CN203288656U - A micro thermoelectric device - Google Patents
A micro thermoelectric device Download PDFInfo
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- CN203288656U CN203288656U CN2013203362626U CN201320336262U CN203288656U CN 203288656 U CN203288656 U CN 203288656U CN 2013203362626 U CN2013203362626 U CN 2013203362626U CN 201320336262 U CN201320336262 U CN 201320336262U CN 203288656 U CN203288656 U CN 203288656U
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Abstract
The utility model provides a micro thermoelectric device comprising a first substrate, a first barrier layer, a silicon dioxide layer, thermoelectric elements, a patterned second barrier layer, a second electrode layer, and a second substrate. The first substrate is equipped with a patterned first electrode layer. The first barrier layer is disposed on the first electrode layer. The silicon dioxide layer is disposed on the first substrate and the first barrier layer. The thermoelectric elements are disposed in the silicon dioxide layer. The patterned second barrier layer is disposed on the silicon dioxide layer and the thermoelectric element. The second electrode layer is disposed on the patterned second barrier layer. The second substrate is disposed on the second electrode layer. The structure of the micro thermoelectric device is suitable for semiconductor integration technology and resolves a problem of difficultly-achieved large-scale precise processing existing in the industrialization process of micron-order thermoelectric devices.
Description
Technical field
The utility model relates to the thermal generator manufacture technology field, more specifically, relates to a kind of minisize thermoelectric device and preparation method thereof.
Background technology
The thermo-electric generation technology is a kind of migration that utilizes microcosmic particle in semi-conductor thermoelectric material (electronics or hole), the hot-fluid of temperature difference generation is directly changed into the technology of electric energy.Thermal generator only is comprised of solid structure, not gassiness, liquid cycle fluid, and there is no a moving-member, therefore can be made into arbitrary size and shape, be installed on the occasion of various needs, can be widely used in the waste heat recovery of power plant, and the utilization of the regenerative resource such as underground heat, oceanic energy, solar energy.
The core of thermal generator is thermoelectric device, the array that namely highly integrated semi-conductor thermoelectric material, consists of.Compare with refrigeration, the technology of heating with traditional generation technology, thermoelectric device has the following advantages: movement-less part, simple in structure, reliability is high, the life-span is long, noise is little, pollute less, adaptive temperature scope wide (200 ?1400K) etc.At present, industry-wide conventional yardstick (grade) thermoelectric device is comprised of the semiconductor heat electric device of many P types and N-type usually.Connect by metal wire between these thermoelectric elements, form the electricity series connection, then with the thermal conductive ceramic plate holder of insulation, live, form heat in parallel.
In recent years, the integrated technology of thermoelectric device is towards the trend development of high integration and cost degradation, and thermoelectric device also progressively develops to microminiaturization.But in the process of thermoelectric device microminiaturization, thermoelectric element metallization problem becomes the difficult point in technique, has restricted the raising of minisize thermoelectric device (micron order) efficiency and reliability.So-called thermoelectric element metallization refers to prepare metal electrode at the thermoelectric element two ends, and its difficult point is need to form good ohmic contact between thermoelectric material and metal electrode on the one hand, needs on the other hand to stop metal electrode material to spread in thermoelectric material.The researcher once attempted the barrier material that the grade thermoelectric device uses is applied to the micron order thermoelectric device, but blocking effect is all undesirable, and the manufacture craft of existing thermoelectric device can not meet the requirement of micron order thermoelectric device to precision, can only complete the preparation of grade thermoelectric device.
For example, in publication number is the Chinese patent utility model of CN102412366A, a kind of metallized method of bismuth-telluride-based thermoelectric element has been proposed, metal or its alloys such as electrode material aluminium, copper, nickel, barrier material is selected antimony, aluminium antimonide, nickel antimonide or antimony copper etc., pack into successively in graphite jig according to the order of bismuth telluride-based thermoelectric layer material, barrier material, electrode layer material, carry out in a vacuum hot pressed sintering, finally obtain Mechanical Reliability grade thermoelectric device preferably.Propose a kind of method of electric arc spraying of utilizing and realized the metallization process on aluminium electrode, molybdenum barrier layer in publication number is the Chinese patent utility model of CN101409324A, can realize equally the metallization of grade thermoelectric device.Yet existing thermoelectric device structurally is unsuitable for extensive precise machining process, and the thermoelectric device that makes only is grade, can't meet the required precision of minisize thermoelectric device; In addition, in existing thermoelectric device, the barrier effect on barrier layer also can't meet the demand of micron order thermoelectric device.
The utility model content
In order to solve the extensive precision machined problem that exists in the industrialization of present micron order thermoelectric device, the utility model provides a kind of minisize thermoelectric device.This minisize thermoelectric device is very suitable for micro machining technique on structure arranges, make the extensive Precision Machining of thermoelectric device be achieved.
One side of the present utility model is to provide a kind of minisize thermoelectric device, and this minisize thermoelectric device comprises: first substrate is provided with the first electrode layer of patterning; The first barrier layer, be arranged on the first electrode layer; Silicon dioxide layer, be arranged on first substrate and the first barrier layer; Thermoelectric element, be arranged in silicon dioxide layer; The second barrier layer, be arranged on silicon dioxide layer and thermoelectric element and be patterned; The second electrode lay, be arranged on the second barrier layer; And second substrate, be arranged on the second electrode lay.
Preferably, above-mentioned thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, and the N-type thermoelectric element forms the first thermoelectric element group, and P type thermoelectric element forms the second thermoelectric element group, and the first thermoelectric element group and the second thermoelectric element group are arranged alternately.
Preferably, above-mentioned thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, and above-mentioned thermoelectric element is arranged in the matrix that is formed by multirow and multiple row, and N-type thermoelectric element and P type thermoelectric element in matrix in any multirow and multiple row are arranged alternately.
