CN103199188B

CN103199188B - The miniature thermoelectric device of laminated construction manufactured by thin-film thermoelectric material and manufacture method

Info

Publication number: CN103199188B
Application number: CN201210006868.3A
Authority: CN
Inventors: 王为; 庞可可
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 2012-01-09
Filing date: 2012-01-09
Publication date: 2016-06-08
Anticipated expiration: 2032-01-09
Also published as: CN103199188A

Abstract

The invention discloses a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material and manufacture method thereof, thermoelectric lower limb therein is in layer to be piled up by thin-film thermoelectric material to form, the number of plies of the thin-film thermoelectric material piled up in thermoelectric lower limb is determined according to the performance requirement to miniature thermoelectric device, electrically coupled in series or electrically in parallel by between each thermoelectric lower limb, forms miniature thermoelectric device. The present invention is conducive to being mutually matched of different thermoelectric performance storeroom, plays the advantage of different thermoelectric material layer, can be effectively increased in miniature thermoelectric device the height of thermoelectric lower limb, is conducive to setting up the bigger temperature difference.

Description

The miniature thermoelectric device of laminated construction manufactured by thin-film thermoelectric material and manufacture method

Technical field

The invention belongs to thermoelectric technical field, particularly to a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material.

Background technology

The thermoelectric device prepared based on thermoelectric effect mainly has: 1) thermoelectric cell; 2) thermoelectric refrigerator; 3) thermoelectric Infrared Detectors; 4) thermoelectric temperature measurer. Thermoelectric cell is the thermoelectric device that the temperature difference is converted to electric energy, and it can utilize various heat energy to generate electricity, and especially in low-quality heat energy utilization, advantage is notable. The feature of thermoelectric cell be cleaning, noiselessness, without noxious emission, high efficient and reliable, long service life, be the physical power source of a kind of green, environmental protection. Thermoelectric refrigerator is then the thermoelectric device converting electrical energy into the temperature difference. The feature of thermoelectric refrigerator is cleaning, noiselessness, unharmful substance discharge, high efficient and reliable, long service life. Thermoelectric Infrared Detectors and thermoelectric temperature measurer are then the instruments utilizing the thermo-electrically effect of thermoelement to carry out infrared imaging and temperature test.

High performance thermoelectric device, does not structurally require nothing more than device and can hold thermoelectric lower limb as much as possible in unit volume, and the height of thermoelectric lower limb should ensure that and sets up the significant temperature difference at the two ends of device. Traditional thermoelectric material manufacture method is sintering process and metallurgical method. The thermoelectric material block manufactured by this kind of method needs the thermoelectric lower limb that the mechanical means such as warp cutting are sized to. These thermoelectric lower limbs are subsequently assembled into thermoelectric device. Owing to the fragility of thermoelectric material is very big, minimum also at mm-scale by the size of the thermoelectric lower limb of the mechanical means cuttings such as line cutting. The size of the thermoelectric device assembled by so large-sized thermoelectric lower limb is also big, and the quantity of the thermoelectric lower limb assembled in this kind of thermoelectric device unit volume is extremely limited. Therefore, the electric energy output power density of the thermoelectric cell being made up of the block thermoelectric material of sintering or metallurgical this kind of method manufacture is low, and output voltage is also low; The refrigerating efficiency of the thermoelectric refrigerator made is low; The detectivity of the thermoelectric Infrared Detectors made is low; The temperature measurement accuracy of the thermoelectric temperature measurer made is also low.

In recent years, thin-film thermoelectric material manufacture the research of miniature thermoelectric device and obtain extensive concern. The thickness of this kind of thin-film thermoelectric material is in micron dimension. Adopt the thermoelectric device that this thickness manufactures at the thin-film thermoelectric material of micro-meter scale, in its unit volume can integrated a large amount of thermoelectric lower limbs, this not only substantially reduces the volume of thermoelectric device, and is conducive to thermoelectric device to obtain high-performance. But owing to the thickness of thin-film thermoelectric material is in micron dimension, which greatly limits the height of thermoelectric lower limb, become the bottleneck that the temperature difference device performance manufactured by thin-film thermoelectric material improves.

At present, the manufacture method of thin-film thermoelectric material mainly has physical vapour deposition (PVD) (PVD), electrochemical deposition, chemical vapour deposition (CVD) (CVD), sputtering method etc. The thermoelectric device volume manufactured by this kind of thin-film thermoelectric material is little, it is achieved that the microminiaturization of thermoelectric device. But the thickness of the thin-film thermoelectric material manufactured due to said method is at micro-meter scale, is unfavorable for that the miniature thermoelectric device being produced from obtains high-performance. SNYDER in 2003 et al. [SNYDERGJ, LIMJR, HUANGCK, etal.ThermoelectricmicrodevicefabricatedbyaMEMS-likeelec trochemicalprocess.NatMater, 2003,2:528-531] difference electrochemical deposition Bi in photoengraving microcell is adopted₂Te₃The method of doping n-type and p-type thermoelectric material and conducting metal, has prepared a minitype thermoelectric cell being made up of 126 n-type and p-type thermoelectric lower limb (high 20 ��m, diameter 60 ��m). This minitype thermoelectric cell maximum power density under infrared bulb irradiates is only 40 �� W/cm²��

This patent proposes a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material. The feature of this miniature thermoelectric device structure mainly has: 1) the thermoelectric lower limb in miniature thermoelectric device has multiple structure, and it is piled up by thin-film thermoelectric material in layer and forms; 2) composition of thermoelectric lower limb and structure in miniature thermoelectric device, can change along with thin-film thermoelectric material in layer, that is the composition of the thin-film thermoelectric material of composition multiple structure thermoelectric lower limb or structure can change according to certain rule, it is also possible to constant; 3) constitute and can be joined directly together between the thin-film thermoelectric material of multiple structure thermoelectric lower limb, it is also possible to transition zone is set between the layers; 4) the multiple structure thermoelectric lower limb within miniature thermoelectric device, is embedded among insulant or is individually present.

The miniature thermoelectric device of above-mentioned laminated construction is in the feature of configuration aspects, make to go out following two aspect advantages according to the miniature thermoelectric device major embodiment of this patent manufacture: 1) be conducive to being mutually matched of different thermoelectric performance storeroom, play the advantage of different thermoelectric material layer; 2) can be effectively increased in miniature thermoelectric device the height of thermoelectric lower limb, be conducive to setting up the bigger temperature difference. The advantage of above-mentioned two aspects is all conducive to improving the performance of miniature thermoelectric device, is in particular in: the output power density of the minitype thermoelectric cell being made up of thin-film thermoelectric material is high, and output voltage is also high; The refrigerating efficiency of the thermoelectric refrigerator made is high; The detectivity of the thermoelectric Infrared Detectors made is high; The temperature measurement accuracy of the thermoelectric temperature measurer made is also high.

Summary of the invention

It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material, wherein thermoelectric lower limb is in layer to be piled up by thin-film thermoelectric material to form. Electrically coupled in series or electrically in parallel by between each thermoelectric lower limb, forms minitype thermoelectric cell.

The purpose of the present invention is achieved by following technical proposals:

A kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material, wherein thermoelectric lower limb is to be piled up layer by layer by thin-film thermoelectric material to form, in series or in parallel by between thermoelectric lower limb, forms miniature thermoelectric device. As follows specifically:

The structure (Fig. 1-10) of the miniature thermoelectric device of described laminated construction includes the implant 9 between positive pole exit 1, negative pole exit 2, outer enclosure layer 3, heat conduction articulamentum 4, hard shell 5, top conductive articulamentum 6, n-type thermoelectric lower limb 7, p-type thermoelectric lower limb 8, thermoelectric lower limb, bottom conductive articulamentum 12, transition zone 13, barrier layer 14.

The described n-type thermoelectric lower limb 7 n-type thin film thermoelectric material that (Fig. 3,4,5,6,7,8,9,10) are made up of multilamellar and structure is all identical is in layer piled up and is formed, or it is made up of multilamellar or n-type thin film thermoelectric material that structure is different is in layer piled up and formed, or be made up of multilamellar and the n-type thin film thermoelectric material that n-type thin film thermoelectric material forms from multilamellar or structure is different that structure is identical alternates in layer to pile up and formed, the described p-type thermoelectric lower limb 8 p-type thin film thermoelectric material that (Fig. 3,4,5,6,7,8,9,10) are made up of multilamellar and structure is all identical is in layer piled up and is formed, or it is made up of multilamellar or p-type thin film thermoelectric material that structure is different is in layer piled up and formed, or be made up of multilamellar and the p-type thin film thermoelectric material that p-type thin film thermoelectric material forms from multilamellar or structure is different that structure is identical alternates in layer to pile up and formed, formation n-type thermoelectric lower limb 7 is in layer piled up according to the n-type thin film thermoelectric material that composition and structure are all identical, the p-type thin film thermoelectric material that employing forms and structure is all identical in layer piles up formation p-type thermoelectric lower limb 8, then such in layer packing structure can be effectively increased n-type thermoelectric lower limb 7 and the height of p-type thermoelectric lower limb 8, solve the temperature difference caused because thin-film thermoelectric material thickness (only several microns to tens microns) is too thin and set up a difficult problem for difficulty, the performance of the miniature thermoelectric device manufactured by thin-film thermoelectric material can be effectively improved, the n-type thin film thermoelectric material all differed according to composition and structure in layer piles up formation n-type thermoelectric lower limb 7, the p-type thin film thermoelectric material that composition and structure all differ is adopted in layer to pile up formation p-type thermoelectric lower limb 8, then such in layer packing structure is possible not only to the height that is effectively increased n-type thermoelectric lower limb 7 and p-type thermoelectric lower limb 8, solve the temperature difference caused because thin-film thermoelectric material thickness (only several microns to tens microns) is too thin and set up a difficult problem for difficulty, and different composition and the respective performance advantage of structural membrane thermoelectric material can be given full play to, can more efficiently improve the performance of the miniature thermoelectric device manufactured by thin-film thermoelectric material, formation n-type thermoelectric lower limb 7 is alternately piled up layer by layer according to all identical n-type thin film thermoelectric material all differed with composition and structure of composition and structure, composition and all identical p-type thin film thermoelectric material all differed with composition and structure of structure is adopted to pile up formation p-type thermoelectric lower limb 8 layer by layer, then such packing structure layer by layer has not only been taken into account the height increasing thermoelectric lower limb and has given full play to the advantage of different composition and each atman characteristic of structural membrane thermoelectric material, and can ensure that better matching relationship between different components and structure thermoelectric material, thus the performance of the miniature thermoelectric device manufactured by thin-film thermoelectric material can be made to have bigger raising.

