CN102220637A - Micron/nanometer hierarchical structure of BiOCl, BiOBr and Bi2S3 - Google Patents

Micron/nanometer hierarchical structure of BiOCl, BiOBr and Bi2S3 Download PDF

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CN102220637A
CN102220637A CN201110145301XA CN201110145301A CN102220637A CN 102220637 A CN102220637 A CN 102220637A CN 201110145301X A CN201110145301X A CN 201110145301XA CN 201110145301 A CN201110145301 A CN 201110145301A CN 102220637 A CN102220637 A CN 102220637A
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biox
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田野
郭传飞
刘前
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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Abstract

The invention provides a micron/nanometer hierarchical structure of BiOX(X is Cl or Br) and Bi2S3. A preparation method for a Bi2S3 membrane comprises the following steps of: 1) preparing an amorphous bismuth oxide membrane (a-BiOx) on a substrate by a magnetron sputtering method, wherein x ranges from 1 to 2; 2) putting the a-BiOx membrane into solution containing H<+>, X<-> and thioacetamide, and soaking for 48 to 96 hours, wherein the temperature of a reaction system is more than 40 DEG C; and 3) taking the soaked membrane out, and washing by using deionized water. The preparation method is simple and controllable, and the product has uniform dimension and appearance, an ordered structure, a moderate production period and low cost and is suitable for large-scale industrial production; and micron/nanometer grids of the BiOX and Bi2S3 prepared by the technology have wide application prospects in fields of photocatalysis, photoelectric membranes, resistance variable devices, nanometer coatings, pearly-luster pigments and the like.

Description

BiOCl, BiOBr and Bi 2S 3The micro-/ nano hierarchy
Technical field
The present invention relates to a kind of micro Nano material, relate in particular to BiOX (X=Cl or Br) and Bi 2S 3Film and preparation method thereof.
Technical background
BiOX (X=Cl, Br) and Bi 2S 3As the important bismuth based compound of two classes, have the characteristics such as unique light, electricity, magnetic, have broad application prospects in fields such as photocatalysis, optoelectronic film, resistive device, nano coating, pearlescent pigments.For BiOX and Bi with micrometer/nanometer hierarchy feature 2S 3, the specific area that it is huge and nanoscale and structural unusual performance are so that BiOX and Bi 2S 3Application prospect more tempting, also caused numerous researchers' interest.
The method of traditional preparation process BiOX nanostructure is difference with the difference of X element.For example, the people (CN 200510086291.1) such as Li Yadong is with Bi (NO 3) 3, NaOH and surfactant cetyl chloride ammonium be raw material, adopts hydro-thermal method to synthesize the BiOCl nanometer pearlescent pigment; The people such as Jun Zhang are with Bi (NO 3) 35H 2O, NaBr, alcohol be raw material prepared the three-dimensional microballoon of BiOBr (Chem.Mater.2008 (20), 2937-2941); And tradition preparation Bi 2S 3Nanostructured generally adopts hydro-thermal or solvent thermal process.Zhang Weixin etc. are take bismuth nitrate and vulcanized sodium as raw material, with two one-step hydrothermal Bi 2S 3Micron ring, Chen Shuguang etc. are with BiCl 35H 2O, Na 2S 2O 3With polyethylene glycol be that raw material has prepared Bi 2S 3Nanometer rods, Lu Juan etc. have prepared Bi take bismuth nitrate, thioacetamide, nitrilotriacetic acid as the prepared using hydro-thermal method 2S 3Nanobelt, Ye Changhui etc. have prepared Bi take bismuth sulfide as the raw material chemical vapour deposition (CVD) 2S 3Nanotube.
Yet all there is following common drawback in above these synthetic methods: 1) synthesis cycle is long, productive rate is relatively low; 2) product size, pattern are difficult to homogenization; 3) do not possess electricity and send a telegraph electrology characteristics such as resistance.
