CN112038472A - Method for manufacturing bismuth telluride-based thin film thermoelectric module, thermoelectric module and thermoelectric generator - Google Patents
Method for manufacturing bismuth telluride-based thin film thermoelectric module, thermoelectric module and thermoelectric generator Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 119
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000010409 thin film Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 168
- 239000002184 metal Substances 0.000 claims abstract description 168
- 239000010408 film Substances 0.000 claims abstract description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 239000011265 semifinished product Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 6
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000005459 micromachining Methods 0.000 abstract description 2
- 238000000427 thin-film deposition Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 9
- 238000013461 design Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000005678 Seebeck effect Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 229920001486 SU-8 photoresist Polymers 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 229910007657 ZnSb Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
- H02N11/002—Generators
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The invention discloses a manufacturing method of a bismuth telluride based thin film thermoelectric module, the thermoelectric module and a thermoelectric generator, wherein the manufacturing method comprises the following steps: depositing a silicon dioxide film layer on the heat sink substrate; preparing a plurality of metal strips which are arranged at intervals on the silicon dioxide film layer; alternately depositing a P-type bismuth telluride-based film and an N-type bismuth telluride-based film on the upper surface of the silicon dioxide film between different metal strips to obtain a first semi-finished product; coating photoresist on the upper surface of the first semi-finished product, removing part of the photoresist on the metal strips, and alternately arranging the metal strips with the photoresist removed and the metal strips without the photoresist removed; depositing a metal layer on the metal belt with the photoresist removed to obtain a second semi-finished product; coating photoresist on the upper surface of the second semi-finished product, and removing the photoresist on the metal layer; and depositing a heat conduction insulating layer on the metal layer with the photoresist removed. The invention realizes the expandability of the planar bismuth telluride based thin film thermoelectric generator by utilizing the MEMS micromachining technology and the thin film deposition technology.
Description
Technical Field
The invention relates to the field of thermoelectric material power generation, in particular to a manufacturing method of a planar bismuth telluride-based thin film thermoelectric module, the thermoelectric module and a thermoelectric generator.
Background
The environment energy collection technology is expected to realize the application of portable, wearable and distributed sensor network systems in the society of Internet of things. Available energy sources include sunlight, room lighting, radio waves, mechanical vibration, and heat. The effective utilization of thermal energy has been a long-standing problem, and Thermoelectric (TE) generators that convert temperature differences into electrical energy using the Seebeck effect have also received much attention. The energy conversion efficiency of TE generation depends mainly on the advantages of TE materials, ZT ═ S2σT k-1Wherein S represents the Seebeck coefficient, sigma and k represent the electrical conductivity and the thermal conductivity, respectively, and T represents the average temperature of the cold and heat source. Increasing ZT can improve conversion efficiency, but the correlation between S, σ, and k prevents this. Only a few materials, such as bismuth-tellurium, lead-tellurium, are known to achieve high conversion efficiencies.
The basic understanding of electricity and heat transfer has improved over the last two decades. With the help of micro-nano technology, the understanding leads to the substantial enhancement of the performance of the TE material. Bismuth telluride-based low dimensional materials have become promising TE candidates because they retain the properties of low thermal and high electrical conductivity. Highly compatible, low-contamination (unlike Pb) bismuth telluride-based TE generators are also increasingly being manufactured and reported.
The Thermoelectric (TE) phenomenon is also called a thermoelectric phenomenon. In 1822, Thomas Seebeck discovered the effect of thermo-electromotive force (TE material power generation principle); in 1834, Jean Peltier discovered the effect of temperature reduction at the junction interface of two different material conductors in the current loop (TE material refrigeration principle). Some good semiconductor TE materials were found in the 50 s of the 20 th century. The material with ZT ≧ 0.5 is generally referred to as TE material. The larger the ZT, the higher the TE device efficiency. In order to overcome the obstacle of lacking of high ZT TE material types, people turn to the structural design of natural TE materials and the development of artificially synthesized TE materials, namely low-dimensional thermoelectric materials. Mesoscopic physical theory research shows that the TE material with the low-dimensional thin film structure has a higher ZT value than other bulk materials under the same working condition.
