CN106007403A - Preparation method of chlorine-doped bismuth ferrite photoelectric film - Google Patents
Preparation method of chlorine-doped bismuth ferrite photoelectric film Download PDFInfo
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- CN106007403A CN106007403A CN201610339433.9A CN201610339433A CN106007403A CN 106007403 A CN106007403 A CN 106007403A CN 201610339433 A CN201610339433 A CN 201610339433A CN 106007403 A CN106007403 A CN 106007403A
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- temperature
- bismuth
- chlorine
- nitrate
- bismuth ferrite
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 51
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 27
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 52
- 238000004528 spin coating Methods 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 32
- 239000010409 thin film Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 25
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 229910001887 tin oxide Inorganic materials 0.000 claims description 10
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 7
- 230000005693 optoelectronics Effects 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000003483 aging Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract 1
- 239000012703 sol-gel precursor Substances 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 50
- 238000005352 clarification Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000005290 antiferromagnetic effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3494—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising other salts, e.g. sulfate, phosphate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
The invention relates to a preparation method of chlorine-doped bismuth ferrite photoelectric film. The method includes: mixing and dissolving bismuth nitrate, iron nitrate and ferric trichloride in ethylene glycol monomethyl ether, heating and stirring, cooling to room temperature, adding glacial acetic acid, continuing to stir, ageing and filtering to obtain sol-gel precursor solution, spinning to a substrate, and annealing at a set temperature to obtain the chlorine-doped bismuth ferrite photoelectric film. The chlorine-doped bismuth ferrite photoelectric film sample obtained through the method described herein has trigonal perovskite structure as well as good light-absorbing characteristic and is potentially applicable to the field of multifunctional photoelectric devices. The method described herein has simple steps and low equipment cost and facilitates large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of chlorine doped bismuth ferrite optoelectronic film, belong to inorganic photovoltaic thin film materials art.
Background technology
Bismuth ferrite (BiFeO3, BFO) and it is a kind of iron electromagnet material with the perovskite structure (belonging to R3C point group) that triangle distorts
Material, have under room temperature simultaneously two kinds structurally ordered, i.e. ferroelectric order (Tc=1103K) and G type antiferromagnetic order (TN=643K), be
There is under minority room temperature one of ferroelectricity and anti-ferromagnetic iron electromagnet material simultaneously.The coexisting of ferroelectricity and magnetic not only make its
Magnetic and ferro-electric device aspect have important application prospect, and make it have magneto-electric coupled character, and this character is considered newly
Type memory device aspect is significant.
In order to improve the optical, electrical performance of bismuth ferrite, in recent years, the doping that it is enriched by domestic and international researcher further
Study on the modification, current cation doping is achieved with great successes, but anion doped being operated in is made slow progress both at home and abroad.
Main cause is the purpose that common process is relatively inaccessible to anion incorporation bismuth ferrite crystal lattices.Patent of invention (CN102826610A) is public
Open chlorine doped bismuth ferrite raw powder's production technology.It is mainly characterized by by bismuth nitrate, ferric nitrate, alkali, bismuth chloride at room temperature
Mixed grinding or ball milling, the powder that will obtain heating, then with raw material unreacted in concentrated nitric acid lysate and by-product, then enter
Row washing, is dried, i.e. obtains chlorine and be efficiently entering the sample of bismuth ferrite crystal lattices.In prepared by doping film, it is impossible to go with concentrated nitric acid
Unreacting material and by-product, the therefore preparation of the inapplicable thin-film material of preparation method described in this patent except residual.Thin
Membrane material is with a wide range of applications in field of optoelectronic devices, and technique is simple, mild condition, the chloride ion that is easily controlled are mixed
Miscellaneous bismuth ferrite thin film preparation method has important practical value.
Summary of the invention
Present invention aim at, it is provided that the preparation method of a kind of chlorine doped bismuth ferrite optoelectronic film, the method is by bismuth nitrate, nitric acid
Ferrum, ferric chloride mixed dissolution, in ethylene glycol monomethyl ether solution, are cooled to room temperature after heated and stirred a period of time, add glacial acetic acid
Continue stirring, carry out ageing subsequently and filter, obtain sol gel solution, be then spin coated onto on substrate, at the lower temperature set
Annealing, i.e. obtains the bismuth ferrite thin film of chlorine doping.The chlorine doped bismuth ferrite film sample obtained by the method for the invention is had
Trigonal system perovskite structure, has preferable optical absorption characteristics simultaneously, has potential application in multifunctional photoelectric devices field.
