U.S. patent application number 12/410641 was filed with the patent office on 2009-10-01 for photoreduction processing method of three-dimensional metal nanostructure.
This patent application is currently assigned to RIKEN. Invention is credited to Satoshi Kuwata, Nobuyuki Takeyasu, Takuo Tanaka.
Application Number | 20090242381 12/410641 |
Document ID | / |
Family ID | 41115470 |
Filed Date | 2009-10-01 |
United States Patent
Application |
20090242381 |
Kind Code |
A1 |
Tanaka; Takuo ; et
al. |
October 1, 2009 |
PHOTOREDUCTION PROCESSING METHOD OF THREE-DIMENSIONAL METAL
NANOSTRUCTURE
Abstract
In a method of producing a metal structure by photoreducing
metal ion, a substance capable of suppressing growth of metal
crystal is added to a medium in which metal ion is dispersed to
prevent growth of the metal crystal produced by photoreduction of
the metal ion, thereby processing resolution of a metal structure
formed of the metal crystal is improved
Inventors: |
Tanaka; Takuo; (Wako-Shi,
JP) ; Takeyasu; Nobuyuki; (Wako-shi, JP) ;
Kuwata; Satoshi; (Wako-Shi, JP) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
RIKEN
Wako-shi
JP
|
Family ID: |
41115470 |
Appl. No.: |
12/410641 |
Filed: |
March 25, 2009 |
Current U.S.
Class: |
204/157.4 |
Current CPC
Class: |
B22F 1/0018 20130101;
C30B 29/605 20130101; C30B 29/02 20130101; C30B 7/00 20130101; B82Y
30/00 20130101; B22F 2999/00 20130101; B22F 9/24 20130101; C23C
18/143 20190501; B22F 2999/00 20130101; B22F 9/24 20130101; B22F
2202/11 20130101 |
Class at
Publication: |
204/157.4 |
International
Class: |
B01J 19/12 20060101
B01J019/12 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 25, 2008 |
JP |
2008-077913 |
Claims
1. A method of producing a metal structure composed of metal
crystal, comprising a step of irradiating a medium containing metal
ion dispersed therein with light, to thereby photoreduce the metal
ion to produce metal crystal, wherein the medium contains a
substance which blocks growth of the metal crystal.
2. The method according to claim 1, wherein the substance has one
or more functional groups selected from the group consisting of
ionic functional groups and coordinating functional groups.
3. The method according to claim 2, whereon the substance having
the ionic functional group is represented by the general formula
(I) or a salt thereof: R.sup.1--COOH (I) In the general formula
(I), R.sup.1 represents a saturated or unsaturated hydrocarbon
group in which any hydrogen atom may be replaced by one or more
substituents selected from the group consisting of carboxy, amino,
thiol, hydroxyl and cyano groups, and any --CH.sub.2-- may be
replaced by --C(.dbd.O)-- or --N(R.sup.2)--, and R.sup.2 represents
an alkyl group.
4. The method according to claim 2, wherein the substance having
the ionic functional group is represented by the general formula
(II) or a salt thereof: R.sup.1--NH.sub.2 (II) In the general
formula (II), R.sup.1 represents a saturated or unsaturated
hydrocarbon group in which any hydrogen atom may be replaced by one
or more substituents selected from the group consisting of
carboxyl, amino, thiol, hydroxyl and cyano groups, and any
--CH.sub.2-- may be replaced by --C(.dbd.O)-- or --N(R.sup.2)--,
and R.sup.2 represents an alkyl group.
5. The method according to claim 2, wherein the substance having
the coordinating functional group is represented by the general
formula (III) or a salt thereof: R.sup.1--SH (III) In the general
formula (III), R.sup.1 represents a saturated or unsaturated
hydrocarbon group in which any hydrogen atom may be replaced by one
or more substituents selected from the group consisting of
carboxyl, amino, thiol, hydroxyl and cyano groups, and any
--CH.sub.2-- may be replaced by --C(.dbd.O)-- or --N(R.sup.2)-- and
R.sup.2 represents an alkyl group.
6. The method according to claim 2, wherein the substance having
the coordinating functional group is represented by the general
formula (IV) or a salt thereof: R.sup.1--OH (IV) In the general
formula (IV), R.sup.1 represents a saturated or unsaturated
hydrocarbon group in which any hydrogen atom may be replaced by one
or more substituents selected from the group consisting of
carboxyl, amino, thiol, hydroxyl and cyano groups, and any
--CH.sub.2-- may be replaced by --C(.dbd.O)-- or --N(R.sup.2)--,
and R.sup.2 represents an alkyl group.
