CN107093663A - The ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable and preparation method and thermo-electric device unit - Google Patents
The ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable and preparation method and thermo-electric device unit Download PDFInfo
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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
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
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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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
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Abstract
The present invention relates to a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable and preparation method and thermo-electric device unit, the film is formed by multilayer material lontitudinal series.Being composed in series the layers of material of film can use the one or more in following methods that film is made, including liquid phase method, physical vapor method, electrochemical process etc., such as magnetron sputtering, electron beam evaporation or molecular beam epitaxy deposition film in physical vapor method, wherein every layer can use above-mentioned one of which film preparation mode simultaneously, and two or more film preparation modes can be also used respectively.Thermo-electric device unit includes the substrate (1) being sequentially overlapped, hearth electrode (2), ultra-thin longitudinal multilayer cascaded structure thermal electric film post (3), top electrode (4).Compared with prior art, the present invention ultra-thin longitudinal multilayer cascaded structure thermal electric film structure and performance editable, the thermo-electric device size being made and deadweight are smaller, and relative to the block thermo-electric device of body structure, performance boost space is bigger, and application is wider.
Description
Technical field
The present invention relates to thermal electric film technical field, the ultra-thin longitudinal multilayer cascaded structure thermoelectricity of editable is related in particular to
Film and preparation method and the thermo-electric device unit containing longitudinal multilayer cascaded structure thermal electric film.
Background technology
Thermoelectric material can utilize solid interior carrier moving, realize the directly mutually phase transformation of heat energy and electric energy, effectively will
Hot-cast socket, into electric energy, is a kind of all solid state energy conversion regime, without chemical reaction or fluid media (medium).Thermo-electric device is often by two kinds
Different types of thermoelectric material (such as P-type semiconductor and N-type semiconductor) makes column structure (P posts and N posts), and by its one end knot
Conjunction is placed under the condition of high temperature, and the other end is opened a way in low-temperature condition, due to the effect of high temperature so that the hole of temperature end and electronics are dense
Degree is different from low-temperature end, forms concentration difference, it is achieved thereby that the migration of carrier, and then electrical potential difference is realized, by many in face
Bigger voltage is obtained to P posts and the series connection of N posts.Thermo-electric device is a kind of clean energy resource process units, with movement-less part, nothing
Noise, high pollution-free, easily controllable, reliability, small volume, lightweight, conveniently moving, service life length, stable output electric energy
Etc. series of advantages.
The main evaluation index for weighing thermo-electric device conversion efficiency is the thermoelectric figure of merit (ZT values) of thermoelectric material, ZT=S2·
σ·κ-1T, wherein S represent Seebeck coefficients, and σ represents electrical conductivity, and κ represents thermal conductivity, and thermal conductivity includes electron thermal conductivity κe
With lattice thermal conductivity κl, by Wiedemann-Franz laws κe=L σ T, show electron thermal conductivity and conductance linear correlation, and right
For semiconductor, electron thermal conductivity is much smaller than lattice thermal conductivity.ZT values are bigger, and thermoelectricity capability is better.Can by ZT expression formula
Know, the approach for improving the ZT values of thermoelectric material is exactly to increase the Seebeck coefficients of material, the electrical conductivity for improving material, reduction material
The thermal conductivity of material.However, these parameters in thermoelectric material intercouple together, it is difficult to be adjusted in synchronism so that thermoelectricity
The figure of merit and conversion efficiency of thermoelectric are difficult to increase substantially.And lattice thermal conductivity is the ginseng that only one is not determined by electronic structure
Number, has relatively independent space, phon scattering is increased by introducing the methods such as point defect, crystal boundary, to reduce lattice thermal conductivity
Rate, while not influenceing or strengthening the transmission of electronics, to reach the purpose of " electron crystal-phonon glasses " passage, effectively improves ZT
Value, improves thermoelectricity capability.
