CN105228273A - For the preparation of the precursor solution of semiconductor thermoelectric film, Electric radiant Heating Film and preparation method - Google Patents
For the preparation of the precursor solution of semiconductor thermoelectric film, Electric radiant Heating Film and preparation method Download PDFInfo
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- CN105228273A CN105228273A CN201510683050.9A CN201510683050A CN105228273A CN 105228273 A CN105228273 A CN 105228273A CN 201510683050 A CN201510683050 A CN 201510683050A CN 105228273 A CN105228273 A CN 105228273A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 58
- 239000002243 precursor Substances 0.000 title claims abstract description 57
- 238000010438 heat treatment Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000014121 butter Nutrition 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 239000001103 potassium chloride Substances 0.000 claims abstract description 13
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims abstract description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 5
- 230000000873 masking effect Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 117
- 239000000203 mixture Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005485 electric heating Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- -1 caddy Chemical compound 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
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- 239000002305 electric material Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 239000011265 semifinished product Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 101150051314 tin-10 gene Proteins 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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- Chemically Coating (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
<b> precursor solution for the preparation of semiconductor thermoelectric film, Electric radiant Heating Film and preparation method thereof.First, the precursor solution preparing semiconductor thermoelectric film be mixed to form with butter of tin, nano-stannic oxide, trichloride antimony, hydrofluoric acid, boric acid, potassium chloride, triethanolamine and related solvents is provided; Secondly, additionally provide by the film-forming process being sprayed into membrane process and impregnation technology and combining, and be aided with gradient Technology for Heating Processing, obtain the semiconductor thermoelectric film that high, the suitable large scale of quality of forming film is produced.The present invention improves the adhesion of Electric radiant Heating Film and matrix, obtains the Electric radiant Heating Film that thermal shock resistance is strong; Improve homogeneity and the masking efficiency of large area film forming; Obtain the large Electric radiant Heating Film of square resistance adjustable extent to adapt to different industries demand.</b>
Description
Technical field
The invention belongs to Electric radiant Heating Film field, particularly relate to a kind of precursor solution for the preparation of semiconductor thermoelectric film, Electric radiant Heating Film and preparation method thereof.
Background technology
Traditional electrical hot material, as tungsten, molybdenum, nickel and alloy thereof etc., also exists the shortcomings such as consumable quantity is large, useful life is short, shape difficulty, operating mode is unstable.In recent years, gradually by new electrically heating material and device replace.Wherein, Electric radiant Heating Film progressively replaces traditional thermo electric material in increasing field.
Electric radiant Heating Film is facial heating material, and form thermal conductive surface to greatest extent with heated object, heat transfer resistance is little.During electrified regulation, heat can pass to heated object very soon, and because this mode of heating heat conductivity is good, so Electric radiant Heating Film self-temperature is very not high, rubescent, red-hot phenomenon is not had to produce, radiation heat loss is very little, therefore with the electric heating appliance that Electric radiant Heating Film is made, the heat efficiency is quite high, generally all about 90%.And traditional heat point source due to area of dissipation little, other objects to be leaned on indirectly to conduct with heated object, in electric heating transfer process, the heat energy that electric energy produces can not pass to heated object very soon, cause heat on electric heating element too concentrated, element itself becomes red-hot very soon, and a big chunk of electric energy becomes luminous energy and scatters and disappears, and causes electric conversion efficiency lower.In addition, the features such as Electric radiant Heating Film also has long service life, technological requirement is simple, processing cost is low, safe and reliable.
Semiconductor thermoelectric film, also known as metal oxide Electric radiant Heating Film, closely to combine on dielectric surfaces, the film-form semi-conductive heating substance of planar thermal source is become after energising, it has the features such as fusing point is high, hardness is large, resistance is low, the heat efficiency is high, chemical stability is good, particularly resistance to bronsted lowry acids and bases bronsted lowry, the characteristic of the flames of anger in heating process, is subject to people's attention in electric heating field.