Preferably, in an embodiment provided by the utility model, be provided with the first silicon dioxide separator in the first electrode layer of patterning; Be provided with the second silicon dioxide separator in the second electrode lay of patterning.
Preferably, silicon dioxide layer is separated into a plurality of the first thermoelectric element separators and a plurality of the second thermoelectric element separator by thermoelectric element, the first thermoelectric element separator is connected with the first silicon dioxide separator, and the second thermoelectric element separator is connected with the second silicon dioxide separator.
Preferably, the height of the thermoelectric element of the thermoelectric device that provides of the utility model is 5 to 200 microns.
Preferably, above-mentioned thermoelectric element is cylinder or hexahedron.
When above-mentioned thermoelectric element was cylinder, cylindrical diameter was 1 to 40 micron; When thermoelectric element was hexahedron, hexahedral length and width were 1 to 40 micron.
Preferably, the first barrier layer in the thermoelectric device that provides of the utility model and the thickness on the second barrier layer are 2 to 300 nanometers.
Preferably, the first electrode in the thermoelectric device that provides of the utility model and the thickness of the second electrode are 0.3 to 72 micron.
Can be found out by technique scheme, its structure of minisize thermoelectric device that the utility model provides is applicable to the semiconductor integration making technology, deposition forms thermoelectric element in silicon dioxide layer, has solved the extensive precision machined problem that exists in present micron order thermoelectric device industrialization process.
Description of drawings
Accompanying drawing form this specification a part, be used for further understanding the utility model, accompanying drawing shows preferred embodiment of the present utility model, and is used for illustrating principle of the present utility model together with specification.In figure:
Fig. 1 shows the cross-sectional view of a kind of minisize thermoelectric device that the utility model embodiment provides;
Fig. 2 shows a kind of arrangement schematic diagram of thermoelectric element in minisize thermoelectric device shown in Figure 1;
Fig. 3 shows the another kind of arrangement schematic diagram of thermoelectric element in minisize thermoelectric device shown in Figure 1;
Fig. 4 shows the cross-sectional view of another minisize thermoelectric device that the utility model embodiment provides;
Fig. 5 shows the schematic flow sheet of the minisize thermoelectric device manufacture method that the utility model provides;
Figure 6 ?16 show each step of implementing minisize thermoelectric device manufacture method provided by the utility model after, the cross-sectional view of gained thermoelectric device.
Figure 17 shows the thermoelectric device connected mode schematic diagram in the temperature difference heat motor that the utility model provides.
Embodiment
Below, describe in more detail according to exemplary embodiment of the present utility model with reference to the accompanying drawings.Yet these exemplary embodiments can be implemented by multiple different form, and should not be interpreted as being only limited to the embodiments set forth herein.To should be understood that, to provide these embodiment of the present utility modelly to disclose thoroughly and complete in order making, and the design of these exemplary embodiments is fully conveyed to those of ordinary skills.But the multitude of different ways that the utility model can be defined by the claims and cover is implemented.
By background technology as can be known, there is extensive precision machined problem in micron order thermoelectric device industrialization process at present, utility model people of the present utility model studies for above problem,, in order to adopt semiconductor integrated technique technology to make the minisize thermoelectric device, provide a kind of novel minisize thermoelectric device.This minisize thermoelectric device comprises first substrate, is provided with the first electrode layer of patterning; The first barrier layer, be arranged on described the first electrode layer; Silicon dioxide layer, be arranged on first substrate and the first barrier layer; Thermoelectric element, be arranged in silicon dioxide layer; The second barrier layer of patterning, be arranged on silicon dioxide layer and thermoelectric element; The second electrode lay, be arranged on the second barrier layer of patterning; And second substrate, be arranged on the second electrode lay.That is to say, the thermoelectric device that the utility model provides comprises the first substrate of the first electrode layer that is provided with patterning; The first barrier layer further is set on the first electrode layer; On the relative direction of first substrate, second substrate is set, be provided with the second barrier layer and the second electrode lay of patterning on this second substrate, there is silicon dioxide layer between above-mentioned first substrate and second substrate, and be provided with thermoelectric element on above-mentioned silicon dioxide layer.
In above-mentioned thermoelectric device, thermoelectric element upper surface and lower surface are metallized, and the existence due to the first barrier layer and the second barrier layer, not only make between thermoelectric element and the first electrode layer and the second electrode and form good being electrically connected to (electronics can freely pass through between thermoelectric element and the first electrode layer or the second electrode lay), but also effectively stoped the electrode material of the first electrode layer and the second electrode to spread in thermoelectric element.In addition, this thermoelectric device exists between first substrate and second substrate silicon dioxide layer not only plays insulation effect, but also has played good supporting role.And, due to can be directly in silicon dioxide layer etching, deposition form thermoelectric element, can utilize existing semiconductor preparing process to make the minisize thermoelectric device, solved the extensive precision machined problem that exists in present micron order thermoelectric device industrialization process.
, in order to further illustrate thermoelectric device provided by the utility model, further set forth the structure of this thermoelectric device below in conjunction with Fig. 1.
As shown in Figure 1, this minisize thermoelectric device comprises first substrate 10, is provided with the first electrode layer 20 of patterning on this first substrate 10; Be provided with the first barrier layer 30 on the first electrode layer 20, the first electrode layer 20 of patterning can form by the first silicon dioxide separator 12; This minisize thermoelectric device also comprises the second substrate 90 that is oppositely arranged with first substrate 10, be provided with the second barrier layer 70 and the second electrode lay 80 of patterning on this second substrate 90, the second barrier layer 70 of patterning and the second electrode lay 80 can form by the second silicon dioxide separator 62, there is silicon dioxide layer 40 between first substrate 10 and second substrate 90, and be provided with thermoelectric element (52,54) in silicon dioxide layer 40.
