JP5846524B2 - Method for forming conductive pattern and substrate device - Google Patents

Description

  The present invention relates to a method for forming a conductive pattern and a substrate device.

  Compared to noble metal materials such as platinum and gold, carbon materials have a wide potential window, are stable in a wide potential region, and are inexpensive, so for example, electrode materials such as disposable sensors It is suitable as.

  When the carbon material is used as a sensor electrode material, the influence of the dissolution reaction of the carbon electrode itself made of the carbon material is reduced, and the substance can be detected electrochemically in a wide potential region. In addition, since the carbon electrode has a small residual current and a small background noise, it can be expected to detect a substance with high sensitivity.

  A carbon electrode used for such a sensor is formed on a substrate such as a polymer film using an ink or carbon paste in which fine particles made of a carbon material and a resin binder, a thickener (polymer), a solvent, and the like are mixed. The initial pattern corresponding to the conductive pattern is screen-printed, and then the initial pattern is dried to remove the solvent to form the conductive pattern. See).

  However, when carbon electrodes are produced by screen printing as in the methods described in Patent Documents 1 and 2, drying is usually performed at a temperature of 200 ° C. or less that can be withstood by a polymer film or the like used as a substrate. In the later conductive pattern, the resin binder and the thickener contained in the ink and carbon paste remain as impurities that do not contribute to the exchange of electrons in the electrode without being carbonized. For this reason, in the carbon electrode produced by screen printing, the electrode reaction is hindered by the remaining impurities, and thus the sensitivity of the sensor may not be sufficiently increased.

On the other hand, an organic molecule having an aromatic ring (for example, polyimide) formed on the surface of a heat-resistant substrate such as a quartz glass plate or a silicon wafer is subjected to a high vacuum or an inert gas atmosphere (oxygen-deficient atmosphere). It has been proposed to form a conductive thin film made of a pyropolymer on the surface of a substrate by heat treatment at a high temperature of 600 ° C. or higher (for example, 1000 ° C.) (see, for example, Patent Document 3). According to the method described in Patent Document 3, since high-temperature heat treatment is performed in an oxygen-deficient atmosphere, a high-purity carbon electrode that does not contain impurities that do not contribute to electron transfer can be obtained.
Therefore, the conductive thin film made of this pyropolymer exhibits excellent conductive performance.

Japanese Patent Laid-Open No. 5-256811 Japanese translation of PCT publication No. 2002-535615 Japanese Patent No. 2963951

  However, in the method described in Patent Document 3, since a heat treatment is performed at a high temperature when forming a thin film made of a pyropolymer, it is necessary to use an expensive heat-resistant substrate that can withstand this heat treatment. Therefore, the method described in Patent Document 3 increases the manufacturing cost. As a result, the carbon electrode obtained by the method described in Patent Document 3 is unsuitable as an electrode of a sensor to be disposed of.

  The present invention has been made in view of such circumstances, and a conductive pattern capable of forming a conductive pattern made of a high-purity carbon material on a substrate such as a polymer film having relatively low heat resistance. It is an object of the present invention to provide a forming method, a substrate device having this conductive pattern, and a substrate device that can be manufactured at low cost and can exhibit excellent conductive performance.

The method for forming a conductive pattern of the present invention is a method for forming a conductive pattern in which a conductive pattern made of a pyropolymer is formed on the surface of a low heat resistant substrate,
(A) A heat-resistant substrate different from the low-heat-resistant substrate on which a conductive pattern made of a pyropolymer is formed, and having a pyrol on a heat- resistant substrate having a heat- resistant temperature higher than that of the low-heat-resistant substrate. Forming an initial pattern corresponding to the conductive pattern with a polymer precursor polymer;
(B) heating the precursor polymer constituting the initial pattern on the heat resistant substrate in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat resistant substrate; C) The conductive pattern formed on the heat-resistant substrate has a heat-resistant temperature lower than that of the heat-resistant substrate and the heat-resistant temperature lower than the heating temperature when forming the pyropolymer. It includes a step of transferring onto a heat resistant substrate.

In the method for forming a conductive pattern according to the present invention, a conductive pattern made of a pyropolymer is once formed on a heat-resistant substrate, and then the conductive pattern is formed with a low heat resistance temperature lower than that of the heat-resistant substrate. Transferred to the surface of the heat-resistant substrate. Therefore, the low heat resistant substrate which is the target for finally forming the conductive pattern may not withstand the heating temperature when forming the conductive pattern made of pyropolymer.
Therefore, in the method for forming a conductive pattern of the present invention, a polymer film having a relatively low heat resistance such as a polycarbonate film, a polyethylene terephthalate film, a polylactic acid film, or a polyimide film can be used as the low heat resistant substrate. . Thereby, a conductive pattern can be formed at a low manufacturing cost, and the manufacturing cost of a substrate device such as a sensor can be reduced.
Moreover, according to the method for forming a conductive pattern of the present invention, the precursor polymer of the pyropolymer can be heated at a temperature sufficient to eliminate impurities that do not contribute to the transfer of electrons. Thereby, compared with the case where a conductive pattern is formed by screen printing, it is possible to obtain a carbon electrode having a higher purity and excellent conductive performance.
Therefore, according to the conductive pattern forming method of the present invention, it is possible to increase the sensitivity of a sensor or the like.

In the method for forming a conductive pattern of the present invention, the low heat resistant substrate is a substrate made of a thermoplastic resin, and in the step (C), the low heat resistant substrate is heated to at least the low heat resistant substrate. The conductive pattern may be transferred onto the low heat resistant substrate by press-contacting the heat resistant substrate with the surface softened.
In this case, since the surface of the low heat resistant substrate is softened by heating, the conductive pattern is easily transferred to the surface of the low heat resistant substrate. Thereby, the said electroconductive pattern can be transcribe | transferred on the said low heat resistant board | substrate in a favorable state.
In this case, the low heat resistant substrate is preferably a polymer film made of a thermoplastic resin material having a heat resistant temperature lower than the heating temperature in the step (B).
Further, in this case, the low heat resistant substrate is a substrate made of a thermoplastic resin, and in the step (C), after the low heat resistant substrate is heated and pressed against the heat resistant substrate, It is preferable to transfer the conductive pattern onto the low heat resistant substrate by cooling the pressed low heat resistant substrate and the heat resistant base material.

In the method for forming a conductive pattern of the present invention, the surface of each of the conductive pattern formed on the heat resistant substrate and the low heat resistant substrate is activated, and the activation of the conductive pattern and the low heat resistant substrate is performed. The conductive pattern may be transferred onto the low heat-resistant substrate by bringing the formed surfaces into contact with each other.
In this case, the surface of each of the conductive pattern and the low heat-resistant substrate is activated, and a highly reactive functional group is generated on each surface. By these functional groups, the surface of the conductive pattern and the surface of the conductive pattern are formed. Both surfaces of the low heat resistant substrate are easily bonded to each other. Thereby, the said electroconductive pattern can be transcribe | transferred on the said low heat resistant board | substrate in a favorable state.
In this case, it is preferable to activate the surface by irradiating the conductive pattern formed on the heat resistant substrate and the surfaces of the low heat resistant substrate with ultraviolet rays. Further, the same effect can be expected even when plasma of oxygen or the like is used as the surface activation means.

In the method for forming a conductive pattern of the present invention, in the step (C), the conductive pattern and the surface of the heat-resistant substrate on the conductive pattern side are coated with an uncured curable resin to form a coating film. After forming and curing the curable resin constituting the coating film to form the low heat resistant substrate, the low heat resistant substrate is peeled off from the heat resistant base material to thereby form the conductive pattern. It may be transferred onto a low heat resistant substrate.
In this case, when the curable resin in the uncured state is cured, the low heat resistant substrate is formed in a state where high adhesion and adhesiveness are maintained between the curable resin in the uncured state and the conductive pattern. The Therefore, high adhesion and adhesiveness are ensured between the formed low heat resistant substrate and the conductive pattern. Thereby, the said electroconductive pattern can be transcribe | transferred on the said low heat resistant board | substrate in a favorable state.

In the method for forming a conductive pattern of the present invention, in the step (A), a concavo-convex shape in which a polymer layer made of a precursor polymer of a pyropolymer is formed on a heat-resistant substrate and the concavo-convex shape of the conductive pattern is inverted. It is preferable to form the initial pattern by pressing the stamping surface of the stamper having the stamping surface on which is formed, against the polymer layer and further etching the recess formed in the polymer layer.
In this case, the initial pattern can be easily formed with fewer steps compared to forming the initial pattern on the polymer layer formed on each low heat resistant substrate by photolithography. Moreover, since this stamper can be used repeatedly, resource saving and cost reduction can be achieved when forming the conductive pattern.
In this case, prior to the step (A),
(A) a step of forming a photoresist layer on the surface of the stamper profile;
(B) a step of aligning a mask provided with a reversal pattern obtained by reversing the conductive pattern with respect to the shaped material, and exposing the photoresist layer;
(C) developing the exposed photoresist layer;
(D) A step of forming the reversal pattern on the shaped material by etching the exposed portion of the shaped material exposed from the developed photoresist layer. (E) A photoresist from the shaped material on which the reversal pattern is formed. Removing the layer;
A stamper manufacturing process including the above may be further performed.

