CN102867906A - Method for electrochemically preparing thermoelectric film by using seeding layer - Google Patents
Method for electrochemically preparing thermoelectric film by using seeding layer Download PDFInfo
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- CN102867906A CN102867906A CN2012103517063A CN201210351706A CN102867906A CN 102867906 A CN102867906 A CN 102867906A CN 2012103517063 A CN2012103517063 A CN 2012103517063A CN 201210351706 A CN201210351706 A CN 201210351706A CN 102867906 A CN102867906 A CN 102867906A
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- electromotive force
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Abstract
The invention belongs to the field of electrochemical preparation of a thermoelectric material, and relates to a method for electrochemically preparing a thermoelectric film by using a seeding layer, which comprises the following steps: preparing a seeding layer having a nano-level thickness on a substrate through molecular beam epitaxy, magnetron sputtering and other modes; and electrochemically growing a thermoelectric film material, wherein the thickness of the film can be of the nano level. By using the method, the growth orientation of the epitaxial film can be controlled, and a thermoelectric film having an obviously column structure orientation is prepared, so that the thermoelectric properties of the electrochemically grown film can be improved. Due to the self characteristics of electrochemistry such as low cost and convenient growing process, a material preparation foundation is provided for the assembly of a thermoelectric device in future.
Description
Technical field
The present invention relates to the method that Seed Layer electrochemistry prepares thermal electric film, belong to electrochemistry and prepare the thin film technique field.
Background technology
Electrochemical deposition technique refers in an electrolytic cell work electrode (negative electrode) is arranged, and deposits needed material in the above, such as traditional metal, and present semi-conducting material.Whole deposition process is to carry out in the electrolyte that redox reaction occurs.Mix electrode (anode) and reference electrode, just can accurately control the size of the electric current of two interpolars and electromotive force to reach the purpose that deposits at substrate.The basic principle of electrochemical deposition is exactly the theory about nucleation and crystalline growth, and namely reducing solution intermediate ion at first carries out nucleation at substrate surface, then makes it along certain direction of growth crystalline growth.
Thermoelectric material attracts more and more people's attentiveness at present, because compare refrigerator and the generator of inner routine with refrigerator based on the thermoelectric generator of thermoelectric material many advantages are arranged, do not need to safeguard such as solid-state operation, tight, good scalability, zero discharge, the long operational time of design etc.In order to make thermoelectric material can obtain practical application, technology of preparing there is very high requirement, require the preparation method to have low cost, high production has good thermoelectricity capability simultaneously.Prepare thermoelectric material because have above-mentioned advantage with electrochemical deposition method, become a kind of technology with applications well prospect.Simultaneously, in order to be applied on the thermoelectric microdevice, just seem very important at silicon base growth thermoelectric film material.
In recent years, electrochemical deposition technique has a great development in metallic substrates or Conducting Glass preparation thermoelectric material, because electrochemical process has low-cost and easy-operating characteristics.Best thermoelectric material Bi under the present known room temperature for example
2Te
3Just can prepare its thin-film material by electrochemical method.Can be on conductive substrates by electrochemical method, for example metal carries out electro-deposition on the ITO electro-conductive glass etc.Yet, directly at the report of silicon base deposition thermoelectric material seldom because silicon has good conductivity like that not as metal, on silicon the Direct precipitation thermal electric film usually and the associativity of silicon very poor, crystallinity is bad, the relative metal electrode of quality of forming film is relatively poor.And have the uncontrollable problem of high preferred orientation with the grown by electrochemistry method thermal electric film, and cause the variation of experimental situation very large for effect of film formation, so both be unfavorable for improving thermoelectricity capability, also be unfavorable for suitability for industrialized production.But utilize the Seed Layer of the method preparations such as molecular beam epitaxy to have definite high preferred orientation, carry out again electrochemical growth, can obtain controlled high preferred orientation, also be beneficial to the film growth research on mechanism.
In silicon and substrate thereof, first with magnetron sputtering or molecular beam epitaxy deposition Seed Layer, and then be prepared in the above this depositional mode of thick film with electrochemical method and can well address the above problem.By electrochemical deposition process, can realize economically simply again the growth of film, and grow thickness and reach the good orientation of having of micron dimension and crystalline thermal electric film, for later industrial large-scale production provides technical support and material foundation.
Summary of the invention
What the present invention adopted is that electrochemical deposition method prepares thin-film material in Seed Layer, utilize the characteristics of electrochemical deposition mode, low such as growth temperature, cost is low, deposition rate is high, and the characteristics with definite growth orientation of Seed Layer, and growth orientation is namely arranged, has again certain thickness film, for the thin-film material that has certain thickness and good nature in the assembled heat electric device provides a good approach.