At present, there is electrothermal film technology prepared by various recipe optimization in disclosed document.Typically, such as, CN200910108880.3 discloses a kind of Electric radiant Heating Film and manufacture method thereof, and it mainly adopts butter of tin, titanium tetrachloride, four nickel chlorides, titanium trichloride, ferric trichloride, trichloride antimony, U-Ramin MC, potassium chloride, caddy, tin ash, four tin oxide, hydrofluoric acid, boric acid, ethanol, isopropyl alcohol and inorganic water.Adopt above-mentioned formula to heat through mix and blend, make Electric radiant Heating Film treatment fluid, be then half-finished product of electric heating film by Electric radiant Heating Film treatment fluid spray of negative pressure on Electric radiant Heating Film carrier, in half-finished product of electric heating film, being then coated with silver oxide slurry being Electric radiant Heating Film finished product through drying burning.For another example, CN201210178276.X discloses a kind of high efficiency energy saving new nano-material electrothermal film, its composition and ratio (mass percent) is: butter of tin 10 ~ 25, four nickel chlorides 2 ~ 8, iron oxide 10 ~ 20, titanium tetrachloride 5 ~ 10, sodium chloride 2 ~ 5, tin ash 10 ~ 15, hydrochloric acid 5 ~ 10, glycerol 5 ~ 15, ionized water, 20 ~ 40 through mixed at high speed agitating heating, make Electric radiant Heating Film treatment fluid, then utilize PVD technology to be deposited on base material by Electric radiant Heating Film treatment fluid and form nano electroheating film, then coat silver oxide slurry at nano electroheating film semi-finished product two ends and be nano electroheating film finished product through drying burning.Similarly, CN201210395154.6 discloses a kind of nano electroheating plate and manufacture method thereof of applied chemistry gas phase deposition technology.Primary raw material comprises: butter of tin, titanium tetrachloride, titanium trichloride, ferric trichloride, trichloride antimony, U-Ramin MC, potassium chloride, caddy, tin ash, hydrofluoric acid, boric acid, ethanol, isopropyl alcohol and pure water.Above-mentioned material agitating heating is measured by constant weight percentage, make electric heating nanometer film solution, solution spray is just become nano electroheating boards half-finished product by applied chemistry gas phase deposition technology on nano electroheating plate, and coating silver oxide slurry through sintering and reducing at nano electroheating plate is that silver electrode just defines nano electroheating board finished product.In addition, the patent of invention improved is carried out in addition for film build method and film for additive, such as CN201210460789x, CN201410233398.3 etc.; Patent comparatively early, then the formula of spininess to film forming improves, such as CN02122773.x, CN92106609.0 etc.Although conduct extensive research film-forming process and film component in prior art, but still there is many technical problems needs to solve further and perfect.
Following technical problem is mainly there is: (1) film forming stability is not enough in prior art.Existing spraying or other cladding processes, make Electric radiant Heating Film be combined with substrate not tight, easily ftracture or come off under external force or thermal stress effect; When adopting pvd or cvd method film forming, high to equipment requirement, add production cost, be unfavorable for the low price requirement of dairy products; (2) during large area film forming, film forming efficiency is low, especially spraying coating process film forming, spray rate and limited area, and need repeatedly to spray, when requiring high to thickness, film forming period is long; (3) thickness direction crystal grain is uneven, bears thermal stress scarce capacity.
Therefore, need that a kind of quality of forming film is good badly, good stability, be applicable to the process of large area film forming, prepare corresponding Electric radiant Heating Film.
Summary of the invention
The adhesion of the substrates such as the present invention is intended to solve following technical problem: the adhesion improving Electric radiant Heating Film and matrix, especially quartzy, ceramic, obtains the Electric radiant Heating Film that thermal shock resistance is strong; Improve homogeneity and the masking efficiency of large area film forming; Obtain the large Electric radiant Heating Film of square resistance adjustable extent to adapt to different industries demand.
For solving the problems of the technologies described above, the invention provides that a kind of quality of forming film is good, good stability, the precursor solution being applicable to the semiconductor thermoelectric film of large area film forming and Electric radiant Heating Film preparation method prepared corresponding semiconductor thermoelectric film accordingly.
