JP2005216907A - Method of manufacturing metal wiring and mold for transferring metal wiring used therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which can easily manufacture fine metal wiring on a polymer substrate. <P>SOLUTION: The method of manufacturing the metal wiring includes, for example, a step (1) of forming a second polymer layer (alkylsilane fluoride) on a part except the desired pattern on a silicon substrate by a photolithogaphy method, and a step of then forming selectively a first polymer layer (octadecyltrimethoxysilane) on a desired pattern part. The method further includes a step (2) of performing a metal (nickel) plating, thereby forming a plating layer made of the metal selectively on the first polymer layer, and a transfer mold is obtained. The method further includes a step (3) of bringing the transfer mold into pressure contact with the polymer substrate (polymethylmethacrylate, a molecular weight of about 25,000, a glass transition point of 105°C) at 180°C by 10 MPa, and transferring the wiring made of the metal plating layer to the polymer substrate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a technique for producing fine metal wiring on a substrate surface. Specifically, the present invention relates to a method for producing a metal wiring by transferring a metal onto a substrate to which a metal can adhere, a tool such as a metal transfer mold used for the production, and a method for producing them.

A substrate made of a polymer such as a thermoplastic resin (hereinafter referred to as “polymer substrate”) has a metal wiring formed by a method similar to that of a general inorganic substrate due to the properties such as a high thermal expansion coefficient of the polymer ( Patterning) is difficult. For this reason, the development of a method capable of efficiently forming fine metal wiring on a polymer substrate has been conventionally performed.
For example, in Patent Document 1, a metal film is vapor-deposited on an inorganic substrate in advance and patterned by a photolithography method to form a desired metal pattern (wiring), and the inorganic substrate on which the metal pattern is formed Is used as a transfer mold, and a metal pattern is formed on the surface of a target plastic substrate by transferring the metal pattern onto a plastic substrate.
However, in the method disclosed in Patent Document 1, in order to form a transfer mold, two complicated processes, that is, a metal deposition process and a subsequent photolithography process (resist application, photomask exposure, development, etching, resist removal, etc.) In other words, the production efficiency is not good. In addition, since most of the deposited metal material is removed (discarded) by the etching process in the photolithography process, it is not preferable from the viewpoint of manufacturing cost. In addition, it is difficult to form a high-density pattern having 10 μm lines and spaces or finer intervals.

On the other hand, the nanoimprint method disclosed in Non-Patent Document 1 is currently being studied for practical application as a next-generation fine nano-level lithography technique. By directly applying such nanoimprinting method, a polymer thin film coated on a substrate or a mold having a fine concavo-convex structure is pressed on a polymer substrate, and the pattern is transferred onto the polymer by compression molding. Can do. However, the nanoimprint method only considers the transfer of the shape onto the polymer, and when forming a pattern made of metal, the metal is finely processed by etching or lift-off using the patterned polymer film or polymer substrate as a resist. There is a need. That is, the metal pattern cannot be directly formed by the imprint method.
Therefore, there is a need for a new method that can easily produce fine metal wiring (pattern) on a polymer substrate, which is different from the prior art.

JP 2003-78235 A “Appl. Phys. Lett.”, Vol. 71, No. 13, p. 1881-1883, September 29, 1997

  Accordingly, the present invention has been developed to solve such conventional problems, and an object of the present invention is to provide a method capable of easily producing fine metal wiring on a polymer substrate. Moreover, it aims at providing apparatuses, such as a metal transfer mold used suitably for the production, and its manufacturing method. Further, a substrate or other structure on which metal wiring is formed by the method disclosed herein is provided.

One of the methods provided by the present invention is a method for producing a metal wiring having a desired pattern on a substrate surface to which metal can adhere. This method includes a step of forming a first polymer layer of the pattern on a substrate constituting a metal wiring transfer mold body, and forming a second polymer layer on a portion other than the pattern on the substrate. And performing a plating process under the predetermined conditions to selectively form a plating layer made of the metal on the first polymer layer to obtain the transfer mold; and And a step of pressing the substrate on which the metal plating layer can be attached and transferring the wiring made of the metal plating layer to the substrate. The first polymer layer is formed of a first polymer material on which a plating layer made of the metal can be deposited under predetermined plating conditions, while the second polymer layer is made of the metal under the condition. The plating layer is formed of a second polymer substance that does not substantially precipitate.
In this specification, “metal wiring” refers to metal wires formed on various substrates in a predetermined form (pattern). For example, the conductive wire (conductor) having a specific pattern constituting the electronic circuit formed on the circuit board is a typical example of the metal wiring here, but is not limited thereto.
Further, in this specification, the “substrate” refers to a base material (support material) for forming such metal wiring, and is not limited to a predetermined material or shape. A thin plate-like or chip-like substrate on which an electronic circuit can be formed is a typical example included in the substrate referred to herein.