7. The method according to claim 2, wherein the substance having
the coordinating functional group is represented by the general
formula (V) or a salt thereof: R.sup.1--CN (V) In the general
formula (V), R.sup.1 represents a saturated or unsaturated
hydrocarbon group in which any hydrogen atom may be replaced by one
or more substituents selected from the group consisting of
carboxyl, amino, thiol, hydroxyl and cyano groups, and any
--CH.sub.2-- may be replaced by --C(.dbd.O)-- or --N(R.sup.2)--,
and R.sup.2 represents an alkyl group.
8. The method according to claim 1, wherein the substance is
represented by the general formula (VI) or a salt thereof:
R.sup.1--O--R.sup.3 (VI) In the general formula (VI), R.sup.1 and
R.sup.3 each represents a saturated or unsaturated hydrocarbon
group in which any hydrogen atom maybe replaced by one or more
substituents selected from the group consisting of carboxyl, amino,
thiol hydroxyl and cyano groups, and any --CH.sub.2-- may be
replaced by --C(.dbd.O)-- or --N(R.sup.2)--, and R.sup.2 represents
an alkyl group.
9. The method according to claim 1, wherein the substance is
represented by the general formula (VII) or a salt thereof:
R.sup.1--C(.dbd.O)--NH--R.sup.3 (VII) In the general formula (VII),
R.sup.1 and R.sup.3 each represents a saturated or unsaturated
hydrocarbon group in which any hydrogen atom may be replaced by one
or more substituents selected from the group consisting of
carboxyl, amino, thiol, hydroxyl- and cyano groups, and any
--CH.sub.2-- may be replaced by --C(.dbd.O)-- or --N(R.sup.2)--,
and R.sup.2 represents an alkyl group.
10. The method according to claim 1, wherein the substance is a
polymer or a copolymer composed of a monomer having one or more
functional groups selected from the group consisting of amino,
carboxyl, carbonyl and thiol groups.
11. The method according to any one of claim 1, wherein the metal
ion is a silver ion.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention relates to a method of producing a
metal structure by photoreduction of metal ion. More specifically,
the present invention relates to a method of manufacturing a metal
structure, whereby processing resolution thereof is improved by
suppressing growth of metal crystal constituting the metal
structure.
[0003] 2. Background Art
[0004] In recent years, fine processing technologies using light
such as optical lithography technology and optical disk
manufacturing technology are widely utilized, and such technologies
have been studied in a variety of fields.
[0005] For example, the fine processing technology using light,
which is most widely applied at present, is the above-mentioned
optical lithography technology. The optical lithography technology
is a backbone technology for manufacturing a variety of electronic
devices such as semiconductor chips. The technology relates to a
massive copying technology using a photo-transferring technology in
principle, in which a metal in a specified region is dissolved,
separated out, or removed finally in a chemical manner, thereby a
desired metal pattern is formed as a metal structure. Therefore,
this method may be used only for two-dimensional processing, and it
is impossible to use the method to freely form a metal structure
having a three-dimensional structure.
[0006] On the other hand, a technique for forming a metal pattern
by irradiating directly a laser beam on a specified material is
known as a technology for forming a desired metal pattern as a
metal structure other than the above-mentioned optical lithography
technology. More specifically, there are a technique involving
irradiating a focused laser beam onto a medium having metal
nanoparticles dispersed therein, to thereby melt and bind the metal
nanoparticles at the focal point of the laser beam, thereby a metal
pattern is formed as a metal structure; and a technique involving
irradiating focused light onto metal ion, thereby the metal ion is
photoreduced and a metal body as separated out, thereby a metal
pattern is formed as a metal structure.
[0007] Here, in the above-mentioned technique involving separating
out the metal body by photoreducing the metal ion, an arbitrary
metal pattern can be formed as a metal structure in response to the
track of scanned focused laser beam by scanning the focused laser
beam which irradiates the material ion. Accordingly, a metal
structure having a three-dimensional structure can be freely
formed, and its applicable range is extremely wide, thereby studies
and developments have been made upon the technique in a variety of
fields in recent years.
[0008] A method of improving the processing resolution of the metal
structure in the technique involving photoreducing the metal Ion to
separate out the metal body is also known.
[0009] In general, an absorption rate of light increases when metal
structure is separated out, and hence there are many cases where
the reaction proceeds explosively just at the moment when an
increased a amount of the metal structure exceeds a certain
threshold value. There is a problem that, when such a phenomenon
occurs, the photoreduction of the metal ions existing in the
vicinity of the focal point proceeds at the,same time, thereby the
processing resolution of the metal structure degrades. In the
method disclosed in JP2006-31631A, a specified pigment is added to
a material, thereby an absorption spectrum and an absorption cross
section of a non-processed material are maintained at constant, and
the processing resolution is prevented from degradation by
propagating energy of the laser beam to an area other than the
focal point of the laser beam, besides photoreduction efficiency at
the focal point of the laser beam is improved.
[0010] This method could improve the processing resolution to a
micrometer order, but a higher-precision nanometer-order processing
resolution was yet required.
