CN100418874C - Magnetic field induced deposition method for preparing magnetic nano-gap electrode - Google Patents
Magnetic field induced deposition method for preparing magnetic nano-gap electrode Download PDFInfo
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- CN100418874C CN100418874C CNB2004100659513A CN200410065951A CN100418874C CN 100418874 C CN100418874 C CN 100418874C CN B2004100659513 A CNB2004100659513 A CN B2004100659513A CN 200410065951 A CN200410065951 A CN 200410065951A CN 100418874 C CN100418874 C CN 100418874C
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Abstract
The present invention provides a magnetic field induced deposition method for producing a magnetic nanometer gap electrode, which relates to a technique for processing nanometer structures and nanometer devices. Oriented growth is synchronously induced by selective deposition of magnetic metal on an ordinary light etching electrode and a magnetic field along the direction of an electrode couple, the gap of the ordinary electrode couple is shortened to a nanometer level under the condition that the side width of the electrode is not correspondingly widened, and thus, a magnetic nanometer gap electrode can be conveniently and cheaply processed. The method for producing a magnetic nanometer gap electrode comprises the following steps: first of all, ordinary light etching technology is used for producing an original micron or submicron gap electrode; bifunctional molecules and bonding initiating agents are assembled on the surface of the original electrode, and thus, the surface of the electrode can have catalytic activity; the original electrode having catalytic expansion performance is put in a magnetic metal or chemical alloy plating solution, an external magnetic field is simultaneously exerted along the direction of an original electrode couple, and magnetic metal or alloy is synchronously induced to preferentially deposit at the tip of the electrode couple so as to obtain the magnetic nanometer gap electrode.
Description
Technical field
The present invention is the process technology of a kind of nanostructured, nano-device, and the selective chemical deposition prepares the method for magnetic nano-gap electrode under especially a kind of induced by magnetic field, belongs to the nano-device machining technology.
Background technology
Nano electron device, its characteristic size is in nanometer scale (1-100nm), no longer follow the microelectronic basic moving law of tradition, and The Wave Behavior of Electrons, quantum effect etc. will play an important role in this type of device, the breakthrough of its key technology will be expected to become new economic growing point, and will the various aspects of human society be exerted far reaching influence.Nanofabrication technique then is the basis of development nanometer electronic device.
Nano-gap electrode is the especially key structure or the basis of single-electron device of development nanometer electronic device.Adopt electron beam lithography (Appl.Phys.Lett., 2002,80 (2): 865-867), focused-ion-beam lithography (Thin Solid Films, 2003,438 439:374-377), binding molecule beam epitaxy etching (Appl.Phys.Lett., 2002,81 (4): 730-732), SPM microprobe processing (Nanotechnology, 1999,10:458-463; Jpn.J.Appl.Phys., 2001,40:4365-4367; Nano Lett., 2003,3 (1): 43-45) etc. method is processed nano-electrode needs expensive instrument and equipment, and cost is higher, and related technology is difficult, is difficult to popularize for the moment.Construct controllable nano structure and device in conjunction with " from top to bottom " with " from bottom to top " two kinds of process technology routes, be an important directions of the simple and easy to do nanofabrication technique of current development, and carried out good try aspect the method for nano-gap electrode seeking to prepare.As electroless plating method (ZL01113578.6), galvanoplastic (NL1019733C; Thin Solid Films, 2003,438-439:317-321), electron transfer method (Appl.Phys.Lett., 2002,81 (24): 4613-4615; Chinese patent application number: 200310106004.X), at first adopt " from top to bottom " lithographic technique to prepare micron or sub-micron clearance electrode as the prototype electrode, use method plated metal on the prototype electrode of chemistry, physics then, make electrode gap be reduced to nanometer scale.Wherein, galvanoplastic and electroless plating method all are to reduce its gap by the online deposition growing of metal on electrode pair, but also increased the lateral width of electrode simultaneously, and galvanoplastic need go between with applied voltage at preparation process mesarcs electrode two ends, only are suitable for concrete device is carried out individual operation; The electron transfer method not only need be electrically connected at prototype electrode two ends lead-in wire, and the gap that requires the prototype electrode pair can not be too big (be in accurate nanometer or submicron-scale usually, prior art all be to adopt the electron beam lithography method to prepare its prototype electrode structure).