According to the present invention, relate generally to several processes, Seed Layer growth and electrochemical deposition.The effect of Seed Layer is at substrate surface extension or the growth orientation of sputter one deck film preferably, thereby increases associativity and Lattice Matching between film and the substrate, increases simultaneously the crystallinity of film.Can overcome so the bad shortcoming of traditional chemical growing film and substrate associativity, thereby realize the growth course of micron dimension.
The Seed Layer growth take molecular beam epitaxy as example, under the certain vacuum degree, keeps constant substrate temperature and electron gun furnace temperature, obtains the film of desired thickness by the control epitaxial growth time.
Electrochemical deposition, i.e. electrochemical growth on Seed Layer, as negative electrode, platinum guaze is as to electrode the silicon chip that is coated with Seed Layer, and saturated calomel solution carries out electro-deposition as reference electrode in electrochemical workstation.With thermoelectric material Bi best under the current room temperature
2Te
3Be example, selected solution is Bi (NO during deposition
3)
35H
2O, TeO
2And HNO
3Mixed liquor.Study reaction mechanism and determine sedimentation potential with cyclic voltammetry, select overpotential as sedimentation potential, depositional mode is permanent electromotive force deposition, and sedimentation time is 1 hour.Deposit later sample place and put into first 0.1 M/L HNO
3Soak slightly, then clean with ultra-pure water, alcohol is cleaned, and is natural drying in air.
The preparation of Seed Layer can be selected a kind of in molecular beam epitaxy, magnetron sputtering, electron beam evaporation, chemical vapour deposition (CVD), the electrochemical deposition; It is permanent electromotive force deposition, galvanostatic deposition, ladder electromotive force deposition or grading current deposition that institute is used on the seed electrochemical deposition mode.Seed Layer like this can be in the poor substrate of conduction, as carrying out electro-deposition on glass, the low-doped silicon chip as the electrochemistry cathode terminal.Annealing can improve the associativity of Seed Layer and epitaxial loayer.The thermal electric film of deposition can be Bi in this way
2Te
3, Bi
2Se
3, Sb
2Te
3, Bi
1-xSb
x, (Bi
1 xSb
x)
2Te
3, Bi
2Te
3 ySe
y, PbTe, PbSe, PbSe
1-xTe
x, CoSb
3
Concrete process is that the substrate of selecting is Si (111).At first will clean silicon chip, clean with traditional RCA wet chemistry cleaning process, concrete steps are: first at A liquid (H
2O:H
2O
2: NH
3H
2O=5:1:1) 80 ℃ of water-bath 10min in, purpose is to remove the organic substance on silicon chip surface, then at B liquid (HCl:H
20
2: H
280 ℃ of water-bath 10min 0=1:1:6), purpose is in order to remove the metal ion of silicon chip adsorption, then at C liquid BOE(HF:NH
4F=1:6) soaked 5 minutes in, purpose is in order to remove the oxide layer on surface, to use at last a large amount of deionized water rinsings, ultrapure N
2Dry up, be placed in the sample box and preserve.
Use the molecular beam epitaxial growth Seed Layer, design parameter is: vacuum degree is 3*10
-7Pa, the silicon base temperature is 300 ℃, and Bi electron gun furnace temperature is 490 ℃, and Te electron gun furnace temperature is 280 ℃, and the extension time is 30 minutes, the gained film thickness is 30nm.
Electrochemical growth on seed is with thermoelectric material Bi best under the current room temperature
2Te
3Be example, concrete steps are: being coated with 30nmBi
2Te
3The silicon of Seed Layer is as negative electrode, and the platinum guaze conduct is to electrode, and saturated calomel solution is as reference electrode.Carry out electro-deposition in electrochemical workstation (CHI660D, Shanghai occasion China Instr Ltd.), selected solution is that concentration is the Bi (NO of 0.008 M/L
3)
35H
2O, concentration is the TeO of 0.01 M/L
2, concentration is the HNO of 1M/L
3Determine with cyclic voltammetry that sedimentation potential, design parameter are selected as: initial potential and select 1v, high potential 1v, electronegative potential-1v, sweep speed 0.02v/s.Select overpotential as sedimentation potential, our depositional mode selected is permanent electromotive force deposition here, and deposition potential is-0.15 V, and sedimentation time is 1 hour.Deposit later sample treatment: put into first 0.1 M/L HNO3 and soak slightly, then clean with ultra-pure water, alcohol is cleaned, and is natural drying in air.
