JP4905038B2 - Conductive pattern substrate and manufacturing method thereof - Google Patents

Description

  The present invention is applied to, for example, an organic electroluminescence element, a solar cell, an organic semiconductor, an organic thin film transistor, and the like, and relates to a conductive pattern substrate using a polythiophene derivative and a method for manufacturing the same.

  In recent years, conductive polymers represented by polythiophene derivatives have been used in various fields. In particular, the conductive polymer is an electron such as organic electroluminescence (hereinafter, electroluminescence may be abbreviated as EL), an organic semiconductor, an organic thin film transistor (hereinafter, the thin film transistor may be abbreviated as TFT), and a solar cell. Much research has been done to introduce it into devices.

  When using a conductive polymer for an electrode or the like in an electronic device, it is necessary to form the conductive polymer in a pattern. Conventionally, patterning of a conductive polymer film has been studied using printing techniques such as screen printing, gravure printing, offset printing, flexographic printing, and inkjet. However, it has been very difficult to form a high-definition pattern having a line width of 10 μm or less with these printing techniques.

  Among conductive polymers, polythiophene derivatives such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) are easy to form, so a hole injection layer in an organic EL element, organic Widely used for electrodes in EL elements, solar cells, organic semiconductors, organic TFTs, and the like.

  As a method of patterning the polythiophene derivative film, for example, a soluble polythiophene derivative is formed on the entire surface of the substrate, and the irradiated portion of the polythiophene film is insolubilized by irradiating the polythiophene film with ultraviolet rays or a laser. A method is disclosed in which a part is removed to form a pattern, and a polythiophene derivative is oxidized with an iron salt or a gold salt to impart conductivity to the pattern (see Patent Document 1). However, this method has problems that an oxidizing agent such as an iron salt and a gold salt is expensive, and that a complicated apparatus is required when a laser is used.

  As a method for patterning a polythiophene derivative film, for example, a composition containing poly (3,4-substituted thiophene) and a photoinitiator is formed on a substrate, and the polythiophene film is irradiated with ultraviolet rays. A method of forming a pattern by curing an irradiated portion of a polythiophene film and removing an unirradiated portion of the polythiophene film is disclosed (see Patent Document 2). In this method, since it is not necessary to use an oxidizing agent and a laser, the above problem can be solved. However, this method has a problem that a special photoinitiator is required.

  Furthermore, in any of the above methods, the characteristics of the polythiophene derivative may be deteriorated because an oxidizing agent or a photoreaction initiator is added and the portion where the pattern is formed is irradiated with ultraviolet rays or the like. There is.

US Pat. No. 5,561,030 Special table 2003-509869

  The present invention has been made in view of the above problems, and is a conductive pattern substrate having a conductive pattern using a polythiophene derivative and a method for manufacturing the same, and the conductive pattern substrate in which the characteristics of the polythiophene derivative are unlikely to deteriorate And a method for manufacturing the same.

  As a result of intensive studies in view of the above circumstances, the present inventors have radiated electromagnetic waves to polythiophene derivatives such as poly (3,4-alkylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS). It was found that / PSS reacts photochemically to change the solubility and conductivity of the irradiated part in the solvent. Specifically, PEDOT / PSS is photochemically reacted and denatured by the irradiation of electromagnetic waves, and the irradiated part of PEDOT / PSS becomes soluble in solvents that are less polar than water, ethanol, etc., and PEDOT The present inventors have found that the conductivity of the irradiated part of / PSS is lowered and have reached the present invention.

  That is, the present invention includes a substrate and a polythiophene layer formed on the substrate and containing a conductive polythiophene derivative, and the polythiophene layer has a conductive portion having conductivity and a conductivity. There is provided a conductive pattern substrate characterized by having a non-conductive portion that does not.

According to the present invention, by utilizing the change in the conductivity of the polythiophene derivative due to the irradiation of electromagnetic waves as described above, the region where the electromagnetic waves are irradiated and the conductivity is reduced (non-conductive portion having no conductivity) and Thus, it is possible to obtain a polythiophene layer having a region in which conductivity is maintained without being irradiated with electromagnetic waves (conductive portion having conductivity). In this polythiophene layer, since the conductive portion constitutes a conductive pattern that conducts electricity, the conductive pattern does not require an additive and does not irradiate an electromagnetic wave to a portion where the conductive pattern is formed. Can be obtained. Therefore, deterioration of the characteristics of the polythiophene derivative can be prevented.
In addition, since the polythiophene layer is formed flush with the substrate, there is no step between the conductive portion and the non-conductive portion, so that a conductive pattern substrate having no step can be obtained. Therefore, when the conductive pattern substrate of the present invention is used for an electronic device or the like, other layers can be uniformly formed on the polythiophene layer.
Furthermore, since the polythiophene layer containing a polythiophene derivative that is a polymer material has flexibility, a flexible electronic device can be obtained by using the conductive pattern substrate of the present invention.

  In the above invention, the polythiophene derivative is preferably poly (3,4-alkylenedioxythiophene) doped with an acid. This is because the conductivity can be easily changed by changing the blending ratio of poly (3,4-alkylenedioxythiophene) and acid.

  In the present invention, a conductive layer forming step of forming a conductive layer containing a conductive polythiophene derivative on a substrate, and irradiating the conductive layer with electromagnetic waves in a pattern, There is provided a method for producing a conductive pattern substrate, characterized by having an electromagnetic wave irradiation step of forming a conductive part having conductivity and a non-conductive part not having conductivity, by reducing conductivity.