To date, there are three typical classes of TE materials with low dimensional thin film structures: (1) quantum dot structures (quantum-dot structures) which increase the density of states at near-fermi levels by means of quantum-confinement effects (quantum-confining effects) and thus increase the conductivity of the material; (2) phonon-low-pass/electron-high-pass superlattices (phonon-blocking/electron-transmitting superlattices), which reduce the lattice thermal conductivity (kL) of materials by introducing so-called "acoustic-mismatch" between the superlattice components, unlike conventional TE alloy materials, which generally have significantly reduced carrier scattering rate, i.e. high electrical conductivity; (3) the ZT value of the material is improved by using the electron thermal effect (thermal effects in heterojunction) of the semiconductor heterojunction. Hicks and Dresslhaus propose that quantum well superlattices can greatly improve ZT values of materials, while quantum wire superlattices can even bring about a larger improvement.
To date, the main material is bismuth telluride (Bi) as an intermetallic compound of bismuth2Te3) Lead telluride (PtTe), zinc antimonide (ZnSb), germanium, iron silicide (FeSi)2) Etc., wherein especially Bi2Te3The base compound has a large ZT value at a relatively low temperature, continuously increases from room temperature to about 450K, and is a thermoelectric conversion material that is widely used at present. The research of the novel low-dimensional TE structural material has important theoretical and application values. Discovery of high ZT value materials (ZT)>4) Will initiate the technical revolution in the refrigeration industry, energy industry and semiconductor microelectronics industry. Although quantum dots or superlattice materials can obtain thermoelectric materials with more than 2 dimensionless figure of merit, the application of the thermoelectric materials is limited by factors such as complex process, high cost, difficulty in mass production and the like of the materials with similar structures for completing device manufacturing, and therefore, the development of thermoelectric devices with micro-nano structures is likely to be more practical for the industrial application of thermoelectric materials(ii) a pathway. In the conventional structure of a planar bismuth telluride-based TE generator, a bismuth telluride-based thin film is typically suspended over a cavity to cut off a bypass. Although the cavity ensures the temperature difference between the two ends of the film, the structure weakens the mechanical strength of the device and greatly increases the manufacturing cost.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a manufacturing method of a planar bismuth telluride based thin film thermoelectric module, the thermoelectric module and a thermoelectric generator, and the technical scheme is as follows:
in one aspect, the invention provides a method for manufacturing a planar bismuth telluride-based thin film thermoelectric module, which comprises the following steps:
s1, depositing a silicon dioxide film layer on the heat sink substrate;
s2, preparing a plurality of metal strips arranged at intervals on the silicon dioxide film layer;
s3, alternately depositing a P-type bismuth telluride-based film and an N-type bismuth telluride-based film on the upper surface of the silicon dioxide film layer between different metal strips, so that the P-type bismuth telluride-based film is deposited on one side of each metal strip, and the N-type bismuth telluride-based film is deposited on the other side of each metal strip, and obtaining a first semi-finished product;
s4, coating photoresist on the upper surface of the first semi-finished product, removing the photoresist on part of the metal strips, and enabling the metal strips with the photoresist removed and the metal strips without the photoresist removed to be alternately arranged;
s5, depositing a metal layer on the metal strip with the photoresist removed to obtain a second semi-finished product;
s6, coating photoresist on the upper surface of the second semi-finished product, and removing the photoresist on the metal layer deposited in the step S5;
and S7, depositing a heat conduction insulating layer on the metal layer with the photoresist removed.
Further, after the step of S7, removing the thermal insulation layer deposited outside the metal layer is further included.
Further, step S1 is preceded by: and (3) carrying out micro-arc oxidation treatment on the upper surface and the lower surface of the heat sink substrate to obtain a ceramic oxide layer, wherein the thickness range of the ceramic oxide layer is 5-15 mu m.