With this method, the metal pattern (metal layer) can be selectively formed substantially only on the first polymer layer of the transfer mold (base material) to be used. Therefore, by manufacturing a transfer mold having a highly accurate metal pattern and transferring the metal pattern using the mold, fine metal wiring can be easily formed on the substrate. Such transfer is easily realized by press-contacting the mold and the substrate.
Moreover, in this method, since a metal wiring pattern (metal plating layer) is formed on the first polymer layer by plating (typically electroless plating), the metal wiring pattern can be formed efficiently. it can. For this reason, metal wiring can be produced on a substrate with high production efficiency by using the mold provided by the present invention.

Preferably, in the step of forming the first polymer layer and the second polymer layer, the second polymer layer is formed on the substrate, and the pattern of the second polymer layer is formed. Removing a corresponding portion and selectively forming the first polymer layer in a portion corresponding to the pattern from which the second polymer layer has been removed.
According to this aspect, the first polymer layer can be formed with high accuracy only in the portion corresponding to the desired pattern on the substrate. Therefore, a metal wiring pattern (plating layer) with higher accuracy can be formed by a subsequent plating process. As a result, by using the mold manufactured in this manner, it is possible to form a metal wiring with higher accuracy on the substrate.

In the above aspect, it is particularly preferable that the portion corresponding to the pattern from the second polymer layer is removed by light or electromagnetic wave irradiation to the portion. Irradiation of such light or electromagnetic waves (preferably vacuum ultraviolet light) is preferably performed through a photomask having a transmission part (opening part) corresponding to a desired pattern (that is, employing a photopatterning technique). Alternatively, scanning is performed so that a predetermined pattern can be formed using a light beam or electromagnetic wave beam that is a high-energy wave (that is, a beam scan that scans the beam itself and / or a mechanical scan that scans an irradiation object with respect to the beam) May be.
According to this aspect, the second polymer layer can be removed only for the irradiated portion of light or electromagnetic waves (preferably vacuum ultraviolet light). Accordingly, it is possible to form a pattern (that is, a plating layer forming portion) composed of the first polymer layer having a clear boundary with the surrounding second polymer layer.

Preferably, in the production of a transfer mold, the second polymer layer is formed of an organic compound having an alkyl group, an alkenyl group, or an alkynyl group partially or entirely substituted with fluorine. .
By forming the second polymer layer from the compound having such a fluorine-substituted carbon chain, the reactivity of the surface of the second polymer layer is reduced (in other words, the stability is increased), and the metal plating is applied to the portion. Formation of the layer can be prevented. Moreover, the adhesiveness, friction resistance, etc. of a 2nd polymer layer can be restrained low by use of the said compound. As a result, undesired adhesion between the transfer mold and the target substrate during the transfer (pressure contact) step can be suppressed, and peeling after the metal pattern transfer is facilitated.

More preferably, in the production of a transfer mold, the first polymer layer is a carbon chain longer than the fluorine-containing organic compound, and a partially substituted or unsubstituted alkyl group, alkenyl group or alkynyl group. It is formed from the organic compound provided with.
By forming the first polymer layer from the compound having such a long chain, the plating layer corresponding to the desired pattern can be formed and transferred.
In a particularly preferred embodiment, in the transfer mold production, the substrate is substantially composed of silicon having a reactive group (for example, a silanol group or other hydrophilic group) on the surface, and the second polymer layer is The first polymer is formed from an organosilicon compound having a functional group capable of reacting with a reactive group (for example, an alkoxy group) and an alkyl group, an alkenyl group, or an alkynyl group partially or wholly substituted with fluorine. The layer is an organic having a functional group capable of reacting with the reactive group and a carbon chain longer than the fluorine-containing organosilicon compound, and a partially substituted or unsubstituted alkyl group, alkenyl group or alkynyl group. It is formed from a silicon compound.
By using such a silicon substrate and an organosilicon compound (for example, a mono, di or trialkoxysilane having one, two or three alkoxy groups such as methoxy groups as functional groups capable of reacting with silanol groups) A mold for forming a high-precision metal wiring pattern can be manufactured, and a high-precision metal wiring pattern can be produced on the substrate by transfer.

  Preferably, the first polymer layer and / or the second polymer layer is constituted by a monomolecular layer. When the polymer layer is a monomolecular layer, the thickness of the polymer layer can be made almost constant. For this reason, it is possible to realize transfer of a fine metal pattern with higher accuracy.