Summary of the invention
Therefore, the defective that exists in order to overcome above-mentioned prior art the invention provides a kind of BiOX and Bi 2S 3Film and preparation method thereof.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
According to a first aspect of the invention, provide a kind of Bi 2S 3The thin film technology method may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +, X -And soaked 48 to 96 hours in the solution of thioacetamide, temperature of reaction system is more than 40 ℃;
3) film after taking-up is soaked, and use deionized water wash.
In above-mentioned preparation method, in described step 1) also comprise afterwards: with described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
According to a second aspect of the invention, provide a kind of Bi 2S 3The thin film technology method may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +And X -Solution in soaked 30 seconds to 8 minutes, this temperature of reaction system is 20 ℃-90 ℃, to obtain the BiOX film;
3) solution of described BiOX film being put into again thioacetamide soaked 48 to 96 hours, and temperature of reaction system is more than 40 ℃;
4) film after taking-up is soaked, and use deionized water wash.
In above-mentioned preparation method, in described step 1) also comprise afterwards: with described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
According to a third aspect of the invention we, provide the preparation method of another kind of BiOX film, wherein X is Cl, Br, may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +And X -Solution in soaked 30 seconds to 8 minutes, this temperature of reaction system is 20 ℃-90 ℃;
3) film after taking-up is soaked, and use deionized water wash.
In above-mentioned preparation method, in described step 1) also comprise afterwards: with described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
In aforesaid method, described substrate is a single crystalline Si, silica glass, simple glass, transparent conductive glass, PMMA, PC substrate.
In aforesaid method, in described step 1), preparation a-BiO xBase reservoir temperature during film is between 20 ℃-400 ℃, and oxygen flow is between 3-10sccm.
In aforesaid method, described a-BiO xThe thickness of film is 50-1000nm.
In said method, with described a-BiO xFilm places 300 ℃-500 ℃ lower heating 3 to 5 hours.
The Bi of the above method preparation of a kind of basis is provided according to a forth aspect of the invention, 2S 3Film, wherein this film is by Bi 2S 3Nanometer sheet consists of, or by Bi 2S 3Nanometer sheet and the Bi that grows in this nanometer sheet 2S 3Nano wire consists of.
Wherein, described Bi 2S 3The thickness of nanometer sheet is 10-200nm.
Wherein, described Bi 2S 3The diameter of nano wire is 20-30nm.
Wherein, described Bi 2S 3The thickness of film is 50-1000nm.
According to a fifth aspect of the invention, provide a kind of basis BiOX film that above method is made, wherein this film is made of the BiOX nanometer sheet, and wherein X is Cl or Br.
Wherein, the thickness of described BiOX nanometer sheet is 10-200nm.
Wherein, the thickness of described BiOX film is 50-1000nm.
According to a sixth aspect of the invention, provide a kind of hetero-junctions, wherein by the fluorine doped tin oxide substrate and be positioned at this suprabasil Bi 2S 3Film consists of, wherein said Bi 2S 3Film is the described Bi of claim 11 2S 3Film, when when writing different voltage signals, the resistance of hetero-junctions is changed between different resistances.
Compared with prior art, the invention has the advantages that:
1) preparation method adopts the magnetically controlled sputter method commonly used of film preparation in the suitability for industrialized production, has simple and convenient, low-cost, characteristics of sedimentation preparation of film in substrate on a large scale, and this film is by containing H +And X -, soak BiOX or Bi that the steps such as different time, washing can the large tracts of land preparation have the micro-/ nano network in the solution of thioacetamide (TAA) or its mixture 2S 3Film;
2) do not introduce any surfactant, soft template and hard template among the whole preparation technology, get final product large tracts of land, controllably BiOX and the Bi of preparation size, pattern homogeneous by simple adjusting process parameter 2S 3The micro-/ nano grid;
3) this method production cycle moderate, cost is low, the productive rate height, the technology simple controllable is easy to realize suitability for industrialized production.The micro-/ nano grid structure of products obtained therefrom and huge specific surface area make it have broad application prospects in fields such as photochemical catalysis, optoelectronic film, non-volt device, nano coating, pearly pigments.
