CN102719886B - A kind of method of large area deposition zinc oxide micrometer wall - Google Patents
A kind of method of large area deposition zinc oxide micrometer wall Download PDFInfo
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- CN102719886B CN102719886B CN201210205920.8A CN201210205920A CN102719886B CN 102719886 B CN102719886 B CN 102719886B CN 201210205920 A CN201210205920 A CN 201210205920A CN 102719886 B CN102719886 B CN 102719886B
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- zinc oxide
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Abstract
The present invention discloses a kind of zinc oxide micrometer walling material and preparation method, by utilizing low temperature immersion method to obtain zinc oxide micrometer wall on the silicon based gallium nitride substrate with crackle.Adopt with zinc acetate, hexamethylenetetramine and deionized water are raw material, to have the silicon based gallium nitride of crackle for substrate, utilize crackle induced oxidation zinc at cracks Preferential Nucleation and form a micron wall by self-assembly mode.It is simple that the method applied in the present invention has reaction conditions, and the zinc oxide micrometer wall specific surface area of growth is large, and have higher length-to-diameter ratio, purity is high, and highly controlled.The invention solves the problem of the low-temperature growth of big area controllable growth zinc oxide micrometer wall, be expected to obtain important application at microelectronics and microelectronics photoelectric device, sensor field.Described preparation technology does not have particular requirement to heating environment, easy control simple to operate, and repeatability is strong, and raw material sources are extensive, with low cost, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to silicon based gallium nitride film that a kind of utilization has a crackle for substrate prepares the method for zinc oxide micrometer wall, belongs to semiconductor material and preparing technical field thereof.
Background technology
Zinc oxide (zinc oxide) is a kind of broad stopband (Eg=3.4eV) direct band-gap semicondictor material, there is higher fusing point and exciton bind energy (60mev), these substantially increase the excitation mechanism of zinc oxide material, reduce the excitation threshold under room temperature.In addition, the fusing point of zinc oxide is 1975 ° of C, has very high thermostability and chemical stability.Simultaneously it is also a kind of multi-functional oxide material, and it has the excellent properties of the aspects such as piezoelectricity, electricity and optics, is widely used in preparing the function material component such as transparency electrode of gas sensor, ultrasonator, solar cell.Zinc oxide, as luminescent material, is also widely used in fields such as photodiode, laser apparatus, cathodoluminescences, and adding that raw material resources is abundant, low price, to the application prospect of environment toxicological harmless, is the study hotspot of people in recent years.Along with the development of wide band gap semiconducter physics, and people are to the peculiar change of deepening continuously of being familiar with of micron and nano and material property that nanoscale science and technology brings, the preparation of zinc oxide micrometer nano structural material and correlative study thereof is made to become a new direction gradually.
Having much research to be grow zinc oxide material by changing various reaction conditions at present, studying carefully its main method, or the transfer of metal catalytic gas phase, high temperature pyrolytic cracking (HTP) and the high temperature substrate method of evaporation of adopting prepares zinc oxide material more.But because this class methods temperature of reaction is higher than 1000 ° of C, atmospheric condition requires strict, and apparatus expensive etc., be unfavorable for scale operation, incompatible with semiconductor technology, be also unfavorable for the integrated of device.And many zinc oxide reports are all based on nanometer scale, also have the report of zinc oxide micro belt aspect, but totally less.The current controllable growth for zinc oxide material, often utilizes the masterplate of photoetching to carry out orientation, thus has higher cost, be unfavorable for scale operation simultaneously.
The substrate that the present invention adopts is the gallium nitride material grown on a silicon substrate, it is low that silicon substrate has price, excellent electric conductivity, high heat conductance, the advantages such as major diameter single crystal can be obtained, in addition, due to the complete processing of silicon materials and integrated technology very ripe, GaN device photoelectric device prepared by silicon substrate can to combine the photoelectricity realized on same chip integrated with the Si electron device integrated technique of maturation, but with the GaN that Si (111) is Grown, due to difference of thermal expansion coefficients comparatively large (54%), cause GaN film in temperature-fall period, produce huge tension stress.When the thickness of usual Si substrate growth GaN layer exceedes certain thickness (about 1 μm), film peeling will be caused.GaN film after cracking cannot be prepared into device.
