CN1654230B - Method for manufacturing nano-patterns with dynamic combination mode "dipping pen" nano-etching technology - Google Patents
Method for manufacturing nano-patterns with dynamic combination mode "dipping pen" nano-etching technology Download PDFInfo
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- CN1654230B CN1654230B CN 200410016197 CN200410016197A CN1654230B CN 1654230 B CN1654230 B CN 1654230B CN 200410016197 CN200410016197 CN 200410016197 CN 200410016197 A CN200410016197 A CN 200410016197A CN 1654230 B CN1654230 B CN 1654230B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000005530 etching Methods 0.000 title claims abstract description 9
- 238000007598 dipping method Methods 0.000 title claims description 4
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 7
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 7
- 239000010445 mica Substances 0.000 claims description 20
- 229910052618 mica group Inorganic materials 0.000 claims description 20
- 239000002096 quantum dot Substances 0.000 claims description 12
- 230000005661 hydrophobic surface Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 7
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种以动态组合模式“蘸笔”纳米刻蚀技术制造纳米图形的方法，采用以下步骤：A、对基底表面进行处理，使其达到原子级的平整；B、对原子力显微镜针尖进行修饰，将针尖直接浸入到蛋白质或DNA或其他感兴趣的溶液中约几分钟后，拿起吹干，备用；C、对环境温度、湿度进行控制；D、制造纳米图形：用修饰后的针尖先在基底表面上扫描成像，选定所需要的区域；用该针尖在选定的区域上制造纳米图形；仍然用此针尖对所制造的纳米图形进行再次扫描成像，检查所制造的图形。弥补了现有技术的不足，不但可实现在柔软的生物大分子表面制造纳米图形的工作，同时也可在其他物体表面制造纳米图形。
A method for manufacturing nano-patterns using the "pen" nano-etching technology in a dynamic combination mode. The following steps are used: A. Treating the surface of the substrate to make it flat at the atomic level; B. Modifying the tip of the atomic force microscope, and After the needle tip is directly immersed in the protein or DNA or other solution of interest for about a few minutes, take it up and blow it dry, and set it aside; C. Control the ambient temperature and humidity; D. Make nano-patterns: use the modified needle tip to first place on the substrate Scanning and imaging on the surface, select the required area; use the needle tip to manufacture nanometer graphics on the selected area; still use the needle tip to scan and image the manufactured nanometer graphics again, and check the manufactured graphics. The invention makes up for the deficiency of the prior art, and not only can realize the work of manufacturing nano-patterns on the surface of soft biomacromolecules, but also can manufacture nano-patterns on the surfaces of other objects.
Description
Technical field
The invention belongs to the nano-manipulation field, particularly utilize the nano-manipulation technology to make nano graph.
Background technology
Now, nanoscale science and technology development is very rapid, has created new opportunity as the development of the nano-manipulation technology of one of nanoscale science and technology to us and has finished the work that original technology institute can not realization.The invention of " dip in pen " nanometer etching technology makes us can pass through AFM (AFM), and manipulation nanoscale atomic-force microscope needle-tip with dipping in electrodeposition substance on needle point to body surface, produces nano graph.But, utilize existing " dip in pen " nanometer etching technology (DPN) can on different body surfaces such as conductor, semiconductor surface, carry out, but can not be implemented in the purpose of making nano-scale pattern on the soft large biological molecule.
Summary of the invention
The object of the present invention is to provide a kind of dynamic combined pattern " dip in pen " nanometer lithographic method (CD-DPN), remedy the deficiencies in the prior art, be implemented in the target of making nano graph on the soft biomolecule.
For the DPN technology is applied to life science, introduce the nano-array that adopts the CD-DPN technology on the single DNA large biological molecule, to make at this, adopt the CD-DPN technology to the locator qualification on the single DNA molecules nanometer level in other words.In order to emphasize that the CD-DPN molecule not only can be implemented in the work that nano graph is made on soft large biological molecule surface, it also can make the advantage of nano graph simultaneously at other body surfaces, and we adopt the CD-DPN technology also to prepare nano graph on the surface of mica.
Adopt the step of D-DPN nano-manipulation technology manufacturing nano graph as follows:
1. the processing of substrate surface: can adopt the substrate surface of hydrophobic surface and water-wetted surface to make nano-array respectively.The mica surface of new cleavage and clean glass surface are water-wetted surface substantially, can be directly used in the manufacturing of nano graph as needs.Can adopt 3-aminopropyl silane (APTES) aqueous solution of 5%-1 ‰ to handle activation on mica or glass as the need hydrophobic surface, the hydrophobicity of silicon chip own be stronger, can directly prepare nano graph as hydrophobic surface.No matter substrate is hydrophobic surface or hydrophilic surface, and surface that handled or undressed all need reach the smooth of atom level;
2. the modification of atomic-force microscope needle-tip: after needle point directly is immersed in the interested solution of protein or DNA or other approximately a few minutes, picks up and dry up, standby;
3. the control of environment temperature, humidity: temperature can be between 20-30C.And humidity needs to adjust according to different substrate surface character is different with the solution of the nano graph of manufacturing, and as the mica surface that APTES modifies, humidity need reach and just relatively be fit to preparation protein nano array more than 70%; And on the mica surface of new cleavage, preparing nano graph with protein solution, the humidity more than 30% is just passable.
