CN106784287A - High temperature quantum-well superlattice thick film thermoelectric material and its production method - Google Patents
High temperature quantum-well superlattice thick film thermoelectric material and its production method Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 230000005619 thermoelectricity Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
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- JKUUTODNPMRHHZ-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)germyl]methanamine Chemical compound CN(C)[Ge](N(C)C)(N(C)C)N(C)C JKUUTODNPMRHHZ-UHFFFAOYSA-N 0.000 claims description 6
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052782 aluminium Inorganic materials 0.000 claims description 5
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- 238000010521 absorption reaction Methods 0.000 description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 4
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- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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Abstract
The invention discloses a kind of production method of high temperature SQW thick film superlattice thermoelectric material, comprise the following steps：By the method for ald, in porous silicon, thermoelectric material is grown on the silicon substrate of Woelm Alumina or doping.Thermoelectric material can grow since the inwall in hole, then radially successively growing to hole, so as to generate thick film superlattice thermoelectric material.Basic thermoelectric material is SiGe.The present invention utilizes technique for atomic layer deposition, and with foraminous die plate as matrix, the method Fast back-projection algorithm via chemistry is suitable to the superlattice thermoelectric material of high temperature application, so as to realize the figure of merit high, conversion efficiency of thermoelectric high.High-temperature thermoelectric material on doping or flexible electrically-conductive backing plate, and can quickly be produced under conditions of non-high vacuum, and thickness and quantum-well superlattice structure with setting, be particularly suited for high temperature, that is, use 700 1100 degree of temperature range.
Description
Technical field
The common film of a kind of quantum-well superlattice the present invention relates to field of thermoelectric material technique covers the engineering of shape growth, especially relates to
And quantum-well superlattice thick film thermoelectric material and its production method.
Background technology
SiGe alloys are a kind of high-temperature thermoelectric materials conventional at present, are commonly applied to thermoelectric generator, it is adaptable to 700K
High temperature above, its optimal operation temperature is about 1300 DEG C.SiGe as important high-temperature thermoelectric material, with face-centered cubic knot
Structure and Parabolic band structure, with Seebeck coefficients high and high conductivity, therefore thermoelectric figure of merit is higher, can reach
0.7 or so.Because the thermal conductivity of SiGe alloys is also higher, so the ZT values of SiGe can not be improved further always.In the recent period with
The development of nanometer synthetic technology, the thermoelectricity capability of sige material is greatly improved, its research and development is achieved with application
It is obvious progressive.Used as a kind of potential thermoelectric material, SiGe alloys have been applied to aerospace field, such as 1977
American Tourister's aerospace detection device application SiGe makes thermoelectric generator, instead of PbTe, hereafter in serial NASA space programs
Also using SiGe thermoelectric materials.
, mainly for the preparation of polycrystal powder material, using ball milling, sintering and smelting technology are final for traditional powder metallurgic method
Obtain desired thermoelectric material.Although the mechanical performance of the material of metallurgy method synthesis has strengthened due to polycrystalline structure, can with
Avoid the sige material legibility that zone melting method is obtained from shortcoming, but on crucial thermoelectricity capability due to material density not
Ideal, causes thermoelectric figure of merit（ZT）Relatively low [1,2].
Technology for preparing high-quality thermoelectricity superlattice film mainly has molecular beam epitaxy (MBE), electrochemistry atom
Layer epitaxy（EC-ALE）With metal organic chemical compound vapor deposition (MOCVD).Prefered method is molecular beam epitaxy (MBE), many
Well known, it is complicated to there is equipment in this method, the defect such as expensive and complex technical process, it is this at a slow speed and expensive skill
Just possess can only when the quantum-well superlattice thickness of manufacture is in 100 nanometer scale or when product is used for high-grade, precision and advanced national defense industry for art
Row.
MOCVD methods are similar with MBE methods, there is complex process equipment, production cost costliness and complex technical process
Etc. defect, the limitation of its maximum also resides in raw material, and its raw material is metallo-organic compound, and synthesis is difficult, high cost and big
It is all poisonous, explosive, inflammable, toxic gas can be discharged in the preparation process of film such as (H2Te, H2Se), cause environment dirty
Dye.
