WO2001043196A1 - Procede de formation de structure ordonnee de fines particules de metal - Google Patents
Procede de formation de structure ordonnee de fines particules de metal Download PDFInfo
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- WO2001043196A1 WO2001043196A1 PCT/JP2000/008638 JP0008638W WO0143196A1 WO 2001043196 A1 WO2001043196 A1 WO 2001043196A1 JP 0008638 W JP0008638 W JP 0008638W WO 0143196 A1 WO0143196 A1 WO 0143196A1
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- WIPO (PCT)
- Prior art keywords
- metal
- thiol
- particles
- fine particles
- substrate
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002923 metal particle Substances 0.000 title claims abstract description 27
- 229910001111 Fine metal Inorganic materials 0.000 title abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 85
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 134
- 239000002184 metal Substances 0.000 claims description 134
- 239000002245 particle Substances 0.000 claims description 122
- 239000010419 fine particle Substances 0.000 claims description 86
- 229910052737 gold Inorganic materials 0.000 claims description 71
- 239000010931 gold Substances 0.000 claims description 71
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 62
- -1 2-amino-ethylamino Chemical group 0.000 claims description 36
- 239000000084 colloidal system Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract 3
- 238000001338 self-assembly Methods 0.000 abstract 3
- 150000003573 thiols Chemical class 0.000 description 113
- 239000000243 solution Substances 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000007796 conventional method Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 101100390805 Mus musculus Fkbp8 gene Proteins 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- WKVAXZCSIOTXBT-UHFFFAOYSA-N octane-1,1-dithiol Chemical compound CCCCCCCC(S)S WKVAXZCSIOTXBT-UHFFFAOYSA-N 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/701—Organic molecular electronic devices
Definitions
- the present invention relates to a method for treating metal fine particles deposited on a substrate with an organic solvent. More specifically, the present invention relates to a method for forming a two-dimensional ordered structure of metal fine particles deposited on a self-assembled film.
- Single-electron devices use the “Coulomb blockade” phenomenon, in which electron tunneling is suppressed by Coulomb energy, and control electrons one by one.
- Single electron devices have the following excellent features.
- the material may be a conductor or a semiconductor.
- the ordered structure used in a single-electron device may be a conductor as long as it is on the order of nanometers
- an aggregate of metal fine particles having a size of several nanometers is applied to the single-electron device.
- Of particular interest is a method of forming metal thiol particles by coating fine metal particles with thiol molecules.
- Fine metal particles of several nm have a large ratio of surface area to volume and are highly reactive. Therefore, the metal fine particles will aggregate if left untouched. Therefore, the surface of the metal fine particles is coated with thiol molecules to prevent aggregation of the metal fine particles.
- a method of depositing metal fine particles on a substrate first, there is a method in which an aqueous solution of metal thiol particles is dropped on the substrate and the solvent is dried.
- this method has a drawback that it is difficult to control the number of fine metal particles constituting the aggregate (cluster) and the pattern formation of the aggregate (cluster 1).
- gold is used as the metal.
- a SAM is formed on the silicon oxide film using APTS (3- (2-amino-ethylamino) propyltrimetoxy-silane).
- This substrate is immersed in a solution (gold colloid solution) containing a gold particle colloid prepared separately to deposit gold colloid on the SAM.
- gold colloid solution containing a gold particle colloid prepared separately to deposit gold colloid on the SAM.
- a loose electrostatic bond is formed between the amino group of APTS and the gold colloid surface, and the gold colloid is fixed on the SAM (Fig. 3 (c)).
- gold colloid refers to individual gold colloid particles.
- Gold colloids are positively charged, repel each other, and do not form agglomerates (clusters) but exist at a distance specified by the amount of charge possessed by the colloids. At this stage, it is impossible to combine gold colloids into aggregates (clusters). In addition, the upper limit of the number of gold colloids per unit area of the substrate was limited (Fig. 3 (a)).
- the SAM with the gold colloid attached thereto is immersed in the thiol solution together with the substrate, and the surface of the gold fine particles is covered with thiol molecules.