In the method for forming a conductive pattern of the present invention, the heat resistant substrate after transferring the conductive pattern onto the low heat resistant substrate in the step (D) is used as the heat resistant substrate in the step (A). Further use is preferable.
In this case, since the heat-resistant substrate can be used repeatedly, resource saving and cost reduction can be achieved when forming the conductive stamper.

In the method for forming a conductive pattern of the present invention, it is preferable that the low heat resistant substrate is a sensor substrate, and the conductive pattern is an electrode of the sensor.
In this case, an inexpensive and highly sensitive sensor can be obtained.

In the method for forming a conductive pattern according to the present invention, in the step (B), the precursor polymer constituting the initial pattern on the heat-resistant substrate is heated in an oxygen-deficient atmosphere to form a conductive polymer comprising a pyropolymer. A pattern is formed on the heat-resistant substrate, a wiring pattern made of metal is further formed on the surface of the heat-resistant substrate on which the conductive pattern is formed, and in the step (C), the heat-resistant substrate In addition to the conductive pattern formed on the heat-resistant substrate, the wiring pattern formed on the heat-resistant substrate may be transferred onto the low heat-resistant substrate.
In this case, the conductive pattern and the wiring pattern can be simultaneously transferred onto the low heat resistant substrate.
In this case, it is preferable to heat the heat-resistant substrate on which the conductive pattern and the wiring pattern are formed after the step (B) and prior to the step (C).
Thereby, a conductive pattern and a wiring pattern can be simultaneously and satisfactorily transferred onto a low heat resistant substrate.
Furthermore, in the method for forming a conductive pattern of the present invention, prior to the step (A), a barrier layer is formed on the surface of the heat resistant substrate to improve the peelability between the heat resistant substrate and the conductive pattern. It is preferable to form a barrier layer.
In this case, in the step (C), the releasability of the conductive pattern from the heat resistant substrate is improved by suppressing element interdiffusion and alloying between the heat resistant substrate and the conductive pattern. A conductive pattern can be satisfactorily transferred onto a low heat resistant substrate.

In one aspect, the substrate device of the present invention is a substrate device having a low heat resistant substrate and a conductive pattern made of a pyropolymer formed on the low heat resistant substrate,
The conductive pattern has the following steps (A) to (C):
(A) A heat-resistant substrate different from the low-heat-resistant substrate on which a conductive pattern made of a pyropolymer is formed, and having a pyrol on a heat-resistant substrate having a heat-resistant temperature higher than that of the low-heat-resistant substrate. Forming an initial pattern corresponding to the conductive pattern with a polymer precursor polymer;
(B) heating the precursor polymer constituting the initial pattern on the heat-resistant substrate in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat-resistant substrate; and
(C) The conductive pattern formed on the heat-resistant substrate has a heat-resistant temperature lower than that of the heat-resistant substrate and has a heat-resistant temperature lower than the heating temperature when forming the pyropolymer. Transfer process onto low heat resistant substrate
Is a conductive pattern obtained by a method for forming a conductive pattern comprising
The low heat resistant substrate, such a substrate and wherein the Rukoto that having a heat resistant temperature lower than the heating temperature in step (B) is a relatively inexpensive low heat resistant substrate, a conductive consisting pyropolymer pattern Therefore, it can be manufactured at low cost and can exhibit excellent conductive performance.
The substrate device may be a sensor.

In another aspect of the substrate device of the present invention, a low heat resistant substrate, a conductive pattern made of a pyropolymer formed on the low heat resistant substrate, and a conductive pattern of the low heat resistant substrate are formed. Board device having a wiring pattern made of metal formed on the surface on the other side, wherein the conductive pattern and the wiring pattern include the following steps (A) to (C):
(A) A heat-resistant substrate different from the low-heat-resistant substrate on which a conductive pattern made of a pyropolymer is formed, and having a pyrol on a heat-resistant substrate having a heat-resistant temperature higher than that of the low-heat-resistant substrate. Forming an initial pattern corresponding to the conductive pattern with a polymer precursor polymer;
(B) heating the precursor polymer constituting the initial pattern on the heat-resistant substrate in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat-resistant substrate; and
(C) The conductive pattern formed on the heat-resistant substrate has a heat-resistant temperature lower than that of the heat-resistant substrate and has a heat-resistant temperature lower than the heating temperature when forming the pyropolymer. Transfer process onto low heat resistant substrate
Including
In the step (B), the precursor polymer constituting the initial pattern on the heat-resistant substrate is heated in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat-resistant substrate. And further forming a metal wiring pattern on the surface of the heat-resistant substrate on which the conductive pattern is formed, and
In the step (C), the conductive pattern formed on the heat resistant substrate and the wiring pattern formed on the heat resistant substrate are transferred onto the low heat resistant substrate by the conductive pattern forming method. It is a pattern formed on a low heat resistant substrate,
The low heat resistant substrate, wherein the Rukoto that having a heat resistant temperature lower than the heating temperature in step (B).
Such a substrate device is obtained by transferring a conductive pattern made of a pyropolymer and a wiring pattern made of a metal to a relatively inexpensive low heat resistant substrate, so that it can be manufactured at low cost and has excellent conductivity. Performance can be expressed.

  According to the method for forming a conductive pattern of the present invention, a conductive pattern made of a high-purity carbon material can be formed on a substrate such as a polymer film having relatively low heat resistance. In addition, the substrate device of the present invention can be manufactured at a low cost and can exhibit excellent conductive performance.

It is a schematic explanatory drawing which shows the structure of the sensor which is a board | substrate apparatus of one Embodiment of this invention. It is process drawing which shows the procedure of the formation method of the electroconductive pattern which concerns on 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the stamper formation process in the formation method of the electroconductive pattern which concerns on 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern duplication process in the formation method of the electroconductive pattern which concerns on 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern duplication process in the formation method of the electroconductive pattern which concerns on 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern transfer process in the formation method of the electroconductive pattern which concerns on 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern transfer process in the formation method of the electroconductive pattern which concerns on the modification of 1st Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern transfer process in the formation method of the electroconductive pattern which concerns on 2nd Embodiment of this invention. It is process drawing which shows the detailed procedure of the pattern transfer process in the formation method of the electroconductive pattern which concerns on 3rd Embodiment of this invention. It is process drawing which shows the procedure of the formation method of the conductive pattern which concerns on 4th Embodiment of this invention. It is a graph which shows the result of having investigated the relationship between secondary ion intensity and the depth from the surface about the conductive pattern and wiring pattern which were simultaneously transferred by the formation method of the conductive pattern which concerns on 4th Embodiment of this invention. It is process drawing which shows the procedure of the formation method of the conductive pattern which concerns on 5th Embodiment of this invention. It is process drawing which shows the procedure of the formation method of the conductive pattern which concerns on 5th Embodiment of this invention. It is drawing substitute photograph which shows the result of having observed the electroconductive pattern formed with the formation method of the electroconductive pattern which concerns on 5th Embodiment of this invention with the electron microscope. (A) is schematic explanatory drawing which shows the structure of the heat resistant base material model of Example 1, (b) is schematic explanatory drawing which shows the structure of the heat resistant base material model of Example 2, (c) is Example 3 FIG. 4D is a schematic explanatory diagram illustrating a configuration of a heat resistant substrate model, and FIG. 6D is a schematic explanatory diagram illustrating a configuration of a heat resistant substrate model of Example 4. FIG.

[Configuration of substrate device]
Hereinafter, a substrate apparatus according to an embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic explanatory diagram showing the configuration of a sensor that is a substrate device according to an embodiment of the present invention.

  A biosensor 100 shown in FIG. 1 includes sensor parts A, B, and C arranged on a polymer film 201, a sample inlet 241 for supplying blood as a sample, and plasma components and blood cell components contained in blood. A separation unit 242 that separates the plasma component, a plasma channel 243 that delivers the plasma component separated by the separation unit 242 to each of the sensor units A, B, and C, and a blood cell discharge that discharges the blood cell component separated by the separation unit 242 A flow path 244 and a plasma discharge port 245 for discharging the remaining plasma components delivered to the sensor units A, B, and C are provided.

  The sensor units A, B, and C function as sensors that detect different detection target substances a, b, and c, respectively.

  The sensor part A includes a working electrode 211, a counter electrode 212, and a silver / silver chloride reference electrode 213. Similarly to the sensor part A, the sensor parts B and C are also composed of working electrodes 221 and 231, counter electrodes 222 and 232, and silver-silver chloride reference electrodes 223 and 233, respectively.

