CN101969096B - Nanostructured thermoelectric material and device and production method thereof - Google Patents

Nanostructured thermoelectric material and device and production method thereof Download PDF

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CN101969096B
CN101969096B CN2010102645370A CN201010264537A CN101969096B CN 101969096 B CN101969096 B CN 101969096B CN 2010102645370 A CN2010102645370 A CN 2010102645370A CN 201010264537 A CN201010264537 A CN 201010264537A CN 101969096 B CN101969096 B CN 101969096B
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thermoelectric
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nanostructured
thermoelectric material
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CN101969096A (en
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任山
叶志超
李立强
李义兵
洪澜
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses a nanostructured thermoelectric material, a nanostructured thermoelectric device and a production method thereof. The thermoelectric material comprises an insulating substrate and a nanostructured thermoelectric membrane, wherein the nanostructured thermoelectric membrane is composed of at least two nano-thickness thermoelectric material layers and at least two phonon scattering layers, and the thermoelectric material layers and the phonon scattering layers are overlapped alternately. The thermoelectric material can be a p-type thermoelectric material or an n-type thermoelectric material, which depends on the type of charge carrier of the thermoelectric material layers. Connecting electrodes are plated between the thermoelectric membranes of a p-type nanostructured thermoelectric material and a n-type nanostructured thermoelectric material so as to form a thermoelectric pair; and then a plurality of thermoelectric pairs are connected in parallel or in series so as to form the thermoelectric device. The nanostructured thermoelectric material of the invention has the advantages of good thermal stability, high nanostructured membrane deposition efficiency, high thermoelectric conversion efficiency, and lower cost; and the nanostructured thermoelectric device has the advantages of simple structure, easy preparation, low internal resistance, and great practical value in the fields such as refrigeration/calorification or temperature differential power generation, and the like.

Description

Nanostructured thermoelectric materials, device and preparation method thereof
Technical field
The invention belongs to the field of thermo-electric converting material, particularly a kind of nanostructured thermoelectric materials, device and preparation method thereof.
Background technology
Thermoelectric material is a kind of functional material that can realize that heat-electricity and electricity-Re directly change.Power generating device and the refrigeration device processed by thermoelectric material have the incomparable advantages of traditional devices such as simple in structure, in light weight and movement-less part, so thermoelectric material is at energy field with have very big using value and unrivaled advantage aspect the refrigeration.
According to existing theoretical, the conversion efficiency of thermoelectric material is by its ZT value decision.Wherein Z is the thermoelectric figure of merit factor (figure of merit), the temperature that T is to use.The ZT of material thermoelectric material can be expressed as, ZT=(S 2The T of σ/k), T is an absolute temperature in the formula, and S is Seebeck coefficient (V/K), and σ is conductivity (Ω -1m -1), k is thermal conductivity (W m -1K -1), k forms S by lattice thermal conductivity kl and electronics thermal conductivity ke two parts 2σ is the power factor of material.The ZT value is big more, and conversion efficiency of thermoelectric is high more.In order to improve thermoelectric material ZT value, should make Seebeck coefficient S and conductivity big as far as possible and thermal conductivity k is as far as possible little, but these three parameters and dependent, they all are decided by the scattering situation of electronic structure, charge carrier and the phonon of material.Therefore, optimizing carrier concentration and improve the material power factor, and reduce material thermal conductivity with the means of doping and low dimensionization, make it to obtain the material of high ZT value, is the focus of present thermoelectric material area research.
The low-dimension nano material structure is one of important channel of the follow-on thermoelectric material of development.Wherein based on the phonon scattering length different with electronics, the inner boundary of nanostructure can be designed as phon scattering strong and little to the electrical conductivity influence, makes it to reduce thermal conductivity and little to the conductivity influence.
Groups such as groups such as Ren Z.F., Li Jingfeng; And many papers have reported that employing mechanical alloying (MA) forms after the nano-crystalline granule; Use discharge plasma sintering method (SPS) sintering granule; Prepared high performance Bi-Te system, Si-Ge system, and Ag-Pb-Sb-Te system nano crystal block thermoelectric material, and these bulk nano-crystalline thermoelectric materials are carried out being assembled into thermoelectric device after the machine cuts.But crystal boundary faces a large amount of in these nano crystal block thermoelectric materials are in the thermodynamics unsteady state, and when higher temperature used, nanocrystal was grown up easily, cause thermoelectric conversion performance to reduce.
