JPWO2009098996A1 - Thin film device, manufacturing method thereof, and electronic component - Google Patents

Abstract

In a method for manufacturing a thin film device having an organic film forming step of forming an organic film on a substrate using a resin composition comprising a resin, a curing agent, and a solvent, the resin has a protic polar group It is a manufacturing method of a thin film device which is an alicyclic olefin resin and the curing agent is a compound having an alicyclic structure portion and three or more epoxy groups.

Description

  The present invention relates to a thin film device such as a thin film transistor, a thin film secondary battery, a thin film solar cell, and a composite thin film device obtained by combining these, a manufacturing method thereof, and an electronic component using the thin film device.

  Note that in this specification, a thin film device refers to a semiconductor element that is an active element formed using a semiconductor thin film, or an electronic device that includes passive elements that consume, store, and emit supplied power. The thin film device includes an organic thin film device and an inorganic thin film device. An example of the former is an organic thin film transistor, and an example of the latter is a lithium thin film secondary battery.

  A thin film device such as a thin film transistor, a thin film secondary battery, and a thin film solar cell is generally configured by forming a circuit layer including an electrode layer and an insulating layer on a substrate and covering the uppermost layer with a protective layer. An undercoat layer may be disposed between the substrate and the circuit layer. As a thin film transistor, Japanese Patent Application Laid-Open No. 2005-289054 has a description of having an organic resin layer (planarization layer) on a substrate of an organic field effect transistor, and a thermoplastic resin as a material of the organic resin layer, Thermosetting resins, photocurable resins, and the like are disclosed.

  International Publication WO 2006/129718 pamphlet describes an undercoat layer, a gate insulating film, and a protective film of an organic thin film transistor. As each material, the undercoat layer is an undercoat layer containing a compound selected from a polymer or an inorganic oxide and an inorganic nitride, and the gate insulating film does not have a functional group having an unshared electron pair and has a π electron in the molecular structure. A gate insulating film and a protective film which are films containing an organic polymer compound having no bond are formed by a silicon oxide film, a silicon nitride film or a silicon oxynitride film formed by a CVD method or a sputtering method, or a thermal CVD method. A protective film such as a polyparaxylene film, a polyimide film formed by coating, an alicyclic olefin polymer film, an ultraviolet curable epoxy resin film, an acrylic resin film, or the like is disclosed. It also discloses that the organic thin film transistor substrate and / or protective film is preferably made of an alicyclic olefin polymer.

As a thin film solar cell, Japanese Patent Application Laid-Open No. 5-63218 has a description of a passivation layer made of a polymer resin above the semiconductor layer. The polymer resin is polyester, ethylene vinyl acetate copolymer, acrylic, It is disclosed that it comprises a component selected from epoxy and polyurethane. As a thin film secondary battery, Japanese Patent Application Laid-Open No. 2002-42863 discloses a silicon nitride material such as Si ₃ N ₄ or SiN as a protective film of a thin film solid secondary battery cell.

  In such a thin film device, resin materials have come to be used as the undercoat layer, the insulating layer, and the protective film from the viewpoint of facilitating production, etc., and the resin material has the function of each layer. From the viewpoint, an appropriate material is selected. These undercoat layer, insulating layer, and protective film need to improve surface smoothness and adhesiveness in order to maintain good performance over a long period of time. There is also a need to simplify the manufacturing process and reduce manufacturing costs.

  In addition, if the gate insulating film of the conventional organic thin film transistor is not secured to a large thickness, a gate leakage current due to a tunnel phenomenon flows through the insulating film, and the insulating property cannot be maintained. In some cases, a high on / off ratio cannot be obtained. Moreover, hysteresis appeared, there were many carrier traps, and the expression of n-type characteristics was insufficient.

  Therefore, an object of the present invention is to enable the manufacture of an inexpensive thin film device that can maintain good performance over a long period of time.

  Another object of the present invention is to provide an organic thin film transistor which can suppress a leakage current in a gate insulating film, obtain a high insulating film capacity, hardly cause hysteresis, and can operate at a low gate voltage.

Summary of the Invention

  In order to achieve the above-mentioned object, the present inventors have studied various film materials conventionally used for the undercoat layer, the insulating layer (including the insulating layer between devices, the gate insulating layer, etc.) and the protective layer. As a result, it was found that by using a specific resin material, the smoothness and adhesion of the surface are good, and good device performance can be maintained over a long period of time, and the present invention is completed based on this finding. It came. Conventionally, appropriate materials have been selected as the undercoat layer, the insulating layer, and the protective layer from the viewpoint of the functions of the respective layers, but they can be used for any of these layers. New resin materials have been found, and the present invention has been completed based on this finding.