In minisize thermoelectric device provided by the utility model, thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, and those skilled in the art can arrange according to the real work situation layout of N-type thermoelectric element and P type thermoelectric element.For example, above-mentioned thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, the N-type thermoelectric element forms the first thermoelectric element group, P type thermoelectric element forms the second thermoelectric element group, the first thermoelectric element group and the second thermoelectric element group are arranged alternately, as shown in Figure 2, the first thermoelectric element group and the second thermoelectric element group be arranged in parallel, and the first thermoelectric element group and the second thermoelectric element group are with the form setting of row; Perhaps, this thermoelectric element is arranged in the matrix that is formed by multirow and multiple row, and N-type thermoelectric element and the P type thermoelectric element in multirow and multiple row is arranged alternately arbitrarily, as shown in Figure 3.
Can find out from structure shown in Figure 1, the difference of minisize thermoelectric device provided by the utility model and existing thermoelectric device is, thermoelectric element (52,54) is formed in silicon dioxide layer 40, silicon dioxide layer 40 not only plays insulation effect, but also has played good supporting role.In addition, thermoelectric element (52,54) there are the first barrier layer 30 and the second barrier layer (70) and between the first electrode layer 20 and the second electrode lay 80, this not only makes thermoelectric element (52,54) with between the first electrode layer 20 and the second electrode 80 can form good being electrically connected to, but also effectively stoped the electrode material of the first electrode layer 20 and the second electrode 80 to spread in thermoelectric element (52,54).
In structure shown in Figure 1, there is the first silicon dioxide separator 12 in the first electrode layer 20 of patterning, namely by the first silicon dioxide separator 12, form the first electrode layer 20 of patterning; There is the second silicon dioxide separator 62 in the second electrode lay 80 of patterning, namely by the second silicon dioxide separator 62, form the second barrier layer of patterning.Also can adopt other patterning method of this area to make the first electrode layer 20 or the second electrode lay 80 of patterning.
More preferably, silicon dioxide layer 40 is separated into a plurality of the first thermoelectric element separators 42 and a plurality of the second thermoelectric element separator 44 by thermoelectric element, the first thermoelectric element separator 42 is connected with the first silicon dioxide separator 12, and the second thermoelectric element separator 44 is connected with the second silicon dioxide separator 62.
The thermoelectric material that the utility model adopts can be thermoelectric material commonly used in prior art, and is well-known, and the thermoelectricity capability of thermoelectric material is characterized by its figure of merit Z, and the figure of merit is large, and its conversion efficiency of thermoelectric is just high.The formula of figure of merit Z is: Z=α 2 σ/К, and wherein, α is Seebeck coefficient, and σ is the conductivity of material, and К is the thermal conductivity of material.At present, the alloy semiconductor material has higher Sai Beier coefficient, is the preferred material of thermoelectric device.Preferably, the thermoelectric material of the utility model thermoelectric element employing is selected from (Bi, Sb)
2Te
3Sill, PbTe sill or CoSb
3Sill, (Bi, Sb)
2Te
3The optimal operation temperature of base thermoelectricity material, less than 450 ℃, is most widely used low-temperature space thermoelectric material; PbTe has the NaCl crystal structure, is widely used in the thermoelectric material in mesophilic range, and its optimal operation temperature is approximately 1000 ℃; CoSb
3Have cubic crystal structure, fusing point is higher, is applicable to the high-temperature region thermoelectric material.
The utility model can be the barrier material of commonly using for the preparation of the material on the first and second barrier layers, and preferably, the material that adopt on the first and second barrier layers is selected from Au, Ag, Ta, Cu, Ti, TiN, TiW, Ni, Mo and Cr
80Si
20In a kind of; The utility model can be the electrode material of commonly using for the preparation of the material of the first and second electrode layers, and preferably, the material that the first and second electrodes adopt is selected from Cu, Al, Au, Ag, In, porous Ni, Mo, Cu ?Mo alloy and Cu ?a kind of in W alloy.
Preferably, the utility model has adopted different barrier materials and electrode material for different warm area thermoelectric materials, formed different Re Dian Cai Liao ?Zu Dang Ceng ?electrode structure, purpose is to solve metal electrode diffusion problem.In existing preparation technology, do not propose preparation Re Dian Cai Liao ?Zu Dang Ceng ?the optimum organization of material of electrode, and applicant of the present utility model has proposed the combination of materials of following optimization:
In an embodiment of the present utility model, the material that above-mentioned thermoelectric element adopts is (Bi, Sb)
2Te
3Sill, the material that adopt on the first and second barrier layers is selected from Au, Ag, Ta, TiN, a kind of in TiW and Ni, the material that the first and second electrodes adopt is selected from Cu, Al, a kind of in Au and Ag.The barrier film that adopts above-mentioned material to make is very fine and close, has hindered the diffusion of electrode material, and can form good being electrically connected between thermoelectric element and the first electrode layer and the second electrode lay.
In another embodiment that the utility model provides, the material that above-mentioned thermoelectric element adopts is the PbTe sill, and the material that adopt on the first and second barrier layers is selected from Cu, a kind of in Ni and Mo, the material that the first and second electrodes adopt is selected from Cu, In, a kind of in Au and porous Ni.
In the another embodiment that the utility model provides, the material that above-mentioned thermoelectric element adopts is CoSb
3Sill, the material that adopt on the first and second barrier layers is selected from Ti, Ni, Mo and Cr
80Si
20In a kind of, the material that the first and second electrodes adopt is selected from Cu, Mo, Cu ?Mo alloy and Cu ?a kind of in W alloy.Above-mentioned barrier material has very high fusing point, and at high temperature electrode material is difficult to diffuse through barrier layer, has protected thermoelectric element.
