CN106876571A - Quantum-well superlattice thick film thermoelectric material and its production method - Google Patents
Quantum-well superlattice thick film thermoelectric material and its production method Download PDFInfo
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Abstract
The invention discloses a kind of production method of SQW thick film superlattice thermoelectric material, comprise the following steps：By the method for ald, thermoelectric material is grown in alumina nanohole interior orientation.Thermoelectric material grows since the inwall of nano-pore, is then successively grown to the axis direction of nano-pore, forms thick film superlattice thermoelectric material.Nano-pore mould material can be Al2O3, TiO2 or SiO2, and basic thermoelectric material is Bi2Te3.The present invention utilizes technique for atomic layer deposition, with superelevation depth-width ratio porous alumina formwork as matrix, via the method Fast back-projection algorithm Bi2Te3 superlattices thick film thermoelectric materials of chemistry, so as to realize the figure of merit high, conversion efficiency of thermoelectric high.The thick film thermoelectricity super crystal lattice material can be under conditions of non-high vacuum, quick production, and thickness and quantum-well superlattice micro-structural with setting, and performance is much better than existing technology report.
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
Thermoelectric material is that transmission and interaction using solid carriers and phonon are mutual to realize heat energy and electric energy
The semiconductor functional material of conversion, has the advantages that without making an uproar, light, green, has in thermo-electric generation and refrigerating field important
Application value and prospect.After energy crisis, developed country all seeking efficient, free of contamination energy conversion regime, with
Reach the purpose of the energy such as rational and efficient use waste heat, used heat, underground heat, solar energy and ocean thermal gradients.
Bi2Te3 is the commercialized main thermoelectric material of current thermoelectricity industry, is widely used in new device, new energy
Contour new green environmental protection industry.Bi2Te3 semi-conducting materials are as raw material, by certain chemical composition and doping work with bismuth, tellurium etc.
Skill is prepared.Thermo-electric generation is application of the Seebeck effect in terms of generation technology, and the ZT values of Seebeck coefficient or material
Determine the generating efficiency of thermo-electric device.The ZT values of commercialized Bi2Te3 are only capable of reaching 0.70 or so, corresponding device heat
Photoelectric transformation efficiency is extremely low, seriously limits its application.
Traditional directional solidification method early stage is used to produce Bi2Te3 crystal bar materials, the cooldown rate grown by controlled material
Etc. preparing high-quality Bi2Te3 monocrystal materials, but this method energy consumption is big, and mechanical performance is poor, and what is be unfavorable for is laggard
The production and processing of one step, causes the working life for wasting and influenceing integral device in device manufacturing processes, causes higher giving up
Product rate.Also a kind of conventional method is powder metallurgic method, mainly for the preparation of polycrystal powder material, using traditional ball milling and molten
Sweetening process finally gives desired thermoelectric material.Although the mechanical performance of the material of metallurgy method synthesis has due to polycrystalline structure
Strengthened, also effectively prevent area's melt material legibility from shortcoming, but due to low compactedness material on crucial thermoelectricity capability
Structure is unsatisfactory, especially thermoelectric figure of merit（ZT）It is lower.
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.
Although EC-ALE methods are simple, equipment cost is cheap, and it is complicated to there is influence factor, such as deposition potential, electrode,
The reciprocal effects such as backing material characteristic, solution temperature, electrolyte concentration, so as to second-rate, the composition that causes film to be likely to occur
The nonstoichiometry defect such as when pattern is inconsistent.Therefore use EC-ALE method prepared compositions complicated or high performance superlattices
Thermoelectric film material is more difficult.
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 [1,
2].Manin etc. obtains Bi2Te3 nano-wire arrays using the method, and the A.Stacy of University of California Berkeley is successfully obtained
Obtained edge<110>The Bi2Te3 nano-wire arrays [3-5] with single crystal characteristics of direction oriented growth.These nano wire thermoelectricity materials
Though the performance of material has improvement, the quality of materials of synthesis is still unsatisfactory, and the crystallinity of nano wire is not high, with less quantum
Trap or atomic layer interfacial structure.
