CN105744661A - Preparation method of semiconductor electrothermal film - Google Patents
Preparation method of semiconductor electrothermal film Download PDFInfo
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- CN105744661A CN105744661A CN201610087088.4A CN201610087088A CN105744661A CN 105744661 A CN105744661 A CN 105744661A CN 201610087088 A CN201610087088 A CN 201610087088A CN 105744661 A CN105744661 A CN 105744661A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 235000014121 butter Nutrition 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 1
- 239000010408 film Substances 0.000 description 58
- 239000012528 membrane Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
- H05B3/143—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds applied to semiconductors, e.g. wafers heating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to a preparation method of a semiconductor electrothermal film. The method mainly comprises the following steps: cleaning a substrate; preparing a source solution, wherein the source solution is prepared from the following components in parts by weight: 20-30 parts of stannic chloride, 10-30 parts of graphite, 10-20 parts of antimony trichloride and the like; spraying the substrate; carrying out first thermal treatment; carrying out dipping for film formation; and carrying out second thermal treatment. The semiconductor electrothermal film prepared according to the preparation method has relatively high adhesive force on the substrate and is over 190N; the leakage current is smaller than 0.10mA; the electrothermal conversion efficiency is greater than or equal to 99%; the square resistance is 45-400ohm/square; and the lifetime is over 5,000 hours.
Description
Technical field
The invention belongs to Electric radiant Heating Film field, particularly relate to the preparation method of a kind of semiconductor thermoelectric film.
Background technology
In recent years, tradition thermo electric material because consumable quantity is big, service life is short, shape difficulty, operating mode is unstable etc., and shortcoming is gradually replaced by new electrically heating material.Wherein, semiconductor thermoelectric film, owing to can closely combine on dielectric surfaces, the film like semi-conductive heating substance of planar thermal source is become after energising, there is the features such as fusing point is high, hardness is big, resistance is low, the thermal efficiency is high, chemical stability is good, the most resistance to bronsted lowry acids and bases bronsted lowry, the characteristic of the flames of anger in heating process, it is subject to people's attention in electric heating field, becomes the important materials replacing tradition thermo electric material.
Chinese patent CN201210250016.9 discloses a kind of method for manufacturing semiconductor electric heating membrane, and it mainly uses butter of tin, titanium tetrachloride, titanous chloride., Butter of antimony., ethanol to be that raw material passes through spraying plating, annealing, electrode sintering prepare semiconductor thermoelectric film.Being similar to, patent CN201310099190.2 also discloses a kind of method for manufacturing semiconductor electric heating membrane, its mainly by configure Electric radiant Heating Film treatment fluid, base mask, spray, anneal, electrode sintering preparation Electric radiant Heating Film.
Patent CN201510683050.9 discloses a kind of precursor solution for preparing semiconductor thermoelectric film, include by weight: butter of tin 25 ~ 45, nano-stannic oxide 5 ~ 25, Butter of antimony. 1 ~ 6, Fluohydric acid. 0.5 ~ 4, boric acid 0.1 ~ 1.5, potassium chloride 0.3 ~ 0.5, triethanolamine 0.2 ~ 0.8, solvent 20 ~ 60.And obtain, by spraying process, dipping film formation step, heat treatment step, the Electric radiant Heating Film that a kind of square resistance adjustable extent is bigger, although improve the adhesion of Electric radiant Heating Film and substrate, and the stability of operating resistance to a certain extent, but still need to be improved further.Additionally, patent CN201510638248.5 also discloses a kind of preparation method for preparing semiconductor thermoelectric film, selecting Pyrex, quartz glass, devitrified glass is base material, with butter of tin, titanium tetrachloride, Butter of antimony., titanous chloride., surplus dehydrated alcohol is stock；Being placed in heating cavity, temperature controls at 600-620 DEG C, by nozzle by source solution atomization the substrate surface that is sprayed onto in heating cavity, the base material being coated with Electric radiant Heating Film is carried out resistance test；The two ends of base material coated surface are uniformly coated with silver electrode paste；Then heating prepares semiconductor thermoelectric film.
The electrothermal semiconductor membrane preparation method of prior art still suffers from techniques below problem: the Electric radiant Heating Film stability of preparation is not enough, and Electric radiant Heating Film is combined defective tightness with substrate, easily ftractures or come off under external force or thermal stress effect；Square resistance controls difficulty；The defects such as leakage current is bigger.
Summary of the invention
It is desirable to provide a kind of method that can prepare high stability Electric radiant Heating Film, meanwhile, the semiconductor thermoelectric film leakage current obtained by the method is low, and electric conversion efficiency is high；Further, the semiconductor thermoelectric film square resistance adjustable extent being prepared by the method for the present invention is big and easily controllable, thus, the method for the present invention is particularly suitable for preparing the semiconductor thermoelectric film of different square resistance.