The method disclosed here is a method suitable for producing a metal wiring on the surface of a polymer substrate. Preferably, a substrate made of a polymer exhibiting glass transition or a substrate in which a surface portion forming a metal wiring is formed of the polymer (hereinafter referred to as “polymer-coated substrate”) is used as the substrate, and the transfer step includes The temperature is higher than the glass transition point of the polymer, and the temperature is within a temperature range in which the shape of the polymer-forming portion of the substrate can be maintained.
By transferring in this temperature range, the adhesion between the polymer substrate (or polymer-coated substrate) and the metal plating layer can be improved.

  As another aspect, the present invention provides a substrate or other structure having a metal wiring manufactured by any of the methods disclosed herein. According to the method of the present invention, since a metal pattern can be formed with high accuracy, it is possible to obtain a structure such as an electronic material or a biochemical material having particularly fine metal wiring.

Moreover, this invention provides the mold used for the metal wiring preparation method disclosed here as another aspect, and its manufacturing method. That is, one of the mold manufacturing methods disclosed herein is a method for manufacturing a mold for transferring a metal wiring of a desired pattern onto a substrate surface to which metal can adhere, and is a metal wiring transfer mold. Forming a first polymer layer of the pattern on a substrate constituting the main body, and forming a second polymer layer on a portion other than the pattern on the substrate; and plating under the predetermined condition Forming a plating layer made of the metal selectively on the first polymer layer. The first polymer layer is formed of a first polymer material on which a plating layer made of the metal can be deposited under predetermined plating conditions, while the second polymer layer is made of the metal under the condition. The plating layer is formed of a second polymer substance that does not substantially precipitate.
And, typically, by such a method, a base material constituting the mold body, and a first polymer layer of the pattern formed on the base material, which is formed from the metal under predetermined plating conditions. And a second polymer layer formed on a portion other than the pattern on the substrate under the plating conditions. A metal wiring having a second polymer layer formed of a polymer material on which a plating layer made of metal does not substantially precipitate, and a plating layer made of the metal selectively formed on the first polymer layer A transfer mold is provided. Preferably, a mold having the characteristics described in the metal wiring manufacturing method according to any one of the aspects described above and a manufacturing method thereof are provided.

  As another aspect of the present invention, there is provided a template for manufacturing a mold for transferring a metal wiring of a desired pattern onto a substrate surface to which metal can adhere (that is, a mold before a metal plating layer is formed). provide. Typically, a base material constituting the mold body, and a first polymer layer of the pattern formed on the base material, and a plating layer made of the metal can be deposited under predetermined plating conditions. A first polymer layer formed of a polymer substance and a second polymer layer formed on a portion other than the pattern on the substrate, wherein the plating layer made of the metal under the plating process condition A template is provided having a second polymeric layer formed of a polymeric material that does not substantially precipitate. Preferably, a mold template having the characteristics described in the metal wiring manufacturing method according to any one of the aspects described above is provided.

  Hereinafter, preferred embodiments of the present invention will be described. It should be noted that matters other than matters specifically mentioned in the present specification (for example, means for forming the first polymer layer, the second polymer layer, and the metal plating layer on a predetermined substrate) Matters necessary for implementation can be grasped as design matters of those skilled in the art based on the prior art in the field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

  First, in order to contribute to an understanding of the technical contents disclosed herein, a specific example of a metal transfer mold and a manufacturing method thereof will be schematically described with reference to the drawings. FIG. 1 schematically shows a metal wiring preparation template 1 used for manufacturing a metal transfer mold. This metal wiring preparation template 1 includes a base material 3, a first polymer layer 5 defined as described above, and a second polymer layer 7.

As the substrate 3, any substrate can be used without particular limitation as long as it has a surface capable of forming a polymer layer. In particular, a substrate made of an inorganic material having high mechanical strength, thermal stability, etc., such as silicon, glass, ceramics (oxides such as silica, alumina and zirconia, non-oxides such as silicon nitride and silicon carbide) and the like is preferable. In particular, silicon and silica are suitable because a reactive group (typically a hydrophilic group such as a silanol group) capable of bonding a polymer to the surface can be easily introduced and a polymer layer can be easily formed. . For example, a silanol group (Si—OH) can be introduced on the surface of the silicon substrate provided with a surface oxide layer (silica layer) by performing various hydrophilic treatments.
In addition, the base material which consists of a polymer (for example, thermosetting resin) may be sufficient as long as the objective of this invention can be achieved.

