CN102503167B - 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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- CN102503167B CN102503167B CN201110329561.2A CN201110329561A CN102503167B CN 102503167 B CN102503167 B CN 102503167B CN 201110329561 A CN201110329561 A CN 201110329561A CN 102503167 B CN102503167 B CN 102503167B
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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 materials and devices technical field, relate to particularly a kind of SnO
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 periodic structure of feather inside, but not pigment in feather.The photonic crystal forming about periodic structure is because it unique light-transfer characteristic possessing etc. is widely studied.And another kind of photon non-crystalline material, especially be operated in the photon amorphous in visible-range, also have its unique light transport phenomena, such as photon localization and Random Laser etc., what photon amorphous was different from photon crystal material is only have short-range order and lack long-range order.The method that current people prepare vesicular structure comprises that self-assembly method, split-phase method etc. all can not be used for preparing the photon amorphous in visible-range that is operated in that lacks long-range order.
Research is found, the color of peach face parrot feather comes from the three-dimensional porous photon non-crystal structure of its inside and the interaction of extraneous light, and the photon amorphous that this bioprotein is formed changes into conductor oxidate and just can obtain the conductor oxidate with 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, the density of states(DOS) that this is conducive to suppress in the counterfeit band gap of photon amorphous, has great importance for photon localization.
Self-assembly method can be used for preparing three-dimensional porous structure, but it can only prepare periodic structure, cannot prepare and only there is the photon amorphous that short-range order lacks long-range order, split-phase method also can be prepared three-dimensional porous structure with opening, but it prepares to such an extent that hole is too large, cannot be comparable with the wavelength of visible-range.
The invention solves the SnO of above-mentioned prior art in visible-range
2the non-crystal preparation method difficulty of photon, cannot prepare the problem such as photon amorphous only with short-range order, proposed one utilize 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 easily obtains, and method is simple, cost is low, repeated high beneficial effect.SnO prepared by the present invention
2three-dimensional porous photon amorphous semiconductor material has high light transmittance, high refractive index, is operated in the advantages such as visible-range, have the schemochrome of obvious green, can under photon microscope, clearly see, can be used as good photoelectric material, be applicable to the application of nano photoelectronic devices simultaneously, aspect photoelectric device and photon localization research aspect there is applications well prospect.
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 described glass substrate surface
2three-dimensional porous photon non-crystal structure crystal.
Wherein, described 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 opticmicroscope.
Wherein, the bore dia 100-110nm of described three-dimensional porous structure, the murus length of described network structure is 60-90nm.
The invention allows for a kind of SnO
2the preparation method of three-dimensional porous photon amorphous semiconductor material, comprising:
Step a, by SnCl
22H
2o xln, dehydrated alcohol and deionized water mix, and through stirring, leaving standstill, make precursor solution;
Step b, described precursor solution is dripped to the edge of peach face parrot feather section, described section is at room temperature dried;
Step c, described section is warming up to after 450-600 ℃ with 1 ℃/min, reaction 1-2 hour, obtains described SnO
2three-dimensional porous photon amorphous semiconductor material.
Wherein, SnCl in described step a
22H
2the mol ratio of O xln, dehydrated alcohol and deionized water is 1:100:100-1:150:150.
Wherein, SnCl in described step a
22H
2the purity of O xln is 98.5%; Described dehydrated alcohol is analytical pure.
Wherein, in described step c, described section is placed in to quartz boat, is put in the alumina tube furnace of horizontal positioned and heats up.
One of object of the present invention is to provide a kind of SnO being operated in 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, described SnO
2photon non-crystal structure crystal has three-dimensional porous biconnected network structure.In the present invention, SnO
2three-dimensional porous photon non-crystal structure crystal is short-range order structure, has the schemochrome of visible green under opticmicroscope, and therefore in the statistical significance of three-dimensional porous pore structure, cycle and visible-range medium green light wavelength (500-560nm) comparability are intended.SnO
2network itself is continuous, can regard a communicating passage as, and pore structure is wherein also continuous, can regard another communicating passage as, so formed biconnected network structure.