Mainly manufactured at present using the thermo-electric device of comparative maturity using body processing method, thickness reaches several centimeters grades
Not, size and deadweight are larger.In order to further reduce the low-dimensional of device deadweight and lifting thermoelectrical efficiency, in recent years thermoelectric material
Change is a focus trend, is currently in the thin film thermoelectric device thickness in research also up to hundreds of microns to millimeter rank, concentrates
Still immature in single thin film, the performance of thermal electric film device is restricted to a certain extent.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of editable is ultra-thin vertical
To multilayer cascaded structure thermal electric film and preparation method and thermo-electric device unit.
The purpose of the present invention can be achieved through the following technical solutions：A kind of ultra-thin longitudinal multilayer cascaded structure of editable
Thermal electric film, it is characterised in that the film is formed by multilayer material lontitudinal series.
Thickness in described film per layer material is less than 1000nm.Ultra-thin multilayer lontitudinal series structure thermal electric film total thickness
Degree is less than 10 μm.
The layers of material that the film of lontitudinal series composition is used includes metal, oxide, semiconductor, organic matter or inorganization
Compound, during series connection, at least has a class material of thermoelectric property, i.e. thermoelectric material containing more than one.For to sum up enumerating (including
Material with thermoelectric property), metal such as Au, Ag, Cu, Pt, Pd etc..Organic matter such as conducting polymer etc., semiconductor is such as
Bi2Te3、Sb2Te3, PbTe, Si, Ge, Bi, Te, Sb, Sn, Se, Pb etc..Oxide such as SiO2、ZnO、Al2O3、In2O3、SnO2
Deng.Inorganic compound such as Skutterudite and Clathrate filling compounds etc..
Layers of material can be the cycle or aperiodic in longitudinal multilayer cascaded structure thermal electric film, if periodicity, then the cycle
For 1~1000.
It is preferred that, described film m cycle of alternately being connected by n kinds material constitutes, wherein, n and m are the integer more than 1.
Further preferably, described n is that 2, m is 2, and vertical structure alternant is A1A2A1A2。
It is preferred that, described film is composed in series by n kind material aperiodicity, and n is the integer more than 1, meanwhile, in n kind materials
Expect in aperiodicity series connection, same material may occur in which repeatedly.If m is 3, vertical structure such as A1A2A3。
In described film multilayer material lontitudinal series mode include one or more thermoelectric materials and metal, oxide,
Semiconductor or inorganic compound series connection, or connected by thermoelectric material with thermoelectric material.
In the multilayer material for constituting film, it can lead to and produce hole using preparation means control in uniform material or mix
Enter tiny impurity particle, with hole be less than 50nm for pore layer, with particle be less than 50nm for doping stratum granulosum, its
The remaining uniform material of constituent is conforming layer.Wherein pore layer, stratum granulosum can be described as functional layer again, with exciting carrier
(excitation layer) or the effect for absorbing phonon (absorbed layer).
In view of multilayer cascaded structure layer thermal electric film and interelectrode combination problem, tack coat can be added, its thickness 3~
100nm。
A kind of preparation method of the ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable, it is characterised in that be composed in series
The layers of material of film can use the one or more in following methods that film, including liquid phase method, physical vapor method, electrification is made
Such as magnetron sputtering, electron beam evaporation or molecular beam epitaxy deposition film in method etc., physical vapor method, wherein every layer can be same
When use above-mentioned one of which film preparation mode, two or more film preparation modes can be also used respectively.
The thermo-electric device unit of the described ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable is included, including is folded successively
Plus substrate, hearth electrode, ultra-thin longitudinal multilayer cascaded structure thermal electric film post, top electrode, if wherein adhesion between layers
It is weak, tack coat can be increased in interlayer.