4. following process is exactly the step that the D-DPN technology is made nano graph:
● with the needle point elder generation scanning imagery on substrate surface after modifying, selected needed zone;
● still on selected zone, make nano graph such as nano dot, nano wire, nano-array etc. with this needle point;
● still the nano graph of manufacturing is carried out scanning imagery once more, check the figure of manufacturing with this needle point.
Description of drawings
Fig. 1 is the nano-array that utilizes the present invention to make on single DNA molecules.
Fig. 2 is dynamic combined pattern of the present invention " dip in pen " nanometer etching technology (CD-DPN) step schematic diagram.
Fig. 3 is the nano-array that utilizes the present invention to make on the mica substrate surface.
The specific embodiment
The nano graph that embodiment 1 makes on the large biological molecule of softness
The manufacturing of protein nano-array on the single DNA molecules, can adopt following steps:
With the mica of new cleavage with 1% APTES solution-treated activation after, be placed on (concrete operations step standby in the drying basin, see also the patent of invention that name is called " manufacture method of the mica substrate that a kind of DNA of being used for handles ", application number: 00116715.4, the applying date: 20000623);
2. the DNA sample solution is dropped on the activated mica, utilize the molecular comb technology that dna molecular is stretching and fixing.Specific practice is, with the TE buffer solution λ DNA is diluted in the concentration 1-20ng/ul scope, take out mica one end that the above-mentioned solution point of 2-5ul is modified at APTES, contact with drop gently with clean cover glass or mica sheet, at leisure whole cover glass or mica are moved along the surface of APTES mica.In this process, because the effect of current meniscus is stretching with DNA, the ATPES mica is fixed in the substrate it to the suction-operated of DNA.Sample after the drying, is prepared to carry out scanning imagery and manipulation with AFM in air or in the nitrogen;
3.AFM needle point dries up standby after modifying 1 minute with protein solution;
4. will modify good needle point is installed on the AFM;
5. adopt AFM that stretching dna molecular is carried out scanning imagery, determine the good zone that needs to make nano graph;
6. in this zone, select a stretching single DNA molecules.Preparation nano graph on the single DNA molecules or say single DNA molecules carried out locator qualification on the nanoscale, can be chosen in the zone of having only a dna molecular or a plurality of dna moleculars in the substrate, need adorned accurate location on the single DNA molecules but will lock;
7. utilize dynamic combined pattern " the dip in pen " nanometer etching technology (CD-DPN) of AffM, be deposited on the original select location dipping in-be used to make nano graph on the position of certain specified point on the single DNA molecules at the protein solution on the afm tip.
The specific operation process of CD-DPN technology is as follows: step 1: earlier with the pattern of rapping of AFM, obtain the feature image in selected zone, further determine some particular locations again in this zone; Step 2: on this position, carry out the scanning of contact mode, make to dip in to deposit to gradually on the surface of substrate at the protein solution on the afm tip, thus the manufacturing of realization nano graph; Step 3; Convert contact mode to rapping pattern, once more image scanning is carried out in original selected zone, obtain feature image, thereby realize inspection to the nano graph of making, as shown in Figure 2. from Fig. 2, the characteristics of CD-DPN are as can be seen: in the manufacturing process of whole nano graph, contact mode and rap the carrying out that conversion between the pattern can be at random and needle point need not be lifted, withdraw from operating system. that is to say that CD-DPN is by the pattern of rapping-contact mode, or rap pattern-contact mode-rap conversion that does not stop between pattern, realize the making of nano graph. when on single stretching dna molecular, making nano-array, earlier selected interested single DNA molecules, lock the particular section on the single DNA molecules again. at this moment, reducing the afm tip height directly contacts afm tip with dna molecular, make dip in to come according to different needs in the time of the contact to the dna molecular of the substance transfer on the needle point fixed, the time of the big more required contact of the yardstick of nano dot or line is just long more. after a nano dot is made, at once the height of afm tip is raised scanning, the image of the nano graph that can obtain to have prepared just. by so continuous lock onto target, reduce the needle point height, raise the process of needle point height and just can on dna molecular, make nano graph, even realized locator qualification single DNA molecules.
As with fluorescently-labeled protein solution as the solution of modifying afm tip, the nano graph of making also can adopt the fluorescence microscope detection method to detect, with the AFM result that checking mutually obtained that comes together.
This tests resulting result is at NanoScope IIIa, and (Santa Barbara finishes on CA) for DigitalIntruments/Veeco, Inc. in AFM MutiMode system.Probe is E or J type.The probe of AFM is (MikroMasch company) NSC 11 (coefficient of elasticity 4.5Nm
-1) noncontact silicon needle point.
The afm tip that uses in this experimental example is single needle point.Temperature when imaging and manipulation is controlled at about 25 ℃, and humidity is about 75%.