SUMMARY OF INVENTION
[0011] An object of the present invention is to provide a method of
producing a metal structure by photoreduction of metal ion, whereby
processing resolution is significantly improved compared with
conventional techniques. More specifically, an object of the
present invention is to provide a method of producing a metal
structure, whereby processing resolution thereof is improved by
suppressing growth of metal crystal constituting the metal
structure.
[0012] The inventors of the present invention have found that metal
crystal produced by photoreduction continues to grow for a while
even after light irradiation is stopped, and grows into a several
micrometer size, and that such a phenomenon restricts the
processing resolution of the metal structure produced by
photoreduction of metal ion. Then, the inventors have made
extensive studies, and as a result, they have found that a
substance which can suppress growth of metal crystal when the
substance is contained in a medium in which metal ion is dispersed,
thereby completed the present invention.
[0013] That is, the present invention is as follows.
[0014] [1] A method of producing a metal structure composed of
metal crystal, comprising a step of irradiating a medium containing
metal ion dispersed therein with light, to thereby photoreduce the
metal ion to produce metal crystal, wherein the medium contains a
substance which blocks growth of the metal crystal.
[0015] [2] The method according to [1], wherein the substance has
one or more functional groups selected from the group consisting of
ionic functional groups and coordinating functional groups.
[0016] [3] The method according to [2], wherein the substance
having the ionic functional group is represented by the general
formula (I) or a salt thereof:
R--COOH (I)
[0017] In the general formula (I), R.sup.1 represents a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group.
[0018] [4] The method according to [2], wherein the substance
having the ionic functional group is represented by the general
formula (II) or a salt thereof:
R.sup.2--NH.sub.2 (II)
[0019] In the general formula (II), R.sup.1 represents a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group.
[0020] [5] The method according to [2], wherein the substance
having the coordinating functional group is represented by the
general formula (III) or a salt thereof:
R.sup.1--SH (III)
[0021] In the general formula (III), R.sup.1 represents a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group,
[0022] [6] The method according to [2], wherein the substance
having the coordinating functional group is represented by the
general formula (IV) or a salt thereof:
R.sup.1--OH (IV)
[0023] In the general formula (IV), R.sup.1 represents a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group.
[0024] [7] The method according to [2], wherein the substance
having the coordinating functional group is represented by the
general formula (V) or a salt thereof:
R.sup.1--CN (V)
[0025] In the general formula (V), R.sup.1 represents a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group.
[0026] [8] The method according to [1], wherein the substance is
represented by the general formula (VI) or a salt thereof:
R.sup.1--O--R.sup.3 (VI)
[0027] In the general formula (VI), R.sup.1 and R.sup.3 each
represents a saturated or unsaturated hydrocarbon group in which
any hydrogen atom may be replaced by one or more substituents
selected from the group consisting of carboxyl, amino, thiol
hydroxyl and cyano groups, and any --CH.sub.2-- may be replaced by
--C(.dbd.O)-- or --N(R.sup.2)--, and R.sup.2 represents an alkyl
group.
[0028] [9] The method according to [1], wherein the substance is
represented by the general formula (VII) or a salt thereof:
R.sup.1--C(.dbd.O)--NH--R.sup.3 (VII)
[0029] In the general formula (VII), R.sup.1 and R.sup.3 each
represents a saturated or unsaturated hydrocarbon group in which
any hydrogen atom may be replaced by one or more substituents
selected from the group consisting of carboxyl, amino, thiol,
hydroxyl and cyano groups, and any --CH.sub.2-- may be replaced by
--C(.dbd.O)-- or --N(R.sup.2)--, and R.sup.2 represents an alkyl
group.
[0030] [10] The method according to [1], wherein the substance is a
polymer or a copolymer composed of a monomer having one or more
functional groups selected from the group consisting of amino,
carboxyl, carbonyl and thiol groups.
[0031] [12] The method according to any one of [1], wherein the
metal ion is a silver ion.
BRIEF DESCRIPTION OF DRAWINGS
[0032] FIG. 1 is a drawing illustrating the action of a substance
which blocks growth of a silver crystal.
[0033] FIG. 2 is an electron micrograph of a silver line obtained
by adding NDSS as the substance which blocks growth of metal
crystal to a medium.
[0034] FIG. 3 is an electron micrograph of a silver line obtained
by adding no substance which blocks growth of metal crystal to a
medium.
[0035] FIG. 4 is an electron micrograph of silver lines obtained by
adding DL-alanine as the substance which blocks growth of metal
crystal to a medium.
[0036] FIG. 5 is an electron micrograph of a silver line obtained
by adding DL-alanine as the substance which blocks growth of metal
crystal to a medium (enlarged micrograph of FIG. 4).
[0037] FIG. 6 is an electron micrograph of silver lines obtained by
adding sodium decanoate as the substance which blocks growth of
metal crystal to a medium.