The substrate requirements meet it is smooth, can bearing structure, insulation, such as silicon chip, sheet glass, stainless steel plate (if
It is conductive substrates, a layer insulating, such as SiO is deposited between substrate and hearth electrode2, Si3N4, AlN etc., thickness is more than 50nm), base
Base thickness degree is more than 50 μm；
The hearth electrode is placed in substrate, top electrode is placed on thermal electric film, using material such as Au, Ag, Cu, Pt etc., thick
Degree is more than 50nm；
Compared with prior art, the inventive method causes the thickness of thermal electric film device to be further thinned, and deadweight is further
Reduce, the fields such as Aerospace Satellite station, chip cooling generate electricity, automobile exhaust pipe Waste Heat Reuse generates electricity are can apply to, while design is logical
Cross the functional layer material cascaded structure of suitable longitudinal multilayer, including pore layer, stratum granulosum, conforming layer etc., wherein pore layer,
Granulosa has the effect for exciting carrier (excitation layer) or absorbing phonon (absorbed layer).Pass through different structure layer series connection shape simultaneously
Into boundary layer, strengthen phon scattering, do not influence or strengthen the transmission of electronics, to form " electron crystal-phonon glasses " passage,
Further improve thermoelectricity capability.
Brief description of the drawings
Fig. 1 is the ultra-thin longitudinal multilayer cascaded structure thin film thermoelectric unit schematic cross-section of editable；
Fig. 2 is the ultra-thin longitudinal multilayer cascaded structure thermal electric film schematic cross-section of editable；A is ultra-thin longitudinal multilayer n kinds
M periodic structure thermal electric film schematic diagram of material in series；B is ultra-thin longitudinal multilayer n kinds material aperiodicity cascaded structure thermoelectricity
Film schematic diagram；C is ultra-thin longitudinal multilayer cascaded structure thermal electric film schematic diagram；
Fig. 3 is the ultra-thin longitudinal multilayer cascaded structure thermal electric film equivalent circuit diagram of editable；A is ultra-thin longitudinal multilayer n kinds
M periodic structure thermal electric film equivalent circuit diagram of material in series；B is ultra-thin longitudinal multilayer n kinds material aperiodicity cascaded structure
Thermal electric film equivalent circuit diagram；
Fig. 4 is the ultra-thin longitudinal multilayer cascaded structure thermal electric film section example schematic of editable；A be uniform layer material,
Particle layer material and m periodic structure schematic diagram of pore layer material in series；B is stratum granulosum A1, pore layer A2... uniform thermoelectric layer
An-2, uniform alumina nitride layer An-1, homogenous metal layer AnAperiodicity cascaded structure schematic diagram；
Fig. 5 is the ultra-thin longitudinal sectional view of multilayer cascaded structure thin film thermoelectric unit example 1 of editable；A is ultra-thin multilayer string
It is coupled structure thermoelectric material Si/Ge (SEM sections), b is ultra-thin multilayer cascaded structure thermoelectric material Si/Ge schematic diagrames；C is ultra-thin many
Layer cascaded structure thermoelectric material Si/Ge equivalent circuit diagrams；
Fig. 6 is the ultra-thin longitudinal sectional view of multilayer cascaded structure thin film thermoelectric unit example 2 of editable；A is ultra-thin multilayer string
It is coupled structure thermoelectric material Au/Sb2Te3(SEM sections), b is ultra-thin multilayer cascaded structure thermoelectric material Au/Sb2Te3Schematic diagram；c
For ultra-thin multilayer cascaded structure thermoelectric material Au/Sb2Te3Equivalent circuit diagram.
Embodiment
Enumerated below by way of the accompanying drawing of the present invention, and magnetron sputtering deposition thin film thermoelectric unit in conjunction with specific embodiments,
The more detailed description present invention.It is pointed out that the present invention can be realized in different forms, and should be according to actual feelings
Condition makes corresponding adjustment.Propose that these examples are intended to reach sufficient complete disclosure, make those skilled in the art complete
Understand the scope of the present invention, should not be construed as being limited by the embodiment of this proposition.It is all such as when selecting the technique of deposition film
Such as liquid phase method, electrochemical process and the electron beam evaporation or molecular beam epitaxy in physical vapor method can deposition film mode
, it is not limited to the magnetron sputtering in example, herein example do not enumerate.
