CN101560663B - Method for electrochemically preparing nano-array structure materials on basis of nano-mask preparation technique - Google Patents
Method for electrochemically preparing nano-array structure materials on basis of nano-mask preparation technique Download PDFInfo
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Abstract
The invention provides a method for electrochemically preparing nano-array structure materials on the basis of a nano-mask preparation technique, which is applied in the field of manufacturing nano-optoelectronic devices, particularly photonic crystal materials and devices. The method comprises the following steps: a) uniformly distributing monodispersed organic/inorganic nano-spheres on the surface of a substrate to form nano-arrays or graphic arrangement; b) taking the nano-arrays or graphs as a mask, adopting an electrochemical etching process to etch the nano-arrays or the graphs and forming the nano-arrays or graphic structures on the surface of the substrate; and c) removing organic/inorganic nano-materials on the surface and obtaining the nano-arrays or the graphic structures. The method is suitable for preparing the nano-array structures of metal or semiconductor materials, and can reach the minimum size of below 10 nanometers. The adopted electrochemical etching process has the advantages of high efficiency, low cost, convenience, capability of being performed in atmospheric environment and the like, and is convenient for popularization and application.
Description
Technical field
That the present invention relates to is a kind of nano array structure preparation method, particularly a kind of electrochemical preparation nano array structure method based on the nanometer mask technology.Be used for the sub-manufacturing technology of nano photoelectric and photon crystal material and devices field.
Technical background
In this century, novel high-performance material, device and system will depend on the development of nanotechnology.Utilize nanotechnology to realizing high performance device, be of great practical significance and social influence as high sensor, high density of integration nano-device etc.But, be difficult to make dimension of picture, even tens nanometers near 100 nanometers because conventional lithographic techniques is subjected to the restriction of aspects such as self optical diffraction.In recent years; atomic power nanometer processing, laser interference etching and photoetching technique of new generation as: nanofabrication techniques such as extreme ultraviolet (EUV), X ray, electron beam projection and ionic fluid projection have extensively been carried out; but; all there is the very expensive problem of etching apparatus in these technology; input cost is higher; and the equipment etching speed that has is slow, and etching needs to finish under vacuum condition, is difficult to satisfy the commercial production scale requirement.
By literature search, find (Advanced Materials, 2003,15:1065 such as Kuo C-W in 2003; J.Phys.Chem.B2003,107,9950) reported spin coating polystyrene microsphere mask, and deposition Cr film, by CH2Cl2 solution removal polystyrene,, obtained the result of columnar nanometer silicon array then by ion beam etching.Relevant Chinese invention patent, 1, the patent No. is 02136120.7, authorizes publication number is CN 1391264A, name is called " a kind of photoetching method of the nanoparticle pattern based on self-organization ", 2, the patent No. 200410054208.8, to authorize publication number be CN 1606137A, and name is called " the nanometer lithographic method of arranging based on nano material ".Lithographic technique in above document and the patent all adopts the ion beam etching technology, because there is apparatus expensive in ion beam etching, etching speed waits not enough more slowly, thereby has limited the development of its industrial scale.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of electrochemical etching to prepare the method for nano array structure based on nanometer mask.It mainly is that to utilize yardstick be the nano material of tens～hundreds of, by self-assembly, spin coating, spontaneous evaporation, vertically lift or technology such as LB membrane technique forms the nano-array mask at material surface, and adopt electrochemical etching method to realize the preparation of nano-pattern on this basis.Because yardstick is that the preparation technology of nano material of tens～hundreds of is comparatively ripe, and overcome the deficiency of conventional lithographic techniques and photoetching technique of new generation, the mask technique that adopts both can be realized nano-porous structure simultaneously, can realize nanometer column array structure again, there are advantages such as equipment cheapness, technology is simple, efficient and can carry out in the electrochemical etching technology that is adopted under atmospheric environment, not only simplify technology, and improved preparation efficiency.The present invention has characteristics such as equipment cheapness, technology is simple, efficient and can carry out under atmospheric environment, and can realize the controllability of figure.Can on the substrate material of difference conduction, realize the nano-pattern preparation.Realize that for extensive, efficient, low-cost the ordered nano array structure material provides a kind of technical scheme.