People such as Yang P.D. have reported that electrochemistry synthesizes large tracts of land, the coarse silicon nanowire array of chip dimension.Its diameter is from 20~300nm.The Seebeck effect of these nano wires and resistance value are suitable with the doping buik silicon.But the thermal conductivity of the nano wire of 50nm diameter is 1/100th of an original buik silicon, and the ZT value under the room temperature is 0.6.In said nano wire, thermal conductance reduces, its conductivity and the unconspicuous variation of Seebeck coefficient, and they think what caused the scattering of phonon on coarse surface.But nano wire difficulty becomes device, even nano-wire array also difficulty make device, this has just hindered its use.Also the someone reports and adopts electrochemical method in aluminium oxide or high molecular nanometer template, to produce the thermoelectric material nano-wire array, and is assembled into thermoelectric device through a plurality of steps, and this moment, nano wire was perpendicular to substrate.But in these nano wire thermoelectric devices, because the length of nano wire is little, heat refluxes easily, causes conversion efficiency of thermoelectric low, need separate with mould material between the nano wire simultaneously, causes space availability ratio low, has also caused these device internal resistances big.Above reason makes these thermoelectric devices can't obtain practical application.
Venkatasubramanian etc. have made p type Bi with the MOCVD method 2Te 3-Sb 2Te 3With n type Bi 2Te 3/ Sb 2Te 2.83Se 0.17Nano super-lattice film (Thin-film thermoelectric devices with highroom-temperature figures of merit.Rama Venkatasubramanian; Edward Siivola; Thomas Colpitts; Brooks O ' Quinn Nature 413,597-602 (11October 2001)).These two kinds of materials have reached 2.4 and 1.4 respectively in the room temperature ZT value perpendicular to the interface direction.But this is that metal organic chemical vapor deposition growth (MOCVD) deposit film speed is slow, and apparatus expensive can't realize large-scale industrial production.
In sum, generally there is such problem in existing material: though block thermoelectric material is prone to the preparation thermoelectric device, be difficult to realize the blocks of large nanostructure of low cost, efficient, good thermal stability.Though and thermoelectric material function admirables such as nano dot, nano wire but are difficult to device, can't obtain actual practicality.Comparatively speaking, the thin film thermoelectric material is relatively easily realized nanostructure, also is easy to device simultaneously, but nano thin-film preparation of devices efficient is still not high at present, and thermal stability can not satisfy the hot environment of thermoelectric device in use simultaneously.
And traditional thin film thermoelectric switching device is general such, and thermal electric film is clipped between the upper and lower base plate, between thermal electric film and the substrate metal electrode is arranged.Through the electric current and the hot-fluid vertical thin-film direction of film, because film thickness is in micron dimension, hot-fluid refluxes easily, influence generating and refrigeration.Simultaneously, it is longer to deposit the required preparation time of these thick relatively films, and production efficiency is low.The conversion efficiency of conventional films device is unsatisfactory.
General thin film thermoelectric material or thin-film device, its heat delivered has dual mode, and a kind of is the vertical plane transmission means, and a kind of in addition is along the planar transmission mode.
M.Taashiri has reported a thin-film device along the parallel heat transfer of film, they with the method for flash distillation at the substrate surface vapor deposition thin film thermoelectric device of BiTe system.This film is a uniform single organization structure, the inner nanostructure that does not possess good thermal stability, main performance through adjustment phase structure and film thickness control thermoelectric device.General film, if thinner thickness, its ZT value is higher, but sectional area causes internal resistance big for a short time, and device efficiency is low.If film is done thick, because quantum confinement effect is not obvious, the ZT value has reduced again.(Fabrication?and?characterization?of?bismuth-telluride-based?alloy?thinfilm?thermoelectric?generators?by?flash?evaporation?method?M.Takashiri?et?al./Sensors?and?Actuators?A?138(2007)329-334)
Germany Fraunhofer research institute has reported a thin film thermoelectric device of being made by thin film technique and microsystems technology; Its hot-fluid and electric current are the vertical thin-film planar transmission; The block thermoelectric device that similar is traditional, this film inside does not have nanostructure yet simultaneously.This device helps with the conditional electronic device integrated, but is unfavorable for direct power generation applications.(New?Thermoelectric?Components?using?MicrosystemTechnologies.Journal?of?microelectro-mechanical?systems,Vol.13,No3,June?2004)
In two-dimensional nano thermoelectric material system in the past, the general performance of paying close attention to perpendicular to the film surface direction of people utilizes the interfacial effect that combination obtains between the different thermal electric films to improve its thermoelectricity capability emphatically.Traditional thin film thermoelectric switching device generally is that thermal electric film is clipped between the thicker relatively upper and lower base plate of thickness, between thermal electric film and the substrate metal electrode is arranged.Through the electric current and the hot-fluid vertical thin-film direction of film, because film thickness is in micron dimension, hot-fluid refluxes easily, influence generating and refrigeration.So the conversion efficiency of conventional films device is unsatisfactory.