Illustrated first against the ultra-thin multilayer lontitudinal series structure thermal electric film thermoelectric unit of editable, Fig. 1 is in fact
One of schematic diagram is applied, it is thin that vertical structure is followed successively by the ultra-thin multilayer lontitudinal series structure thermoelectricity of dielectric base 1, hearth electrode 2, editable
Film 3, top electrode 4.Temperature difference is formed by longitudinal two ends, electrical potential difference is produced, the difference at cold and hot end is positioned over according to upper and lower surface,
The positive and negative difference of electrical potential difference of generation.
Wherein the ultra-thin structure of multilayer lontitudinal series structure thermal electric film 3 of editable is as illustrated, such as Fig. 2 (a), its longitudinal direction can
Alternately connected m cycle for n kinds material, n and m are the integer more than 1, if n is 2 for 2, m, then vertical structure alternant
For A1A2A1A2.Such as Fig. 2 (b), or n kind materials aperiodicity is connected, n is the integer more than 1, if m is 3, longitudinal direction knot
Structure such as A1A2A3.Meanwhile, in the series connection of n kind materials aperiodicity, same material may occur in which repeatedly.
Fig. 3 is the ultra-thin multilayer lontitudinal series structure thermal electric film equivalent circuit diagram of editable, and Fig. 3 (a) is n kind material in series
M period film equivalent circuit diagram, Fig. 3 (b) is n kind material aperiodicity tandem thin-film equivalent circuit diagrams.
Fig. 4 is the ultra-thin longitudinal multilayer cascaded structure thermal electric film example schematic of editable, and Fig. 4 (a) is conforming layer, particle
Layer and m cycle schematic diagram of pore layer lontitudinal series, Fig. 4 (b) are stratum granulosum A1, pore layer A2... uniform thermoelectric layer An-2, it is uniform
Oxide skin(coating) An-1, homogenous metal layer AnLongitudinal aperiodicity series connection schematic diagram.
Secondly it is directed to ultra-thin longitudinal multilayer cascaded structure thermal electric film and can be directly used for the preparation of thermoelectric unit generated electricity,
With reference to magnetron sputtering deposition thermal electric film embodiment 1 and embodiment 2, illustrate.
Embodiment 1
Wherein substrate uses the oxidized silicon chip of 3 cun of single-sided polishings, and Si is doped to P, crystal orientation<100>, resistivity 1-20 Ω
Cm, 400 ± 10 μm of thickness, 500 ± 30nm of oxidated layer thickness.
Substrate steeps 10min using acetone clear liquid, then rapid to take out, and is rinsed with absolute ethyl alcohol, deionized water rinsing uses N2
Drying.
It is 10 that substrate is placed in into background vacuum-6In Torr Denton multi-target magnetic control sputtering coating systems, first using height
Pure Ar cleans 1min, then proceeds by deposition film.
In view of the combination problem in physical vapour deposition (PVD) between layers, tack coat is added, tack coat uses material such as
Cr, Ni, Ti etc., 5~100nm of thickness.In the present embodiment using 20nm Cr as tack coat, wherein in substrate in sequence according to
Secondary deposition 20nm Cr (tack coat), 200nm Au (hearth electrode), 20nm Cr (tack coat),
Then in the longitudinal multilayer cascaded structure thermal electric film of depositing ultrathin, the present embodiment, 20nm Si, Ran Houchen are first deposited
Product 20nm Ge, successively 25 cycles of alternating deposit, totally 1 μm, Fig. 5 is prepared ultra-thin longitudinal multilayer cascaded structure thermal electric film
Si/Ge sections SEM schemes.
Embodiment 2
Substrate and hearth electrode processing are same as Example 1, at the ultra-thin multilayer lontitudinal series structure thermal electric film of editable
Reason is as follows：20nm Au are first deposited on hearth electrode, 20nm Sb are then deposited2Te3, 25 cycles of alternating deposit successively, totally 1 μm,
Fig. 6 is prepared ultra-thin longitudinal multilayer cascaded structure thermal electric film Au/Sb2Te3Section SEM schemes.