Using aluminum oxide (AAO) nano-pore template, combined with electrochemical deposition process is very effective monodimension nanometer material
Synthetic method, inventor once using aluminum oxide (AAO) nano-pore template successfully synthesizing carbon nanotubes and cobalt nanowire array [3,
4].The SiGe nanostructureds [5] that Boston College Zhifeng Ren are obtained, the holt of Commissariat A L'Energie Atomique believes receiving for speech
The sige material nano-wire array [6] with high-compactness characteristic of rice composite growth.The property of these nanostructured thermoelectric materials
Though improvement can have, the material cost of synthesis is high, and quality is still unsatisfactory, mainly nano wire without SQW or original
Sublayer interfacial structure.
1. a kind of preparation method of silicon-germanium pyroelectric material, CN200710118217.2.
2. the method that liquid quenching cooperated with spark plasma sintering prepares silicon-germanium-based thermoelectric material, the B of CN 101307393
3. Hongguo Zhang et al, J. of The Electrochemical Society, 2007, 154(2):
H124-H126
4. Hongguo Zhang et al, Electrochem. Solid-State Lett. 2008 11:K57-K60
5. the method for high quality factor in nanostructured thermoelectric materials, the A. of CN 101803050 are used for
6. there is the SiGe substrate nano composites of the thermoelectric figure of merit for improving, the A. of CN 102149845
The content of the invention
The technical problems to be solved by the invention are directed to above-mentioned the deficiencies in the prior art, there is provided a kind of high-temperature thermoelectric material
Production method and high temperature SQW thick film superlattice thermoelectric material, the present invention can produce micron order thickness thick film thermoelectricity surpass
Lattice material, and production technology cost is low, efficiency high, equipment are relatively easy, and the pyroelectric material performance for being produced is good, conversion effect
Rate is high.
To realize above-mentioned technical purpose, the technical scheme that the present invention takes is：
The production method of high temperature SQW thick film superlattice thermoelectric material, it is characterised in that comprise the following steps：
By the method for ald, thermoelectric material is grown in the hole on substrate, the thermoelectric material is opened from the inwall in hole
Begin to grow, then successively grown along aperture direction, untill hole covers with, form the thick film heat with quantum-well superlattice structure
Electric material；The thermoelectric material is SiGe.
Further, the substrate is conducting metal substrate, the silicon substrate of doping, porous silicon substrate or Woelm Alumina
Substrate.
Further, the porous oxidation aluminium base is alumina nanohole substrate.
Further, the aperture of alumina nanohole substrate is no more than 50 nanometers.
Further, the hole of the alumina nanohole substrate is the doubled via of both-side opening.
Further, the pore wall thickness of the alumina nanohole is 5-50nm.
Further, comprise the following steps：
（1）Pulse Si vaporous precursors：
To being continually introduced into Si vaporous precursors in reaction chamber, the Si vaporous precursors are（Three（Dimethylamino）Silicon Tris
(dimethylamino)silicon 3DMAS 99.9999%）；Underlay substrate temperature in the reaction chamber for 200 oC-
400 oC；The substrate is the silicon or porous alumina formwork of doping；
（2）Cleaning Si vaporous precursors：
Work as template（Internal surface of hole）When surface reaches the saturation state of chemisorbed, stop introducing the Si vaporous precursors；Together
When introduce inert gas, Si vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Ge vaporous precursors：
To being continually introduced into Ge vaporous precursors in reaction chamber；The Ge vaporous precursors are (four（Dimethylamino）Germanium
Tetrakis(dimethylamino)germanium TDMAGe 99.9999%)；Substrate substrate temperature in the reaction chamber
It is 150 oC -200oC to spend；The substrate is alumina nanohole substrate；
（4）Cleaning Ge vaporous precursors：
When alumina nanohole substrate surface reaches the saturation state of chemisorbed, stop introducing the Ge vaporous precursors；
Inert gas is introduced simultaneously, and Ge vaporous precursors remaining in reaction chamber are cleaned up；
（5）Reaction cycle：
Step（1）-（4）Circulation is carried out, untill the nano-pore of alumina nanohole substrate is covered with.
Further, the radial growth of superlattice thermoelectric material film is controlled by controlling reaction cycle number, is ultimately formed
Longitudinal thick film superlattice thermoelectric material.