1. Hongguo Zhang et al, J. of The Electrochemical Society, 2007, 154
(2): H124-H126
2. Hongguo Zhang et al, Electrochem. Solid-State Lett. 2008 11:K57-K60
3. S.Sapp, C.Martin, Advanced Materials, 1999, JJ, 402.
4. A.Priet, A.Stacy, J. of American Chemical Society, 2001,123,7160.
5. M.Sander, A.Stacy, Advanced Materials, 2002,14,665.
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 one kind production has thick film
The method of the thermoelectric material of superlattice quantum well structure, the present invention can produce the thick film thermoelectricity superlattices material of micron order thickness
Material, and production technology cost is low, efficiency high, equipment are relatively easy, and the pyroelectric material performance for being produced is good, high conversion efficiency.
To realize above-mentioned technical purpose, the technical scheme that the present invention takes is：
The production method of 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 nano-pore of nano-pore template, the thermoelectric material is from receiving
The inwall of metre hole starts growth, is then successively grown along nano-pore radial direction, and untill nano-pore is covered with, being formed has amount
The thick film thermoelectric material of sub- trap superlattice structure.
Further, the nano-pore template can be Al2O3, TiO2 or SiO2.
Further, nano-pore template is that nano-pore aperture is no more than 200 nanometers.
Further, the nano-pore of the nano-pore template be both-side opening and connect doubled via or only side is opened
The single-pass hole of mouth or the combination for the through hole and single-pass hole.
Further, the pore wall thickness footpath of the nano-pore is 5-50nm.
Further, the thermoelectric material is the compound thermoelectricity materials of Bi2Te3 or Sb2Te3 or Bi2Te3/Sb2Te3
Material.
Further, comprise the following steps：
（1）Pulse Te vaporous precursors：
To Te vaporous precursors are continually introduced into reaction chamber, the Te vaporous precursors are tellurium organic precursor tellurium source material；
Underlay substrate temperature in the reaction chamber is 100 oC -200oC；The substrate is alumina nanohole template；
（2）Cleaning Te vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing the Te vaporous precursors；
Inert gas is introduced simultaneously, and Te vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Bi and/or Sb vaporous precursors：
To being continually introduced into Bi and/or Sb vaporous precursors in reaction chamber；Bi the and/or Sb vaporous precursors are the organic gas of bismuth
Phase precursor source material and/or antimony organic vapors precursor source material；Substrate underlayer temperature in the reaction chamber is 100
oC -200oC；The substrate is alumina nanohole template；
（4）Cleaning Bi and/or Sb vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing Bi the and/or Sb gas phases
Presoma；Inert gas is introduced simultaneously, Bi and/or Sb 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 template is covered with.
Further, the radially or laterally growth of superlattice thermoelectric material film is controlled by controlling reaction cycle number, most
End form is into longitudinal thick film superlattice thermoelectric material.
Further, in cleaning Bi vaporous precursors and cleaning gas phase Te presoma steps, the purge gas for using are high
Pure nitrogen gas or argon gas.
Further, by adjusting open-assembly time of the alumina nanohole template in vaporous precursors, it is ensured that in profundity
Conformal overlay film growth Bi2Te3 quantum-well superlattice thermoelectric materials on the alumina nanohole template inwall of width-ratio structure.
Further, the tellurium organic precursor tellurium source material is di-t-butyl tellurium.
Further, the bismuth organic vapors precursor source material is three bismuths（DPM dpm,dipivalomethane）.
Further, the antimony organic precursor tellurium source material is di-t-butyl tellurium or antimony triethyl.
To realize above-mentioned technical purpose, another technical scheme that the present invention takes is：Using above-mentioned SQW thick film
The quantum-well superlattice thick film thermoelectric material that the production method of superlattice thermoelectric material is produced.
Present invention application depth-width ratio alumina nanohole template, conformal film overgrowth thick film quantum-well superlattice thermoelectricity material long
Material；The present invention utilizes technique for atomic layer deposition, with superelevation depth-width ratio porous nano casement plate（Such as alumina nanohole template）
It is substrate, via the method Fast back-projection algorithm thick film superlattice thermoelectric material of chemistry（Such as Bi2Te3 superlattices thick film thermoelectricity material
Material）, the thickness of the thick film superlattice thermoelectric material of generation 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 super crystal lattice material, and performance is much better than existing technology report.