- the sulfur atom of the thiol molecule is very easily bonded to gold, and the thiol molecule replaces the loose electrostatic bond between the gold colloid and the SAMamino group, and forms a covalent bond with gold. In this way, the fine gold particles are coated with the thiol molecules to become gold thiol particles (FIG. 3 (d)).
- the gold thiol particles can diffuse across the SAM surface.
- the gold thiol particles are diffused on the SAM, and when they come into contact with each other, they are combined by Van der Waals forces, forming a two-dimensional ordered structure (Fig. 3 (b)).
- this method is very subtle and has the advantage that the ordered structure of metal fine particles of about several nm can be obtained with good reproducibility.
- the conventional method has a disadvantage that the fine metal particles adhering to the SAM are released from the SAM during the thiol treatment. Depending on the processing conditions and the particle size of the metal microparticles, all of the attached metal microparticles may be released. This is because the “thiol molecule-metal fine particle bond” is generated during the thiol treatment, and the electrostatic bond between the metal colloid and the SAM amino group is formed. Is lost. As a result, the fine metal particles that have been bonded to the SAM surface are released from the bond and can diffuse on the SAM. However, at the same time, the loss of electrostatic binding weakens the force that binds the metal thiol particles on the SAM, and the metal thiol particles are released into solution.
- the present invention has been made in view of such a problem, and has been made to prevent the metal thiol particles from being released from the SAM at the time of coating the metal fine particles deposited on the SAM with thiol molecules. Aim.
- the present invention relates to a method for forming an ordered structure of metal fine particles on a substrate
- a substrate having a metal colloid adhered to the SAM surface is used as a first electrode, a second electrode is provided in the solution, and a voltage of a predetermined magnitude is applied.
- a voltage is applied between the substrate and the thiol solution, thereby forming a static electricity between the metal thiol particles and the substrate. This has made it possible to suppress the release of metal thiol particles from the SAM due to the attractive force.
- the amount released from M also increases. For this reason, it was very difficult to leave small metal particles on the SAM. For example, when gold was used as the metal, it was virtually impossible to leave fine gold particles having a particle size of 1 nm or less on the SAM.
- the number of metal fine particles released from the SAM is reduced as compared with the conventional method, so that waste of metal fine particles is eliminated and an ordered structure of metal fine particles can be efficiently formed.
- the effective movement length of the metal thiol particles on the SAM can be adjusted, and the size of the two-dimensional ordered structure of the metal fine particles can be easily controlled. It became.
- the effective moving length of the metal thiol particles is the moving distance of the metal thiol particles on the SAM per unit time, and is a measure of the ease of diffusion of the metal thiol particles on the SAM. The greater the effective length, the more easily the metal thiol particles diffuse over the SAM.
- the individual metal thiol particles move easily on the SAM (the effective movement length is long), and therefore, the probability that the metal thiol particles collide with each other is large. Become. In such cases, a two-dimensional ordered structure with a small number but a large area is likely to occur.
- the effective moving length is short
- the number of metal thiol particles on the substrate decreases because the probability of collision between the metal fine particles decreases. It is easy to produce a two-dimensional ordered structure with many but small areas.
- the effective transfer length also depends on the particle size of the metal fine particles. Other things being equal, the larger the particle size, the smaller the effective movement length of the metal thiol particles.
- the size of the two-dimensional ordered structure and the areal density of the metal fine particles can be controlled through the particle diameter of the metal fine particles and the applied voltage.
- FIG. 1 is a schematic view showing the formation of an ordered structure of metal fine particles according to the present invention.
- FIG. 2 is a schematic diagram showing the state of voltage application during thiol molecule treatment according to the present invention.
- FIG. 3 is a schematic diagram showing the deposition of metal fine particles and the formation of an ordered structure according to the conventional technique.
- US AM 12 is a gold colloid
- 13 is a substrate
- 15 and 23 are power supplies
- 16 is gold thiol particles
- 21 is a counter electrode
- 22 is a substrate
- And 24 represents a thiol alcohol solution.
- a metal oxide film having a hydroxyl group on its surface for reacting with APTS is suitable.
- examples include a titanium oxide film, a nickel oxide film, an alumina film, quartz, and glass. Silicon oxide is particularly preferable because a high-quality silicon single crystal can be easily obtained.