Publication number is that the one Chinese patent application of CN200510082038.9 discloses a kind of thin film thermoelectric device, utilizes semiconductive thin film and VLSI (very large scale integration technology) to make the high density array of thermoelectric elements.Do not introduce nanostructure in this film.
Publication number is the device that the one Chinese patent application of CN200910105172.4 discloses the parallel film direction generating in a kind of edge; A kind of thin film temperature difference battery and preparation method thereof is disclosed; On substrate, be coated with P type thermal electric film layer, insulating material film layer and N type thermoelectric material film; Form one three layers PN junction, the PN junction series connection of a plurality of trilamellar membranes can be arranged, have one deck insulating material film to be separated by between each PN junction of series connection.This film inside does not possess nanostructure.
Publication number is that the one Chinese patent application of CN200820083617.4 discloses a kind of nano thermal electric material with coaxial cable structure.It has comprised the wire nanometer inner core overcoat outer with being coated on the nanometer inner core, and the nanometer inner core is coaxial with overcoat.The nanometer inner core adopts different thermoelectric materials with overcoat.With respect to traditional thermoelectric material, coaxial cable structure thermoelectric material interfacial area increases, and can significantly strengthen phonon and transport scattering, reduces thermoelectric material and conducts heat, and has improved conversion efficiency of thermoelectric.But this material is difficult to make device, and the device internal resistance is big, is unfavorable for practical application.
Publication number is that the one Chinese patent application of CN01819961.5 discloses the thermoelectric device of a kind of thin film coated on the conical tip inclined-plane.It has utilized the lattice mismatch of the thermoelectric material on the most advanced and sophisticated wedge angle of wedge angle, reduces thermal conductivity, thereby improves the quality factor (ZT value) of material, and then improves the efficient of device.This invention part that communicates with thinking of the present invention has embodied the thinking of modern high efficiency thermoelectric materials development equally.But the cold junction of this device and hot junction close together, hot reflux easily influences thermoelectric effect.Simultaneously, this device architecture with make complicatedly, be fit to the heat radiation of expensive chip and be not suitable for more common thermoelectric power generation and use.
Summary of the invention
Be difficult for device in order to solve above-mentioned existing nanostructured thermoelectric materials, bad deficiency and the shortcoming of while thermal stability, primary and foremost purpose of the present invention is to provide a kind of nanostructured thermoelectric materials with good thermal stability.
Another object of the present invention is to provide the preparation method of above-mentioned nanostructured thermoelectric materials, it is simple that this method has technology, and cost is lower, to equipment requirements advantages of higher not.
A purpose more of the present invention is to provide thermoelectric device based on above-mentioned nanostructured thermoelectric materials and preparation method thereof; Thermoelectric transmission does not receive the restriction of material thickness in the device of processing, and thermoelectric conversion efficiency is high, Heat stability is good, and have good refrigeration and thermo-electric generation function.This thermoelectric device prepares that process is simple, production efficiency is high simultaneously, controllable structure, cost be low.
The present invention realizes through following technical proposals: a kind of nanostructured thermoelectric materials, this thermoelectric material comprise insulation low heat conductivity substrate and pyroelectric film; Said pyroelectric film comprises at least 2 layers of thermoelectric layer and at least 2 layers of phon scattering layer, and thermoelectric layer and phonon scattering layer alternately cover, and 1 layer of the most inboard thermoelectric layer covers on the substrate, and the thickness of said thermoelectric layer is 1nm~200nm; The thickness of said phon scattering layer is 1nm~100nm.
The number of plies of said thermoelectric layer is 2 to 10000; The number of plies of said phon scattering layer is 2 to 10000; Said substrate is glass, silicon dioxide, aluminium oxide, aluminium nitride, magnesia, mica, polyamide, polybutylene terephthalate (PBT), PEN, Merlon, polyamide 6, copolyamide 6-X (the wherein natural number between X=6~12), poly aromatic acid amides MXD6, polyphenylene sulfide; Said thermoelectric layer is simple substance thermoelectric material or compound thermoelectric material; Said phon scattering layer is nano-particle layer or insulating nano thin layer.