First, the invention provides a kind of precursor solution of semiconductor thermoelectric film, the following technical scheme of concrete employing:
This prepares the precursor solution of semiconductor thermoelectric film, comprises by weight:
Butter of tin 25 ~ 45
Nano-stannic oxide 5 ~ 25
Trichloride antimony 1 ~ 6
Hydrofluoric acid 0.5 ~ 4
Boric acid 0.1 ~ 1.5
Potassium chloride 0.3 ~ 0.5
Triethanolamine 0.2 ~ 0.8
Solvent 20 ~ 60.
Particularly, described nano-stannic oxide is preferably the amorphous nano stannic oxide particle of particle diameter 20 ~ 200nm.Further, in the preferred technical scheme of the present invention, the described precursor solution preparing semiconductor thermoelectric film can be only made up of said components.
" nano-stannic oxide " described in the present invention or " amorphous stannic oxide particle " are the related chemistry raw material of indication on ordinary meaning in this area.Wherein " nano-stannic oxide " focuses on the dimensional parameters embodying raw material, and under normal circumstances, the size of nano-stannic oxide is less than the crystallite dimension in the tin dioxide thin film after film forming, in film forming in earlier stage, when not adding nano-stannic oxide, according to island growth model, first free nucleus is formed, the cycle formed is longer, and by with substrate contact first nucleation and growth process, and be later than the nucleation with substrate contact place away from the part nucleation of substrate, cause both growth course asynchronous, the final phenomenon easily formed from the outside ladder nucleation and growth process of substrate, this is to supporting thermal shock resistance, adhesive force is all disadvantageous with becoming film uniformity.The present invention, by initiatively increasing nano-stannic oxide, provides nucleus in early stage, is conducive to interface synchronous nucleation inner with film.Further, " amorphous stannic oxide particle " refers to that this material chemical component is tin ash, and proterties is solid granular, and crystalline state is amorphous state.Citing ground, common preparation technology has, adopt sol-gal process that Xi Yuan and oxidant and suitable solvent and catalyst (as NaOH, ammoniacal liquor etc.) are mixed to form colloidal sol, spray-dried or vacuumize, heat treatment form amorphous stannic oxide particle; Or, after aging formation gel, drying, obtain corresponding solid precursor, calcining form amorphous state tin ash, obtain corresponding particulate material through conventional crushing and screening means such as grinding, sieve.
Further, for improving the uniformity of nucleation further, the amorphous nano tin ash of employing is made up of following component:
The amorphous stannic oxide particle 10 ~ 30wt% of 20nm≤particle diameter < 50nm,
The amorphous stannic oxide particle 30 ~ 50wt% of 50nm≤particle diameter < 100nm,
The amorphous stannic oxide particle 30 ~ 40wt% of 100nm≤particle diameter≤200nm.
The different amorphous stannic oxide particle of particle diameter is equivalent to the nucleus providing each nucleation stage.The more important thing is, the crystalline rate of amorphous tin ash in heat treatment process of different-grain diameter is different, thus ensure that the close-fitting relationship between final crystal grain, contributes to the compactness improving film forming.
Secondly, for improving the scope of resistance adjustment, described precursor solution also comprises:
Magnesium chloride 0.1 ~ 0.5
Zirconium chloride 0.1 ~ 0.5.
In addition, for improving the electric property of film, adoptable technology also comprises, and described precursor solution also comprises:
Four nickel chlorides 0.6 ~ 1.5
Titanium tetrachloride 0.01 ~ 1.
Those skilled in the art, on the basis of technical scheme of the present invention, optionally, can also add the trace meters such as rare earth element and salt forms corresponding precursor solution to obtain the film of various electric heating property, do not limit and enumerate at this.
According to the difference of film forming thickness and film build method, optionally, described solvent is one or more in water, ethanol, isopropyl alcohol.