The present invention is achieved through the following technical solutions, and concrete steps are as follows:
A kind of electrochemical preparation nano array structure material method based on the nanometer mask technology of preparing is characterized in that, comprises the steps:
A) mixture with monodispersed inorganic, organic nano particle or inorganic nano-particle and polymer blending evenly is arranged in substrate material surface, forms the nano-array figure;
B) be mask with nano-array figure in a), adopt electrochemical etching to carry out the etching of nano graph and array, form the orderly two-dimensional array structure of the nano-array pattern and the degree of depth at substrate surface;
C) remove the remained on surface nano material, obtain nano-array pattern and orderly two-dimensional array structure.
Described nanometer mask technology of preparing is in the step a), and employed inorganic nano-particle is silicon oxide, aluminum oxide or titanium oxide; Organic nano particle is polystyrene (PS), polymethylmethacrylate (PMMA), stearic acid nanometer ball (SA-NP), ciclosporin A stearic acid nanometer ball (CYA-SA-NP) or poly-furfural nanometer ball and chitosan synthetic and crude substance nanoparticle.
Described nanoparticle evenly is arranged in substrate material surface, be specially: adopt self-assembly, spin coating, spontaneous evaporation, vertically lift or the LB membrane technique forms the nano particle display that is evenly distributed orderly in substrate material surface, the preparation of unitary film can obtain best etching effect.
The mixture of step a) inorganic nano-particle and polymer blending evenly arrange for: adopt chemical reaction method to remove inorganic nano-particle or thermal evaporation is removed organism, form the array mask that porous nano array mask that organism constitutes or inorganic nano-particle are arranged.
The etching of nano graph described in the step b) and array is: earlier to heat-treating behind inorganic or the organic nano particle uniform distribution, temperature is decided on material, and organism nanometer mask temperature is at 100～300 ℃, and inorganic nano mask temperature is at 200～500 ℃; The mixture of inorganic nano-particle and polymer blending is evenly arranged, and then the electrochemical etching substrate material.
Described substrate material is nickel, copper, iron, cobalt, aluminium, titanium or zinc, and alloy is titanium base alloy, cobalt base alloy, copper base alloy, nickel-base alloy or ferrous alloy; Semiconductor material is cupric oxide, nickel oxide or the stannic oxide of germanium, silicon, gallium arsenide, indium phosphide, gallium phosphide, indium arsenide or zinc oxide and conduction.
In the step c), the described remained on surface nano material of removing is to utilize physics or chemical process to remove the residual nano material on surface, comprises pyroprocessing and chemical process.
Electrolytic solution in the described electrochemical method is acid, alkali or salts solution, and acid strength is 0.01mol/L-5mol/L; Concentration of lye is 0.01mol/L-5mol/L; Concentration of salt solution is the 0.01mol/L-saturated salt solution, and the pH value is 3～12.
Described electrochemical method and equipment used are specially, and utilize constant voltage or constant current mode, and the equipment of employing is electrochemical workstation or constant current regulated power supply.
Description of drawings
Fig. 1 nanometer column array structure and porous array structure form synoptic diagram;
The InP ordered nano columnar arrays structure that obtains under Fig. 2 galvanostatic conditions;
The ordered nano porous array structure of the InP that obtains under Fig. 3 galvanostatic conditions.
Embodiment
Embodiment 1
At first, obtain the SiO of about 100 nanometers of diameter by the Stober method
2Microballoon, with it by weight, SiO
2Microballoon: dehydrated alcohol=carry out proportioning at 1: 500, utilized ultrasonic agitation 20 minutes, form single dispersoid.Utilize spin coating proceeding at n type InP substrate (heavy doping) surface preparation unitary film, then 80 ℃ of following thermal treatments 20 minutes.Then the sample of handling well is bonded on the copper post, and carries out electrochemical treatment in 3M NaCl solution, last, obtaining diameter is 10 to 50 nanometer column array structures, and resulting structures as shown in Figure 2.