The first polymer layer 5 is formed in the same pattern as the target metal wiring pattern. The first polymer layer 5 is formed of a first polymer material on which a plating layer made of a predetermined metal can be deposited under predetermined plating conditions. For example, a comparison in which a functional group capable of binding to a substrate is partially substituted (for example, introduction of a hydrophilic group such as an amino group as a terminal functional group) or substituted so as to increase the reactivity with a metal. A polymer material having an alkyl group, alkenyl group, alkynyl group or the like having a particularly long carbon chain (preferably having 10 or more, for example, 10 to 30 carbon atoms constituting the carbon chain) is preferably used.
When such a compound having a relatively long alkyl (or alkenyl or alkynyl) chain is bonded to the surface of the substrate, it can easily be formed into a monolayer having a high density and high orientation by van der Waals force between the chains. (Ie, a self-assembled monolayer) is preferable. In addition, a metal plating layer formed on a relatively hydrophobic group (chain) such as a long-chain alkyl group is easy to peel off and is preferable for transferring a metal wiring pattern to a substrate.
For example, when the base material constituting the mold body is silicon having silanol groups on the surface, the first polymer substance has a main chain or side chain with a relatively long chain length, such as a methoxy group. An organosilicon compound having a functional group capable of binding to a base material (preferably binding to a reactive group present on the surface of the base material) is suitable. For example, an alkyltrialkoxysilane represented by the general formula: C _n H _{2n + 1} Si (OC _m H _{2m + 1} ) ₃ (preferably n is any natural number selected from 10 to 30, and m is 1 or 2. ) Is a preferred example of the first polymer substance.

On the other hand, the second polymer layer 7 is a portion other than a portion corresponding to a desired metal wiring pattern, that is, a portion where the first polymer layer 5 on the substrate 3 is not formed as shown in FIG. Is formed. The second polymer layer 7 is formed of a second polymer material that does not deposit a metal-plated layer under predetermined plating conditions. For example, the second polymer substance is preferably a polymer substance that has extremely low reactivity with metals. Preferable examples include an organic compound having a functional group capable of binding to a substrate and an alkyl group, alkenyl group, alkynyl group or the like partially or entirely substituted with fluorine. A compound having a relatively long alkyl (or alkenyl or alkynyl) chain is preferable because a monomolecular layer can be easily formed.
The substitution rate of fluorine is not particularly limited, but a majority of the hydrogen atoms constituting the alkyl chain (for example, 70% or more hydrogen atoms) or substantially all of the hydrogen atoms are preferably substituted with fluorine atoms. For example, in the alkyltrialkoxysilane represented by the above general formula, those in which 70% by number or more of the hydrogen atoms constituting the alkyl chain are replaced by fluorine (see Examples described later) are preferable.

  As shown in the drawing, regarding the thickness (film thickness) of the first polymer layer and the second polymer layer, the first polymer layer is preferably thicker than the second polymer layer. For example, although not particularly limited, when the first polymer layer and the second polymer layer are each composed of a monomolecular layer made of a compound having a carbon chain (main chain or side chain) as described above, It is preferred to form the first polymer layer using a compound having a carbon chain longer than the compound used to form the polymer layer. As a result, the metal plating layer formed on the first polymer layer at the time of pressure contact with the polymer substrate can easily come into contact with the polymer substrate, and can contribute to accurate transfer of the metal plating layer.

FIG. 2 schematically shows the metal transfer mold 11. The metal transfer mold 11 includes a base material 3, a first polymer layer 5, a second polymer layer 7, and a metal plating layer 13. That is, the metal plating layer 13 is formed on the first polymer layer 5 in the metal wiring preparation template 1.
There is no restriction | limiting in particular in the metal which comprises the metal plating layer 13, Any metal seed | species which can be precipitated by various plating processes may be sufficient. Suitable metal species include, but are not limited to, nickel and gold, which can easily form a plating layer by electroless plating, and are not limited to silver, copper, tin, zinc, iron, cobalt, chromium, platinum, palladium, and others. Examples include platinum group elements.
Note that the metal plating layer is not limited to a single layer and may be formed in two or more layers. For example, a nickel layer (underlying plating layer) is first formed on the first polymer layer by electroless plating, and then another plating layer (for example, a gold plating layer) is laminated by electroless plating or electroplating. Also good.

Next, a preferred example of a metal wiring manufacturing method including a manufacturing process of the metal wiring manufacturing template 1 and the metal transfer mold 11 will be described with reference to the drawings.
As shown in FIG. 3, a suitable base material 3 (here, a silicon base material) is prepared, and the second polymer layer 7 is formed from the second polymer material ((1) in FIG. 3). As a means for forming the second polymer layer 7, a conventionally known method can be applied without particular limitation.
Typically, first, the surface of the substrate 3 is subjected to activation treatment such as chemical treatment, plasma treatment, ultraviolet light irradiation treatment, etc., and the first polymer substance and the second polymer substance are used as the substrate. Various reactive groups (surface functional groups) for chemically bonding to the surface are introduced into the substrate surface. For example, in the case of the silicon substrate 3, it is preferable that the surface of the substrate 3 be hydrophilized (specifically, a silanol group, that is, a hydroxyl group is introduced) by irradiation with vacuum ultraviolet light. At the same time, organic substances remaining on the substrate surface can be removed by ozone generated from atmospheric oxygen by the ultraviolet light irradiation.

