CN104671668A - Preparation method of single micro/nano hole based on glass materials - Google Patents
Preparation method of single micro/nano hole based on glass materials Download PDFInfo
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- CN104671668A CN104671668A CN201410840938.4A CN201410840938A CN104671668A CN 104671668 A CN104671668 A CN 104671668A CN 201410840938 A CN201410840938 A CN 201410840938A CN 104671668 A CN104671668 A CN 104671668A
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- nano hole
- single micro
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of single micro/nano hole based on glass materials. The preparation method comprises the following steps of: firstly adopting electrochemical electric-spark compound processing method to etch a concave pit on a glass capillary, then using a heat shrinking tube or solid paraffin to carry out encapsulation on the part beyond the concave pit, and finally in the etching process of the micro/nano hole, adopting an electrochemical working station to monitor the level of ion current passing through the single micro/nano hole, and obtaining single micro/nano holes with different diameters by stopping chemical etching when different ending currents are adopted. The preparation method disclosed by the invention has the beneficial effects that the preparation process is simple and easy, the preparation process is easy to control, no special requirement is needed for equipment, and the obtained micro/nano holes have the advantages of controllable particle-diameter size, firm and stable effects, hole-shaped morphology and good physical and chemical properties and the like.
Description
Technical field
The present invention relates to a kind of solid-state micro-/preparation method of receiving bore, a kind of particularly method preparing single micro-/ nano hole based on glass material.
Background technology
Nanoporous, the i.e. small hole of internal diameter 1 ~ 100 nm, general aperture should be greater than hole depth, or is in the same order of magnitude, is 3-D nano, structure truly.In recent years, scientific worker utilizes the dimensional structure of nanoporous uniqueness and character thereof to achieve atomic little material as ion, molecule etc. control accurately, transport.Because nanoporous technology can realize high throughput testing to atomic little material and analysis under few solution condition, thus in the field such as biological chemistry, life science, there is potential using value, be successfully applied to preparation biology, chemical reaction sensor, and be expected to realize the detection screening of biomolecules and the quick order-checking etc. of DNA molecular.
At present, conventional nanoporous is divided into the large class in the solid nano hole two of natural biological nano hole and artificial.Wherein, with
α-hemolysin is that the molecular structure in the biological nano hole of representative and hole size are determined, and can be modified by the site of atomic accuracy, functionalization and assembling analyze selectivity to improve, and can realize detection mineral ion, organic and Medicine small molecule, biomacromolecule being comprised to DNA, RNA, enzyme molecule etc. under few solution condition.But, because biological nano hole is by bioprotein life-span and active restriction, there is the shortcomings such as poor stability, life-span be short, and because of its aperture single, limit its application in more wide-range.
Compared with biological nano hole, solid nano hole has the advantages such as Heat stability is good, sturdy construction is firm, aperture is controlled, in the practical detection technique of development, have larger superiority.Current people adopt the technology such as ion beam etching technology, electron beam lithography, heavy ion bombardment technology and wet etching respectively at SiO
2, Si
3n
4, Al
2o
3prepare the nanoporous of different pore size with on the films such as organic polymer, and achieved certain achievement in the detection analysis of biomolecules and solid nanoparticles.Arora utilizes electrochemical-discharge combined machining method technology to etch hole (the Arun Arora of diameter about 500 μm on the glass sheet, Rapid, inexpensive and stress free drilling in glass substrates or thermally bonded glass chips using electrochemical spark erosion method, Chips & Tips (Lab on a Chip), 25 January 2011).By the hole using the electrode of minor diameter can obtain small diameter.But when electrode diameter is less, the energy of the electrical spark that electrode produces can by electrode self melting.Therefore, owing to being subject to electrode diameter and the quantitative limitation of electrical spark energy, adopt the method can not obtain the hole that diameter is nanoscale.Wang etc. (Gou-Jen Wang, Wei-Zheng Chen, Kang J. Chang, A Two-Step Etching Method to Fabricate Nanopores in Silicon,
dTIP of MEMS & MOEMS, Stresa, Italy, 25-27 April 2007.) and utilize the method for wet method photoetching and the combination of chemical track etching phase can obtain the hole that diameter is Nano grade on silicon chip.First then photoetching pit on silicon chip is that chemical etching liquid etches perforation further to the pit formed with NaOH solution, and carrys out the diameter of control punch by electrochemical method record and the size of monitoring nanoporous forming process ion current.But photoetching technique needs specific equipment, and complex process.There is the problems such as complex process, expensive and yield rate be low in the making due to solid nano hole, is thus never promoted and applies.