Method step of the present invention is simple, equipment cost is low, it is easy to large-scale production.
The preparation method of a kind of chlorine ion doped bismuth ferrite optoelectronic film of the present invention, the method with bismuth nitrate, ferric nitrate,
Ferric chloride is raw material, uses sol-gal process, by controlling doping content and annealing temperature, obtains chlorine ferrite-doping bismuth thin film,
Concrete operations follow these steps to carry out:
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.01-0.10:1:1.05 mix, then with solvent ethylene glycol
Methyl ether mixes, temperature 50 C heated and stirred 10-60min, is then cooled to room temperature, and adds and ethylene glycol monomethyl ether peer
Long-pending glacial acetic acid, stirs 1-6h, still aging 12h, is filtrated to get clear liquor under room temperature, wherein the adding of solvent ethylene glycol methyl ether
Enter amount be in solute the amount of bismuth ion material and solvent volume than for 0.21-0.84mol/L；
B, take the clear liquor obtained in step a, by Substrate Area 10 μ l/cm2, drop in the tin oxide transparent that substrate is doped with fluorine
On electro-conductive glass, tin indium oxide transparent conductive glass or silicon chip, use the spin coating under the rotating speed of 2000-4000r/min of spin coating instrument
The 10-30 second；
C, by step b gained sample in being placed on tube furnace, at temperature 200-300 DEG C heat 5-10min, the coldest
But to room temperature；
On d, sample obtained by step c, repeat 5-20 time by step b and step c；
E, sample step d obtained are put in tube furnace, and anneal at temperature 450-550 DEG C 30-60min, afterwards at sky
Gas is cooled to room temperature, i.e. obtains chlorine ion doped bismuth ferrite thin film.
In step a, ferric chloride, ferric nitrate, bismuth nitrate mix for 0.01-0.05:1:1.05 in molar ratio.
In step b, spin speed is 3000r/min, and spin-coating time is 20s.
In step c, in tube furnace, heating-up temperature is 300 DEG C, and heat time heating time is 5min.
In step e, annealing temperature is 500 DEG C.
The preparation method of a kind of chlorine doped bismuth ferrite optoelectronic film of the present invention, the method step is simple, it is not necessary to use table
Face activating agent or strong acid, highly basic.The chlorine ferrite-doping bismuth thin film prepared by the method is not destroyed the microcosmic thing of bismuth ferrite and ties mutually
Structure, the incorporation of chloride ion effectively increases bismuth ferrite thin film absorptivity, material can be made effectively to absorb under same thickness more
Sunlight, the photoelectric properties of bismuth ferrite thin film can be improved.Chlorine ferrite-doping bismuth thin film prepared by the method for the invention has to be mixed
Miscellaneous concentration and film thickness are easily controlled, are suitable for the advantages such as multiple film-substrate, it is possible to meet photoelectric device requirement useful industrially.
Accompanying drawing illustrates:
Fig. 1 is the XRD figure of inventive samples, impurity phase does not occurs as seen from the figure in chlorine ferrite-doping bismuth thin film；
Fig. 2 is the ultraviolet-ray visible absorbing collection of illustrative plates of inventive samples, and after mixing chloride ion as seen from the figure, the film light of bismuth ferrite absorbs
Intensity is remarkably reinforced, and the chlorine ion doped raising being conducive to bismuth ferrite material optical property is described；
Fig. 3 is by the X-ray obtaining chlorine ion doped bismuth ferrite thin film after 10% addition ferric chloride of the molal quantity of ferric nitrate
Energy spectrum analysis, as can be seen from the figure the atom number ratio of Bi:Fe:O is close to 1:1:3, and Cl atom in product detected
Account for 0.99%, it was demonstrated that chloride ion is mixed with bismuth ferrite crystal lattices.