Said simple substance thermoelectric material is bismuth or silicon; Said compound thermoelectric material is that alloy, cobalt antimony are that alloy, SiGe are that alloy, bismuth antimony are that alloy, plumbous tellurium are that alloy, zinc antimony are alloy or magnesium Si system alloy for the bismuth tellurium; Said nano-particle layer is nano-metal particle layer or nanometer insulated particle layer, does not wherein contact each other between the metallic particles in the nano-metal particle layer.
Said nano-metal particle layer is refractory metal, transition metal, semimetal or metalloid; Said nanometer insulated particle layer is silicon dioxide, aluminium oxide, aluminium nitride, magnesia, carborundum, titanium oxide or titanium nitride; The granularity of said metallic particles and insulated particle is 1nm~100nm; Said insulating thin layer is silicon dioxide, aluminium oxide, aluminium nitride, magnesia, titanium oxide or titanium nitride.
Said refractory metal is tungsten, molybdenum, gold, titanium, niobium or their alloy; Said transition metal is nickel, iron, cobalt, chromium or their alloy; Said semimetal is bismuth, antimony or their alloy; Said metalloid is silicon, germanium or their alloy.
Said thermoelectric layer is a p type thermoelectric material, obtains p type nanostructured thermoelectric materials; Said thermoelectric layer is a n type thermoelectric material, obtains n type nanostructured thermoelectric materials.
The preparation method of above-mentioned a kind of nanostructured thermoelectric materials comprises following operating procedure:
(1) cleans substrate, remove grease and attachment;
(2) adopt physical gas-phase deposite method or chemical gaseous phase depositing process on the substrate that cleaned, to deposit one deck thermoelectric layer, deposit one deck phon scattering layer again, electroless copper deposition operation is 2~10000 times repeatedly, obtains having the nanostructure pyroelectric film of periodic structure;
(3) with pyroelectric film in vacuum or atmosphere of inert gases, under 60~1000 ℃, heat-treated 10 minutes~100 hours, obtain stabilized nano structure thermoelectric material; Heat treated purpose is in order to improve degree of crystallinity, the adjustment phase structure.
The said physical gas-phase deposite method of step (2) is sputtering method, hot steaming method, electron beam vapor deposition method or laser beam evaporation sedimentation.
The phon scattering interface that heat insulating lamina constitutes, its interface roughness is determined by depositing operation.For example prepare in the process at magnetron sputtering, can be through the adjustment of sputter operating air pressure and operating power, and the control of underlayer temperature, the thickness at scattering interface is controlled through sputtering time and sputtering power.
Gather the phon scattering layer that the interface constitutes by particle, its rough interface degree is by granular size and the control of distribution of particles density.In magnetron sputtering, it is controlled that the size of particle and density can be adjusted operating air pressure, sputtering power, the underlayer temperature of magnetron sputtering.
Under different temperatures, the phonon in the material is corresponding to different phonon free paths.The thermoelectric multilayer film of under different temperature, working, its thermoelectric layer also corresponding the thickness of different the best.Thermoelectric layer thickness can be by sputtering time and power control.
Above-mentioned a kind of nanostructured thermoelectric materials can be applicable to prepare thermoelectric device.
Said thermoelectric device prepares by following operating procedure: will replace between banded p type nanostructured thermoelectric materials that parallel interval arranges and the n type nanostructured thermoelectric materials along substrate and plate connection electrode; It is thermoelectric right to constitute, and this moment, electric current was (being parallel substrate direction) transmission along the phon scattering interface; A plurality of thermoelectricity are obtained thermoelectric device to parallel connection or series connection.
The mode that thermoelectric device forms has multiple; Mode is that the p type or the multilayer film of n type that are in respectively on a plurality of individual substrate connect the device (like Fig. 4) that forms mutually; Also can be that a substrate deposits a thermoelectricity to (like Fig. 2), also can be the integrated device form (like Fig. 3) that on a substrate, has a plurality of thermoelectricity right.
On substrate of the present invention, have in the right embodiment of more than one thermoelectricity, the method that is used to make thermoelectric device may further comprise the steps:
Clean substrate, remove grease and attachment.Mode through mask or photoetching alternately deposits p type thermoelectric material layer and phonon scattering layer on the substrate specific region, obtain the thermoelectric multilayer film of p type.Mode through mask or photoetching is used in and alternately deposits n type thermoelectric material and phonon scattering layer on the substrate specific region, obtains n type nanometer thermoelectric multilayer film.Mode through mask or photoetching prevents the diffusion between thermoelectric material and the metal electrode material with magnetron sputtering depositing electrode barrier layer on the substrate specific region.Said electrode barrier layer can be materials such as W, Mo, Ti, Ni, and their alloy material.Mode through mask or photoetching connects p type and n type thermoelectric material, and draws external electrode with magnetron sputtering deposit metal electrodes on the barrier layer.Said metal electrode can be materials such as Cu, Al, Ni, W, Mo, and their alloy material.Device to depositing is heat-treated under vacuum or inert gas shielding, and selecting temperature for use is 60~1000 degree, different according to different materials.Heat treatment is intact just to obtain basic device cell, can carry out various forms of assemblings, thus the device of the refrigeration of formation or generating.