  According to the present invention, by utilizing the change in conductivity of the polythiophene derivative due to the irradiation of electromagnetic waves as described above, the conductive portion is formed by irradiating the conductive layer with electromagnetic waves in a pattern without requiring an additive. It can be formed in a pattern. Moreover, since the unirradiated portion of the conductive layer becomes a conductive portion, the conductive portion is not directly irradiated with electromagnetic waves. Therefore, it is possible to avoid deterioration of the characteristics of the polythiophene derivative due to the irradiation of the additive or electromagnetic wave.

  In the said invention, you may perform the image development process which develops the said conductive layer and removes the irradiation part of the said conductive layer after the said electromagnetic wave irradiation process. By utilizing the change in the solubility of the polythiophene derivative in the solvent due to the electromagnetic wave irradiation as described above, only the non-conductive part, which is the irradiated part of the conductive layer, can be developed using a predetermined solvent. This is because it is possible to completely insulate between the patterns of the conductive portions which are unirradiated portions of the layer.

  In the present invention, the polythiophene derivative is preferably poly (3,4-alkylenedioxythiophene) doped with an acid. This is because, as described above, the conductivity can be easily changed by changing the blending ratio of poly (3,4-alkylenedioxythiophene) and acid.

  Furthermore, in the present invention, the electromagnetic wave is preferably visible light or ultraviolet light having a wavelength of 500 nm or less. This is because the photochemical reaction of the polythiophene derivative can be favorably progressed by irradiating such an electromagnetic wave.

  In the present invention, the electromagnetic wave irradiation step is preferably performed in an oxygen atmosphere. This is because the photochemical reaction of the polythiophene derivative, particularly the photodecomposition reaction, is promoted by the oxidation action.

  In the present invention, a conductive pattern substrate can be obtained by utilizing the change in conductivity of the polythiophene derivative due to irradiation of electromagnetic waves as described above, and the characteristics of the polythiophene derivative can be deteriorated by irradiation of additives and electromagnetic waves. There is an effect that it can be prevented.

  Hereinafter, the conductive pattern substrate and the method for producing the conductive pattern substrate of the present invention will be described in detail.

A. Conductive pattern substrate First, the conductive pattern substrate of the present invention will be described.
The conductive pattern substrate of the present invention includes a substrate, and a polythiophene layer formed on the substrate and containing a conductive polythiophene derivative. The polythiophene layer includes a conductive portion having conductivity, a conductive portion And a non-conductive portion having no property.

  Polythiophene derivatives such as the following structural formula (1)

When poly (3,4-alkylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) shown in FIG. 2 is irradiated with electromagnetic waves, the physical properties of the irradiated part change, for example, the conductivity decreases. It is assumed that PEDOT / PSS is photochemically reacted and denatured by electromagnetic wave irradiation, and the conductivity changes. For example, Synthetic Metals, 141 (2004) p67, S. Marciniak et al. Shows that the thiophene skeleton is oxidatively decomposed. From this, it is considered that the thiophene skeleton of PEDOT is photooxidized, photodegraded, etc. by the irradiation of electromagnetic waves, and the conductivity is changed.

  As described above, when the polythiophene derivative is irradiated with electromagnetic waves, the conductivity of the irradiated portion is reduced. Therefore, by irradiating the layer containing the polythiophene derivative with electromagnetic waves in a pattern, the irradiated portion is reduced in conductivity. The region (non-conductive portion having no conductivity) and the non-irradiated portion can be made a region (conducting portion having conductivity) in which conductivity is maintained.

The conductive pattern substrate of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a conductive pattern substrate of the present invention. As illustrated in FIG. 1, a conductive pattern substrate 1 includes a substrate 2, a polythiophene derivative formed on the substrate 2, containing a conductive polythiophene derivative, and having a conductive portion 4 and a nonconductive portion 5. Layer 3.

  In the present invention, as described above, a polythiophene layer having a conductive portion and a nonconductive portion can be obtained by irradiating a layer containing a polythiophene derivative with electromagnetic waves in a pattern. The conductive portion is a region in which conductivity is maintained and has conductivity, whereas the non-conductive portion is a region in which conductivity is lowered and does not have conductivity. That is, only the conductive part can conduct electricity satisfactorily. Therefore, in the conductive pattern substrate of the present invention, the conductive portion of the polythiophene layer becomes a conductive pattern that conducts electricity.

  According to the present invention, since the polythiophene layer having the conductive portion and the nonconductive portion is formed on the same plane on the substrate, no step is generated between the conductive portion and the nonconductive portion. It can be set as the electroconductive pattern board | substrate without this. For this reason, when the conductive pattern is used as an electrode in an electronic device such as an organic EL element, a solar cell, an organic semiconductor, or an organic TFT, the surface of the polythiophene layer is flat. Other layers can be formed uniformly on the pattern. Further, when the conductive pattern is used as, for example, a hole injection layer in an organic EL element, since the surface of the polythiophene layer is flat as in the above case, the polythiophene layer is formed on the polythiophene layer, that is, the hole injection layer. Other layers can be uniformly formed on the pattern, and since there is no step due to the pattern of the hole injection layer, it is possible to avoid disconnection of the electrode due to the step.