Description of drawings:
Fig. 1 is embodiment 1 prepared β-Bi 2O 3Film XRD figure;
Fig. 2 is the SEM figure of embodiment 1 prepared orderly BiOCl nano slice graticule;
Fig. 3 is the TEM figure of single nanometer sheet in the embodiment 1 prepared BiOCl grid;
Fig. 4 is the SEM figure of embodiment 2 prepared random BiOBr nano slice graticules;
Fig. 5 is embodiment 3 prepared orderly Bi 2S 3The SEM figure of nano slice graticule;
Fig. 6 is embodiment 4 prepared random Bi 2S 3The SEM figure of nano wire grid;
Fig. 7 is embodiment 4 prepared Bi 2S 3The TEM figure of nano wire grid;
Fig. 8 is embodiment 5 prepared orderly Bi 2S 3The SEM figure of nano wire grid;
Fig. 9 is embodiment 5 prepared FTO and Bi 2S 3The electricity of the hetero-junctions that the micro-/ nano grid consists of is sent a telegraph the resistance characteristic;
Figure 10 is BiOX and the Bi of different-shape 2S 3The preparation flow block diagram of micro-/ nano grid.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, structure of the present invention and preparation method are described in further details below in conjunction with drawings and Examples.Need explanation, " grid " mentioned herein refers to the nanometer sheet by BiOX, or Bi 2The nanometer sheet of S or nano wire are interweaved and the grid structure that forms." hierarchy " refers on micro Nano material (such as nanometer sheet) again, and further growth goes out micro Nano material (such as nano wire).
Embodiment 1:
At first FTO (fluorine doped tin oxide) substrate is adopted acetone, alcohol, deionized water to take out after each ultrasonic 10 minutes and dry up, 120 ℃ of vacuum-drying is 1 hour then, the taking-up of cooling back; On the silicon chip of as above handling, adopt magnetron sputtering deposition amorphous bismuth oxide (a-BiO x, wherein the x span is 1～2) and film, mode of deposition: background pressure 1 * 10 -5Pa, sputtering power 50W, Ar flow are 20sccm, O 2Flow is 5sccm deposition pressure 0.1Pa, 250 ℃ of base reservoir temperatures, depositing time 5760 seconds (s); Follow the amorphous bismuth oxide (a-BiO that deposition is obtained x) film puts into 350 ℃ of retort furnaces annealing preparation in 3 hours β-Bi 2O 3Film; Then with β-Bi 2O 3Film is put into the HCl solution that concentration is 0.04mol/L, and temperature is 80 ℃, soaks and goes to the back to take out in 1 minute, and the film after will soaking is again used deionized water rinsing 5 minutes, dries up final vacuum and is drying to obtain by arranging the film that orderly BiOCl grid constitutes.
Fig. 1 is this β-Bi 2O 3The XRD figure of film therefrom can find out by annealing, a-BiO xBe converted into β-Bi 2O 3
Fig. 2 is the SEM figure of this BiOCl film, therefrom can find out the immersion by HCl solution, β-Bi 2O 3Be converted into the orderly grid that the BiOCl nanometer sheet is interwoven, wherein the thickness of nanometer sheet is approximately 50～100nm, and the thickness that records the BiOCl film is 800nm.
Fig. 3 is the TEM figure of this BiOCl film, can find out that therefrom consisting of BiOCl film nano sheet has good mono-crystalline structures.
