CN106098925A - A kind of ceramic membrane does the manufacture method of the thin film thermoelectric semiconductor device of base material - Google Patents
A kind of ceramic membrane does the manufacture method of the thin film thermoelectric semiconductor device of base material Download PDFInfo
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Classifications
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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
-
- 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
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention provides a kind of method using ceramic membrane base material to manufacture resistant to elevated temperatures thin film thermoelectric semiconductor device, first by the p-type heavily mixed and N-type thermoelectric semiconductor material, makes thermoelectric semiconductor powder body material slurry；The ceramic size of preparation simultaneously and the physical parameter similar properties such as specific thermoelectric semiconductor material solid state crystallization characteristic, thermal coefficient of expansion and inner conductive material paste, the ceramic membrane of demand thickness is made by casting technique, and ceramic membrane is cut into the size of regulation, shape (5), then on ceramic membrane, print inner conductive electrode (6) and N-type (8) and p-type (9) thermoelectric semiconductor material, through isostatic pressed, binder removal and sintering process, produce the thin film thermoelectric semiconductor device making base material of ceramic membrane.
Description
Technical field
The present invention relates to the manufacturing technology of novel thin film thermoelectric semiconductor device.
Background technology
The basic structure of Conventional thermoelectric semiconductor device is shown in Fig. 1, N-type thermoelectric semiconductor elements (1) and p-type thermoelectricity partly lead
Body member (2), by conductor (3), (4), is electrically coupled connection by N-type, p-type thermoelectric semiconductor elements, constitute one common
Refrigeration thermoelectric pile, is generally referred to as a pair thermocouple by a pair N-type, the thermoelectric pile of p-type thermoelectric semiconductor elements composition.
The thermocouple element crystal grain of Conventional thermoelectric semiconductor device, be cleaved with the semi-conducting material of bulk, be polished into spy
Sizing, is then made by the welding of said structure order, the distance in the cold end of finished product thermo-electric device and hot junction, big according to power
Little, substantially between 2-5 millimeter, the basic structure of thermo-electric device and operation principle, determine thermoelectric semiconductor device in refrigeration
During operating mode work, two work surfaces ((3) and (4) of Fig. 1) up and down of device, one side heats, and one side refrigeration is (by flowing through P/N heat
The sense of current of electricity semiconductor element determines), due to the physical characteristic that thermoelectric semiconductor material is intrinsic, such as: the heat of material
The coefficient of conductivity, the parameter such as specific insulation of material, result in the heat exchange mechanism within thermoelectric semiconductor elements is difficult to overcome,
The internal heat exchange that these intrinsic physical characteristics produce, counteracts heating and making of thermoelectric semiconductor material self-characteristic generation
Cold performance.
In other words, the cold end of the outside that Conventional thermoelectric semiconductor device shows and hot junction (generally have 2-5 millimeter away from
From) temperature difference index be that thermoelectric element materials internal heat exchange (hot and cold counteracting) balances later result, this also be restriction heat
The main cause of electrical part overall performance, manages to reduce the internal heat exchange impact on thermo-electric device performance indications, is whole heat
The emphasis direction that thermoelectric material is studied by electricity semicon industry, such as, changes the crystallite dimension of thermoelectric material, changes thermoelectric material
Phon scattering mechanism, utilize nanotechnology change material dimension, limit material quantum tunneling effect and make nanometer
Thin film etc., is all the thermal conductivity for reducing material internal, promotes the figure of merit of thermoelectric material with this, but, it is limited by
The architectural feature of Conventional thermoelectric semiconductor device, above-mentioned effort produces little effect, and constrains the popularization application of pyroelectric technology.
Owing to using the inherent shortcoming of the Conventional thermoelectric semiconductor device of bulk making, it is difficult to promote thermo-electric device further
Overall performance, industry has turned to the research of thermal electric film device research direction, and result of study shows: thin film thermoelectric materials
Comprehensive physical performance is better than bulk, is promising, but, thin-film device is just formed without a crucial restriction of industry
To be difficult to solve for growing the film substrate of semi-conducting material, problem concentrate on the temperature-resistance characteristic of thin-film material, mechanical strength,
Bond strength between dielectric strength, material etc..
Summary of the invention
The purpose of the present invention, is to provide one and uses ceramic membrane base material to manufacture resistant to elevated temperatures thin film thermoelectric semiconductor device
The method of part.