Described n-type thermoelectric lower limb 7 and the shape of cross section of p-type thermoelectric lower limb 8 can be rule can also be irregular; The arrangement mode of n-type thermoelectric lower limb 7 and p-type thermoelectric lower limb 8 can be rule can also be irregular; N-type thermoelectric lower limb and p-type thermoelectric lower limb need to by certain regularly arranged, electrically coupled in series or electrically in parallel with what realize between n-type thermoelectric lower limb and p-type thermoelectric lower limb; Constitute n-type thermoelectric lower limb 7 and the shape of each layer film thermoelectric material of p-type thermoelectric lower limb 8, area and thickness can be the same or different; The material constituting n-type thermoelectric lower limb 7 can be the n-type thin film thermoelectric material being applied to high-temperature region, such as SiGe based material, CrSi₂��MnSi_1.73��CoSi��Ge_0.3Si_0.7��Na_xCo_x/2Ti_1-x/2O₂��Na_xNi_x/2Ti_1-x/2O₂��Na_xFe_x/2Ti_1-x/2O₂��AlxZnO��Ag_1-xPb₁₈SbTe₂₀��Ba_1-xSr_xPbO₃��SrAl₂Si₂Deng, it is also possible to it is the n-type thin film thermoelectric material being applied to middle warm area, such as PbTe based material, Bi2 (GeSe) 3, CoSb₃Sm_x��CoSb₃Pr_x��FeVSb��Zr_0.5HF_0.5NiSn��TiNiSn��ZrNiSn��HfNiSn��ZrCoSb��HfCoSb��TiCoSb��Ce_yFe_4-xCo_xSb₁₂��La_yFe_4-xCo_xSb₁₂��Ba_yFe_4-xCo_xSb₁₂��Fe_0.5Ni_0.5Sb₃��FeSb₂Te��Mg₂Si_1-xSn_x��HoCoO₃��LaCoO₃��Zn₄Sb₃��Ag_2-ySb_yTe_1+y��Eu_xPb_1-xTe��Bi(SiSb)₂��Bi₂(GeSe)₃��Ba_0.3Ni_xCo_4-xSb₁₂��AgPb₁₀SbTe₁₂��AgPb₁₈SbTe₂₀Deng, it is also possible to it is the n-type thin film thermoelectric material being applied to low-temperature space, such as n-type Bi₂Te₃Based material, Bi₂Te_2.7Se_0.3��Bi₂Sb₃Ce_x��Bi₂Sb₃Nd_x��Bi₂Sb₃Re_x��Bi₂Sb₃La_x��ZnSb��HgTe��Bi₂Se₃��CdInO4��La_1-xSr_xCuO_3-y, Sb2Se3 based material, Zr_0.5Hf_0.5NiSn, n-type Bi₂Te₃/Sb₂Te₃Nano super-lattice, etc.; The material constituting p-type thermoelectric lower limb (8) can be the p-type thin film thermoelectric material being applied to high-temperature region, such as SiGe based material, FeSi₂��Fe_0.9Mn_0.1Si₂��Ca₃Co_4-xAg_xO₉��Ca_1-xSm_xMnO₃��Ca_2.5Yb_0.5Co₄O₉, Ca2CoO3 etc., it is also possible to be the p-type thin film thermoelectric material being applied to middle warm area, such as PbTe based material, Bi (SiSb2), GeTe, SbTe, Al₇₁Pb₂₀Re₉��(GeTe)_x(Mn_aSn_1-aTe)_1-x��FeV_1-xTi_xSb��HoPdSb��ErPdSb��DyPdSb��Ce_fFe_4-xCo_xSb₁₂And La_fFe_4-xCo_xSb₁Deng, it is also possible to it is the p-type thin film thermoelectric material being applied to low-temperature space, such as p-type Bi₂Te₃Based material, Sb₂Se₃Based material/Sb₂Te₃��Bi_0.5Sb_1.5Te₃��Bi_xPb_2-xTe₃��Bi_2-xCd_xTe₃��Bi_xSn_2-xTe₃��FeV_0.85Ti_0.15Sb, p-type Bi₂Te₃/Sb₂Te₃Nano super-lattice, etc.

Can be joined directly together (Fig. 5,6,7) between thin-film thermoelectric material layer in described n-type thermoelectric lower limb 7 and p-type thermoelectric lower limb 8, it is also possible to transition zone 13 (Fig. 8,9,10) is set between the layers. Transition zone 13 can be the monolayer material that the Nomenclature Composition and Structure of Complexes is all identical, it is also possible to be that the multilayer material all differed by the Nomenclature Composition and Structure of Complexes is constituted; The material constituting transition zone 13 need to have good electric conductivity, and with there is between adjacent thin-film thermoelectric material good composition and structure matching relation, its effect is possible not only to reduce interfacial stress, and the diffusion between adjacent different components thin-film thermoelectric material can be stoped, such as metallic nickel, nickel cobalt (alloy), metal platinum, cobalt-copper alloy, etc. The material composition of the transition zone 13 in n-type thermoelectric lower limb and the transition zone 13 in p-type thermoelectric lower limb can be identical with structure, it is also possible to different.

Described barrier layer 14 (Fig. 5,6,7,8,9,10) can be the monolayer material that the Nomenclature Composition and Structure of Complexes is all identical, it is also possible to be that the multilayer material all differed by the Nomenclature Composition and Structure of Complexes is constituted. The material constituting barrier layer 14 need to have good electric conductivity, and with have good structure matching relation between adjacent thin-film thermoelectric material, top conductive articulamentum 6 and bottom conductive articulamentum 12 to reduce interfacial stress, and the phase counterdiffusion of element between thin-film thermoelectric material with top conductive articulamentum 6 and bottom conductive articulamentum 12 can be stoped.

Implant 9 (Fig. 5,6,7 between described thermoelectric lower limb, 8,9,10) being be made up of the homogenous material that the Nomenclature Composition and Structure of Complexes is all identical, it is also possible to be that the multilayer material all differed by the Nomenclature Composition and Structure of Complexes is constituted, its effect is that n-type thermoelectric lower limb 7 and p-type thermoelectric lower limb 8 are played a supportive role.

The described positive pole exit 1 in miniature thermoelectric device, negative pole exit 2, top conductive articulamentum 6, bottom conductive articulamentum 12 are to be made up of the homogenous material that the Nomenclature Composition and Structure of Complexes is all identical, it is also possible to be that the multilayer material all differed by the Nomenclature Composition and Structure of Complexes is constituted; Constitute positive pole exit 1, negative pole exit 2, top conductive articulamentum 6, bottom conductive articulamentum 12 material should have good electric conductivity, it is possible to be metal or conducting polymer composite; The effect of top conductive articulamentum 6 and bottom conductive articulamentum 12 is realize between n-type thermoelectric lower limb and p-type thermoelectric lower limb electrically coupled in series or electrically in parallel, and its shape, area and arrangement mode are determined by the shape of thermoelectric lower limb, area and arrangement mode.

In the miniature thermoelectric device of described laminated construction, the effect of heat conduction articulamentum 4 is the upper and lower that hard shell 5 adheres to miniature thermoelectric device, the material constituting heat conduction articulamentum 4 need to have good electrical insulation capability, good heat conductivility and good adhesion property, it is possible to is organic binder bond or inorganic binder; Hard shell 5 constitutes the rigid support of minitype thermoelectric cell, the internal structure of protection minitype thermoelectric cell, and the material constituting hard shell 5 need to have good insulating properties, good heat conductivility and suitable hardness and intensity, it is possible to is organic or inorganic material; The effect of outer enclosure layer 3 is the internal structure of protection minitype thermoelectric cell, and it is made up of the organic or inorganic material with good electrical insulating properties and poor thermal conductivity.

The miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material that this patent proposes can adopt following methods manufacture:

The first step: according to need to prepare thermoelectric lower limb in miniature thermoelectric device the space consuming size flaky material that selects area suitable be substrate 15. To ask substrate to have good electric conductivity, then selected substrate material should be conductive material, or select the non-conductive flaky material that an area is suitable, adopt physics or chemistry method after non-conductive flaky material surface deposition layer of conductive material as substrate 15 (Figure 11). If the substrate selected is non-conductive and during heat conductivity is good flaky material, substrate can also directly as hard shell 5

Second step: the method adopting photoengraving, produces the microcell figure 16 (Figure 12) for deposited bottom conductive tie layers 12 at substrate surface.

3rd step: first deposit the material that electric conductivity is good in microcell figure, prepare bottom conductive articulamentum 12, it is further continued for afterwards in microcell figure and deposits one layer of material being used as barrier layer, prepare barrier layer 14, finally remove the microcell figure 16 (Figure 13) for deposited bottom conductive tie layers 12 and barrier layer 14. If the structure of miniature thermoelectric device is not provided with barrier layer 14, then without deposit barrier material in microcell figure.

4th step: the method adopting photoengraving, produces the microcell figure 18 (Figure 14) for depositing ground floor n-type thin film thermoelectric material on the barrier layer 14 prepared. In this figure, the position of microcell 17 and shape are corresponding with the position of n-type thermoelectric lower limb in standby miniature thermoelectric device of drawing up and shape. If being not provided with barrier layer 14 in the structure of miniature thermoelectric device, then the microcell figure 18 for depositing ground floor n-type thin film thermoelectric material is directly produced on bottom conductive articulamentum 12.

5th step: first depositing n-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone 13, prepare ground floor n-type thin film thermoelectric material 19 and transition zone 13 (Figure 15), and remove the microcell figure 18 for depositing ground floor n-type thin film thermoelectric material. If in the structure of miniature thermoelectric device, between adjacent n-type thin film thermoelectric material, it is not provided with transition zone 13, then without depositing one layer of buffer layer material in microcell figure.

6th step: the method adopting photoengraving, produces the microcell figure 20 (Figure 16) for depositing ground floor p-type thin film thermoelectric material on the barrier layer 14 prepared. In this figure, the position correspondence of microcell 17 is drawn up the position of p-type thermoelectric lower limb in standby miniature thermoelectric device. The upper surface of the ground floor n-type thin film thermoelectric material prepared is covered by the photoresist of thin layer.

7th step: first depositing p-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone 13, prepare ground floor p-type thin film thermoelectric material 21 and transition zone 13, and remove a thin layer photoresist (Figure 17) covering ground floor n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and forms the implant 9 between thermoelectric lower limb. If in the structure of miniature thermoelectric device, between adjacent p-type thin film thermoelectric material, it is not provided with transition zone 13, then without depositing one layer of buffer layer material in microcell figure.

8th step: the method adopting photoengraving, produces the microcell figure 18 (Figure 18) for depositing second layer n-type thin film thermoelectric material on the ground floor n-type prepared and p-type thin film thermoelectric material. In this figure, the position of microcell 17 is identical with the position of the ground floor n-type thin film thermoelectric material prepared.

9th step: first depositing n-type thin-film thermoelectric material layer 22 in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone 13, prepare second layer n-type thin film thermoelectric material 22 and transition zone 13, and remove the microcell figure 18 (Figure 19) for depositing second layer n-type thin film thermoelectric material. The Nomenclature Composition and Structure of Complexes of second layer n-type thin film thermoelectric material and ground floor n-type thin film thermoelectric material can be identical, it is also possible to different. If in the structure of miniature thermoelectric device, between adjacent n-type thin film thermoelectric material, it is not provided with transition zone 13, then without depositing one layer of buffer layer material in microcell figure.