Embodiment 2
At first, obtain the SiO of about 100 nanometers of diameter by the Stober method
2Microballoon, with it by weight, SiO
2Microballoon: dehydrated alcohol=carry out proportioning at 1: 500, utilized ultrasonic agitation 20 minutes, form single dispersoid.Tritonx-100 is added wherein, and ratio is according to SiO
2Microballoon: Tritonx-100: dehydrated alcohol=1: 1: 500 (weight ratio), utilize ultrasonic agitation to make it even in 20 minutes again, utilize spin coating proceeding at n type InP substrate (heavy doping) surface preparation unitary film, then 80 ℃ of following thermal treatments 20 minutes.Then the sample of handling well is bonded on the copper post, and removes SiO with 5% HF solution
2Microballoon carries out electrochemical treatment then in 3M NaCl solution, last, obtains diameter and is about 10 nanometer porous array structures, and resulting structures as shown in Figure 3.
Claims (4)
1. the electrochemical preparation nano array structure material method based on the nanometer mask preparation method is characterized in that, comprises the steps:
A) mixture with monodispersed inorganic nano-particle and polymer blending evenly is arranged in substrate material surface, forms the nano-array figure;
B) be mask with nano-array figure in a), adopt electrochemical etching to carry out the etching of nano graph and array, form the orderly two-dimensional array structure of the nano-array pattern and the degree of depth at substrate surface;
C) remove the remained on surface nano material, obtain nano-array pattern and orderly two-dimensional array structure.
2. according to the method described in the claim 1, it is characterized in that: in the described step a), the inorganic nano-particle that uses is silicon oxide, aluminum oxide or titanium oxide.
3. method according to claim 1 is characterized in that: described substrate is metal, alloy or semiconductor material, and wherein metal is nickel, copper, iron, cobalt, aluminium, titanium or zinc; Alloy is titanium base alloy, cobalt base alloy, copper base alloy, nickel-base alloy or ferrous alloy; Semiconductor material is germanium, silicon, gallium arsenide, indium phosphide, gallium phosphide, indium arsenide or zinc oxide.
4. method according to claim 1 is characterized in that: the electrolytic solution in the described electrochemical etching method is acid, alkali or salts solution, and acid strength is 0.01mol/L-5mol/L; Concentration of lye is 0.01mol/L-5mol/L; Concentration of salt solution is the 0.01mol/L-saturated salt solution, and the pH value of electrolytic solution is 3-12.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101916042A (en) * | 2010-07-23 | 2010-12-15 | 长春理工大学 | Multi-beam semiconductor laser interference nanoimprinting technology and system |
| CN102173376B (en) * | 2011-02-25 | 2013-10-16 | 复旦大学 | Preparation method for small silicon-based nano hollow array with orderly heights |
| CN102321905B (en) * | 2011-10-10 | 2013-11-06 | 吉林大学 | Method for preparing multilevel-structure alumina by pattern prefabrication through micro-nano ball arrangement |
| CN103059610B (en) * | 2012-12-05 | 2016-04-20 | 湘能华磊光电股份有限公司 | The preparation method of mask agent and the substrate with nano-scale pattern |
| CN106115617B (en) * | 2016-06-28 | 2018-12-11 | 北京随能科技有限公司 | A kind of polymer nanocomposite column array without method for preparing template |
| CN111863605A (en) * | 2020-07-31 | 2020-10-30 | 合肥维信诺科技有限公司 | Thin film transistor, preparation method thereof and display |
| CN111893505B (en) * | 2020-08-13 | 2021-07-02 | 沧州信联化工有限公司 | Method for preparing tetramethyl ammonium hydroxide by electrolysis |
| CN113241301B (en) * | 2021-03-31 | 2022-04-15 | 深圳市思坦科技有限公司 | Method for producing nitride semiconductor substrate |
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