The activated substrate can then be treated in the gas phase of a second polymeric material to grow a second polymeric layer (see Examples below).
Preferably, the second polymer layer is formed as a monomolecular layer in which the second polymer substance is oriented in a predetermined direction. By using a monomolecular layer, the thickness of the layer can be made constant and a finer pattern can be formed. When the second polymer layer 7 grows more than the monomolecular layer, the excessively adsorbed molecules can be removed to form a monomolecular layer as desired. The monomolecular layer forming means is not particularly limited, and an acid treatment, an alkali treatment, a water washing treatment and the like can be appropriately combined depending on the substance used.

  Next, the portion corresponding to the pattern of the second polymer layer 7 is removed so that the same pattern as the desired metal wiring pattern is formed ((2) in FIG. 3). For this, application of a photolithography method is preferable. For example, a photomask 8 in which the same transmission part (light-transmitting opening) as the desired pattern is formed is prepared, and high energy light (eg, vacuum ultraviolet light) is transmitted from a predetermined light source 10 (eg, excimer lamp) through the photomask 8. Light). This makes it possible to selectively decompose and remove only the second polymer layer 7 in the light irradiated portion, that is, the pattern portion, as described in the examples described later ((3) in FIG. 3).

  Next, the first polymer material is applied to the substrate 3 to form the first polymer layer 5 in a portion where the second polymer layer 7 is removed, that is, a desired pattern portion. Here, by selecting a material having low reactivity with the second polymer material as the first polymer material, the first polymer material reacts with the portion where the second polymer layer 7 is formed. First, the first polymer substance can be selectively bonded only to the portion where the second polymer layer 7 is not formed (removed) ((4) in FIG. 3). The first polymer layer forming means can be performed by a gas phase reaction of the first polymer substance, as in the formation of the second polymer layer. Thus, the metal wiring production template 1 is completed.

Next, a metal transfer mold 11 is manufactured using the metal wiring preparation template 1. That is, a metal plating layer 13 is selectively formed on the first polymer layer 5 by performing various metal plating processes on the metal wiring preparation template 1 ((5) in FIG. 3).
Examples of the metal plating treatment include conventionally known plating treatment methods such as electroless plating, vacuum plating (PVD, CVD), and electroplating. Preferably, electroless plating is preferred in which a plating metal is deposited on the surface of an object by dipping in a predetermined metal plating solution and utilizing a reduction reaction. Electroless plating has extremely high film thickness accuracy, and a plating layer 13 having a substantially uniform film thickness can be obtained over the entire first polymer layer 5.

As the plating treatment conditions, a condition in which a plating layer is formed on the first polymer layer and a plating layer is not substantially formed on the second polymer layer can be appropriately selected. For example, the treatment of the surface of the first polymer layer and / or the second polymer layer, the type and concentration of the plating solution, the plating temperature or the treatment time may be appropriately determined.
If necessary or desired, the first polymer layer 5 may be surface-treated in advance in order to perform a suitable plating treatment. For example, in the case of electroless plating, the pretreatment includes various activation treatments, reaction promotion treatments, surface cleaning treatments, and the like. The pretreatment associated with these plating treatments may be any conventionally known treatment and does not characterize the present invention, and thus detailed description thereof is omitted.

  Metal wiring is produced on the surface of various substrates using the metal transfer mold 11 thus manufactured. Specifically, as shown in FIG. 4 (1), the metal transfer mold 11 is preferably pressed into contact with a substrate 21 (here, a polymer substrate 21 made of a thermoplastic resin having a predetermined glass transition point) under heating conditions. To do. Thereby, the metal plating layer 13 can be transferred and formed in a predetermined pattern on the surface of the substrate 21. Then, after the metal plating layer 13 is transferred to the substrate 21, the mold 11 is separated from the substrate 21. Thereby, as shown in FIG. 5, a structure 31 (for example, a circuit board) in which the metal wiring 23 having a desired pattern is formed on the surface of the substrate 21 can be obtained.