Tenth step: the method adopting photoengraving, produces the microcell figure 20 (Figure 20) for depositing second layer p-type thin film thermoelectric material on the ground floor n-type prepared and p-type thin film thermoelectric material. In this figure, the position of microcell 17 is identical with the position of the ground floor p-type thin film thermoelectric material prepared. The upper surface of the second layer n-type thin film thermoelectric material prepared is covered by the photoresist of thin layer.

11st step: first depositing p-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone 13, prepare second layer p-type thin film thermoelectric material 23 and transition zone 13, and remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface, remaining microcell figure is then retained, and forms the implant 9 (Figure 21) between thermoelectric lower limb. The Nomenclature Composition and Structure of Complexes of second layer p-type thin film thermoelectric material and ground floor p-type thin film thermoelectric material can be identical, it is also possible to different. If in the structure of miniature thermoelectric device, between adjacent p-type thin film thermoelectric material, it is not provided with transition zone 13, then without depositing one layer of buffer layer material in microcell figure.

12nd step: repeatedly repeat the 4th step to the manufacturing process of the 11st step, it is possible to prepare by the N shell number of plies of thermoelectric material (N represent) the n-type thermoelectric lower limb that n-type thin film thermoelectric material is piled up and the p-type thermoelectric lower limb piled up by N shell p-type thin film thermoelectric material. When the height of n-type thermoelectric lower limb and p-type thermoelectric lower limb reaches the designing requirement of miniature thermoelectric device, complete the preparation of thermoelectric lower limb. After depositing n-th layer n-type thin film thermoelectric material 24 and n-th layer p-type thin film thermoelectric material 25 in microcell, it is not necessary to deposit buffer layer material again in microcell figure.

13rd step: the method adopting photoengraving, produces the microcell figure 26 (Figure 22) for depositing top conductive articulamentum 6 on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb.

14th step: first deposit one layer of barrier material in microcell figure, forms barrier layer 14, is further continued for afterwards in microcell figure and deposits the material that electric conductivity is good, prepares top conductive articulamentum 6 and barrier layer 14 (Figure 23). If the structure of minitype thermoelectric cell is not provided with barrier layer 14, then without deposit barrier material in microcell.

15th step: be coated with one layer of conducting adhesive agent material on the top conductive articulamentum 6 prepared and form heat conduction articulamentum 4, then adhere to hard Heat Conduction Material formation hard shell 5 (Figure 24) on conducting adhesive agent material.

16th step: be coated with the material of electrically insulating but thermally conductive property difference in the thermoelectric leg outer side surrounding prepared, prepare outer enclosure layer 3 (Figure 24).

17th step: if select substrate be non-conductive and that heat conductivity is good flaky material, and using substrate as hard shell 5 time, the preparation process of the 18th step can be made directly. Substrate can not as hard shell 5 time, then need remove bottom substrate 15, expose the bottom conductive articulamentum 12 (Figure 25) prepared. On bottom conductive articulamentum 12, it is coated with one layer of conducting adhesive agent material forms heat conduction articulamentum 4, then on conducting adhesive agent material, adhere to hard Heat Conduction Material formation hard shell 5 (Figure 26).

18th step: 2 conductive materials are connected respectively to positive pole exit 1 and the negative pole exit 2 of bottom conductive layer, completes the manufacture (Figure 27) of miniature thermoelectric device.

Second step in above-mentioned 18 step manufacturing steps and the 3rd step prepare the process on bottom conductive articulamentum (12) and barrier layer 14 can also change following second step and the 3rd step into:

Second step: first deposit the material that the electric conductivity being used as bottom conductive articulamentum 12 is good on substrate 15, be further continued for deposition one layer afterwards and be used as the conductive material (Figure 28) on barrier layer 14.

3rd step: the method adopting photoengraving, produces the microcell figure 16 (Figure 29) for etching bottom conductive articulamentum 12 on the conductive material deposited. Afterwards, etch away the unwanted conductive material deposited, and after removing microcell figure 16, prepare bottom conductive articulamentum 12 and barrier layer 14 (Figure 13)

The 13rd step in above-mentioned 18 step manufacturing steps and the 14th step prepare the process on top conductive articulamentum 6 and barrier layer 14 can also change the 13rd following step and the 14th step into:

13rd step: first deposit one layer of conductive material being used as barrier layer 14 on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb, is further continued for depositing the material (Figure 30) that the electric conductivity being used as top conductive articulamentum 6 is good afterwards.

14th step: the method adopting photoengraving, produces the microcell figure (Figure 31) for etching top conductive articulamentum 6 on the conductive material deposited. Afterwards, etch away the unwanted conductive material deposited, and after removing microcell figure 16, prepare top conductive articulamentum 6 and barrier layer 14 (Figure 23)

The structure of the miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material that this patent proposes mainly has the following characteristics that 1) thermoelectric lower limb in miniature thermoelectric device has multiple structure, and it is piled up by thin-film thermoelectric material in layer and forms; 2) composition of thermoelectric lower limb and structure in miniature thermoelectric device, can change along with thin-film thermoelectric material in layer, that is the composition of the thin-film thermoelectric material of composition multiple structure thermoelectric lower limb or structure can change according to certain rule, it is also possible to constant; 3) constitute and can be joined directly together between the thin-film thermoelectric material of multiple structure thermoelectric lower limb, it is also possible to transition zone is set between the layers; 4) the multiple structure thermoelectric lower limb within miniature thermoelectric device, is embedded among insulant or is individually present.

Detailed description is as follows:

The internal structure of the miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material that the present invention proposes includes: the implant (9) between positive pole exit (1), negative pole exit (2), heat conduction articulamentum (4), top conductive articulamentum (6), n-type thermoelectric lower limb (7), p-type thermoelectric lower limb (8), bottom conductive articulamentum (12), thermoelectric lower limb, transition zone (13), barrier layer (14). The side, front, rear, left and right of miniature temperature difference device and upper and lower two surfaces are respectively arranged with outer enclosure layer (3) and hard shell (5) that battery structure is shielded.

The miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material that the present invention proposes, the temperature difference is set up along thermoelectric lower limb short transverse (namely constituting the thickness direction of the thin-film thermoelectric material of thermoelectric lower limb). Its architectural feature is, p-type thermoelectric lower limb 8 is piled up by multilamellar p-type thin film thermoelectric material 10 and formed, and n-type thermoelectric lower limb 7 is piled up by multi-layer n-type thin-film thermoelectric material 11 and formed.

N-type thermoelectric lower limb 7 within miniature thermoelectric device can have following several ways with the composition of p-type thermoelectric lower limb 8: 1) be made up of multilamellar and P type thin-film thermoelectric material or n-type thin film thermoelectric material that structure is all identical are piled up and formed; 2) it is made up of multilamellar or P type thin-film thermoelectric material or n-type thin film thermoelectric material that structure is different are piled up and formed; 3) be made up of multilamellar or P type thin-film thermoelectric material (or n-type thin film thermoelectric material) that structure is different with form or P type thin-film thermoelectric material (or n-type thin film thermoelectric material) that structure is identical is piled up according to certain rule and to be formed; 4) composition n-type can be identical with the thickness of each layer film thermoelectric material of p-type thermoelectric lower limb, it is also possible to different.

The shape of cross section of n-type and p-type thermoelectric lower limb is rule or arbitrary shape. The arrangement mode of n-type and p-type thermoelectric lower limb is by the impact of its shape of cross section, need to by certain regularly arranged, what ensure that on the one hand between n-type thermoelectric lower limb and p-type thermoelectric lower limb is electrically coupled in series or electrically in parallel, on the other hand with can realize this kind of thermoelectric device optimal performance arrangement mode for the best. P type thin-film thermoelectric material 10 and the shape of n-type thin film thermoelectric material 11, area and thickness can be identical or different, and their thickness range is at 0.1��100 micron, and areal extent is in 0.01 square micron��1 square centimeter.

Conduct along the region beyond thermoelectric lower limb to reduce hot-fluid, the temperature difference bigger to realize miniature thermoelectric device two ends, implant 9 between n-type thermoelectric lower limb and p-type thermoelectric lower limb is made up of the material of the electrically insulating but thermally conductive property difference of monolayer or multilamellar, can be organic or inorganic material, it is also possible to be air. As required, can also be vacuum between the n-type thermoelectric lower limb in miniature thermoelectric device and p-type thermoelectric lower limb.

The heat conduction articulamentum 4 that the top of n-type thermoelectric lower limb and p-type thermoelectric lower limb and bottom are arranged has good electrical insulation capability, heat conductivility and adhesion property concurrently. They good adhesion properties can ensure that hard shell 5 and the bond strength miniature thermoelectric device within, and it is internal and in the big as far as possible temperature difference of thermoelectric device two ends maintenance that they good heat conductivilitys can ensure that heat enters miniature thermoelectric device to greatest extent. Heat conduction articulamentum 4 is the organic or inorganic material having good electrical insulating properties and heat conductivility concurrently, and thickness range is at 0.01��1000 micron.

Positive pole exit (1) within miniature thermoelectric device, negative pole exit (2), top conductive articulamentum 6, bottom conductive articulamentum 12, barrier layer 14 and transition zone 13 are made up of single or multiple lift conductive material, and the material of each layer conductive material in multilayer conductive material is identical or different conducting polymer composites or metal material. Top conductive articulamentum 6 within miniature thermoelectric device and the Main Function of bottom conductive articulamentum 12 are realize between n-type thermoelectric lower limb and p-type thermoelectric lower limb electrically coupled in series or electrically in parallel, its shape, area and arrangement mode are determined by the shape of thermoelectric lower limb, area and arrangement mode, and its thickness range is at 0.01��500 micron. The effect of transition zone 13 is to ensure that the matched well of the composition between the adjacent films thermoelectric material layer in n-type thermoelectric lower limb and p-type thermoelectric lower limb and structure, and its thickness range is at 1 nanometer��100 microns. The thickness range on barrier layer 14 is at 1 nanometer��500 microns.

The side, front, rear, left and right of miniature thermoelectric device and upper and lower surface are respectively arranged with outer enclosure layer 3 and hard shell 5. The effect of outer enclosure layer 3 is the internal structure for protecting miniature thermoelectric device, and it is made up of the organic or inorganic material with good electrical insulating properties and poor thermal conductivity, and thickness range is at 0.01��3000 micron. Hard shell 5 constitutes the rigid support of miniature thermoelectric device, protects the internal structure of miniature thermoelectric device. Hard shell 5 is made up of the organic or inorganic material that electrically insulating but thermally conductive property is good, and thickness range is at 0.01��2000 micron.