[0038] FIG. 7 is an electron micrograph of silver lines obtained by
adding disodium sebacate as the substance which blocks growth of
metal crystal to a medium.
[0039] FIG. 8 is an electron micrograph of silver lines obtained by
adding sodium laurate as the substance which blocks growth of metal
crystal to a medium.
[0040] FIG. 9 is an electron micrograph of silver lines obtained by
adding DL-2-amino-n-octanoic acid as the substance which blocks
growth of metal crystal to a medium.
[0041] FIG. 10 is an electron micrograph of silver lines obtained
by adding sodium N-lauroyl sarcosinate hydrate as the substance
which blocks growth of metal crystal to a medium.
[0042] FIG. 11 is an electron micrograph of silver lines obtained
by adding poly(vinylpyrrolidone) as the substance which blocks
growth of metal crystal to a medium.
[0043] FIG. 12 is an electron micrograph of a silver rod formed by
adding NDSS as the substance which blocks growth of metal crystal
to a medium.
[0044] FIG. 13 is an electron micrograph of a silver rod formed by
adding NDSS as the substance which blocks growth of metal crystal
to a medium.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] Hereinafter, embodiments of the present invention are
described in detail.
[0046] In the present invention, the "metal structure" refers to a
structure formed of metal crystals produced by photoreduction of
metal ion. Therefore, as the size of each metal crystal becomes
smaller, the processing resolution of the metal structure may be
improved. The shape of the metal structure manufactured by the
method of the present invention includes a one-dimensional
structure such as a line or curve, a flat two-dimensional
structure, and a spatial three-dimensional structure. According to
the method of the present invention, a metal structure can be
formed in an arbitrary pattern at any part in a medium. For
example, it is easy to produce the metal structure on a part or
whole of the surface of the medium or to form the metal structure
at the inside thereof.
[0047] The light irradiated in the method of the present invention
pro-ides energy to reduce metal ion, therefore, the light to be
irradiated has a wavelength at which the metal ion has an
absorption. However, in the case where the medium contains a
substance, which converts the wavelength of the irradiated light
into the wavelength at which the metal ion has an absorption, the
light to be irradiated is not limited to light having the
wavelength at which the metal ion has an absorption. Examples of
the light source include laser light sources, light-emitting
diodes, and lamps, and the laser light sources are preferably used
because high energy is required to photoreduce the metal ion.
Usually, the light to be irradiated is focused using a focus lens
and focused in a medium in which metal ion is dispersed. Focusing
of the light can increase the photon density at the focal point to
a very high level, and may localize light energy necessary for
reduction of the metal ion at the focal point. As a result, the
metal ion can be photoreduced only in the vicinity of the focal
point, and a fine metal structure can be manufactured along the
track of the focal point by scanning the focal point. Moreover, the
light may be focused to perform fine processing at a size scale of
the focal point. In addition, femtosecond short pulse laser beam,
or the like may be used to provide higher light energy per unit
time.
[0048] The intensity of the irradiated light required for
photoreducing metal ion depends on the type of the metal ion or the
absorbance of the metal ion at the wavelength of the irradiated
light. That is, in the case where the absorbance of the metal ion
at the wavelength of the irradiated light is low, the intensity of
the irradiated light required for photoreducing the metal ion is
relatively high, while in the case where the absorbance of the
metal ion at the wavelength of the irradiated light is high, the
intensity of the irradiated light required for photoreducing the
metal ion is relatively low. Meanwhile, in the case where the
medium contains a substance which absorbs or scatters the
irradiated light, the intensity of the irradiated light becomes
smaller as the irradiated light passes through the medium.
Therefore, it is necessary to relatively increase the intensity of
the irradiated light. Thus, the intensity of the irradiated light
necessary for photoreducing the metal ion may not be simply
determined, but may be adjusted to a range of, for example, about
0.1 mW to 10 mW before incidence to the medium. It is not necessary
to maintain the intensity of the irradiated light to a
constant-level during processing, and the intensity may
appropriately be changed.
[0049] As well as the intensity of the irradiated light, the scan
rate of the focal point may appropriately be adjusted depending on
the absorbance of the metal ion at the wavelength of the irradiated
light or the presence of a substance in the medium. Therefore, the
scan rate necessary for photoreducing the metal ion may not be
simply determined, but may be adjusted to a range of, for example,
about 0.1 .mu.m/s to 100 .mu.m/s. It is not necessary to maintain
the scan rate to a constant level during processing, and the rate
may appropriately be changed.
[0050] Scanning of the focal point may be performed by, for
example, irradiating light to a medium, in which metal ion is
dispersed, and which is placed on a XYZ-axis stage, while the stage
is moved one-dimensionaly, two-dimensionally, and
three-dimensionally. The focal point in the medium can be
arbitrarily scanned by moving the stage. Also, the scanning of the
focal point may also be performed by arbitrarily moving the
position of the focal point in the medium, while the position of
the medium, in which the metal ion is dispersed, is fixed. The
medium in which the metal ion is dispersed and the focal point of
the irradiated light can be moved simultaneously for scanning the
focal point.