Further, when cleaning remaining Si and Ge vaporous precursors, the purge gas for using are high pure nitrogen or argon gas.
Further, by adjusting open-assembly time of the alumina nanohole substrate in vaporous precursors, it is ensured that in profundity
Conformal overlay film growth SiGe quantum-well superlattice thermoelectric materials on the alumina nanohole substrate inwall of width-ratio structure.
To realize above-mentioned technical purpose, another technical scheme that the present invention takes is：Using above-mentioned high temperature SQW
The quantum-well superlattice thick film thermoelectric material that the production method of thick film superlattice thermoelectric material is produced.
Beneficial effect：
Present invention application depth-width ratio alumina nanohole substrate, conformal film overgrowth thick film quantum-well superlattice thermoelectric material long；This
Invention utilizes technique for atomic layer deposition, with superelevation depth-width ratio porous nano casement plate（Such as alumina nanohole substrate）It is lining
Bottom, via the method Fast back-projection algorithm thick film superlattice thermoelectric material of chemistry（SiGe superlattices thick film thermoelectric materials）, the thickness of generation
The thickness of film superlattice thermoelectric material up to 50-500 μm, so as to realize the thermoelectric figure of merit high of material（ZT）, and potential device
Conversion efficiency of thermoelectric high；The present invention can be under conditions of non-high vacuum, and the quick production of low cost has setting thickness superlattices material
Material, and performance is much better than existing technology report, is particularly suited for high temperature, that is, use temperature range 700-1100 oC.
The theoretical and all verified thermoelectric material with atomic layer quantum-well superlattice nano-micro structure of experiment is necessarily gathered around
There is excellent thermoelectricity capability (referring to 1. HicksLD et a1.Physics RevB, 1993,47：12 727；2. Hicks LD
Et a1.Appl Phys Lett, 1993,63：3230；3. Broido D A et a1.ApplPhys Lett, 1997,70：
2834；4. HicksLD ela1.Phys Rev B, 1996,53：R10 493；5. Venkatasubramanian R et
A1.Nature, 2001,413：597), because：(1) density of states of material is increased near fermi level, so as to improve
Seebeck coefficients；(2) because SQW is constrained, by doping, the mobility of carrier is increased；(3) atom bed boundary increases,
The interface scattering of phonon can be dramatically increased, the thermal conductivity factor of material is substantially reduced；（4）With super crystal lattice material micro-structural nanometer
Change and lower dimension, thermoelectric figure of merit will be greatly increased with the reduction of material microstructure yardstick.
ALD techniques have the feature of a uniqueness, are exactly to high-aspect-ratio (High Aspect Ratio) structure shape
Looks have good conformality（Conformal overlay film）, we make full use of this characteristic superiority, with reference to commercialized AAO nanometers
Casement plate, can successfully obtain thick film thermoelectricity with quantum-well superlattice structure of the thickness at 1-500 microns in a short time
Material.
In a word, the present invention is based on bilateral alumina nanohole substrate, using ald（ALD）Method grow
A kind of thick film quantum-well superlattice thermoelectric material, there is provided strategy of inexpensive fast-growth high performance thermoelectric material, realizes super
The effective ways of high-quality superlattice thermoelectric material are produced in depth-width ratio template high, and ensures the excellent performance of material.
Particular technique effect is：
（1）There is provided a kind of utilization superelevation depth-width ratio template production low-cost and high-performance thick film quantum-well superlattice thermoelectric material
Method, and the thermoelectric material for being grown has excellent thermoelectricity capability, so that realize when thermo-electric device is commercialized, it is remaining, useless
Hot Efficient Conversion is electric energy, or excellent refrigeration performance；
（2）The thermoelectric material thermoelectric figure of merit for being grown is high, can reach 1.10, and can be realized in various substrates, especially
In doped silicon, aluminium, aluminium alloy or other flexible conductive base plates, so as to reduce the manufacturing cost of thermo-electric device.
（3）Si light weights, rich reserves, asepsis environment-protecting, the electronic application and technique about silicon is highly developed, is developed
The thermoelectric material of SiGe, and its reliability is high, can not only can be used to send out as most important material in semi-conductor industry
Electricity, and consumption electronic product is can be applied to, realize that the self-powered of electronic product is used.