The height of the thermoelectric element of the utility model gained thermoelectric device is 5 to 200 microns, and existing thermoelectric element is grade, and thermoelectric element provided by the utility model can be realized micron order.This thermoelectric element be shaped as hexahedron, preferably, hexahedral length and width are 1 to 40 micron.More preferably, the proportional control between hexahedral length or width and height is in the scope of 1:5 left and right, if exceed this ratio, thermoelectric element is easy to fracture, and the device that makes is easy to damage; Certainly, except hexahedron shown in Figure 1, this thermoelectric element can be also cylinder, and cylindrical diameter can be the scope of 1 to 40 micron; To hexahedral explanation, cylindrical diameter and highly preferred control are in the reasonable scope as above-mentioned.
In the embodiment that the utility model provides, the thickness on the first barrier layer and the second barrier layer is 2 to 300 nanometers, and the thickness of the first electrode and the second electrode is 0.3 to 72 micron, and the device performance under this thickness range is better.
In addition, the first substrate of the thermoelectric device that the utility model provides or second substrate are preferably silicon chip or heat conductive insulating pottery, also can adopt other device materials well known in the art.
Except thermoelectric device shown in Figure 1, Fig. 4 also shows another thermoelectric device.The element of this thermoelectric device is same as shown in Figure 1, only further to comprise silica insulation film 102 and TiN film 104 between first substrate 10 and the first electrode layer 20, the thickness of this silica insulation film 102 is 1 to 5 micron, and the thickness of TiN film 104 is 0.3 to 1 micron.Silica insulation film 102 and TiN film 104 can play insulating effect,, if the insulation property of the first substrate that adopts are very good, fully silica insulation film 102 and TiN film 104 can be set.
The utility model also provides a kind of manufacture method of minisize thermoelectric device, and the manufacture method of this minisize thermoelectric device as shown in Figure 5, comprising:
S101, the first electrode layer of formation patterning on first substrate;
S102, deposition the first barrier layer on the first electrode layer of patterning;
S103, deposition of silica layer on first substrate;
S104, etching forms the thermoelectric element figure in silicon dioxide layer, and thermoelectric material is deposited in the thermoelectric element figure, forms thermoelectric element;
S105, the second barrier layer of formation patterning on silicon dioxide layer and thermoelectric element;
S106, deposit the second electrode lay on the second barrier layer; And
S107, arrange second substrate on the second electrode lay, form the minisize thermoelectric device.
Can find out from above-mentioned manufacture craft, the minisize thermoelectric device manufacture method that the utility model provides has adopted semiconductor integrated technique technology, comprise thin film deposition, photoetching, etching etc., solved the extensive precision machined problem that exists in present micron order thermoelectric device industrialization process.
Figure 6 ?16 show each step of implementing minisize thermoelectric device manufacture method provided by the utility model after, the cross-sectional view of gained thermoelectric device.Below in conjunction with figure 6 ?16 manufacture methods of further explaining the minisize thermoelectric device that the utility model provides.
At first, implementation step S101, the first electrode layer 20 of formation patterning, form thermoelectric device cross-section structure as shown in Figure 6 on first substrate 10; The first substrate 10 that adopts can be silicon chip or heat conductive insulating pottery.In the embodiment that the utility model provides, the concrete technology of this step can comprise:
The default layer of deposition the first silicon dioxide on first substrate (for example, silicon chip or heat conductive insulating ceramic substrate) 10, the thickness of the default layer of this first silicon dioxide can 3 ?the scope of 100 microns.The technique that deposits the default layer of this first silicon dioxide comprises thermal oxidation, magnetron sputtering, plasma reinforced chemical vapour deposition, because above-mentioned technique is this area silica deposit method commonly used, concrete technology just repeats no more at this.
Further, can be before the default layer of deposition the first silicon dioxide, on first substrate 10 deposition 1 ?silica insulation film 102 and the TiN film 104 of 5 microns, form thermoelectric device cross-section structure shown in Figure 7.The technique of deposition of silica dielectric film 102 comprises thermal oxidation, magnetron sputtering, plasma enhanced chemical vapor deposition.The technique of depositing TiN film 104 comprises magnetron sputtering, plasma enhanced chemical vapor deposition, and above-mentioned preparation technology is conventional preparation technology, and the concrete technology step does not repeat them here.
After forming the default layer of the first silicon dioxide on first substrate 10, etch away the default layer of part the first silicon dioxide by photoetching and etching technics, form groove, be the first electrode pattern 14, and form the first silicon dioxide separator 12.Preferably, the degree of depth of this first electrode pattern 14 be 0.3 ?100 microns, width be 3 ?120 microns.Photoetching and etching technics are prior art, no longer describe in detail here.
Deposition the first electrode material, form the first electrode layer 20 on the first electrode pattern 14 that forms, and the thermoelectric device cross-section structure of formation as shown in Figure 6.Kept apart by the first silicon dioxide separator 12 between the first electrode layer 20.The material that forms this first electrode can be selected from Cu, Al, Au, Ag, In, porous Ni, Mo, a kind of in Cu ?Mo alloy and Cu ?W alloy.
Implementation step S102, deposition the first barrier layer 30 on the first electrode layer 20 of patterning, polish upper surface and can form as shown in Figure 8 thermoelectric device cross-section structure.The selected material in this first barrier layer 30 is selected from Au, Ag, Ta, Cu, Ti, TiN, TiW, Ni, Mo and Cr
80Si
20In a kind of.The technique that deposits the first barrier layer 30 comprises magnetron sputtering, electron beam evaporation and vacuum thermal evaporation.Above-mentioned technique is this area deposition process commonly used, and concrete technology just repeats no more at this.
Implementation step S103, on the surface on the first barrier layer 30 deposit thickness be 5 ?the silicon dioxide layer 40 of 200 microns.Then, by photoetching and etching technics, etch away part silicon dioxide layer 40, form groove, namely P type (or N-type) thermoelectric element pattern 50, form thermoelectric device cross-section structure as shown in Figure 9.The technique of deposition of silica layer 40 comprises thermal oxidation, magnetron sputtering, plasma enhanced chemical vapor deposition, and the technique of photoetching and etching thermoelectric element pattern 50 is also routine techniques, at this, just repeats no more.