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 template, 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；Specific skill
Art 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 1.50, and can be realized in various substrates, especially
In aluminium, aluminium alloy or other flexible conductive base plates, so as to reduce the manufacturing cost of thermo-electric device.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of alumina nanohole template in embodiment 1.
Fig. 2 is that the SEM of the Bi2Te3 quantum-well superlattice thermoelectric materials of ALD growths in embodiment 1 is shone
Piece.
Fig. 3 is the thermoelectric figure of merit of the Bi2Te3 of difference ALD cycle number growth of the invention.
Fig. 4 is the thermoelectric figure of merit of the Sb2Te3 of present invention growth.
Fig. 5 is the thermoelectric figure of merit of the Bi2Te3/Sb2Te3 of present invention growth.
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 quantum-well superlattice thick film thermoelectric material, comprises the following steps：
（1）Pulse Te vaporous precursors：
To Te vaporous precursors are continually introduced into reaction chamber, the Te vaporous precursors are tellurium organic precursor tellurium source material；
Underlay substrate temperature in the reaction chamber is 100 oC -200oC；The substrate is alumina nanohole template；
（2）Cleaning Te vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing the Te vaporous precursors；
Inert gas is introduced simultaneously, and Te vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Bi and/or Sb vaporous precursors：
To being continually introduced into Bi and/or Sb vaporous precursors in reaction chamber；Bi the and/or Sb vaporous precursors are the organic gas of bismuth
Phase precursor source material and/or antimony organic vapors precursor source material；Substrate underlayer temperature in the reaction chamber is 100
oC -200oC；The substrate is alumina nanohole template；
（4）Cleaning Bi and/or Sb vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing Bi the and/or Sb gas phases
Presoma；Inert gas is introduced simultaneously, Bi and/or Sb 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 template 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 Te vaporous precursors and Bi vaporous precursors；The Te vaporous precursors are di-t-butyl tellurium（Di(t-butyl)
Tellurium, DTBTe, purity 99.99%）, the Bi vaporous precursors are three（DPM dpm,dipivalomethane）Bismuth
Tris (2,2,6,6-tetramethylheptan-3,5-dionato) bismuth, Bi (thd) 3, purity 99.99%）；It is described
Temperature in reaction chamber is 100-200oC；The substrate is alumina nanohole template；When alumina nanohole template table
When face reaches the saturation state of chemisorbed, the introduced vaporous precursors of absorption are automatically stopped；Alumina nanohole template is
Super depth-width ratio alumina nanohole template, referring to Fig. 1；Inert gas is argon gas.
（2）Reaction cycle alternately, until the nano-pore of alumina nanohole template is filled up；Each reaction cycle is included
Following four step：
Pulse Bi presomas,
Cleaning Bi presomas；
Pulse Te presomas,
Cleaning Te 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 Bi presomas and cleaning Te presoma steps, the purge gas for using are high
Pure nitrogen gas or argon gas.By adjusting open-assembly time of the alumina nanohole template in vaporous precursors, realize Bi or Te in table
The saturation absorption in face, reaches the conformal overlay film growth Bi2Te3 quantum on the alumina nanohole template inwall of high aspect ratio structure
Trap superlattice thermoelectric material, ultimately forms Bi2Te3 thick film superlattice thermoelectric materials.
In the present embodiment, thick film superlattice thermoelectric material is Bi2Te3 thick film superlattice thermoelectric materials, AAO substrates aperture
It is 150nm or so, uses ald（ALD）Method prepares Bi2Te3 thick film superlattice thermoelectric materials, and vaporous precursors source is
Three（DPM dpm,dipivalomethane）Bismuth Tris (2,2,6,6-tetramethylheptan-3,5-dionato)
Bismuth, Bi (thd) 3）With di-t-butyl tellurium（Di (t-butyl) tellurium, DTBTe）, substrate is super depth-width ratio oxidation
Aluminium nano-pore template, carrier gas is argon gas, and design parameter is as follows：Underlayer temperature：150℃；Cleaning：N2/Ar；Line temperature：100
℃；Reaction chamber heating-up temperature：60-200℃；Chamber： 100-200℃；Reaction process pressure：0.10 torr；According to
The reaction pressure of 0.10torr, sets carrier gas flux, there is three pipelines of argon gas, and flow is respectively 30,20,16 sccm；
Technological parameter：Dose-Reaction--Purge-Goto-End 1s 2.5s 80s 800 are circulated.