Further, the metal belt has a thickness ranging from 10 to 30 μm, a length ranging from 15 to 30mm, and a width ranging from 0.8 to 1.2 μm; the thickness ranges of the P-type bismuth telluride-based thin film and the N-type bismuth telluride-based thin film are both 30-80nm, the length ranges are both 0.8-1.2 mu m, and the width ranges are both 0.6-0.8 mu m.
Further, the thickness range of the silicon dioxide film layer deposited in the step S1 is 80-120 μm, and the silicon dioxide film layer is obtained by rapidly depositing an amorphous silicon film by a PECVD method and then oxidizing the amorphous silicon film by wet oxygen at high temperature; the thickness of the photoresist coated in the step S4 and the thickness of the photoresist coated in the step S6 are both 50-100 μm; the thickness of the metal layer deposited in the step S5 is in the range of 50-100 mu m; the thickness of the heat conductive insulating layer in the step S7 is in the range of 50 to 100 μm, and the heat conductive insulating layer is made of aluminum nitride.
On the other hand, the invention provides a planar bismuth telluride-based thin film thermoelectric module, which comprises a heat sink substrate, a silicon dioxide film layer, a plurality of first metal strips, a plurality of second metal strips, a bismuth telluride-based thin film, a photoresist and a heat conduction insulating layer, wherein the silicon dioxide film layer is arranged on the upper surface of the heat sink substrate, and the first metal strips and the second metal strips are alternately arranged on the upper surface of the silicon dioxide film layer at intervals; the first metal band and the second metal band which are adjacent are connected and conducted through a bismuth telluride-based film deposited on the silicon dioxide film layer, the bismuth telluride-based film comprises a P-type bismuth telluride-based film and an N-type bismuth telluride-based film, the two sides of the first metal band and the second metal band are distributed with different types of bismuth telluride-based films, and one or more bismuth telluride-based films of the same type are distributed between the first metal band and the second metal band which are adjacent;
the surface of the second metal strap is covered by the heat conduction insulating layer, the surface except the surface covered by the heat conduction insulating layer is covered by the photoresist, and the height of the heat conduction insulating layer is larger than that of the photoresist.
Furthermore, the adjacent first metal strips and the second metal strips are arranged at equal intervals, the width of each first metal strip is the same as that of each second metal strip, and the lengths of the P-type bismuth telluride-based film and the N-type bismuth telluride-based film are both equal to the distance between the adjacent first metal strips and the adjacent second metal strips.
Further, the thickness of the second metal strip is not less than that of the first metal strip, the thickness of the first metal strip is in the range of 10-30 μm, the length of the first metal strip and the length of the second metal strip are both in the range of 15-30mm, the width of the first metal strip and the width of the second metal strip are both in the range of 0.8-1.2 μm, the first metal strip and the second metal strip are made of the same or different materials, and the first metal strip and the second metal strip are made of aluminum, gold or silver.
Further, the P-type bismuth telluride-based thin films and the N-type bismuth telluride-based thin films are alternately arranged on the upper surface of the silicon dioxide film layer in rows;
and the distance between the plurality of bismuth telluride-based films of the same type between the adjacent first metal strips and the second metal strips in the longitudinal direction is equal to the width of the bismuth telluride-based films of the same type.
In yet another aspect, the invention provides a thermoelectric generator comprising the planar bismuth telluride-based thin film thermoelectric module.
The technical scheme provided by the invention has the following beneficial effects:
a. by utilizing the MEMS micromachining technology and the film deposition technology, the planar bismuth telluride-based film thermoelectric module and the thermoelectric generator have good expansibility;
b. the length of the bismuth telluride-NW is shortened to a submicron scale, so that the thermoelectric power density is effectively improved;
c. the method is suitable for synthesis and preparation of planar thin film TE generators of various material systems, and has strong applicability;
d. the application range is wide, and the method can be widely applied to the fields of portable, wearable and distributed sensor network systems and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a cross-sectional view of a planar bismuth telluride-based thin film thermoelectric generator according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a top layer structure of a planar bismuth telluride-based thin film thermoelectric generator provided in an embodiment of the present invention;
fig. 3 is a structural diagram of a planar bismuth telluride-based thin film thermoelectric generator unit according to an embodiment of the present invention.