- the metal fine particles used in the present invention preferably have a range of 0.8 nm to 10 mn.
- the electrostatic force that maintains the bond between the SAM and the metal thiol particles is compensated for.
- the effect of binding metal thiol particles centered on the following metal fine particles is seen.
- the lower limit of 0.8 nm is a provisional value. This is the smallest particle size of the metal fine particles available to the inventors (Nanoprobes, Inc., gold fine particles, average particle size 0.8 nm). According to the evaluations of the present inventors, no gold fine particles were released from the SAM even when the particle size of the gold fine particles was 0.8 nm. From this, it is considered that the present invention exerts an effect of suppressing release from SAM even when the particle size of the gold fine particles is less than 0.8 nm.
- the thiol molecule covering the metal thiol particles those having an aliphatic saturated hydrocarbon chain or an aromatic hydrocarbon chain are used. For example, dodecanethiol, hexanethiol, benzenethiol and the like. According to the study of the present inventors, as the chain length of the thiol hydrocarbon chain becomes longer, a higher voltage is required to bind the metal thiol particles on the SAM. According to the evaluations of the present inventors, the number of carbon atoms should be in the range of 8 to 14 in the case of a linear aliphatically saturated hydrocarbon chain in terms of binding metal thiol particles on a substrate. Is desirable.
- the chain length of the thiol molecule is also related to the ease of diffusion of the metal thiol particles coated with the thiol molecule on the SAM (easiness of release from the SAM).
- a good result means that the gold particles were not released from the SAM and the ordered structure of the gold particles was quickly formed on the SAM.
- the carbon number of the thiol molecule determines the distance between metal particles in a two-dimensional ordered structure.
- the distance between the metal particles is an important factor that determines the size of the tunnel barrier of a single-electron device.
- the desirable distance between the fine metal particles is 1 nm or less.
- the chain length of the thiol molecule giving this distance is experimentally a thiol molecule having 10 to 12 carbon atoms.
- ethanol is suitably used as a solvent for dissolving the thiol molecule.
- the concentration of the thiol solution greatly affects the binding of the thiol molecule to the surface of the fine metal particles. Strictly speaking, the concentration of the thiol solution seems to depend on the concentration of the fine metal particles in the solution and the type of the thiol molecule used, but when dodecane thiol is used as the thiol molecule, the thiol solution concentration is reduced. Desirably, it is 0.1 to 10 mmol / l.
- the concentration of the thiol solution is 0.1 mmol / l or more, the amount of thiol molecules covering the metal fine particles is sufficient, and metal fine particles completely covered with thiol molecules can be obtained.
- it is 10 mmol / l or less, the reactivity with the metal fine particles does not become poor due to the thiol molecules becoming micelles.
- the term "self-assembled film” means that one end of a molecule has a functional group that reacts with and binds to a substrate surface atom, and the skeleton is composed of an alkyl chain or the like.
- the functional groups are bonded to the substrate surface atoms, the lattice period of the molecule adsorption is a multiple of the lattice of the substrate surface atoms, and the molecules are linked by the interaction of the backbone alkyl chains. It is oriented in a certain direction from the substrate surface. If the surface of the substrate is covered with molecules, the atoms of the substrate surface are no longer exposed, and the deposition of the molecules constituting the self-assembled film on the substrate ends with a monomolecular layer.
- the “ordered structure” is a structure obtained by two-dimensionally aggregating metal fine particles on a SAM.
- the metal thiol particles are It is desirable to apply a voltage that is not released from the surface of the plate and that allows the metal thiol particles to spread on the self-assembled film.
- a feature of the configuration of the present invention is that the effect of suppressing the release of metal thiol particles does not depend on the polarity of the voltage applied to the electrode. Similar effects can be obtained regardless of whether the substrate is an anode or a cathode when a voltage is applied. However, when the applied voltage is increased, the fine metal particles are less likely to be released from the SAM, so the force acting on the fine metal particles is considered to be electrostatic.
- the metal thiol particles have a size that does not separate from the AM surface, and that the metal thiol particles can be two-dimensionally diffused on the SAM even when the applied voltage is large.