The invention provides the SnO that grows in glass substrate
2the semiconductor material of three-dimensional porous photon non-crystal structure crystal, its SnO
2the nm structure of three-dimensional porous photon non-crystal structure crystal has short-range order, 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 two connectivity structures.Described SnO provided by the invention
2three-dimensional porous photon amorphous semiconductor material, report in the world still belongs to the first time.
Second object 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 can be used for preparing three-dimensional porous structure as self-assembly method, but it can only prepare periodic structure, cannot prepare and only there is the photon amorphous that short-range order lacks long-range order, in addition, split-phase method also can be prepared three-dimensional porous structure with opening, but the method is prepared to such an extent that hole is too large, cannot be comparable with the wavelength of visible-range.Preparation 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 difficulty of photon, provide a kind of low cost, the novel method of high duplication.
In the inventive method, precursor solution has formed SnO along the section filling of Hole of parrot feather and the removal of the high temperature of template
2first network structure, specifically insert three-dimensional porous template by micro-precursor, controls the amount of precursor, thereby then utilize high temperature to remove the three-dimensional porous structure that biological template has synthesized tindioxide by control the temperature of reaction of tube furnace and holding time etc.With respect to former synthetic nm structure, outstanding feature of the present invention is: the peach face parrot feather section template adopting is biological template, comes from the Nature, environment friendly and pollution-free, cost is low, quantity is many.Precursor preparation is simple, does not need heating, does not need long-time stirring, has reduced the requirement to equipment.Template is at high temperature easily removed, also pollution-free to stove, can reuse for a long time.Preparation method of the present invention is simple, and cost is low, reproducible.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.
Accompanying drawing explanation
Fig. 1 is the SEM enlarged view of former peach face parrot feather template, and illustration is 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 embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection domain.
The present invention utilizes peach face parrot feather for the synthetic SnO of template
2the preparation method of three-dimensional porous photon amorphous semiconductor material, comprises the steps:
Step a, by SnCl
22H
2o xln, dehydrated alcohol and deionized water mix and are put in beaker as source using the molar ratio of 1:100:100-1:150:150, and magnetic agitation left standstill 12 hours after 2 hours, made precursor; Wherein, SnCl
22H
2the purity of O is 99.5%; Dehydrated 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, then section is at room temperature dried approximately 2 hours.
Step c, section is placed in 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 growth furnace length of horizontal positioned is 70-100cm, and diameter is 6-10cm.
embodiment 1
The present invention utilizes peach face parrot feather for the synthetic SnO of template
2the method of three-dimensional porous photon amorphous semiconductor material, concrete steps are as follows:
1, parrot feather being cleaned to section is placed in glass substrate.
2, by SnCl
22H
2o xln, dehydrated alcohol and deionized water mix and are put in beaker as source using the molar ratio of 1:100:100, form muddy solution.
3, by solution, through magnetic agitation, after 2 hours, hold over night is after approximately 12 hours, and solution becomes transparent single-phase liquid, makes precursor solution.
4, the edge that 2 μ L precursor solution is dropped in to peach face parrot feather section in glass substrate, utilizes capillary effect precursor to be penetrated in the space of feather, then section is at room temperature dried approximately 2 hours.
5, section is placed in quartz boat, is put into tube furnace middle part, temperature setting is set to 1 ℃/min, keeps 2 hours after being raised to 450 ℃.
6, take out quartz boat and sheet glass, on sheet glass, former feather section is removed, and leaves SnO in glass substrate
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 region, what illustration showed is former peach face parrot feather formwork integral slice map.That Fig. 2 shows is SnO
2the SEM overall diagram of three-dimensional porous photon non-crystal structure crystal.That Fig. 3 shows is SnO
2in three-dimensional porous photon non-crystal structure crystal, there is the enlarged view in the region of three-dimensional porous photon non-crystal structure, the bore dia 100-110nm of three-dimensional porous structure, SnO
2in the middle of the murus of network structure, be more carefully 60nm left and right, end is more slightly 90nm left and right.