Implementation step is 104, and deposition P type (or N-type) thermoelectric material, after deposition is completed, polish upper surface on P type (or N-type) thermoelectric element pattern 50, forms P type (or N-type) thermoelectric element 52, and the thermoelectric device cross-section structure of formation as shown in figure 10.Preferably, depositing operation comprises magnetron sputtering, masterplate electro-deposition, accurate patterning method, film etching, little printing, little spraying.Thermoelectric material can be selected from (Bi, Sb)
2Te
3Sill, PbTe sill or CoSb
3Sill.
After the making of completing above-mentioned thermoelectric element 52, further deposition of silica buildup layer 46 on the surface that silicon dioxide layer 40 polishes, add etching technics by photoetching and etch away part silicon dioxide layer 40 and silicon dioxide buildup layer 46, form N-type (or P type) thermoelectric element figure 50 '.Form the thermoelectric device cross-section structure as Figure 11.The technique of deposition of silica buildup layer 46 comprises thermal oxidation, magnetron sputtering, plasma enhanced chemical vapor deposition.
Then, at the upper deposition N-type (or P type) of N-type (or P type) thermoelectric element figure 50 ' thermoelectric material, after deposition is completed, polish upper surface, form N-type (or P type) thermoelectric element 54, form thermoelectric device cross-section structure as shown in figure 12.Depositing operation comprises magnetron sputtering, masterplate electro-deposition, accurate patterning method, film etching, little printing, little spraying.Thermoelectric material can be selected from (Bi, Sb)
2Te
3Sill, PbTe sill or CoSb
3Sill.
Next, etching is removed silicon dioxide buildup layer 46 and is polished, and exposes all N-types and P type thermoelectric element, forms thermoelectric device cross-section structure as shown in figure 13.The technique that polishes that adopts comprises chemico-mechanical polishing, mechanical lapping etc.
Implementation step S105, at silicon dioxide layer 40 and the default layer 60 of the upper deposition of thermoelectric element (52,54) the second silicon dioxide.The thickness of the default layer 60 of this second silicon dioxide can 3 ?the scope of 100 microns.The technique that deposits the default layer 60 of this second silicon dioxide comprises thermal oxidation, magnetron sputtering, plasma reinforced chemical vapour deposition, because above-mentioned technique is this area silica deposit method commonly used, concrete technology just repeats no more at this.Then,, by photoetching and the default layer 60 of etching technics etched portions the second silicon dioxide, form groove 64 and the second silicon dioxide separator 62, the thermoelectric device structure of formation as shown in figure 14.
Implementation step S106, deposition the second barrier layer 70 on above-mentioned groove, then the second electrode lay 80 corresponding to deposition, polish upper surface after deposition is completed, and forms thermoelectric device structure as shown in figure 15.Depositing operation comprises magnetron sputtering, electron beam evaporation and vacuum thermal evaporation.
Implementation step S107, at the upper surface encapsulation second substrate 90 of the second electrode lay 80, cold junction (as lower surface) reserves electrode, and its structure is as shown in figure 16.Wherein P type thermoelectric arm is corresponding anodal 32, and the corresponding negative pole 34 of N-type thermoelectric arm, form the minisize thermoelectric device.By bonding equipment, the electrode of above-mentioned thermoelectric device is carried out series and parallel and connect, form electrothermal module.
Figure 17 also shows a kind of temperature difference heat motor, and this temperature difference heat motor comprises the one or more above-mentioned minisize thermoelectric device of serial or parallel connection.Preferably, the material that adopts of the thermoelectric element in a plurality of minisize thermoelectric devices is different.More preferably, above-mentioned temperature difference heat motor comprises the first minisize thermoelectric device of consisting of the CoSb3 thermoelectric element, the second thermoelectric device that consists of the PbTe thermoelectric element and the 3rd thermoelectric device that consists of the Bi2Te3 thermoelectric element, wherein, the thermal source of the contiguous temperature difference heat motor of the first thermoelectric device, the cold junction of the contiguous temperature difference heat motor of the 3rd thermoelectric device.
Below will further illustrate with specific embodiment structure and the performance of minisize thermoelectric device provided by the utility model.
Embodiment 1
1. form the first electrode layer and the first barrier layer on first substrate
Successively deposit silica insulation film 102 and 0.3 micron TiN film 104 of 1 micron on silicon chip by plasma enhanced chemical vapor deposition technique.Then, deposit the default layer of the first silicon dioxide of 60 microns on silicon chip 10 by plasma enhanced chemical vapor deposition technique; Then, by photoetching and etching technics, etch away the default layer of part the first silicon dioxide, form groove, be the first electrode pattern 14.The degree of depth of this first electrode pattern 14 is 1 micron, and width is 50 microns.Then,, by magnetron sputtering technique deposition of electrode material on the first electrode pattern 14, form the first electrode layer 20; Then deposit the barrier material of 10 nanometers by magnetron sputtering technique on the first electrode layer 20,, as the first barrier layer 30, polish upper surface.
2. formation thermoelectric element
It is the silicon dioxide layer 40 of 30 microns by plasma enhanced chemical vapor deposition technique deposit thickness on the surface on the first barrier layer 30.Then, by photoetching and etching technics, etch away part silicon dioxide layer 40, form groove, i.e. P type (or N-type) thermoelectric element pattern 50.Deposit P type (or N-type) thermoelectric material (Bi on P type (or N-type) thermoelectric element pattern 50 by magnetron sputtering technique
2Te
3Low-temperature thermoelectric material or PbTe warm thermoelectric material or CoSb
3The high temperature thermoelectric material), after deposition is completed, polish upper surface, form P type (or N-type) thermoelectric element 52.