Brief description of the drawings
Fig. 1 is the microphotograph after porous alumina formwork in embodiment 1 and SiGe growths.
Fig. 2 be embodiment 2 in ALD2000 cycling deposition of porous silicon SiGe thermoelectric materials before and after sweep microphotograph.
Fig. 3 sweeps microphotograph for the SiGe thermoelectric materials for showing growth in doped silicon in embodiment 3
Fig. 4 is the thermoelectric figure of merit that the SiGe that this alumina nanohole substrate difference ALD cycle number grows is measured.
Fig. 5 is the thermoelectric figure of merit that the SiGe that the porous silicon substrate difference ALD cycle number for adulterating grows is measured.
The thermoelectric figure of merit that the SiGe of the silicon substrate difference ALD cycle number growth of Fig. 6 doping is measured.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is expanded on further.These embodiments are merely to illustrate the present invention rather than limit
The scope of the present invention processed.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition or according to system
Make the condition proposed by manufacturer.Unless otherwise defined, all specialties used in text and scientific words and the skilled people in this area
Meaning familiar to member institute is identical.Additionally, any method similar to described content or impartial and material all can be applied to this hair
In bright method.Preferable implementation described in text only presents a demonstration with material and is used.
Embodiment 1
The production method of this high temperature quantum-well superlattice thick film thermoelectric material, comprises the following steps：
（1）Pulse Si vaporous precursors：
To Si vaporous precursors are continually introduced into reaction chamber, the Si vaporous precursors are three（Dimethylamino）Silicon, Tris
(dimethylamino) silicon, 3DMAS, 99.9999%；Underlay substrate temperature in the reaction chamber is 200oC -
400 oC；The substrate is alumina nanohole substrate；
（2）Cleaning Si vaporous precursors：
When alumina nanohole substrate surface reaches the saturation state of chemisorbed, stop introducing the Si vaporous precursors；
Inert gas is introduced simultaneously, and Si vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Ge vaporous precursors：
To being continually introduced into Ge vaporous precursors in reaction chamber；The Ge vaporous precursors are four（Dimethylamino）Germanium,
Tetrakis (dimethylamino) germanium, TDMAGe, 99.9999%；Substrate underlayer temperature in the reaction chamber
It is 200oC -400 oC；The substrate is alumina nanohole substrate；
（4）Cleaning Ge vaporous precursors：
When alumina nanohole substrate surface reaches the saturation state of chemisorbed, stop introducing the Ge vaporous precursors；
Inert gas is introduced simultaneously, and Ge vaporous precursors remaining in reaction chamber are cleaned up；
（5）Reaction cycle：
Step（1）-（4）Circulation is carried out, untill the nano-pore of alumina nanohole substrate is covered with.
In the present embodiment, alternately two kinds of vaporous precursors are continually introduced into in reaction chamber；Described two vaporous precursors
It is respectively Si vaporous precursors and Ge vaporous precursors；The Si vaporous precursors are dimethylamino silicon, Tris
(dimethylamino) silicon, 3DMAS, 99.9999%, the Ge vaporous precursors are four（Dimethylamino）Germanium,
Tetrakis (dimethylamino) germanium, TDMAGe, 99.9999%；Temperature in the reaction chamber for 200-
400oC；The substrate is alumina nanohole substrate；When alumina nanohole substrate surface reaches the saturation shape of chemisorbed
During state, the introduced vaporous precursors of absorption are automatically stopped；Alumina nanohole substrate is super depth-width ratio alumina nanohole base
Plate, referring to Fig. 1；Inert gas is argon gas.
（2）Reaction cycle alternately, until the nano-pore of alumina nanohole substrate is filled up；Each reaction cycle is included
Following four step：
Pulse Si presomas,
Cleaning Si presomas；
Pulse Ge presomas,
Cleaning Ge presomas.
Further, SQW superlattice thermoelectric material nano-interface micro-structural is controlled by controlling reaction cycle number, most
End form is into thick film superlattice thermoelectric material.In cleaning Si presomas and cleaning Ge presoma steps, the purge gas for using are high
Pure nitrogen gas or argon gas.By adjusting open-assembly time of the alumina nanohole substrate in vaporous precursors, realize Si or Ge in table
The saturation absorption in face, reaches the conformal overlay film growth SiGe SQWs on the alumina nanohole substrate inwall of high aspect ratio structure
Superlattice thermoelectric material, ultimately forms SiGe thick film superlattice thermoelectric materials.