Wherein the reference numerals include: the manufacturing method comprises the following steps of 1-heat sink substrate, 2-silicon dioxide film layer, 3-first metal strip, 4-second metal strip, 5-P type bismuth telluride base film, 6-N type bismuth telluride base film, 7-heat conduction insulating layer and 8-photoresist.
Detailed Description
In order to make the technical solutions of the present invention better understood and more clearly understood by those skilled in the art, the technical solutions of the embodiments of the present invention will be described below in detail and completely with reference to the accompanying drawings. It should be noted that the implementations not shown or described in the drawings are in a form known to those of ordinary skill in the art. Additionally, while exemplifications of parameters including particular values may be provided herein, it is to be understood that the parameters need not be exactly equal to the respective values, but may be approximated to the respective values within acceptable error margins or design constraints. It is to be understood that the described embodiments are merely exemplary of a portion of the invention and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this invention, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In one embodiment of the present invention, there is provided a method for manufacturing a planar bismuth telluride-based thin film thermoelectric module, comprising the steps of:
s1, depositing a silicon dioxide film layer on the heat sink substrate;
s2, preparing a plurality of metal strips arranged at intervals on the silicon dioxide film layer;
s3, alternately depositing a P-type bismuth telluride-based film and an N-type bismuth telluride-based film on the upper surface of the silicon dioxide film layer between different metal strips, so that the P-type bismuth telluride-based film is deposited on one side of each metal strip, and the N-type bismuth telluride-based film is deposited on the other side of each metal strip, and obtaining a first semi-finished product;
s4, coating photoresist on the upper surface of the first semi-finished product, removing the photoresist on part of the metal strips, and enabling the metal strips with the photoresist removed and the metal strips without the photoresist removed to be alternately arranged;
s5, depositing a metal layer on the metal strip with the photoresist removed to obtain a second semi-finished product;
s6, coating photoresist on the upper surface of the second semi-finished product, and removing the photoresist on the metal layer deposited in the step S5;
and S7, depositing a heat conduction insulating layer on the metal layer with the photoresist removed.
Wherein, step S1 is preceded by: micro-arc oxidation treatment is carried out on the upper surface and the lower surface of the heat sink substrate to obtain a ceramic oxide layer, and the thickness range of the ceramic oxide layer is 5-15 mu m; after the step of S7, removing the thermal insulation layer deposited outside the metal layer, specifically removing the excess thermal insulation layer by electron beam evaporation;
specifically, the thickness of the silicon dioxide film layer deposited in the step S1 is in the range of 80-120 μm, and the silicon dioxide film layer is obtained by quickly depositing an amorphous silicon film with a loose structure by adopting a PECVD method and then oxidizing the amorphous silicon film by wet oxygen at high temperature, wherein the density of the amorphous silicon film is less than 2.2g/cm3(ii) a Prepared in step S2The thickness of the metal belt is 10-30 μm, preferably 20 μm, the length is 15-30mm, preferably 20mm, and the width is 0.8-1.2 μm, preferably 1 μm; the thickness ranges of the P-type bismuth telluride-based thin film and the N-type bismuth telluride-based thin film deposited in the step S3 are both 30-80nm, preferably 50nm, the length ranges are both 0.8-1.2 μm, preferably 1 μm, the width ranges are both 0.6-0.8 μm, and preferably 0.7 μm; the photoresist coated in the step S4 and the photoresist coated in the step S6 are both spin-coated by a spin coater, the thickness ranges of the photoresist and the photoresist are both 50-100 μm, and the photoresist are preferably SU8 photoresist; the thickness of the metal layer deposited in the step S5 is in the range of 50-100 mu m; the thickness range of the heat conduction insulating layer in the step S7 is 50-100 mu m, and the heat conduction insulating layer is made of aluminum nitride; in steps S3 to S7, metal strips, P-type bismuth telluride-based thin films, N-type bismuth telluride-based thin films, metal layers, and photoresists and heat conductive insulating layers are deposited and removed by using processes such as masking, electron beam evaporation, and photolithography. It should be noted that, in this embodiment, the silicon dioxide film layer deposited on the heat sink substrate is mainly used to facilitate the processes of photolithography and the like of the metal strip and the bismuth telluride-based thin film, and has certain electrical insulation and thermal insulation properties, and based on the functions of the silicon dioxide film layer, if the silicon dioxide film layer is simply replaced, the silicon dioxide film layer is also within the protection range of this embodiment, for example, the silicon dioxide film layer may be doped to form a silicon oxynitride film layer, which has similar functions to the silicon dioxide film layer, and has better electrical insulation and thermal insulation properties.