The main processes of the present embodiment are as follows with advantage：
By in a heating（100-200oC）In reaction chamber）Upper alternating is continually introduced into two kinds of uncles of vaporous precursors species two
Butyl tellurium（Di (t-butyl) tellurium, DTBTe, purity 99.99%）With three（DPM dpm,dipivalomethane）
Bismuth Tris (2,2,6,6-tetramethylheptan-3,5-dionato) bismuth, Bi (thd) 3, purity 99.99%）；
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（100-200oC）Precursor molecule can be hindered to exist
The physical absorption of AAO substrate surfaces；
4）Circulation（cycles）Constantly repeat, untill AAO nano-pores are filled up；Each four step of circulation：
Pulse Bi presomas,
Cleaning Bi presomas；
Pulse Te presomas,
Cleaning Te presomas.
Growth time depends on nanometer pore radius, by controlling reaction cycle number（cycles）Accurately control the life of film
It is long, the film of atomic layer level thickness precision can be reached；
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 Bi2Te3 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 1.5,
Referring to Fig. 3；Fig. 2 show the SEM of the Bi2Te3 nano super-lattice thick film samples prepared using the inventive method
Photo.
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 the instrument of fast temperature adjustment, microfluid, medical treatment, biomedical and pharmacy（PCR, blood point
Analysis, medicine is reclaimed）, emitter temperature stabilization（Laser, LEDs）Deng.
The Bi2Te3 quantum-well superlattices material that the present embodiment is grown in room temperature the hot figure of merit up to 1.56, if entering one
Step optimize technique, the thermoelectric figure of merit of material should be more than 2.0, 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 underlayer temperature in the reaction chamber is 180 with the difference of embodiment 1 oC；It is described
Substrate is Al2O3 nano-pore templates；Reaction chamber heating-up temperature： 100℃；Something in common is no longer described in detail.
Embodiment 3
The present embodiment 3 is that the substrate is TiO2 nano-pore templates with the difference of embodiment 1；In the reaction chamber
Substrate underlayer temperature be 175 oC；Reaction chamber heating-up temperature：150℃；Something in common is no longer described in detail.
Embodiment 4
Referring to Fig. 4, the present embodiment 4 is that a kind of presoma in introduced reaction chamber is three with the difference of embodiment 1
Ethyl antimony（Triethylantimony, TESb purity 99.99%）Or other antimony sources, substrate underlayer temperature is 180 oC；The lining
Bottom is Al2O3 nano-pore templates；Reaction chamber heating-up temperature：150℃；Something in common is no longer described in detail.
Embodiment 5
Referring to Fig. 5, the present embodiment 5 is that a kind of presoma being alternatively introduced into reaction chamber is with the difference of embodiment 1
Bismuth, antimony and tellurium precursor source；Substrate underlayer temperature is 180 oC；The substrate is Al2O3 nano-pore templates；Reaction chamber is heated
Temperature：150℃；Something in common is no longer described in detail.
Claims (14)
1. the production method of 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 nano-pore of nano-pore template, the thermoelectric material is from receiving
The inwall of metre hole starts growth, is then successively grown along nano-pore radial direction, and untill nano-pore is covered with, being formed has amount
The thick film thermoelectric material of sub- trap superlattice structure.
2. the production method of SQW thick film superlattice thermoelectric material according to claim 1, it is characterised in that：It is described to receive
Metre hole template can be Al2O3, TiO2 or SiO2.
3. the production method of SQW thick film superlattice thermoelectric material according to claim 2, it is characterised in that：Nano-pore
Template is that nano-pore aperture is no more than 200 nanometers.
