CN102719886A - Method for growing large-area zinc oxide micron wall - Google Patents
Method for growing large-area zinc oxide micron wall Download PDFInfo
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- CN102719886A CN102719886A CN2012102059208A CN201210205920A CN102719886A CN 102719886 A CN102719886 A CN 102719886A CN 2012102059208 A CN2012102059208 A CN 2012102059208A CN 201210205920 A CN201210205920 A CN 201210205920A CN 102719886 A CN102719886 A CN 102719886A
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Abstract
The invention discloses a zinc oxide micron wall material and a preparation method thereof. A method for obtaining a zinc oxide micron wall on a silica-based gallium nitride substrate with cracks by the low-temperature water bathing method includes utilizing zinc acetate, hexamine and deionized water as raw materials and silica-based gallium nitride with cracks as a substrate, inducing the zinc oxide to preferentially form a core via the cracks and forming the zinc oxide micron wall in self-assembly manner. The method is simple in reaction conditions, and the zinc oxide micron wall grown is large in specific surface area, high in length diameter ratio and purity and controllable in height. The low-temperature preparation of the large-area zinc oxide micron wall controllable in growth is realized. The large-area zinc oxide micron wall can be hopefully and importantly applied in the fields of microelectronics, microelectronic photoelectric devices and sensors. The preparation method has no special requirements for heating environment, is simple and easily controllable to operate, high in repeatability and suitable for industrialized production, and raw materials are easy to obtain and low in cost.
Description
Technical field
The present invention relates to a kind of utilization and have the method for the silicon based gallium nitride film of crackle, belong to semiconductor material and preparing technical field thereof for substrate preparation zinc oxide micrometer wall.
Background technology
Zinc oxide (zinc oxide) is a kind of broad stopband (Eg=3.4eV) direct band-gap semicondictor material, has high melt point and exciton bind energy (60mev), and the excitation mechanism that these have improved zinc oxide material has greatly reduced the excitation threshold under the room temperature.In addition, the fusing point of zinc oxide is 1975 ° of C, has very high thermostability and chemicalstability.It also is a kind of multi-functional oxidation thing material simultaneously, and it has the excellent properties of aspects such as piezoelectricity, electricity and optics, is widely used in preparing the functional materials devices such as transparency electrode of gas sensor, ultrasonator, solar cell.Zinc oxide also is widely used in fields such as photodiode, laser apparatus, cathodoluminescences as luminescent material, adds that raw material resources is abundant, low price, to the application prospect of environment toxicological harmless, is people's in recent years research focus.Development along with wide band gap semiconducter physics; And the peculiar variation of people's material property that deepening continuously of micron and nano understanding brought with nanoscale science and technology, make the preparation of zinc oxide micrometer nano structural material and correlative study thereof become a new direction gradually.
It is through changing the various reaction conditionss zinc oxide material of growing, study carefully its main method that many researchs are arranged at present, and the still transfer of metal catalytic gas phase, high temperature pyrolytic cracking (HTP) and high temperature substrate method of evaporation of adopting prepare zinc oxide material more.But because of this class methods temperature of reaction is higher than 1000 ° of C, atmospheric condition is strict, and apparatus expensive etc., be unfavorable for scale operation, incompatible with semiconductor technology, also be unfavorable for the integrated of device.And many zinc oxide report all is based on nanometer scale, and the report of zinc oxide micro belt aspect is also arranged, but totally less.At present for the controllable growth of zinc oxide material, often utilize the masterplate of photoetching to carry out orientation, thereby have higher cost simultaneously, be unfavorable for scale operation.
The gallium nitride material of the substrate that the present invention adopts on silicon substrate, growing; Silicon substrate has low, the good electric conductivity of price, high heat conductance, can obtain advantages such as major diameter single crystal; In addition; Because the complete processing of silicon materials and integrated technology are very ripe, the GaN device photoelectric device for preparing on the silicon substrate can combine to realize that the photoelectricity on the same chip is integrated with sophisticated Si electron device integrated technique, is Grown GaN on the substrate with Si (111) still; Because difference of thermal expansion coefficients is big (54%), causes the GaN film in temperature-fall period, to produce huge tension stress.When the thickness of Si substrate growing GaN layer surpasses certain thickness (about 1 μ m) usually, will cause the film cracking.GaN film behind the cracking can't be prepared into device.