In an embodiment of the invention, the heat sink substrate is an aluminum substrate which is subjected to surface micro-arc oxidation treatment, the micro-arc oxidation can be carried out by controlling plasma electrolysis process parameters to adjust the thickness, compactness and thermal conductivity of an oxidation layer, the aluminum substrate can be replaced by a copper substrate to carry out surface micro-arc oxidation treatment according to requirements, the upper surface and the lower surface of the heat sink substrate are both ceramic oxidation layers, and the thickness range of the ceramic oxidation layers is 5-15 μm, preferably 10 μm; the material of the metal layer and the material of the metal band deposited correspondingly can be the same or different, for example, when the metal band is preferably an aluminum band, the deposited metal layer can be an aluminum layer, and can also be a gold layer or a silver layer, and a silver band or a gold band can be used to replace the aluminum band on the premise of cost permission.
In an embodiment of the present invention, a planar bismuth telluride-based thin film thermoelectric module is provided, referring to fig. 1 and 2, including a heatsink substrate 1, a silicon dioxide film layer 2, a plurality of first metal strips 3, a plurality of second metal strips 4, a bismuth telluride-based thin film, a photoresist 8, and a heat conducting insulating layer 7; the heat sink substrate 1 is an aluminum substrate or a copper substrate, preferably an aluminum substrate; the silicon dioxide film layer 2 is arranged on the upper surface of the heat sink substrate 1; the first metal strips 3 and the second metal strips 4 are alternately arranged on the upper surface of the silicon dioxide film layer 2 at intervals, the first metal strips 3 and the second metal strips 4 are made of the same or different materials, the first metal strips 3 and the second metal strips 4 are made of aluminum, gold or silver, and the first metal strips 3 and the second metal strips 4 are preferably aluminum strips for economic reasons; the first metal band 3 and the second metal band 4 which are adjacent are connected and conducted through a bismuth telluride-based film deposited on the silicon dioxide film layer 2, the bismuth telluride-based film comprises a P-type bismuth telluride-based film 5 and an N-type bismuth telluride-based film 6, the P-type bismuth telluride-based film 5 and the N-type bismuth telluride-based film 6 are thermoelectric materials with opposite Seebeck coefficients and deposited in the plane heat flow transmission direction, different types of bismuth telluride-based films are distributed on two sides of the first metal band 3 and the second metal band 4, and one or more bismuth telluride-based films with the same type are distributed between the first metal band 3 and the second metal band 4 which are adjacent;
the surface of the second metal strip 4 is covered by the heat conductive and insulating layer 7, preferably made of aluminum nitride, which serves as a heat source interface for heat injection, except that the surface covered by the heat conductive and insulating layer 7 is covered by the photoresist 8, and the height of the heat conductive and insulating layer 7 is greater than the height of the photoresist 8.