The method of the present invention can be applied to substrates (base materials) of various materials and shapes, but can be preferably implemented on polymer substrates.
As the polymer substrate 21, as long as it is a substrate on which a metal wiring can be formed, it can be applied without particular limitation. In particular, a polymer substrate made of a thermoplastic, highly moldable or adhesive polymer, or a polymer-coated substrate having a surface portion composed of such a polymer is preferable because the metal plating layer 13 is easily transferred. A thermoplastic resin having a glass transition temperature around 100 ° C. (for example, about 70 to 150 ° C.) is suitable. Specific examples include acrylic resins such as polymethyl acrylate, methacrylic resins such as polymethyl methacrylate, polycarbonate, polyethylene terephthalate, and polystyrene.
When a polymer substrate or a polymer-coated substrate having a glass transition point (temperature) is used, the temperature range is equal to or higher than the glass transition temperature of the polymer substrate 21 and the form of the polymer substrate 21 (that is, the form of the polymer forming portion) can be maintained. It is preferable that the substrate 21 and the mold 11 are heated and pressed with an appropriate pressure. As a result, as shown in FIG. 4B, the metal plating layer 13 (metal wiring) is transferred to the substrate in a state of being embedded in the polymer substrate 21 in accordance with the pressure at the time of pressure contact. Thereby, the metal wiring 23 excellent in adhesiveness can be produced on the polymer substrate 21 (FIG. 5).
Such a temperature range can be appropriately changed depending on the material of the polymer substrate 21 used. For example, in the case of a substrate made of polymethyl methacrylate, the temperature is 105 to 250 ° C, particularly 150 to 200 ° C. Moreover, although the pressure at the time of press-contact may differ suitably according to the material and process temperature of the polymer substrate 21 to be used, 3-30 MPa, especially about 5-15 MPa are suitable.

As described above, the structure 31 in which the metal wiring 23 having a desired pattern is formed can be manufactured. According to the method disclosed herein, a metal wiring having a desired pattern can be produced on various shapes of substrates (base materials). Therefore, it will be understood by those skilled in the art that the structure provided by the present invention is not limited to a specific shape and application in a specific industrial field.
For example, the structure provided by the present invention includes a printed wiring board for high-density mounting, other electronic devices, electronic components, various analysis chips (DNA chips, etc.) that can be used in the biochemical field, analysis devices, and medical applications. Sensors that can be applied to diagnostic devices and other measuring devices, and micro components equipped in various types of micromachines are included.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not intended to be limited to those shown in the examples.

<Example 1>
(1) Substrate processing:
According to the method described in the following document, the substrate surface was cleaned and hydrophilized, and a second polymer layer was formed on the surface.
“Surface and Interface Analysis” Vol. 34, No. 1, 550-554, 2002.
That is, first, a base material was prepared by cutting an n-type Si (100) wafer (product of Shin-Etsu Semiconductor Co., Ltd.) into a predetermined size. This was exposed for about 10 minutes by vacuum ultraviolet light (UVU) generated from an excimer lamp (Ushio Inc., model UER20-172V, wavelength λ = 172 and output power 10 mWcm ⁻² ). In this example, the distance in the air from the lamp to the substrate was 10 mm. By this UVU irradiation, oxygen molecules present in the atmospheric air were photoexcited to generate oxygen atoms and ozone molecules (hereinafter referred to as “active oxygen species”). On the other hand, organic molecules as impurities present on the surface of the substrate were decomposed by oxidation by the generated active oxygen species while the carbon-carbon and carbon-hydrogen bonds were dissociatively excited. Therefore, the irradiated substrate surface was washed by photochemical desorption of organic molecules on the substrate surface.
By the above treatment, the surface of the silicon substrate was covered with a thin silica layer of 2 nm or less, and hydroxyl groups (silanol groups) could be introduced on the surface.

(2) Formation of second polymer layer:
A second polymeric material, here a fluoroalkylsilane, specifically hepadecafluoro-1,1,2, represented by F ₃ C (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ 2-tetrahydro-decyl-1-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.
Thus, the surface-treated SiO ₂ / Si substrate is placed in a 65 cm ³ volume Teflon® container with a glass cup filled with 0.2 cm ³ of the second polymer solution, After sealing the vessel, it was placed in a furnace maintained at 150 ° C. and held there for 3 hours.
By this treatment, a terminal hydroxyl group on the substrate surface and a methoxy group of heptadecafluoro-1,1,2,2-tetrahydro-decyl-1-trimethoxysilane, and further a elimination reaction (dealcoholization reaction) between the methoxy groups As shown in FIG. 6, a polysiloxane film having a fluorine-substituted alkyl group as a side chain was formed on the surface of the substrate 3.
As shown in the figure, the side chain of this film forms a monomolecular layer extending in a uniaxial direction, and this monomolecular layer corresponds to the second polymer layer according to this example.

(3) Patterning (removal process) of the second polymer layer:
The second polymer layer was finely processed by a general photolithography technique. That is, excimer lamp light having a wavelength of 172 nm is irradiated through a photomask formed in a portion other than a desired pattern, and the second polymer layer corresponding to the desired pattern is decomposed and removed depending on the light energy. did.