The thermoelectric device that the present invention is made up of nano thin-film can be realized highly effective refrigeration or generating.In film, its structure is the sandwich construction of thermoelectric layer stack phon scattering layer; Through introduce the nanometer phon scattering layer that constitutes by non-thermoelectric material at the thermoelectric material interlayer; Controlled particular interface is provided; The thickness and the phon scattering layer state of regulation and control thermoelectric material layer make that the phonon in the thermoelectric material receives big scattering, and its electric transmission are influenced little.And after deposition, heat-treat, make the degree of crystallinity of thermal electric film improve, improve the performance of thermoelectric material layer.Select for use the material of good thermal stability to do the phonon scattering layer, can be after heat treatment, it is stable that the phon scattering layer keeps.Because the structure of film is the sandwich construction of parallel substrate, its structure can make hot-fluid and electric current flow with the direction of parallel thermoelectric film material, and the distance of its cold and hot end can be kept enough temperature difference.Through above design, can obtain thin film thermoelectric material efficiently, thereby prepare high-performance thermal electric film device.The film that the present invention designed and superlattice thermoelectric film all have significant different on theory and structure; Super crystal lattice material is two-layer different thermoelectric material alternating growth, and film of the present invention be thermoelectric material layer and the phon scattering layer that constitutes by non-thermoelectric material alternately stack constitute the film that periodic structure is arranged of tool.
The relative prior art of the present invention has following advantage and beneficial effect:
The present invention is through introducing the nanometer phon scattering layer of the thermal electric film interlayer of being made up of non-thermoelectric material; Controlled special interface is provided; The thickness and the phon scattering layer state of regulation and control thermoelectric material layer make that the phonon in the thermoelectric material receives big scattering, and its electric transmission are influenced little.And after deposition, heat-treat, make the crystallinity of thermal electric film improve, obtain high performance thermoelectric film material at last.Simultaneously, its structure can make electric current flow with the direction of parallel thermoelectric film material, and the distance of its cold and hot end can be kept enough temperature difference.Simultaneously, pyroelectric film of the present invention has overcome the situation of the reduction of quantum confinement effect in the thicker pyroelectric film, makes when its thin-film device resistance descends, and keeps high ZT value, has than practical value greatly in refrigeration/heating or the application of generating electricity.
Description of drawings
Fig. 1 is the nanostructured thermoelectric materials sketch map, and wherein 1 is dielectric substrate, and 2 is thermoelectric material layer, and 3 are the phon scattering layer, and 4 is that electric current is parallel film surface direction with the hot-fluid flow direction.
Fig. 2 is the device sketch map, and wherein 21 is the low heat conductivity dielectric substrate, and 22 is barrier layer and electrode, and 23 is n type thermal electric film, and 24 is p type thermal electric film, and 25 is hot plate, and 26 is cold drawing.
Fig. 3 is for there being the right integrated thermal electric device sketch map of a plurality of thermoelectricity on a substrate, wherein 34 are insulation low heat conductivity substrate, and 31 is barrier layer and electrode, and 32 is thermoelectric right.
Fig. 4 connects the device sketch map that forms mutually for p type or the multilayer film of n type that is in respectively on a plurality of individual substrate, and wherein 41 be the hot junction, and 42 be electrode, and 43 is to go between, and 44 is p type thermoelectric arm, and 45 is n type thermoelectric arm, and 46 is cold junction.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but the working of an invention mode is not limited thereto.
Embodiment 1:
Use the thermoelectric multilayer film device of mask magnetron sputtering deposition:
This example selects for use glass to do substrate, and bismuth tellurium pyroelectric material is done thermoelectric layer, and tungsten particle gathers the interface and does the phonon scattering layer.Membrane deposition method is a rf magnetron sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.7Pa.
With acetone and alcohol and deionized water ultrasonic cleaning glass substrate successively, dry up substrate with dry pure nitrogen gas.
On substrate, cover p type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck p type thermoelectric material, power density is 1~10W/cm 2, thickness is 10nm, plates one deck tungsten particle then, power density can be 1~5W/cm 2, granularity is 5nm, interfacial thickness is 5nm, repeats this process 100 times, then in a vacuum, under 300 ℃, heat-treats 10 hours, obtains the p type thin film thermoelectric arm of multilayer.
