CN102092678A - Force modulation mode-based dip-pen nanolithography method - Google Patents
Force modulation mode-based dip-pen nanolithography method Download PDFInfo
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- CN102092678A CN102092678A CN201010619477XA CN201010619477A CN102092678A CN 102092678 A CN102092678 A CN 102092678A CN 201010619477X A CN201010619477X A CN 201010619477XA CN 201010619477 A CN201010619477 A CN 201010619477A CN 102092678 A CN102092678 A CN 102092678A
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Abstract
The invention provides a force modulation mode-based dip-pen nanolithography method in the technical field of nanometer manufacture, which is realized by combining a tapping mode and the force modulation technology, imaging by the tapping mode and lithographing on a setpoint by the force modulation technology. The method can accurately control the acting force and the acting time between a tip and a substrate, so the lithographing effect can be better controller, and the repeatability of lithographing operation is improved; and furthermore, the method can perform multi-point automatic location and dip-pen lithography operation once, is convenient and practical, and is advantageous to industrialization.
Description
Technical field
What the present invention relates to is the method in a kind of nano-fabrication technique field, specifically is a kind of nanometer lithographic method that dips in based on the power modulating mode that is used for nano electron device and biochip.
Background technology
Nanometer etching technology (Dip-pen nanolithography) is a kind of needle point by AFM " to dip in pen ", and the material that adsorbs on the needle point is transferred to suprabasil nano-fabrication technique by the effect of meniscus.People are analogous to needle point in " pen ", and the material on needle point is analogous to " ink ", and the process of etching is analogous to pen and writes on paper, so it is called " dipping in pen " nanometer etching technology visually.By this technology, people can realize large biological molecules such as inorganic salts, organic molecule and albumen are shifted on different base, the figure of preparation functionalization.(Science，1999，283：661-663；Nature?chemistry，2009，1：353-358；PNAS，2001，98：13660-13664)
At present, the method that realizes both at home and abroad " dipping in pen " nanometer etching technology mainly contains: contact mode, rap pattern, contact and rap mixed mode and dynamic combined pattern.Wherein, contact mode is because the distance between needle point and substrate is less, can carry out etching easily by the method that changes the SETPOINT value, but there is shear action in needle point in the process of etching and between substrate, can only operates at hard substrate surface with 1/6 image scanning speed; Rap in the pattern needle point and substrate surface and be interrupted and contact, and friction and shear action are very little, can carry out etching by the method that changes DRIVE AMPLITUDE value, the nano-pattern of manufacturing large biological molecule; Contact and rap mixed mode and utilize contact mode to carry out etching, rap mode imaging, combine that easy etching and the pattern of rapping can be to the characteristics of soft sample imaging under the contact mode, but the subsequent conversion that needs after the etching to carry out contact mode and rap pattern, operations such as needle point replacing and reorientation, cumbersome; The dynamic combined pattern can realize changing immediately rapping pattern and contact mode, realizes that the making and the imaging inspection of nano graph carries out on same position.Above method all is to impel the formation of meniscus by the distance that reduces between needle point and substrate, thereby carries out etching.But change SETPOINT, DRIVE AMPLITUDE and these parameters of LIFT HEIGHT can only change the distance between needle point and substrate qualitatively, and the active force between needle point and substrate can't accurately be controlled, and needs experience to infer; And the coefficient of elasticity that is subjected to needle point is isoparametric influences, even the change amount of parameter is identical, their caused variations all can be different, and etching result is difficult to repeat; In addition, must pointwise carry out repetitive operation when these methods are carried out etching, take a large amount of time.(J Am ChemSoc, 2003,125:580-583; J Am ChemSoc, 2007,129:6668-6669; Chinese science, 2004,49:444-447; Chinese patent: publication number CN1654230A, CN1615457A)
Summary of the invention
The present invention is directed to the prior art above shortcomings, an a kind of nanometer lithographic method that dips in based on the power modulating mode is provided, by rapping pattern and the power modulation technique combines, utilize the pattern of rapping to carry out imaging, the power modulation technique of the utilization etching of fixing a point realizes.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step, in substrate, construct Nanosurface by spin coating, evaporation drying, photoetching technique, soft lithographic technique, electron beam lithography technology or ion beam etching technology, obtain sample with nanostructured at the substrate surface of atomically flating;
Second goes on foot, probe is immersed in inorganic salt solution, organic molecule solution, colloidal solution or the biological macromolecule solns takes out, and dries up;
The environment temperature of the 3rd step, control AFM is 4 ℃ to 80 ℃, and ambient humidity is that 30%RH is between the 80%RH;
The 4th goes on foot, has with probe scanning after the modification and record the sample surface information of nanostructured with selected one or more etchings position, then on the etching position with same probe structure nano graph, scan with check etching result at sample surfaces with this probe at last, be specially:, in this zone, need to determine the position of etching again with the structural information of the sample surfaces that raps the selected zone of mode record of AFM; Fix a point to deposit on the etching position, the needle point after the modification contacts with the select location of sample surfaces, makes the material transfer that is adsorbed on the needle point to the relevant position, thereby realizes the manufacturing of nano graph; The force curve pattern is switched back the pattern of rapping, and original selected zone is scanned, obtain the sample surfaces structural information, check etching result.