  In addition, the conductive portion can be formed in a pattern by irradiating the layer containing the polythiophene derivative with an electromagnetic wave in a pattern without requiring an additive such as an oxidizing agent or a photoreaction initiator. Therefore, deterioration of the properties of the polythiophene derivative due to the additive can be avoided. Furthermore, since the irradiated portion is a non-conductive portion and the non-irradiated portion is a conductive portion, deterioration of the characteristics of the polythiophene derivative due to irradiation of electromagnetic waves can be avoided in the conductive portion.

  Furthermore, since the polythiophene derivative is a polymer material, the polythiophene layer containing the polythiophene derivative has flexibility. For this reason, a flexible electronic device can be obtained by using a conductive pattern as an electrode in an electronic device, for example.

  Hereinafter, each structure in the electroconductive pattern board | substrate of this invention is demonstrated.

1. Polythiophene layer The polythiophene layer used in the present invention is formed on a substrate and contains a conductive polythiophene derivative, and has a conductive portion having conductivity and a non-conductive portion having no conductivity. It is what you have.

  The polythiophene derivative used in the present invention is not particularly limited as long as it has electrical conductivity. Usually, a polythiophene derivative doped with an acid is used. This is because the conductivity of the polythiophene derivative is improved by doping the acid.

  The polythiophene derivative doped with an acid may be either a polythiophene simple substance or a derivative in which a functional group is added to the polythiophene skeleton. Examples of the derivative in which a functional group is added to the polythiophene skeleton include poly (3,4-alkylenedioxythiophene). Examples of the alkylene group in the poly (3,4-alkylenedioxythiophene) include ethylene, 1,2-cyclohexylene, phenylethylene, propylethylene, methylene, 1,3-propylene and the like.

  Examples of the acid to be doped include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, polyperfluorosulfonic acid, and the like.

  As the polythiophene derivative doped with an acid, poly (3,4-alkylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) or the like is preferably used. This is because PEDOT / PSS is commercially available and is easily available. In addition, the conductivity can be easily changed by changing the blending ratio of PEDOT and PSS.

  The polythiophene layer has a conductive portion having conductivity and a non-conductive portion not having conductivity. Here, the non-conductive portion refers to a region having lower conductivity than the conductive portion.

  The difference in conductivity between the conductive part and the non-conductive part is not particularly limited, but the ratio of the conductivity in the non-conductive part to the conductivity (unit: S / cm) in the conductive part is When the conductivity in the conductive portion is 100, it is preferably 70 or less, more preferably 50 or less, and still more preferably 30 or less.

The non-conductive portion is not particularly limited as long as it has a lower conductivity than the conductive portion, but preferably has a predetermined insulating property. Specifically, the electrical resistance in the non-conductive portion is preferably 10 ⁴ Ω · cm or more, more preferably 10 ⁵ Ω · cm or more, and further preferably 10 ⁶ Ω · cm or more. If the electrical resistance of the non-conductive portion is in the above range, electricity can be conducted only to the conductive portion, and a conductive pattern composed of the conductive portion can be used in, for example, an electrode in an electronic device or an organic EL element. This is because the function can be sufficiently exerted when used as a hole injection layer or the like.

  In addition, as a method for measuring the above-described conductivity and electrical resistance, a general resistivity meter is used to measure the material itself constituting the conductive portion and the non-conductive portion, or the entire surface of the layer is conductive. Element and the entire surface of the layer are non-conductive parts, and the current-voltage characteristics of these elements are measured using a source meter or the like. Methods for calculating conductivity and electrical resistance can be used.

  Further, as described above, the non-conductive portion may be a region having lower conductivity than the conductive portion, and the conductivity in the non-conductive portion may be uniform or non-uniform.

The pattern shape of the conductive portion is appropriately selected according to the use of the conductive pattern substrate of the present invention.
Similarly, the area ratio between the conductive part and the non-conductive part is appropriately selected according to the use of the conductive pattern substrate of the present invention.
Furthermore, the width of the pattern of the conductive portion is also appropriately selected according to the use of the conductive pattern substrate of the present invention.

  The film thickness of the polythiophene layer is not particularly limited as long as it can cause a photochemical reaction when irradiated with electromagnetic waves, and is appropriately selected according to the use of the conductive pattern substrate of the present invention. Specifically, the film thickness of the polythiophene layer can be set to about 10 nm to 1 μm. If the film thickness of the polythiophene layer is too thick, electromagnetic waves will not reach the deep part of the polythiophene layer, making it difficult for photochemical reaction to occur, or it takes a long time to react photochemically to the deep part of the polythiophene layer, producing This is because the efficiency may decrease. In addition, if the thickness of the polythiophene layer is too thin, for example, the conductive pattern composed of the conductive portion may not function as an electrode or the like, or it may be difficult to form a uniform polythiophene layer on the substrate. Because there is.

2. Substrate The substrate used in the present invention is appropriately selected according to the use of the conductive pattern substrate of the present invention, and is generally an electron such as an organic EL element, a solar cell, an organic semiconductor, and an organic TFT. The substrate used for the device can be used.