The present invention solves the problems referred to above by following electrothermal semiconductor membrane preparation method:
(1) substrate is cleaned: cleaned up by substrate distilled water, dry stand-by；
(2) preparation source solution: weigh following parts by weight of component, after mixing, be heated to 40-80 DEG C, stirring 1-2h, obtains semiconductor thermoelectric film source solution: butter of tin 20-30 part, graphite 10-30 part, Butter of antimony. 10-20 part, titanium tetrachloride 2-8 part, fluoboric acid 0.6-1.5 part, fuller olefinic carbon 60 .1-0.8 part, sodium chloride 0.3-0.5 part, water 1-3 part, toluene 2-4 part, ethanol 30-50 part；
(3) spraying substrate: the substrate of step (1) is placed in heating cavity, control heating cavity temperature in the range of 400-600 DEG C, treat that substrate surface temperatures reaches 300-500 DEG C, the semiconductor thermoelectric film source solution atomization of gained in step (2) is sprayed into substrate surface；
(4) heat treatment for the first time: the substrate of heating intracavity is heated to 600-800 DEG C, keeps 1-2h；Then, take out substrate, naturally cool to 300-450 DEG C；
(5) dipping film forming: will be in the semiconductor thermoelectric film source solution of step (2) gained is immersed in the substrate that step (4) process, pulling film forming；
(6) heat treatment for the second time: the substrate heat treatment 30-60min at 900-1000 DEG C after step (5) being processed, naturally cools to room temperature, it is thus achieved that semiconductor thermoelectric film.
As preferred scheme, the component of step (2) preparation source solution is made up of following: butter of tin 20-25 part, graphite 12-25 part, Butter of antimony. 10-15 part, titanium tetrachloride 4-6 part, fluoboric acid 0.8-1.2 part, fuller olefinic carbon 60 .2-0.6 part, sodium chloride 0.3-0.5 part, water 1-3 part, toluene 2-4 part, ethanol 30-50 part.
It is further preferred that substrate is heated to surface temperature by step (3) reaches 350-450 DEG C, then spray.
Further, it is preferable to the expulsion pressure that step (3) sprays is 8 ~ 15kpa, injection flow is 3 ~ 8ml/s.
Preferentially, step (4) heat treatment for the first time, the substrate of heating intracavity is heated to 600-700 DEG C, keeps 1-2h, be subsequently cooled to 350-400 DEG C.
Further, the pulling film forming condition of the inventive method is: 50-100mm/min.
Titanium tetrachloride in film-forming components of the present invention is conducive to improving the electric property of thin film, and fluoboric acid can strengthen the electrothermal semiconductor membrane coat permeability to insulating matrix material, improves the adhesion of electrothermal semiconductor membrane coat and base material so that it is be not easy breakage or come off.
Wherein, graphite usually makes the electric conversion of coating keep stable, prevent the rapid decay of its electric thermal power, and make coating surface can reach certain hardness, and in the present invention, inventor finds the consumption by regulating graphite, achieve the regulation to square resistance unexpectedly, can adjust by adjusting the consumption of graphite according to the reality needs to square resistance sizes.
Wherein, Butter of antimony. can improve the stability of electrothermal semiconductor membrane coat, improves its aging-resistant ability further, reaches the purpose increased the service life.
The present invention uses secondary heat treatment, can be effectively improved the adhesive force of Electric radiant Heating Film and substrate, improve the stability of Electric radiant Heating Film simultaneously, significantly reduce the rate of change of Electric radiant Heating Film in use resistance.
Prepared according to the methods of the invention semiconductor thermoelectric film adhesive force on base material is less than 0.10mA at more than 190N, leakage current, and electric conversion efficiency is more than or equal to 99%, and square resistance is 45-400 Ω/, and the life-span is more than 5000 hours.
Compared to prior art, the method for the present invention possesses following beneficial effect:
(1) the electrothermal semiconductor membrane preparation method of the present invention, have employed secondary heat treatment, is found to the adhesive force significantly improving Electric radiant Heating Film with substrate, can reach more than 190N, improve its stability simultaneously, resistance change rate is little, work has no inefficacy in more than 5000 hours continuously, is hardly damaged.
(2) present invention is by adding graphite and appropriate Graphene in the composition of semiconductor thermoelectric film so that the semiconductor thermoelectric film leakage current of the application is minimum, and makes its electric conversion keep stable, prevents the rapid decay of its electric thermal power；And can adjust by adjusting the consumption of graphite according to the reality needs to square resistance sizes.
Detailed description of the invention
For making technical scheme and technique effect thereof clearer, clear and definite, enumerate example below and the specific embodiment of the invention is further described by comparative example, but be not intended to limit the present invention.