After the making of completing above-mentioned thermoelectric element 52, by plasma enhanced chemical vapor deposition deposition of silica buildup layer 46 on the surface that silicon dioxide layer 40 polishes, add etching technics by photoetching and etch away part silicon dioxide layer 40 and silicon dioxide buildup layer 46, form groove, i.e. N-type (or P type) thermoelectric element figure 50 '.Then upward deposit N-type (or P type) Bi by magnetron sputtering technique at N-type (or P type) thermoelectric element figure 50 '
2Te
3Thermoelectric material, after deposition is completed, polish upper surface, forms N-type (or P type) thermoelectric element 54.Next, etching is removed silicon dioxide buildup layer 46 and is utilized CMP (Chemical Mechanical Polishing) process to polish, and exposes all N-types and P type thermoelectric element.
3. form minisize thermoelectric device and thermal generator
By plasma reinforced chemical vapour deposition technique on silicon dioxide layer 40 and thermoelectric element (52,54).Then,, by photoetching and the default layer 60 of etching technics etched portions the second silicon dioxide, form groove 64.Form the second barrier layer 70 by magnetron sputtering technique on groove 64, then deposit the second electrode lay 80, polish upper surface after deposition is completed.At the upper surface encapsulation second substrate 90 of the second electrode lay 80, cold junction (as lower surface) reserves electrode.Wherein P type thermoelectric arm is corresponding anodal 32, and the corresponding negative pole 34 of N-type thermoelectric arm, form the minisize thermoelectric device.
By bonding equipment, the electrode of above-mentioned thermoelectric device is carried out series and parallel and connect, form electrothermal module.The second electrothermal module and Bi with the first electrothermal module of thermoelectric device formation, PbTe thermoelectric device formation
2Te
3The 3rd electrothermal module that thermoelectric device forms stacks up, and wherein, the first electrothermal module is near thermal source, and the 3rd electrothermal module is near cold junction.Then, electromagnetic relay, insulated side wall, temperature-detecting device and controller are installed, are formed the temperature difference heat motor.The barrier material and the electrode material that adopt in the present embodiment are asked for an interview table 1.
Table 1
| Barrier material | Electrode material |
| Bi 2Te 3Thermoelectric device | TiN | Cu |
| The PbTe thermoelectric device | Ni | Au |
| CoSb 3Thermoelectric device | Ti | Mo |
4. thermoelectric conversion efficiency test
By adopting heat-flow meter to measure the heat Q that flows into the thermoelectricity components and parts, utilize the common power table to measure the electrical power P of thermoelectricity components and parts, utilize formula η=P/Q to calculate the thermoelectric conversion efficiency η of thermoelectricity components and parts, test result is asked for an interview table 4.
Embodiment 2
1. form the first electrode layer and the first barrier layer on first substrate
Deposit the default layer of the first silicon dioxide of 120 microns on first substrate (heat conductive insulating ceramic substrate) 10 by plasma enhanced chemical vapor deposition technique; Then, by photoetching and etching technics, etch away the default layer of part the first silicon dioxide, form groove, be the first electrode pattern 14.The degree of depth of this first electrode pattern 14 is 55 microns, and width is 110 microns.Then,, by magnetron sputtering technique deposition of electrode material on the first electrode pattern 14, form the first electrode layer 20; Then deposit the barrier material of 150 nanometers by magnetron sputtering technique on the first electrode layer 20,, as the first barrier layer 30, polish upper surface.
2. formation thermoelectric element
It is the silicon dioxide layer 40 of 100 microns by plasma enhanced chemical vapor deposition technique deposit thickness on the surface on the first barrier layer 30.Then, by photoetching and etching technics, etch away part silicon dioxide layer 40, form groove, i.e. P type (or N-type) thermoelectric element pattern 50.Deposit P type (or N-type) thermoelectric material (Bi on P type (or N-type) thermoelectricity figure 50 by magnetron sputtering technique
2Te
3Low-temperature thermoelectric material or PbTe warm thermoelectric material or CoSb
3The high temperature thermoelectric material), after deposition is completed, polish upper surface, form P type (or N-type) thermoelectric element 52.
After the making of completing above-mentioned thermoelectric element 52, by plasma enhanced chemical vapor deposition deposition of silica buildup layer 46 on the surface that silicon dioxide layer 40 polishes, add etching technics by photoetching and etch away part silicon dioxide layer 40 and silicon dioxide buildup layer 46, form groove, i.e. N-type (or P type) thermoelectric element figure 50 '.Then upward deposit N-type (or P type) Bi by magnetron sputtering technique at N-type (or P type) thermoelectric element figure 50 '
2Te
3Thermoelectric material, after deposition is completed, polish upper surface, forms N-type (or P type) thermoelectric element 54.Next, etching is removed silicon dioxide buildup layer 46 and is utilized CMP (Chemical Mechanical Polishing) process to polish, and exposes all N-types and P type thermoelectric element.
3. form minisize thermoelectric device and thermal generator
Preset layer 60 by plasma reinforced chemical vapour deposition technique at silicon dioxide layer 40 and upper the second silicon dioxide that deposits 60 microns of thermoelectric element (52,54).Then,, by photoetching and the default layer 60 of etching technics etched portions the second silicon dioxide, form groove 64.Deposit the second barrier layer 70 by magnetron sputtering technique on groove 64, then deposit the second electrode lay 80, polish upper surface after deposition is completed.At the upper surface encapsulation second substrate 90 of the second electrode lay 80, cold junction (as lower surface) reserves electrode.Wherein P type thermoelectric arm is corresponding anodal 32, and the corresponding negative pole 34 of N-type thermoelectric arm, form the minisize thermoelectric device.
By bonding equipment, the electrode of above-mentioned thermoelectric device is carried out series and parallel and connect, form electrothermal module.With CoSb
3The second electrothermal module and Bi that the first electrothermal module that thermoelectric device forms, PbTe thermoelectric device form
2Te
3The 3rd electrothermal module that thermoelectric device forms stacks up, and wherein, the first electrothermal module is near thermal source, and the 3rd electrothermal module is near cold junction.Then, electromagnetic relay, insulated side wall, temperature-detecting device and controller are installed, are formed the temperature difference heat motor.The barrier material and the electrode material that adopt in the present embodiment are asked for an interview table 2.