The substrate may or may not have transparency. About transparency of a board | substrate, as described in the use of the electroconductive pattern board | substrate of this invention, and the term of the "B. manufacturing method of an electroconductive pattern board | substrate" mentioned later, according to the electromagnetic wave irradiation direction in an electromagnetic wave irradiation process, etc. Are appropriately selected.
For example, when the conductive pattern substrate of the present invention is applied to an organic EL element and light is extracted from the substrate side, the substrate is required to be transparent. In addition, when the conductive pattern of the present invention is applied to a solar cell and receives light from the substrate side, the substrate is required to be transparent. On the other hand, when the conductive pattern of the present invention is applied to an organic semiconductor or an organic TFT, the substrate is not required to be transparent.
Further, for example, in the process of manufacturing the conductive pattern substrate of the present invention, when an electromagnetic wave is irradiated from the substrate side, the substrate is required to be transparent. On the other hand, when the electromagnetic wave is irradiated from the polythiophene layer side (conductive layer side), the substrate is not required to be transparent.

  The substrate may be flexible, such as a resin film, or may be non-flexible, such as a glass substrate. Among these, the substrate is preferably flexible. This is because the polythiophene layer is made of a polythiophene derivative that is a polymer material and has flexibility, so that if the substrate has flexibility, a flexible conductive pattern substrate can be obtained. . Thereby, a flexible electronic device can be obtained by using the conductive pattern substrate of the present invention.

3. Applications The conductive pattern substrate of the present invention can be applied to electronic devices such as organic EL elements, solar cells, organic semiconductors, organic TFTs, RFID (Radio Frequency Identification), and computer memories. Specifically, the conductive pattern can be used for electrodes in organic EL elements, solar cells, organic semiconductors, organic TFTs, hole injection layers in organic EL elements, RFID tags, and the like.

4). Other Configurations When the conductive pattern substrate of the present invention is used for the above-described uses, various layers are formed between the substrate and the polythiophene layer depending on the use.
For example, when the conductive pattern is used as a hole injection layer in an organic EL element, an anode (lower electrode) is formed between the substrate and the polythiophene layer. When the conductive pattern is used as a cathode (upper electrode) in an organic EL element, an anode (lower electrode), a light emitting layer, and the like are formed between the substrate and the polythiophene layer. Further, when the conductive pattern is used as an upper electrode in a solar cell, a lower electrode, a semiconductor layer, and the like are formed between the substrate and the polythiophene layer. Further, when the conductive pattern is used as a gate electrode, a source electrode, and a drain electrode in an organic TFT, a semiconductor layer, an insulating layer, and the like are formed between the substrate and the polythiophene layer.

  FIG. 2 is an example in which the conductive pattern substrate of the present invention is used for an organic EL element, and is an example in which the conductive pattern is used as a hole injection layer in the organic EL element. The organic EL element 11 illustrated in FIG. 2 is formed on the entire surface of the substrate 2 so as to cover the substrate 2, the anode (lower electrode) 12 formed in a pattern on the substrate 2, and the anode 12. 4 and a non-conductive portion 5, a light emitting layer 13 formed on the polythiophene layer 3, and a cathode (upper electrode) 14 formed on the light emitting layer 13. In this organic EL element 11, the conductive portion 4 in the polythiophene layer 3 can function as a hole injection layer, and the nonconductive portion 5 can function as an insulating layer.

  In addition, since the manufacturing method of the conductive pattern board | substrate of this invention is described in detail in the term of the "B. manufacturing method of a conductive pattern board | substrate" mentioned later, description here is abbreviate | omitted.

B. Next, a method for manufacturing a conductive pattern substrate of the present invention will be described.
The method for producing a conductive pattern substrate of the present invention includes a conductive layer forming step of forming a conductive layer containing a conductive polythiophene derivative on a substrate, and irradiating the conductive layer with electromagnetic waves in a pattern, It has an electromagnetic wave irradiation step of reducing the conductivity of the irradiated portion of the conductive layer to form a conductive portion having conductivity and a non-conductive portion not having conductivity.

  As described in the above section “A. Conductive pattern substrate”, the polythiophene derivative is reduced in the conductivity of the irradiated portion when irradiated with an electromagnetic wave. Therefore, the polythiophene derivative has a pattern on the conductive layer containing the polythiophene derivative. By irradiating, it is possible to form a region with reduced conductivity (non-conductive portion having no conductivity) and a region with conductivity maintained (conductive portion with conductivity).

The manufacturing method of the conductive pattern board | substrate of this invention is demonstrated referring drawings.
FIG. 3 is a process diagram showing an example of a method for producing a conductive pattern substrate of the present invention. First, a conductive layer 3 ′ containing a conductive polythiophene derivative is formed on the substrate 2 (FIG. 3A, a conductive layer forming step). Next, a photomask 21 on which a required pattern is drawn is placed on the conductive layer 3 'side, and ultraviolet rays 22 are irradiated through the photomask 21 (FIG. 3B). Thereby, the electroconductivity of the irradiation part of a conductive layer falls, the electroconductive part 4 and the nonelectroconductive part 5 are formed, and the electroconductive pattern comprised from the electroconductive part 4 can be formed (FIG. 3). (C)). 3B and 3C show an electromagnetic wave irradiation process.

  In the present invention, as described above, the conductive portion and the nonconductive portion can be formed by irradiating the conductive layer with electromagnetic waves in a pattern. Thereby, an electroconductive part can be formed in pattern shape, ie, an electroconductive pattern can be formed.