The substrate that the present invention uses is quartz and prepares semiconductor thermoelectric film:
Embodiment 1
(1) substrate is cleaned: cleaned up by substrate distilled water, dry stand-by；
(2) preparation source solution: weigh following parts by weight of component, after mixing, be heated to 50 DEG C, stirring 1-2h, obtains semiconductor thermoelectric film source solution: butter of tin 22 parts, 15 parts of graphite, Butter of antimony. 10 parts, titanium tetrachloride 6 parts, fluoboric acid 1.0 parts, fuller olefinic carbon 60 .4 part, 0.5 part of sodium chloride, 1 part of water, toluene 4 parts, ethanol 45 parts；
(3) spraying substrate: the substrate of step (1) is placed in heating cavity, control heating cavity temperature in the range of 450-500 DEG C, treat that substrate surface temperatures reaches about 350 DEG C, start the semiconductor thermoelectric film source solution atomization of gained in step (2) is sprayed into substrate surface；
(4) heat treatment for the first time: the substrate of heating intracavity is heated to 650-700 DEG C, keeps 1.5h；Then, take out substrate, naturally cool to 380 DEG C
(5) dipping film forming: will be in the semiconductor thermoelectric film source solution of step (2) gained is immersed in the substrate that step (4) process, pulling film forming, pulling film forming condition is: 50mm/min；
(6) heat treatment for the second time: the substrate heat treatment 60min at 900-950 DEG C after step (5) being processed, naturally cools to room temperature, it is thus achieved that semiconductor thermoelectric film.
Embodiment 2
(1) substrate is cleaned: cleaned up by substrate distilled water, dry stand-by；
(2) preparation source solution: weigh following parts by weight of component, after mixing, be heated to 75 DEG C, stirring 2h, obtains semiconductor thermoelectric film source solution: butter of tin 25 parts, 20 parts of graphite, Butter of antimony. 13 parts, titanium tetrachloride 4 parts, fluoboric acid 0.9 part, fuller olefinic carbon 60 .6 part, 0.3 part of sodium chloride, 3 parts of water, toluene 2 parts, ethanol 35 parts；
(3) spraying substrate: the substrate of step (1) is placed in heating cavity, control heating cavity temperature in the range of 500-550 DEG C, treat that substrate surface temperatures reaches about 400 DEG C, start the semiconductor thermoelectric film source solution atomization of gained in step (2) is sprayed into substrate surface；
(4) heat treatment for the first time: the substrate of heating intracavity is heated to 650-700 DEG C, keeps 1.5h；Then, take out substrate, naturally cool to 350 DEG C
(5) dipping film forming: will be in the semiconductor thermoelectric film source solution of step (2) gained is immersed in the substrate that step (4) process, pulling film forming, pulling film forming condition is: 100mm/min；
(6) heat treatment for the second time: the substrate heat treatment 30min at 950-1000 DEG C after step (5) being processed, naturally cools to room temperature, it is thus achieved that semiconductor thermoelectric film.
After comparative example 1: omitting step (4), remaining operation is same as in Example 1, i.e. step (3) spraying, do not carry out heat treatment for the first time, be directly entered step (5).
After comparative example 2: omitting step (4), remaining operation is same as in Example 2, i.e. step (3) spraying, do not carry out heat treatment for the first time, be directly entered step (5).
The performance test of semiconductor thermoelectric film:
(1) adhesive force test is carried out according to the related request of country machinery industry standard JB/T 8,554 1997 " vapor deposition film and the scratch method for test of matrix adhesive force ".Using the WS-2005 automatic scratching instrument of type coating adhesion to test, method of testing is: acoustic emission metering system is tested.Loading speed 5N/min, cut speed 2mm/min, result sees table 1
(2) other tests: the performance tests such as film thickness, square resistance, leakage current all use traditional test methods.Wherein square resistance: Rs=ρ/t (wherein ρ is the resistivity of bulk, and t is bulk thickness) or write as the expression formula of electrical conductivity: Rs=1/ (σ t), result sees table 1
(3) resistance change rate: operating temperature is resistance change rate A% at room temperature to 1500 DEG C；Resistance change rate B% after working 5000 hours, result sees table 1
(4) the examination graphite levels impact on Electric radiant Heating Film square resistance, with embodiment 1 for examination object, is changed the graphite levels in embodiment 1, other components unchanged, preparing different semiconductor thermoelectric films by identical preparation method, test its square resistance, result sees table 2.