The distinguishing feature of the miniature thermoelectric device of laminated construction of the present invention includes: 1) the thermoelectric lower limb in miniature thermoelectric device has multiple structure, and it is piled up by thin-film thermoelectric material in layer and forms; 2) composition of thermoelectric lower limb and structure in miniature thermoelectric device, can change along with thin-film thermoelectric material in layer, that is the composition of the thin-film thermoelectric material of composition multiple structure thermoelectric lower limb or structure can change according to certain rule, it is also possible to constant; 3) constitute and can be joined directly together between the thin-film thermoelectric material of multiple structure thermoelectric lower limb, it is also possible to transition zone is set between the layers; 4) the layer structure thermoelectric lower limb within miniature thermoelectric device, is embedded among implant (9) or is individually present.

The miniature thermoelectric device of above-mentioned laminated construction is in the feature of configuration aspects, make to have the advantage that 1 according to the miniature thermoelectric device of this patent manufacture) be conducive to being mutually matched of different thermoelectric performance storeroom, play the advantage of different thermoelectric material layer; 2) can be effectively increased in miniature thermoelectric device the height of thermoelectric lower limb, be conducive to setting up the bigger temperature difference. The advantage of above-mentioned two aspects is all conducive to improving the performance of miniature thermoelectric device. The miniature thermoelectric device adopted the structure has bigger output, the refrigerating efficiency adopting the thermoelectric refrigerator of this structure is higher, adopts the Infrared Detectors of this structure and temperature measuring device to have the certainty of measurement of bigger measurement scope and Geng Gao.

Accompanying drawing explanation

The miniature thermoelectric device stereoscopic structural representation of Fig. 1

Fig. 2 removes the perspective view after the hard shell 5 on miniature thermoelectric device top and heat conduction articulamentum 4 within miniature thermoelectric device

Fig. 3 removes the internal perspective view of miniature thermoelectric device after the hard shell 5 on miniature thermoelectric device top, heat conduction articulamentum 4 and outer enclosure layer 3

Fig. 4 goes miniature thermoelectric device internal structure schematic top plan view after the implant 9 fallen between hard shell 5, heat conduction articulamentum 4, outer enclosure layer 3 and thermoelectric lower limb on miniature thermoelectric device top

One of internal AA ' cross-sectional view of miniature thermoelectric device in Fig. 5 Fig. 3

In Fig. 6 Fig. 3 the two of the internal AA ' cross-sectional view of miniature thermoelectric device

In Fig. 7 Fig. 3 the three of the internal AA ' cross-sectional view of miniature thermoelectric device

In Fig. 8 Fig. 3 the four of the internal AA ' cross-sectional view of miniature thermoelectric device

In Fig. 9 Fig. 3 the five of the internal AA ' cross-sectional view of miniature thermoelectric device

In Figure 10 Fig. 3 the six of the internal AA ' cross-sectional view of miniature thermoelectric device

Figure 11 is for manufacturing the structure cross-sectional schematic of the substrate of miniature thermoelectric device

The structure cross-sectional schematic of the microcell figure (16) for deposited bottom conductive tie layers (12) made on Figure 12 substrate

Bottom conductive articulamentum (12) that Figure 13 prepares on substrate and the structure cross-sectional schematic of barrier layer (14)

Figure 14 is for depositing the structure cross-sectional schematic of the microcell figure (18) of ground floor n-type thin film thermoelectric material

Ground floor n-type thin film thermoelectric material (19) that Figure 15 prepares and the structure cross-sectional schematic of transition zone (13)

Figure 16 is for depositing the structure cross-sectional schematic of the microcell figure (20) of ground floor p-type thin film thermoelectric material

Ground floor p-type thin film thermoelectric material (21) that Figure 17 prepares and the structure cross-sectional schematic of transition zone (13)

Figure 18 is for depositing the structure cross-sectional schematic of the microcell figure (18) of second layer n-type thin film thermoelectric material

Second layer n-type thin film thermoelectric material (22) that Figure 19 prepares and the structure cross-sectional schematic of transition zone (13)

Figure 20 is for depositing the structure cross-sectional schematic of the microcell figure (20) of second layer p-type thin film thermoelectric material

Second layer p-type thin film thermoelectric material (23) that Figure 21 prepares and the structure cross-sectional schematic of transition zone (13)

Figure 22 is used for depositing the structure cross-sectional schematic of the microcell figure (26) of top conductive articulamentum (6)

Top conductive articulamentum (6) that Figure 23 prepares and the structure cross-sectional schematic of barrier layer (14)

What Figure 24 prepared is positioned at the structure cross-sectional schematic of the heat conduction articulamentum (4) on miniature thermoelectric device top, hard shell (5) and outer enclosure layer (3)

Figure 25 removes the structure cross-sectional schematic after bottom substrate (15)

What Figure 26 prepared is positioned at the heat conduction articulamentum (4) of miniature thermoelectric device bottom and the structure cross-sectional schematic of hard shell (5)

Figure 27 top view (a) after the positive pole exit (1) of bottom conductive layer and negative pole exit (2) connect conductive material respectively and structure cross-sectional schematic (b)

The structure cross-sectional schematic of the conductive material being used as bottom conductive articulamentum (12) and barrier layer (14) of Figure 28 deposition on substrate

The microcell figure (27) for etching bottom conductive tie layers (12) and barrier layer (14) that Figure 29 makes on the conductive material as bottom conductive articulamentum (12) and barrier layer (14)

The structure cross-sectional schematic of the conductive material being used as top conductive articulamentum (6) and barrier layer (14) that Figure 30 deposits on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb

What Figure 31 made on the conductive material as bottom conductive articulamentum (12) and barrier layer (14) is used for etching the microcell figure (28) of top conductive articulamentum (6) and barrier layer (14)

Label declaration:

Positive pole exit 1, negative pole exit 2, outer enclosure layer 3, heat conduction articulamentum 4, hard shell 5, top conductive articulamentum 6, n-type thermoelectric lower limb 7, p-type thermoelectric lower limb 8, implant 9 between thermoelectric lower limb, bottom conductive articulamentum 12, p-type thin film thermoelectric material 10, n-type thin film thermoelectric material 11, transition zone 13, barrier layer 14, substrate 15, microcell figure 16 for deposited bottom conductive tie layers 12, microcell 17, microcell figure 18 for depositing n-type thin-film thermoelectric material, ground floor n-type thin film thermoelectric material 19, microcell figure 20 for depositing p-type thin-film thermoelectric material, ground floor p-type thin film thermoelectric material 21, second layer n-type thin film thermoelectric material 22, second layer p-type thin film thermoelectric material 23, n-th layer n-type thin film thermoelectric material 24, n-th layer p-type thin film thermoelectric material 25, for depositing the microcell figure 26 of top conductive articulamentum 6, for the microcell figure 27 of etching bottom conductive tie layers 12, for etching the microcell figure 28 of top conductive articulamentum 6.

Detailed description of the invention

Below in conjunction with accompanying drawing, the present invention is described in further details:

The stereoscopic structure of the miniature thermoelectric device of laminated construction that the present invention proposes is as it is shown in figure 1, its external structure is mainly made up of positive pole exit 1, negative pole exit 2, outer enclosure layer 3, heat conduction articulamentum 4 and hard shell 5. Inside battery structure is mainly shielded by outer enclosure layer 3, is separately positioned on the side, front, rear, left and right of miniature thermoelectric device, and its material should be the organic or inorganic material of electrically insulating but thermally conductive property difference, and thickness range is at 0.01��3000 micron. For ensureing that heat enters miniature thermoelectric device inside to greatest extent and can maintain maximum temperature difference at thermoelectric lower limb two ends, heat conduction articulamentum 4 it is both provided with respectively at the top of n-type and p-type thermoelectric lower limb and bottom, they are made up of the organic or inorganic material of single or multiple lift, these materials to have good electrical insulation capability, heat conductivility and adhesion property concurrently, and its thickness range is at 0.01��1000 micron. Hard shell 5 can be set in the outside of heat conduction articulamentum 4, or be not provided with hard shell 5. The Main Function of hard shell 5 is in that protection battery main body, realizes and the heat exchange of environment simultaneously, its material be mainly electric insulation, there is thermal conductive resin and the organic or inorganic material of certain mechanical strength, thickness range is at 0.01��2000 micron

The miniature thermoelectric device of laminated construction removes the inside stereochemical structure after upper guide thermal connection layer 4 and hard shell 5 as shown in Figure 2. The miniature thermoelectric device of laminated construction remove upper guide thermal connection layer 4, top hard shell 5 and outer package layer 3 after stereochemical structure as it is shown on figure 3, pass through top conductive articulamentum 6 between n-type and the p-type thermoelectric lower limb piled up by multilamellar (all for 5 layers in all accompanying drawings) thin-film thermoelectric material and bottom conductive articulamentum 12 is electrically coupled in series. Fig. 4 is the internal structure top view after the miniature thermoelectric device of laminated construction removes upper guide thermal connection layer 4, hard shell 5 and outer package layer 3, illustrates n-type thermoelectric lower limb 7 and p-type thermoelectric lower limb 8 realizes electrically coupled in series by bottom conductive articulamentum 12 in figure. Different according to the constituted mode of thin-film thermoelectric material in n-type and p-type thermoelectric lower limb, AA ' cross-section structure in Fig. 3 mainly has following several types but is not limited to following several: 1) n-type and p-type thermoelectric lower limb are directly piled up formed by n-type thin film thermoelectric material and the p thin-film thermoelectric material of same composition and structure, as shown in Figure 5; 2) n-type and p-type thermoelectric lower limb are made up of difference and n-type thin film thermoelectric material and the p thin-film thermoelectric material of structure are directly piled up and formed, as shown in Figure 6, p1, p2, p3, p4, p5 in figure represents different p-type thin film thermoelectric material 10, n1, n2, n3, n4, n5 represent different n-type thin film thermoelectric materials 11; 3) n-type and p-type thermoelectric lower limb are piled up formed by n-type thin film thermoelectric material and the p thin-film thermoelectric materials of same composition and structure, are provided with transition zone 13, as shown in Figure 7 between adjacent films thermoelectric material; 4) n-type and p-type thermoelectric lower limb are made up of difference and n-type thin film thermoelectric material and the p thin-film thermoelectric material of structure are piled up and formed, and are provided with transition zone 13, as shown in Figure 8 between adjacent films thermoelectric material; 5) n-type and p-type thermoelectric lower limb are alternately piled up according to certain rule by the n-type thin film thermoelectric material of different components and structure and p thin-film thermoelectric material and are formed, as shown in Figure 9; 6) n-type and p-type thermoelectric lower limb are alternately piled up according to certain rule by the n-type thin film thermoelectric material of different components and structure and p thin-film thermoelectric material and are formed, and are provided with transition zone 13, as shown in Figure 10 between adjacent films thermoelectric material.