  According to the present invention, the conductivity of the irradiated portion of the conductive layer is reduced by irradiating the conductive layer with electromagnetic waves in a pattern without requiring an additive such as an oxidizing agent or a photoreaction initiator. Thus, the conductive portion can be formed in a pattern. Further, since the irradiated portion of the conductive layer is a non-conductive portion and the non-irradiated portion is a conductive portion, the conductive portion is not directly irradiated with electromagnetic waves. Therefore, it is possible to avoid deterioration of the characteristics of the polythiophene derivative due to the irradiation of the additive or electromagnetic wave.

  In addition, since the conductive layer containing the polythiophene derivative that is a polymer material has flexibility, it is possible to obtain a conductive pattern substrate that can be applied to a flexible electronic device.

  Furthermore, in general, metal materials used for electrodes and the like in electronic devices use dry processes such as vacuum deposition and sputtering as film formation methods, whereas polythiophene derivatives use spin coating and printing as film formation methods. A wet process such as a method can be used. Therefore, in the present invention, the conductive pattern substrate can be mass-produced without requiring expensive equipment such as vacuum equipment.

  Further, in the method of manufacturing the conductive pattern substrate as illustrated in FIG. 3, the non-conductive portion is left without being removed, so that no step is generated between the conductive portion and the non-conductive portion. A conductive pattern substrate free from the above can be obtained. For this reason, when producing an electronic device using the manufacturing method of the conductive pattern board | substrate of this invention, another layer can be formed uniformly on a conductive part and a nonelectroconductive part. In addition, when forming the hole injection layer in the organic EL element using the method for manufacturing the conductive pattern substrate of the present invention, there is no step due to the pattern of the hole injection layer, and therefore the electrode is disconnected by the step. Can also be avoided.

  In addition, when a polythiophene derivative such as PEDOT / PSS is irradiated with an electromagnetic wave, the physical properties of the irradiated part change, and not only the conductivity as described above but also the solubility in a solvent changes. Originally, PEDOT / PSS is soluble only in very polar solvents such as water and some alcohols such as ethanol. However, PEDOT / PSS is dissolved in a solvent having a lower polarity than water and alcohols when irradiated with electromagnetic waves. It is assumed that PEDOT / PSS is photochemically reacted and denatured by irradiation with electromagnetic waves, and the solubility in a solvent is changed. Specifically, it is considered that the solubility of the thiophene skeleton of PEDOT is changed by photo-oxidation, photolysis, etc.

  As described above, when the polythiophene derivative is irradiated with electromagnetic waves, the solubility of the irradiated portion in the solvent changes, so that the solubility of the solvent can be made different between the irradiated portion and the unirradiated portion. Thereby, it becomes possible to remove only an irradiated part by developing using a predetermined solvent.

  FIG. 4 is a process diagram showing another example of the method for producing a conductive pattern substrate of the present invention. First, a conductive layer 3 ′ containing a conductive polythiophene derivative is formed on the substrate 2 (FIG. 4A, a conductive layer forming step). Next, a photomask 21 on which a required pattern is drawn is disposed on the conductive layer 3 'side, and ultraviolet rays 22 are irradiated through the photomask 21 (FIG. 4B). Thereby, the electroconductivity of the irradiated part of a conductive layer falls and the electroconductive part 4 and the nonelectroconductive part 5 are formed (FIG.4 (c)). At this time, the solubility of the irradiated portion of the conductive layer in the solvent also changes, and the irradiated portion (nonconductive portion 5) is dissolved in a solvent having a lower polarity than water and alcohols. 4B and 4C show an electromagnetic wave irradiation process. Next, for example, acetone is used as a developing solution to dissolve only the non-conductive portion 5 that is the irradiated portion (FIG. 4D, developing step).

  In the present invention, as illustrated in FIG. 4, after the electromagnetic wave irradiation step, a development step of developing the conductive layer and removing the irradiated portion of the conductive layer may be performed. As described above, since the solubility of the solvent can be made different between the irradiated portion and the unirradiated portion, only the irradiated portion can be removed by developing with a predetermined solvent. Thereby, it is possible to completely insulate between the conductive parts by removing the non-conductive parts.

  In the present invention, the conductive portion can be formed in a pattern by irradiating the conductive layer with an electromagnetic wave in a pattern, and further, the conductive layer after the electromagnetic wave irradiation is developed using a predetermined solvent. By doing so, only the non-conductive portion can be removed. That is, a conductive pattern can be obtained using a photolithography method. Therefore, high-definition patterning is possible as compared with conventional patterning by a printing method or the like.

  Hereinafter, each process in the manufacturing method of the electroconductive pattern board | substrate of this invention is demonstrated.

1. Conductive layer forming step The conductive layer forming step in the present invention is a step of forming a conductive layer containing a conductive polythiophene derivative on a substrate.

  As a method for forming a conductive layer, a polythiophene derivative is dissolved or dispersed in a solvent to prepare a conductive layer forming coating solution, and this conductive layer forming coating solution is applied onto a substrate, or a polythiophene derivative is used. A method of electrodepositing on a substrate can be used. Among these, from the viewpoint of productivity, a method of applying a conductive layer forming coating solution is preferably used.

  The solvent used in the coating liquid for forming the conductive layer is not particularly limited as long as it can dissolve or disperse the polythiophene derivative. For example, water and alcohols such as ethanol and isopropanol There can be mentioned. Water and alcohols may be mixed and used.

  The solid content concentration of the conductive layer forming coating solution is appropriately adjusted according to the method of applying the conductive layer forming coating solution.