- the applied voltage is desirably in the range of 0 to 5 V.
- the present invention provides a method for forming a metal fine particle ordered structure by the above-described method for forming a metal fine particle ordered structure, the method comprising: We propose a method for forming an ordered structure of bonded metal fine particles.
- the two-dimensional ordered structure of metal thiol particles is maintained by Van der Waals bonds between metal thiol particles. Van der Waals coupling When the metal thiol particles have a large particle size, the two-dimensional ordered structure may be disturbed by a slight stimulation because the force is not so large.
- the substrate when immersed in a solution containing a polyfunctional thiol molecule having two or more thiol groups after the two-dimensional ordered structure is formed, the monofunctional thiol that binds to the metal thiol particles It replaces a part of the molecule and connects the metal thiol particles with a covalent bond. This makes it possible to obtain a stronger two-dimensional ordered structure.
- Hexanedithiol and octanedithiol are preferred as the polyfunctional thiol used.
- the present invention has the first electrode in a solution containing metal thiol particles in which the surface of metal fine particles having a particle diameter D of 0.8 ⁇ D 10 nm is coated with a substance having at least one thiol group.
- An oxide substrate having a self-assembled film made of APTS on the surface for depositing metal fine particles is provided as a second electrode in the solution, and a voltage is applied between the two electrodes to form a solution.
- a method for forming an ordered structure of metal fine particles in which metal thiol particles therein are deposited on a substrate is provided.
- a solution containing metal fine particles covered with carbon molecules is prepared in advance, and the substrate serving as the first electrode and the second electrode are immersed in the solution to apply a voltage. Then, fine metal particles coated with thiol molecules near the substrate are deposited on the substrate, and a two-dimensional ordered structure can be formed.
- FIG. 1 is a schematic diagram of a process in which a thiol process is performed while a voltage is applied to gold colloid deposited on a substrate.
- a SAM of APTS 11 having a silane at one end and an amino group at the other end is formed on a substrate 13 of an insulating silicon oxide film.
- the substrate is immersed in a solution containing gold colloid.
- the gold colloid 12 becomes static with the amino group of SAM 11 Electrical coupling occurs (Fig. 3 (a), (c)).
- the substrate on which the gold colloid 12 has been deposited is treated with a thiol solution.
- a second electrode is provided in the thiol solution, a voltage of 15 is applied to the substrate, and the substrate is immersed in the thiol solution (FIG. 2).
- the gold colloid 12 is coated with thiol molecules 14 to form gold thiol particles 16, which weakens the adsorbing power with amino groups and can diffuse on the SAM I 1 surface (FIG. 1 ( d)).
- the gold thiol particles 16 are electrostatically attracted by the applied voltage and do not release from the SAM I 1.
- the gold thiol particles move around on SAM11, and when they collide with each other, combine with Van der Waals forces to form a two-dimensional ordered structure (Fig. 1 (b)).
- the effects of the present invention are schematically shown in FIGS. 1 (a) and (b).
- the surface of the gold fine particles is coated with thiol to become gold thiol particles.
- the gold thiol particles were released from the SAM during the thiol treatment.
- the gold fine particles are not lost after the thiol treatment.
- the present invention will be described more specifically with reference to Examples, but the present invention is not limited to only these Examples.
- FIGS. 1 and 2 show examples of forming an ordered structure of metal fine particles produced by the method of the present invention.
- a silicon oxide film was used as a substrate 13 for forming a self-assembled film by APTS. This is obtained by thermally oxidizing the surface of the silicon substrate 13 by 200 nm. Since the cleanliness of the substrate was related to the adhesion of the SAM in the next step, the surface of the substrate was cleaned by O 2 plasma treatment.
- the substrate 13 was washed with pure water, and then water was removed with a N 2 gas probe to complete the bond formation between the substrate 13 and the APTS.
- gold was used as the metal.
- the gold colloid used was an aqueous solution of gold colloid having a particle size of 5 nm from British Bio Cell.
- the substrate 13 obtained in the step (2) is immersed in the aqueous gold colloid solution of the step (3) for 30 minutes.