  The end 211a on the sample contact side of the working electrode 211 constituting the sensor part A has an oxidoreductase a using the detection target substance a as a substrate, and the end 221a on the sample contact side of the working electrode 221 constituting the sensor part B. The oxidoreductase b using the detection target substance b as a substrate, and the oxidoreductase c using the detection target substance c as a substrate are respectively present at the end 231a on the sample contact side of the working electrode 231 constituting the sensor unit C. It is fixed. Further, mediators that promote the transfer of electrons generated when the respective oxidoreductases a, b, and c catalyze the redox reaction to the electrodes (working electrodes) are fixed to the end portions 211a, 221a, and 231a. Has been.

The working electrodes 211, 221, 231 and counter electrodes 212, 222, 232 are transfer patterns in which a conductive pattern made of a pyropolymer is transferred onto the polymer film 201. Since the working electrodes 211, 221, 231 and the counter electrodes 212, 222, 232 are made of pyropolymers produced by heating the precursor polymer of the pyropolymer at a high temperature, they do not contain impurities that do not contribute to the transfer of electrons. Expresses the conductive performance.
Therefore, since the biosensor 100 including these performs electrode reaction satisfactorily, even a small amount of electrons can be exchanged due to the presence of a small amount of the detection target substance, and the detection target substance can be efficiently performed. Can be detected.

The polymer film 201 is made of a polycarbonate film composed of polycarbonate (glass transition point: 140 to 150 ° C.) which is a thermoplastic resin.
Polycarbonate generally has a glass transition point of 140 to 150 ° C., and the heating temperature when generating the pyropolymer cannot maintain the shape of the film, or obtain sufficient mechanical properties to be used as a sensor substrate. Therefore, it has been conventionally considered to be unsuitable as a substrate on which a conductive polymer composed of a pyropolymer is formed.
However, in the biosensor 100 that is the substrate device according to the present embodiment, the working electrodes 211, 221, 231 and the counter electrodes 212, 222, 232 are transfer patterns obtained by transferring a conductive pattern made of a pyropolymer. As a substrate on which a conductive pattern to be formed is formed, a substrate made of a low-heat-resistant thermoplastic resin or the like, which has not been conventionally used, such as polycarbonate, can be used.
Since such a substrate is used, the biosensor 100 that is the substrate device according to the present embodiment is suitable for a disposable application.

In the biosensor 100, the blood sample injected from the sample injection port 241 is separated into a plasma component and a blood cell component in the separation unit 242. The plasma components separated by the separation unit 242 are transported in the plasma channel 243, and the working electrodes 211, 221, 231 and counter electrodes 212, 222, 232 and the reference electrode 213 of each of the sensor units A, B, C are provided. 223,233. The remaining plasma components delivered to each of the sensor units A, B, and C are discharged out of the biosensor 100 from the plasma discharge port 245.
On the other hand, the blood cell component separated by the separation unit 242 is transported through the blood cell discharge channel 244 and discharged from the blood cell discharge port 246 to the outside of the biosensor 100.

In each of the sensor units A, B, and C, the oxidoreductases a, b, and c fixed to the end portions 211a, 221a, and 231a on the sample contact side of the working electrodes 211, 221, and 231 are respectively substrates. When the detection target substances a, b, and c come into contact with each other and an oxidation-reduction reaction is performed, a current flows between the working electrodes 211, 221, 231 and the corresponding counter electrodes 212, 222, 232.
Therefore, in the biosensor 100, in the sensor unit A, the current between the working electrode 211 or the reference electrode 213 and the counter electrode 212 is measured, and the current in the sample is measured based on the current flowing between the working electrode 211 and the counter electrode 212. The presence or absence of the detection target substance a can be examined. Also in the sensor parts B and C, by performing the same operation as in the case of the sensor part A, the presence or absence of the detection target substances b and c in the sample can be examined.

The working electrodes 211, 221, 231 and the counter electrodes 212, 222, 232 can be formed by a conductive pattern forming method described later.
The polymer film 201 may be a film made of polylactic acid, polyethylene terephthalate, polyimide, cycloolefin polymer, polydimethylsiloxane, acrylic resin, or the like, instead of the polycarbonate film.
Furthermore, in this embodiment, an oxidoreductase that performs an oxidation-reduction reaction is fixed to the working electrode. However, instead of such an oxidoreductase, another enzyme that catalyzes a reaction that causes electron transfer may be used. .
In this embodiment, the wiring pattern made of metal for connecting the working electrodes 211, 221, 231 and the counter electrodes 212, 222, 232 and the like to the power source is a polymer film 201 as a transfer pattern together with the conductive pattern made of pyropolymer. It may be transcribed above. Such conductive patterns and wiring patterns can also be formed by a conductive pattern forming method described later.

[Method for Forming Conductive Pattern According to First Embodiment]
Next, a method for forming a conductive pattern according to an embodiment (first embodiment) of the present invention will be described with reference to the accompanying drawings. FIG. 2 is a process diagram showing the procedure of the conductive pattern forming method according to the first embodiment of the present invention. FIG. 3 is a process diagram showing a detailed procedure of a stamper forming process in the conductive pattern forming method according to the first embodiment of the present invention. 4 and 5 are process diagrams showing detailed procedures of the pattern duplication process in the conductive pattern forming method according to the first embodiment of the present invention. FIG. 6 is a process diagram showing a detailed procedure of a pattern transfer process in the conductive pattern forming method according to the first embodiment of the present invention.

  In the method for forming a conductive pattern according to the first embodiment, as shown in FIG. 2, first, a stamper is formed (“stamper formation step S10”).

  In the stamper forming step S10, first, a photoresist is applied to the surface of the stamper material 11 (see FIG. 3A) to form a photoresist layer 12 (“resist applying step S11”, FIG. 3). (See (b)).

  Examples of the material constituting the stamper shape material 11 include silicon, nickel, and nickel-based alloys.

The photoresist may be a negative photoresist or a positive photoresist. Negative photoresists include, for example, rosin-dichromate, polyvinyl alcohol-dichromate, shellac-dichromate, casein-dichromate, polyvinyl alcohol-diazo, polymethyl methacrylate, polycinnamic acid. Examples thereof include vinyl, cyclized rubber-azide, polyvinyl cinnamylidene acetate, and polycinnamic acid β-vinyloxyethyl ester.
Examples of the positive photoresist include 1-methoxy-2-propanol acetate and o-naphthoquinonediazide.
Among these, a positive photoresist is suitable for forming a fine conductive pattern. In addition, a positive photoresist generally has excellent durability against plasma etching.

The photoresist is applied to the base material 11 by a spin coating method using a spin coater or the like.
After a photoresist is applied to the surface of the raw material 11, the raw material 11 is pre-baked to bring the photoresist and the raw material 11 into close contact with each other, thereby forming a photoresist layer 12.
The thickness of the photoresist layer 12 may be sufficient as long as it appropriately protects the base material 11 in the etching process described later.

  After the resist coating step S11, a mask provided with a pattern corresponding to the conductive pattern is aligned with the base material 11, and light is applied to expose the inverted pattern of the conductive pattern on the photoresist layer 12. . Thereafter, the reversal pattern exposed to the photoresist layer 12 of the base material 11 is developed using a developer, and then the base material 11 is washed (“exposure development step S12”, FIG. 3C). )reference).

  In the exposure and development step S12, when the photoresist is a negative photoresist, the unexposed portion of the photoresist layer 12 is dissolved by coming into contact with the developer. On the other hand, when the photoresist is a positive photoresist, the exposed portion of the photoresist layer 12 is dissolved by coming into contact with the developer. Thereby, the excess photoresist on the raw material 11 can be removed.

Examples of the light source used for exposure include a mercury lamp and a laser light source.
The exposure may be performed by contact exposure in which the mask is brought into close contact with the base material 11, and the reverse pattern in the mask is projected onto the surface of the base material 11 in a state where the mask is separated from the base material 11. You may carry out by projection exposure.
When a laser light source is used as the light source, a reverse pattern can be directly drawn on the photoresist layer 12 without using a mask.

Development may be performed by immersion development in which the base material 11 is immersed in a developer, or may be performed by spray development in which the developer is sprayed onto the photoresist layer 12 on the surface of the base material 11. The developing solution can be appropriately selected depending on the type of photoresist used.
The developed shape material 11 is washed with pure water or the like and dried.

After the exposure and development step S12, the reverse pattern is formed on the raw material 11 by etching the exposed portion A (see FIG. 3D) of the raw material 11 exposed from the photoresist layer 13 (“etching”). Step S13 ").
In the etching step S13, the etching progresses in the exposed portion A of the shaped material 11 exposed from the developed photoresist layer 13, while the developed material layer 11 in which the developed photoresist layer 13 is overlaid. The progress of etching is hindered at the non-exposed part (convex part 14). As a result, a reverse pattern corresponding to the conductive pattern is formed on the base material 11.