Afterwards, on substrate, cover n type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck n type thermoelectric material, power density can be 1W/cm 2, thickness is 10nm, plates one deck tungsten particle then, and power density is 5nm, and interfacial thickness is 5nm, repeats this process 100 times, then in a vacuum, under 300 ℃, heat-treats 10 hours, obtains the n type thin film thermoelectric arm of multilayer.
Afterwards, at substrate loam cake top electrode mask plate.Use rf magnetron sputtering to plate one deck Ti, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, draw lead-in wire, just can obtain high-effective multilayer film thermoelectric device.The structural representation of gained thermoelectric device is as shown in Figure 3, and 34 is the insulation and thermal insulation substrate, and 31 is barrier layer and electrode, and 32 is thermoelectric right.
Embodiment 2:
Use the thermoelectric multilayer film device of mask magnetron sputtering deposition:
Mica is done substrate, and bismuth tellurium pyroelectric material is done thermoelectric layer, and silica dioxide granule gathers the interface and does the phonon scattering layer.Membrane deposition method is a rf magnetron sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.1~2Pa.
With acetone and alcohol and deionized water ultrasonic cleaning mica substrate successively, dry up substrate with dry pure nitrogen gas.
On substrate, cover p type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck p type thermoelectric material, power density is 2W/cm 2, thickness is 100nm, plates the layer of silicon dioxide particle then, power density is 2W/cm 2, granularity is 5nm, interfacial thickness is 5nm, repeats this process 2 times, then in a vacuum, under 60 ℃, heat-treats 100 hours, obtains the p type thin film thermoelectric arm of multilayer.
Afterwards, on substrate, cover n type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck n type thermoelectric material, power density is 2W/cm 2, thickness is 100nm, plates one deck SiO then 2Particle, power density are 2W/cm 2, granularity is 5nm, interfacial thickness is 5nm, repeats this process 2 times, then in a vacuum, under 60 ℃, heat-treats 100 hours, can obtain the n type thin film thermoelectric arm of multilayer.
Afterwards, at substrate loam cake top electrode mask plate.Use rf magnetron sputtering to plate one deck Ti, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, draw lead-in wire, just can obtain high-effective multilayer film thermoelectric device.The structural representation of gained thermoelectric device is as shown in Figure 3, and 34 is the insulation and thermal insulation substrate, and 31 is barrier layer and electrode, and 32 is thermoelectric right.
Embodiment 3:
Use the thermoelectric multilayer film device of mask magnetron sputtering deposition:
This example selects for use mica to do substrate, and cobalt antimony pyroelectric material is done thermoelectric layer, and tungsten particle gathers the interface and does the phonon scattering layer.Membrane deposition method is a rf magnetron sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.1~2Pa.
With acetone and alcohol and pure water ultrasonic cleaning mica substrate successively, dry up substrate with dry pure nitrogen gas.
On substrate, cover p type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck p type thermoelectric material, power density is 0.1W/cm 2, thickness is 5nm, plates one deck tungsten particle then, power density is 0.1W/cm 2, granularity is 1nm, interfacial thickness is 1nm, repeats this process 200 times, then in a vacuum, under 1000 ℃, heat-treats 10 minutes, obtains the p type thin film thermoelectric arm of multilayer.
Afterwards, on substrate, cover n type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck n type thermoelectric material, power density is 0.5W/cm 2, thickness is 5nm, plates the layer of silicon dioxide particle then, power density is 0.5W/cm 2, granularity is 1nm, interfacial thickness is 1nm, repeats this process 200 times, then in a vacuum, under 1000 ℃, heat-treats 10 minutes, obtains the n type thin film thermoelectric arm of multilayer.
Afterwards, at substrate loam cake top electrode mask plate.Use rf magnetron sputtering to plate one deck Ti, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, draw lead-in wire, just can obtain high-effective multilayer film thermoelectric device.The structural representation of gained thermoelectric device is as shown in Figure 3, and 34 is the insulation and thermal insulation substrate, and 31 is barrier layer and electrode, and 32 is thermoelectric right.
Embodiment 4:
Use the thermoelectric multilayer film device of mask magnetron sputtering deposition:
This example selects for use the kapton film to do substrate, and silicon-germanium pyroelectric material is done thermoelectric layer, and the phonon scattering layer is done at metal molybdenum particle aggregation interface.Membrane deposition method is a rf magnetron sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.1~2Pa.
