CN102503167A - SnO2 three-dimensional porous photon amorphous semiconductor material and preparation method thereof - Google Patents
SnO2 three-dimensional porous photon amorphous semiconductor material and preparation method thereof Download PDFInfo
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- CN102503167A CN102503167A CN2011103295612A CN201110329561A CN102503167A CN 102503167 A CN102503167 A CN 102503167A CN 2011103295612 A CN2011103295612 A CN 2011103295612A CN 201110329561 A CN201110329561 A CN 201110329561A CN 102503167 A CN102503167 A CN 102503167A
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Abstract
The invention discloses a SnO2 three-dimensional porous photon amorphous semiconductor material which comprises a glass substrate and SnO2 three-dimensional porous photon amorphous-structure crystals growing on the surface of the glass substrate. The invention also provides a preparation method of the SnO2 three-dimensional porous photon amorphous semiconductor material, which comprises the following steps: mixing SnCl2.2H2O crystals, anhydrous alcohol and deionized water into a precursor solution; filling a templet, which is a Agapornis roseicollis feather section, by a sol-gel process; and removing the templet at high temperature. The preparation method disclosed by the invention has the advantages of low cost, high repetitiveness and the like; and the prepared SnO2 three-dimensional porous photon amorphous semiconductor material has favorable application prospects in the aspects of photoconducting devices and photon localization research.
Description
Technical field
The present invention relates to photonic crystal, semiconductor material and device technology field, relate to a kind of SnO particularly
2Three-dimensional porous photon amorphous semiconductor material and preparation method thereof.
Background technology
The feather of a lot of birds of occurring in nature has natural schemochrome, and this color comes from the inner periodic structure of feather, but not the pigment in the feather.The photonic crystal that constitutes about periodic structure since the light-transfer characteristic of it uniqueness that possesses etc. by broad research.And another kind of photon non-crystalline material; Especially be operated in the photon amorphous in the visible-range; Also have its unique light transmission phenomenon, such as photon localization and Random Laser etc., the photon amorphous is different with photon crystal material is only to have SRO and lack long-range order.The method that present people prepare vesicular structure comprises that self-assembly method, split-phase method etc. all can not be used for preparing the photon amorphous in the visible-range that is operated in that lacks long-range order.
Discover; The color of peach face parrot feather comes from its inner three-dimensional porous photon non-crystal structure and the interaction of extraneous light, and the photon amorphous that constitutes this bioprotein changes into the conductor oxidate that conductor oxidate just can obtain to have the three-dimensional photon non-crystal structure.SnO
2It is a kind of broad-band gap transparent semiconductor material; Not only have high transmission rate rare in other semi-conductors; And its refractive index ratio bioprotein is high, and this helps suppressing the density of states(DOS) in the counterfeit band gap of photon amorphous, and localization has great importance for photon.
Self-assembly method can be used for preparing three-dimensional porous structure; Yet it can only prepare periodic structure; Can't prepare and only have the photon amorphous that SRO lacks long-range order; Split-phase method also can be with opening the preparation three-dimensional porous structure, yet it prepares to such an extent that hole is too big, can't compare mutually with the wavelength of visible-range.
The invention solves the SnO of above-mentioned prior art in visible-range
2The non-crystal preparation method of photon difficulty, can't prepare the problems such as photon amorphous that only have SRO, proposed a kind of utilize the sol-gel method filling template again high temperature remove template and obtain SnO
2The preparation method of three-dimensional porous photon amorphous semiconductor material, it has template and is prone to obtain, and method is simple, cost is low, repeated high beneficial effect.The SnO of the present invention's preparation
2Three-dimensional porous photon amorphous semiconductor material has high light transmittance, high refractive index, is operated in advantages such as visible-range; The schemochrome that has tangible green; Can under photon microscope, clearly see; Can be used as good photovaltaic material, be applicable to the application of nano photoelectronic devices simultaneously, aspect photoelectric device, have the applications well prospect with photon localization research aspect.
Summary of the invention
The present invention proposes a kind of SnO
2Three-dimensional porous photon amorphous semiconductor material comprises glass substrate and the SnO that is grown in said glass substrate surface
2Three-dimensional porous photon non-crystal structure crystal.
Wherein, said SnO
2Three-dimensional porous photon non-crystal structure crystal is to have three-dimensional porous biconnected network structure, has the green schemochrome of visible under the opticmicroscope.
Wherein, the bore dia 100-110nm of said three-dimensional porous structure, the murus length of said network structure is 60-90nm.