- gold colloid 12 forms a weak electrostatic bond with the amino group and is adsorbed on the SAM. Since the gold colloids 12 have the same polarity, they repel each other due to electrostatic repulsion, and are dispersed and adsorbed to the SAM 11 at a distance from each other (Fig. 1 (a) ).
- the number of gold colloids on the surface of SAM11 was evaluated by a scanning electron microscope (SEM).
- SEM scanning electron microscope
- a thiol treatment for covering the gold colloid with thiol molecules 14 is performed.
- a counter electrode 21 was provided as a second electrode as shown in FIG. 2, and a voltage 23 was applied to the entire substrate 22.
- the substrate was immersed in a thiol-alcohol solution 24 (5 mmol / l dodecanethiol in ethyl alcohol) 24 for 2 hours.
- the voltage applied at this time was 3 V.
- the voltage is applied using the substrate 22 as an anode, but conversely, the substrate 22 may be used as a cathode.
- the gold electrostatic particles can move on the SAM 11 surface due to the weak electrostatic attraction generated by the applied voltage, but are fixed to the substrate surface to such an extent that they cannot separate from the SAM 11 surface.
- gold thiol particles diffuse on the surface of SAM11 and come into contact with other gold thiol particles, they are combined by Van der Waals force to form an ordered structure.
- the ordered structure was observed by SEM. As a result, it was found that 15 to 20 gold thiol particles were two-dimensionally aggregated and the ordered structure was approximately 100 ⁇ m 2 with an area density of about 100 ⁇ m 2. It was found that it was uniformly distributed on SAM11.
- the size of the ordered structure of the gold thiol particles can be adjusted by the applied voltage. When the applied voltage is increased, the number of gold thiol particles contained in the ordered structure decreases, and the size of the ordered structure decreases. Conversely, when the applied voltage is increased, the number of gold thiol particles included in the ordered structure increases, and the size of the ordered structure increases.
- the number of gold thiol particles contained in the ordered structure was 10 to 15, which is smaller than that in the case of 3 V.
- the number of gold-carbon particles contained in the ordered structure is 30 to 40, which is larger than that in the case of 3 V. density was reduced with 3 0 / / im 2.
- This step may be performed when a large-area ordered structure is formed, and may be omitted if the ordered structure of gold thiol particles having a predetermined diameter and density can be obtained in step (5).
- a gold-thiol particle coated on the surface with a molecule of titanium prepared in the same process as in Example 1 was used to prepare a substrate having a two-dimensional ordered structure with octanedithiol. It was immersed in an ethanol solution containing 5 mmol / l. By performing this operation, a part of the thiol molecules covering the gold thiol particles is replaced and the gold thiol particles that are in contact with each other are connected to each other, and the two-dimensional ordered structure of the substrate surface created in Example 1 is changed. It was even stronger.
- Steps (1) to (4) were performed in the same manner as in Example 1 to prepare a substrate having a SAM having gold colloid adhered to the surface.
- the substrate obtained in step (4) was immersed in a solution containing a bifunctional thiol molecule.
- a bifunctional thiol a 5 mmol / l ethanol solution of octanedithiol was used.
- a counter electrode was set as a second electrode in an octanedithiol ethanol solution, and a voltage of 3 V was applied between both electrodes for 2 hours.
- the two-dimensional ordered structure of the gold thiol particles obtained from this example is extremely strong because the gold thiol particles are connected by a covalent bond, and has a high durability against heat treatment and the like. high.
- a substrate having a SAM on the surface was prepared in the same manner as in the steps (1) and (2) of Example 1.
- a ring-shaped counter electrode 21 was provided as a second electrode, and a substrate 22 having SAM on the surface was immersed in a gold thiol particle dispersion solution 24.
- a voltage of 3 V was applied to the DC power supply 23 so that the counter electrode was used as a cathode and the substrate was used as an anode.
- An ordered structure of gold thiol particles was formed on the SAM in the same manner as in Example 1 except that no voltage was applied during the thiol treatment in step (5).
- step (4) and the completion of step (5) evaluation by SEM was performed in the same manner as in Example 1.
- gold thiol particles on the SAM were reduced by 50% before and after thiol treatment.