Table 2
| Barrier material | Electrode material | |
| Bi 2Te 3Thermoelectric device | Au | Ag |
| The PbTe thermoelectric device | Cu | In |
| CoSb 3Thermoelectric device | Ni | Cu |
4. thermoelectric conversion efficiency test
By adopting heat-flow meter to measure the heat Q that flows into the thermoelectricity components and parts, utilize the common power table to measure the electrical power P of thermoelectricity components and parts, utilize formula η=P/Q to calculate the thermoelectric conversion efficiency η of thermoelectricity components and parts, test result is asked for an interview table 4.
Embodiment 3
1. form the first electrode layer and the first barrier layer on first substrate
Successively deposit 102 and 1 microns TiN film 104 of the default layer of the first silicon dioxide of 5 microns on silicon chip by plasma enhanced chemical vapor deposition technique.Then, deposit the silicon dioxide layer of 120 microns by plasma enhanced chemical vapor deposition technique on first substrate (heat conductive insulating ceramic substrate) 10; Then, by photoetching and etching technics, etch away the part silicon dioxide layer, form groove, be the first electrode pattern 14.The degree of depth of this first electrode pattern 14 is 110 microns, and width is 120 microns.Then,, by magnetron sputtering technique deposition of electrode material on the first electrode pattern 14, form the first electrode layer 20; Then deposit the first barrier layer 30 by magnetron sputtering technique on the first electrode layer 20, polish upper surface.
2. formation thermoelectric element
It is the silicon dioxide layer 40 of 200 microns by plasma enhanced chemical vapor deposition technique deposit thickness on the surface on the first barrier layer 30.Then, by photoetching and etching technics, etch away part silicon dioxide layer 40, form groove, i.e. P type (or N-type) thermoelectric element pattern 50.Deposit P type (or N-type) thermoelectric material (Bi on P type (or N-type) thermoelectric element pattern 50 by magnetron sputtering technique
2Te
3Low-temperature thermoelectric material or PbTe warm thermoelectric material or CoSb
3The high temperature thermoelectric material), after deposition is completed, polish upper surface, form P type (or N-type) thermoelectric element 52.
After the making of completing above-mentioned thermoelectric element 52, by plasma enhanced chemical vapor deposition deposition of silica buildup layer 46 on the surface that silicon dioxide layer 40 polishes, add etching technics by photoetching and etch away part silicon dioxide layer 40 and silicon dioxide buildup layer 46, form groove, i.e. N-type (or P type) thermoelectric element figure 50 '.Then upward deposit N-type (or P type) Bi by magnetron sputtering technique at N-type (or P type) thermoelectric element figure 50 '
2Te
3Thermoelectric material, after deposition is completed, polish upper surface, forms N-type (or P type) thermoelectric element 54.Next, etching is removed silicon dioxide buildup layer 46 and is utilized CMP (Chemical Mechanical Polishing) process to polish, and exposes all N-types and P type thermoelectric element.
3. form minisize thermoelectric device and thermal generator
Preset layer 60 by plasma reinforced chemical vapour deposition technique at silicon dioxide layer 40 and upper the second silicon dioxide that deposits 60 microns of thermoelectric element (52,54).Then,, by photoetching and the default layer 60 of etching technics etched portions the second silicon dioxide, form groove 64.Deposit the second barrier layer 70 by magnetron sputtering technique on groove 64, then deposit the second electrode lay 80, polish upper surface after deposition is completed.At the upper surface encapsulation second substrate 90 of the second electrode lay 80, cold junction (as lower surface) reserves electrode.Wherein P type thermoelectric arm is corresponding anodal 32, and the corresponding negative pole 34 of N-type thermoelectric arm, form the minisize thermoelectric device.
By bonding equipment, the electrode of above-mentioned thermoelectric device is carried out series and parallel and connect, form electrothermal module.With CoSb
3The second electrothermal module and Bi that the first electrothermal module that thermoelectric device forms, PbTe thermoelectric device form
2Te
3The 3rd electrothermal module that thermoelectric device forms stacks up, and wherein, the first electrothermal module is near thermal source, and the 3rd electrothermal module is near cold junction.Then, electromagnetic relay, insulated side wall, temperature-detecting device and controller are installed, are formed the temperature difference heat motor.The barrier material and the electrode material that adopt in the present embodiment are asked for an interview table 3.
Table 3
| Barrier material | Electrode material | |
| Bi 2Te 3Thermoelectric device | Ag | Al |
| The PbTe thermoelectric device | Mo | Cu |
| CoSb 3Thermoelectric device | TMo | Cu ?the Mo alloy |
4. thermoelectric conversion efficiency test
By adopting heat-flow meter to measure the heat Q that flows into the thermoelectricity components and parts, utilize the common power table to measure the electrical power P of thermoelectricity components and parts, utilize formula η=P/Q to calculate the thermoelectric conversion efficiency η of thermoelectricity components and parts, test result is asked for an interview table 4.
Table 4 is the thermoelectric conversion efficiency test result in the utility model embodiment.As shown in table 4, adopted two kinds of cold and hot end test conditions when the thermoelectric conversion efficiency of test thermoelectricity components and parts.A kind of heat source temperature of test condition is 820K, and cold junction temperature is 298K; The heat source temperature of another kind of test condition is 895K, and cold junction temperature is 345K.As can be seen from Table 4, in each embodiment, the conversion efficiency of thermoelectric of the first electrothermal module is the highest, and the second electrothermal module takes second place, and the 3rd electrothermal module is minimum.The conversion efficiency of thermoelectric of the thermal generator that embodiment provides be 22.6 ?24.2, apparently higher than existing thermal generator.