Secondly, present invention also offers a kind of method preparing semiconductor thermoelectric film, specifically adopt with the following method:
(1) precursor solution is configured
By weight:
Butter of tin 25 ~ 45
Nano-stannic oxide 5 ~ 25
Trichloride antimony 1 ~ 6
Hydrofluoric acid 0.5 ~ 4
Boric acid 0.1 ~ 1.5
Potassium chloride 0.3 ~ 0.5
Triethanolamine 0.2 ~ 0.8
Solvent 20 ~ 60
Take raw material, be mixed to form precursor solution; It should be noted that, on the basis of the precursor solution formula provided aforementioned, any one or the multiple combination that above-mentioned precursor solution can be adopted to fill a prescription substitute the formula in step (1), do not repeat at this.Preferably, layoutprocedure specifically can adopt following order: by nano-stannic oxide, triethanolamine and solvent, and vigorous stirring forms mixed solution I; Butter of tin, trichloride antimony, hydrofluoric acid, boric acid, potassium chloride and solvent are formed mixed solution II (if there are other compositions, adding in the lump in this step); Mixed solution I is heated to 40 ~ 60 DEG C, stirs and slowly add mixed solution II, form precursor solution.
(2) spraying process
Substrate is heated to 200 to 300 DEG C, the precursor solution of gained in step (1) is sprayed into substrate surface;
(3) film formation step is flooded
Substrate after step (2) being processed is immersed in the precursor solution of step (1) gained, then pulling film forming;
(4) heat treatment step
Substrate heat treatment 20 to 120min at 500 to 900 DEG C after step (3) being processed, naturally cools to room temperature and obtains semiconductor thermoelectric film.
For improving the adhesion of spraying film forming and matrix, described in step (2), spraying conditions is: expulsion pressure 10 ~ 20kpa, injection flow 1 ~ 10ml/s.
Need summation device situation according to film forming, optionally, the pulling film forming condition described in step (3) is: 0.5 ~ 500mm/min.
For improving the crystalline quality of Electric radiant Heating Film in heat treatment process, the heat treatment described in step (4) is specially: 500 ~ 700 DEG C of insulation 5 ~ 20min, 700 ~ 900 DEG C of insulation 15 ~ 100min.
Finally, present invention also offers a kind of semiconductor thermoelectric film, comprise and adopt the precursor solution of above-mentioned semiconductor thermoelectric film as raw material, adopt any existing technique or technique provided by the invention to be prepared the semiconductor thermoelectric film of acquisition.Natch, the semiconductor thermoelectric film that the above-mentioned a kind of method preparing semiconductor thermoelectric film provided is prepared from is comprised.Prepared Electric radiant Heating Film maximum operating temperature is 1000 ~ 1450 DEG C, and Electric radiant Heating Film is 100 ~ 170N at suprabasil adhesive force, and leakage current is less than 0.2mA, electric conversion efficiency is more than or equal to 98%, thickness is 0.1 ~ 100 μm, and square resistance is 0.1-2000 Ω/, and the life-span is more than or equal to 5000 hours.
Compared to prior art, the present invention possesses following beneficial effect:
(1) the present invention by adding nano-stannic oxide in precursor solution, break the restriction relying on island nucleation in existing technique, facilitate the ability of prepared semiconductor thermoelectric film heat shock resistance and thermal stress greatly, improve the adhesive force of film and matrix, working temperature reaches as high as 1000 ~ 1450 DEG C, and continuous circulation heating has no inefficacy or local failure phenomenon.
(2) by the rational allocation of many granularities amorphous nano tin ash, have increased significantly to film compactness, corresponding Leakage Current is low to moderate 0.01mA, and electric conversion efficiency reaches more than 98%.
(3) filming technology of the present invention is adopted effectively to shorten the production cycle of semiconductor thermoelectric film, through measuring and calculating, compared to the time shorten more than 35% being sprayed into membrane process.
(4) demand of large area film forming is met, at industry heating especially chemical field, the electrothermal semiconductor device prepared after large area film forming, demand as heating tube, thermal reactor etc. is met, through preliminary examination and pilot scale checking, meet diameter 1 ~ 5m large size tubular thermal reactor and prepared demand, have great marketing prospect.