By such electrochemical deposition process, can realize economically simply again the thermal electric film growth, for later on large-scale commercial Application provides a kind of effective ways.
The orientation of film and Seed Layer can decide by the Thickness Ratio of control film and Seed Layer.In general, when the electrochemical deposition film thickness is far longer than the Seed Layer film thickness, we think that Seed Layer reduces for its impact, in fact, we find, by depositing the Seed Layer of 10 ~ 100nm, we can obtain the thin-film material that 1 ~ 10 μ m has good orientation and quality of forming film, in other words, grow in Seed Layer by electrochemistry, can realize hundred times of thickness and have good orientation and a crystalline thermal electric film.
Description of drawings
Fig. 1 is the XRD figure of MBE deposition Seed Layer of the present invention.
Fig. 2 is the SEM surface topography map of MBE deposition Seed Layer of the present invention.
XRD figure when Fig. 3 is the permanent electromotive force deposition-0.15v of the present invention.
SEM when Fig. 4 is the permanent electromotive force deposition-0.15v of the present invention shows shape appearance figure
SEM Cross Section Morphology figure when Fig. 5 is the permanent electromotive force deposition-0.15v of the present invention
Annotate: the material that the accompanying drawing example deposits is Bi
2Te
3, but the related material of patent is as claimed in claim 6.
Embodiment
The present invention is described in detail below in conjunction with embodiment:
Embodiment one: galvanostatic deposition Seed Layer on the sheet glass, then permanent electromotive force growth Bi
2
Te
3
The cleaning of sheet glass: be stained with cotton at first that cleaning agent is manual to be cleaned, with ultrasonic 10 minutes of the water that contains cleaning agent, then removed residual cleaning agent in 5 minutes with the ultra-pure water ultrasonic cleaning again, then use respectively acetone, ultrasonic 10 minutes of absolute ethyl alcohol.Dry up with high-purity N 2, it is stand-by to put into sample box.
With the preparation of galvanostatic deposition as Seed Layer, design parameter is: current density 1mA/cm
2, sedimentation time is 2 minutes, resulting seed layer thickness is about 100m.
The selected solution of electrochemical growth is Bi (NO
3)
35H
2O, concentration is 0.008 M/L; TeO
2, concentration is 0.01 M/L; HNO
3Concentration is 1M/L.Determine sedimentation potential by cyclic voltammetric, design parameter is selected as: initial potential and is selected 0.8v, high potential 0.8v, and electronegative potential-0.4v, sweep speed 0.02v/s selects overpotential to carry out permanent electromotive force growth.Grow with permanent electromotive force deposition, the parameter of selection is that current potential size-0.4v, sedimentation time are 1 hour.Deposit later sample treatment: put into first 0.1 M/L HNO
3Soak slightly, clean with ultra-pure water, then use alcohol wash, natural drying in air.
Embodiment two: silicon chip magnetron sputtering Seed Layer, then permanent electromotive force growth Bi
2
Te
3
The cleaning of silicon chip: clean with RCA chemical cleaning technology method, concrete steps are: first at A liquid (H
2O:H
2O
2: NH
3H
2O=5:1:1) 80 ℃ of water-bath 10min in are then at B liquid (HCl:H
20
2: H
280 ℃ of water-bath 10min 0=1:1:6) are then at C liquid BOE(HF:NH
4F=1:6) soaked 5 minutes in, use at last a large amount of deionized water rinsings, ultrapure N
2Dry up, be placed in the sample box and preserve.
The design parameter that magnetron sputtering prepares Seed Layer is: adopt the method for Bi target, Te target co-sputtering, base vacuum is less than 2*10
-6Torr, sputter working gas are the high-purity argon gas of purity 99.999%, and the operating pressure of argon gas is 1.5mTorr, Bi target sputtering power is 15 w, and Te target sputtering power is 22 w, and the chip bench rotating speed is 20 rpm, the plated film time is 5 min, and film thickness is 50 nm.
The selected solution of electrochemical growth is Bi (NO
3)
35H
2O, concentration is 0.008 M/L; TeO
2, concentration is 0.01 M/L; HNO
3Concentration is 1M/L.With cyclic voltammetry determine sedimentation potential, design parameter select for: initial potential is selected 1 v, high potential 1 v, electronegative potential-0.5 v, sweep speed 0.02 v/s.Select overpotential as sedimentation potential, the depositional mode of selecting is permanent electromotive force deposition, and deposition potential is-0.2 V, and sedimentation time is 1 hour.Deposit later sample treatment: put into first 0.1 M/L HNO
3Soak slightly, clean with ultra-pure water, then use alcohol wash, natural drying in air.