- I was According to the present invention, the release of metal thiol particles from SAM can be suppressed during the process of coating metal fine particles deposited on a substrate with thiol molecules.
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Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/149,547 US6755953B2 (en) | 1999-12-13 | 2000-12-07 | Method for forming ordered structure of fine metal particles |
EP20000979953 EP1239521A4 (en) | 1999-12-13 | 2000-12-07 | Method for forming ordered structure of fine metal particles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP35296599A JP2001168317A (ja) | 1999-12-13 | 1999-12-13 | 金属微粒子秩序構造形成方法 |
JP11/352965 | 1999-12-13 |
Publications (1)
Publication Number | Publication Date |
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WO2001043196A1 true WO2001043196A1 (fr) | 2001-06-14 |
Family
ID=18427669
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/008638 WO2001043196A1 (fr) | 1999-12-13 | 2000-12-07 | Procede de formation de structure ordonnee de fines particules de metal |
Country Status (5)
Country | Link |
---|---|
US (1) | US6755953B2 (ja) |
EP (1) | EP1239521A4 (ja) |
JP (1) | JP2001168317A (ja) |
KR (1) | KR100499594B1 (ja) |
WO (1) | WO2001043196A1 (ja) |
Families Citing this family (20)
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KR100968560B1 (ko) * | 2003-01-07 | 2010-07-08 | 삼성전자주식회사 | 박막 트랜지스터 기판 및 박막 트랜지스터 기판의금속배선 형성방법 |
US7968273B2 (en) | 2004-06-08 | 2011-06-28 | Nanosys, Inc. | Methods and devices for forming nanostructure monolayers and devices including such monolayers |
AU2005253604B2 (en) * | 2004-06-08 | 2011-09-08 | Scandisk Corporation | Methods and devices for forming nanostructure monolayers and devices including such monolayers |
CN101426639B (zh) * | 2004-06-08 | 2012-11-14 | 奈米系统股份有限公司 | 纳米结构的后沉积包封:组合物、器件及包含它们的系统 |
US7776758B2 (en) | 2004-06-08 | 2010-08-17 | Nanosys, Inc. | Methods and devices for forming nanostructure monolayers and devices including such monolayers |
WO2006009807A1 (en) * | 2004-06-17 | 2006-01-26 | Cornell Research Foundation, Inc. | Growth of inorganic thin films using self-assembled monolayers as nucleation sites |
KR100590476B1 (ko) * | 2004-10-04 | 2006-06-19 | 변종식 | 온열 및 초장파 치료용 보료 |
JP4707995B2 (ja) * | 2004-11-05 | 2011-06-22 | 富士フイルム株式会社 | 規則配列したナノ構造材料 |
JP5013723B2 (ja) | 2006-03-09 | 2012-08-29 | キヤノン株式会社 | 微粒子パターン形成方法及びデバイスの製造方法 |
JP2007246417A (ja) | 2006-03-14 | 2007-09-27 | Canon Inc | 感光性シランカップリング剤、表面修飾方法、パターン形成方法およびデバイスの製造方法 |
JP2007246418A (ja) | 2006-03-14 | 2007-09-27 | Canon Inc | 感光性シランカップリング剤、パターン形成方法およびデバイスの製造方法 |
JP5132117B2 (ja) | 2006-10-10 | 2013-01-30 | キヤノン株式会社 | パターン形成方法 |
US20080085479A1 (en) * | 2006-10-10 | 2008-04-10 | Canon Kabushiki Kaisha | Pattern forming method and device production process using the method |
JP2008161857A (ja) * | 2006-12-08 | 2008-07-17 | Catalysts & Chem Ind Co Ltd | 金属含有コロイド粒子担持担体およびその製造方法 |
JP5669276B2 (ja) * | 2010-04-27 | 2015-02-12 | 独立行政法人物質・材料研究機構 | 金属ナノ粒子配列構造体、その製造装置及びその製造方法 |
WO2011135922A1 (ja) * | 2010-04-27 | 2011-11-03 | 独立行政法人物質・材料研究機構 | 近接場光源2次元アレイとその製造方法、2次元アレイ型表面プラズモン共振器、太陽電池、光センサー及びバイオセンサー |
US9823246B2 (en) | 2011-12-28 | 2017-11-21 | The Board Of Trustees Of The Leland Stanford Junior University | Fluorescence enhancing plasmonic nanoscopic gold films and assays based thereon |