Embodiment
For making technical scheme of the present invention and technique effect thereof clearly, clearly, below embodiment and comparative example the specific embodiment of the invention is further described.Should be appreciated that following embodiment is only the better embodiment of technical solution of the present invention, be not intended to limit the present invention.
(1) configuration of the precursor solution of semiconductor thermoelectric film is prepared
In following examples and comparative example, collocation method is:
By nano-stannic oxide, triethanolamine and solvent, vigorous stirring forms mixed solution I; Butter of tin, trichloride antimony, hydrofluoric acid, boric acid, potassium chloride and solvent are formed mixed solution II (if there are other compositions, adding in the lump in this step); Mixed solution I is heated to 40 ~ 60 DEG C, stirs and slowly add mixed solution II, form precursor solution.
Embodiment 1-1
The configuration of the precursor solution of prepared semiconductor thermoelectric film comprises by weight:
Butter of tin 40
Nano-stannic oxide 15
Trichloride antimony 3
Hydrofluoric acid 2.5
Boric acid 1.8
Potassium chloride 0.4
Triethanolamine 0.5
Ethanol 50
Wherein, nano-stannic oxide is the amorphous stannic oxide particle of average grain diameter 20nm.
Embodiment 1-2
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the amorphous stannic oxide particle of average grain diameter 50nm.
Embodiment 1-3
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the amorphous stannic oxide particle of average grain diameter 100nm.
Embodiment 1-4
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the amorphous stannic oxide particle of average grain diameter 150nm.
Embodiment 1-5
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the amorphous stannic oxide particle of average grain diameter 200nm.
Embodiment 1-6
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the mixture of the amorphous stannic oxide particle of following domain size distribution:
The amorphous stannic oxide particle 20wt% of 20≤particle diameter < 50nm,
The amorphous stannic oxide particle 50wt% of 50≤particle diameter < 100nm,
The amorphous stannic oxide particle 30wt% of 100≤particle diameter≤200nm.
Embodiment 1-7
The configuration composition proportion by weight of the precursor solution of prepared semiconductor thermoelectric film is identical with embodiment 1-1.
Unlike, nano-stannic oxide is the mixture of the amorphous stannic oxide particle of following domain size distribution:
The amorphous stannic oxide particle 15wt% of 20≤particle diameter < 50nm,
The amorphous stannic oxide particle 45wt% of 50≤particle diameter < 100nm,
The amorphous stannic oxide particle 40wt% of 100≤particle diameter≤200nm.
Embodiment 1-8
The configuration of the precursor solution of prepared semiconductor thermoelectric film comprises by weight:
Butter of tin 40
Nano-stannic oxide 15
Trichloride antimony 3
Hydrofluoric acid 2.5
Boric acid 1.8
Potassium chloride 0.4
Triethanolamine 0.5
Ethanol 50
Magnesium chloride 0.3
Zirconium chloride 0.2
Nano-stannic oxide is the mixture of the amorphous stannic oxide particle of following domain size distribution:
The amorphous stannic oxide particle 20wt% of 20≤particle diameter < 50nm,
The amorphous stannic oxide particle 50wt% of 50≤particle diameter < 100nm,
The amorphous stannic oxide particle 30wt% of 100≤particle diameter≤200nm.
Embodiment 1-9
The configuration of the precursor solution of prepared semiconductor thermoelectric film comprises by weight:
Butter of tin 40
Nano-stannic oxide 15
Trichloride antimony 3
Hydrofluoric acid 2.5
Boric acid 1.8
Potassium chloride 0.4
Triethanolamine 0.5
Ethanol 50
Four nickel chlorides 1
Titanium tetrachloride 0.5
Nano-stannic oxide is the mixture of the amorphous stannic oxide particle of following domain size distribution:
The amorphous stannic oxide particle 20wt% of 20≤particle diameter < 50nm,
The amorphous stannic oxide particle 50wt% of 50≤particle diameter < 100nm,
The amorphous stannic oxide particle 30wt% of 100≤particle diameter≤200nm.