Summary of the invention
For the above deficiency existed in the preparation of solid nano hole, the present invention proposes a kind of method combined based on electrochemical-discharge Compound Machining and chemical etching, and the glass baseplate such as cover glass, kapillary is prepared the method in single micro-/ nano hole.
To achieve these goals, the present invention is by the following technical solutions:
Based on the preparation method in the single micro-/ nano hole of glass material, etch a pit first on the glass substrate, in pit, then etch single micro-/ nano hole.
The above-mentioned pit that etches on the glass substrate takes electrochemical-discharge combined machining method, and electrolytic solution is NaOH solution, and negative electrode and anode adopt Pt silk electrode respectively.The volumetric molar concentration of described NaOH solution is 4-8 M, and voltage is 20 ~ 120 V, and etching time is 3 ~ 120 s, and etching temperature is 15 ~ 40 DEG C.
The preparation method in above-mentioned single micro-/ nano hole, it in pit, etches single micro-/ nano hole adopt chemical etching method, and ionogen is HF-HNO
3-H
2o or HF-NaF-H
2o or HF-H
2o etching liquid, etching temperature is 15 ~ 40 DEG C.In the etching process of micro-/ nano hole, adopt electrochemical workstation monitoring by the size of single micro-/ nano hole ion current, stop chemical etching can obtaining the single micro-/ nano hole of different diameter when difference stops electric current.
Specifically, first on glass capillary, adopt electrochemical-discharge combined machining method to etch a pit, then the part heat-shrink tube outside pit or solid paraffin are encapsulated, finally carrying out in the etching process of micro-/ nano hole, adopt electrochemical workstation monitoring by the size of single micro-/ nano hole ion current, stop chemical etching can obtaining the single micro-/ nano hole of different diameter when difference stops electric current.
Preparation is simple for the inventive method, and making processes is easy to control, and to equipment without particular requirement, the micro-/ nano hole of acquisition has controlled, solid firm, the hole shape pattern of pore size and the advantage such as physical and chemical performance is good.
figure of description
Fig. 1 is electrochemical-discharge combined machining method Experimental equipment;
Fig. 2 is the glass capillary of band pit;
Fig. 3 is chemical etching method experimental installation schematic diagram;
Fig. 4 is electrochemical workstation record and the current versus time curve of monitoring;
Fig. 5 chemical etching liquid is HF:HNO
3: H
2o=1:2:17(volume ratio), the optical photograph of the single elliptical aperture obtained at glass capillary wall when temperature is 40 DEG C;
Fig. 6 chemical etching liquid is HF:HNO
3: H
2o=1:2:2(volume ratio), the optical photograph of the single elliptical aperture obtained at glass capillary wall when temperature is 40 DEG C;
Fig. 7 chemical etching liquid is HF:HNO
3: H
2o=1:2:7(volume ratio), the stereoscan photograph of the single elliptical aperture obtained at glass capillary wall when temperature is 20 DEG C;
Fig. 8 chemical etching liquid is HF:H
2o=1:4(volume ratio), temperature be 25 DEG C of single circular holes obtained on the cover slip optical photograph;
9-the water-bath of 1-NaOH solution, 2-Pt silk electrode, 3-electrical spark, 4-glass capillary, 5-pit, 6-suction nozzle, 7-stop buffer, 8-chemical etching liquid.