The invention allows for a kind of SnO
2The preparation method of three-dimensional porous photon amorphous semiconductor material comprises:
Step a, with SnCl
22H
2O xln, absolute ethyl alcohol and deionized water mix, and through stirring, leaving standstill, process precursor solution;
Step b, said precursor solution is dripped to the edge of peach face parrot feather section, said section is at room temperature dried;
Step c, said section is warming up to 450-600 ℃ with 1 ℃/min after, reacted 1-2 hour, obtain said SnO
2Three-dimensional porous photon amorphous semiconductor material.
Wherein, SnCl among the said step a
22H
2The mol ratio of O xln, absolute ethyl alcohol and deionized water is 1:100:100-1:150:150.
Wherein, SnCl among the said step a
22H
2The purity of O xln is 98.5%; Said absolute ethyl alcohol is an analytical pure.
Wherein, among the said step c said section is placed quartz boat, be put in the alumina tube furnace of horizontal positioned and heat up.
One of the object of the invention is to provide a kind of SnO that is operated in the visible-range
2Three-dimensional porous photon amorphous semiconductor material comprises glass substrate and the SnO that is grown in substrate surface
2Three-dimensional porous photon non-crystal structure crystal.Wherein, said SnO
2Photon non-crystal structure crystal has three-dimensional porous biconnected network structure.Among the present invention, SnO
2Three-dimensional porous photon non-crystal structure crystal is the SRO structure, has the green schemochrome of visible under the opticmicroscope, and therefore cycle and visible-range medium green light wavelength (500-560nm) comparability are intended on the statistical significance of three-dimensional porous pore structure.SnO
2Network itself is a successive, can regard a communication passage as, and pore structure wherein also is a successive, can regard another communication passage as, so constituted biconnected network structure.
The present invention is provided at the SnO that grows on the glass substrate
2Three-dimensional porous photon non-crystal structure crystalline semiconductor material, its SnO
2Three-dimensional porous photon non-crystal structure crystalline nm structure has SRO, and the bore dia of three-dimensional porous structure is about 100-110nm, SnO
2Network is murus middle thin (about 60nm), and end is the structure of thick (about 90nm).In the present invention, three-dimensional porous pore structure can be regarded the passage of a connection as, and SnO
2Network structure can be regarded another passage as, forms the logical structure of doubly-linked.Described SnO provided by the invention
2Three-dimensional porous photon amorphous semiconductor material, report in the world still belongs to the first time.
Second purpose of the present invention is to provide utilizes biological template to prepare SnO
2The preparation method of three-dimensional porous photon amorphous semiconductor material.Existing method such as self-assembly method can be used for preparing three-dimensional porous structure; Yet it can only prepare periodic structure; Can't prepare the photon amorphous that only has SRO shortage long-range order, in addition, split-phase method also can be with opening the preparation three-dimensional porous structure; Yet this method is prepared to such an extent that hole is too big, can't compare mutually with the wavelength of visible-range.Preparing method of the present invention can solve the SnO of above-mentioned work on hand in visible-range
2The problem of the non-crystal preparation method of photon difficulty, a kind of low cost is provided, the novel method of high duplication.
In the inventive method, the high temperature of the filling of hole and template was removed and has been formed SnO during precursor solution was cut into slices along the parrot feather
2Network structure is specifically at first inserted three-dimensional porous template with micro-precursor, the amount of control precursor, thus the temperature of reaction again through the control tube furnace waits the three-dimensional porous structure utilize high temperature removal biological template to synthesize tindioxide with holding time.With respect to former synthetic nm structure, outstanding feature of the present invention is: the peach face parrot feather that adopted section template is a biological template, comes from the Nature, and is environment friendly and pollution-free, cost is low, quantity is many.The precursor preparation is simple, does not need heating, does not need long-time stirring, has reduced the requirement to equipment.Template at high temperature is prone to remove, and is also pollution-free to stove, can reuse for a long time.Preparing method of the present invention is simple, and cost is low, good reproducibility.The present invention adopts transparent glass as substrate, synthetic SnO
2Three-dimensional porous photon amorphous semiconductor material has been inherited the schemochrome of original template, is applicable in the development of nano photoelectronic devices.
Description of drawings
Fig. 1 is the SEM enlarged view of former peach face parrot feather template, and illustration is an overall diagram.
Fig. 2 is SnO
2The SEM overall diagram of three-dimensional porous photon amorphous semiconductor material.