With acetone and alcohol and pure water ultrasonic cleaning mica substrate successively, dry up substrate with dry pure nitrogen gas.
On substrate, cover p type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck p type thermoelectric material, power density is 20W/cm 2, thickness is 80nm, plates one deck molybdenum particle then, power density is 20W/cm 2, granularity is 20nm, interfacial thickness is 20nm, repeats this process 50 times, in nitrogen atmosphere, under 700 ℃, heat-treats 20 hours then, obtains the p type thin film thermoelectric arm of multilayer.
Afterwards, on substrate, cover n type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck n type thermoelectric material, power density is 20W/cm 2, thickness is 80nm, plates one deck molybdenum particle then, power density is 20W/cm 2, granularity is 20nm, interfacial thickness is 20nm, repeats this process 50 times, then in a vacuum, under 700 ℃, heat-treats 20 hours, obtains the n type thin film thermoelectric arm of multilayer.
Afterwards, at substrate loam cake top electrode mask plate.Use rf magnetron sputtering to plate one deck titanium, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, draw lead-in wire, just can obtain high-effective multilayer film thermoelectric device.The structural representation of gained thermoelectric device is as shown in Figure 3, and 34 is the insulation and thermal insulation substrate, and 31 is barrier layer and electrode, and 32 is thermoelectric right.
Embodiment 5:
Use the thermoelectric multilayer film device of mask magnetron sputtering deposition:
Glass is done substrate, and bismuth antimony pyroelectric material is done thermoelectric layer, and magnesia film is done the phonon scattering layer.Membrane deposition method is radio frequency or magnetically controlled DC sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.1~2Pa.
With acetone and alcohol and pure water ultrasonic cleaning mica substrate successively, dry up substrate with dry pure nitrogen gas.
On substrate, cover p type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck p type thermoelectric material, power density is 10W/cm 2, thickness is 50nm, plates one deck magnesium oxide layer then, power density is 10W/cm 2, thickness is 10nm, repeats this process 200 times, in argon atmosphere, under 300 ℃, heat-treats 70 hours then, obtains the p type thin film thermoelectric arm of multilayer.
Afterwards, on substrate, cover n type thermoelectric arm mask plate.Use rf magnetron sputtering to plate one deck n type thermoelectric material, power density is 10W/cm 2, thickness is 50nm, plates one deck magnesium oxide layer then, power density is 10W/cm 2, thickness is 10nm, repeats this process 200 times, in argon atmosphere, under 300 ℃, heat-treats 70 hours then, obtains the n type thin film thermoelectric arm of multilayer.
Afterwards, at substrate loam cake top electrode mask plate.Use rf magnetron sputtering to plate one deck titanium, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, draw lead-in wire, just can obtain high-effective multilayer film thermoelectric device.
Embodiment 6
This example selects for use PEN to do substrate, and bismuth antimony pyroelectric material is done thermoelectric layer, and silica dioxide granule is done the phonon scattering layer, and deposition has the independently thermoelectric device of PN type thermoelectric arm.
Membrane deposition method is a rf magnetron sputtering, and the base vacuum degree is 1*10 -4Pa, operating air pressure are 0.4Pa.
The laser cutting substrate is bar shaped.With acetone and alcohol and pure water ultrasonic cleaning substrate successively, dry up substrate with dry pure nitrogen gas.
Use rf magnetron sputtering to plate one deck p type thermoelectric material at the part substrate, power density is 2W/cm 2, thickness is 10nm, plates the layer of silicon dioxide stratum granulosum then, thickness is 10nm, repeats this process 100 times, then in a vacuum, under 500 ℃, heat-treats 60 hours, obtains p type thin film thermoelectric arm.
Afterwards, on the part individual substrate, use rf magnetron sputtering to plate one deck n type thermoelectric material, power density is 2W/cm 2, thickness is 10nm, plates one deck magnesium oxide layer then, thickness is 10nm, repeats this process 100 times, then in a vacuum, under 500 ℃, heat-treats 60 hours, can obtain n type thin film thermoelectric arm.
Afterwards, on p type and n type thermoelectric arm, cover the electrode mask plate respectively.Use rf magnetron sputtering to plate one deck titanium, do the electrode barrier layer, power density is 2W/cm 2, thickness is 50nm.And then the copper that plates 1 micron thick does electrode, and power density is 2W/cm 2
So far, connect the electrode on p type and the n type thermoelectric arm, just can obtain having the independently multilayer film thermoelectric device of PN type thermoelectric arm with lead-in wire.The structural representation of gained thermoelectric device is as shown in Figure 4, and 41 is the hot junction, and 42 is electrode, and 43 are lead-in wire, and 44 is p type thermoelectric arm, and 45 is that n type thermoelectricity is right, and 46 is cold junction.