The solution of the present invention is, by the p-type heavily mixed and N-type thermoelectric semiconductor material, makes thermoelectric semiconductor powder
Body material paste；Simultaneously according to the physical characteristic that specific thermoelectric semiconductor material is relevant, prepare close the leading of physical property therewith
Plasma-based material and ceramic size；Utilize film casting technique, make the thin film with pottery as base material of demand thickness, at this ceramic thin
Print inner conductive electrode and thermoelectric semiconductor material according to design pattern layering on film, and stack according to application demand some
Layer, then use isostatic pressing process the thin film of above-mentioned lamination is pressed into one, through technical processs such as binder removal, sintering, make with
Ceramic membrane is the thin film thermoelectric semiconductor device of base material.
The enforcement of the solution of the present invention is realized by following technology path: first, according to selected thermoelectricity half
The physical parameters such as the solid state crystallization characteristic of conductor material, thermal coefficient of expansion, select matched ceramic composition, and the present invention is led to
Cross the proportioning selecting the materials such as the main crystal phase material of ceramic material, property-modifying additive, sintering flux, modulate and can meet and heat
The ceramic powder material that electricity semi-conducting material burns altogether.
The concrete manufacturing process of ceramic membrane that the present invention provides is as follows: ceramic membrane base material, select Al O or
BaTiO powder uses in BaO, TiO, MgO, CaO, MnO, SrO as the main crystal phase material of ceramic material, property-modifying additive
One or more of La O, sintering flux uses SiO, ZnO, B O, Bi O, CuO, BaO, V O, Nb
One or more in O, the percentage by weight of each component, according to principal crystalline phase 50-80wt%, property-modifying additive 0-15wt%,
Sintering flux 15-40wt% preparation.
The proportioning of above-mentioned ceramic formula is: the usage amount of main crystal phase material is: Al O: 50-70 wt%；BaTiO:
60-90 wt%；The usage amount of property-modifying additive is: BaO:0-3 wt%, TiO: 0-3 wt%, MgO:0-5 wt%, CaO:0-3
Wt%, MnO:0-3 wt%, SrO:0-5 wt%, La O: 0-3 wt%；The usage amount of sintering flux is: SiO: 0-30
Wt%, ZnO:0-5wt%, B O: 0-2 wt%, Bi O: 0-5 wt%, CuO:0-3 wt%, V O: 0-5 wt%, Nb
O:0-5 wt%, adjusts proportioning and the consumption of ceramic material according to the sintering temperature demand of thermoelectric semiconductor material.
In above-mentioned ceramic formula, sintering flux need in advance according to formulation ratio and after being sufficiently mixed 1000
The temperature melting of DEG C 1300 DEG C, pulverizes after chilling and is ground to submicron order powder body.
Each component material of above-mentioned preparation is uniformly mixed, through ball mill grinding to sub-micron powder, then adds height
Molecule organic adhesive such as ethyl cellulose, hydrogenated rosin resin, nitrocellulose, vistanex, polyvinyl alcohol, poly-first
One or more in base styrene, polymethyl methacrylate etc., and terpineol, acetic acid butyl carbitol, ethylene glycol ethyl ethers
One or more in ether acetate, tributyl citrate, dibutyl phthalate, lecithin equal solvent, ground mixing
Make ceramic size, make the ceramic membrane of demand thickness (20 μ---100 μ) through casting technique.
Secondly, the inner conductive electrode metal that the ceramic material with above-mentioned formula and thermoelectric semiconductor material match is selected
Material, by adding the material such as sintering aid and dispersant, ground modulating can meet and thermoelectric semiconductor material burns altogether
Inner conductive electrode powder body material.
The inner conductive electrode that the present invention provides uses Ni-based or cuprio or silver base conductive metal (alloy) powder, adds
Entering sintering aid and surfactant such as toluene, ethanol, Ketohexamethylene etc., the percentage by weight of each component, according to conducting metal
Powder 60-90wt%, sintering flux 5-20wt%, surfactant are 0.3-10 wt % configuration, add organic carrier (bonding agent
And solvent) technique such as the most ground, dispersion, make electrocondution slurry, for the printing of inner conductive electrode.
3rd, the thermoelectric semiconductor material that the present invention provides uses p-type and the thermoelectric semiconductor material of N-type conduction type
The resistant to elevated temperatures thermoelectric semiconductor material powder body such as Si or SiGe alloy or PbTe, PbSe or β-FeSi, are separately added into
Sintering aid and surfactant, the percentage by weight of each component, according to thermoelectric semiconductor material 70-90wt%, sintering flux
2-10wt%, surfactant are 0.3-10 wt % preparation, and addition organic carrier (bonding agent and solvent) is the most ground, makes
P-type and N-type thermoelectric semiconductor material slurry, for the printing of thermoelectric semiconductor material.