The nano graph that embodiment 2 makes at other body surfaces
The manufacturing of nano-array on the APTES mica, can adopt following steps:
With the mica of new cleavage with 1% APTES solution-treated activation after, be placed on (concrete operations step standby in the drying basin, see also the patent of invention that name is called " manufacture method of the mica substrate that a kind of DNA of being used for handles ", application number: 00116715.4, the applying date: 20000623);
2. the solution (this example is protein solution) that will be used for making nano graph is modified afm tip after a few minutes, dries up standby;
3. will modify good needle point is installed on the AFM;
4. adopt AFM that mica surface is carried out scanning imagery, determine the good zone that needs to make nano graph;
5. utilize dynamic combined pattern " the dip in pen " nanometer etching technology (CD-DPN) of AFM will dip in and be deposited on the original selected zone, form a nano dot on the array at the protein solution on the afm tip.As needs can be in time scanning imagery once more, check the nano dot that has been deposited on the mica surface, also can by adjusting the parameter of X-axis or Y-axis, be transformed into position, an other place not on inspection, directly carry out the making of another one nano dot.Like this, constantly change the parameter of X-axis or Y-axis, carry out the making of nano dot again, just can obtain designed nano graph, this routine result is the nano-array of 2X4.The size of nano dot is below 30 nanometers, and the height of point is below 1.5 nanometers, and spacing between points is about between the 150-200 nanometer, and it can be adjusted according to actual needs;
Experimental result shows: as shown in Figure 3, use in this experimental example afm tip be single needle point, also can be crosspointer point or pinpoint array.
Temperature when imaging and manipulation is controlled at about 25 ℃, and humidity is about 75%.
Claims (3)
1. make the method for nano graph with dynamic combined pattern " dip in pen " nanometer etching technology for one kind, adopt following steps:
A, substrate surface is handled, made it reach the smooth of atom level;
B, atomic-force microscope needle-tip is modified, needle point directly is immersed in protein or the dna solution approximately a few minutes after, pick up and dry up, standby;
C, environment temperature, humidity are controlled;
D, manufacturing nano graph:
1.. with the needle point elder generation scanning imagery on substrate surface after modifying, selected needed zone;
2.. on selected zone, make nano graph with this needle point;
3.. still the nano graph of manufacturing is carried out scanning imagery once more with this needle point, check the figure of manufacturing, it is characterized in that: the selected operation 1. in the D step is the rap pattern of elder generation with AFM, obtain the feature image in selected zone, in this zone, further determine some particular locations again; Manufacturing operation 2. in the D step is the scanning of carrying out contact mode on this position, makes to dip in to be deposited on gradually on the zone of being scanned under the contact mode at protein on the atomic-force microscope needle-tip or dna solution, thus the manufacturing of realization nano graph; Scan operation once more 3. in the D step is to convert contact mode to rapping pattern, once more image scanning is carried out in original selected zone, obtains feature image.
2. method according to claim 1 is characterized in that: adopt in the A step to have the material of hydrophobic surface or water-wetted surface as substrate.
3. method according to claim 1, it is characterized in that: the manufacturing operation 2. in the D step is to be deposited on the original selected zone dipping at protein on the atomic-force microscope needle-tip or dna solution, forms a nano dot or a nano wire figure on the nano graph; Scanning imagery is checked the nano dot or the nano wire that have been deposited on the mica surface once more, perhaps not on inspection, by adjusting the parameter of X-axis or Y-axis, is transformed into position, an other place, directly carries out the making of another one nano dot or another line; Constantly the parameter of conversion X-axis or Y-axis is carried out the making of nano dot or line, obtains designed nano graph.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102092678B (en) * | 2010-12-31 | 2013-07-10 | 上海交通大学 | Force modulation mode-based dip-pen nanolithography method |
| CN102303840B (en) * | 2011-06-24 | 2014-12-31 | 上海交通大学 | Preparation method of nano-imprint template in vector type AFM (atomic force microscopy) nano processing system |
| CN102992259B (en) * | 2011-09-15 | 2015-10-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Under solution system, dynamic mode nanometer etching technology manufactures the method for nano graph |
| CN102344115B (en) * | 2011-09-28 | 2015-04-15 | 清华大学 | Micronscale/nanoscale connection method based on dip-pen principle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003052514A2 (en) * | 2001-12-17 | 2003-06-26 | Northwestern University | Patterning of solid state features by direct write nanolithographic printing |
| US6635311B1 (en) * | 1999-01-07 | 2003-10-21 | Northwestern University | Methods utilizing scanning probe microscope tips and products therefor or products thereby |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6635311B1 (en) * | 1999-01-07 | 2003-10-21 | Northwestern University | Methods utilizing scanning probe microscope tips and products therefor or products thereby |
| WO2003052514A2 (en) * | 2001-12-17 | 2003-06-26 | Northwestern University | Patterning of solid state features by direct write nanolithographic printing |
Non-Patent Citations (1)
| Title |
|---|
| 魏莉,洪霞,郭薇,白玉白,李铁津.Dip-Pen刻蚀技术直接制造蛋白质纳米阵列.高等学校化学学报Vol.23 No.7.2002,Vol.23(No.7),1386-1388. * |
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