The shape of cross section of n-type and p-type thermoelectric lower limb is arbitrary shape or the shape of rule (all for square in all accompanying drawings of the present invention). The arrangement mode of thermoelectric lower limb, by the impact of its shape of cross section, arranges by certain rule or symmetrical structure, with can realize this kind of thermoelectric device optimal performance arrangement mode for the best. P-type thin film thermoelectric material 10 and the shape of n-type thin film thermoelectric material 11, area and thickness can be identical or different, and their thickness range is at 0.1��100 micron, and areal extent is in 0.01 square micron��1 square centimeter. The shape of top conductive material layer 6 and bottom conductive material layer 12 and size need to be consistent with n-type and p-type thermoelectric lower limb, and thickness is at 0.01��500 micron. The shape of transition zone 13 and size need to be consistent with the n-type constituting thermoelectric lower limb and p-type thin film thermoelectric material, and its thickness range is at 1 nanometer��100 microns.

Conducting along the region beyond thermoelectric lower limb to reduce hot-fluid, to ensure to set up the bigger temperature difference in n-type and p-type thermoelectric lower limb two ends, the implant 9 between thermoelectric lower limb must be made up of the material of the electrically insulating but thermally conductive property difference of single or multiple lift.

Positive pole exit 1 within miniature thermoelectric device, negative pole exit 2, top conductive articulamentum 6, bottom conductive articulamentum 12, transition zone 13 and barrier layer 14 are by the conductive material group of single or multiple lift, it is possible to be conducting polymer composite or metal material. Wherein, top conductive articulamentum 6 within miniature thermoelectric device and bottom conductive articulamentum 12, its Main Function is realize between n-type and p-type thermoelectric lower limb electrically coupled in series or electrically in parallel, and its shape, area and arrangement mode are determined by n-type and the shape of p-type thermoelectric lower limb, area and arrangement mode.

Embodiment

Embodiment 1: by the low temperature n-type Bi of same composition and structure₂Te_2.7Se_0.3Thin-film thermoelectric material and low-temperature p-type Bi_0.5Sb_1.5Te₃Thin-film thermoelectric material manufactures laminated construction minitype thermoelectric cell.

Manufacture method is as follows:

The first step: selecting a metal copper sheet being of a size of 25mm �� 15mm �� 0.5mm is substrate.

Second step: the method adopting photoengraving, produces the microcell figure for deposited bottom conductive tie layers with positive glue on copper base surface, and microcell therein is uniformly distributed on metallic copper substrate.

3rd step: first deposit the metallic copper of 20 micron thickness in microcell figure as bottom conductive articulamentum, be further continued for the metallic cobalt of one layer of 8 micron thickness of deposition afterwards as barrier layer, prepare bottom conductive articulamentum and barrier layer. In bottom conductive articulamentum, for realizing the rectangle being shaped as 0.2mm �� 0.8mm of metal copper layer electrically coupled in series between n-type and p-type thermoelectric lower limb. Finally remove microcell figure.

4th step: the method adopting photoengraving, produces the microcell figure for depositing ground floor n-type thin film thermoelectric material with positive glue on the barrier layer prepared.

5th step: the n-type Bi of deposit thickness about 20 microns in microcell figure₂Te_2.7Se_0.3Thin-film thermoelectric material, prepares ground floor n-type thin film thermoelectric material, and its section configuration is the rectangle of 200 �� m 200 ��m. Remove the microcell figure for depositing ground floor n-type thin film thermoelectric material.

6th step: the method adopting photoengraving, produces the microcell figure for depositing ground floor p-type thin film thermoelectric material with positive glue on the barrier layer prepared. The upper surface of the ground floor n-type thin film thermoelectric material prepared is covered by the positive glue of thin layer.

7th step: the p-type Bi of deposit thickness about 20 microns in microcell figure_0.5Sb_1.5Te₃Thin-film thermoelectric material, prepares ground floor p-type thin film thermoelectric material, and its section configuration is the rectangle of 400 �� m 200 ��m. Remove the positive glue of a thin layer covering ground floor n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

8th step: the method adopting photoengraving, produces the microcell figure for depositing second layer n-type thin film thermoelectric material with positive glue on the ground floor n-type prepared and p-type thin film thermoelectric material. In this figure, the shape of microcell, size and position are identical with the ground floor n-type thin film thermoelectric material prepared.

9th step: the n-type Bi of deposit thickness about 20 microns in microcell figure₂Te_2.7Se_0.3Thin-film thermoelectric material layer, prepares second layer n-type thin film thermoelectric material, and its section configuration is identical with ground floor n-type thin film thermoelectric material, is still the rectangle of 200 �� m 200 ��m. Remove the microcell figure for depositing second layer n-type thin film thermoelectric material.

Tenth step: the method adopting photoengraving, produces the microcell figure for depositing second layer p-type thin film thermoelectric material with positive glue on the ground floor n-type prepared and p-type thin film thermoelectric material. In this figure, the shape of microcell, size and position are identical with the ground floor p-type thin film thermoelectric material prepared. The upper surface of the second layer n-type thin film thermoelectric material prepared is covered by the positive glue of thin layer.

11st step: the p-type Bi of deposit thickness about 20 microns in microcell figure_0.5Sb_1.5Te₃Thin-film thermoelectric material, prepares second layer p-type thin film thermoelectric material, and its section configuration is identical with ground floor p-type thin film thermoelectric material, is still the rectangle of 400 �� m 200 ��m. Remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

12nd step: repeatedly repeat the 4th step manufacturing process to the 11st step, it is possible to prepare by 40 layers of n-type Bi₂Te_2.7Se_0.3N-type thermoelectric lower limb 500 that thin-film thermoelectric material is piled up and by 40 layers of p-type Bi_0.5Sb_1.5Te₃The p-type thermoelectric lower limb 500 that thin-film thermoelectric material is piled up. N-type thermoelectric lower limb is identical with the height of p-type thermoelectric lower limb, about 800 ��m.

13rd step: the method adopting photoengraving, produces the microcell figure for depositing top conductive articulamentum with positive glue on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb.

14th step: the metallic cobalt of first deposit thickness about 8 microns is as barrier layer in microcell figure, is further continued for the metallic copper of deposit thickness about 20 microns afterwards as top conductive articulamentum, prepares top conductive articulamentum and barrier layer. Since then, it is electrically coupled in series that the bottom conductive articulamentum prepared and top conductive articulamentum achieve between 500 n-type thermoelectric lower limbs and p-type thermoelectric lower limb.

15th step: the heat-conducting silicone grease of coating thickness about 50 microns is as heat conduction articulamentum on the top conductive articulamentum prepared, then on heat-conducting silicone grease the hard aluminium sesquioxide sheet of adhesive thickness about 500 microns as hard shell. The area of hard shell aluminium sesquioxide sheet is 22mm �� 12mm.

16th step: at the epoxy resin of the thermoelectric leg outer side surrounding coating thickness about 300 microns prepared as outer enclosure layer.

17th step: remove metallic copper substrate, expose bottom conductive articulamentum. On bottom conductive articulamentum, the heat-conducting silicone grease of coating thickness about 50 microns is as heat conduction articulamentum, then on heat-conducting silicone grease the hard aluminium sesquioxide sheet of adhesive thickness about 500 microns as hard shell. The area of hard shell aluminium sesquioxide sheet is 22mm �� 12mm.

18th step: 2 filamentary silvers are welded to the positive pole exit on bottom conductive layer and negative pole exit, completes the manufacture of minitype thermoelectric cell.

The overall dimensions of prepared minitype thermoelectric cell is 22mm �� 12mm �� 2mm, and the peak power output under room temperature, 20 DEG C of temperature difference conditions can reach 5mW.

N-type low temperature thin film thermoelectric material in the present embodiment can also is that Bi₂Te_2.7Se_0.3��Bi₂Sb₃Ce_x��Bi₂Sb₃Nd_x��Bi₂Sb₃Re_x��Bi₂Sb₃La_x��ZnSb��HgTe��Bi₂Se₃��CdInO4��La_1-xSr_xCuO_3-y, Sb2Se3 based material, Zr_0.5Hf_0.5NiSn and Bi₂Te₃It is other material, etc. P-type low temperature thin film thermoelectric material in the present embodiment can also is that such as, Sb₂Se₃Based material, Bi_0.5Sb_1.5Te₃��Bi_xPb_2-xTe₃��Bi_x2-xCdTe₃��Bi_xSn_2-xTe₃��FeV_0.85Ti_0.15Sb��FeV_0.85Ti_0.15Sb��Bi₂Te₃/Sb₂Te₃Nano super-lattice, Bi₂Te₃It it is other material etc. Embodiment 2: the miniature thermoelectric temperature sensor of laminated construction manufactured by the n-type of same composition and structure and p-type low temperature thin film thermoelectric material, and then manufacture Infrared Detectors. Its structure is provided with transition zone between adjacent films thermoelectric material.

The structure of miniature thermoelectric temperature sensor: use n-type Bi₂Se₃Thin-film thermoelectric material manufactures n-type thermoelectric lower limb, uses p-type Bi_xPb_2-xTe₃Thin-film thermoelectric material manufactures p-type thermoelectric lower limb. N-type thermoelectric lower limb is by the Bi of thickness about 80 microns₂Se₃Thin-film material is piled up and is formed, and its section configuration is circular, and area is 0.03 square micron, is highly 1mm, and quantity is 1000. P-type thermoelectric lower limb is by the p-type Bi of thickness about 80 microns_xPb_2-xTe₃Thin-film material is piled up and is formed, and its section configuration is circular, and area is 0.03 square micron, is highly 1mm, and quantity is 1000. Transition zone is prepared with the metallic nickel that thickness is 10 microns. Bottom conductive articulamentum and top conductive articulamentum is prepared with the argent conductive film that thickness is 0.01 micron. Positive pole exit 1 and negative pole exit 2 is prepared with copper wire. With positive glue as the implant 9 between thermoelectric lower limb. Making heat conduction articulamentum with heat-conducting silicone grease, its thickness is 0.01 micron. Two hard shells are made with the silicon carbide plate of two thickness respectively 0.5mm and 10 microns. Preparing outer enclosure layer 3 with epoxy resin, its thickness is 1mm.

The manufacture process of said structure miniature thermoelectric temperature sensor is as follows:

The first step: selecting a silicon carbide plate being of a size of 25mm �� 21mm �� 0.5mm is substrate.

Second step: be used as bottom conductive articulamentum at the argent that deposition on substrate thickness is 0.01 micron.

3rd step: the method adopting photoengraving, produces the microcell figure for etching bottom conductive articulamentum with positive glue on the metallic silver layer deposited. Afterwards, etch away unwanted argent, and after removing microcell figure, prepare bottom conductive articulamentum. In bottom conductive articulamentum, it is shaped as the rectangle of 0.4 �� m 0.8 ��m for realizing electrically coupled in series silver layer between n-type and p-type thermoelectric lower limb.

4th step: the method adopting photoengraving, produces for depositing ground floor n-type Bi with positive glue on the silver conductive layer prepared₂Se₃The microcell figure of thin-film thermoelectric material.

5th step: the n-type Bi of first deposit thickness about 80 microns in microcell figure₂Se₃Thin-film thermoelectric material, is further continued for the metallic nickel of deposition 10 micron thickness afterwards, prepares ground floor n-type thin film thermoelectric material and transition zone thereon, and its section configuration is area is the circle of 0.03 square micron. Remove the microcell figure for depositing ground floor n-type thin film thermoelectric material.