Embodiment
The present invention proposes a kind of preparation method based on the single micro-/ nano hole of glass material, that cover glass (or glass capillary wall) is immersed in certain density NaOH solution, small one and large one two Pt silk electrodes are immersed in this solution, small electrode cover alignment slide (or glass capillary wall) (Fig. 1) wherein; Switch on power, adjustment operating voltage, the electrical spark produced at small electrode place causes glass melting and etches a pit (Fig. 2); Then with heat-shrink tube or solid paraffin by this cover glass (or glass capillary) except the part of pit is encapsulated, be arranged in the middle of electrolyzer (glass capillary), in the electrolyzer of both sides, (or glass capillary is inside and outside) adds NaOH-KCl stop buffer and HF-HNO respectively
3-H
2o(or HF-NaF-H
2o, or HF-H
2o) etching liquid, Pt silk electrode is inserted in both sides, apply the monitoring (Fig. 3,4) that certain voltage carries out current versus time curve, pass through once there be electric current and obviously increase to certain value (termination electric current), cover glass (or glass capillary) is taken out and first rinses by a large amount of filtered water, then respectively with rare NaOH solution and filtered water cleaning.By stopping chemical etching can obtaining the micro-/ nano hole (Fig. 5, Fig. 6, Fig. 7, Fig. 8) of different diameter when difference stops electric current.
embodiment 1
1) under 8 M NaOH solution and 45 V voltage conditions, be that the little Pt silk electrode of 250 μm aims at glass capillary tube wall as anode with diameter, switch on power, electrical spark continues 4 s and forms a pit;
2) utilize and be equipped with the transparent heat draw in hole with electric arc in advance and aim to heat with the glass capillary pit in step 1) and seal, then carry out encapsulating (Fig. 2) with the suction pipette head of 200 μ L of tip cut, and in glass capillary, be full of 1 M KCl+1 M NaOH stop buffer;
3) step 2) in the glass capillary that assembles be placed in 40 DEG C at HF:HNO
3: H
2o(volume ratio)=1:2:17 etching liquid in, electrode insertion, connection electrochemical workstation monitors the current versus time curve (Fig. 3 in its etching process, Fig. 4), stop chemical etching can obtaining diameter to be about the single micro-/ nano hole of 25 × 40 μm when stopping electric current and being about 0.6 μ A (Fig. 5 a).
embodiment 2
Similar to the method preparing single micro-/ nano hole in embodiment 1 on glass capillary, stop chemical etching can obtaining the single micro-/ nano hole (Fig. 5 b) that diameter is about 30 × 60 μm when termination electric current is about 1.2 μ A.
embodiment 3
Similar to the method preparing single micro-/ nano hole in embodiment 1 on glass capillary, difference is that the proportioning of used etching liquid is for HF:HNO
3: H
2o=1:2:2(volume ratio), etching temperature is 40 DEG C (Fig. 6).Stop chemical etching can obtaining the single micro-/ nano hole (Fig. 6 a, b) that diameter is about 25 × 60 μm when termination electric current is about 1 μ A.
embodiment 4
Similar to the method preparing single micro-/ nano hole in embodiment 1 on glass capillary, difference is that the proportioning of used etching liquid is for HF:HNO
3: H
2o=1:2:7(volume ratio), etching temperature is 20 DEG C (Fig. 7).Stop chemical etching can obtaining diameter to be about the single micro-/ nano hole of 15 × 10 μm when stopping electric current and being about 0.09 μ A (Fig. 7 a).
embodiment 5
Similar to the method preparing single micro-/ nano hole in embodiment 4 on glass capillary, stop chemical etching can obtaining the single micro-/ nano hole (Fig. 7 b) that diameter is about 20 × 10 μm when termination electric current is about 0.15 μ A.