The substrate of described atomically flating is mica, graphite or silicon chip.
The surface of described mica is carried out hydrophobization through 3-aminopropyl silane and is handled.
Described Nanosurface is meant: even curface, the surface that is adsorbed with nano particle, nano wire, nanometer band, nanotube or nanometer lamella and the surface that is etched with regular pattern.
Described needle point is the single probe or the probe array of AFM.
Described inorganic salt solution is meant: cation is potassium, sodium, magnesium, calcium, zinc or ammonium radical ion, and anion is the deionized water solution that halide ion, carbanion, sulfate ion or phosphate anion are formed.
Described organic molecule solution is meant: molecular weight is less than 10000 mercaptan or siloxanes, and solvent is water or organic solvent.
Described colloidal solution is meant: the nano particle of metallic gold, argent, metal platinum, titanium dioxide, zinc oxide or iron oxide and quantum dot are dispersed in the solution that forms in water or the organic solvent.
Compared with prior art, this method not only is applicable to nearly all base material, and can accurately control active force and action time between needle point and substrate, can control the etching result better, improves the repeatability of etching operation; Simultaneously, this method can be carried out the automatic location of multiple spot once and be dipped in an etching operation, and is easy, practical, helps industrialization.
Description of drawings
Fig. 1 is a step schematic diagram of the present invention.
Fig. 2 utilizes the force curve that the present invention gathers and the reflected signal (deflection signal) and time relation figure of probe.
Fig. 3 is the nano dot that utilizes the present invention to make on silicon chip.
Fig. 4 is the nano-dot matrix that utilizes the present invention to make on mica sheet.
The specific embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Utilize NSC-18 type needle point, in relative humidity is 78%～85% environment, carry out etching.The power that is adopted is 20nN, and sample is the silicon chip of hexa methoxy disilane after handling, and ink is a glycerine.Regulating TRIGGER TRESHOLD occurs until the force curve as Fig. 2 A shape.If can not obtain the complete force curve of shape, no matter time of contact how long all can not the etching success.Put as can be seen among Fig. 2 B 3 and SURFACE DELAY time of putting between 4 be 1s.
Embodiment 2
Utilize NSC-18 type needle point, in relative humidity is 78%～85% environment, carry out etching.Institute's employing power is 20nN, and sample is the silicon chip after the silane hydrophobic treatment, and ink is a glycerine.Accurately the control needle point is the point that was obtained in 10 seconds in the time of staying of sample surfaces.Fig. 3 A is the pattern of silicon chip surface before the etching, and Fig. 3 B is the pattern after the etching.Contrast two figure as can be known, can successfully realize the etching of nano dot with this understanding with this method.
Embodiment 3
Utilize NSC-11 type needle point, in relative humidity is 43.4%～46.5% environment, carry out etching.Fig. 4 A is that the power that is adopted is 40nN, sample be new explanation from mica, ink is a glycerine, accurately the control needle point is 20 seconds in the time of staying of sample surfaces, obtains the nano-pattern that gap periods is 400nm, and Fig. 4 B is 80nN for the power that adopts, sample be new explanation from mica, ink is a horseradish peroxidase, and the time of staying is 30 seconds, " mouth " font nano-dot matrix that obtains.Contrast this two figure as can be seen, can successfully obtain nanometer lattice row by this method; And because power and time have all obtained better controlled, under the identical operations parameter, the shape of these points is very consistent with size.
Claims (9)
1. the nanometer lithographic method that dips in based on the power modulating mode is characterized in that, may further comprise the steps:
The first step, in substrate, construct Nanosurface by spin coating, evaporation drying, photoetching technique, soft lithographic technique, electron beam lithography technology or ion beam etching technology, obtain sample with nanostructured at the substrate surface of atomically flating;
Second goes on foot, probe is immersed in inorganic salt solution, organic molecule solution, colloidal solution or the biological macromolecule solns takes out, and dries up;
The environment temperature of the 3rd step, control AFM is 4 ℃ to 80 ℃, and ambient humidity is that 30%RH is between the 80%RH;
The 4th goes on foot, has with probe scanning after the modification and record the sample surface information of nanostructured with selected one or more etchings position, then on the etching position with same probe structure nano graph, scan with check etching result at sample surfaces with this probe at last.
2. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1 is characterized in that the substrate of described atomically flating is mica, graphite or silicon chip.
3. the nanometer lithographic method that dips in based on the power modulating mode according to claim 2 is characterized in that, the surface of described mica is carried out hydrophobization through 3-aminopropyl silane and handled.
4. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1, it is characterized in that described Nanosurface is meant: even curface, the surface that is adsorbed with nano particle, nano wire, nanometer band, nanotube or nanometer lamella and the surface that is etched with regular pattern.
5. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1 is characterized in that described needle point is the single probe or the probe array of AFM.
6. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1, it is characterized in that, described inorganic salt solution is meant: cation is potassium, sodium, magnesium, calcium, zinc or ammonium radical ion, and anion is the deionized water solution that halide ion, carbanion, sulfate ion or phosphate anion are formed.
7. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1 is characterized in that described organic molecule solution is meant: molecular weight is less than 10000 mercaptan or siloxanes, and solvent is water or organic solvent.
8. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1, it is characterized in that described colloidal solution is meant: the nano particle of metallic gold, argent, metal platinum, titanium dioxide, zinc oxide or iron oxide and quantum dot are dispersed in the solution that forms in water or the organic solvent.
9. the nanometer lithographic method that dips in based on the power modulating mode according to claim 1, it is characterized in that, selected one or more etchings position described in the 4th step is meant: with the structural information of the sample surfaces that raps the selected zone of mode record of AFM, need to determine the position of etching again in this zone; Described structure nano graph is meant: the deposition of on the etching position, fixing a point, and the needle point after the modification contacts with the select location of sample surfaces, makes the material transfer that is adsorbed on the needle point to the relevant position, thereby realizes the manufacturing of nano graph; Described scanning at sample surfaces is meant: the force curve pattern is switched back the pattern of rapping, and original selected zone is scanned, obtain the sample surfaces structural information, check etching result.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344115A (en) * | 2011-09-28 | 2012-02-08 | 清华大学 | Micronscale/nanoscale connection method based on dip-pen principle |
| CN102950099A (en) * | 2011-08-21 | 2013-03-06 | 比亚迪股份有限公司 | Super-hydrophobic material and preparation method thereof |
| CN102992259A (en) * | 2011-09-15 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for manufacturing nano-grade graph with dynamic-mode nanolithography technology under solution system |
| CN108538765A (en) * | 2018-05-08 | 2018-09-14 | 国家纳米科学中心 | The transfer method of etching device and figure |
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| WO2003038033A2 (en) * | 2001-10-02 | 2003-05-08 | Northwestern University | Protein and peptide nanoarrays |
| CN1615457A (en) * | 2001-12-17 | 2005-05-11 | 西北大学 | Patterning of solid state features by direct write nanolithographic printing |
| CN1654230A (en) * | 2004-02-10 | 2005-08-17 | 中国科学院上海应用物理研究所 | Method for manufacturing nanometer pattern by nanometer etching technology dipping in dynamic combination mode |
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| WO2003038033A2 (en) * | 2001-10-02 | 2003-05-08 | Northwestern University | Protein and peptide nanoarrays |
| CN1615457A (en) * | 2001-12-17 | 2005-05-11 | 西北大学 | Patterning of solid state features by direct write nanolithographic printing |
| CN1654230A (en) * | 2004-02-10 | 2005-08-17 | 中国科学院上海应用物理研究所 | Method for manufacturing nanometer pattern by nanometer etching technology dipping in dynamic combination mode |
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| 《科学通报》 20040331 李宾 等 动态组合模式"蘸笔"纳米刻蚀与单个DNA分子上的物理纳米图形制造 第49卷, 第5期 * |
| 李宾 等: "动态组合模式"蘸笔"纳米刻蚀与单个DNA分子上的物理纳米图形制造", 《科学通报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950099A (en) * | 2011-08-21 | 2013-03-06 | 比亚迪股份有限公司 | Super-hydrophobic material and preparation method thereof |
| CN102950099B (en) * | 2011-08-21 | 2015-08-26 | 比亚迪股份有限公司 | A kind of super hydrophobic material and preparation method thereof |
| CN102992259A (en) * | 2011-09-15 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for manufacturing nano-grade graph with dynamic-mode nanolithography technology under solution 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 |
| CN102344115A (en) * | 2011-09-28 | 2012-02-08 | 清华大学 | Micronscale/nanoscale connection method based on dip-pen principle |
| CN108538765A (en) * | 2018-05-08 | 2018-09-14 | 国家纳米科学中心 | The transfer method of etching device and figure |
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