[0051] To manufacture a metal structure having a three-dimensional
structure by scanning the focal point, it is preferred that metal
crystals produced in advance do not block the track of the focal
point. To achieve this, a metal structure could be manufactured by
the sequential reductions of the metal ions by continuously
scanning the focal point from a part, which is far from the
incidence position of the irradiated light to the medium, to a Dart
near to the incidence position. However, if the track of the focal
point is not blocked, it is not necessary to scan the light from
the farthest part to the nearest part. The focal point may be
scanned in such a manner to manufacture a fine metal structure
having an arbitrary three-dimensional structure, and to easily
manufacture even a hollow metal structure such as a box. Meanwhile,
in the case where the track of the focal point may be blocked by
the metal crystals produced in advance, there may be employed a
method involving: vanishing the irradiated light; appropriately
changing the incidence angle of the irradiated light to the medium;
and starting irradiation from a position not to block the track of
the focal point to scan the focal point again.
[0052] In the present invention, as the metal ions to be
photoreduced, the following are exemplified.
[0053] (1) Ions of transition elements from the IIIA group to IB
group in the periodic table. Of those, Cr ion, Mn ion, Fe ion, Co
ion, Ni ion, Pd ion, Pt ion, Cu ion, Ag ion, and Au ion are
preferred.
[0054] (2) Ions of elements in the IIIB group. Of those, Al ion and
In ion are preferred.
[0055] (3) Zn ion, Cd ion, Hg ion, Na ion, K ion, Mg ion, and Ca
ion.
[0056] The state in which metal ion to be photoreduced is dispersed
in a medium includes, for example, a state in which metal ion is
dissolved in an aqueous medium and a state in which metal ion is
dispersed in a medium such as an organic solvent or resin. The
state in which metal ion is dispersed includes a state in which the
ion is dispersed as a form of colloid or micelle.
[0057] In the present invention, the concentration of the metal ion
dispersed in a medium is not particularly limited, and is
preferably in the range of 0.001 M to 10 M. The concentration of
the metal ion is more preferably in the range of 0.01 to 1 M.
[0058] The medium which can be used in the present invention is not
particularly limited as long as metal ion can be dispersed therein,
and the medium includes: liquids or fluids such as water, organic
solvents, and fats and oils; semisolids such as gel; and solids
such as a resin (which is preferably a substance soluble in an
organic solvent such as PMMA or FVA, or water), amorphous materials
such as glass, inorganic crystals which may be doped with metal
ion, such as lithium niobate, and the medium is preferably water.
The medium in which metal ion is dispersed may be directly
irradiated with light, or may be placed in a container or placed on
a substrate and then irradiated with light through the container or
substrate. In the case where the medium in which metal ion is
dispersed is a liquid or fluid, light may be convergently
irradiated on a contact surface between the container and the
medium or between the substrate and the medium to form a metal
structure on the inner surface of the container or on the
substrate.
[0059] In the present invention, the "substance which blocks growth
of metal crystal" refers to a substance which prevents crystals
formed by separating out of a metal from binding together and
blocking the metal crystals from becoming larger. Examples of such
a substance include a substance having an effect of covering the
surface of metal crystal to prevent binding of the metal crystal to
another metal crystal (FIG. 1). Based on this perspective, the
substance which blocks growth of metal crystal preferably has all
of the following properties.
[0060] (1) To have an atom which has affinity for or binds directly
to a metal or metal ion in its molecule.
[0061] (2) To be dispersed in a solvent in which metal ion is
dispersed.
[0062] (3) To have a low ability to directly reduce metal ion.
[0063] (4) To form no precipitates by binding to metal ion.
However, if the precipitates can be dissolved again by pH
adjustment of the solvent or by formation of complex ion of metal
ion, such a substance may be used.
[0064] Of those substances, which are considered to satisfy the
above-mentioned conditions, the substance which can be used in the
present invention is a hydrocarbon chain further having at least
one of the following properties.
[0065] (5) To have an ionic functional group in its molecular
structure.
[0066] (6) To have a coordination linkage functional group having
an unshared electron pair (lone pair) in its molecular
structure.
[0067] (7) To have a peptide bond or a similar structure thereof,
an ether bond, or an ester bond in its molecular structure.
[0068] (8) To have a carbonyl group in its molecular structure.
[0069] The above-mentioned hydrocarbon chain includes a saturated
or unsaturated hydrocarbon chain and preferably includes a
saturated hydrocarbon chain, because the saturated hydrocarbon has
a lower ability to reduce metal ion.