Embodiment three: molecular beam epitaxy deposition Seed Layer on the sheet glass, then permanent electromotive force growth Bi
2
Te
3
The cleaning of sheet glass: be stained with cotton at first that cleaning agent is manual to be cleaned, with ultrasonic 10 minutes of the water that contains cleaning agent, then removed residual cleaning agent in 5 minutes with the ultra-pure water ultrasonic cleaning again, then use respectively acetone, ultrasonic 10 minutes of absolute ethyl alcohol.Use high-purity N
2Dry up, it is stand-by to put into sample box.
With the growth of molecular beam epitaxy Seed Layer, design parameter is: vacuum degree is 3*10
-7Pa, the sheet glass temperature is 200 ℃, and Bi electron gun furnace temperature is 490 ℃, and Te electron gun furnace temperature is 280 ℃, and the extension time is 20 minutes, the gained film thickness is 30nm.
Electrochemical growth, selected solution are Bi (NO
3)
35H
2O, concentration is 0.008 M/L; TeO
2, concentration is 0.01 M/L; HNO
3Concentration is 1M/L.Determine with cyclic voltammetry that sedimentation potential, design parameter are selected as: initial potential and select 0.8v, high potential 0.8v, electronegative potential-0.4v, sweep speed 0.02v/s.
Select overpotential as sedimentation potential, our depositional mode selected is permanent electromotive force deposition here, and deposition potential is-0.4V that sedimentation time is 1 hour.Deposit later sample treatment: put into first 0.1 M/L HNO
3Soak slightly, clean with ultra-pure water, then use alcohol wash, ultra-pure water is cleaned, and is natural drying in air.
Claims (4)
1. utilize Seed Layer electrochemistry to prepare the method for thermal electric film, it is characterized in that, utilize silicon chip, aluminium flake, sheet glass or stainless steel substrates as substrate, silicon chip cleans with RCA wet chemistry cleaning process before deposition; Sheet glass is used respectively cleaning agent, acetone and absolute ethyl alcohol ultrasonic cleaning; Be the Seed Layer of 10 ~ 200nm with molecular beam epitaxy or magnetron sputtering deposition one deck Nano grade thickness, carry out permanent electromotive force deposition with electrochemistry in Seed Layer again; As anode, silicon chip or sheet glass are as negative electrode with platinum guaze for electrochemical deposition; Deposition process adopts permanent electromotive force deposition, and potential range is-0.05 v ~-5 v, and depositing temperature carries out thermal anneal process to improve degree of crystallinity with sample at 10 ~ 50 ℃ after having deposited, and annealing temperature is 100 ℃ ~ 500 ℃.
2. the method for claim 1 is characterized in that, the preparation of Seed Layer can be selected a kind of in molecular beam epitaxy, magnetron sputtering, electron beam evaporation, chemical vapour deposition (CVD), the electrochemical deposition; It is permanent electromotive force deposition, galvanostatic deposition, ladder electromotive force deposition or grading current deposition that institute is used on the seed electrochemical deposition mode.
3. the method for claim 1 is characterized in that, Seed Layer as the electrochemistry cathode terminal, is carried out electro-deposition at the bottom of the poor glass of conduction or low-doped silicon wafer-based.
4. the method for claim 1 is characterized in that, described thermal electric film is Bi
2Te
3, Bi
2Se
3, Sb
2Te
3, Bi
1-xSb
x, (Bi
1 xSb
x)
2Te
3, Bi
2Te
3 ySe
y, PbTe, PbSe, PbSe
1-xTe
x, CoSb
3In a kind of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107620034A (en) * | 2017-07-20 | 2018-01-23 | 西南交通大学 | One kind prepares transparent Bi2Se3The method of film |
| CN108368599A (en) * | 2015-11-10 | 2018-08-03 | 山特维克知识产权股份有限公司 | A kind of surface to for coating carries out pretreated method |
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2012
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108368599A (en) * | 2015-11-10 | 2018-08-03 | 山特维克知识产权股份有限公司 | A kind of surface to for coating carries out pretreated method |
| CN108368599B (en) * | 2015-11-10 | 2020-11-06 | 山特维克知识产权股份有限公司 | Method for pretreating surface for coating |
| CN107620034A (en) * | 2017-07-20 | 2018-01-23 | 西南交通大学 | One kind prepares transparent Bi2Se3The method of film |
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Application publication date: 20130109 |