Detailed description of the invention
Embodiment 1
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.01:1:1.05 mixing (i.e. ferric chloride 0.0033g,
Ferric nitrate 0.4847g, bismuth nitrate 0.8295g), by the amount of bismuth ion material in solute with solvent ethylene glycol methyl ether volume ratio be
0.21mol/L, then mix with solvent ethylene glycol methyl ether 10ml, temperature 50 C heated and stirred 30min, it is subsequently cooled to room
Temperature, adds glacial acetic acid 10ml, stirs 3h, still aging 12h, be filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2The tin oxide transparent conductive glass lined of doped with fluorine
, spin coating instrument spin coating 20 seconds under the rotating speed of 3000r/min are used at the end；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 10 times by step b and step c, the clarification that will obtain in step a
Drop, in the tin oxide transparent conductive glass substrate of doped with fluorine, uses spin coating instrument spin coating 20 seconds under the rotating speed of 3000r/min；
By gained sample in being placed on tube furnace, heating 5min, be cooled to room temperature in atmosphere at temperature 300 DEG C, obtaining thickness is
The sample of 10 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 500 DEG C 30min, cools down the most in atmosphere
To room temperature, i.e. obtain chlorine ion doped bismuth ferrite thin film.
Embodiment 2
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.02:1:1.05 mixing (i.e. ferric chloride 0.0129g,
Ferric nitrate 0.9694g, bismuth nitrate 1.6589g), by the amount of bismuth ion material in solute and solvent volume than for 0.42mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 10min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 1h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2Silicon substrate on, use spin coating instrument at 2000r/min
Rotating speed under spin coating 20 seconds；
C, by step b gained sample in being placed on tube furnace, at temperature 200 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 10 times by step b and step c, the clarification that will obtain in step a
Drop on a silicon substrate, uses spin coating instrument spin coating 20 seconds under the rotating speed of 2000r/min；Gained sample is being placed on tube furnace
In, at temperature 200 DEG C, heat 5min, be cooled to room temperature in atmosphere, obtain the sample that thickness is 10 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 500 DEG C 30min, cools down the most in atmosphere
To room temperature, i.e. obtain chlorine ion doped bismuth ferrite thin film.
Embodiment 3
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.02:1:1.05 mixing (i.e. ferric chloride 0.0194g,
Ferric nitrate 1.4541g, bismuth nitrate 2.4884g), by the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 20min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 6h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2Tin indium oxide transparent conductive glass substrate on,
Use spin coating instrument spin coating 20 seconds under the rotating speed of 4000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 10 times by step b and step c, i.e. takes the clarification obtained in step a
Drop, on tin indium oxide transparent conductive glass substrate, uses spin coating instrument spin coating 20 seconds under the rotating speed of 4000r/min；Gained
Sample, in being placed on tube furnace, heats 5min at temperature 300 DEG C, is cooled to room temperature in atmosphere, and obtaining thickness is 10 layers
Sample；
E, sample step d obtained are put in tube furnace, and anneal at 500 DEG C 30min, is cooled to room the most in atmosphere
Temperature, i.e. obtains chlorine ion doped bismuth ferrite thin film.
Embodiment 4
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.03:1:1.05 mixing (i.e. ferric chloride 0.0292g,
Ferric nitrate 1.4541g, bismuth nitrate 2.4884g), by the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 60min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 4h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2The tin oxide transparent conductive that substrate is doped with fluorine
On glass, use spin coating instrument spin coating 10 seconds under the rotating speed of 2500r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 10min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 5 times by step b and step c, i.e. takes the clarification obtained in step a
Drop, on the tin oxide transparent conductive glass that substrate is doped with fluorine, uses the spin coating 10 under the rotating speed of 2500r/min of spin coating instrument
Second；By gained sample in being placed on tube furnace, at temperature 300 DEG C, heat 10min, be cooled to room temperature in atmosphere, obtain
Thickness is the sample of 5 layers；
E, sample step d obtained are put in tube furnace, and anneal at 500 DEG C 40min, is cooled to room the most again in air
Temperature, i.e. obtains chlorine ion doped bismuth ferrite thin film.
Embodiment 5
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.04:1:1.05 mixing (i.e. ferric chloride 0.0389g,
Ferric nitrate 1.4541g, bismuth nitrate 2.4884g), by the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 40min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 2h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2Substrate be on Si sheet, use spin coating instrument exist
Spin coating 30 seconds under the rotating speed of 3000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 250 DEG C heat 7min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 20 times by step b and step c, i.e. takes the clarification obtained in step a
Drop is on Si sheet at substrate, uses spin coating instrument spin coating 30 seconds under the rotating speed of 3000r/min；Gained sample is being placed on pipe
In formula stove, at temperature 250 DEG C, heat 7min, be cooled to room temperature in atmosphere, obtain the sample that thickness is 20 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 450 DEG C 60min, cools down in air the most again
To room temperature, i.e. obtain chlorine ion doped bismuth ferrite thin film.