[0070] The chain length of the hydrocarbon is not particularly
limited and may appropriately be selected so that the hydrocarbon
can be easily dispersed in a medium in consideration of the type of
the medium to be used or the presence of a hydrophilic group in the
molecular structure. In the case where water is used as a solvent
and the molecular chain includes no hydrophilic group, the length
of the carbon chain is preferably about 5 to 10.
[0071] The above-mentioned Ionic functional group refers to a
functional group which can be ionized in an aqueous solution and
includes anionic and cationic functional groups. Examples of the
anionic functional groups include carboxyl, sulfonyl, phosphate,
and silanol groups and salts thereof, while examples of the
cationic functional groups include amino and pyridinium groups and
salts thereof. Among the salts of the ionic functional groups, the
salts of the anionic functional groups include sodium and potassium
salts; while the salts of the cationic functional groups include
halogenated salts.
[0072] Examples of the above-mentioned coordination linkage
functional groups include thiol, hydroxyl, and cyano groups. The
thiol group can form a thiol bond together with gold, silver,
copper, or the like.
[0073] A substance having the above-mentioned properties has
affinity for a metal or binds directly to a metal atom, and hence
the substance can coat the surface of the metal to prevent growth
of metal crystal.
[0074] Substances represented by the following general formulae (I
to VII) and salts thereof are included in the substance which
blocks growth of metal crystal according to the present
invention.
R.sup.1--NH.sub.2 (II)
R.sup.1--SH (III)
R.sup.1--OH (IV)
R.sup.1--CN (V)
R.sup.1--O--R.sup.3 (VI)
R.sup.1--C(.dbd.O)--NH--R.sup.3 (VII)
[0075] In the formulae, R.sup.1 and R.sup.3 represent a saturated
or unsaturated hydrocarbon group in which any hydrogen atom may be
replaced by one or more substituents selected from the group
consisting of carboxyl, amino, thiol, hydroxyl and cyano groups,
and any --CH.sub.2-- may be replaced by --C(.dbd.O)-- or
--N(R.sup.2)--, and R.sup.2 represents an alkyl group.
[0076] The chain length of the alkyl group represented by R.sup.2
is not particularly limited and may appropriately be selected in
consideration of the type of a medium to be used and the presence
of a hydrophilic group in the molecule structure. In the case where
water is used as a solvent and the molecular chain includes no
hydrophilic group, the length of the carbon chain is preferably
about 5 to 10.
[0077] Examples of the salts of the substances represented by the
above general formulae (I to VII) include substances having a
sodium salt of a carboxyl group (--COONa), a potassium salt of a
carboxyl group (--COOK), a calcium salt of a carboxyl group
((--COO).sub.2Ca), or a silver salt of a carboxyl group (--COOAg).
In addition, the substances represented by the above general
formulae (I to VII) or salts thereof include substances obtained by
ionizing such substances, and the substance which blocks growth of
metal crystal according to the present invention includes a
substance having, for example, --COO.sup.- (produced by ionizing a
carboxyl group or a salt thereof), --NH.sub.3.sup.+ (produced by
ionizing an amino group), or --SO.sub.3.sup.- (produced by ionizing
a sulfonic group).
[0078] Specific examples of the substance represented by the above
general formula (I) or the salts thereof include DL-alanine,
decanoic acid, sodium decanoate, sebacic acid, disodium sebacate,
lauric acid, sodium laurate, DL-2-amino-n-octanoic acid, sodium
[0079] DL2-amino-n-octanoate, N-decanoyl sarcosic acid, sodium
N-decanoyl sarcosinate, N-lauroyl sarcosic acid, and sodium-lauroyl
sarcosinate.
[0080] Specific examples of the substance represented by the above
general formula (II) and the salts thereof include amines such as
1-butyl amine and 1-hexyl amine.
[0081] Specific examples of the substance represented by the above
general formula (III) and the salts thereof include thiols such as
1-butane thiol and 2-aminoethane thiol.
[0082] Specific examples of the substance represented by the above
general formula (IV) and the salts thereof include some alcohols
such as 6-amino-l-propanol and butanol.
[0083] Specific examples of the substance represented by the above
general formula (V) and the salts thereof include
butyronitorile.
[0084] Specific examples of the substance represented by the above
general formula (VI) and the salts thereof include a substance
having an ether bond such as 3,3'-oxydipropionitorile.
[0085] Specific examples of the substance represented by the above
general formula (VII) and the salts thereof include peptides such
as a diner of alanine.
[0086] In addition, a polymer or copolymer formed of a monomer
having one or more functional groups selected from amino, carboxyl,
carbonyl, thiol, hydroxyl, and cyano groups is also included in the
substance which blocks growth of metal crystal according to the
present invention. Specific examples of the substance include
poly(vinylpyrrolidone). The molecular weight of the polymer or
copolymer is preferably about 40,000 to 80,000.