The present invention adopts aqua-solution method to prepare zinc oxide micrometer level material, mainly pays attention to its defect of micron-sized zinc oxide very little, and mainly single crystal structure, is applicable to make opto-electronic device etc.But existing micron-sized zinc oxide or complicated process of preparation, desired raw material is expensive high purity metal zinc, and cost of manufacture is high, or the purity of obtained product is low.Therefore, can realize synthesis and the controllability growth of the synthesis of zinc oxide material, particularly zinc oxide micrometer magnitude material in a mild condition, be that zinc oxide micrometer material realizes applying the necessary problem faced.
Summary of the invention
The object of the invention is at nanoelectronic, the controlledly synthesis of the zinc oxide micrometer wall that the aspects such as photoelectric device have wide application prospects provides a simple effective method, this method does not need catalyzer, do not need pyroprocessing, utilize silicon based gallium nitride material discarded in growth as substrate, utilize the crackle induced growth zinc oxide micrometer wall that its surface produces, thus realize the oriented growth that big area obtains overlength zinc oxide micrometer wall.
An aspect of of the present present invention is open a kind of zinc oxide micrometer walling material, it is prepared by following method: silicon based gallium nitride substrate growth with crackle, be placed in the aqueous solution that zinc acetate and hexamethylenetetramine are configured to, by low-temperature aqueous solution method, the surface crack inducing action of silicon based gallium nitride substrate is utilized to make zinc oxide material then be self-assembled into zinc oxide micrometer walling material at cracks Preferential Nucleation.
The silicon based gallium nitride substrate of what the growth that the present invention utilizes was discarded have crackle, specifically refer to that metal organic chemical vapor deposition (MOCVD) grows the silicon based gallium nitride substrate that rear surface has crackle, this substrate is for utilizing MOCVD system at Si (111) substrate slice GaN film grown, because GaN and substrate also exist larger lattice mismatch and coefficient of thermal expansion mismatch, in order to discharge stress larger in the epitaxial film that causes due to above-mentioned mismatch, thus usually there is crackle at the epitaxial layer of gallium nitride of silicon substrate growth.And this gallium nitride substrate with crackle is owing to cannot be prepared into device, often go out of use, the present invention make use of its crackle produced just, makes it serve as masterplate, utilizes crackle inducing action developing zinc oxide micron wall construction material.
An aspect of of the present present invention is the preparation method of openly above-mentioned zinc oxide micrometer walling material, and the low-temperature aqueous solution method preparation synthesis that adopts of zinc oxide micrometer wall construction material product obtains, and its concrete technology step is as follows:
(1) choose the discarded silicon based gallium nitride substrate with crackle of growth, cleaning-drying is for subsequent use;
(2) configure growth solution, according to the ratio of 30 ~ 50mM:30 ~ 50mM:100ml, take zinc acetate, six methyne four ammonia and deionized waters respectively, mix and make it fully dissolve, wherein, the mol ratio of zinc acetate, six methyne four ammonia is 1:1, makes it dissolve after mixing;
(3) the silicon based gallium nitride substrate with crackle that step (1) obtains is placed in the growth solution that step (2) obtains, after being warming up to 90 DEG C, reacts 30min ~ 90min at such a temperature;
(4), after reaction terminates, substrate is taken out, and clean with deionized water rinsing, dry.
In the preparation method of the zinc oxide micrometer wall stated on the invention, under following condition, effect is more excellent: in described step (2), the ratio of zinc acetate, six methyne four ammonia and deionized water is 50mM:50mM:100ml or 30mM:30mM:100ml.
In the preparation method of the zinc oxide micrometer wall stated on the invention, under following condition, effect is more excellent: in described step (3), the reaction times is 90min.
The prepared zinc oxide micrometer walling material obtained of preparation method of the zinc oxide micrometer wall utilizing the present invention above-mentioned, by the morphology characterization in following specific embodiment, proves that the method for the invention is simple and effective, and applicable large-scale industrial production.