Comparative example (experiment 1-10)
The configuration of the precursor solution of prepared semiconductor thermoelectric film comprises by weight:
Butter of tin 70
Trichloride antimony 3
Hydrofluoric acid 2.5
Boric acid 1.8
Potassium chloride 0.4
Ethanol 50;
(2) method of semiconductor thermoelectric film is prepared
For convenience of contrast, the substrate adopted in following examples is quartz substrate.
Embodiment 2-1
(1) precursor solution is configured
The precursor solution of semiconductor thermoelectric film is prepared by embodiment 1-1 configuration.
(2) spraying process
Substrate is heated to 200 DEG C, the precursor solution of gained in step (1) is sprayed into substrate surface; Spraying conditions is: expulsion pressure 20kpa, injection flow 5ml/s.
(3) film formation step is flooded
Substrate after step (2) being processed is immersed in the precursor solution of step (1) gained, then pulling film forming; Pulling film forming condition is: 50mm/min.
(4) heat treatment step
Substrate after step (3) being processed is at 600 DEG C of insulation 15min, and 900 DEG C of insulation 60min, naturally cool to room temperature and obtain semiconductor thermoelectric film.
Embodiment 2-2
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-2 configuration in step (1).
Embodiment 2-3
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-3 configuration in step (1).
Embodiment 2-4
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-4 configuration in step (1).
Embodiment 2-5
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-5 configuration in step (1).
Embodiment 2-6
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-6 configuration in step (1).
Embodiment 2-7
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-7 configuration in step (1).
Embodiment 2-8
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-8 configuration in step (1).
Embodiment 2-9
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by embodiment 1-9 configuration in step (1).
Comparative example 2-10
With embodiment 2-1 unlike, prepare the precursor solution of semiconductor thermoelectric film by comparative example 1-10 configuration in step (1).
Comparative example (experiment 2-11)
With embodiment 2-1 unlike, step (4) is: by step (3) process after substrate heat treatment 75min at 900 DEG C, naturally cool to room temperature obtain semiconductor thermoelectric film.
Comparative example (experiment 2-12)
With embodiment 2-1 unlike, omit step (2) spraying process.
(3) performance test of prepared Electric radiant Heating Film
It should be noted that: adhesive force is tested
Related request according to national machinery industry standard JB/T8554-1997 " scratch method for test of vapor deposition film and matrix adhesive force " carries out adhesive force test.Adopt the automatic scratching instrument of WS-2005 type coating adhesion to test, method of testing is: acoustic emission metering system is tested.Loading speed 5N/min, cut speed 2mm/min.
Resistance change rate: (1) working temperature is from resistance change rate I at room temperature to 1000 DEG C; (2) resistance change rate II after working 2500 hours.
Other tests: the performance tests such as film thickness, square resistance, leakage current all adopt conventionally test means.
To embodiment 2-1 to embodiment 2-9, comparative example 2-11,2-12 carry out performance test, and respective sample numbering is respectively 2-1 to 2-11, the results are shown in Table 1.
Table 1. sample 2-1 to 2-12 Specifeca tion speeification test result.
From the data of sample 2-1 to 2-12, adopt technical scheme of the present invention, namely add on the basis of relevant nanometer tin ash, when film build method, film forming thickness are identical: effectively can improve film at suprabasil adhesive force, when thickness about 0.6 μm, adhesive force reaches as high as about 160N, effectively improves the ability of resisting thermal shock; Meanwhile, leakage current and intensification resistance change rate, long-term work resistance change rate all effectively decline.Experiment display, the combination of spraying coating process and infusion process also has active influence to the raising of adhesive force and the raising of Electric radiant Heating Film job stability.
Claims (10)
1. for the preparation of a precursor solution for semiconductor thermoelectric film, it is characterized in that, described solution comprises by weight:
Butter of tin 25 ~ 45
Nano-stannic oxide 5 ~ 25
Trichloride antimony 1 ~ 6
Hydrofluoric acid 0.5 ~ 4
Boric acid 0.1 ~ 1.5
Potassium chloride 0.3 ~ 0.5
Triethanolamine 0.2 ~ 0.8
Solvent 20 ~ 60.