Embodiment 6
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.05:1:1.05 mixing (i.e. ferric chloride 0.0487g,
Ferric nitrate 1.4541g, bismuth nitrate 2.4884g), by the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 60min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 1h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2Substrate be on tin indium oxide transparent conductive glass,
Use spin coating instrument spin coating 25 seconds under the rotating speed of 3000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 10 times by step b and step c, the clear liquor i.e. obtained in step a
Dropping in substrate is on tin indium oxide transparent conductive glass, uses spin coating instrument spin coating 25 seconds under the rotating speed of 3000r/min；By institute
Sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room temperature in atmosphere, obtaining thickness is 10
The sample of layer；
E, sample step d obtained are put in tube furnace, and anneal at 500 DEG C 50min, is cooled to room the most again in air
Temperature, i.e. obtains chlorine ion doped bismuth ferrite thin film.
Embodiment 7
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.06:1:1.05 mixing (i.e. ferric chloride 0.0584g,
Ferric nitrate 1.4541g, bismuth nitrate 2.4884g), by the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 25min, be cooled to room temperature afterwards, add ice
Acetic acid solvent 10ml, stirs 1h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2The tin oxide transparent conductive that substrate is doped with fluorine
On glass, use spin coating instrument spin coating 10 seconds under the rotating speed of 2000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 5 times by step b and step c, i.e. takes the clarification obtained in step a
Drop, on the tin oxide transparent conductive glass that substrate is doped with fluorine, uses the spin coating 10 under the rotating speed of 2000r/min of spin coating instrument
Second；By gained sample in being placed on tube furnace, at temperature 300 DEG C, heat 5min, be cooled to room temperature in atmosphere, obtain thickness
Degree is the sample of 5 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 450 DEG C 50min, cools down in air the most again
To room temperature, i.e. obtain chlorine ion doped bismuth ferrite thin film.
Embodiment 8
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.1:1:1.05 mixing (i.e. ferric chloride 0.1297g,
Ferric nitrate 1.9388g, bismuth nitrate 3.3178g), by the amount of bismuth ion material in solute and solvent volume than for 0.84mol/L,
Mix with solvent ethylene glycol methyl ether 10ml again, temperature 50 C heated and stirred 45min, be then cooled to room temperature, add ice
Acetic acid solvent 10ml, stirs 3h, still aging 12h, is filtrated to get clear liquor under room temperature；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2Substrate be on tin indium oxide transparent conductive glass,
Use spin coating instrument spin coating 10 seconds under the rotating speed of 4000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 8min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 20 times by step b and step c, i.e. takes the clarification obtained in step a
Drop is on tin indium oxide transparent conductive glass at substrate, uses spin coating instrument spin coating 10 seconds under the rotating speed of 4000r/min；Will
Gained sample, in being placed on tube furnace, heats 8min at temperature 300 DEG C, is cooled to room temperature in atmosphere, and obtaining thickness is
The sample of 20 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 550 DEG C 60min, cools down in air the most again
To room temperature, i.e. obtain chlorine ion doped bismuth ferrite thin film.
Embodiment 9 (comparison)
A, by ferric nitrate, bismuth nitrate in molar ratio for 1:1.05 mix (i.e. ferric nitrate 1.4541g, bismuth nitrate 2.4884g),
By the amount of bismuth ion material in solute and solvent volume than for 0.63mol/L, then mix with solvent ethylene glycol methyl ether 10ml,
Temperature 50 C heated and stirred 30min, is cooled to room temperature afterwards, adds glacial acetic acid solvent 10ml, stirs 3h, stand under room temperature
Ageing 12h, is filtrated to get clear liquor；
B, take the clear liquor 40 μ l obtained in step a and drop in a size of 4cm2The tin oxide transparent conductive that substrate is doped with fluorine
On glass, use spin coating instrument spin coating 20 seconds under the rotating speed of 3000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 300 DEG C heat 5min, be cooled to room in atmosphere
Temperature；
On d, sample obtained by step c, it is repeated 20 times by step b and step c, i.e. takes the clarification obtained in step a
Drop, on the tin oxide transparent conductive glass that substrate is doped with fluorine, uses the spin coating 20 under the rotating speed of 3000r/min of spin coating instrument
Second；By gained sample in being placed on tube furnace, at temperature 300 DEG C, heat 5min, be cooled to room temperature in atmosphere, obtain thickness
Degree is the sample of 20 layers；
E, sample step d obtained are put in tube furnace, and anneal at temperature 500 DEG C 30min, cools down in air the most again
To room temperature, i.e. obtain the bismuth ferrite thin film control sample of pure phase.