Etching can be performed by reactive ion etching. In such reactive ion etching, active species present in the plasma of the reactive gas react with atoms on the surface of the exposed portion A of the raw material 11 to be etched to generate a volatile reaction product. Etching is performed by detaching from the surface of the exposed portion A of the base material 11.
Examples of the reactive gas include fluorine-based gas such as sulfur hexafluoride (SF ₆ ) gas.

Then, after the etching step S13, the photoresist layer 13 is removed from the base material 11 on which the reverse pattern is formed (“resist removal step S14”, see FIG. 3E).
In the resist removing step S14, the stamper 10 can be obtained by removing the photoresist layer 13 existing on the surface of the unexposed portion (convex portion 14) of the base material 11 using an organic solvent or the like.

  In the method for forming a conductive pattern according to the first embodiment, as shown in FIG. 2, next, the conductive pattern is replicated on the surface of the heat-resistant substrate (“pattern replication step S20”).

  In the pattern duplication step S20, first, a precursor polymer of a pyropolymer is applied on the heat resistant substrate 21 (see FIG. 4A) to form a polymer layer 31 (“polymer application step S21”, FIG. 4). (See (b)).

  Here, the heat-resistant substrate is a group made of a material capable of maintaining the shape of the substrate even under a temperature condition equal to or higher than the heating temperature in pyrolysis of the pyropolymer precursor polymer in the pyrolysis step S33 described later. Say the material.

In the pattern transfer step described later, from the viewpoint of satisfactorily transferring the conductive pattern made of pyropolymer to the low heat resistant substrate, between the material constituting the heat resistant substrate 21 and the conductive pattern made of pyropolymer. It is preferable that the adhesiveness is lower than the adhesiveness between the low heat resistant substrate to which the conductive pattern is transferred and the conductive pattern made of pyropolymer. Therefore, from such a viewpoint, for example, quartz, silicon, silicon oxide, silicon nitride, or the like is preferable as the material constituting the heat-resistant substrate 21. Of these, the heat-resistant substrate 21 made of silicon nitride is more suitable because the conductive pattern is easily peeled off.
The adhesive property is obtained by, for example, attaching an adhesive tape to a pyropolymer layer formed on a heat-resistant substrate or a low heat-resistant substrate and made of a pyropolymer having a grid-like cut, and this adhesive The degree of peeling of the pyropolymer layer when the tape is peeled can be evaluated by visually observing.

  The heat-resistant substrate 21 includes a first heat-resistant substrate made of one of the materials constituting the heat-resistant substrate 21 and a first of the materials constituting the heat-resistant substrate 21. It may be a layered body composed of a second heat-resistant substrate made of a material different from the heat-resistant substrate. In the pattern transfer step described later, from the viewpoint of satisfactorily transferring the conductive pattern made of the pyropolymer to the low heat resistant substrate, the second heat resistant made of silicon nitride on the first heat resistant substrate made of silicon. A layered body in which a layer of a conductive substrate is formed is preferable.

Examples of the precursor polymer of the pyropolymer include 1-methoxy-2-propanol acetate (for example, product name: AZ P4620 manufactured by Clariant Corporation), polymethyl methacrylate, polyimide, and the like.
The thickness of the polymer layer 31 can be appropriately set according to the conductive pattern to be formed.

Next, in the pattern duplication step S20, the stamper 10 is brought into pressure contact with the polymer layer 31, thereby processing the uneven shape on the polymer layer 31 to form an initial pattern corresponding to the conductive pattern ("embossing step S31 ", see FIGS. 5A to 5C).
As described above, by performing the embossing step S31, an initial pattern corresponding to the conductive pattern can be easily formed, so that the cost required for pattern formation can be reduced.
In the stamping step S31, first, the stamper 10 is pressed into contact with the polymer layer 31 on the heat-resistant substrate 21 while heating (S31-1 to S31-2).
Then, the stamper 10 is peeled off from the polymer layer 31 on the heat resistant substrate 21 (S31-3).
At this time, the heating temperature is preferably 140 to 180 ° C., more preferably 155 to 165 ° C., from the viewpoint of processing the uneven shape corresponding to the conductive pattern so that the polymer layer 31 has a good finish.
Further, the pressure applied at the time of press contact is preferably 0.5 to 3 MPa, more preferably 1 to 2 MPa from the viewpoint of processing the uneven shape corresponding to the conductive pattern so that the polymer layer 31 has a good finish. It is.
By this pattern duplication step S20, the concavo-convex shape including the convex portions 32 and the concave portions 33 is processed into the polymer layer 31 (see FIG. 5C).

Next, in the pattern duplication step S20, the precursor polymer remaining in the recess 31 is removed by etching to form an initial pattern corresponding to the conductive pattern (see “Etching Step S32”, FIG. 5D). ).
Etching is preferably performed by oxygen plasma etching from the viewpoint of selectively removing the polymer.
The etching time may be a time sufficient for removing the precursor polymer remaining in the recess 31.

  In the pattern duplication step S20, the heat-resistant substrate 21 is then heated in an oxygen-deficient atmosphere to pyrolyze the pyropolymer precursor polymer constituting the initial pattern, and the conductive pattern 30 made of pyropolymer. ("Thermal decomposition step S33", see FIG. 5E).

  Examples of the oxygen-deficient atmosphere include an inert gas atmosphere such as nitrogen gas and argon gas, and a vacuum atmosphere.

The heating temperature differs depending on the type of pyropolymer precursor polymer used and so cannot be determined unconditionally, but is usually preferable from the viewpoint of obtaining a conductive pattern having high purity and high conductivity. Is 600 ° C. or higher, more preferably 800 ° C. or higher, and still more preferably 1000 ° C. or higher. The upper limit of the heating temperature may be a temperature sufficient for the pyropolymer precursor polymer to thermally decompose to produce a pyropolymer (for example, 3000 ° C. or less). When 1-methoxy-2-propanol acetate (for example, product name: AZ P4620 manufactured by Clariant Corporation) is used as the precursor polymer of the pyropolymer, the heating temperature is preferably 800 ° C. or higher. By doing so, the adhesiveness to the below-mentioned low heat-resistant board | substrate is securable. As described above, by setting the heating temperature to 800 ° C. or higher, it is possible to sufficiently ensure the peelability from the heat-resistant substrate.
The heating time can be appropriately set according to the thickness of the initial pattern (the thickness of the polymer layer 31). Usually, when the temperature is raised at 10 ° C./min and lowered at 2 ° C./min, the maximum temperature is reached. The holding time may be 0 to 240 minutes (for example, 120 minutes at the maximum temperature).

  Thereafter, in the method for forming a conductive pattern according to the first embodiment, as shown in FIG. 2, while heating, the conductive pattern 30 on the heat-resistant base material 21 and the low heat-resistant substrate 41 are mutually connected. The conductive pattern 30 is transferred to the surface of the low heat resistant substrate 41 by pressure contact (“pattern transfer step S30”).

  In the pattern transfer step S30, the heat-resistant substrate 20 and the heat-resistant substrate 20 are arranged such that the conductive pattern 30 on the heat-resistant substrate 20 faces the surface of the low heat-resistant substrate 41 on which the conductive pattern 30 is transferred. The low heat resistant substrate 41 is set (see “setting step S41”, FIGS. 6A and 6B).

The low heat resistant substrate 41 may be any of a film shape, a sheet shape, and a plate shape.
The low heat-resistant substrate 41 is made of a low heat-resistant material having a higher adhesiveness to the conductive pattern 30 than an adhesive property between the heat-resistant substrate 20 and the conductive pattern 30.

Here, the low heat-resistant substrate refers to the shape of the base material under a temperature condition equal to or higher than the lower limit value of the heating temperature at the time of thermal decomposition of the pyropolymer precursor polymer in the thermal decomposition step S33, for example, 600 ° C. or higher. A substrate made of a material that cannot be maintained or cannot obtain sufficient mechanical properties to be used as a substrate under the above temperature conditions.
Specifically, as the low heat-resistant substrate 41, for example, a polymer film made of a thermoplastic resin such as polycarbonate, polyethylene terephthalate, or polylactic acid, or heating during pyrolysis of a precursor polymer of a pyropolymer in the thermal decomposition step S33. A polymer film made of polydimethylsiloxane or the like obtained from a curable resin composition that is cured by heat at a temperature lower than the lower limit of temperature, light (for example, ultraviolet rays), or the like can be used.

Next, while heating, the conductive pattern 30 in the heat-resistant substrate 20 and the surface of the low heat-resistant substrate 41 on the side to which the conductive pattern 30 is transferred are pressed against each other (“heating and pressurizing step S42”, FIG. 6 (c)).
For example, when the low heat resistant substrate 41 is a polymer film made of a thermoplastic resin, the conductive pattern 30 is formed by pressing the low heat resistant substrate 41 to the heat resistant substrate 20 while being softened by heating. It can be transferred onto the surface of the low heat resistant substrate 41.
At this time, the heating temperature may be a temperature at which at least the surface of the low heat resistant substrate 41 is softened.
In addition, the pressure applied during the press contact may be such that the conductive pattern 30 and the surface of the low heat resistant substrate 41 can be sufficiently adhered to each other.
As described above, in the heating and pressurizing step S42, by heating, a combination of the elements having less mutual diffusion between the respective atoms as in the heat resistant substrate 20 and the conductive pattern 30 is obtained. Are in a state where they are easily peeled from each other, and on the other hand, in the case of a combination of those having a large amount of interdiffusion between the respective atoms, such as between the low heat resistant substrate 41 and the conductive pattern 30, It is considered that they are in a state of being easily bonded to each other. Moreover, since the conductive pattern 30 and the surface of the low heat resistant substrate 41 are sufficiently adhered by pressurization, the conductive pattern 30 can be transferred to the low heat resistant substrate 41 satisfactorily.