[0087] The concentration of the substance which blocks growth of
metal. crystal in a medium is not particularly limited and is
preferably in the range of 0.001 M to 10 M. The concentration is
more preferably in the range of 0.01 M to 1 M.
[0088] The temperature at which a metal structure is produced in
the present invention is not particularly limited but is preferably
in a temperature range in which the medium can maintain its
original properties. For example, in the case where water is used
as a medium, water freezes at a temperature below zero and
evaporates at too high temperature. Therefore, it is impossible to
maintain the original properties of water, and metal ion is reduced
only at a high temperature, which is not preferable. In such case,
the reaction temperature is preferably about 5 to 60.degree. C.,
and usually, processing can be performed at room temperature. If
optical energy is absorbed by metal ion, or the like, the energy is
converted into heat, which may cause an increase in the temperature
of the medium during processing. Therefore, if necessary, a cooling
apparatus may be used to suppress an increase in the
temperature.
EXAMPLES
[0089] Hereinafter, the present invention will be explained in more
detail in examples described below. However, the scope of the
present invention is not limited to the examples.
Example 1
[0090] Shape of Metal Structure Obtained by Adding a Substance
which Blocks Growth of Metal Crystal to the Medium
[0091] Sodium N-decanoyl sarcosinate (NDSS) (formula VIII) was
added to an aqueous solution of silver nitrate, and the solution
was dropped on a glass substrate (Micro Cover Glass, manufactured
by Matsunami Glass Ind., Ltd.). Laser beam (light source: Titanium:
sapphire femtosecond laser (Tsunami (registered trademark),
manufactured by Spectra-Physics K.K.), center wavelength: 800 nm,
pulse width: 80 fsec), which was controlled to be focused on the
upper surface of the glass substrate, was irradiated from the
bottom of the glass substrate and the focal point was scanned
linearly in a horizontal direction to the surface of the substrate.
The final concentration of NDSS was 0.1 M, the concentration of
silver nitrate was 0.05M, the strength of the irradiated laser beam
was 0. 8 mW, and the scan rate was 7 .mu.m/s. Processing was
performed at room temperature.
CH.sub.3(CH.sub.2).sub.8--CO--N(CH.sub.3)--CH.sub.2--COONa
(VIII)
NDSS
Comparative Example
Shape of Metal Structure Obtained by Adding No Substance Which
Blocks Growth of Metal Crystal to the Medium
[0092] A solution obtained by adding a solution of Coumarin 400
(manufactured by Exciton, purchased from Tokyo Instruments, Inc.)
in 0.01 wt % ethanol to an aqueous solution of silver nitrate was
dropped on a glass substrate (Micro Cover Glass, manufactured by
Matsunami Glass Ind., Ltd.). Laser beam (light source: Titanium:
sapphire femtosecond laser (Tsunami (registered trademark),
manufactured by Spectra-Physics K.K.), center wavelength: 800 nm,
pulse width: 80 fsec), which was controlled to be focused on the
upper surface of the glass substrate, was irradiated from the
bottom of the glass substrate, and the focal point was scanned
linearly in a horizontal direction to the surface of the substrate.
The concentration of silver nitrate was 0.05 M, the strength of the
irradiated laser beam was 0.8 mW, and the scan rate was 7 .mu.m/s.
Processing was performed at room temperature.
[0093] FIG. 2 shows an electron micrograph of a linear silver
structure (silver line) formed of silver crystals formed on the
substrate by the method of Example 1, and FIG. 3 shows an electron
micrograph of a silver line formed on the substrate by the method
of Comparative Example. FIG. 2 indicates that the formed silver
line has a width of about 150 nm and that the particle of each
silver crystal in the silver line has a nanometer size. On the
other hand, FIG. 3 indicates that the silver line has a width of
about 1 .mu.m and that the surface is bumpy because of large rocky
aggregates formed by growth of small particulate silver crystals.
If such large aggregates are present, it is difficult to form a
line with a smaller width by the method of Comparative Example,
because the final line width depends on the sizes of the large
particles.
[0094] Further it should be noted that, although the size of the
laser focal point is about 1 .mu.m, a silver line with a width
about ten times smaller could be drawn by the method described in
Example 1.
[0095] FIG. 2 indicates that the particle size of each silver
crystal is very small compared with the width of the silver liner
which suggests that it is possible to achieve finer processing if
the spot size of the focal point of the laser beam is controlled to
be smaller or if light is irradiated only to a smaller region.
Examples 2 to 8
[0096] The same experiments were performed using aqueous solution
of silver nitrate, to which various substances according to the
present invention (the following chemical formulae IX to XV) were
added instead of NDSS used in Example 1, to thereby form silver
lines- The silver lines thus formed are shown in FIGS. 4 to 11.