In the present embodiment, thick film superlattice thermoelectric material is SiGe, and AAO substrates aperture is 150nm or so, uses ald
（ALD）Method prepares Bi2Te3 thick film superlattice thermoelectric materials, and vaporous precursors source is dimethylamino）Silicon, Tris
(dimethylamino) silicon and dimethylamino）Germanium, Tetrakis (dimethylamino) germanium, substrate is super
Depth-width ratio alumina nanohole substrate, carrier gas is argon gas, and design parameter is as follows：Underlayer temperature：350℃；Cleaning：N2/Ar；Pipeline
Temperature：200℃；Reaction chamber heating-up temperature：200-400℃；Chamber： 200-400℃；Reaction process pressure：0.05
torr；According to the reaction pressure of 0.05torr, carrier gas flux is set, there are three pipelines of argon gas, flow is respectively 25,15,12
sccm；
Technological parameter：Dose-Reaction--Purge-Goto-End 3.0s 5.0s 80s 800 are circulated.
The main processes of the present embodiment are as follows with advantage：
1）By in a heating（200 -400oC）In reaction chamber）Upper alternating is continually introduced into two kinds of vaporous precursors species
Vaporous precursors source is dimethylamino）Silicon, Tris (dimethylamino) silicon and dimethylamino）Germanium, Tetrakis
(dimethylamino)germanium；
2）AAO substrate surfaces are automatically stopped when reaching the saturation state of chemisorbed, can equably growing film；
The homogeneity of presoma flow, appropriate heating-up temperature need not be controlled（200-400oC）Precursor molecule can be hindered to exist
AAO substrates（That is alumina nanohole substrate）The physical absorption on surface；
4）Circulation（cycles）Constantly repeat, untill AAO nano-pores are filled up；Each four step of circulation：
Pulse Si presomas,
Cleaning Si presomas；
Pulse Ge presomas,
Cleaning Ge presomas.
5）Growth time depends on nanometer pore radius, by controlling reaction cycle number（cycles）Accurately control film
Growth, can reach the film of atomic layer level thickness precision；
6）Purge gas can be high pure nitrogen or inert gas, such as argon gas；
The quality of material depends on the diffusion of precursor gas；ALD system can adjust the exposure of persursor material with flexibility
Time.The presoma being passed through（Reacting gas）Longer time is stopped in reaction chamber, precursor gas can be increased in sky
The open-assembly time of wall surface, so that it is guaranteed that reaching the full of forerunner's element of volume in the AAO sample inner wall surfaces of high aspect ratio structure
And absorption, and conformal overlay film growth SiGe quantum-well superlattice materials；
Real material thickness depends on the depth of AAO nano-pores；
From the point of view of to the characterization result of the material for being grown, the thermoelectric figure of merit of material has obtained effective raising, has reached 0.9,
Referring to Fig. 4；The SEM that Fig. 1 show the SiGe nano super-lattice thick film samples prepared using the inventive method is shone
Piece.
The thermoelectric material that the present embodiment is produced possesses high-quality, high-performance, low cost, be conducive to opening it is many mini and
Interesting microelectronics market：Such as fast electronic product radiating, the instrument of fast temperature adjustment, infrared acquisition, the transmitting of biomedical and light
Device temperature stabilization（Laser, LEDs）Deng.
The SiGe quantum-well superlattices material that the present embodiment is grown in 1100K thermoelectric figure of merit up to 0.9, if further
Optimize technique, the thermoelectric figure of merit of material should be more than 1.0, with greatly commercialization value and wide application prospect.
The scope of the present invention is not limited by the specific embodiments described, and the embodiment is only used as illustrating of the invention each
Also include the method and component of functional equivalent in the single example of individual aspect, the scope of the invention.In fact, except as herein described
Outside content, those skilled in the art can be easily grasped to various improvement of the invention with reference to described above and accompanying drawing.Institute
Improvement is stated to also fall within the scope of the appended claims.Every bibliography mentioned above all lists this paper conducts in full
With reference to.