Thereafter, the heat-resistant substrate 21 is peeled from the low heat-resistant substrate 41, the conductive pattern 30 is peeled from the heat-resistant substrate 21, and the low-heat resistant substrate 41 and the conductive pattern 30 are adhered ("peeling step" S43 ", see FIG. 6 (d)).
Thereby, the conductive pattern 30 on the heat resistant substrate 21 can be transferred to the low heat resistant substrate 41.

  As described above, according to the method for forming a conductive pattern according to the first embodiment, a conductive pattern can be formed on a low heat resistant substrate. Therefore, the conductive pattern formed by the conductive pattern forming method according to the present embodiment is suitable as an electrode of a substrate device using a low heat resistant substrate.

[Modification of Method for Forming Conductive Pattern According to First Embodiment]
The conductive pattern forming method according to the modification of the first embodiment is different from the conductive pattern forming method according to the first embodiment in that a cooling step is performed after the heating and pressurizing step in the pattern transfer step. ing. Hereinafter, only the pattern transfer process in the conductive pattern forming method according to the modification of the first embodiment will be described with reference to the accompanying drawings. FIG. 7 is a process diagram showing a detailed procedure of a pattern transfer process in the conductive pattern forming method according to the modification of the first embodiment of the present invention.

In the pattern transfer process in the conductive pattern forming method according to the modification of the first embodiment, the conductive pattern 30 on the heat-resistant base material 21 and the conductive property on the low heat-resistant substrate 41 are shown in FIG. The heat-resistant base material 21 and the low heat-resistant substrate 41 are set so that the surface on the side to which the conductive pattern 30 is transferred faces and contacts with each other (see “setting step S51”, FIG. 7A).
In the method for forming a conductive pattern according to the modification of the first embodiment, the conductive pattern 30 can be satisfactorily transferred, and therefore, the material constituting the low heat resistant substrate 41 is preferably polycarbonate or the like. .

Next, both the heat resistant base material 20 and the low heat resistant substrate 41 are heated by sandwiching the set heat resistant base material 20 and the low heat resistant substrate 41 with two plate-shaped heating means 51 preheated. However, the heat resistant substrate 20 and the low heat resistant substrate 41 are pressurized in the compression direction (see “heating and pressing step S52”, FIG. 7B).
Since the heating temperature and pressure differ depending on the types of the heat-resistant substrate 20 and the low heat-resistant substrate 41, they cannot be determined unconditionally. When the layered body in which the layer of the second heat resistant substrate made of silicon nitride is formed on the first heat resistant substrate made of silicon is used as the heat resistant substrate 20, for example, the heating temperature is set to 160. C. and the pressure can be 2.5 MPa.

Next, the heat-resistant base material 21 and the low heat-resistant substrate 41 after the heating and pressing step are cooled (see “Cooling step S53”, FIG. 7C).
The cooling temperature can be appropriately set according to the glass transition point of the low heat resistant substrate, but usually 20 ° C. when polycarbonate, acrylic resin, cycloolefin copolymer or cycloolefin polymer is used as the low heat resistant substrate. It is preferably ~ 120 ° C.

Thereafter, the heat-resistant substrate 21 is peeled from the low heat-resistant substrate 41, the conductive pattern 30 is peeled from the heat-resistant substrate 21, and the low-heat resistant substrate 41 and the conductive pattern 30 are adhered ("peeling step" S54 ", see FIG. 7 (d)).
Thereby, the conductive pattern 30 on the heat resistant substrate 21 can be transferred to the low heat resistant substrate 41.

[Method for Forming Conductive Pattern According to Second Embodiment]
In the conductive pattern forming method according to the second embodiment, the procedure of the pattern transfer process is different from that of the conductive pattern forming method according to the first embodiment and the modification of the first embodiment. Hereinafter, only the pattern transfer process in the conductive pattern forming method according to the second embodiment will be described with reference to the accompanying drawings. FIG. 8 is a process diagram showing a detailed procedure of a pattern transfer process in the conductive pattern forming method according to the second embodiment of the present invention.

In the method for forming a conductive pattern according to the second embodiment, first, as shown in FIG. 8, the surface of the conductive pattern 30 on the heat resistant substrate 21 and the conductive pattern 30 on the low heat resistant substrate 41. The surface 41a on the side to be transferred is irradiated with ultraviolet rays under aerobic conditions to activate these surfaces (see “surface activation step S61”, FIG. 8A).
In this surface activation step S61, by activating the surface of the conductive pattern 30, highly reactive functional groups are generated on the respective surfaces, and the surface of the conductive pattern 30 and the low heat resistance are generated by these functional groups. Both surfaces 41a of the conductive substrate 41 are easily bonded to each other. Since the surface activation step S61 improves the adhesion between the surface of the conductive pattern 30 and the surface 41a of the low heat resistant substrate 41, the conductive pattern 30 is placed on the low heat resistant substrate 41 in a good state. Can be transferred.

In the method for forming a conductive pattern according to the second embodiment, since the activation of the surface is easy, a cycloolefin polymer, polydimethylsiloxane, or the like is suitable as a material constituting the low heat resistant substrate 41. .
Moreover, the material which comprises the heat resistant base material 21 is the same as that used for the formation method of the electroconductive pattern which concerns on 1st Embodiment.

  The irradiation conditions of the ultraviolet rays on the surface of the conductive pattern 30 and the surface 41 a of the low heat resistant substrate 41 are the precursor polymer of the pyropolymer used for forming the conductive pattern 30 and the type of material constituting the low heat resistant substrate 41. It can set suitably according to etc. For example, 1-methoxy-2-propanol acetate (for example, manufactured by Clariant Corporation, trade name: AZ P4620) is used as a precursor polymer of a pyropolymer, and a cycloolefin polymer (Nippon Zeon ( When using a substrate made of Co., Ltd., trade name: ZF-140, ZF-160) or polydimethylsiloxane, the conditions for irradiating ultraviolet rays with a wavelength of 172 nm at an output of 20 W for 100 seconds are adopted as the irradiation conditions. Can do.

  In the method for forming a conductive pattern according to the second embodiment, activation of the surface of the conductive pattern 30 and the surface 41a of the low heat resistant substrate 41 is performed by thiolation [for example, mercapto It can also be carried out by immersion in an ethanolic solution of undecanoic acid (concentration around 15 mM) for 1 to 1.5 hours and drying], oxygen plasma treatment, corona discharge or the like.

Next, the conductive pattern 30 on the heat-resistant substrate 21 is set so that the surface 41a on the side where the conductive pattern 30 on the low heat-resistant substrate 41 is transferred faces each other (“setting step S62”, FIG. 8 ( b)), the heat-resistant substrate 21 and the low heat-resistant substrate 41 are brought into contact ("contact process S63", see FIG. 8C).
In the method for forming a conductive pattern according to the second embodiment, since the surface of the conductive pattern 30 and the surface 41a of the low heat resistant substrate 41 are activated, the heat resistant base 21 is changed to the low heat resistant substrate 41. The conductive pattern 30 can be transferred at room temperature and normal pressure.

Thereafter, the heat-resistant substrate 21 is peeled from the low heat-resistant substrate 41, the conductive pattern 30 is peeled from the heat-resistant substrate 21, and the low-heat resistant substrate 41 and the conductive pattern 30 are adhered ("peeling step" S64 ", see FIG. 8 (d)).
Thereby, the conductive pattern 30 on the heat resistant substrate 21 can be transferred to the low heat resistant substrate 41.

[Method for Forming Conductive Pattern According to Third Embodiment]
In the conductive pattern forming method according to the third embodiment, the procedure of the pattern transfer process is different from that of the first embodiment, the modified example of the first embodiment, and the conductive pattern forming method according to the second embodiment. Yes. Therefore, only the pattern transfer process in the conductive pattern forming method according to the third embodiment will be described below with reference to the accompanying drawings. FIG. 9 is a process diagram showing a detailed procedure of a pattern transfer process in the conductive pattern forming method according to the third embodiment of the present invention.
In the method for forming a conductive pattern according to the third embodiment, the material constituting the low heat resistant substrate 41 has a heat resistant temperature lower than that of the heat resistant base material 21 and is cured by heat, ultraviolet irradiation, or the like. Resin is used. Hereinafter, the case where polydimethylsiloxane is used as the curable resin will be described as an example.

