en) | 2004-01-28 | 2004-01-28 | Thermoelectric conversion module and manufacturing method therefor |
| JP2004019874 | 2004-01-28 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410089674XA Division CN100397671C (en) | 2003-10-29 | 2004-10-29 | Thermoelectric inverting model |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101232071A true CN101232071A (en) | 2008-07-30 |
| CN100595941C CN100595941C (en) | 2010-03-24 |
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| CN200710305713A Expired - Fee Related CN100595941C (en) | 2003-10-29 | 2004-10-29 | Thermoelectric module and package thereof |
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| JP (1) | JP4363958B2 (en) |
| CN (1) | CN100595941C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110268536A (en) * | 2017-02-06 | 2019-09-20 | Lg伊诺特有限公司 | Thermoelectric element |
| CN112352324A (en) * | 2018-06-26 | 2021-02-09 | Lg 伊诺特有限公司 | Thermoelectric element |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4274134B2 (en) | 2005-02-15 | 2009-06-03 | ヤマハ株式会社 | Thermoelectric module and method for manufacturing the same |
| JP4873888B2 (en) * | 2005-05-27 | 2012-02-08 | 京セラ株式会社 | Thermoelectric conversion module, and power generation device and cooling device using the same |
| JP6089979B2 (en) * | 2013-06-03 | 2017-03-08 | ヤマハ株式会社 | Thermoelectric conversion parts |
| JP6022419B2 (en) * | 2013-07-09 | 2016-11-09 | 株式会社Kelk | Thermoelectric module |
| JP6586352B2 (en) * | 2015-11-12 | 2019-10-02 | 日東電工株式会社 | Manufacturing method of semiconductor device |
| JP2019220546A (en) | 2018-06-19 | 2019-12-26 | 三菱マテリアル株式会社 | Thermoelectric conversion module, and manufacturing method of thermoelectric conversion module |
-
2003
- 2003-10-29 JP JP2003369113A patent/JP4363958B2/en not_active Expired - Lifetime
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110268536A (en) * | 2017-02-06 | 2019-09-20 | Lg伊诺特有限公司 | Thermoelectric element |
| CN110268536B (en) * | 2017-02-06 | 2023-10-27 | Lg伊诺特有限公司 | thermoelectric element |
| US11937506B2 (en) | 2017-02-06 | 2024-03-19 | Lg Innotek Co., Ltd. | Thermoelectric element |
| CN112352324A (en) * | 2018-06-26 | 2021-02-09 | Lg 伊诺特有限公司 | Thermoelectric element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005136075A (en) | 2005-05-26 |
| JP4363958B2 (en) | 2009-11-11 |
| CN100595941C (en) | 2010-03-24 |
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