Magnetic nano-gap electrode the manipulation of magnetic nano-particle and in order assembling, biomolecule The Research of Electromagnetic Control, detect aspects such as sensing technology and electrons transport property research and have special application prospect, but magnetic nano-gap electrode is also very rare at present, related preparation method also only limits to galvanoplastic and electroless plating method, and related application research aspect is very limited.
Summary of the invention
Technical problem: the method that the objective of the invention is to propose a kind of magnetic field induced deposition method for preparing magnetic nano-gap electrode, by the selective deposition of magnetic metal on common photoetching electrode and synchronous induced orientation growth along the magnetic field of electrode pair direction, gap with common photoetching electrode pair under the lateral width situation of not corresponding increase electrode is reduced to nanoscale, realizes easy the to be cheap processing of nano-gap electrode.
Technical scheme: induced by magnetic field is combined with the selective chemical plating method, on the direction of common photoetching electrode pair (prototype electrode), apply an external magnetic field, allow magnetic metal promptly be magnetized in the moment of the selective chemical deposition generation of electrode/solution interface, and by the further inducing action in magnetic field make magnetic metal at the most advanced and sophisticated place of electrode pair on the electrode pair direction preferential deposition and oriented growth, the electrode pair gap is reduced to nanoscale from micron order or submicron order, obtains magnetic nano-gap electrode.
The method of preparation is as follows: at first, prepare the prototype electrode in micron order or submicron order gap with the normal optical carving technology; At prototype electrode surface assembling bifunctional molecule (X-R-Y), chemisorbed chemical plating initator, make electrode surface have catalytic activity; The prototype electrode that will have catalytic activity is put into the chemical plating solution of magnetic metal or alloy, simultaneously on prototype electrode pair direction, apply an external magnetic field, locate preferential deposition and oriented growth with one-step inducing magnetic metal or alloy at the electrode pair tip, realize reducing of electrode gap, finally obtain magnetic nano-gap electrode.
Wherein, the prototype electrode refers to the silica-base material to be base material, and with the electrode pair structure with micron or sub-micron gap that the normal optical carving technology processes, electrode material is a metal material, is generally gold, silver, copper, platinum.
Bifunctional molecule X-R-Y does not have reactivity for silica-base material.Wherein X for can with the spontaneous functional group that carries out molecule assembling of prototype electrode metal material, prototype electrode for gold, silver, copper product, preferred group is for containing S (sulphur) group, as sulfydryl (SH) or disulfide group (as-S-S-R-Y) or single sulfenyl (as among the thioether molecule Y-R-S-R-Y-S-R-Y); For the prototype electrode of alloy platinum material, preferred group be hydroxyl (OH) or amino (NH
2); Y be can with the active group of chemical plating initator bonding, contain S, N (nitrogen), P (phosphorus), O (oxygen) element usually, as amino, sulfydryl, phosphoryl, carboxyl; R is the organic molecule skeleton, as carbochain, aromatic ring, allows to comprise the active group of a plurality of S of containing, N, P, O element among the R.
The chemical plating initator is the nano particle of argent, palladium, nickel, cobalt; Or palladium ion, silver ion.
The material that is used to reduce electrode gap and is nano-gap electrode is magnetic metal and the alloy thereof that is suitable for chemical plating, as nickel, cobalt and alloy material thereof.
The external magnetic field that applies is external discrete magnetic field, and magnetic direction is parallel to prototype electrode pair direction (the parallel electrode pair direction of passing of the magnetic line of force), and the magnetic field intensity scope is 0.01～2 tesla.