  In the method for forming a conductive pattern according to the third embodiment, first, the conductive pattern side surface of the heat-resistant substrate 21 is coated with the uncured raw material 40 of polydimethylsiloxane (“Coating Step S71”, FIG. 9). (See (a)).

The material constituting the heat-resistant substrate 21 is the same as that used in the conductive pattern forming method according to the first embodiment.
As the uncured raw material 40, for example, a mixture having a volume ratio of the main agent to the curing agent (main agent / curing agent) of 4/1 is used.

Next, the uncured raw material 40 is cured by heating to form the low heat resistant substrate 41 (see “Curing Step S72”, FIG. 9B).
The main curing step S72 can be performed, for example, by placing the coated base material on a hot plate that has been heated to 70 ° C. in advance.

Thereafter, the heat-resistant substrate 21 is peeled from the low heat-resistant substrate 41, the conductive pattern 30 is peeled from the heat-resistant substrate 21, and the low-heat resistant substrate 41 and the conductive pattern 30 are adhered ("peeling step" S73 ", see FIG. 9 (c)).
Thereby, the conductive pattern 30 on the heat resistant substrate 21 can be transferred to the low heat resistant substrate 41.

  In the method of forming a conductive pattern according to the third embodiment, if the material constituting the low heat resistant substrate 41 has a heat resistant temperature lower than that of the heat resistant substrate 21, it is cured instead of polyoxysiloxane. As the curable resin, other thermosetting resins, photocurable resins, and the like (for example, polycarbonate, acrylic resin, cycloolefin copolymer, cycloolefin polymer, and the like) may be used. Specifically, examples of the thermosetting resin include Toray Dow Corning Co., Ltd., trade name: Sylpot (polydimethylsiloxane), OSETECH, trade name: mr-9000 series, and the like. Moreover, as photocurable resin, the Toyo Gosei Co., Ltd. make, brand name: PAK-01 etc. are mentioned, for example. In this case, an uncured thermosetting resin or an uncured photocurable resin can be used as the uncured raw material 40 in the coating step S71.

  In the method for forming a conductive pattern according to the third embodiment, when an uncured curable resin is cured, high adhesion and adhesion between the uncured curable resin and the conductive pattern are obtained. A low heat-resistant substrate is formed in a maintained state. Therefore, high adhesion and adhesiveness are ensured between the formed low heat resistant substrate and the conductive pattern. Thereby, the said electroconductive pattern can be transcribe | transferred on the said low heat resistant board | substrate in a favorable state.

[Method for Forming Conductive Pattern According to Fourth Embodiment]
In the method for forming a conductive pattern according to the fourth embodiment, before applying a pyropolymer precursor polymer on a heat-resistant group, the surface of the heat-resistant substrate is coated with the heat-resistant substrate and the conductive pattern. There are significant features in that a barrier layer for improving the peelability is formed and that the conductive pattern and the wiring pattern are simultaneously transferred to a low heat resistant substrate. Hereinafter, a method for forming a conductive pattern according to the fourth embodiment will be described with reference to the accompanying drawings. FIG. 10 is a process diagram showing the procedure of the conductive pattern forming method according to the fourth embodiment of the present invention.
The material constituting the heat resistant substrate 21 and the material constituting the low heat resistant substrate 41 used in the conductive pattern forming method according to the fourth embodiment are the same as described above.

In the method for forming a conductive pattern according to the fourth embodiment, first, the barrier layer 61 is formed on the surface of the heat-resistant substrate 21 (see FIG. 10A) [“barrier layer forming step S81”, FIG. 10 (b)].
As a material constituting the barrier layer 61, for example, silicon oxide, silicon nitride, or the like is used.
When silicon oxide is used, the thickness of the barrier layer 61 is preferably 500 nm or more from the viewpoint of ensuring sufficient peelability. In this case, the upper limit of the thickness of the barrier layer 61 is not particularly limited, and may be approximately the same as the thickness of the heat resistant substrate.
When silicon nitride is used, the thickness of the barrier layer 61 is preferably 200 nm or more from the viewpoint of ensuring sufficient peelability. In this case, the upper limit of the thickness of the barrier layer 61 is not particularly limited, and may be approximately the same as the thickness of the heat resistant substrate.
The barrier layer 61 can be formed by using, for example, a steam thermal oxidation method, a plasma CVD method, or a spin coater, and a method of coating the surface of the heat resistant substrate 21 with a material constituting the barrier layer 61.

  After the barrier layer forming step S81, the conductive pattern 30 is formed on the surface of the heat resistant substrate 21 on the side where the barrier layer 61 is formed ["Conductive pattern forming step S82", see FIG. 10 (c)]. The conductive pattern forming step S82 can be performed by the same method as the embossing step S31, the etching step S32, and the thermal decomposition step S33 in the conductive pattern forming method according to the first embodiment.

After the conductive pattern forming step S82, a wiring pattern 71 made of metal is further formed on the surface of the heat resistant substrate 21 on which the conductive pattern 30 is formed ["Wiring pattern forming step S83", FIG. 10 (d). reference〕.
Examples of the metal constituting the wiring pattern 71 include gold, chromium, copper, aluminum, silver, platinum, nickel, and the like. Of these, gold is preferable because of its excellent adhesion to the conductive pattern 30.
The wiring pattern 71 can be formed by, for example, a resistance heating vacuum deposition method.

After the wiring pattern forming step S83, the surface of the metal constituting the wiring pattern 71 on the heat resistant substrate 21 is activated by thiolation, and the surface of the low heat resistant substrate 41 is activated by vacuum ultraviolet treatment [ “Surface activation step S84”, FIG. 10 (e)].
Thiolation of the metal surface can be performed by bringing a metal surface into contact with an ethanol solution of mercaptoundecanoic acid.
Further, the vacuum ultraviolet ray treatment on the surface of the low heat resistant substrate 41 can be performed by irradiating ultraviolet rays having a wavelength of 172 nm.

After the surface activation step S84, the conductive pattern 30 and the wiring pattern 71 in the heat resistant substrate 20 and the surface of the low heat resistant substrate 41 on which the conductive pattern 30 and the wiring pattern 71 are transferred face each other and come into contact with each other. As described above, the heat-resistant substrate 20 and the low heat-resistant substrate 41 are set ["setting step S85", see FIG. 10 (f)].
In this setting step S85, the heat-resistant substrate 20 is placed in an oxygen-deficient atmosphere (for example, a nitrogen atmosphere, a vacuum atmosphere) from the viewpoint of satisfactorily transferring both the conductive pattern 30 and the wiring pattern 71 to the low heat-resistant substrate 41. Etc.) It is preferable to heat down. Since the heating temperature varies depending on the type of metal used for the wiring pattern 71, it cannot be determined unconditionally. In the case where the metal is gold, the heating is performed from the viewpoint of improving the adhesion between the metal and the pyropolymer constituting the conductive pattern 30 and favorably transferring both the conductive pattern 30 and the wiring pattern 71. The temperature is preferably 300 to 800 ° C, more preferably 400 to 700 ° C, still more preferably 550 to 650 ° C, and particularly preferably around 600 ° C. Especially, it is preferable to heat the heat-resistant substrate 20 in a vacuum atmosphere at around 600 ° C. for about 2 hours.

After the setting step S85, the heat-resistant substrate 20 and the low heat-resistant substrate 41 are brought into contact under pressure ("Pressurization step S86", see FIG. 10 (g)).
The pressure at the time of pressurization is preferably about 0.1 to 20 MPa, particularly preferably about 10 MPa from the viewpoint of satisfactorily transferring the conductive pattern 30 and the wiring pattern 71 to the low heat resistant substrate 41. In the pressurizing step S86, it is preferable to heat the heat-resistant substrate 20 and the low heat-resistant substrate 41 during pressurization from the viewpoint of improving the yield. In this case, the heating temperature is preferably 50 to 140 ° C.

After the pressurizing step S86, the heat resistant substrate 21 is peeled from the low heat resistant substrate 41, both the conductive pattern 30 and the wiring pattern 71 are peeled from the heat resistant substrate 21, and the low heat resistant substrate 41 and the conductive material are removed. Both the pattern 30 and the wiring pattern 71 are bonded (see “Peeling Step S43”, FIG. 10H).
Thereby, both the conductive pattern 30 and the wiring pattern 71 on the heat resistant substrate 21 can be transferred to the low heat resistant substrate 41 in a good state.
In the low heat resistant substrate 41 obtained by the method for forming a conductive pattern according to the fourth embodiment, for example, as can be seen from the result shown in the graph of FIG. 11, gold is formed under the conductive pattern made of a pyropolymer. A wiring pattern 71 is formed, and both the conductive pattern 30 and the wiring pattern 71 are transferred well.