In one embodiment of the present invention, the adjacent first metal strips 3 and the second metal strips 4 are arranged at equal intervals, the width of the first metal strips 3 is the same as that of the second metal strips 4, the thickness of the second metal strips 4 is not less than that of the first metal strips 3, preferably, the thickness of the second metal strips 4 is 60 μm greater than that of the first metal strips 3, the thickness of the first metal strips 3 is 10-30 μm, the length of each of the first metal strips 3 and the second metal strips 4 ranges from 15-30mm, preferably 20mm, and the width ranges from 0.8-1.2 μm, preferably 1 μm;
the P-type bismuth telluride-based thin films 5 and the N-type bismuth telluride-based thin films 6 are arranged on the upper surface of the silicon dioxide film layer 2 in a staggered and spaced manner, the lengths of the P-type bismuth telluride-based thin films 5 and the N-type bismuth telluride-based thin films 6 are equal to the distance between the adjacent first metal belt 3 and the second metal belt 4, and the longitudinal distance between the plurality of same-type bismuth telluride-based thin films between the adjacent first metal belt 3 and the second metal belt 4 is equal to the width of the same-type bismuth telluride-based thin films.
In one embodiment of the invention, the length and width of the P-type bismuth telluride-based thin film and the N-type bismuth telluride-based thin film can be reduced to less than 100nm on a processing platform with higher resolution, so that higher thermoelectric material performance and energy conversion efficiency are obtained; the cooperative control among the film size parameters in steps S1 to S5 can modulate the heat flow transport and current transport characteristics to obtain the highest electric transmission performance and the lowest heat transfer performance, the process flow is also suitable for the preparation of a gradient thermoelectric material energy conversion TE planar thin film generator, it should be noted that the manufacturing method of this embodiment is also suitable for the preparation of short planar thin film thermoelectric material TE generators of different components and without cavity structures, the bismuth telluride-based thin film in this embodiment can be replaced by similar high-quality thermoelectric materials such as lead telluride-based, silicon-based, and these equivalent replaced materials are also within the protection scope of this embodiment.
In one embodiment of the invention, a thermoelectric generator is provided comprising a planar bismuth telluride-based thin film thermoelectric module as described above.
In an embodiment of the present invention, referring to fig. 3, the second metal strip 4 directly contacts with a heat source to perform heat transfer through a heat conducting insulating layer 7 on the surface thereof, so as to form a high temperature end at the bottom thereof, the first metal strip 3 forms a low temperature end at the bottom thereof through heat transfer of a cold source, the first metal strip 3 is connected with the second metal strip 4 at one side thereof through a P-type bismuth telluride-based thin film 5, a temperature difference occurs at both ends of the P-type bismuth telluride-based thin film 5, referring to fig. 2, a bismuth telluride-based thin film generator without a cavity structure, as shown by a thick arrow, heat flow is perpendicular to a silicon substrate, as shown by a thin arrow, heat flux forms a steep temperature gradient in the bismuth telluride-based thin film, a steeper temperature gradient can be obtained by using a shorter bismuth telluride-based thin film generator array, and a potential difference is formed by carriers on the P-type bismuth telluride-based thin film 5 moving from the high temperature end to the low, the potential of the first metal strip 3 is smaller than that of the second metal strip 4 connected with the same P-type bismuth telluride based film 5, similarly, the first metal strip 3 is connected with the second metal strip 4 on the other side through the N-type bismuth telluride based film 6, a potential difference is also formed at two ends of the N-type bismuth telluride based film 6, but because the sign of the seebeck coefficient of the N-type bismuth telluride based film 6 is opposite to that of the P-type bismuth telluride based film 5, the potential of the first metal strip 3 is higher than that of the second metal strip 4 connected with the same N-type bismuth telluride based film 6, the currents formed by the two potential differences are in the same direction, so that a larger potential difference exists between the second metal strips 4 at two ends of the first metal strip 3, a plurality of bismuth telluride based films exist between the adjacent first metal strips 3 and the second metal strips 4, and a plurality of groups of the first metal strips 3 and the second metal strips 4 exist, a further developed potential difference is finally obtained in order to improve the generation of higher power. It should be noted that the seebeck effect belongs to the prior art, the cause of the seebeck effect can be simply explained as that the current carriers in the conductor move from the hot end to the cold end under the temperature gradient and are accumulated at the cold end, so that a potential difference is formed inside the material, a reverse charge flow is generated under the action of the potential difference, when the thermally moving charge flow and an internal electric field reach dynamic balance, stable thermoelectric electromotive force is formed at two ends of the semiconductor, and two current carriers, namely electrons and holes, exist in the semiconductor.