Utilize the zinc oxide micrometer walling material that the above-mentioned preparation method of the present invention obtains, it is at nanoelectronic, and the 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 hundreds of micron, and height can reach more than micron dimension, and preparation method's technique is simple, and controllability is strong, with low cost.
What the present invention utilized has crackle silicon based gallium nitride substrate, achieves the discarded gallium nitride substrate recycling with crackle.
The method applied in the present invention prepared product purity is high, and preparation process is simple, energy-conservation, processing ease, expense are lower, and be applicable to large-scale industrial production, be expected at nanoelectronic, the aspects such as photoelectric device have wide application prospects.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) and the power spectrum Element area profile of zinc oxide micrometer wall obtained in the embodiment of the present invention 1.Wherein: (a) is SEM shape appearance figure, (b) is corresponding oxygen element mapping with (a) pattern, and (c) is corresponding zinc element mapping with (a) pattern.
Fig. 2 is the SEM shape appearance figure of obtained zinc oxide micrometer wall in the embodiment of the present invention 1.Wherein: (a) is SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Fig. 3 is the SEM shape appearance figure of zinc oxide micrometer wall obtained in the embodiment of the present invention 2.Wherein: (a) is SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Fig. 4 is the SEM shape appearance figure of zinc oxide micrometer wall obtained in the embodiment of the present invention 3.Wherein: (a) is SEM low power shape appearance figure, (b) is SEM high power shape appearance figure.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Following adopted silicon based gallium nitride substrate comes from and utilizes mocvd method under non-optimized conditions or after growth, to have the silicon based gallium nitride material of crackle on silicon (111) substrate.
Embodiment 1
One. the preparation method of overlength zinc oxide micrometer wall:
1. first will the silicon based gallium nitride substrate of crackle be had to clean, dry for standby.
2. accurately take 50mM hexamethylenetetramine (0.7009g) and zinc acetate (1.0975g) respectively with electronic balance, put into beaker.Then add 100ml deionized water, rapid stirring is even.
3. the gallium nitride substrate in step 1 is put into the beaker of step 2, wrap beaker mouth with masking foil, then put into water-bath, start heating.Arranging final Heating temperature is 90 ° of C, thermostatically heating 30min.
4. reaction terminates rear deionized water and repeatedly rinses substrate slice to remove unnecessary ammonium salt and ion, dries in order to characterizing.
For the material grown in embodiment above, adopt scanning electron microscope (SEM), power spectrum elemental map analyzes, below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing 1 is for preparing surface topography and the power spectrum Element area profile of sample by method described in example 1, as can be seen from the surperficial SEM figure of Fig. 1 (a) sample, the cracks of material all along gallium nitride surface of growth is grown.Can find out significantly from the surperficial zinc oxygen element of power spectrum elemental map Fig. 1 (b) of corresponding diagram 1 (a) and Fig. 1 (c) and zinc element distribution plan, zinc and oxygen element be cracks distribution all surfacewise also, with the pattern one_to_one corresponding on surface topography map, simultaneously only containing zinc and oxygen two kinds of elements, other element detection does not arrive, and confirms that along the material of surface arrangement be zinc oxide material.
Accompanying drawing 2 is that product obtained by the embodiment of the present invention 1 is at inclination certain angle SEM shape appearance figure, can find out that from the low power shape appearance figure of Fig. 2 (a) sample product morphology is unified neat, all along sample surfaces crack growth, have longer length, length can reach hundreds of micron simultaneously.In addition as can be seen from the high power shape appearance figure of Fig. 2 (b), sample presents the pattern of certain micron wall, and it is highly about 1 μm, and its surface is smooth simultaneously.
Can be reached a conclusion by above-mentioned analytical structure, we adopt simple water at low temperature hydrothermal process, utilize and have the zinc oxide structures material that the silicon based gallium nitride Material growth of crackle big area has micron wall pattern.
Embodiment 2
The present embodiment is identical with the step of embodiment 1, and difference is the reaction times in embodiment 1 to change.