  In addition, as a result of various studies on conventionally used organic gate insulating film materials, the present inventors have found that organic polymer compounds that do not have a functional group having an unshared electron pair and have no π-electron bond in the molecular structure Is made into a solution with a specific solvent, and a low dielectric film is formed using the solution, and the gate dielectric film is formed by stacking the low dielectric film and the high dielectric film. The film has a significantly improved performance and is a high-quality film that is difficult to pinhole, the leakage current in the gate insulating film is suppressed, a high insulating film capacity is obtained, and the electron mobility is further improved, with a low gate voltage. It has been found that an organic thin film transistor can be obtained. The present inventors have completed the present invention based on this finding.

  That is, according to the first aspect of the present invention, a thin film device having an organic film forming step of forming an organic film on a substrate using a resin composition comprising a resin, a curing agent, and a solvent. In the production method, there is provided a method for producing a thin film device in which the resin is an alicyclic olefin resin having a protic polar group, and the curing agent is a compound having an alicyclic structure portion and three or more epoxy groups. The

  In this case, the organic film forming step can be performed once or more before and after the step of forming the electrode. Further, at least one of the organic film forming steps includes an application step of applying the resin composition on the substrate, a first heat treatment step of performing heat treatment at 130 ° C. or less after the application step, And a second heat treatment step in which heat treatment is performed at 150 ° C. or higher after the one heat treatment step. Moreover, all the said organic film formation processes can have the said application | coating step, a 1st heat processing step, and a 2nd heat processing step.

  According to the second aspect of the present invention, each of the step of forming the electrode and the step of forming the organic film using the resin composition containing the resin and the solvent before and after the step are performed once each. In the manufacturing method of the thin film device having the above, the resin used in at least one of the organic film forming steps is an alicyclic olefin resin having a structural unit (a) represented by the following formula (1) or formula (2). A method of manufacturing a thin film device is provided. Moreover, the alicyclic olefin resin which has the structural unit (a) represented by following formula (1) or Formula (2) can be used in all the said film formation processes.

  According to a third aspect of the present invention, there is provided a thin film device having a first organic film, a first electrode group, a second organic film, and a second electrode group in this order on a substrate. There is provided a thin film device comprising an alicyclic olefin resin in which an organic film of 1 and a second organic film have a structural unit (a) represented by the following formula (1) or formula (2). In this case, the first or second organic film can be an organic film formed using a resin composition containing a resin and a solvent. The resin composition may further include a curing agent having an alicyclic structure portion and three or more epoxy groups.

  According to a fourth aspect of the present invention, in the method of manufacturing a thin film transistor having a step of forming a gate insulating film using a resin composition containing a resin and a solvent, the resin is represented by the following formula (1) or There is provided a method for producing a thin film transistor, which is an alicyclic olefin resin having a structural unit (a) represented by the formula (2) and whose solvent is an aliphatic hydrocarbon compound having a boiling point of 150 ° C. or higher.

(However, in formula, R1-R4 is respectively independently a hydrogen atom, a C1-C10 hydrocarbon group, or a polar group, and n is an integer of 0-2.)

  According to a fifth aspect of the present invention, there is provided a thin film device manufactured by using the manufacturing method according to the first or second aspect, or an electronic component using the thin film device according to the third aspect. Provided. Here, examples of the electronic component include a thin film transistor, a thin film secondary battery, and a thin film solar battery. In addition, examples of the electronic component include a composite thin film device or a laminated device in which different types or the same type of thin film devices such as a thin film transistor and a thin film solar cell, a thin film secondary battery and a thin film solar cell are stacked.

  According to the present invention, there is an effect that an inexpensive thin film device and an electronic component using the same can be manufactured while maintaining good performance over a long period of time. In addition, according to the present invention, a leakage current in the gate insulating film is suppressed, a high insulating film capacity is obtained, a higher electron mobility is obtained, hysteresis is hardly generated, and an organic thin film transistor that can operate at a low gate voltage is obtained. There is an effect that can be manufactured.