Beneficial effect:
1. on selective chemical deposition basis based on the good localization of molecular self-assembled monolayer, in conjunction with the external magnetic field effect, can make on the electrode in case the metal or alloy that is magnetic deposition takes place promptly by flash magnetization, between electrode pair, form magnetic line of force compact district, thereby further induce magnetic metal or alloy at most advanced and sophisticated preferential reduce deposition in place of the electrode pair of magnetic field gradient maximum and oriented growth, not only can guarantee can not cause the corresponding increase of electrode lateral width when the electrode pair gap reduces, and can on molecular level, improve the surface texture and the pointed shape of the final nano-gap electrode that obtains; In addition, than galvanoplastic or electroless plating method, this law can reduce the unit consumption of chemical reagent such as slaine;
2. the gap to the prototype electrode does not have specific (special) requirements, just can process in conjunction with very general conventional lithographic techniques, and the prototype electrode that the gap reaches several microns even tens microns also is easy to be reduced to the nanoscale interstitial structure;
3. whole device is very simple, equipment input that need not be expensive; Method is simple, and is easy to operate, very easily in realization, has the batch machining potentiality on technology.
4. choose multiple magnetic metal or alloy material easily and obtain the magnetic nano-gap structure to satisfy special application; On this basis, also can prepare the heterojunction structure of other nonmagnetic metal easily by simple chemical deposition, obtaining outer surface layer as nanoscale thin layers such as deposition gold, silver on nickel, cobalt nano-gap electrode is the nano-gap electrode of gold, silver material.
The specific embodiment
Embodiment 1: gold that adopts the normal optical carving technology to process on silica-base material to have micron or submicron order gap or silver or copper electrode are right, and with this as the prototype electrode.After this prototype electrode surface cleaning, put into bifunctional molecule sulfur-containing compound such as mercaptoethylmaine or 1,6-ethanthiol or dimercaptosuccinic acid or TGA or NH
2-(CH
2) n-S-S-(CH
2) n-NH
2(n＞2) or NH
2-(CH
2) n-S-(CH
2) n-NH
2Carry out the molecule assembling in the ethanolic solution of (n＞2); The above-mentioned electrode that is assembled with bifunctional molecule is put into collargol or palladium ion solution carries out the electrode surface activation processing.Above-mentioned electrode through the palladium surface active is put into nickel, cobalt or magnetic alloy chemical plating solution respectively, simultaneously outside the electroless plating reaction device, on the electrode pair direction, apply an external magnetic field (magnetic field intensity is 0.01～2 tesla), induce plating metal at the tip of electrode pair place's preferential deposition and oriented growth, obtain the nano-gap electrode of magnetic metal nickel, cobalt or magnetic alloy material respectively.
Embodiment 2: gold that adopts the normal optical carving technology to process on silica-base material to have micron or sub-micron gap or silver or copper electrode are right, and with this as the prototype electrode.The ethanolic solution of this prototype electrode being put into mercaptoethylmaine after cleaning surfaces is handled carries out the molecule assembling; The above-mentioned electrode that is assembled with bifunctional molecule is put into the colloid nickel solution to be activated.Above-mentioned electrode through the nickel activation is put into the chemical plating solution of nickel or nickel alloy, simultaneously on the electrode pair direction, applying an external magnetic field (magnetic field intensity is 0.01～2 tesla), induce magnetic nickel metal or nickel alloy at the tip of electrode pair place's preferential deposition and oriented growth, finally obtain the nano-gap electrode structure of magnetic nickel or nickel alloy respectively.
Embodiment 3: gold that adopts the normal optical carving technology to process on silica-base material to have micron or sub-micron gap or silver or copper electrode are right, and with this as the prototype electrode.The ethanolic solution of this prototype electrode being put into mercaptoethylmaine after cleaning surfaces is handled carries out the molecule assembling; The above-mentioned electrode that is assembled with bifunctional molecule is put into the colloid cobalt liquor to be activated.Above-mentioned electrode through the cobalt activation is put into the chemical plating solution of cobalt or cobalt alloy respectively, simultaneously on the electrode pair direction, applying an external magnetic field (magnetic field intensity is 0.01～2 tesla), induce magnetic cobalt or cobalt alloy at the tip of electrode pair place's preferential deposition and oriented growth, obtain the nano-gap electrode structure of magnetic cobalt or cobalt alloy respectively.