Table 4
As can be seen from the above embodiments, the above-mentioned example of the utility model has been realized following technique effect:
1. the minisize thermoelectric device manufacture method that provides of the utility model has adopted semiconductor integrated technique technology, comprise thin film deposition, photoetching, etching etc., its manufacturing process can be complementary with the semiconductor integrated technique, be conducive to the extensive industry manufacturing of minisize thermoelectric device, solved the extensive precision machined problem that exists in present micron order thermoelectric device industrialization process.
The minisize thermoelectric device manufacture method that provides of the utility model also for the thermoelectric material of different temperatures scope be designed to different Re Dian Cai Liao ?Zu Dang Ceng ?electrode structure, make thermoelectric material and electrode form good ohmic contact, also stop the diffusion of electrode material to thermoelectric material, solved the metal electrode diffusion problem that exists in present micron order thermoelectric device industrialization process.
3. the manufacture method that provides by the utility model has improved the conversion efficiency of thermoelectric of minisize thermoelectric device, and device size is very little, has reduced raw-material consumption, has reduced production cost.
These are only preferred embodiment of the present utility model, be not limited to the utility model, for a person skilled in the art, the utility model can have various modifications and variations.All within spirit of the present utility model and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection range of the present utility model.
Claims (10)
1. a minisize thermoelectric device, is characterized in that, described minisize thermoelectric device comprises:
First substrate, be provided with the first electrode layer of patterning;
The first barrier layer, be arranged on described the first electrode layer;
Silicon dioxide layer, be arranged on described first substrate and described the first barrier layer;
Thermoelectric element, be arranged in described silicon dioxide layer;
The second barrier layer, be arranged on described silicon dioxide layer and described thermoelectric element and be patterned;
The second electrode lay, be arranged on described the second barrier layer; And
Second substrate, be arranged on described the second electrode lay.
2. minisize thermoelectric device according to claim 1, it is characterized in that, described thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, described N-type thermoelectric element forms the first thermoelectric element group, described P type thermoelectric element forms the second thermoelectric element group, and described the first thermoelectric element group and the second thermoelectric element group are arranged alternately.
3. minisize thermoelectric device according to claim 1, it is characterized in that, described thermoelectric element comprises N-type thermoelectric element and P type thermoelectric element, described thermoelectric element is arranged in the matrix that is formed by multirow and multiple row, and the N-type thermoelectric element in described matrix in any described multirow and multiple row and P type thermoelectric element are arranged alternately.
4. minisize thermoelectric device according to claim 1, is characterized in that, is provided with the first silicon dioxide separator in the first electrode layer of described patterning, is provided with the second silicon dioxide separator in the second electrode lay of described patterning.
5. minisize thermoelectric device according to claim 4, it is characterized in that, described silicon dioxide layer is separated into a plurality of the first thermoelectric element separators and a plurality of the second thermoelectric element separator by described thermoelectric element, described the first thermoelectric element separator is connected with described the first silicon dioxide separator, and described the second thermoelectric element separator is connected with described the second silicon dioxide separator.
6. minisize thermoelectric device according to claim 1, is characterized in that, the height of described thermoelectric element is 5 to 200 microns.
7. minisize thermoelectric device according to claim 6, is characterized in that, described thermoelectric element is cylinder or hexahedron.
8. minisize thermoelectric device according to claim 7, is characterized in that, when described thermoelectric element was cylinder, described cylindrical diameter was 1 to 40 micron; When described thermoelectric element was hexahedron, described hexahedral length and width were 1 to 40 micron.
9. minisize thermoelectric device according to claim 1, is characterized in that, the thickness on described the first barrier layer and the second barrier layer is 2 to 300 nanometers.
10. minisize thermoelectric device according to claim 1, is characterized in that, the thickness of described the first electrode and the second electrode is 0.3 to 72 micron.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311262A (en) * | 2013-06-09 | 2013-09-18 | 中国华能集团清洁能源技术研究院有限公司 | Micro thermoelectric device, production method thereof and temperature difference generator with same |
| CN106486593A (en) * | 2015-08-26 | 2017-03-08 | 中国科学院上海微***与信息技术研究所 | Minisize thermoelectric energy collecting device of bilateral pore structure and preparation method thereof |
| TWI579543B (en) * | 2014-10-20 | 2017-04-21 | Denso Corp | State detection sensor |
| CN108156678A (en) * | 2016-12-06 | 2018-06-12 | 财团法人工业技术研究院 | Flexible thermoelectric structure and method for forming the same |
-
2013
- 2013-06-09 CN CN2013203362626U patent/CN203288656U/en not_active Withdrawn - After Issue
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311262A (en) * | 2013-06-09 | 2013-09-18 | 中国华能集团清洁能源技术研究院有限公司 | Micro thermoelectric device, production method thereof and temperature difference generator with same |
| CN103311262B (en) * | 2013-06-09 | 2015-12-30 | 中国华能集团清洁能源技术研究院有限公司 | Micro thermoelectric device, manufacture method and comprise its thermal generator |
| TWI579543B (en) * | 2014-10-20 | 2017-04-21 | Denso Corp | State detection sensor |
| CN106486593A (en) * | 2015-08-26 | 2017-03-08 | 中国科学院上海微***与信息技术研究所 | Minisize thermoelectric energy collecting device of bilateral pore structure and preparation method thereof |
| CN106486593B (en) * | 2015-08-26 | 2018-09-28 | 中国科学院上海微***与信息技术研究所 | Minisize thermoelectric energy collecting device of bilateral pore structure and preparation method thereof |
| CN108156678A (en) * | 2016-12-06 | 2018-06-12 | 财团法人工业技术研究院 | Flexible thermoelectric structure and method for forming the same |
| US11812663B2 (en) | 2016-12-06 | 2023-11-07 | Industrial Technology Research Institute | Method for manufacturing flexible thermoelectric structure |
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