embodiment 6
Similar to the method preparing single micro-/ nano hole in embodiment 1 on glass capillary, difference is: electrical spark continues melting and etches 5 s and produce a pit on the cover slip; Be arranged in the middle of electrolyzer after the cover glass sealed through transparent heat draw cleaning is dried up, have in the electrolyzer side of pit that to add proportioning be HF:H
2o=1:4(volume ratio) etching liquid, do not have the side of pit to add 1M KCl+1M NaOH stop buffer; Electrode insertion, connects electrochemical workstation and monitors the current versus time curve of its etching process, can obtain diameter be about the single micro-/ nano hole of 20 μm (Fig. 8 a) stopping stopping when electric current is about 0.3 μ A chemical etching.
embodiment 7
Similar to the method preparing single micro-/ nano hole in embodiment 6 on glass capillary, stop chemical etching can obtaining the single micro-/ nano hole (Fig. 8 b) that diameter is about 60 μm when termination electric current is about 2 μ A.
Claims (6)
1. based on the preparation method in the single micro-/ nano hole of glass material, it is characterized in that: etch a pit first on the glass substrate, in pit, then etch single micro-/ nano hole.
2. the preparation method in single micro-/ nano hole according to claim 1, it is characterized in that etching pit on the glass substrate takes electrochemical-discharge combined machining method, electrolytic solution is NaOH solution, and negative electrode and anode adopt Pt silk electrode respectively.
3. the preparation method in single micro-/ nano hole according to claim 2, is characterized in that: the volumetric molar concentration of NaOH solution is 4-8 M, and voltage is 20 ~ 120 V, and etching time is 3 ~ 120 s, and etching temperature is 15 ~ 40 DEG C.
4. the preparation method in single micro-/ nano hole according to claim 1, it is characterized in that in pit, etch single micro-/ nano hole adopts chemical etching method, ionogen is HF-HNO
3-H
2o or HF-NaF-H
2o or HF-H
2o etching liquid, etching temperature is 15 ~ 40 DEG C.
5. the preparation method in single micro-/ nano hole according to claim 4, it is characterized in that: in the etching process of micro-/ nano hole, adopt electrochemical workstation monitoring by the size of single micro-/ nano hole ion current, stop chemical etching can obtaining the single micro-/ nano hole of different diameter when difference stops electric current.
6. the preparation method in single micro-/ nano hole according to claim 5, it is characterized in that: on glass capillary, first adopt electrochemical-discharge combined machining method to etch a pit, then the part heat-shrink tube outside pit or solid paraffin are encapsulated, finally carrying out in the etching process of micro-/ nano hole, adopt electrochemical workstation monitoring by the size of single micro-/ nano hole ion current, stop chemical etching can obtaining the single micro-/ nano hole of different diameter when difference stops electric current.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459264A (en) * | 2017-08-08 | 2017-12-12 | 东北大学 | A kind of method for preparing single nano-pore interface on the glass substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320564A (en) * | 2011-09-02 | 2012-01-18 | 厦门大学 | Nanopore preparation method based on tungsten needle tip and thick-wall glass tube |
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2014
- 2014-12-30 CN CN201410840938.4A patent/CN104671668A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320564A (en) * | 2011-09-02 | 2012-01-18 | 厦门大学 | Nanopore preparation method based on tungsten needle tip and thick-wall glass tube |
Non-Patent Citations (3)
| Title |
|---|
| GOU-JEN WANG ET.AL: "A two-step etching method to fabricate nanopores in silicon", 《MICROSYSTEM TECHNOLOGIES》 * |
| 郭永丰等: "非导电材料的电化学电火花复合加工工艺研究", 《电加工》 * |
| 鹿昌剑: "电解电火花复合加工在微细加工中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107459264A (en) * | 2017-08-08 | 2017-12-12 | 东北大学 | A kind of method for preparing single nano-pore interface on the glass substrate |
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Application publication date: 20150603 |