The present invention adopts aqua-solution method to prepare zinc oxide micrometer level material, and it is very little mainly to pay attention to its defective of micron-sized zinc oxide, and mainly is single crystal structure, is applicable to and makees opto-electronic device etc.But existing micron-sized zinc oxide or complicated process of preparation, desired raw material are expensive high purity metal zinc, and cost of manufacture is high, or it is low to make degree of purity of production.Therefore, can under mild conditions, realize the synthetic of the synthetic of zinc oxide material, particularly zinc oxide micrometer magnitude material and controllability growth, be that the zinc oxide micrometer material realizes using the necessary problem that faces.
Summary of the invention
The objective of the invention is at nanoelectronic; The controlledly synthesis of the zinc oxide micrometer wall that aspects such as photoelectric device have wide application prospects provides a simple effective method; This method does not need catalyzer, does not need pyroprocessing, and depleted silicon based gallium nitride material is as substrate in the utilization growth; The crackle induced growth zinc oxide micrometer wall that utilizes its surface to produce, thus realize that big area obtains the oriented growth of overlength zinc oxide micrometer wall.
One side of the present invention is to disclose a kind of zinc oxide micrometer walling material; It prepares through following method: the silicon based gallium nitride substrate that growth is had crackle; The aqueous solution that places zinc acetate and hexamethylenetetramine to be configured to; Through the water at low temperature solution methods, utilize the surface crack inducing action of silicon based gallium nitride substrate to make zinc oxide material be self-assembled into zinc oxide micrometer walling material then in the preferential nucleation of cracks.
The growth depleted that the present invention utilized has the silicon based gallium nitride substrate of crackle; Be meant that specifically surface, metal organic chemical vapor deposition (MOCVD) growth back has the silicon based gallium nitride substrate of crackle; This substrate is for utilizing the MOCVD system at Si (111) substrate slice GaN film grown; Because GaN and substrate exist bigger lattice mismatch and coefficient of thermal expansion mismatch; In order to discharge stress bigger in the epitaxial film that causes owing to above-mentioned mismatch, thereby usually exist crackle at the epitaxial layer of gallium nitride of silicon substrate growth.And this gan substrate with crackle often goes out of use owing to being prepared into device, and the present invention has utilized the crackle of its generation just, makes it serve as masterplate, utilizes crackle inducing action developing zinc oxide micron wall construction material.
One side of the present invention is to disclose above-mentioned zinc oxide micrometer wall preparation methods, and the water at low temperature solution methods that adopts of zinc oxide micrometer wall construction material product prepares synthetic obtaining, and its concrete process step is following:
(1) choose the silicon based gallium nitride substrate that the growth depleted has crackle, cleaning-drying is subsequent use;
(2) the configuration growth solution according to the ratio of 30 ~ 50mM:30 ~ 50mM:100ml, takes by weighing zinc acetate, six methynes, four ammonia and deionized water respectively; Mixing also fully dissolves it; Wherein, the mol ratio of zinc acetate, six methynes, four ammonia is 1:1, makes its dissolving after the mixing;
(3) growth solution that the silicon based gallium nitride substrate with crackle that step (1) is obtained places step (2) to obtain, be warming up to 90 ℃ after, under this temperature, react 30min ~ 90min;
(4) after reaction finishes, take out substrate, and rinse well, oven dry with deionized water.
In the preparation method of the above-mentioned zinc oxide micrometer wall of the present invention, effect is more excellent under the following condition: the ratio of zinc acetate, six methynes, four ammonia and deionized water is 50mM:50mM:100ml or 30mM:30mM:100ml in the described step (2).
In the preparation method of the above-mentioned zinc oxide micrometer wall of the present invention, effect is more excellent under the following condition: the reaction times is 90min in the described step (3).
Utilize the zinc oxide micrometer walling material of the prepared acquisition of preparation method of the above-mentioned zinc oxide micrometer wall of the present invention, characterize, prove that the method for the invention is simple and effective through the pattern in the following specific embodiment, and suitable large-scale industrial production.
The zinc oxide micrometer walling material that utilizes the above-mentioned preparation method of the present invention to be obtained, it is at nanoelectronic, and aspects such as photoelectric device have wide application prospects.
Character of innovation of the present invention is:
Zinc oxide micrometer wall pattern is unified neat, smooth surface, and length can reach the hundreds of micron, and height can reach more than the micron dimension, and preparing method's technology is simple, and controllability is strong, with low cost.
Utilization of the present invention have a crackle silicon based gallium nitride substrate, realized that the discarded gan substrate with crackle utilizes again.
Method prepared product purity that the present invention adopted is high, and the preparation process is simple, energy-conservation, processing ease, expense are lower, is fit to large-scale industrial production, is expected at nanoelectronic, and aspects such as photoelectric device have wide application prospects.