JP5642317B2 (ja) * | 2012-03-19 | 2014-12-17 | 三菱電機株式会社 | 半導体装置の製造方法 |
TW201438247A (zh) * | 2013-03-06 | 2014-10-01 | Sk Innovation Co Ltd | 具有一致圖案排列之奈米粒子的單電子電晶體及其製造方法 |
CN118103322A (zh) * | 2021-11-19 | 2024-05-28 | 索尼集团公司 | 结构体、结构体制造方法和前体组合物 |
Citations (1)
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WO1997036333A1 (fr) * | 1996-03-26 | 1997-10-02 | Samsung Electronics Co., Ltd | Dispositif a effet de tunnel et procede de fabrication de ce dispositif |
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GB9418289D0 (en) * | 1994-09-10 | 1994-10-26 | Univ Liverpool | Solutions or dispersions and a method of synthesising materials having controlled electronic and optical properties therefrom |
WO1998010289A1 (en) * | 1996-09-04 | 1998-03-12 | The Penn State Research Foundation | Self-assembled metal colloid monolayers |
US6099897A (en) * | 1997-01-29 | 2000-08-08 | Mitsuboshi Belting Ltd. | Method for producing metal particulate dispersion and metal particle-carrying substance |
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1999
- 1999-12-13 JP JP35296599A patent/JP2001168317A/ja active Pending
-
2000
- 2000-12-07 US US10/149,547 patent/US6755953B2/en not_active Expired - Fee Related
- 2000-12-07 WO PCT/JP2000/008638 patent/WO2001043196A1/ja not_active Application Discontinuation
- 2000-12-07 EP EP20000979953 patent/EP1239521A4/en not_active Withdrawn
- 2000-12-07 KR KR10-2002-7007503A patent/KR100499594B1/ko not_active IP Right Cessation
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---|---|---|---|---|
WO1997036333A1 (fr) * | 1996-03-26 | 1997-10-02 | Samsung Electronics Co., Ltd | Dispositif a effet de tunnel et procede de fabrication de ce dispositif |
Non-Patent Citations (6)
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R. RESCH ET AL.: "Building and manipulating three-dimensional and linked two-dimensional structures of nanoparticles using scanning force microscopy", LANGMUIR, vol. 14, no. 23, 10 November 1998 (1998-11-10), pages 6613 - 6616, XP002937496 * |
RONALD P. ANDRES ET AL.: "Self-assembly of a two-dimensional superlattice of molecularly linked metal clusters", SCIENCE, vol. 273, 20 September 1996 (1996-09-20), pages 1690 - 1693, XP002937495 * |
See also references of EP1239521A4 * |
T. SATO AND H. AHMED: "Observation of a coulomb staircase in electron transport through a molecularly linked chain of gold colloidal particles", APPLIED PHYSICS LETTERS, vol. 70, no. 20, 19 May 1997 (1997-05-19), pages 2759 - 2761, XP002937493 * |
TOSHIHIKO SATO ET AL.: "Single electron transistor using a molecularly linked gold colloidal particle chain", JOURNAL OF APPLIED PHYSICS, vol. 82, no. 2, 15 July 1997 (1997-07-15), pages 696 - 701, XP002937494 * |
TOSHIHIKO SATO, DAVID BROWN AND BRIAN F.G. JOHNSON: "Nucleation and growth of nano-gold colloidal lattices", CHEMICAL COMMUNICATIONS, no. 11, 1997, pages 1007 - 1008, XP002937492 * |
Also Published As
Publication number | Publication date |
---|---|
KR20020069210A (ko) | 2002-08-29 |
EP1239521A4 (en) | 2005-09-14 |
KR100499594B1 (ko) | 2005-07-07 |
EP1239521A8 (en) | 2002-11-20 |
US6755953B2 (en) | 2004-06-29 |
US20020189952A1 (en) | 2002-12-19 |
JP2001168317A (ja) | 2001-06-22 |
EP1239521A1 (en) | 2002-09-11 |
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