Aforementioned p-type and the thermoelectric semiconductor material of N-type conduction type, the course of processing is required to heavily mix, carrier concentration
It is greater than more than 10.
Above-mentioned ceramic size, electrocondution slurry and the preparation of thermoelectric semiconductor material slurry, add organic carrier (bonding agent and
Solvent) time, solid constituent and liquid component proportioning are 65:35%.
The solution implementation process signal of the present invention, based on above-mentioned ceramic base material thin film, is first according to design and wants
Ask and curtain coating ceramic membrane is cut into the size of regulation, shape (5), see schematic diagram Fig. 2；Then at ceramic substrate surface with above-mentioned
Electrocondution slurry prints inner conductive electrode (6), sees Fig. 3；N is printed respectively with above-mentioned thermoelectric semiconductor material slurry again after drying
Type (8) and p-type (9) thermoelectric semiconductor material, be shown in Fig. 4；The flatness later in order to ensure lamination, partly leads at the thermoelectricity produced
Between body material and ceramic size (10) that around reprinting is identical with ceramic base material again, see Fig. 5, complete single thin film thermo-electric device
Making；According to step same as described above, if lamination makes dried layer, finally add one layer of ceramic membrane and close printing surface, then
Use Vacuum Package, carry out isostatic pressed solidification, after the techniques such as binder removal, high temperature sintering, making lead-in wire, encapsulation, make complete heat
Electricity semiconductor device, is shown in Fig. 6, (11), and (13) are cold end and hot junction thermal conductive surface respectively, and (12) are conduction positive and negative electrodes.
The thermoelectric semiconductor device that the method that the present invention provides makes, according to different material mixture ratios, hot junction operating temperature
Scope is: 200 DEG C--500 DEG C；Cool and heat ends temperature range: 150 DEG C---450 DEG C, much larger than current bulk device ginseng
Number.
Accompanying drawing illustrates:
Fig. 1, Conventional thermoelectric Physics of Semiconductor Devices schematic diagram；
Fig. 2, ceramic base material cast film cutting schematic diagram；
Fig. 3, ceramic membrane base material silk-screened conductive slurry schematic diagram；
Fig. 4, on the basis of Fig. 3 schematic diagram print thermoelectric semiconductor material schematic diagram；
Fig. 5, on the basis of Fig. 5, reprinting ceramic size fills and leads up gap schematic diagram；
Fig. 6, the finished product schematic diagram encapsulated.
Detailed description of the invention:
The purport of the present invention is to prepare suitable ceramic size and electrocondution slurry, meets the solid-state of relevant thermoelectric semiconductor material
Crystallization property, under close sintering process conditions, it is achieved produce thin film thermoelectric quasiconductor on resistant to elevated temperatures film substrate
Device；Being further explained present invention below in conjunction with embodiment, the content mentioned by embodiment is not to the present invention
Restriction, the different choice of material prescription, simply to concrete processing technique and the fine setting of properties of product, the enforcement to the present invention is tied
Fruit is without substantial impact.
Embodiment 1: the present embodiment selects heavily to mix the Si semi-conducting material manufacturing high temperature thermoelectric semiconductor device of p-type and N-type
Part, conductive electrode material selects Ni sill；The main crystal phase material of ceramic membrane material selects Al O；Property-modifying additive is used
BaO、TiO₂ 、MgO、CaO；Sintering flux uses the relevant slurry of SiO, ZnO, B O, Bi O different materials preparation；
Ceramic size according to one of principal crystalline phase 65wt%, property-modifying additive 5wt%(proportioning therein is: BaO:2 wt %, TiO:
0.5wt %, MgO:1.5 wt %, CaO:1 wt %)；One of sintering flux 30wt%(proportioning therein is: SiO: 18.5
Wt %, ZnO:1 wt %, B O: 10 wt %, Bi O: 0.5 wt %) preparation.
Specific implementation process is as follows: firstly the need of sintering flux material after proportioning mixes 1300 DEG C of meltings,
After chilling, material disintegrating is ground to the powder of submicron order, at preparation electrocondution slurry, thermoelectric semiconductor slurry and ceramic size
Middle use.