Description of drawings
Fig. 1 is the ESEM (SEM) and the ability spectral element mapping of prepared zinc oxide micrometer wall in the embodiment of the invention 1.Wherein: (a) be the SEM shape appearance figure, (b) be and the corresponding oxygen element mapping of (a) pattern, (c) be and the corresponding zinc element mapping of (a) pattern.
Fig. 2 is the SEM shape appearance figure of obtained zinc oxide micrometer wall in the embodiment of the invention 1.Wherein: (a) being SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Fig. 3 is the SEM shape appearance figure of prepared zinc oxide micrometer wall in the embodiment of the invention 2.Wherein: (a) being SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Fig. 4 is the SEM shape appearance figure of prepared zinc oxide micrometer wall in the embodiment of the invention 3.Wherein: (a) being SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Embodiment
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
The following silicon based gallium nitride substrate that adopts comes from and utilizes mocvd method having the silicon based gallium nitride material of crackle under the unoptimizable condition or after the growth on silicon (111) substrate.
Embodiment 1
One. the preparation method of overlength zinc oxide micrometer wall:
1. at first will there be the silicon based gallium nitride substrate of crackle to clean dry for standby.
2. accurately take by weighing 50mM hexamethylenetetramine (0.7009g) and zinc acetate (1.0975g) respectively with electronic balance, put into beaker.Add the 100ml deionized water then, stir fast.
3. the gan substrate in the step 1 is put into the beaker of step 2, wrapped the beaker mouth, put into water-bath then, begin heating with masking foil.It is 90 ° of C that final Heating temperature is set, thermostatically heating 30min.
4. wash substrate slice repeatedly to remove unnecessary ammonium salt and ion with deionized water after reaction finishes, oven dry is in order to characterizing.
For the material of being grown among the top embodiment, adopt ESEM (SEM), can analyze by the spectral element face, below in conjunction with accompanying drawing the present invention is described further.
Accompanying drawing 1 is the surface topography for preparing sample by instance 1 said method and can the spectral element mapping, can find out that from the surperficial SEM figure of Fig. 1 (a) sample the material of growth is all grown along the cracks of gallium nitride surface.Can find out significantly from ability spectral element mapping 1 (b) of corresponding diagram 1 (a) and surperficial zinc oxygen element and the zinc element distribution plan of Fig. 1 (c); Zinc and oxygen element be all cracks distributions surfacewise also; Corresponding one by one with the pattern on the surface topography map; Only contain simultaneously zinc and two kinds of elements of oxygen, other element does not detect, and confirms that along the material of surface arrangement be zinc oxide material.
Accompanying drawing 2 be in the embodiment of the invention 1 obtained product at inclination certain angle SEM shape appearance figure; Can find out that from the low power shape appearance figure of Fig. 2 (a) sample the product pattern is unified neat; All along the sample surfaces crack growth, have long length simultaneously, length can reach the hundreds of micron.Can find out from the high power shape appearance figure of Fig. 2 (b) that in addition sample presents the pattern of certain micron wall, it highly is about 1 μ m, simultaneously the product smooth surface.
Can be reached a conclusion by above-mentioned analytical structure, we adopt simple low temperature hydro-thermal liquid method, utilize silicon based gallium nitride material with crackle big area of having grown to have the zinc oxide structured material of micron wall pattern.
Embodiment 2
Present embodiment is identical with the step of embodiment 1, and difference is the reaction times among the embodiment 1 is changed.
Present embodiment hexamethylenetetramine and zinc acetate are respectively 50mM, i.e. 0.7009g and 1.0975g, and be dissolved in the 100ml deionized water.The water-bath thermostatically heating reaction times is 90min in the present embodiment.
Referring to accompanying drawing 3, prepare the surface topography map of sample by instance 2 said methods.Fig. 3 (a) is the ESEM low power figure of prepared overlength zinc oxide micrometer wall in the embodiment of the invention 2, the certain angle of inclination of while sample, and as can be seen from the figure the product pattern is unified neat, and all along the direction of check growth, length reaches the hundreds of micron simultaneously.Fig. 3 (b) is the ESEM high power figure of prepared zinc oxide micrometer wall in the embodiment of the invention 2, from figure, can obtain the product smooth surface, highly is about 3.5 μ m.