Fig. 3 is SnO
2The high power SEM figure of three-dimensional porous photon amorphous semiconductor material.
Embodiment
In conjunction with following specific embodiment and accompanying drawing, the present invention is done further detailed description, protection content of the present invention is not limited to following examples.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.
The present invention utilizes peach face parrot feather to be the synthetic SnO of template
2The preparation method of three-dimensional porous photon amorphous semiconductor material comprises the steps:
Step a, with SnCl
22H
2O xln, absolute ethyl alcohol and deionized water are put in the beaker as the source with the molar ratio mixing of 1:100:100-1:150:150, and magnetic agitation left standstill after 2 hours 12 hours, processed precursor; Wherein, SnCl
22H
2The purity of O is 99.5%; Absolute ethyl alcohol and deionized water purity are analytical pure.
Step b, 1～5 μ L precursor is dripped to the edge of peach face parrot feather section, will cut into slices then and at room temperature dry about 2 hours.
Step c, section is placed in the quartz boat, is put into the alumina tube furnace middle part of horizontal positioned, heat-up rate is set to 1 ℃/min, keeps 1-2 hour after being warming up to 450-600 ℃, obtains product SnO of the present invention
2Three-dimensional porous photon amorphous semiconductor material.Wherein, the aluminum oxide tubular type reactors length of horizontal positioned is 70-100cm, and diameter is 6-10cm.
Embodiment 1
The present invention utilizes peach face parrot feather to be the synthetic SnO of template
2The method of three-dimensional porous photon amorphous semiconductor material, concrete steps are following:
1, the parrot feather being cleaned section is placed on the glass substrate.
2, with SnCl
22H
2O xln, absolute ethyl alcohol and deionized water are put in the beaker as the source with the molar ratio mixing of 1:100:100, form muddy solution.
3, hold over night is after about 12 hours after 2 hours through magnetic agitation with solution, and solution becomes transparent single-phase liquid, processes precursor solution.
4, with the edge of 2 μ L precursor drips of solution peach face parrot feather section on glass substrate, utilize capillary effect precursor to be penetrated in the space of feather, will cut into slices then and at room temperature dry about 2 hours.
5, section is placed in the quartz boat, is put into tube furnace middle part, temperature is set to 1 ℃/min, keeps 2 hours after being raised to 450 ℃.
6, take out quartz boat and sheet glass, former feather section is removed on the sheet glass, on glass substrate, stays SnO
2Three-dimensional porous photon non-crystal structure crystal.
Observe template and detect prepared SnO of the present invention
2Three-dimensional porous photon amorphous semiconductor material, what Fig. 1 showed is the enlarged view that original template has photon non-crystal structure zone, what illustration showed is former peach face parrot feather formwork integral slice map.That Fig. 2 shows is SnO
2Three-dimensional porous photon non-crystal structure crystalline SEM overall diagram.That Fig. 3 shows is SnO
2The enlarged view that has the zone of three-dimensional porous photon non-crystal structure in the three-dimensional porous photon non-crystal structure crystal, the bore dia 100-110nm of three-dimensional porous structure, SnO
2In the middle of the murus of network structure more carefully is about 60nm, and end more slightly is about 90nm.
Cycle and visible-range medium green light wavelength (500-560nm) comparability are intended on the statistical significance of three-dimensional porous pore structure.SnO
2Network itself is a successive, forms a communication passage, and pore structure wherein also is a successive, forms another communication passage, has constituted biconnected network structure.SnO
2Three-dimensional porous photon non-crystal structure crystalline light microscopic figure has shown and the same green schemochrome of former peach face parrot feather template.
Embodiment 2
The present invention utilizes peach face parrot feather to be the synthetic SnO of template
2The method of three-dimensional porous photon amorphous semiconductor material, concrete steps are following:
1, the parrot feather being cleaned section is placed on the glass substrate.
2, with SnCl
22H
2O xln, absolute ethyl alcohol and deionized water are put in the beaker as the source with the molar ratio mixing of 1:150:150, form muddy solution.
3, hold over night is after about 12 hours after 2 hours through magnetic agitation with solution, and solution becomes transparent single-phase liquid, processes precursor solution.
4, with the edge of 5 μ L precursor drips of solution peach face parrot feather section on glass substrate, utilize capillary effect precursor to be penetrated in the space of feather, will cut into slices then and at room temperature dry about 2 hours.
5, section is placed in the quartz boat, is put into tube furnace middle part, temperature is set to 1 ℃/min, keeps 1 hour after being raised to 600 ℃.