6th step: the method adopting photoengraving, produces for depositing ground floor p-type Bi with positive glue on the silver conductive layer prepared_xPb_2-xTe₃The microcell figure of thin-film thermoelectric material. The upper surface of the ground floor n-type thin film thermoelectric material prepared is covered by the positive glue of thin layer.

7th step: the p-type Bi of first deposit thickness about 80 microns in microcell figure_xPb_2-xTe₃Thin-film thermoelectric material, is further continued for the metallic nickel of deposition 10 micron thickness afterwards, prepares ground floor p-type thin film thermoelectric material and transition zone thereon, and its section configuration is area is the circle of 0.03 square micron. Remove the positive glue of a thin layer covering ground floor n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

8th step: the method adopting photoengraving, produces for depositing second layer n-type Bi on the ground floor n-type prepared and p-type thin film thermoelectric material with positive glue₂Se₃The microcell figure of thin-film thermoelectric material. The shape of microcell, size and position and the ground floor n-type Bi that prepared in this figure₂Se₃Thin-film thermoelectric material is identical.

9th step: the n-type Bi of first deposit thickness about 80 microns in microcell figure₂Se₃Thin-film thermoelectric material, it is further continued for the metallic nickel of deposition 10 micron thickness afterwards, preparing second layer n-type thin film thermoelectric material and transition zone thereon, its section configuration is identical with ground floor n-type thin film thermoelectric material, be still area for section configuration is the circle of 0.03 square micron. Remove the microcell figure for depositing second layer n-type thin film thermoelectric material.

Tenth step: the method adopting photoengraving, produces for depositing second layer p-type Bi on the ground floor n-type prepared and p-type thin film thermoelectric material with positive glue_xPb_2-xTe₃The microcell figure of thin-film thermoelectric material. In this figure, the shape of microcell, size and position are identical with the ground floor p-type thin film thermoelectric material prepared. The upper surface of the second layer n-type thin film thermoelectric material prepared is covered by the positive glue of thin layer.

11st step: the p-type Bi of first deposit thickness about 80 microns in microcell figure_xPb_2-xTe₃Thin-film thermoelectric material, it is further continued for the metallic nickel of deposition 10 micron thickness afterwards, preparing second layer p-type thin film thermoelectric material and transition zone thereon, its section configuration is identical with ground floor p-type thin film thermoelectric material, be still area for section configuration is the circle of 0.03 square micron. Remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

12nd step: repeatedly repeat the 4th step manufacturing process to the 11st step, it is possible to prepare by 11 layers of n-type Bi₂Se₃N-type thermoelectric lower limb 1000 that thin-film thermoelectric material is piled up and by 11 layers of p-type Bi_xPb_2-xTe₃The p-type thermoelectric lower limb 1000 that thin-film thermoelectric material is piled up. N-type thermoelectric lower limb is identical with the height of p-type thermoelectric lower limb, about 1mm. 11th layer n-type Bi is deposited in microcell₂Se₃Thin-film thermoelectric material and 11th layer p-type Bi_xPb_2-xTe₃After thin-film thermoelectric material, it is not necessary to deposit the metallic nickel as transition zone again in microcell figure.

13rd step: the argent of deposit thickness about 0.01 micron is used as top conductive articulamentum on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb.

14th step: the method adopting photoengraving, produces the microcell figure for etching top conductive articulamentum with positive glue on the metallic silver layer deposited. Afterwards, etching away unwanted argent, and after removing microcell figure, prepare top conductive articulamentum, it is shaped as the rectangle of 0.4 �� m 0.8 ��m. Since then, it is electrically coupled in series that the bottom conductive articulamentum prepared and top conductive articulamentum achieve between 1000 n-type thermoelectric lower limbs and p-type thermoelectric lower limb.

15th step: the heat-conducting silicone grease of coating thickness about 0.01 micron is as heat conduction articulamentum on the top conductive articulamentum prepared, then on heat-conducting silicone grease the hcird silica carbide sheet of adhesive thickness about 10 microns as hard shell. The area of hard shell silicon carbide plate is 25mm �� 21mm.

16th step: at the epoxy resin of the thermoelectric leg outer side surrounding coating thickness about 1000 microns prepared as outer enclosure layer.

17th step: 2 copper wires are connected to conducting resinl respectively the positive pole exit on bottom conductive layer and negative pole exit, complete the manufacture of miniature thermoelectric temperature sensor.

Thermoelectric Infrared Detectors can be produced with manufactured above-mentioned miniature thermoelectric temperature sensor. Such Infrared Detectors has significantly high detection accuracy.

P-type low temperature thermoelectric material in the present embodiment can also is that p-type Bi₂Te₃Based material, Sb₂Se₃Based material/Sb₂Te₃��Bi_0.5Sb_1.5Te₃��Bi_2-xCd_xTe₃��Bi_xSn_2-xTe₃��FeV_0.85Ti_0.15Sb, p-type Bi₂Te₃/Sb₂Te₃Nano super-lattice, etc. N-type low temperature thermoelectric material in the present embodiment can also is that n-type Bi₂Te₃Based material, Bi₂Te_2.7Se_0.3��Bi₂Sb₃Ce_x��Bi₂Sb₃Nd_x��Bi₂Sb₃Re_x��Bi₂Sb₃La_x��ZnSb��HgTe��CdInO4��La_1-xSr_xCuO_3-y, Sb2Se3 based material, Zr_0.5Hf_0.5NiSn, n-type Bi₂Te₃/Sb₂Te₃Nano super-lattice, etc.;

Embodiment 3: be made up of difference and laminated construction minitype thermoelectric cell that Structures at Low Temperature, middle temperature and high temperature n-type and p-type thin film thermoelectric material manufacture. Its structure is provided with transition zone between adjacent films thermoelectric material.

The structure of minitype thermoelectric cell: n-type thermoelectric lower limb is respectively by n-type low temperature Bi₂Sb₃Ce_xTemperature AgPb in thin-film thermoelectric material, n-type₁₈SbTe₂₀Thin-film thermoelectric material and n-type high temperature Ge_0.3Si_0.7Thin-film thermoelectric material alternates to pile up and forms. P-type thermoelectric lower limb is respectively by p-type low temperature FeV_0.85Ti_0.15Temperature SbTe thin-film thermoelectric material and p-type high temperature FeSi in Sb thin-film thermoelectric material, p-type₂Thin-film thermoelectric material alternates to pile up and forms. In n-type thermoelectric lower limb, n-type low temperature Bi₂Sb₃Ce_xThe thickness of thin-film thermoelectric material is 20 microns, temperature AgPb in n-type₁₈SbTe₂₀The thickness of thin-film thermoelectric material is 40 microns, n-type high temperature Ge_0.3Si_0.7The thickness of thin-film thermoelectric material is 30 microns. In p-type thermoelectric lower limb, p-type low temperature FeV_0.85Ti_0.15The thickness of Sb thin-film thermoelectric material is 20 microns, the thickness of temperature SbTe thin-film thermoelectric material is 20 microns, p-type high temperature FeSi in p-type₂The thickness of thin-film thermoelectric material is 20 microns. The height of n-type and p-type thermoelectric lower limb is 1.2 millimeters. The square that section configuration is 5mm �� 5mm of n-type thermoelectric lower limb, is highly 1.2mm, and quantity is 200. The square that section configuration is 5cm �� 5cm of p-type thermoelectric lower limb, is highly 1.2mm, and quantity is 200. The transition zone between p-type thin film thermoelectric material is prepared with the cobalt-nickel alloy that thickness is 20 microns. The transition zone between n-type thin film thermoelectric material is prepared with the cobalt-nickel alloy that thickness is 10 microns. Bottom conductive articulamentum and top conductive articulamentum is prepared with the metallic nickel conductive film that thickness is 200 microns. Positive pole exit 1 and negative pole exit 2 is prepared with nickel wire. With positive glue as the implant 9 between thermoelectric lower limb. Making heat conduction articulamentum with silicate binder, its thickness is 0.5 millimeter. Two hard shells are made with the zirconium oxide sheet of two thickness respectively 0.5mm. Preparing outer enclosure layer with silicate binder, its thickness is 3mm.

The manufacture process of said structure minitype thermoelectric cell is as follows:

The first step: selecting a zirconium oxide sheet being of a size of 160mm �� 130mm �� 0.5mm is substrate.

Second step: be used as bottom conductive articulamentum at the metallic nickel that deposition on substrate thickness is 200 microns.

3rd step: the method adopting photoengraving, produces the microcell figure for etching bottom conductive articulamentum with positive glue on the metal nickel dam deposited. Afterwards, etch away unwanted metallic nickel, and after removing microcell figure, prepare bottom conductive articulamentum. In bottom conductive articulamentum, it is shaped as the rectangle of 5mm �� 11mm for realizing electrically coupled in series nickel dam between n-type and p-type thermoelectric lower limb.

4th step: the method adopting photoengraving, produces the microcell figure for depositing ground floor n-type thin film thermoelectric material with positive glue on the nickel conductive layer prepared.

5th step: the n-type low temperature Bi of first deposit thickness about 20 microns in microcell figure₂Sb₃Ce_xThe cobalt-nickel alloy depositing 10 micron thickness again after thin-film thermoelectric material makes transition zone, subsequently again in microcell figure in the n-type of deposit thickness about 40 microns temperature AgPb₁₈SbTe₂₀The cobalt-nickel alloy depositing 10 micron thickness again after thin-film thermoelectric material makes transition zone, continues the n-type high temperature Ge of deposit thickness about 30 microns afterwards again in microcell figure_0.3Si_0.7The cobalt-nickel alloy depositing 10 micron thickness again after thin-film thermoelectric material makes transition zone, prepares ground floor n-type thin film thermoelectric material and transition zone thereon, and its section configuration is the square of 5mm �� 5mm. Remove the microcell figure for depositing ground floor n-type thin film thermoelectric material.

6th step: the method adopting photoengraving, produces the microcell figure for depositing ground floor p-type thin film thermoelectric material with positive glue on the nickel conductive layer prepared. The upper surface of the ground floor n-type thin film thermoelectric material prepared is covered by the positive glue of thin layer.