20nm Cr (tack coat), 200nm Au (top electrode) are deposited on ultra-thin longitudinal multilayer cascaded structure thermal electric film,
Obtain thermo-electric device unit.
Following table is to prepare the ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable obtained in film implementation process
Partial properties are enumerated, and have obtained ultralow thermal conductivity (0.30Wm-1·K-1) film.Pass through preferred preparation method, material simultaneously
Material, structure, cycle, the combination of thickness degree are expected to obtain the lower film of thermal conductivity, while obtaining matched suitable plug
Seebeck coefficient and electrical conductivity, obtain more preferable conversion efficiency of thermoelectric.
Therefore, by being used in the present invention in different method for manufacturing thin film and combination, such as physical vapor method
Ultra-thin longitudinal multilayer string of magnetron sputtering, electron beam evaporation or molecular beam epitaxy, the different-thickness that can be obtained and different micro-structurals
Be coupled structure thermal electric film, it is possible to by this film design into thermoelectric unit device is made, realize ultra-thin thermo-electric device prepare with
And the expansion of application.
Described above is only the embodiment citing of the present invention, it should be pointed out that the present invention is not intended to be limited to herein
Shown example, but to be combined the widest range consistent with features of novelty with principles disclosed herein.
Claims (10)
1. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable, it is characterised in that the film is by multilayer material longitudinal direction
It is in series.
2. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable according to claim 1, it is characterised in that institute
Thickness in the film stated per layer material is less than 1000nm.
3. the ultra-thin longitudinal multilayer cascaded structure thermal electric film of a kind of editable according to claim 1, it is characterised in that vertical
The layers of material used to the film being composed in series includes metal, oxide, semiconductor, organic matter or inorganic compound, series connection
When, at least there is a class material of thermoelectric property, i.e. thermoelectric material containing more than one.
4. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable according to claim 1, it is characterised in that institute
The film stated m cycle of alternately being connected by n kinds material constitutes, wherein, n and m are the integer more than 1.
5. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable according to claim 4, it is characterised in that institute
The n stated is that 2, m is 2, and vertical structure alternant is A1A2A1A2。
6. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable according to claim 1, it is characterised in that institute
The film stated is composed in series by n kind material aperiodicity, and n is the integer more than 1, meanwhile, in the series connection of n kind materials aperiodicity
In, same material may occur in which repeatedly.
7. the ultra-thin longitudinal multilayer cascaded structure thermal electric film of a kind of editable according to claim 1 or 2 or 3, its feature
It is, multilayer material lontitudinal series mode includes one or more thermoelectric materials and metal, oxide, partly led in described film
Body or inorganic compound series connection, or connected by thermoelectric material with thermoelectric material.
8. a kind of ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable according to claim 7, it is characterised in that group
Have into the multilayer material of film hole be less than 50nm for pore layer, with doping particle be less than 50nm for doping particle
Layer, remaining constituent is uniformly conforming layer；Wherein pore layer, doping stratum granulosum can be described as functional layer again, with exciting load
Stream (excitation layer) or the effect for absorbing phonon (absorbed layer).
9. a kind of preparation method of the ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable as described in claim 1~8, its
It is characterised by, is composed in series the layers of material of film and is made film using the one or more in following methods, including liquid phase method,
Such as magnetron sputtering, electron beam evaporation or molecular beam epitaxy deposition are thin in physical vapor method, electrochemical process etc., physical vapor method
Film, wherein every layer can use above-mentioned one of which film preparation mode simultaneously, two or more film preparations can be also used respectively
Mode.
10. the thermo-electric device unit of the ultra-thin longitudinal multilayer cascaded structure thermal electric film of editable described in claim 1 is included, bag
Include the substrate (1) being sequentially overlapped, hearth electrode (2), ultra-thin longitudinal multilayer cascaded structure thermal electric film post (3), top electrode (4).
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| CN110233201A (en) * | 2019-07-12 | 2019-09-13 | 中国科学院化学研究所 | A kind of plural layers device of six cyano trimethylene cyclopropane doping CuPc |
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