6, take out quartz boat and sheet glass, former feather section is removed on the sheet glass, on glass substrate, stays SnO
2Three-dimensional porous photon non-crystal structure crystal.
Observe template and detect prepared SnO of the present invention
2Three-dimensional porous photon amorphous semiconductor material, what Fig. 1 showed is the enlarged view that original template has photon non-crystal structure zone, what illustration showed is former peach face parrot feather formwork integral slice map.That Fig. 2 shows is SnO
2Three-dimensional porous photon non-crystal structure crystalline SEM overall diagram.That Fig. 3 shows is SnO
2The enlarged view that has the zone of three-dimensional porous photon non-crystal structure in the three-dimensional porous photon non-crystal structure crystal, the bore dia 100-110nm of three-dimensional porous structure, SnO
2In the middle of the murus of network structure more carefully is about 60nm, and end more slightly is about 90nm.
Cycle and visible-range medium green light wavelength (500-560nm) comparability are intended on the statistical significance of three-dimensional porous pore structure.SnO
2Network itself is a successive, forms a communication passage, and pore structure wherein also is a successive, forms another communication passage, has constituted biconnected network structure.SnO
2Three-dimensional porous photon non-crystal structure crystalline light microscopic figure has shown and the same green schemochrome of former peach face parrot feather template.
Claims (7)
1. SnO
2Three-dimensional porous photon amorphous semiconductor material is characterized in that, comprises glass substrate and the SnO that is grown in said glass substrate surface
2Three-dimensional porous photon non-crystal structure crystal.
2. SnO according to claim 1
2Three-dimensional porous photon amorphous semiconductor material is characterized in that, said SnO
2Three-dimensional porous photon non-crystal structure crystal is to have three-dimensional porous biconnected network structure, has the green schemochrome of visible under the opticmicroscope.
3. SnO according to claim 2
2Three-dimensional porous photon amorphous semiconductor material is characterized in that, the bore dia of said three-dimensional porous structure is 100-110nm, and the murus length of said network structure is 60-90nm.
4. one kind like any said SnO of claim among the claim 1-3
2The preparation method of three-dimensional porous photon amorphous semiconductor material is characterized in that, comprising:
Step a, with SnCl
22H
2O xln, absolute ethyl alcohol and deionized water mix, and through stirring, leaving standstill, process precursor solution;
Step b, said precursor solution is dripped to the edge of peach face parrot feather section, said section is at room temperature dried;
Step c, said section is warming up to 450-600 ℃ with 1 ℃/min after, reacted 1-2 hour, obtain said SnO
2Three-dimensional porous photon amorphous semiconductor material.
5. preparation method according to claim 4 is characterized in that, SnCl among the said step a
22H
2The mol ratio of O xln, absolute ethyl alcohol and deionized water is 1:100:100-1:150:150.
6. preparation method according to claim 4 is characterized in that, SnCl among the said step a
22H
2The purity of O xln is 98.5%; Said absolute ethyl alcohol is an analytical pure.
7. preparation method according to claim 4 is characterized in that, among the said step c section is placed quartz boat, is put in the alumina tube furnace of horizontal positioned to heat up.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430294A (en) * | 2016-07-26 | 2017-02-22 | 黑龙江大学 | Method for preparing stannic oxide micropipes with multilevel structure through solvothermal method |
Citations (2)
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|---|---|---|---|---|
| CN1444292A (en) * | 2003-01-09 | 2003-09-24 | 中国科学院等离子体物理研究所 | New-type nano porous film and its preparation method |
| CN101752093A (en) * | 2010-02-26 | 2010-06-23 | 上海交通大学 | Preparation method for photonic crystal structure film electrode of dye solar cell |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444292A (en) * | 2003-01-09 | 2003-09-24 | 中国科学院等离子体物理研究所 | New-type nano porous film and its preparation method |
| CN101752093A (en) * | 2010-02-26 | 2010-06-23 | 上海交通大学 | Preparation method for photonic crystal structure film electrode of dye solar cell |
Non-Patent Citations (1)
| Title |
|---|
| 胡春田等: "三维有序多孔SnO2膜的制备及表征", 《材料工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430294A (en) * | 2016-07-26 | 2017-02-22 | 黑龙江大学 | Method for preparing stannic oxide micropipes with multilevel structure through solvothermal method |
| CN106430294B (en) * | 2016-07-26 | 2018-01-09 | 黑龙江大学 | Solvent-thermal method prepares the method with multilevel hierarchy tin ash micro-pipe |
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