Experimental conditions of respective examples are shown in Table
1. Processing was performed at room temperature.
Example 2
[0097] NH.sub.2--CH(CH.sub.3)--COOH (IX)
DL-Alanine
Example 3
[0098] CH.sub.3(CH.sub.2).sub.8--COONa (X)
Sodium Decanoate
Example 4
[0099] NaCOC--(CH.sub.2).sub.8--COONa (XI)
Disodium Sebacate
Example 5
[0100] CH.sub.3(CH.sub.2)--.sub.10--COH (XII)
Sodium Laurate
Example 6
[0101] CH.sub.3--CH.sub.2).sub.5--CH(NH.sub.2)--COOH (XIII)
DL-2-amino-n-octanoic Acid
Example 7
[0102]
CH.sub.3--(CH.sub.2).sub.10--CO--N(CH.sub.3)--CH.sub.2--COONa.xH.s-
ub.2O (XIV)
Sodium N-lauroyl Sarcosinate Hydrate
Example 8
##STR00001##
[0103] Poly(vinylpyrrolidone)
TABLE-US-00001 [0104] TABLE 1 Final concentration of substance
which blocks growth of metal crystal, concentration of silver
nitrate, laser intensity at focal point, and scan rate
Concentration Intensity of of substance Concentration of irradiated
Example in medium silver nitrate laser beam Scan rate 2 0.1M 0.05M
2.0 mW 6 .mu.m/s 3 0.09M 0.3M 1.2 mW 10 .mu.m/s 4 0.09M 0.3M 1.2 mW
10 .mu.m/s 5 0.09M 0.3M 1.2 mW 10 .mu.m/s 6 0.09M 0.3M 0.8 mW 10
.mu.m/s 7 0.09M 0.3M 1.2 mW 10 .mu.m/s 8 2 wt % 0.05M 1.6 mW 6
.mu.m/s
[0105] In all the examples, the widths of the silver lines were in
the range of 200 to 300 nm, which are very small compared with the
size in the case of the comparative example. Meanwhile, also in the
case where sodium sorbate was added as an unsaturated hydrocarbon,
a line was formed. However, the metal ion was reduced directly by
the sodium sorbate with time, which suggests that, in the case
where a substance containing an run saturated hydrocarbon is used,
it was necessary to offset the reduction ability of the unsaturated
hydrocarbon by, for example, adding an antioxidant immediately
after processing, or previously adding an antioxidant to a material
containing the metal ion.
Example 9
[0106] Formation of Three-Dimensional Structure
[0107] A metal structure having a three-dimensional structure was
formed by the method of producing a metal structure of the present
invention.
[0108] NDSS (Chemical formula V) was added to an aqueous solution
of silver nitrate, and the solution was dropped on a glass
substrate (Micro Cover Glass, manufactured by Matsunami Glass Ind.
Ltd.). Laser beam (light source: Titanium:sapphire laser (Tsunami
(registered trademark), manufactured by Spectra-Physics K.K.),
center wavelength: 800 nm, pulse width: 80 fsec), which was
controlled to be focused on the upper surface of the glass
substrate (spot size of focal point is about 1 .mu.m), was
irradiated through the glass substrate from the bottom of the glass
substrate, and the focal point was scanned linearly in a
perpendicular direction to the surface of the substrate. The final
concentration of NDSS was 0.1 M, the concentration of silver
nitrate was 0.04 M, the strength of the irradiated laser beam was
1.21 mW, and the scan rate was 2 .mu.m/s (first round) and 4
.mu.m/s (second round).
[0109] FIG. 12 shows an electron micrograph taken from obliquely
above of a cylindrical silver structure (silver rod) which is
formed of silver crystals formed on a substrate under the condition
at the first round and stands upright on the substrate. This
confirms that a silver rod having a cross section diameter of about
300 nm and having a smooth surface was formed. The magnified
micrograph of a silver rod obtained by processing under the
conditions at the second round (FIG. 13) shows that a silver rod
with the finest width of about 100 nm was successfully
processed.
[0110] The result demonstrated that, according to the present
invention, a finer metal structure having a three-dimensional
structure can be easily formed only by controlling the direction of
light scanning.
INDUSTRIAL APPLICABILITY
[0111] According to the present invention, the particle size of
metal crystal produced by photoreduction of metal ion can be
controlled to a nanometer size, thereby the method significantly
improves the processing resolution of a metal structure formed of
the metal crystal. Therefore, an arbitrary pattern of fine and
precise three-dimensional structure of a metal structure can be
formed easily. The present invention can be used for manufacture of
a micromachine, formation of a magnetic field in a microspace by
forming of a small metal coil, or control of the refractive
index.
[0112] While the invention has been described in detail with
reference to preferred embodiments thereof, it will be apparent to
one skilled in the art that various changes can be made, and
equivalents employed, without departing from the scope of the
invention. Each of the aforementioned documents including the
priority application JP2008-077913 is incorporated by reference
herein in its entirety.
* * * * *