7th step: the p-type low temperature FeV of first deposit thickness about 20 microns in microcell figure_0.85Ti_0.15The cobalt-nickel alloy depositing 20 micron thickness again after Sb thin-film thermoelectric material makes transition zone, the cobalt-nickel alloy depositing 20 micron thickness after being further continued for depositing in microcell figure in the p-type of 20 micron thickness temperature SbTe thin-film thermoelectric material subsequently again makes transition zone, is further continued for depositing the p-type high temperature FeSi of 20 micron thickness afterwards in microcell figure₂The cobalt-nickel alloy depositing 20 micron thickness again after thin-film thermoelectric material makes transition zone, prepares ground floor p-type thin film thermoelectric material and transition zone thereon, and its section configuration is the square of 5mm �� 5mm. Remove the positive glue of a thin layer covering ground floor n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

9th step: the n-type low temperature Bi of first deposit thickness about 20 microns in microcell figure₂Sb₃Ce_xThe cobalt-nickel alloy depositing 10 micron thickness again after thin-film thermoelectric material makes transition zone, subsequently again in microcell figure in the n-type of deposit thickness about 40 microns temperature AgPb₁₈SbTe₂₀After deposit the cobalt-nickel alloy of 10 micron thickness again and make transition zone, in microcell figure, continue the n-type high temperature Ge of deposit thickness about 30 microns afterwards again_0.3Si_0.7The cobalt-nickel alloy depositing 10 micron thickness again after thin-film thermoelectric material makes transition zone, prepare second layer n-type thin film thermoelectric material and transition zone thereon, its section configuration is identical with ground floor n-type thin film thermoelectric material, is still the square of section configuration 5mm �� 5mm. Remove the microcell figure for depositing second layer n-type thin film thermoelectric material.

11st step: the p-type low temperature FeV of first deposit thickness about 20 microns in microcell figure_0.85Ti_0.15The cobalt-nickel alloy depositing 20 micron thickness again after Sb thin-film thermoelectric material makes transition zone, the cobalt-nickel alloy depositing 20 micron thickness after being further continued for depositing in microcell figure in the p-type of 20 micron thickness temperature SbTe thin-film thermoelectric material subsequently again makes transition zone, is further continued for depositing the p-type high temperature FeSi of 20 micron thickness afterwards in microcell figure₂The cobalt-nickel alloy depositing 20 micron thickness again after thin-film thermoelectric material makes transition zone, prepare second layer p-type thin film thermoelectric material and transition zone thereon, its section configuration is identical with ground floor p-type thin film thermoelectric material, is still the square of 5mm �� 5mm for section configuration. Remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

12nd step: repeatedly repeat the 4th step manufacturing process to the 11st step, it is possible to prepare the n-type thermoelectric lower limb 200 piled up by 10 layers of n-type thin film thermoelectric material and the p-type thermoelectric lower limb 200 piled up by 10 layers of p-type thin film thermoelectric material. The height of n-type thermoelectric lower limb and p-type thermoelectric lower limb is 1.2mm.

13rd step: deposit thickness is that the metallic nickel of 200 microns is as top conductive articulamentum on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb.

14th step: the method adopting photoengraving, produces the microcell figure for etching top conductive articulamentum with positive glue on the metal nickel dam deposited. Afterwards, etch away unwanted metallic nickel, and after removing microcell figure, prepare top conductive articulamentum. Since then, it is electrically coupled in series that the bottom conductive articulamentum prepared and top conductive articulamentum achieve between 200 n-type thermoelectric lower limbs and p-type thermoelectric lower limb. It is shaped as the rectangle of 5mm �� 11mm for realizing electrically coupled in series nickel dam between n-type and p-type thermoelectric lower limb

15th step: the silicate binder of coating thickness about 0.5 millimeter is as heat conduction articulamentum on the top conductive articulamentum prepared, then adhesive thickness is that the hardening oxidation zirconium sheet of 0.5 millimeter is as hard shell on silicate binder. The area of hardening oxidation zirconium sheet is 160mm �� 130mm.

16th step: be about the silicate binder of 3mm as outer enclosure layer at the thermoelectric leg outer side surrounding coating thickness prepared.

17th step: 2 nickel wires are connected respectively to the positive pole exit on bottom conductive layer and negative pole exit, completes the manufacture of miniature thermoelectric temperature sensor.

The overall dimensions of prepared minitype thermoelectric cell is about 160mm �� 130mm �� 3.6mm. This thermoelectric cell can be applicable in the wide temperature range of low temperature, middle gentle high temperature, and the peak power output under 50 DEG C of temperature difference conditions can reach 5W.

N-type high temperature film thermoelectric material in the present embodiment can also is that n-type SiGe based material, CrSi₂��MnSi_1.73��CoSi��Na_xCo_x/2Ti_1-x/2O₂��Na_xNi_x/2Ti_1-x/2O₂��Na_xFe_x/2Ti_1-x/2O₂��AlxZnO��Ag_1-xPb₁₈SbTe₂₀��Ba_1-xSr_xPbO₃��SrAl₂Si₂Deng. In n-type in the present embodiment, temperature thin-film thermoelectric material can also is that n-type PbTe based material, Bi2 (GeSe) 3, CoSb₃Sm_x��CoSb₃Pr_x��FeVSb��Zr_0.5HF_0.5NiSn��TiNiSn��ZrNiSn��HfNiSn��ZrCoSb��HfCoSb��TiCoSb��Ce_yFe_4-xCo_xSb₁₂��La_yFe_4-xCo_xSb₁₂��Ba_yFe_4-xCo_xSb₁₂��Fe_0.5Ni_0.5Sb₃��FeSb₂Te��Mg₂Si_1-xSn_x��HoCoO₃��LaCoO₃��Zn₄Sb₃��Ag_2-ySb_yTe_1+y��Eu_xPb_1-xTe��Bi(SiSb)₂��Bi₂(GeSe)₃��Ba_0.3Ni_xCo_4-xSb₁₂��AgPb₁₀SbTe₁₂, etc. N-type low temperature thin film thermoelectric material in the present embodiment can also is that n-type Bi₂Te₃Based material, Bi₂Te_2.7Se_0.3��Bi₂Sb₃Nd_x��Bi₂Sb₃Re_x��Bi₂Sb₃La_x��ZnSb��HgTe��Bi₂Se₃��CdInO4��La_1-xSr_xCuO_3-y, Sb2Se3 based material, Zr_0.5Hf_0.5NiSn, n-type Bi₂Te₃/Sb₂Te₃Nano super-lattice, etc. P-type high temperature film thermoelectric material in the present embodiment can also is that p-type SiGe based material, Fe_0.9Mn_0.1Si₂��Ca₃Co_4-xAg_xO₉��Ca_1-xSm_xMnO₃��Ca_2.5Yb_0.5Co₄O₉, Ca2CoO3 etc. In p-type in the present embodiment, temperature thin-film thermoelectric material can also is that p-type PbTe based material, Bi (SiSb2), GeTe, Al₇₁Pb₂₀Re₉��(GeTe)_x(Mn_aSn_1-aTe)_1-x��FeV_1-xTi_xSb��HoPdSb��ErPdSb��DyPdSb��Ce_fFe_4-xCo_xSb₁₂And La_fFe_4-xCo_xSb₁Deng. P-type low temperature thin film thermoelectric material in the present embodiment can also is that p-type Bi₂Te₃Based material, Sb₂Se₃Based material, Sb₂Te₃��Bi_0.5Sb_1.5Te₃��Bi_xPb_2-xTe₃��Bi_2-xCd_xTe₃��Bi_xSn_2-xTe₃, p-type Bi₂Te₃/Sb₂Te₃Nano super-lattice etc.

Embodiment 4: by the low temperature n-type Sb of same composition and structure₂Se₃Thin-film thermoelectric material and low-temperature p-type Bi_2-xCd_xTe₃Thin-film thermoelectric material manufactures the miniature thermoelectric refrigerator of laminated construction.

The structure of miniature thermoelectric refrigerator: use n-type Sb₂Se₃Thin-film thermoelectric material manufactures n-type thermoelectric lower limb, uses p-type Bi_2-xCd_xTe₃Thin-film thermoelectric material manufactures p-type thermoelectric lower limb. N-type thermoelectric lower limb is by the n-type Sb of thickness about 50 microns₂Se₃Thin-film material is piled up and is formed, and its section configuration is the square of 0.5mm �� 0.5mm, is highly 0.5mm, and quantity is 100. P-type thermoelectric lower limb is by the p-type Bi of thickness about 50 microns_2-xCd_xTe₃Thin-film thermoelectric material is piled up and is formed, and its section configuration is the square of 0.5mm �� 0.5mm, is highly 0.5mm, and quantity is 100. Bottom conductive articulamentum and top conductive articulamentum is prepared with the metallic copper conductive film that thickness is 30 microns. Barrier layer is prepared with the metal nickel dam of thickness 10 microns. Positive pole exit 1 and negative pole exit 2 is prepared with copper wire. With positive glue as the implant between thermoelectric lower limb. Making heat conduction articulamentum with heat-conducting silicone grease, its thickness is 30 microns. Hard shell is made with the silicon carbide plate that two thickness is 0.5mm. Preparing outer enclosure layer with silicate binder, its thickness is 1mm.

Manufacture method is as follows:

The first step: selecting a silicon carbide plate being of a size of 22mm �� 12mm �� 0.5mm is substrate.

Second step: in the metal copper layer that deposition on substrate thickness is 30 microns for making bottom conductive articulamentum, then the nickel dam of deposit thickness 10 microns is used for making barrier layer.

3rd step: the method adopting photoengraving, produces the microcell figure for etching bottom conductive articulamentum with positive glue on the metal nickel dam deposited. Afterwards, etch away unwanted metal level, and after removing microcell figure, prepare bottom conductive articulamentum and barrier layer. In bottom conductive articulamentum, it is shaped as the rectangle of 0.5mm �� 1.5mm for realizing electrically coupled in series layers of copper between n-type and p-type thermoelectric lower limb.

5th step: the n-type Sb of deposit thickness about 50 microns in microcell figure₂Se₃Thin-film thermoelectric material, prepares ground floor n-type thin film thermoelectric material, and its section configuration is the square of 0.5mm �� 0.5mm. Remove the microcell figure for depositing ground floor n-type thin film thermoelectric material.

7th step: the p-type Bi of deposit thickness about 50 microns in microcell figure_2-xCd_xTe₃Thin-film thermoelectric material, prepares ground floor p-type thin film thermoelectric material, and its section configuration is the square of 0.5mm �� 0.5mm. Remove the positive glue of a thin layer covering ground floor n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

9th step: the n-type Sb of deposit thickness about 50 microns in microcell figure₂Se₃Thin-film thermoelectric material layer, prepares second layer n-type thin film thermoelectric material, and its section configuration is identical with ground floor n-type thin film thermoelectric material, is still the square of 0.5mm �� 0.5mm. Remove the microcell figure for depositing second layer n-type thin film thermoelectric material.

11st step: the p-type Bi of deposit thickness about 50 microns in microcell figure_2-xCd_xTe₃Thin-film thermoelectric material, prepares second layer p-type thin film thermoelectric material, and its section configuration is identical with ground floor p-type thin film thermoelectric material, is still the square of 0.5mm �� 0.5mm. Remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface. Remaining microcell figure is then retained, and becomes the implant between thermoelectric lower limb.

12nd step: repeatedly repeat the 4th step manufacturing process to the 11st step, it is possible to prepare by 10 layers of n-type Sb₂Se₃N-type thermoelectric lower limb 100 that thin-film thermoelectric material is piled up and by 10 layers of p-type Bi_2-xCd_xTe₃The p-type thermoelectric lower limb 100 that thin-film thermoelectric material is piled up. N-type thermoelectric lower limb is identical with the height of p-type thermoelectric lower limb, about 500 ��m.