Embodiment 3
The step of present embodiment and embodiment 1,2 is identical, and difference is the amount and the reaction times of two kinds of reactants among the embodiment 1,2 are changed.Hexamethylenetetramine and zinc acetate in the present embodiment are respectively 30mM, i.e. 0.4205g and 0.6585g, and be dissolved in the 100ml deionized water.The middle water-bath thermostatically heating 90min of present embodiment.
Referring to accompanying drawing 4, prepare the surface topography map of sample by instance 3 said methods.Fig. 4 (a) is the ESEM low power figure of prepared zinc oxide micrometer wall in the embodiment of the invention 1, and as can be seen from the figure the product pattern is unified neat, and length is longer, has higher length-to-diameter ratio.Fig. 4 (b) is the ESEM high power figure of prepared overlength zinc oxide micrometer wall in the embodiment of the invention 1, from figure, can obtain the product smooth surface, highly about 3.5 μ m.
Method prepared product purity that the present invention adopted is high, and the preparation process is simple, energy-conservation, processing ease, expense are lower, is fit to large-scale industrial production, is expected at nanoelectronic, and aspects such as photoelectric device have wide application prospects.Protection scope of the present invention is not limited thereto; Any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; Technical scheme and inventive concept thereof according to invention are equal to replacement or change, all should be encompassed within protection scope of the present invention.
Claims (5)
1. zinc oxide micrometer wall preparation methods, step is following:
(1) choose the silicon based gallium nitride substrate with crackle, cleaning-drying is subsequent use;
(2) the configuration growth solution according to the ratio of 30 ~ 50mM:30 ~ 50mM:100ml, takes by weighing zinc acetate, six methynes, four ammonia and deionized water respectively; Mixing also fully dissolves it; Wherein, the mol ratio of zinc acetate, six methynes, four ammonia is 1:1, makes its dissolving after the mixing;
(3) growth solution that the silicon based gallium nitride substrate with crackle that step (1) is obtained places step (2) to obtain, be warming up to 90 ℃ after, under this temperature, react 30min ~ 90min;
(4) after reaction finishes, take out substrate, and rinse well, oven dry with deionized water.
2. the preparation method of zinc oxide micrometer wall according to claim 2 is characterized in that, the ratio of zinc acetate, six methynes, four ammonia and deionized water is 50mM:50mM:100ml or 30mM:30mM:100ml in the described step (2).
3. according to the preparation method of claim 2 or 3 described zinc oxide micrometer walls, it is characterized in that the reaction times is 90min in the described step (3).
4. zinc oxide micrometer walling material; It prepares through following method: the silicon based gallium nitride substrate that growth is had crackle; The aqueous solution that places zinc acetate and hexamethylenetetramine to be configured to; Through the water at low temperature solution methods, utilize the surface crack inducing action of silicon based gallium nitride substrate to make zinc oxide material be self-assembled into zinc oxide micrometer walling material then in the preferential nucleation of cracks.
5. zinc oxide micrometer walling material according to claim 4 is characterized in that described preparation method according to claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108746A (en) * | 2014-06-09 | 2014-10-22 | 大连民族学院 | Cubic indium hydroxide film and preparing method thereof |
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| CN1948127A (en) * | 2005-10-10 | 2007-04-18 | 中国科学院合肥物质科学研究院 | Single crystal zinc oxide nano yarn array/polycrystalline aluminum substrate complex and preparation method thereof |
| CN101413141A (en) * | 2008-10-28 | 2009-04-22 | 浙江大学 | Method for growing ZnO nano-wire array on flexible substrate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948127A (en) * | 2005-10-10 | 2007-04-18 | 中国科学院合肥物质科学研究院 | Single crystal zinc oxide nano yarn array/polycrystalline aluminum substrate complex and preparation method thereof |
| CN101413141A (en) * | 2008-10-28 | 2009-04-22 | 浙江大学 | Method for growing ZnO nano-wire array on flexible substrate |
Non-Patent Citations (2)
| Title |
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| NAISEN YU ET AL.: "ZnO interconnected network nanostructures grown on cracked GaN by the aqueous solution method", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 505, 1 July 2010 (2010-07-01), pages 27 - 30 * |
| 张雯等: "ZnO纳米墙薄膜的低温水热制备及其性能研究", 《化学工业与工程》, vol. 27, no. 4, 31 July 2010 (2010-07-31), pages 283 - 287 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108746A (en) * | 2014-06-09 | 2014-10-22 | 大连民族学院 | Cubic indium hydroxide film and preparing method thereof |
| CN104108746B (en) * | 2014-06-09 | 2015-10-14 | 大连民族学院 | A kind of cube indium hydroxide thin film and preparation method thereof |
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