Embodiment 2:
Each takes out after ultrasonic 10 minutes and dries up at first silicon substrate to be adopted acetone, alcohol, deionized water, and 120 ℃ of vacuum-drying is 1 hour then, and take out the cooling back; On the cover glass of as above handling, adopt magnetron sputtering deposition amorphous bismuth oxide (a-BiO x) film, mode of deposition: background pressure 1 * 10 -5Pa, sputtering power 50W, Ar flow are 20sccm, O 2Flow is 5sccm deposition pressure 0.1Pa, 28 ℃ of base reservoir temperatures, depositing time 7200 seconds; The a-BiO that deposition is obtained then xFilm is put into the HBr solution that concentration is 0.05mol/L, and soaks at room temperature and went to the back to take out in 30 seconds, and the film after will soaking is again used deionized water rinsing 5 minutes, promptly obtains unordered BiOBr nanometer grid after drying up, and SEM as shown in Figure 4.The unordered grid of gained is interwoven by the BiOBr nanometer sheet as can be seen from the figure, and this nanometer sheet thickness is approximately 100～200nm, and the thickness of this unordered grid is approximately 1000nm.
Embodiment 3:
It is 0.025mol/L that the BiOCl nanometer grid that obtains among the embodiment 1 is put into TAA concentration, temperature is to soak the film usefulness deionized water rinsing that go in 72 hours after rear taking-up will be soaked again in 60 ℃ the solution 5 minutes, dries up at last and namely obtains the orderly Bi that is made of nanometer sheet 2S 3Grid, SEM are as shown in Figure 5.The nanometer grid of gained is by Bi as can be seen from the figure 2S 3Nanometer sheet is interwoven, and records this nanometer sheet thickness and is approximately 10～50nm, and the thickness of nanometer grid is about 800nm on the substrate.
Embodiment 4: preparation Bi 2S 3Micro Nano material (nanometer sheet+nano wire) hierarchy
It is 0.025mol/L that the random BiOBr nanometer grid that obtains among the embodiment 2 is put into TAA concentration, temperature is to soak in 60 ℃ the solution to go rear taking-up in 72 hours, film after will soaking again is with deionized water rinsing 5 minutes, namely obtain after drying up at last nanometer sheet and on the unordered Bi that consists of of nano wire 2S 3The nanometer grid, its SEM, TEM such as Fig. 6 are shown in 7.What Fig. 6 represented is at suprabasil unordered Bi 2S 3Nanometer sheet, that its insertion figure represents is the Bi that grows in this nanometer sheet 2S 3The ordered nano line this shows, Bi 2S 3Nano wire is grown in nanometer sheet, so the nanometer grid of gained is by Bi 2S 3Nanometer sheet and nano wire are interwoven.The diameter that records this nano wire is approximately 20nm.TEM figure explanation Bi 2S 3Nano wire has good mono-crystalline structures.
Embodiment 5: preparation Bi 2S 3Micro Nano material (nanometer sheet+nano wire) hierarchy
Each takes out after ultrasonic 10 minutes and dries up at first FTO to be adopted acetone, alcohol, deionized water, and 120 ℃ of vacuum drying are 1 hour then, take out after the cooling; Adopt magnetron sputtering deposition amorphous bismuth oxide (a-BiO at the cover glass of as above processing x) film, sedimentary condition: background pressure 1 * 10 -5Pa, sputtering power 50W, Ar flow are 20sccm, O 2Flow is 5sccm deposition pressure 0.1Pa, 28 ℃ of base reservoir temperatures, sedimentation time 720 seconds; Amorphous bismuth oxide (the a-BiO that then deposition is obtained x) film puts into 400 ℃ of Muffle furnaces annealing preparation in 3 hours β-Bi 2O 3Film, then β-Bi 2O 3Film is put into HCl concentration 0.025mol/L, and TAA concentration is 0.025mol/L, and temperature is to soak in 60 ℃ the solution to go rear taking-up in 72 hours, and the film usefulness deionized water rinsing after will soaking again 5 minutes dries up at last and namely obtains the Bi that is made of nano wire 2S 3Grid.