In the statistical significance of three-dimensional porous pore structure, cycle and visible-range medium green light wavelength (500-560nm) comparability are intended.SnO
2network itself is continuous, forms a communicating passage, and pore structure is wherein also continuous, forms another communicating passage, has formed biconnected network structure.SnO
2the light microscopic figure of three-dimensional porous photon non-crystal structure crystal, has shown and the same green schemochrome of former peach face parrot feather template.
embodiment 2
The present invention utilizes peach face parrot feather for the synthetic SnO of template
2the method of three-dimensional porous photon amorphous semiconductor material, concrete steps are as follows:
1, parrot feather being cleaned to section is placed in glass substrate.
2, by SnCl
22H
2o xln, dehydrated alcohol and deionized water mix and are put in beaker as source using the molar ratio of 1:150:150, form muddy solution.
3, by solution, through magnetic agitation, after 2 hours, hold over night is after approximately 12 hours, and solution becomes transparent single-phase liquid, makes precursor solution.
4, the edge that 5 μ L precursor solution is dropped in to peach face parrot feather section in glass substrate, utilizes capillary effect precursor to be penetrated in the space of feather, then section is at room temperature dried approximately 2 hours.
5, section is placed in quartz boat, is put into tube furnace middle part, temperature setting is set to 1 ℃/min, keeps 1 hour after being raised to 600 ℃.
6, take out quartz boat and sheet glass, on sheet glass, former feather section is removed, and leaves SnO in glass substrate
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 region, what illustration showed is former peach face parrot feather formwork integral slice map.That Fig. 2 shows is SnO
2the SEM overall diagram of three-dimensional porous photon non-crystal structure crystal.That Fig. 3 shows is SnO
2in three-dimensional porous photon non-crystal structure crystal, there is the enlarged view in the region of three-dimensional porous photon non-crystal structure, the bore dia 100-110nm of three-dimensional porous structure, SnO
2in the middle of the murus of network structure, be more carefully 60nm left and right, end is more slightly 90nm left and right.
In the statistical significance of three-dimensional porous pore structure, cycle and visible-range medium green light wavelength (500-560nm) comparability are intended.SnO
2network itself is continuous, forms a communicating passage, and pore structure is wherein also continuous, forms another communicating passage, has formed biconnected network structure.SnO
2the light microscopic figure of three-dimensional porous photon non-crystal structure crystal, has shown and the same green schemochrome of former peach face parrot feather template.
Claims (5)
1. a SnO
2three-dimensional porous photon amorphous semiconductor material, is characterized in that, comprises glass substrate and the SnO that is grown in described glass substrate surface
2three-dimensional porous photon non-crystal structure crystal; Wherein, described 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 opticmicroscope; The bore dia of described three-dimensional porous structure is 100-110nm, and the murus length of described network structure is 60-90nm.
2. SnO described in a claim 1
2the preparation method of three-dimensional porous photon amorphous semiconductor material, is characterized in that, comprising:
Step a, by SnCl
22H
2o xln, dehydrated alcohol and deionized water mix, and through stirring, leaving standstill, make precursor solution;
Step b, described precursor solution is dripped to the edge of peach face parrot feather section, described section is at room temperature dried;
Step c, described section is warming up to after 450-600 ℃ with 1 ℃/min, reaction 1-2 hour, obtains described SnO
2three-dimensional porous photon amorphous semiconductor material.
3. preparation method according to claim 2, is characterized in that, SnCl in described step a
22H
2the mol ratio of O xln, dehydrated alcohol and deionized water is 1:100:100-1:150:150.
4. preparation method according to claim 2, is characterized in that, SnCl in described step a
22H
2the purity of O xln is 98.5%; Described dehydrated alcohol is analytical pure.
5. preparation method according to claim 2, is characterized in that, in described step c, section is placed in to quartz boat, is put in the alumina tube furnace of horizontal positioned and heats up.
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| CN201110329561.2A CN102503167B (en) | 2011-10-26 | 2011-10-26 | SnO2 three-dimensional porous photon amorphous semiconductor material and preparation method thereof |
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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 |
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| 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 (2)
| Title |
|---|
| 三维有序多孔SnO2膜的制备及表征;胡春田等;《材料工程》;20081231(第10期);232-235 * |
| 胡春田等.三维有序多孔SnO2膜的制备及表征.《材料工程》.2008,(第10期),232-235. |
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