  The method for applying the coating liquid for forming the conductive layer is not particularly limited as long as it is a method capable of applying the coating liquid for forming the conductive layer to the entire surface of the substrate, and the polythiophene derivative used Or, it is appropriately selected according to the viscosity of the coating liquid for forming the conductive layer. Specifically, examples of the method for applying the conductive layer forming coating liquid include spin coating, screen printing, gravure printing, offset printing, flexographic printing, and the like.

  The conductive layer forming coating solution may be applied to the entire surface of the substrate, or may be applied in a pattern on the substrate, but the conductive layer is irradiated with electromagnetic waves in a pattern in an electromagnetic wave irradiation step described later. Thus, the conductive part can be formed in a pattern, and therefore, a conductive layer forming coating solution is usually applied to the entire surface of the substrate.

  The thickness of the conductive layer is not particularly limited as long as a photochemical reaction can occur upon irradiation with electromagnetic waves, and is appropriately selected according to the use of the conductive pattern substrate. Specifically, the film thickness of the conductive layer can be set to about 10 nm to 1 μm. If the conductive layer is too thick, the electromagnetic wave will not reach the deep part of the conductive layer, making it difficult for photochemical reactions to occur, or it takes a long time to react photochemically to the deep part of the conductive layer. This is because the efficiency may decrease. Further, if the conductive layer is too thin, for example, the conductive pattern composed of the conductive portion may not function as an electrode or the like, or it may be difficult to form a uniform conductive layer on the substrate. Because there is.

  The polythiophene derivative and the substrate are the same as those described in the above section “A. Conductive pattern substrate”, and thus description thereof is omitted here.

2. Electromagnetic wave irradiation process The electromagnetic wave irradiation process in this invention irradiates an electroconductive layer with electromagnetic waves in a pattern shape, reduces the electroconductivity of the irradiation part of an electroconductive layer, and has the electroconductive part which has electroconductivity, and non-conductivity This is a step of forming a conductive portion.

  The electromagnetic wave in the present invention is a concept including any electromagnetic wave that can change the conductivity of the conductive layer, and is not limited to ultraviolet rays and visible light.

  The electromagnetic wave is preferably visible light having a wavelength of 500 nm or less, or ultraviolet light. That is, the wavelength of the electromagnetic wave is preferably about 100 nm to 500 nm. This is because when the wavelength of the electromagnetic wave is within the above range, the photochemical reaction of the polythiophene derivative proceeds well. Among these, the wavelength of the electromagnetic wave is preferably in the range of 100 nm to 350 nm or in the range of 400 nm to 500 nm, and particularly preferably in the range of 200 nm to 300 nm. This is because polythiophene derivatives are particularly sensitive to light of these wavelengths.

  The method for irradiating electromagnetic waves is not particularly limited as long as it can irradiate the conductive layer with electromagnetic waves in a pattern, and even if the method irradiates the electromagnetic waves in a pattern through a photomask. A method of drawing irradiation with a laser may be used.

  The light source used for electromagnetic wave irradiation is not particularly limited as long as there is no possibility of degrading the polythiophene derivative, and is appropriately selected according to the electromagnetic wave irradiation method. When using a photomask, examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, and an excimer lamp. In the case of drawing irradiation, a laser such as excimer or YAG can be used as the light source. In the case of using a laser, it is preferable to perform drawing irradiation with relatively low energy so as not to deteriorate the polythiophene derivative.

  The irradiation amount of the electromagnetic wave may be an irradiation amount necessary for changing the conductivity of the conductive layer and the solubility in a solvent.

  Further, the electromagnetic wave irradiation time may be a time required to change the conductivity of the conductive layer and the solubility in a solvent. For example, when the film thickness of the conductive layer is relatively large, the photochemical reaction of the polythiophene derivative can be caused to a deep portion of the conductive layer by relatively increasing the irradiation time of the electromagnetic wave.

  The electromagnetic wave irradiation direction may be either the substrate side or the conductive layer side.

  In addition, irradiation with electromagnetic waves is usually performed in the air (in an oxygen atmosphere). This is because, under the atmosphere (under an oxygen atmosphere), the photochemical reaction of the polythiophene derivative, particularly the photolysis reaction, is promoted by the oxidation action.

  In this step, by irradiating the conductive layer with electromagnetic waves in a pattern, the conductivity of the irradiated part of the conductive layer is lowered, and a conductive part having conductivity and a non-conductive part having no conductivity are formed. To do. That is, by irradiating the conductive layer with electromagnetic waves in a pattern, the conductivity can be changed and the conductive portion can be formed in a pattern.

In the present invention, since the conductivity of the irradiated portion of the conductive layer is reduced by the irradiation of electromagnetic waves, the irradiated portion of the conductive layer becomes a nonconductive portion, and the non-irradiated portion of the conductive layer becomes a conductive portion.
The conductive portion and the non-conductive portion are the same as those described in the section “A. Conductive pattern substrate”, and thus the description thereof is omitted here. However, when the non-conductive portion is removed in the development step described later, the electric resistance in the non-conductive portion may be outside the range described in the section “A. Conductive pattern substrate”.

3. Development process In this invention, you may perform the image development process which develops a conductive layer and removes the irradiation part of a conductive layer after the said electromagnetic wave irradiation process. For example, when the insulating property of the non-conductive portion that is the irradiated portion of the conductive layer is relatively low, electricity may be conducted not only to the conductive portion but also to the non-conductive portion. In such a case, a conductive pattern substrate that can be suitably used for an electrode or the like in an electronic device can be obtained by performing a development step to remove the nonconductive portion.