[Method for Forming Conductive Pattern According to Fifth Embodiment]
The conductive pattern forming method according to the fifth embodiment is greatly characterized in that the conductive pattern 30 is formed with a concavo-convex structure. Hereinafter, a method for forming a conductive pattern according to the fifth embodiment will be described with reference to the accompanying drawings. 12 and 13 are process diagrams showing the procedure of the conductive pattern forming method according to the fifth embodiment of the present invention.
The material constituting the heat resistant substrate 21 and the material constituting the low heat resistant substrate 41 used in the conductive pattern forming method according to the fifth embodiment are the same as described above.

In the method for forming a conductive pattern according to the fifth embodiment, first, the heat-resistant substrate 111 (see FIG. 12A) is subjected to uneven processing to form the concave portions 111a and the convex portions 111b. Step S91 ", see FIG. 12B].
Concavity and convexity processing on the heat-resistant substrate 111 can be performed by the same method as the stamper forming step S10 in the conductive pattern forming method according to the first embodiment.

After the concavo-convex processing step S91, the barrier layer 121 is formed on the surface of the heat-resistant base material 111 subjected to the concavo-convex processing on the side where the concave portions 111a and the convex portions 111b are formed ["barrier layer forming step S92", FIG. 12 (c). ].
This step can be performed in the same manner as the barrier layer forming step S81 in the conductive pattern forming method according to the fourth embodiment.

After the barrier layer forming step S92, a pyropolymer precursor polymer is applied on the barrier layer 121 of the heat-resistant substrate 111 to form the polymer layer 131 (see “polymer applying step S93”, FIG. 12D). .
This polymer coating step S93 can be performed in the same manner as the polymer coating step S21 in the conductive pattern forming method according to the first embodiment.

  After the polymer coating step S93, the concavo-convex shape is processed in the polymer layer 131 by photolithography to form an initial pattern corresponding to the conductive pattern ["photolithography step S94", see FIG. 12 (e)]. Instead of this step, a step similar to the embossing step S31 and the etching step in the conductive pattern forming method according to the first embodiment may be performed.

After the photolithography step S94, the heat resistant substrate 111 is heated in an oxygen-deficient atmosphere to thermally decompose the pyropolymer precursor polymer constituting the initial pattern, thereby forming the conductive pattern 132 made of the pyropolymer. (Refer to “pyrolysis step S95”, FIG. 13 (f)).
The thermal decomposition step S33 can be performed in the same manner as the thermal decomposition step S33 in the conductive pattern forming method according to the first embodiment.

  Thereafter, the heat-resistant substrate 111 and the low heat-resistant substrate are so arranged that the conductive pattern 132 in the heat-resistant substrate 111 and the surface of the low-heat-resistant substrate 141 on the side to which the conductive pattern 132 is transferred face each other and contact each other. 141 is set [see the setting step S96, FIG. 13 (g)].

After the setting step S96, the surface of the low heat resistant substrate 141 on which the conductive pattern is transferred is activated by vacuum ultraviolet treatment ["surface activation step S97", see FIG. 1 (h)].
The vacuum ultraviolet treatment can be performed in the same manner as the vacuum ultraviolet treatment in the conductive pattern forming method according to the fourth embodiment.

After the surface activation step S97, while heating, the conductive pattern 132 in the heat-resistant substrate 111 and the surface of the low heat-resistant substrate 141 on the side to which the conductive pattern 132 is transferred are brought into pressure contact with each other [“heating and pressing step S98 ", see FIG. 13 (i)].
The heating and pressing step S98 can be performed in the same manner as the heating and pressing step 42 in the conductive pattern forming method according to the first embodiment.

  Thereafter, the heat resistant substrate 111 is peeled off from the low heat resistant substrate 141, the conductive pattern 132 is peeled off from the heat resistant substrate 111, and the low heat resistant substrate 141 and the conductive pattern 132to are adhered ("peeling step S99"). "See FIG. 13 (j)).

  According to the method for forming a conductive pattern according to the fifth embodiment, the conductive pattern 132 having a concavo-convex structure composed of the concave portion 132a and the convex portion 132b on the heat-resistant substrate 111 in a good state with a low heat resistance substrate. 141 can be transferred. In addition, for example, a conductive pattern having a fine uneven structure as shown in FIGS. 14A and 14B can be formed.

[Other variations]
In FIG. 1, the biosensor has been described as an example. However, the substrate device of the present invention is not limited to this, and is a device provided with a conductive pattern made of a pyropolymer on a low heat resistant substrate. I just need it.
Examples of the substrate device according to the modification include a carbon contact switch, a flexible display, a flexible carbon solar cell, a fuel cell, and an electric double layer capacitor.

  Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

(Examples 1-4)
The surface of the silicon substrate 21a (see Example 1, FIG. 15 (a)), the surface of the quartz substrate 21b (see Example 2, FIG. 15 (b)), silicon nitride on the silicon substrate 21a Silicon oxide (SiO ₂ ) on the surface of the base material layer in the layered body in which the layer of the base material 21c made of (Si ₃ N ₄ ) is formed (see Example 3, FIG. 15C) and the silicon base material 21a. Each surface of the base material layer (see Example 4, FIG. 15 (d)) in the layered body in which the base material layer of the base material 21d was formed was subjected to 1-methoxy-2-propanol acetate (Clariant Corporation) by a spin coater. Manufactured and trade name: AZ P4620) was applied so that the thickness was 10 μm. The coated substrate was heated at 1000 ° C. for 120 minutes in a nitrogen atmosphere (oxygen-deficient atmosphere) to form a polymer layer 30a made of a pyropolymer on the substrate.

  Thereafter, the polymer layer 30a made of pyropolymer was cut into a grid pattern with a cutter knife, and the heat-resistant substrate models of Examples 1 to 4 (see FIGS. 10A to 10D, respectively). Got.

(Test Example 1)
An adhesive tape (mending tape, manufactured by Sumitomo 3M Co., Ltd., trade name: Scotch Mending Tape) is applied to the polymer layer 30a on the heat-resistant substrate model of Examples 1 to 4, and then the adhesive is applied from the substrate model. The tape was peeled off. Next, the state of the polymer layer 30a made of a pyropolymer attached to the adhesive tape after peeling was visually observed, and the degree of peelability of the pyropolymer from each base material model was evaluated. The evaluation criteria are as follows. The results are shown in Table 1.

〔Evaluation criteria〕
(Double-circle): The polymer layer 30a has adhered to the adhesive tape in the very favorable state, and the peelability of a pyropolymer is very favorable.
○: The polymer layer 30a is adhered to the adhesive tape in a good state, and the peelability of the pyropolymer is good.
X: The polymer layer 30a is not attached to the adhesive tape or is attached to the adhesive tape in an incomplete state, and the peelability of the pyropolymer is poor.

From the results shown in Table 1, all of the silicon substrate 21a, the quartz substrate 21b, the silicon nitride (Si ₃ N ₄ ) substrate 21c, and the silicon oxide (SiO ₂ ) substrate 21d, It is found that the pyropolymer is excellent in peelability, and in particular, the silicon nitride (Si ₃ N ₄ ) base material 21c can peel the pyropolymer very well.
Therefore, from these results, it is possible to use a base material made of silicon, quartz, silicon nitride or silicon oxide as the heat-resistant base material 21 or to dispose at least the surface on the side on which the conductive pattern is formed. It is suggested that the transfer of the conductive pattern from the conductive base material 21 to the low heat resistant substrate 41 can be performed satisfactorily. Among these, it is suggested that a substrate made of silicon nitride is particularly suitable.

(Experimental example 1)
1-methoxy-2-propanol acetate (manufactured by Clariant Corporation, trade name: AZ P4620) was applied to the surface of a silicon substrate (thickness: 525 nm) by a spin coater so that the thickness thereof was 800 nm. The coated substrate was heated at 1000 ° C. for 120 minutes under a nitrogen atmosphere (oxygen-deficient atmosphere) to form a polymer layer made of a pyropolymer on the substrate. Next, the polymer layer was cut into a grid pattern with a cutter knife to obtain a base material model of Experimental Example 1.

(Experimental Examples 2 to 4)
A barrier layer (Experimental Example 2) made of silicon oxide (SiO ₂ ) having a thickness of 200 nm and a barrier layer made of silicon oxide (SiO ₂ ) having a thickness of 500 nm are formed on the surface of a silicon substrate (thickness: 525 nm). Experimental Example 3) or a barrier layer (Experimental Example 4) made of silicon nitride (Si ₃ N ₄ ) having a thickness of 200 nm was formed. The barrier layer made of silicon oxide (SiO ₂ ) was formed by a steam thermal oxidation method. A barrier layer made of silicon nitride (Si ₃ N ₄ ) was formed by a plasma CVD method. Thereafter, 1-methoxy-2-propanol acetate (manufactured by Clariant Corporation, trade name: AZ P4620) was applied to the surface of the barrier layer by a spin coater so as to have a thickness of 800 nm. The coated substrate was heated at 1000 ° C. for 120 minutes under a nitrogen atmosphere (oxygen-deficient atmosphere) to form a polymer layer made of a pyropolymer on the substrate. Next, the polymer layer was cut into a grid pattern with a cutter knife to obtain base material models of Experimental Examples 2 to 4.