2. the precursor solution for the preparation of semiconductor thermoelectric film according to claim 1, is characterized in that, described nano-stannic oxide is the amorphous stannic oxide particle of particle diameter about 20 ~ 200nm.
3. the precursor solution for the preparation of semiconductor thermoelectric film according to aforementioned any one claim, is characterized in that, described precursor solution also comprises:
Magnesium chloride 0.1 ~ 0.5
Zirconium chloride 0.1 ~ 0.5.
4. the precursor solution for the preparation of semiconductor thermoelectric film according to aforementioned any one claim, is characterized in that, described solvent is one or more in water, ethanol, isopropyl alcohol etc.
5. prepare a method for semiconductor thermoelectric film, it is characterized in that:
(1) precursor solution is configured
By weight:
Butter of tin 25 ~ 45
Nano-stannic oxide 5 ~ 25
Trichloride antimony 1 ~ 6
Hydrofluoric acid 0.5 ~ 4
Boric acid 0.1 ~ 1.5
Potassium chloride 0.3 ~ 0.5
Triethanolamine 0.2 ~ 0.8
Solvent 20 ~ 60
Take raw material, be mixed to form precursor solution;
(2) spraying process
Substrate is heated to about 200 to 300 DEG C, the precursor solution of gained in step (1) is sprayed into substrate surface;
(3) film formation step is flooded
Substrate after step (2) being processed is immersed in the precursor solution of step (1) gained, then pulling film forming;
(4) heat treatment step
Substrate heat treatment about 20 to 120min at about 500 to 900 DEG C after step (3) being processed, naturally cools to room temperature and obtains semiconductor thermoelectric film.
6. the method preparing semiconductor thermoelectric film according to claim 5, is characterized in that, described in step (2), spraying conditions is: expulsion pressure 10 ~ 20kpa, injection flow 1 ~ 10ml/s.
7.7 methods preparing semiconductor thermoelectric film according to any one of claim 5 or 6, it is characterized in that, the pulling film forming condition described in step (3) is: 0.5 ~ 500mm/min.
8. the method preparing semiconductor thermoelectric film according to any one of claim 5 to 7, is characterized in that, the heat treatment step described in step (4) is specially: 500 ~ 700 DEG C of insulation 5 ~ 20min, 700 ~ 900 DEG C of insulation 15 ~ 100min.
9. a semiconductor thermoelectric film, is characterized in that, adopts the precursor solution described in claim 1 to 6 to be prepared from, and/or, adopt the method described in claim 7 to 15 to be prepared from.
10. semiconductor thermoelectric film according to claim 9, is characterized in that, described semiconductor thermoelectric film is 100 ~ 170N at suprabasil adhesive force, and leakage current is less than 0.2mA.
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| CN105722257A (en) * | 2016-02-16 | 2016-06-29 | 顾伟 | Composition for preparing semiconductor electrothermal film, electrothermal film and preparation method |
| CN105744661A (en) * | 2016-02-16 | 2016-07-06 | 顾伟 | Preparation method of semiconductor electrothermal film |
| CN105732030A (en) * | 2016-02-02 | 2016-07-06 | 季红军 | Preparation method of electrothermal film composite material |
| CN107682944A (en) * | 2017-10-24 | 2018-02-09 | 张东升 | A kind of semiconductor thermoelectric film and preparation method thereof |
| CN108337746A (en) * | 2018-01-25 | 2018-07-27 | 陈昭 | High stable heating element and preparation method thereof |
| CN108924972A (en) * | 2018-08-03 | 2018-11-30 | 王书珍 | A kind of Electric radiant Heating Film and preparation method thereof |
| JP7162164B1 (en) * | 2021-05-07 | 2022-10-28 | 福建晶▲しい▼新材料科技有限公司 | Semiconductor electrothermal film precursor solution, semiconductor electrothermal film structure, and method for manufacturing electrothermal structure |
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