The invention relates to a design method of a semiconductor device, in particular to a design method of a semiconductor thermoelectric generator, and specifically relates to a design and preparation method of a planar bismuth telluride-based thin film Thermoelectric (TE) generator designed and prepared by combining an MEMS micro-processing technology and a thin film deposition technology. In order to solve the problems of low efficiency, large temperature difference, difficult realization of a high-energy density heat source and the like of the conventional semiconductor thermoelectric device, the invention provides a preparation method of a planar bismuth telluride-based thin film Thermoelectric (TE) generator, so as to overcome the defects of the prior art; the invention obtains an effective temperature gradient maintaining structure through novel heat source and heat sink material selection and structure design, and then deposits the P type/N type thermoelectric material in the plane heat flow transmission direction by utilizing the property of opposite Seebeck coefficient signs of the P type/N type thermoelectric material to obtain the power density of 20mW/cm at the temperature difference of 5 DEG C2Thermoelectric (TE) generators.
The invention provides a manufacturing method of a planar bismuth telluride-based thin film thermoelectric module, the thermoelectric module and a thermoelectric generator. The novel design concept utilizes the steep temperature gradient formed near the main heat flow, and the power density of the generator is more expandable compared with the traditional planar bismuth telluride-based thermoelectric generator by shortening the bismuth telluride-NW to submicron length. The thermoelectric device for heat flow and current transmission parallel to the thin film plane has great promotion on improving the performance of the semiconductor thermoelectric device, and can be widely applied to the fields of portable, wearable and distributed sensor network systems and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A manufacturing method of a planar bismuth telluride-based thin film thermoelectric module is characterized by comprising the following steps:
s1, depositing a silicon dioxide film layer on the heat sink substrate;
s2, preparing a plurality of metal strips arranged at intervals on the silicon dioxide film layer;
s3, alternately depositing a P-type bismuth telluride-based film and an N-type bismuth telluride-based film on the upper surface of the silicon dioxide film layer between different metal strips, so that the P-type bismuth telluride-based film is deposited on one side of each metal strip, and the N-type bismuth telluride-based film is deposited on the other side of each metal strip, and obtaining a first semi-finished product;
s4, coating photoresist on the upper surface of the first semi-finished product, removing the photoresist on part of the metal strips, and enabling the metal strips with the photoresist removed and the metal strips without the photoresist removed to be alternately arranged;
s5, depositing a metal layer on the metal strip with the photoresist removed to obtain a second semi-finished product;
s6, coating photoresist on the upper surface of the second semi-finished product, and removing the photoresist on the metal layer deposited in the step S5;
and S7, depositing a heat conduction insulating layer on the metal layer with the photoresist removed.
2. The method of claim 1, wherein after step S7, the method further comprises removing the thermally conductive and insulating layer deposited on the metal layer.
3. The method of manufacturing a planar bismuth telluride-based thin film thermoelectric module as claimed in claim 1, wherein step S1 is preceded by the steps of: and (3) carrying out micro-arc oxidation treatment on the upper surface and the lower surface of the heat sink substrate to obtain a ceramic oxide layer, wherein the thickness range of the ceramic oxide layer is 5-15 mu m.