The foregoing description is a preferred implementation of the present invention; But execution mode of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. nanostructured thermoelectric materials, it is characterized in that: this thermoelectric material comprises dielectric substrate and pyroelectric film; Said pyroelectric film comprises at least 2 layers of thermoelectric layer and at least 2 layers of phon scattering layer, and thermoelectric layer and phonon scattering layer alternately cover, and 1 layer of the most inboard thermoelectric layer covers on the substrate, and the thickness of said thermoelectric layer is 1nm~200nm; The thickness of said phon scattering layer is 1nm~100nm.
2. a kind of nanostructured thermoelectric materials according to claim 1 is characterized in that: the number of plies of said thermoelectric layer is 2~10000; The number of plies of said phon scattering layer is 2~10000; Said substrate is glass, silicon dioxide, aluminium oxide, aluminium nitride, magnesia, mica, polyamide, polybutylene terephthalate (PBT), PEN, Merlon, polyamide 6, copolyamide 6-X, poly aromatic acid amides MXD6 or polyphenylene sulfide, the natural number between X=6~12 among the said copolyamide 6-X; Said thermoelectric layer is simple substance thermoelectric material or compound thermoelectric material; Said phon scattering layer is nano-particle layer or insulating nano thin layer.
3. a kind of nanostructured thermoelectric materials according to claim 2 is characterized in that: said simple substance thermoelectric material is bismuth or silicon; Said compound thermoelectric material is that alloy, cobalt antimony are that alloy, SiGe are that alloy, bismuth antimony are that alloy, plumbous tellurium are that alloy, zinc antimony are alloy or magnesium Si system alloy for the bismuth tellurium; Said nano-particle layer is nano-metal particle layer or nanometer insulated particle layer; Do not contact each other between the metallic particles in the nano-metal particle layer.
4. a kind of nanostructured thermoelectric materials according to claim 3 is characterized in that: said nano-metal particle layer is refractory metal, transition metal, semimetal or metalloid; Said nanometer insulated particle layer is silicon dioxide, aluminium oxide, aluminium nitride, magnesia, carborundum, titanium oxide or titanium nitride; The granularity of said metallic particles and insulated particle is 1nm~20nm; Said insulating thin layer is silicon dioxide, aluminium oxide, aluminium nitride, magnesia, titanium oxide or titanium nitride.
5. a kind of nanostructured thermoelectric materials according to claim 4 is characterized in that: said refractory metal is tungsten, molybdenum, gold, titanium, niobium or their alloy; Said transition metal is nickel, iron, cobalt, chromium or their alloy; Said semimetal is bismuth, antimony or their alloy; Said metalloid is silicon, germanium or their alloy.
6. a kind of nanostructured thermoelectric materials according to claim 1 is characterized in that: said thermoelectric layer is a p type thermoelectric material, obtains p type nanostructured thermoelectric materials; Said thermoelectric layer is a n type thermoelectric material, obtains n type nanostructured thermoelectric materials.
7. the preparation method of a kind of nanostructured thermoelectric materials according to claim 1 is characterized in that comprising following operating procedure:
(1) cleans substrate, remove grease and attachment;
(2) adopt physical vapor method or chemical method on the substrate that cleaned, to deposit one deck thermoelectric layer, deposit one deck phon scattering layer again, electroless copper deposition operation is 2~10000 times repeatedly, obtains having the pyroelectric film of periodic structure;
(3) with pyroelectric film in vacuum or atmosphere of inert gases, under 60~1000 ℃, heat-treated 10 minutes~100 hours, obtain nanostructured thermoelectric materials.
8. the preparation method of a kind of nanostructured thermoelectric materials according to claim 7, it is characterized in that: the said physical vapor method of step (2) is sputtering method, hot steaming method, electron beam vapor deposition method or laser beam evaporation sedimentation; The power density of said sputter is 0.1W/cm 2~20W/cm 2
9. an application rights requires the thermoelectric device of 1 described nanostructured thermoelectric materials preparation.
10. the preparation method of thermoelectric device according to claim 9; It is characterized in that: said thermoelectric device prepares by following operating procedure: will replace between banded p type nanostructured thermoelectric materials that parallel interval arranges and the n type nanostructured thermoelectric materials along substrate and plate connection electrode; It is right to constitute p-n thermoelectricity, makes electric current along the transmission of pyroelectric film surface; A plurality of thermoelectricity are obtained thermoelectric device to parallel connection or series connection.
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