That Fig. 8 represents is orderly Bi 2S 3The SEM figure of nanometer sheet, that its insertion figure represents is the Bi that grows in this nanometer sheet 2S 3The ordered nano line this shows, Bi 2S 3Nano wire is grown in nanometer sheet, so the nanometer grid of gained is by Bi 2S 3Nanometer sheet and nano wire are interwoven.The diameter that records this nano wire is approximately 30nm.
In order to test its electric property, with the Bi that obtains 2S 3The grid sample connects electrode, and wherein an end is introduced by the FTO substrate, and an end passes through at Bi 2S 3Be stained with conductive silver glue on the grid and introduce, its I-V curve as shown in Figure 9.From this curve, can find out, according to 1 → 2 → 3 → 4 (be 0V → 1V →-order of 1V → 0V) is carried out voltage scanning can make Bi 2S 3The resistance of grid is conversion between two resistance states of height (5000 Ω and 50 Ω).Bi to embodiment 4 2S 3Grid has been done same test, has also obtained similar results.Thus explanation is by the Bi of the present invention's acquisition 2S 3The nanometer grid has electricity and sends a telegraph the resistance characteristic.
Can find out from the preparation method of above-described embodiment, in the present invention, Bi 2S 3The unordered grid of nanometer can synthesize by following two kinds of approach substantially, referring to Figure 10:
Synthetic route A: with a-BiO xPlace the solution of HX to soak 30 seconds to 8 minutes, temperature is 20-90 ℃, obtains the unordered grid of BiOX (embodiment 2), then the unordered grid of gained BiOX is placed TAA solution to soak 48 to 96 hours, and temperature is more than 40 ℃, and reaction can obtain Bi 2S 3The unordered grid of nano wire (embodiment 4).
Synthetic route B: if with a-BiO xDirectly place the mixed solution of HX and TAA to soak 48 to 96 hours, temperature is more than 40 ℃, and reaction can obtain Bi 2S 3The unordered grid of nanometer sheet.
Similarly, also there are two kinds of approach to synthesize Bi 2S 3Nano ordered grid, referring to Figure 10:
Synthetic route C: with a-BiO xAnnealing obtains β-Bi under 350-500 ℃ of temperature in air 2O 3, the β-Bi of gained 2O 3Place the solution immersion of HX can obtain the orderly grid of BiOX (embodiment 1), then the orderly grid of gained BiOX is placed the reaction of TAA solution can obtain Bi 2S 3The orderly grid of nanometer sheet (embodiment 3).
Synthetic route D: with a-BiO xAnnealing obtains β-Bi under 350-500 ℃ of temperature in air 2O 3, the β-Bi of gained 2O 3Place the mixed solution immersion of HX and TAA can obtain Bi 2S 3Nano thread ordered grid (embodiment 5).
This shows that the amorphous bismuth oxide film without anneal obtains not having sequence network the most at last; And the amorphous bismuth oxide film of annealed processing, what finally obtain is that sequence network is arranged.In addition, in other embodiments of the invention, find, prepare Bi at the mixed solution that uses HX and TAA 2S 3During grid, in given TAA concentration range (0.01-0.2mol/L), HX concentration is during greater than 0.04mol/L, and product is Bi 2S 3Nano slice graticule, and HX concentration is during less than 0.04mol/L, product is Bi 2S 3(nanometer sheet+nano wire) hierarchy.