  The developing method is not particularly limited as long as it can remove the irradiated portion of the conductive layer. For example, a method of immersing the substrate on which the conductive layer after irradiation of electromagnetic waves is formed in a developer. For example, a method of spraying a developer in a spray form on a substrate on which a conductive layer after irradiation with electromagnetic waves is formed can be used.

  The development time may be a time required for dissolving only the irradiated portion of the conductive layer without dissolving the unirradiated portion of the conductive layer.

  The developer used in the development is not particularly limited as long as it dissolves only the irradiated portion of the conductive layer without dissolving the unirradiated portion of the conductive layer, such as a polythiophene derivative used. It is appropriately selected depending on. Specifically, as the developer, a solvent having a polarity lower than that of the solvent used in the conductive layer forming coating solution is used. For example, water and an alcohol such as ethanol and isopropanol are lower in polarity. A solvent is used. Examples of such a developer include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl lactate. These solvents may be used alone or in combination.

  In the present invention, high-definition patterning is possible as described above. Specifically, it is possible to obtain a conductive pattern (pattern of conductive portion) having a line width of 10 μm or less, for example, a line width of 5 μm.

4). Other Steps In the present invention, depending on the use of the conductive pattern substrate, a step of forming various layers may be performed before the conductive layer forming step.
In addition, since the use etc. of a conductive pattern board | substrate are the same as that of what was described in the term of the said "A. conductive pattern board | substrate", description here is abbreviate | omitted.

  Moreover, in this invention, as shown, for example in FIG. 3, the conductive pattern board | substrate described in the term of the said "A. conductive pattern board | substrate" can be obtained by performing a conductive layer formation process and an electromagnetic wave irradiation process. . In this case, the conductive layer after the electromagnetic wave irradiation step as shown in FIG. 3C is a polythiophene layer referred to in the above section “A. Conductive pattern substrate”.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described with reference to examples.

[Experimental Example 1]
(Production of Evaluation Element 1)
A 1 inch square substrate having a thickness of 1.1 mm, on which an ITO film was formed in a pattern as a transparent electrode, was washed. Next, 0.5 ml of an aqueous dispersion of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) (manufactured by Starck, Baytron P CH8000) is taken and dropped onto the center of the substrate. Spin coating was performed at 2500 rpm for 20 seconds. Thereby, a PEDOT / PSS layer having a thickness of 800 mm was formed.
Next, the PEDOT / PSS layer was irradiated with ultraviolet light of 254 nm with a high-pressure mercury lamp through quartz glass.
Subsequently, Ag was vapor-deposited on the PEDOT / PSS layer after ultraviolet irradiation with a thickness of 3000 mm to form a metal electrode.
In this way, an evaluation element was produced.

(Preparation of evaluation element 2)
An evaluation element was produced in the same manner as in the production of the evaluation element 1 except that the PEDOT / PSS layer was not irradiated with ultraviolet rays.

(Evaluation of current-voltage characteristics)
About the evaluation elements 1 and 2, the ITO electrode side was connected to the positive electrode, the Ag electrode side was connected to the negative electrode, and a direct current was applied by a source meter. A voltage was applied from 0 V to 10 V, and current-voltage characteristics were evaluated. The results are shown in FIG.
From FIG. 5, the current-voltage characteristics were higher in the evaluation element 2 (unirradiated) than in the evaluation element 1 (irradiation). From this, it was found that the conductivity of the PEDOT / PSS layer was lowered by ultraviolet irradiation.

[Experiment 2]
Spin coating of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) in water dispersion (Stark, Baytron P CH8000) on a glass substrate of 100mm □ and 0.7mm thick. To form a PEDOT / PSS layer.
Next, the PEDOT / PSS layer was irradiated with electromagnetic waves from 240 nm to 480 nm using a spectral irradiation device (manufactured by Spectrometer Co., Ltd., IUV-25CP). After the irradiation, the PEDOT / PSS layer was treated with acetone, and the PEDOT / PSS layer in the portion irradiated with the electromagnetic waves of 240 nm to 350 nm and 420 nm to 470 nm was removed.
From this, it was found that the above PEDOT / PSS is highly sensitive to electromagnetic waves in the vicinity of 240 nm to 350 nm and 420 nm to 470 nm, and the solubility of acetone in the irradiated part of such electromagnetic waves changes.

[Example 1]
(Formation of conductive pattern)
An insulating substrate having a size of 6 inches and a thickness of 1.1 mm was prepared. An aqueous dispersion of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) (Stark, Baytron P CH8000) is dropped onto the center of the substrate and spin coated at 2500 rpm for 30 seconds. Went. Thereby, a conductive layer having a thickness of 80 nm was formed. Next, this conductive layer was dried at 150 ° C. for 10 minutes. Next, the conductive layer was irradiated with ultraviolet light of 254 nm with a high-pressure mercury lamp through a photomask having a 10 μm line and space. Subsequently, the conductive layer was treated with acetone for 5 seconds using a spin developing machine. When the obtained conductive pattern was observed with an optical microscope, a 10 μm line and space were formed according to the pattern of the photomask.