4. The method of manufacturing a planar bismuth telluride-based thin film thermoelectric module as claimed in claim 1, wherein the metal tape has a thickness in the range of 10 to 30 μm, a length in the range of 15 to 30mm, and a width in the range of 0.8 to 1.2 μm; the thickness ranges of the P-type bismuth telluride-based thin film and the N-type bismuth telluride-based thin film are both 30-80nm, the length ranges are both 0.8-1.2 mu m, and the width ranges are both 0.6-0.8 mu m.
5. The method for manufacturing a planar bismuth telluride-based thin film thermoelectric module as claimed in claim 1, wherein the thickness of the silicon dioxide film layer deposited in the step S1 is 80-120 μm, and the amorphous silicon film is rapidly deposited by a PECVD method and then oxidized at high temperature by wet oxygen to obtain the planar bismuth telluride-based thin film thermoelectric module; the thickness of the photoresist coated in the step S4 and the thickness of the photoresist coated in the step S6 are both 50-100 μm; the thickness of the metal layer deposited in the step S5 is in the range of 50-100 mu m; the thickness of the heat conductive insulating layer in the step S7 is in the range of 50 to 100 μm, and the heat conductive insulating layer is made of aluminum nitride.
6. The planar bismuth telluride-based thin film thermoelectric module is characterized by comprising a heat sink substrate (1), a silicon dioxide film layer (2), a plurality of first metal strips (3), a plurality of second metal strips (4), a bismuth telluride-based thin film, a photoresist (8) and a heat conduction insulating layer (7), wherein the silicon dioxide film layer (2) is arranged on the upper surface of the heat sink substrate (1), and the first metal strips (3) and the second metal strips (4) are alternately arranged on the upper surface of the silicon dioxide film layer (2) at intervals; the first metal belt (3) and the second metal belt (4) which are adjacent are connected and conducted through a bismuth telluride-based film deposited on the silicon dioxide film layer (2), the bismuth telluride-based film comprises a P-type bismuth telluride-based film (5) and an N-type bismuth telluride-based film (6), different types of bismuth telluride-based films are distributed on two sides of the first metal belt (3) and two sides of the second metal belt (4), and one or more same types of bismuth telluride-based films are distributed between the first metal belt (3) and the second metal belt (4) which are adjacent;
the surface of the second metal strap (4) is covered by the heat conduction insulating layer (7), the surface covered by the heat conduction insulating layer (7) is covered by the photoresist (8), and the height of the heat conduction insulating layer (7) is larger than that of the photoresist (8).
7. The planar bismuth telluride-based thin film thermoelectric module according to claim 6, wherein the first metal strip (3) and the second metal strip (4) are arranged at equal intervals, the width of the first metal strip (3) is the same as that of the second metal strip (4), and the length of the P-type bismuth telluride-based thin film (5) and the length of the N-type bismuth telluride-based thin film (6) are both equal to the distance between the first metal strip (3) and the second metal strip (4).
8. The planar bismuth telluride-based thin film thermoelectric module according to claim 7, wherein the thickness of the second metal strip (4) is not less than the thickness of the first metal strip (3), the thickness of the first metal strip (3) is in the range of 10 to 30 μm, the length of each of the first metal strip (3) and the second metal strip (4) is in the range of 15 to 30mm, the width of each of the first metal strip and the second metal strip is in the range of 0.8 to 1.2 μm, the first metal strip (3) and the second metal strip (4) are made of the same or different material, and the first metal strip (3) and the second metal strip (4) are made of aluminum, gold, or silver.
9. The planar bismuth telluride-based thin film thermoelectric module as claimed in claim 8, wherein the P-type bismuth telluride-based thin films (5) and the N-type bismuth telluride-based thin films (6) are alternately arranged in a row on the upper surface of the silicon dioxide film layer (2);
the distance between the first metal belt (3) and the second metal belt (4) which are adjacent to each other in the longitudinal direction of the plurality of bismuth telluride-based films of the same type is equal to the width of the bismuth telluride-based films of the same type.
10. A thermoelectric generator comprising a planar bismuth telluride-based thin film thermoelectric module as claimed in claims 6 to 9.
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