In the above-described embodiments, the use Muffle furnace, to one with ordinary skill in the art would appreciate that among other embodiment of the present invention only in order illustrating as heater, can also to adopt such as heaters such as graphite resistor furnaces to substitute.In addition, the cleaning process of substrate is not necessary, and vacuum drying purpose is to remove residual water molecules on the substrate after the cleaning, and this also is the cleaning means of using always to those skilled in the art.Utilize magnetron sputtering method to prepare amorphous bismuth oxide (a-BiO x) film has been preparation method well known in the art, therefore those of ordinary skills can understand, mentioned in the above-described embodiments mode of deposition, for example sputtering power, pressure, gas flow etc. are not necessary, as long as can prepare amorphous bismuth oxide (a-BiO x) film just can realize the object of the invention.Moreover, to a-BiO xWhen carrying out annealing in process, also needn't leave no choice but adopt the temperature and time of above-described embodiment, be β-Bi as long as can obtain crystal formation 2O 3Film get final product.The purpose of utilizing the film after deionized water rinsing soaks is that the product that obtains more to clean is prepared against use when testing, so this step is not to have yet.In other embodiments of the invention, substrate can also be selected quartz glass, simple glass, and transparent conductive glass CTO (comprising ITO, FTO and AZO etc.), PMMA, PC substrates etc. can be realized the object of the invention equally.
In sum, synthesis technique of the present invention is simply controlled, product size pattern homogeneous, structurally ordered, the production cycle is moderate, with low cost, be suitable for large-scale industrial production, adopt BiOX and the Bi of this invention technology preparation 2S 3The micro-/ nano grid have broad application prospects in fields such as photocatalysis, optoelectronic film, resistive device, nano coating, pearlescent pigments.
Although the present invention is made specific descriptions with reference to the above embodiments, but for the person of ordinary skill of the art, should be appreciated that and to make amendment based on content disclosed by the invention within spirit of the present invention and the scope or improve not breaking away from, these modifications and improving all within spirit of the present invention and scope.

Claims (20)

1. Bi 2S 3The thin film technology method may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +, X -And soaked 48 to 96 hours in the solution of thioacetamide, temperature of reaction system is more than 40 ℃, wherein X -Be Cl -Or Br -
3) film after taking-up is soaked, and use deionized water wash.
2. preparation method according to claim 1 is characterized in that, also comprises after described step 1):
With described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
3. Bi 2S 3The thin film technology method may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +And X -Solution in soaked 30 seconds to 8 minutes, this temperature of reaction system is 20 ℃-90 ℃, to obtain BiOX film, wherein X -Be Cl -Or Br -
3) solution of described BiOX film being put into again thioacetamide soaked 48 to 96 hours, and temperature of reaction system is more than 40 ℃;
4) film after taking-up is soaked, and use deionized water wash.
4. method according to claim 3 is characterized in that, also comprises after described step 1):
With described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
5. the preparation method of a BiOX film, wherein X is Cl, Br, may further comprise the steps:
1) in substrate, adopt magnetically controlled sputter method to prepare amorphous bismuth oxide film (a-BiO x), wherein the x span is 1-2;
2) with a-BiO xFilm is put into and is contained H +And X -Solution in soaked 30 seconds to 8 minutes, this temperature of reaction system is 20 ℃-90 ℃, wherein X -Be Cl -Or Br -
3) film after taking-up is soaked, and use deionized water wash.
6. preparation method according to claim 5 is characterized in that, also comprises after described step 1):
With described a-BiO xFilm heating is until become β-Bi 2O 3Film is used this β-Bi then 2O 3Film replacement step 2) a-BiO in xFilm.
7. according to claim 1,3 or 5 described preparation methods, it is characterized in that described substrate is a single crystalline Si, silica glass, simple glass, transparent conductive glass, PMMA, PC substrate.
8. according to claim 1,3 or 5 described preparation methods, it is characterized in that, in described step 1), preparation a-BiO xBase reservoir temperature during film is between 20 ℃-400 ℃, and oxygen flow is between 3-10sccm.
9. according to claim 1,3 or 5 described preparation methods, it is characterized in that described a-BiO xThe thickness of film is 50-1000nm.
10. according to claim 1,3 or 5 described preparation methods, it is characterized in that, described a-BiO xFilm places 300 ℃-500 ℃ to heat 3 to 5 hours down.