[Example 2]
(Production of organic EL element)
A 1 inch square substrate having a thickness of 1.1 mm, on which an ITO film was formed in a pattern as a transparent electrode, was washed. Next, 0.5 ml of an aqueous dispersion of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) (manufactured by Starck, Baytron P CH8000) is taken and dropped onto the center of the substrate. Spin coating was performed at 2500 rpm for 20 seconds. As a result, a hole injection layer having a thickness of 800 mm was formed.

  Next, the hole injection layer was irradiated with ultraviolet light of 254 nm with a high-pressure mercury lamp through a photomask whose light emitting region was shielded from light. Subsequently, the hole injection layer was developed with acetone. Thereby, the hole injection layer was formed only in the light emitting region.

  Next, 1 ml of red light emitting layer forming coating solution (polyvinylcarbazole 70 parts by weight, oxadiazole 30 parts by weight, dicyanomethylenepyran derivative 1 part by weight, monochlorobenzene 4900 parts by weight) is taken to form a hole injection layer. The solution was dropped on the center of the substrate and spin coating was performed at 2000 rpm for 10 seconds. Thereby, a light emitting layer having a thickness of 800 mm was formed. Subsequently, it was dried at 100 ° C. for 1 hour.

Subsequently, Ca was vapor-deposited with a thickness of 500 mm on the light emitting layer, and Ag was vapor-deposited with a thickness of 2500 mm to form a metal electrode.
In this way, an organic EL element was produced.

(Evaluation of light emission characteristics of organic EL elements)
The ITO electrode side was connected to the positive electrode, the Ag electrode side was connected to the negative electrode, and a direct current was applied by a source meter. Light emission was observed from the light emitting layer when 10 V was applied. Even after the entire patterning process including the ultraviolet irradiation process (electromagnetic wave irradiation process), no deterioration of the element characteristics was observed.

[Example 3]
(Production of organic EL element)
A 1 inch square substrate having a thickness of 1.1 mm, on which an ITO film was formed in a pattern as a transparent electrode, was washed. Next, 0.5 ml of an aqueous dispersion of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) (manufactured by Starck, Baytron P CH8000) is taken and dropped onto the center of the substrate. Spin coating was performed at 2500 rpm for 20 seconds. As a result, a hole injection layer having a thickness of 800 mm was formed.

  Next, the hole injection layer was irradiated with ultraviolet light of 254 nm with a high-pressure mercury lamp through a photomask whose light emitting region was shielded from light.

  Next, 1 ml of red light emitting layer forming coating solution (polyvinylcarbazole 70 parts by weight, oxadiazole 30 parts by weight, dicyanomethylenepyran derivative 1 part by weight, monochlorobenzene 4900 parts by weight) is taken to form a hole injection layer. The solution was dropped on the center of the substrate and spin coating was performed at 2000 rpm for 10 seconds. Thereby, a light emitting layer having a thickness of 800 mm was formed. Subsequently, it was dried at 100 ° C. for 1 hour.

Subsequently, Ca was vapor-deposited with a thickness of 500 mm on the light emitting layer, and Ag was vapor-deposited with a thickness of 2500 mm to form a metal electrode.
In this way, an organic EL element was produced.

(Evaluation of light emission characteristics of organic EL elements)
The ITO electrode side was connected to the positive electrode, the Ag electrode side was connected to the negative electrode, and a direct current was applied by a source meter. Light emission was observed from the light emitting layer when 10 V was applied. At this time, light emission was observed in the region where the hole injection layer was not irradiated with ultraviolet rays, but no light emission was observed in the region where the hole injection layer was irradiated with ultraviolet rays. Moreover, even if it went through all the patterning processes including an ultraviolet irradiation process (electromagnetic wave irradiation process), deterioration of element characteristics was not seen.

It is a schematic sectional drawing which shows an example of the electroconductive pattern board | substrate of this invention. It is a schematic sectional drawing which shows an example of the organic EL element using the electroconductive pattern board | substrate of this invention. It is process drawing which shows an example of the manufacturing method of the electroconductive pattern board | substrate of this invention. It is process drawing which shows the other example of the manufacturing method of the electroconductive pattern board | substrate of this invention. 3 is a graph showing current-voltage characteristics of elements in Experimental Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Conductive pattern board | substrate 2 ... Board | substrate 3 ... Polythiophene layer 3 '... Conductive layer 4 ... Conductive part 5 ... Nonconductive part 21 ... Photomask 22 ... Ultraviolet

Claims (4)

A conductive layer forming step of forming a conductive layer containing a conductive polythiophene derivative on the substrate;
An electromagnetic wave irradiation step of irradiating the conductive layer with an electromagnetic wave in a pattern to reduce the conductivity of the irradiated portion of the conductive layer, thereby forming a conductive portion having conductivity and a non-conductive portion having no conductivity. and,
And a developing step of developing the conductive layer to remove the irradiated portion of the conductive layer after the electromagnetic wave irradiation step . The method for producing a conductive pattern substrate according to claim 1 , wherein the polythiophene derivative is poly (3,4-alkylenedioxythiophene) doped with an acid. The method for producing a conductive pattern substrate according to claim 1 or 2 , wherein the electromagnetic wave is visible light or ultraviolet light of 500 nm or less. The electromagnetic wave irradiation step, the conductive pattern method for manufacturing a substrate according to any one of claims 1 to 3, characterized in that it is carried out in an oxygen atmosphere.

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