Embodiment 10
The pure phase bismuth ferric thin film that will obtain in any one chlorine ion doped bismuth ferrite thin film in embodiment 1-8 and embodiment 9
Test its phase structure through X-ray diffractometer, test its optical absorption property through UV-vis DRS instrument, divide through X-ray energy spectrum
Analyse its constituent content.Its result shows: impurity phase do not occur in chlorine ferrite-doping bismuth thin film seen from Fig. 1；Fig. 2 is visible mixes chlorine
After ion, the film light absorption intensity of bismuth ferrite is remarkably reinforced, and carrying of chlorine ion doped beneficially bismuth ferrite material optical property is described
High；As can be seen from Figure 3 the atom number ratio of Bi:Fe:O is close to 1:1:3, and detects that in product, Cl atom accounts for
0.99%, it was demonstrated that chloride ion is mixed with bismuth ferrite crystal lattices.
Claims (5)
1. the preparation method of a chlorine ion doped bismuth ferrite optoelectronic film, it is characterized in that the method, with bismuth nitrate, ferric nitrate, ferric chloride as raw material, uses sol-gal process, by controlling doping content and annealing temperature, obtaining chlorine ferrite-doping bismuth thin film, concrete operations follow these steps to carry out:
A, by ferric chloride, ferric nitrate, bismuth nitrate in molar ratio for 0.01-0.10:1:1.05 mix, mix with solvent ethylene glycol methyl ether again, temperature 50 C heated and stirred 10-60min, it is then cooled to room temperature, add the glacial acetic acid with ethylene glycol monomethyl ether equal volume, under room temperature, stir 1-6h, still aging 12h, being filtrated to get clear liquor, during wherein the addition of solvent ethylene glycol methyl ether is solute, the amount of bismuth ion material and solvent volume are than for 0.21-0.84mol/L；
B, take the clear liquor obtained in step a, by Substrate Area 10 μ l/cm2, drop on tin oxide transparent conductive glass, tin indium oxide transparent conductive glass or the silicon chip that substrate is doped with fluorine, use spin coating instrument spin coating 10-30 second under the rotating speed of 2000-4000r/min；
C, by step b gained sample in being placed on tube furnace, at temperature 200-300 DEG C heat 5-10min, be cooled to room temperature in atmosphere；
On d, sample obtained by step c, repeat 5-20 time by step b and step c；
E, sample step d obtained are put in tube furnace, and anneal at temperature 450-550 DEG C 30-60min, is cooled to room temperature the most in atmosphere, i.e. obtains chlorine ion doped bismuth ferrite thin film.
The preparation method of the most chlorine ion doped bismuth ferrite thin film, it is characterised in that in step a, ferric chloride, ferric nitrate, bismuth nitrate mix for 0.01-0.05:1:1.05 in molar ratio.
The preparation method of the most chlorine ion doped bismuth ferrite thin film, it is characterised in that in step b, spin speed is 3000r/min, spin-coating time is 20s.
The preparation method of the most chlorine ion doped bismuth ferrite thin film, it is characterised in that in step c, heating-up temperature is 300 DEG C in tube furnace, heat time heating time is 5min.
The preparation method of the most chlorine ion doped bismuth ferrite thin film, it is characterised in that in step e, annealing temperature is 500 DEG C.
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| CN108441957A (en) * | 2017-12-08 | 2018-08-24 | 新疆大学 | A kind of preparation method of bismuth ferrite photocatalysis film |
| CN110791732A (en) * | 2019-11-15 | 2020-02-14 | 福建师范大学 | Preparation method of nickel-doped bismuth ferrite film system material |
| CN115579424A (en) * | 2022-10-31 | 2023-01-06 | 内蒙古工业大学 | Preparation method of flexible bismuth ferrite film |
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| CN102826610A (en) * | 2012-09-28 | 2012-12-19 | 中国科学院新疆理化技术研究所 | Preparation method of chlorine-doped bismuth ferrite powder |
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| CN115579424A (en) * | 2022-10-31 | 2023-01-06 | 内蒙古工业大学 | Preparation method of flexible bismuth ferrite film |
| CN115579424B (en) * | 2022-10-31 | 2024-01-26 | 内蒙古工业大学 | Preparation method of flexible bismuth ferrite film |
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