The present embodiment hexamethylenetetramine and zinc acetate are respectively 50mM, i.e. 0.7009g and 1.0975g, and are dissolved in 100ml deionized water.In the present embodiment, the water-bath thermostatically heating reaction times is 90min.
See accompanying drawing 3, prepare the surface topography map of sample by method described in example 2.Fig. 3 (a) is the scanning electron microscope low power figure of overlength zinc oxide micrometer wall obtained in the embodiment of the present invention 2, the certain angle of inclination of sample simultaneously, as can be seen from the figure product morphology is unified neat, and all along direction of check growth, length reaches hundreds of micron simultaneously.Fig. 3 (b) is the scanning electron microscope high power figure of zinc oxide micrometer wall obtained in the embodiment of the present invention 2, can obtain its surface smooth, be highly about 3.5 μm from figure.
Embodiment 3
The step of the present embodiment and embodiment 1,2 is identical, and difference is embodiment 1, and in 2, the amount of two kinds of reactants and reaction times change.Hexamethylenetetramine in the present embodiment and zinc acetate are respectively 30mM, i.e. 0.4205g and 0.6585g, and are dissolved in 100ml deionized water.The middle water-bath thermostatically heating 90min of the present embodiment.
See accompanying drawing 4, prepare the surface topography map of sample by method described in example 3.Fig. 4 (a) is the scanning electron microscope low power figure of zinc oxide micrometer wall obtained in the embodiment of the present invention 1, and as can be seen from the figure product morphology is unified neat, and length is longer, has higher length-to-diameter ratio.Fig. 4 (b) is the scanning electron microscope high power figure of overlength zinc oxide micrometer wall obtained in the embodiment of the present invention 1, can obtain its surface smooth, highly about 3.5 μm from figure.
The method applied in the present invention prepared product purity is high, and preparation process is simple, energy-conservation, processing ease, expense are lower, and be applicable to large-scale industrial production, be expected at nanoelectronic, the aspects such as photoelectric device have wide application prospects.Protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to the technical scheme of inventing and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (5)
1. a preparation method for zinc oxide micrometer walling material, step is as follows:
(1) choose the silicon based gallium nitride substrate with crackle, cleaning-drying is for subsequent use;
(2) configure growth solution, according to the ratio of 30 ~ 50mM:30 ~ 50mM:100ml, take zinc acetate, six methyne four ammonia and deionized waters respectively, mix and make it fully dissolve, wherein, the mol ratio of zinc acetate, six methyne four ammonia is 1:1, makes it dissolve after mixing;
(3) the silicon based gallium nitride substrate with crackle that step (1) obtains is placed in the growth solution that step (2) obtains, after being warming up to 90 DEG C, reacts 30min ~ 90min at such a temperature;
(4), after reaction terminates, substrate is taken out, and clean with deionized water rinsing, dry;
The height of described zinc oxide micrometer wall is micron dimension.
2. the preparation method of zinc oxide micrometer wall according to claim 1, is characterized in that, in described step (2), the ratio of zinc acetate, six methyne four ammonia and deionized water is 50mM:50mM:100ml or 30mM:30mM:100ml.
3. the preparation method of zinc oxide micrometer wall according to claim 1 and 2, is characterized in that, in described step (3), the reaction times is 90min.
4. a zinc oxide micrometer walling material, it is prepared by following method: silicon based gallium nitride substrate growth with crackle, be placed in the aqueous solution that zinc acetate and hexamethylenetetramine are configured to, by low-temperature aqueous solution method, the surface crack inducing action of silicon based gallium nitride substrate is utilized to make zinc oxide material then be self-assembled into zinc oxide micrometer walling material at cracks Preferential Nucleation;
The height of described zinc oxide micrometer wall is micron dimension.
5. zinc oxide micrometer walling material according to claim 4, it is characterized in that, described preparation method as claimed in claim 1.
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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 |
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| 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 (1)
| Title |
|---|
| ZnO interconnected network nanostructures grown on cracked GaN by the aqueous solution method;Naisen Yu et al.;《Journal of Alloys and Compounds》;20100701;第505卷;第L27-L30页 * |
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