Embodiment 4: it is right to adopt the normal optical carving technology to process the platinum electrode with micron or submicron order gap on silica-base material, and with this as the prototype electrode.After this platinum prototype electrode surface cleaning, the ethanolic solution of putting into hydroxycarboxylic acid or hydroxyl phosphine carboxylic acid or amino phosphine carboxylic acid carries out the molecule assembling; The platinum electrode that is assembled with functional molecular is put into colloid palladium or silver ion solution carries out the electrode surface activation processing.Above-mentioned platinum electrode through surface active is put into chemical nickel plating or electroless cobalt plating or chemical plating magnetic alloy solution respectively, simultaneously outside the electroless plating reaction device, on the electrode pair direction, apply an external magnetic field (magnetic field intensity is 0.01～2 tesla), induce nickel or cobalt or magnetic alloy at the tip of electrode pair place's preferential deposition and oriented growth, obtain the nano-gap electrode structure of magnetic metal nickel or metallic cobalt or magnetic alloy material.
Claims (7)
1. the method for a magnetic field induced deposition method for preparing magnetic nano-gap electrode, it is characterized in that this method combines the selective chemical deposition with induced by magnetic field, direction along electrode pair applies an external magnetic field, by the selective deposition of metal on common photoetching electrode and synchronous induced orientation growth along the magnetic field of electrode pair direction, gap with common photoetching electrode pair under the lateral width situation of not corresponding increase electrode is reduced to nanoscale, processes magnetic nano-gap electrode;
The technology of preparation is as follows:
A. prepare the prototype electrode pair in micron order or submicron order gap with the normal optical carving technology;
B. at prototype electrode pair surface-assembled bifunctional molecule " X-R-Y ", chemisorbed chemical plating initator, make the electrode pair surface have catalytic activity;
The prototype electrode pair that c. will have catalytic activity is put into chemical plating solution, simultaneously on the direction of prototype electrode pair, apply an external magnetic field, locate preferential deposition and oriented growth with the one-step inducing metal at prototype electrode pair tip, thereby realize reducing of electrode gap, obtain magnetic nano-gap electrode;
Bifunctional molecule " X-R-Y " does not have reactivity for silica-base material, wherein " X " for can with the spontaneous functional group that carries out molecule assembling of prototype electrode metal material, " Y " be can with the active group of chemical plating initator bonding, R is the organic molecule skeleton; The prototype electrode pair refers to the silica-base material to be base material, and with the bipolar electrode configurations with micron or sub-micron gap that the normal optical carving technology processes, electrode material is gold, silver, copper, alloy platinum material.
2. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1, it is characterized in that can with the spontaneous functional group " X " that carries out molecule assembling of prototype electrode metal material, prototype electrode for gold, silver, copper product, be sulfur-containing group, i.e. " SH " or " S-S-R-Y " or " S-R-Y "; For the prototype electrode of alloy platinum material, " X " group is " OH " or " NH
2".
3. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1; it is characterized in that can with the active group " Y " of chemical plating initator bonding; for containing the active group of S, N, P, O element, i.e. amino, sulfydryl, phosphoryl, carboxyl.
4. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1 is characterized in that organic molecule skeleton " R " is carbochain, aromatic ring, allows to comprise the active group of a plurality of S of containing, N, P, O element simultaneously among the R.
5. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1 is characterized in that the chemical plating initator is the nano particle of argent, palladium, nickel, cobalt or palladium ion, silver ion.
6. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1, the material that it is characterized in that being used to reducing electrode gap is magnetic metal and the alloy thereof that is suitable for chemical plating, i.e. metallic nickel, cobalt and magnetic alloy material thereof.
7. the method for magnetic field induced deposition method for preparing magnetic nano-gap electrode according to claim 1, it is characterized in that the external magnetic field that applies is external discrete magnetic field, magnetic direction is parallel with prototype electrode pair direction, and the magnetic field intensity scope is 0.01～2 tesla.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322855A (en) * | 2001-04-26 | 2001-11-21 | 东南大学 | Selective chemical plating process of preparing nanometer gap electrode |
| WO2003061835A1 (en) * | 2002-01-23 | 2003-07-31 | F. Hoffmann-La Roche Ag | Apparatus for retaining magnetic particles within a flow-through cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322855A (en) * | 2001-04-26 | 2001-11-21 | 东南大学 | Selective chemical plating process of preparing nanometer gap electrode |
| WO2003061835A1 (en) * | 2002-01-23 | 2003-07-31 | F. Hoffmann-La Roche Ag | Apparatus for retaining magnetic particles within a flow-through cell |
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