4. the production method of SQW thick film superlattice thermoelectric material according to claim 3, it is characterised in that：It is described to receive
The nano-pore of metre hole template leads to for the single-pass hole of the doubled via or an only side opening of both-side opening and connection or for described
Hole and the combination in single-pass hole.
5. the production method of SQW thick film superlattice thermoelectric material according to claim 4, it is characterised in that：It is described to receive
The pore wall thickness of metre hole is 5-50nm.
6. the production method of the SQW thick film superlattice thermoelectric material according to claim 1 or 2 or 3 or 4 or 5, it is special
Levy and be：The thermoelectric material is Bi2Te3 or Sb2Te3, or Bi2Te3/Sb2Te3 composite thermoelectric materials.
7. the production method of SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that including with
Lower step：
（1）Pulse Te vaporous precursors：
To Te vaporous precursors are continually introduced into reaction chamber, the Te vaporous precursors are tellurium organic precursor tellurium source material；
Underlay substrate temperature in the reaction chamber is 100 oC -200 oC；The substrate is alumina nanohole template；
（2）Cleaning Te vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing the Te vaporous precursors；
Inert gas is introduced simultaneously, and Te vaporous precursors remaining in reaction chamber are cleaned up；
（3）Pulse Bi and/or Sb vaporous precursors：
To being continually introduced into Bi and/or Sb vaporous precursors in reaction chamber；Bi the and/or Sb vaporous precursors are the organic gas of bismuth
Phase precursor source material and/or antimony organic vapors precursor source material；Substrate underlayer temperature in the reaction chamber is 100
oC -200oC；The substrate is alumina nanohole template；
（4）Cleaning Bi and/or Sb vaporous precursors：
When alumina nanohole template surface reaches the saturation state of chemisorbed, stop introducing Bi the and/or Sb gas phases
Presoma；Inert gas is introduced simultaneously, Bi and/or Sb 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 template is covered with.
8. the production method of SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：By control
Reaction cycle number processed controls the radial growth of superlattice thermoelectric material film, ultimately forms longitudinal thick film superlattice thermoelectric material.
9. the production method of SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：Cleaning is residual
During remaining Bi and Te presomas, the purge gas for using are high pure nitrogen or argon gas.
10. the production method of SQW thick film superlattice thermoelectric material according to claim 6, it is characterised in that：Pass through
Open-assembly time of the adjustment alumina nanohole template in vaporous precursors, it is ensured that in the alumina nanohole of high aspect ratio structure
Conformal overlay film growth Bi2Te3, Sb2Te3 or Bi2Te3/ Sb2Te3 series of quantum well superlattice thermoelectric materials on template inwall
Material.
11. according to the SQW thick film superlattice thermoelectric material described in claim 6 production method, it is characterised in that：The tellurium
Organic precursor tellurium source material is di-t-butyl tellurium.
12. according to the SQW thick film superlattice thermoelectric material described in claim 6 production method, it is characterised in that：The bismuth
Organic vapors precursor source material is three bismuths（DPM dpm,dipivalomethane）.
13. according to the SQW thick film superlattice thermoelectric material described in claim 6 production method, it is characterised in that：The antimony
Organic precursor tellurium source material is di-t-butyl tellurium or antimony triethyl.
The production method institute of the SQW thick film superlattice thermoelectric material any one of a kind of 14. use claim 1-14
The SQW thick film superlattice thermoelectric material produced.
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Cited By (3)
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| CN107620100A (en) * | 2017-08-22 | 2018-01-23 | 滁州玛特智能新材料科技有限公司 | A kind of preparation method of thin film thermoelectric materials |
| CN110828650A (en) * | 2019-11-27 | 2020-02-21 | 东华大学 | Organic-inorganic composite thermoelectric film and preparation method thereof |
| CN113403607A (en) * | 2020-03-16 | 2021-09-17 | 北京动力机械研究所 | Component inner wall ALD coating equipment and method |
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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 |
| CN110828650B (en) * | 2019-11-27 | 2021-11-09 | 东华大学 | Organic-inorganic composite thermoelectric film and preparation method thereof |
| CN113403607A (en) * | 2020-03-16 | 2021-09-17 | 北京动力机械研究所 | Component inner wall ALD coating equipment and method |
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