11. Bi according to the preparation of one of claim 1 to 4 2S 3Film is characterized in that, this film is by Bi 2S 3Nanometer sheet consists of, or by Bi 2S 3Nanometer sheet and the Bi that grows in this nanometer sheet 2S 3Nano wire consists of.
12. Bi according to claim 11 2S 3Film is characterized in that, described Bi 2S 3The thickness of nanometer sheet is 10-200nm.
13. Bi according to claim 11 2S 3Film is characterized in that, described Bi 2S 3The diameter of nano wire is 20-30nm.
14. Bi according to claim 11 2S 3Film is characterized in that, described Bi 2S 3The thickness of film is 50-1000nm.
15. Bi according to claim 11 2S 3Film is characterized in that, described Bi 2S 3Nano wire is ordered arrangement.
16. a BiOX film of making according to claim 5 or 6 is characterized in that this film is made of the BiOX nanometer sheet, wherein X is Cl or Br.
17. BiOX film according to claim 16 is characterized in that, the thickness of described BiOX nanometer sheet is 10-200nm.
18. BiOX film according to claim 16 is characterized in that, the thickness of described BiOX film is 50-1000nm.
19. BiOX film according to claim 16 is characterized in that, described BiOX nanometer sheet is ordered arrangement.
20. a hetero-junctions is characterized in that, by the fluorine doped tin oxide substrate and be positioned at this suprabasil Bi 2S 3Film consists of, wherein said Bi 2S 3Film is the described Bi of claim 11 2S 3Film, when when writing different voltage signals, the resistance of hetero-junctions is changed between different resistances.
CN201110145301XA 2011-05-31 2011-05-31 Micron/nanometer hierarchical structure of BiOCl, BiOBr and Bi2S3 Pending CN102220637A (en)

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CN104588045A (en) * 2015-01-14 2015-05-06 安徽师范大学 Ultra-thin BiOCl nano-sheet, preparation method and application thereof
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CN105692696A (en) * 2016-01-29 2016-06-22 中南大学 Preparation method of bismuth sulfide semiconductor film
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CN102513134B (en) * 2011-11-03 2013-10-09 山东大学 Compound photocatalysis material with bismuth sulfide nano particles/bismuth oxychloride and preparation method thereof
CN103626228A (en) * 2013-12-02 2014-03-12 陕西师范大学 Flaky Bi2S3 powder preparation method
CN104190445A (en) * 2014-08-19 2014-12-10 河北科技大学 Visible-light catalytic activity BiOBr-based heterojunction and preparation method thereof
CN104588045A (en) * 2015-01-14 2015-05-06 安徽师范大学 Ultra-thin BiOCl nano-sheet, preparation method and application thereof
CN104659157A (en) * 2015-03-10 2015-05-27 许昌学院 Preparation method of photoelectric thin-film material based on BiOBr/CdS heterojunction
CN105692696A (en) * 2016-01-29 2016-06-22 中南大学 Preparation method of bismuth sulfide semiconductor film
CN105692696B (en) * 2016-01-29 2017-07-04 中南大学 A kind of preparation method of bismuth sulfide semiconductive thin film
CN106966429A (en) * 2017-03-24 2017-07-21 许昌学院 A kind of preparation method of n-type optoelectronic thin film material
CN109382120A (en) * 2018-11-26 2019-02-26 西南石油大学 A kind of preparation method of the modified two-dimentional composite photo-catalyst of zirconyl oxyhalides bismuthino
CN110282658A (en) * 2019-08-02 2019-09-27 湖南柿竹园有色金属有限责任公司 A kind of high-purity bismuth sulfide preparation method
CN113772725A (en) * 2020-06-10 2021-12-10 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 Bismuth-based semiconductor nano composite material, preparation method and application
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CN113479934A (en) * 2021-07-28 2021-10-08 中国科学院上海硅酸盐研究所 BiOCl nanosheet and preparation method and application thereof

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