13rd step: the nickel dam of deposit thickness about 10 microns is for making barrier layer on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb, the metal copper layer that deposit thickness is about 30 microns is for making top conductive articulamentum.

14th step: the method adopting photoengraving, produces the microcell figure for etching top conductive articulamentum with positive glue on the metal copper layer deposited. Afterwards, etch away unwanted metal level, and after removing microcell figure, prepare top conductive articulamentum and barrier layer. Since then, it is electrically coupled in series that the bottom conductive articulamentum prepared and top conductive articulamentum achieve between 100 n-type thermoelectric lower limbs and p-type thermoelectric lower limb. It is shaped as the rectangle of 0.5mm �� 1.5mm for realizing electrically coupled in series layers of copper between n-type and p-type thermoelectric lower limb

15th step: the heat-conducting silicone grease of coating thickness about 30 microns is as heat conduction articulamentum on the top conductive articulamentum prepared, then on heat-conducting silicone grease the hcird silica carbide sheet of adhesive thickness about 500 microns as hard shell. The area of hard shell silicon carbide plate is 22mm �� 12mm.

16th step: at the silicate binder of the thermoelectric leg outer side surrounding coating thickness about 1 millimeter prepared as outer enclosure layer.

17th step: 2 copper wires are welded to the positive pole exit on bottom conductive layer and negative pole exit, completes the manufacture of miniature thermoelectric refrigerator.

The overall dimensions of prepared miniature thermoelectric refrigerator is 22mm �� 12mm �� 1.6mm.

N-type low temperature thin film thermoelectric material in the present embodiment can also is that Bi₂Te_2.7Se_0.3��Bi₂Sb₃Ce_x��Bi₂Sb₃Nd_x��Bi₂Sb₃Re_x��Bi₂Sb₃La_x��ZnSb��HgTe��Bi₂Se₃��CdInO4��La_1-xSr_xCuO_3-y��Zr_0.5Hf_0.5NiSn and Bi₂Te₃It is other material, etc. P-type low temperature thin film thermoelectric material in the present embodiment can also is that Sb₂Se₃Based material, Bi_0.5Sb_1.5Te₃��Bi_xPb_2-xTe₃��Bi_xSn_2-xTe₃��FeV_0.85Ti_0.15Sb��FeV_0.85Ti_0.15Sb��Bi₂Te₃/Sb₂Te₃Nano super-lattice, Bi₂Te₃It it is other material etc.

Above the present invention has been done exemplary description; should be noted that; when without departing from the core of the present invention, any simple deformation, amendment or other those skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.

Claims

1. the preparation method of the miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material, it is characterised in that be prepared by the following method:

The first step: according to need to prepare thermoelectric lower limb in miniature thermoelectric device the space consuming size flaky material that selects area suitable be substrate (15); To ask substrate to have good electric conductivity, then selected substrate material should be conductive material, or select the non-conductive flaky material that an area is suitable, adopt physics or chemistry method after non-conductive flaky material surface deposition layer of conductive material as substrate (15); If the substrate selected is non-conductive and during heat conductivity is good flaky material, substrate can also directly as hard shell (5);

Second step: the method adopting photoengraving, produces the microcell figure (16) for deposited bottom conductive tie layers (12) at substrate surface;

3rd step: first deposit the material that electric conductivity is good in microcell figure, prepare bottom conductive articulamentum (12), it is further continued for afterwards in microcell figure and deposits one layer of material being used as barrier layer, prepare barrier layer (14), finally remove the microcell figure (16) for deposited bottom conductive tie layers (12) and barrier layer (14);

4th step: the method adopting photoengraving, produces the microcell figure (18) for depositing ground floor n-type thin film thermoelectric material on the barrier layer (14) prepared; In this figure, the position of microcell (17) and shape are corresponding with the position of n-type thermoelectric lower limb in standby miniature thermoelectric device of drawing up and shape;

5th step: first depositing n-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone (13), prepare ground floor n-type thin film thermoelectric material (19) and transition zone (13), and remove the microcell figure (18) for depositing ground floor n-type thin film thermoelectric material; If in the structure of miniature thermoelectric device, between adjacent n-type thin film thermoelectric material, it is not provided with transition zone (13), then without depositing one layer of buffer layer material in microcell figure;

6th step: the method adopting photoengraving, produces the microcell figure (20) for depositing ground floor p-type thin film thermoelectric material on the barrier layer (14) prepared; In this figure, the position of microcell (17) and shape are corresponding with the position of p-type thermoelectric lower limb in standby miniature thermoelectric device of drawing up and shape; The upper surface of the ground floor n-type thin film thermoelectric material prepared is covered by the photoresist of thin layer;

7th step: first depositing p-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone (13), prepare ground floor p-type thin film thermoelectric material (21) and transition zone (13), and remove a thin layer photoresist covering ground floor n-type thin film thermoelectric material surface; Remaining microcell figure is then retained, and forms the implant (9) between thermoelectric lower limb; If in the structure of miniature thermoelectric device, between adjacent p-type thin film thermoelectric material, it is not provided with transition zone (13), then without depositing one layer of buffer layer material in microcell figure;

8th step: the method adopting photoengraving, produces the microcell figure (18) for depositing second layer n-type thin film thermoelectric material on the ground floor n-type prepared and p-type thin film thermoelectric material; In this figure, the position of microcell (17) is identical with the position of the ground floor n-type thin film thermoelectric material prepared;

9th step: first depositing n-type thin-film thermoelectric material layer (22) in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone (13), prepare second layer n-type thin film thermoelectric material (22) and transition zone (13), and remove the microcell figure (18) for depositing second layer n-type thin film thermoelectric material; The Nomenclature Composition and Structure of Complexes of second layer n-type thin film thermoelectric material and ground floor n-type thin film thermoelectric material can be identical, it is also possible to different; If in the structure of miniature thermoelectric device, between adjacent n-type thin film thermoelectric material, it is not provided with transition zone (13), then without depositing one layer of buffer layer material in microcell figure;

Tenth step: the method adopting photoengraving, produces the microcell figure (20) for depositing second layer p-type thin film thermoelectric material on the ground floor n-type prepared and p-type thin film thermoelectric material; In this figure, the position of microcell (17) is identical with the position of the ground floor p-type thin film thermoelectric material prepared; The upper surface of the second layer n-type thin film thermoelectric material prepared is covered by the photoresist of thin layer;

11st step: first depositing p-type thin-film thermoelectric material in microcell figure, it is further continued for afterwards in microcell figure and deposits one layer of buffer layer material formation transition zone (13), prepare second layer p-type thin film thermoelectric material (23) and transition zone (13), and remove a thin layer photoresist covering second layer n-type thin film thermoelectric material surface, remaining microcell figure is then retained, and forms the implant (9) between thermoelectric lower limb; The Nomenclature Composition and Structure of Complexes of second layer p-type thin film thermoelectric material and ground floor p-type thin film thermoelectric material can be identical, can also be different, if in the structure of miniature thermoelectric device, transition zone (13) it is not provided with, then without depositing one layer of buffer layer material in microcell figure between adjacent p-type thin film thermoelectric material;

12nd step: repeatedly repeat the 4th step to the manufacturing process of the 11st step, it is possible to prepare by the N shell number of plies of thermoelectric material (N represent) the n-type thermoelectric lower limb that n-type thin film thermoelectric material is piled up and the p-type thermoelectric lower limb piled up by N shell p-type thin film thermoelectric material; When the height of n-type thermoelectric lower limb and p-type thermoelectric lower limb reaches the designing requirement of miniature thermoelectric device, complete the preparation of thermoelectric lower limb; After depositing n-th layer n-type thin film thermoelectric material (24) and n-th layer p-type thin film thermoelectric material (25) in microcell, it is not necessary to deposit buffer layer material again in microcell figure;

13rd step: the method adopting photoengraving, produces the microcell figure (26) for depositing top conductive articulamentum (6) on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb;

14th step: first deposit one layer of barrier material in microcell figure, form barrier layer (14), it is further continued for afterwards in microcell figure and deposits the material that electric conductivity is good, prepare top conductive articulamentum (6) and barrier layer (14); If the structure of minitype thermoelectric cell being not provided with barrier layer (14), then without deposit barrier material in microcell;

15th step: be coated with one layer of conducting adhesive agent material on the top conductive articulamentum (6) prepared and form heat conduction articulamentum (4), then adhere to hard Heat Conduction Material formation hard shell (5) on conducting adhesive agent material;

16th step: be coated with the material of electrically insulating but thermally conductive property difference in the thermoelectric leg outer side surrounding prepared, prepare outer enclosure layer (3);

17th step: if select substrate be non-conductive and that heat conductivity is good flaky material, and using substrate as hard shell (5) time, the preparation process of the 18th step can be made directly; Substrate can not as hard shell (5) time, then need to remove the substrate (15) of bottom, expose the bottom conductive articulamentum (12) prepared, on bottom conductive articulamentum (12), it is coated with one layer of conducting adhesive agent material forms heat conduction articulamentum (4), then on conducting adhesive agent material, adhere to hard Heat Conduction Material formation hard shell (5);

18th step: 2 conductive materials are connected respectively to positive pole exit (1) and the negative pole exit (2) of bottom conductive layer, complete the manufacture of miniature thermoelectric device.

2. the preparation method of a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material as described in claim 1, it is characterized in that, second step therein and the 3rd step are prepared the manufacturing step of bottom conductive articulamentum (12) and barrier layer (14) and are changed following second step and the 3rd step into:

Second step: first deposit the material that the electric conductivity being used as bottom conductive articulamentum (12) is good on substrate (15), be further continued for deposition one layer afterwards and be used as the conductive material on barrier layer (14);

3rd step: the method adopting photoengraving, produces the microcell figure (27) for etching bottom conductive articulamentum (12) on the conductive material deposited; Afterwards, etch away the unwanted conductive material deposited, and after removing microcell figure (16), prepare bottom conductive articulamentum (12) and barrier layer (14).

3. the preparation method of a kind of miniature thermoelectric device of the laminated construction manufactured by thin-film thermoelectric material as described in claim 1, it is characterized in that, the 13rd step therein and the 14th step are prepared the process of top conductive articulamentum (6) and barrier layer (14) and are changed the 13rd following step and the 14th step into:

13rd step: first deposit one layer of conductive material being used as barrier layer (14) on the n-type thermoelectric lower limb prepared and p-type thermoelectric lower limb, is further continued for depositing the material that the electric conductivity being used as top conductive articulamentum (6) is good afterwards;

14th step: the method adopting photoengraving, produces the microcell figure (28) for etching top conductive articulamentum (6) on the conductive material deposited; Afterwards, etch away the unwanted conductive material deposited, and after removing microcell figure (16), prepare top conductive articulamentum (6) and barrier layer (14).