Table 1. embodiment 1-2 and comparative example 1-2 Specifeca tion speeification test result
The impact on Electric radiant Heating Film square resistance of table 2 graphite levels
As can be seen from Table 1, this invention takes method unlike the prior art, pass through secondary heat treatment, before pulling film forming, i.e. carry out a heat treatment, the adhesion of electric-heating thin film and base material can be effectively improved, in the case of thickness about 0.6 μm, adhesive force all at more than 190N, considerably improves the ability of anti-thermal shock；And the resistance change rate that heats up, long-term work resistance change rate the most effectively decline.From table 2 it can be seen that the square resistance of the semiconductor thermoelectric film of the present invention has large range of square resistance, and can be adjusted by regulation graphite levels so that it is can be adjusted easily according to actual needs.
Although present invention has been a certain degree of description, it will be apparent that, without departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Being appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it includes the equivalent of described each factor.
Claims (6)
1. the preparation method of a semiconductor thermoelectric film, it is characterised in that comprise the following steps:
(1) substrate is cleaned: cleaned up by substrate distilled water, dry stand-by；
(2) preparation source solution: weigh following parts by weight of component, after mixing, be heated to 40-80 DEG C, stirring 1-2h, obtains semiconductor thermoelectric film source solution: butter of tin 20-30 part, graphite 10-30 part, Butter of antimony. 10-20 part, titanium tetrachloride 2-8 part, fluoboric acid 0.6-1.5 part, fuller olefinic carbon 60 .1-0.8 part, sodium chloride 0.3-0.5 part, water 1-3 part, toluene 2-4 part, ethanol 30-50 part；
(3) spraying substrate: the substrate of step (1) is placed in heating cavity, control heating cavity temperature in the range of 400-600 DEG C, treat that substrate surface temperatures reaches 300-500 DEG C, the semiconductor thermoelectric film source solution atomization of gained in step (2) is sprayed into substrate surface；
(4) heat treatment for the first time: the substrate of heating intracavity is heated to 600-800 DEG C, it is preferable that be heated to 600-700 DEG C, keeps 1-2h；Then, take out substrate, naturally cool to 300-450 DEG C, it is preferable that be cooled to 350-400 DEG C
(5) dipping film forming: will be in the semiconductor thermoelectric film source solution of step (2) gained is immersed in the substrate that step (4) process, pulling film forming, pulling film forming condition is: 50-100mm/min；
(6) heat treatment for the second time: the substrate heat treatment 30-60min at 900-1000 DEG C after step (5) being processed, naturally cools to room temperature, it is thus achieved that semiconductor thermoelectric film.
The preparation method of semiconductor thermoelectric film the most according to claim 1, it is characterized in that, the component of described step (2) preparation source solution is made up of following: butter of tin 20-25 part, graphite 12-25 part, Butter of antimony. 10-15 part, titanium tetrachloride 4-6 part, fluoboric acid 0.8-1.2 part, fuller olefinic carbon 60 .2-0.6 part, sodium chloride 0.3-0.5 part, water 1-3 part, toluene 2-4 part, ethanol 30-50 part.
The preparation method of semiconductor thermoelectric film the most according to claim 1 or claim 2, it is characterised in that in step (3), substrate is heated to surface temperature and reaches 350-450 DEG C, then spray.
4., according to the preparation method of semiconductor thermoelectric film described in claim 1-3, it is characterised in that the expulsion pressure that step (3) sprays is 8 ~ 15kpa, injection flow is 3 ~ 8ml/s.
5., according to the preparation method of semiconductor thermoelectric film described in claim 1-4, it is characterised in that the substrate of heating intracavity is heated to 600-700 DEG C by step (4) heat treatment for the first time, keep 1-2h, be subsequently cooled to 350-400 DEG C.
6., according to the preparation method of semiconductor thermoelectric film described in claim 1-5, it is characterised in that the square resistance of described semiconductor thermoelectric film is 45-400 Ω/, leakage current is less than 0.1mA, and semiconductor thermoelectric film adhesive force on base material is at more than 190N.
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| CN201610087088.4A CN105744661A (en) | 2016-02-16 | 2016-02-16 | Preparation method of semiconductor electrothermal film |
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| CN201610087088.4A CN105744661A (en) | 2016-02-16 | 2016-02-16 | Preparation method of semiconductor electrothermal film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107682944A (en) * | 2017-10-24 | 2018-02-09 | 张东升 | A kind of semiconductor thermoelectric film and preparation method thereof |
| CN110028895A (en) * | 2019-04-30 | 2019-07-19 | 蔡国宇 | A kind of preparation method of high conversion efficiency Electric radiant Heating Film |
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| CN107682944A (en) * | 2017-10-24 | 2018-02-09 | 张东升 | A kind of semiconductor thermoelectric film and preparation method thereof |
| CN110028895A (en) * | 2019-04-30 | 2019-07-19 | 蔡国宇 | A kind of preparation method of high conversion efficiency Electric radiant Heating Film |
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