(Test Example 2)
An adhesive tape (mending tape, manufactured by Sumitomo 3M Co., Ltd., trade name: Scotch Mending Tape) was applied to the polymer layer on the base material model of Experimental Examples 1 to 4, and then the adhesive tape was peeled off from the model. . Next, the state of the polymer layer composed of the pyropolymer attached to the adhesive tape after peeling was observed with the naked eye, and the degree of peelability of the pyropolymer from each substrate model was evaluated. The evaluation criteria are as follows. The results are shown in Table 2.

〔Evaluation criteria〕
A: Compared with the degree of peelability of the pyropolymer from the base material model of Experimental Example 1, it is adhered to the adhesive tape in a very good state, and the peelability of the pyropolymer is very good.
◯: Compared with the degree of peelability of the pyropolymer from the base material model of Experimental Example 1, it is adhered to the adhesive tape in a good state, and the peelability of the pyropolymer is good.
(Triangle | delta): It is comparable as the degree of peelability of the pyropolymer from the base material model of Experimental Example 1.
X: Compared with the degree of peelability of the pyropolymer from the base material model of Experimental Example 1, the peelability of the pyropolymer is poor.

From the results shown in Table 2, when a barrier layer is formed on the surface of a silicon substrate that is a heat resistant substrate, the peelability of the pyropolymer from the substrate model of Experimental Example 1 having no barrier layer It can be seen that the same or better peelability can be obtained. Especially, it turns out that the base material of Experimental Example 4 having a barrier layer made of silicon nitride (Si ₃ N ₄ ) can peel the pyropolymer very well. Further, when a barrier layer of silicon oxide (SiO _2), by the thickness of the barrier layer and above 500 nm, it is understood that it is possible to separate the good pyropolymer.
Therefore, these results suggest that the peelability of the pyropolymer from the heat resistant substrate can be improved by forming a barrier layer on the surface of the heat resistant substrate. Among these, it is suggested that a barrier layer made of silicon nitride is particularly suitable.

(Experimental example 5)
1-methoxy-2-propanol acetate (manufactured by Clariant Corporation, trade name: AZ P4620) was applied to the surface of a silicon substrate (thickness: 525 nm) by a spin coater so that the thickness thereof was 800 nm. The coated substrate was heated at 1000 ° C. for 120 minutes under a nitrogen atmosphere (oxygen-deficient atmosphere) to form a polymer layer made of a pyropolymer on the substrate. Next, a metal layer made of gold was formed as a wiring pattern model on the polymer layer by resistance heating vacuum deposition.

  Thereafter, the metal layer and the polymer layer were cut into a grid pattern with a cutter knife to obtain a base material model.

(Experimental Examples 6-9)
1-methoxy-2-propanol acetate (manufactured by Clariant Corporation, trade name: AZ P4620) was applied to the surface of a silicon substrate (thickness: 525 nm) by a spin coater so that the thickness thereof was 800 nm. The coated substrate was heated at 1000 ° C. for 120 minutes under a nitrogen atmosphere (oxygen-deficient atmosphere) to form a polymer layer made of a pyropolymer on the substrate. Next, a metal layer made of gold was formed as a wiring pattern model on the polymer layer by resistance heating vacuum deposition.

  Thereafter, the substrate was heated at 300 ° C. for 2 hours (Experimental Example 6), at 600 ° C. for 2 hours (Experimental Example 7), at 800 ° C. for 2 hours (Experimental Example 8), or at 1064 ° C. for 2 hours (Experimental Example 9). did. Next, the metal layer and the polymer layer were cut in a grid pattern with a cutter knife to obtain a base material model.

(Test Example 3)
An adhesive tape (mending tape, manufactured by Sumitomo 3M Co., Ltd., trade name: Scotch Mending Tape) was applied to the polymer layer on the base material models of Experimental Examples 5 to 9, and then the adhesive tape was peeled off from the model. . Next, the state of the polymer layer composed of the pyropolymer attached to the adhesive tape after peeling was observed with the naked eye, and the degree of peelability of the pyropolymer from each substrate model was evaluated. The evaluation criteria are as follows. The results are shown in Table 3.

〔Evaluation criteria〕
(Double-circle): Both gold | metal | money and a pyropolymer have adhered to the adhesive tape in the very favorable state, and the peelability of both gold | metal | money and a pyropolymer is very favorable.
○: Both gold and pyropolymer are attached to the adhesive tape.
X: Either gold | metal | money and a pyropolymer have not adhered to the adhesive tape at all.

  From the results shown in Table 3, when both the conductive pattern made of pyropolymer and the wiring pattern made of metal are simultaneously transferred to a low heat resistant substrate, the conductive pattern made of pyropolymer is transferred prior to transfer. Further, it is suggested that it is desirable to heat the heat-resistant substrate on which the wiring pattern made of metal is formed.

10 Stamper 11 Stamper Shape 12 Photoresist Layer 21 Heat Resistant Base Material 30 Conductive Pattern 31 Polymer Layer 41 Low Heat Resistant Substrate 61 Barrier Layer 71 Wiring Pattern 111 Heat Resistant Substrate 121 Barrier Layer 131 Polymer Layer 132 Conductive Pattern 141 Low heat resistant substrate A Exposed part

Claims (8)

A method for forming a conductive pattern that forms a conductive pattern made of a pyropolymer on the surface of a low heat resistant substrate,
(A) A heat-resistant substrate different from the low-heat-resistant substrate on which a conductive pattern made of a pyropolymer is formed, and having a pyrol on a heat-resistant substrate having a heat-resistant temperature higher than that of the low-heat-resistant substrate. Forming an initial pattern corresponding to the conductive pattern with a polymer precursor polymer;
(B) heating the precursor polymer constituting the initial pattern on the heat resistant substrate in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat resistant substrate; C) The conductive pattern formed on the heat-resistant substrate has a heat-resistant temperature lower than that of the heat-resistant substrate and the heat-resistant temperature lower than the heating temperature when forming the pyropolymer. Including a step of transferring onto a heat-resistant substrate,
In the step (B), the precursor polymer constituting the initial pattern on the heat-resistant substrate is heated in an oxygen-deficient atmosphere to form a conductive pattern made of a pyropolymer on the heat-resistant substrate. And further forming a wiring pattern made of metal on the surface of the heat-resistant substrate on which the conductive pattern is formed,
After the step (B), by heating the heat-resistant substrate on which the conductive pattern and the wiring pattern are formed, the metal constituting the wiring pattern and the pyrol constituting the conductive pattern are formed. In addition to improving the adhesion between the polymer and the conductive pattern formed on the heat resistant substrate in the step (C), the wiring pattern formed on the heat resistant substrate is formed on the low heat resistant substrate. A method for forming a conductive pattern, which is transferred onto the conductive pattern.   In the step (A), the stamper having a stamped surface on which a polymer layer made of a precursor polymer of a pyropolymer is formed on a heat resistant substrate and an uneven shape obtained by inverting the uneven shape of the conductive pattern is formed. The method for forming a conductive pattern according to claim 1, wherein an initial pattern is formed by pressing a stamping surface against the polymer layer and further etching a recess formed in the polymer layer. Prior to the step (A),
(A) a step of forming a photoresist layer on the surface of the stamper profile;
(B) a step of aligning a mask provided with a reversal pattern obtained by reversing the conductive pattern with respect to the shaped material, and exposing the photoresist layer;
(C) developing the exposed photoresist layer;
(D) A step of forming the reversal pattern on the shaped material by etching the exposed portion of the shaped material exposed from the developed photoresist layer. (E) A photoresist from the shaped material on which the reversal pattern is formed. Removing the layer;
The method for forming a conductive pattern according to claim 1, further comprising a step of manufacturing a stamper including   The heat resistant substrate after transferring the conductive pattern onto the low heat resistant substrate in the step (D) is further used as a heat resistant substrate in the step (A). The formation method of the electroconductive pattern of description.   The method for forming a conductive pattern according to claim 1, wherein the low heat resistant substrate is a sensor substrate, and the conductive pattern is an electrode of the sensor.   Prior to the step (A), the conductive layer according to any one of claims 1 to 5, wherein a barrier layer is formed on the surface of the heat resistant substrate to improve the peelability between the heat resistant substrate and the conductive pattern. Pattern formation method. A low heat resistant substrate,
A transfer pattern formed on the low heat-resistant substrate;
A board device having,
The transfer pattern has a conductive pattern made of pyropolymer and a wiring pattern made of metal,
The low heat resistant substrate, have a heat resistant temperature lower than the heating temperature for forming the pyropolymer,
The transfer pattern in a state where said pyropolymer constituting the metal and the conductive pattern constituting the wiring pattern is adhered by heating, characterized in der Rukoto what the transferred to the low heat resistant substrate A substrate device.   The substrate device according to claim 7, wherein the substrate device is a sensor.