(4) Formation of the first polymer layer:
N-octadecyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by a first polymer substance, here alkyltrialkoxysilane, specifically, H ₃ C (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ Prepared.
Thus, the substrate on which the second polymer layer is formed and further patterned is placed in a 65 cm ³ volume Teflon (registered trademark) container together with a glass cup filled with 0.2 cm ³ of the first polymer material liquid. The container was sealed and placed in a furnace maintained at 150 ° C. and held there for 3 hours.
By this treatment, a terminal hydroxyl group on the substrate surface and the methoxy group of n-octadecyltrimethoxysilane, and further, a elimination reaction (dealcoholization reaction) occurs between the methoxy groups, and as shown in FIG. A polysiloxane film having a long-chain alkyl group having 18 carbon atoms as a side chain was formed on the portion where the second polymer layer was removed by the photo-patterning.
As shown in the figure, the side chain of this film forms a monomolecular layer extending in a uniaxial direction, and this monomolecular layer corresponds to the first polymer layer according to this example.
Note that the second polymer layer is an alkyl group in which all ends are substituted with fluorine, and the reactivity is extremely low. Therefore, the first polymer substance does not react with the second polymer layer portion, It reacted selectively only on the base material surface of the desired pattern part in which the bipolymer layer was not formed.
Through the above steps, a template for manufacturing a mold for transferring metal wiring was obtained.

(5) Plating treatment:
Next, the Ni plating layer was formed by sequentially performing the dipping and cleaning steps as follows. That is, 50 ml of an activation solution (trade name Activator for Platting, P-1, manufactured by High Purity Chemical Co., Ltd.), 50 ml of a reaction accelerating solution (trade name Stabilizer for Platting (reaction promotion), manufactured by High Purity Chemical Co., Ltd.), Ni Plating tanks each containing 50 ml of electroless plating solution (trade names: Ni-701AL, Ni-P (containing P5%), manufactured by High Purity Chemical Co., Ltd.) and 50 ml of ultrapure water were prepared.
First, the substrate obtained above was immersed in a plating tank containing an activation solution at 25 ° C. for 10 minutes for activation treatment. Next, the substrate was taken out from this solution and washed by immersing it in a plating tank containing the first ultrapure water (hereinafter referred to as an ultrapure water tank). Subsequently, the substrate was taken out and immersed in a plating tank containing the reaction promoting solution at 25 ° C. for 3 minutes. Furthermore, the base material was taken out from this solution and immersed in a second ultrapure water bath for cleaning. And it took out from the washing | cleaning liquid, it immersed in the tank for plating containing Ni electroless-plating liquid, and processed for 3 second at 80 degreeC. This was taken out and again immersed in a third ultrapure water tank for cleaning. Through the above steps, nickel was selectively deposited on the first polymer layer to complete a metal transfer mold. This 100 times SEM photograph is shown in FIG. 8 (scale in the figure is 100 μm).

(6) Transfer of metal plating layer Polymethylmethacrylate (molecular weight of about 25000, glass transition point 105 ° C.) was prepared as a polymer substrate to be transferred.
The mold obtained above was pressed against the polymer substrate with a press machine (manufactured by Riken Seiki Co., Ltd., model P-16B) at a temperature of 180 ° C. and a press pressure of 10 MPa.
The mold was then released from the polymer substrate. Here, the mold was excellent in peelability, and the metal plating layer was transferred to the polymer substrate to form metal wiring. FIG. 9 shows an SEM photograph taken at the same magnification as FIG. As is apparent from FIG. 9, it can be seen that fine metal wiring is formed with high accuracy.
In addition, the transferred metal wiring was embedded in the polymer substrate, and the adhesion between the metal wiring and the polymer substrate was excellent. Furthermore, the polymer substrate was not attached to the mold after the transfer. Therefore, it can be reused by forming a metal plating layer again in the same manner as the above (5) plating process.

  The preferred embodiments of the present invention have been described in detail above, but these are only examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the above-described embodiments. In addition, the technical elements described in the present specification or the drawings exhibit technical usefulness alone or in various combinations, and are not limited to the combinations described in the claims at the time of filing. In addition, the technology illustrated in the present specification or the drawings achieves a plurality of objects at the same time, and has technical utility by achieving one of the objects.

Explanatory drawing which shows typically the structure of the template for metal wiring preparation which concerns on one Embodiment. Explanatory drawing which shows typically the structure of the metal transfer mold which concerns on one Embodiment. Explanatory drawing which shows typically the manufacturing process of the template for metal wiring preparation which concerns on one Embodiment, and the mold for metal transfer. Explanatory drawing which shows typically the transfer process of the metal wiring which concerns on one Embodiment. Explanatory drawing which shows typically the structure in which the metal wiring which concerns on one Embodiment was formed. Explanatory drawing which shows the chemical structure of the monomolecular film of the 2nd polymer layer in one Example. . Explanatory drawing which shows the chemical structure of the monomolecular film of the 1st polymer layer in one Example. The SEM photograph of the metal transfer mold in one Example. The SEM photograph of the structure in which the metal wiring in one Example was formed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Metal wiring preparation template 3 ... Base material 5 ... 1st polymer layer 7 ... 2nd polymer layer 11 ... Metal transfer mold 13 ... Metal plating layer 21 ... Polymer substrate 23 ... Metal wiring 31 ... Structure (substrate) with metal wiring