After ceramic size mixes according to said ratio and is ground to the granule of submicron order, add macromolecule organic adhesive
And related solvents, ground mixing is made ceramic size later, is made ceramic membrane (about 50 μ) through casting technique.
The conductive electrode of the present embodiment, is 2 according to conductive metal powder 90wt%, sintering flux 8wt%, surfactant
Wt % prepares, and adds the techniques such as organic carrier (bonding agent and solvent) the most ground, dispersion, makes electrocondution slurry, for interior
The printing of portion's conductive electrode.
Thermoelectric semiconductor material, respectively in p-type and N-type semiconductor Si powder, adds sintering aid and surfactant, respectively
The percentage by weight of component, is that 2 wt % join according to thermoelectric semiconductor material 90wt%, sintering flux 8wt%, surfactant
System, addition organic carrier (bonding agent and solvent) is the most ground, is respectively prepared p-type and N-type thermoelectric semiconductor material slurry, uses
Printing in thermoelectric semiconductor material.
By above-mentioned ceramic membrane according to design specification excision forming, see schematic diagram 2；Thin film is printed inner conductive electrode,
See Fig. 3；Print p-type and N-type thermoelectric semiconductor material the most respectively, see Fig. 4；Reprinting ceramic size keeps surface smoothness, so
After stack lower thin film, repeat said process, until it reaches design requires rear enclosed printing surface, after then carrying out Vacuum Package
Isostatic pressed solidifies, at 1000 DEG C under protection, reducing atmosphere environment after binder removal--sinter in 1200 DEG C of temperature ranges
Molding, products obtained therefrom can be 800K environmental work, and the cool and heat ends temperature difference is up to 500K.
Embodiment 2: the present embodiment selects the SiGe alloy semiconductor material heavily mixing p-type and N-type to make high temperature thermoelectric half
Conductor device, conductive electrode material selects Cu sill；The main crystal phase material of ceramic membrane material selects BaTiO；Modification adds
Add agent SiO, Al O, MgO, CaO；Sintering flux uses Nb O, ZnO, SnO, Bi O different materials to join
The relevant slurry of system；Ceramic size is according to principal crystalline phase 80wt%, property-modifying additive 5wt%, sintering flux 15wt% preparation.
Specific implementation process is as follows: firstly the need of sintering flux material after proportioning mixes 1050 DEG C of meltings,
After chilling, material disintegrating is ground to the powder of submicron order, at preparation electrocondution slurry, thermoelectric semiconductor slurry and ceramic size
Middle use.
After ceramic size mixes according to said ratio and is ground to the granule of submicron order, add macromolecule organic adhesive
And related solvents, ground mixing is made ceramic size later, is made ceramic membrane (about 50 μ) through casting technique.
The conductive electrode of the present embodiment, is 2 according to conductive metal powder 90wt%, sintering flux 8wt%, surfactant
Wt % prepares, and adds the techniques such as organic carrier (bonding agent and solvent) the most ground, dispersion, makes electrocondution slurry, for interior
The printing of portion's conductive electrode.
The thermoelectric semiconductor material of the present embodiment, respectively in p-type and N-type semiconductor SiGe alloyed powder, adds sintering aid
And surfactant, the percentage by weight of each component, live according to thermoelectric semiconductor material 90wt%, sintering flux 8wt%, surface
Property agent be 2 wt % preparations, it is the most ground to add organic carrier (bonding agent and solvent), is respectively prepared p-type and N-type thermoelectricity half
Conductor material paste, for the printing of thermoelectric semiconductor material.
By above-mentioned ceramic membrane according to design specification excision forming, see schematic diagram 2；Thin film is printed inner conductive electrode,
See Fig. 3；Print p-type and N-type thermoelectric semiconductor material the most respectively, see Fig. 4；Reprinting ceramic size keeps surface smoothness, so
After stack lower thin film, repeat said process, until it reaches design requires rear enclosed printing surface, after then carrying out Vacuum Package
Carry out isostatic pressed solidification, at 800 DEG C under protective atmosphere environment after binder removal--sinter in 950 DEG C of temperature ranges
Type, products obtained therefrom can be 600K environmental work, and the cool and heat ends temperature difference is up to 300K.
Claims (10)
1. make a manufacture method for the thin film thermoelectric semiconductor device of base material of ceramic membrane, it is characterized in that: make a kind of with
Pottery is the thin film of base material, and layering prints inner conductive electrode material and thermoelectric semiconductor material, and if stacking on the thin film
Dried layer, is pressed into one with isostatic pressed by the thin film of above-mentioned lamination, through technical processs such as binder removal, sintering, makes with ceramic membrane
Thin film thermoelectric semiconductor device for base material.