Embodiment 2
The present embodiment 2 is that the substrate is the porous silicon template of doping with the difference of embodiment 1；The reaction chamber
Interior substrate underlayer temperature is 350 oC；Reaction chamber heating-up temperature：350℃；Something in common is no longer described in detail.
Embodiment 3
The present embodiment is that the substrate is the silicon substrate of doping with the difference of embodiment 2；Base in the reaction chamber
Plate underlayer temperature is 350 oC；Reaction chamber heating-up temperature：350℃；Something in common is no longer described in detail.
Claims (11)
1. the production method of superlattice thermoelectric material, it is characterised in that comprise the following steps：
By the method for ald, in various grown on substrates high-temperature thermoelectric materials, for porous substrate, the thermoelectricity material
Material grows since the inwall in hole, is then successively grown along hole radial direction, untill hole covers with, forms super with SQW
The thick film thermoelectric material of lattice structure；The thermoelectric material is SiGe.
2. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 1, it is characterised in that：Institute
It is conducting metal substrate, the silicon substrate of doping, porous silicon substrate or porous oxidation aluminium base to state substrate.
3. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 2, it is characterised in that：Institute
Porous oxidation aluminium base is stated for alumina nanohole substrate.
4. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 3, it is characterised in that：Oxygen
The aperture for changing aluminium nano-pore substrate is no more than 50 nanometers, and the aperture of porous silicon substrate is no more than 5 microns.
5. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 4, it is characterised in that：Institute
The hole for stating alumina nanohole substrate is the doubled via of both-side opening；The hole of the porous silicon substrate is the single-pass of single-open
Hole.
6. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 5, it is characterised in that：Institute
The pore wall thickness for stating alumina nanohole is 5-50nm；The pore wall thickness of the porous silicon substrate is about 0.5-1 microns.
7. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that bag
Include following steps：
（1）Pulse Si vaporous precursors：
To being continually introduced into Si vaporous precursors in reaction chamber, the Si vaporous precursors are（Three（Dimethylamino）Silicon Tris
(dimethylamino)silicon 3DMAS 99.9999%）；Underlay substrate temperature in the reaction chamber for 200 oC-
400 oC；The substrate is the silicon or porous alumina formwork of doping；
（2）Cleaning Si vaporous precursors：
Work as template（Internal surface of hole）When surface reaches the saturation state of chemisorbed, stop introducing the Si vaporous precursors；Together
When introduce inert gas, Si vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Ge vaporous precursors：
To being continually introduced into Ge vaporous precursors in reaction chamber；The Ge vaporous precursors are (four（Dimethylamino）Germanium
Tetrakis(dimethylamino)germanium TDMAGe 99.9999%)；Substrate substrate temperature in the reaction chamber
It is 150 oC -200oC to spend；The substrate is alumina nanohole substrate；
（4）Cleaning Ge vaporous precursors：
When alumina nanohole substrate surface reaches the saturation state of chemisorbed, stop introducing the Ge vaporous precursors；
Inert gas is introduced simultaneously, and Ge vaporous precursors remaining in reaction chamber are cleaned up；
（5）Reaction cycle：
Step（1）-（4）Circulation is carried out, untill the nano-pore of alumina nanohole substrate is covered with.
8. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：It is logical
The radial growth that control reaction cycle number controls superlattice thermoelectric material film is crossed, longitudinal thick film superlattice thermoelectric material is ultimately formed
Material.
9. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：Clearly
When washing Si the and Ge vaporous precursors of remnants, the purge gas for using are high pure nitrogen or argon gas.
10. the production method of high temperature SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：
By adjusting open-assembly time of the alumina nanohole substrate in vaporous precursors, it is ensured that received in the aluminum oxide of high aspect ratio structure
Conformal overlay film growth SiGe quantum-well superlattice thermoelectric materials on metre hole substrate inwall.
The producer of the high temperature SQW thick film superlattice thermoelectric material any one of a kind of 11. use claim 1-10
The SQW thick film superlattice thermoelectric material that method is produced.
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| CN110828650A (en) * | 2019-11-27 | 2020-02-21 | 东华大学 | Organic-inorganic composite thermoelectric film and preparation method thereof |
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