Claims (12)

A method for producing a metal wiring having a desired pattern on a substrate surface to which a metal can be attached:
Forming a first polymer layer of the pattern on a substrate constituting a metal wiring transfer mold body, and forming a second polymer layer on a portion other than the pattern on the substrate; One polymer layer is formed from a first polymer material on which a plating layer made of the metal can be deposited under a predetermined plating process condition, while a second polymer layer has a plating layer made of the metal under the condition. Formed from a second polymeric material that does not substantially precipitate;
A step of selectively forming the plating layer made of the metal on the first polymer layer by performing plating under the predetermined condition to obtain the transfer mold; and metal attached to the transfer mold Pressure-contacting to a possible substrate and transferring the wiring made of the metal plating layer to the substrate;
The metal wiring preparation method containing. The step of forming the first polymer layer and the second polymer layer includes
Forming the second polymer layer on the substrate;
Removing a portion of the second polymer layer corresponding to the pattern, and selectively forming the first polymer layer in a portion corresponding to the pattern from which the second polymer layer has been removed. about,
The method of claim 1 comprising:   The method according to claim 2, wherein the portion corresponding to the pattern from the second polymer layer is removed by light or electromagnetic wave irradiation on the portion.   The method according to any one of claims 1 to 3, wherein the second polymer layer is formed from an organic compound having an alkyl group, an alkenyl group, or an alkynyl group partially or entirely substituted with fluorine.   The first polymer layer is formed of an organic compound having an alkyl group, an alkenyl group, or an alkynyl group that is a carbon chain longer than the fluorine-containing organic compound and is partially substituted or unsubstituted. Item 5. The method according to Item 4. The base material is substantially composed of silicon having a reactive group on the surface,
The second polymer layer is formed from an organosilicon compound having a functional group capable of reacting with the reactive group and an alkyl group, an alkenyl group, or an alkynyl group partially or wholly substituted with fluorine,
The first polymer layer includes a functional group capable of reacting with the reactive group, a carbon chain longer than the fluorine-containing organosilicon compound, and a partially substituted or unsubstituted alkyl group, alkenyl group, or 6. The method of claim 5, wherein the method is formed from an organosilicon compound with an alkynyl group.   The method according to claim 1, wherein the first polymer layer and / or the second polymer layer is constituted by a monomolecular layer.   As the substrate, a substrate made of a polymer exhibiting a glass transition or a substrate in which a surface portion forming a metal wiring is formed of the polymer is used, and the transfer step is performed at a temperature equal to or higher than the glass transition point of the polymer. The method in any one of Claims 1-7 performed within the temperature range which can maintain the form of the polymer formation part of a board | substrate.   The structure which has the metal wiring produced by the method in any one of Claims 1-8. A method of manufacturing a mold for transferring a metal wiring having a desired pattern to a substrate surface to which metal can be attached:
Forming a first polymer layer of the pattern on a substrate constituting a metal wiring transfer mold body, and forming a second polymer layer on a portion other than the pattern on the substrate; One polymer layer is formed from a first polymer material on which a plating layer made of the metal can be deposited under a predetermined plating process condition, while a second polymer layer has a plating layer made of the metal under the condition. Forming from a second polymer substance that does not substantially precipitate; and performing a plating process under the predetermined condition to selectively form a plating layer made of the metal on the first polymer layer;
A metal wiring transfer mold manufacturing method comprising: A mold for transferring a metal wiring of a desired pattern to a substrate surface to which metal can adhere,
A base material constituting the mold body;
A first polymer layer of the pattern formed on the substrate, the first polymer layer being formed of a polymer substance on which a plating layer made of the metal can be deposited under predetermined plating conditions; ,
A second polymer layer formed on a portion of the substrate other than the pattern, the second polymer layer being formed of a polymer material that does not substantially deposit a plating layer made of the metal under the plating conditions. A polymer layer;
A plating layer made of the metal selectively formed on the first polymer layer;
A metal wiring transfer mold comprising: A template for manufacturing a mold for transferring metal wiring of a desired pattern to a substrate surface to which metal can adhere,
A base material constituting the mold body;
A first polymer layer of the pattern formed on the substrate, the first polymer layer being formed of a polymer substance on which a plating layer made of the metal can be deposited under predetermined plating conditions; ,
A second polymer layer formed on a portion of the substrate other than the pattern, the second polymer layer being formed of a polymer material that does not substantially deposit a plating layer made of the metal under the plating conditions. A polymer layer;
Template with.