Ceramic membrane the most according to claim 1 is the thin film thermoelectric semiconductor device of base material, it is characterised in that: described heat
Electricity semi-conducting material be the thermoelectric semiconductor material Si of the p-type heavily mixed and N-type conduction type or SiGe alloy or PbTe,
PbSe or β-FeSi etc., carrier concentration is more than 10.
Thermoelectric semiconductor material the most according to claim 2, it is characterised in that: described p-type and N-type semiconductor material divide
Not Jia Ru sintering aid and surfactant, the percentage by weight of each component: thermoelectric semiconductor material: 70-90wt%, sintering help
Flux: 2-10wt%, surfactant be: 0.3-10 wt %；Grind after adding organic carrier, make p-type and N-type thermoelectricity half
Conductor material paste, for the printing of thermoelectric semiconductor material.
Ceramic membrane the most according to claim 1 is the thin film thermoelectric semiconductor device of base material, it is characterised in that: in described
Portion's conductive electrode uses Ni-based or cuprio or silver base conductive metal dust, by adding sintering aid, surfactant etc.
Material, is modulated into inner conductive electrode powder body material, and the percentage by weight of each component: conductive metal powder: 60-90wt%, sintering help
Flux: 5-20wt%, surfactant be: 0.3-10 wt %；Grind after adding organic carrier, make electrocondution slurry, be used for
The printing of inner conductive electrode.
Ceramic membrane the most according to claim 1 is the thin film thermoelectric semiconductor device of base material, it is characterised in that: described pottery
Porcelain thin film is by the proportioning of the materials such as the main crystal phase material of ceramic material, property-modifying additive, sintering flux, modulation and thermoelectricity half
The ceramic powder material that conductor material burns altogether, grinds after adding organic carrier, makes ceramic size, make pottery through casting technique
Porcelain thin film, the thickness of described ceramic membrane is 20 μ--100 μ (0.02mm 0.1mm).
Ceramic membrane base material the most according to claim 5, it is characterised in that: the main crystal phase material of described ceramic material is Al
O or BaTiO powder, described property-modifying additive is one or more in BaO, TiO, MgO, CaO, MnO, SrO, institute
Stating sintering flux is one or more in SiO, ZnO, B O, Bi O, CuO, BaO, V O, Nb O,
The percentage by weight proportioning of each component, principal crystalline phase is: 50-80wt%, property-modifying additive be: 0-15wt%, sintering flux be:
15-40wt%。
Ceramic membrane base material the most according to claim 5, it is characterised in that: the formulation ratio consumption of described ceramic material
It is: the usage amount of main crystal phase material is: Al O: 50-70 wt%, BaTiO: 60-90 wt%；The use of property-modifying additive
Amount is: BaO:0-3 wt%, TiO: 0-3 wt%, MgO:0-5 wt%, CaO:0-3 wt%, MnO:0-3 wt%, SrO:0-5
wt%；The usage amount of sintering flux is: SiO: 0-30 wt%, ZnO:0-5wt%, B O: 0-2 wt%, Bi O: 0-5
Wt%, CuO:0-3 wt%, V O: 0-5 wt%, Nb O:0-5 wt%.
8., according to the sintering flux described in claim 3, claim 4, claim 5, it is characterized in that: according to claim
After 6 are carried sintering flux formulation ratio and are sufficiently mixed, through 1000 DEG C--1300 DEG C of meltings, it is ground to sub-micro after chilling
The powder body of meter level.
9. according to the organic carrier described in claim 3, claim 4, claim 5, it is characterized in that: organic viscous by macromolecule
Connecing agent and solvent is constituted, wherein bonding agent is: ethyl cellulose, hydrogenated rosin resin, nitrocellulose, vistanex, poly-second
One or more in alkene ethanol, polymethylstyrene, polymethyl methacrylate etc.；Solvent is terpineol, acetic acid butyl card
Must one or more in alcohol, ethylene glycol ether acetate, tributyl citrate, dibutyl phthalate, lecithin etc..
10. according to the slurry described in claim 3, claim 4, claim 5, it is characterized in that: when adding organic carrier, Gu
Body composition and liquid component proportioning are 65%:35%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192851A (en) * | 2018-08-29 | 2019-01-11 | 武汉理工大学 | A method of addition sintering aid prepares excellent electronic transport performance flexibility thermoelectricity thick-film material |
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