It is sectional drawing of the thin film secondary battery (with an undercoat layer, without a protective layer) of 1st Embodiment. It is sectional drawing of the thin film secondary battery (with an undercoat layer, without a protective layer, with embossing) of 1st Embodiment. It is sectional drawing of the thin film secondary battery (without an undercoat layer and with a protective layer) of 1st Embodiment. It is sectional drawing of the thin film secondary battery (with an undercoat layer and with a protective layer) of 1st Embodiment. It is a figure which shows the relationship between the charging / discharging capacity | capacitance and cell voltage of the thin film secondary battery of Example 1-1. It is a figure which shows the relationship between the cycle number and charging / discharging capacity | capacitance of the thin film secondary battery of Example 1-1. It is a figure which shows the relationship between the charging / discharging capacity | capacitance and cell voltage of the thin film secondary battery of Example 1-2. It is a figure which shows the relationship between the charging / discharging capacity | capacitance and cell voltage of the thin film secondary battery of Example 1-3. It is a figure which shows the board | substrate with embossing used for the thin film secondary battery of Example 1-3. It is a figure which shows the relationship between the charging / discharging capacity | capacitance of the thin film secondary battery of the comparative example 1, and a cell voltage. It is a figure which shows the relationship between the charging / discharging capacity | capacitance and cell voltage of the thin film secondary battery of Example 1-4. It is a figure which shows the relationship between the charging / discharging capacity | capacitance and cell voltage of the thin film secondary battery of Example 1-5. It is a figure which shows the relationship between the cycle number of the thin film secondary battery of Example 1-5, and charging / discharging capacity | capacitance. It is a figure which shows an optical image at the time of forming a ZNX480 film on the glass substrate of Example 1-6. It is a figure which shows an optical image at the time of forming a ZOP3 film on the glass substrate of Example 1-6. It is a figure which shows the optical image at the time of forming a ZOP3 film on the aluminum vapor deposition glass substrate of Example 1-6. It is a figure which shows an optical image at the time of forming a ZOP3 film on the stainless steel substrate of Example 1-6. It is a figure which shows the optical image at the time of forming a ZNX480 film on the stainless steel substrate of Example 1-6. It is sectional drawing which shows the structure of the transistor which has a single layer gate insulating film of 2nd Embodiment. It is sectional drawing which shows the structure of the transistor which has the two-layer gate insulating film of 2nd Embodiment. It is a VD-ID diagram which shows the measurement result of (Example 2-1). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-1). It is a VD-ID diagram which shows the measurement result of (Example 2-2). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-2). It is a VD-ID diagram which shows the measurement result of (Example 2-3). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-3). It is a VD-ID diagram which shows the measurement result of (Example 2-4). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-4). It is a VD-ID diagram which shows the measurement result of (Example 2-5). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-5). It is a VD-ID diagram which shows the measurement result of (Example 2-6). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-6). It is a VD-ID diagram which shows the measurement result of (Example 2-7). It is a square root vs. VG diagram of ID which shows the measurement result of (Example 2-7). It is a figure which shows the optical image at the time of forming a COP (solvent: limonene) film on the board | substrate of (Example 2-8). It is a figure which shows the optical image at the time of forming a COP (solvent: limonene) film on the board | substrate of (Example 2-8). It is a figure which shows the optical image at the time of forming a COP (solvent: limonene) film on the board | substrate of (Example 2-8). It is a figure which shows an optical image at the time of forming a COP (solvent: cyclohexane) film on the board | substrate of (Example 2-8). It is a figure which shows an optical image at the time of forming a COP (solvent: cyclohexane) film on the board | substrate of (Example 2-8). It is a figure which shows an optical image at the time of forming a COP (solvent: cyclohexane) film on the board | substrate of (Example 2-8). It is a figure which shows an optical image at the time of forming an organic-semiconductor layer on the COP (solvent: limonene) film of (Example 2-8). It is a figure which shows an optical image at the time of forming an organic-semiconductor layer on the COP (solvent: cyclohexane) film of (Example 2-8). It is a diagram which shows the frequency dependence of the dielectric constant which shows the measurement result of (Example 2-9). It is sectional drawing which shows the manufacturing process (the 1) of the thin film device of 3rd Embodiment. It is sectional drawing which shows the manufacturing process (the 2) of the thin film device of 3rd Embodiment. It is sectional drawing which shows the manufacturing process (the 3) of the thin film device of 3rd Embodiment. It is sectional drawing which shows the manufacturing process (the 4) of the thin film device of 3rd Embodiment. It is sectional drawing which shows the manufacturing process (the 5) of the thin film device of 3rd Embodiment. It is sectional drawing which shows the manufacturing process (the 6) of the thin film device of 3rd Embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION

(1) First embodiment (thin film secondary battery)
Hereinafter, as an example of a thin film device, a first embodiment according to a lithium ion thin film secondary battery to which the present invention is applied will be described.

(1-1) Overall Configuration of Lithium Ion Thin Film Secondary Battery FIGS. 1 to 4 are sectional views showing the overall configuration of the lithium ion thin film secondary battery according to this embodiment. First, as shown in FIG. 1, the thin-film secondary battery 1 includes an undercoat layer (base coat) 3, a negative electrode current collector layer 4, a negative electrode active material layer 5, a solid electrolyte layer 6, on a substrate 2. The positive electrode active material layer 7 and the positive electrode side current collector layer 4 are laminated in this order. Note that the stacking order of the layers on the undercoat layer 3 of the substrate 2 is the order in which the positive electrode active material layer 7 and the negative electrode active material layer 5 are interchanged, that is, the positive electrode side current collector layer 4 and the positive electrode active material layer. 7, the order of the solid electrolyte layer 6, the negative electrode active material layer 5, and the current collector layer 4 on the negative electrode side may be used. In the following description, for the sake of simplicity, the entire portion including the negative electrode side current collector layer, the negative electrode active material layer, the electrolyte layer, the positive electrode active material layer, and the positive electrode side current collector layer may be referred to as a secondary battery layer. .

  FIG. 2 is an example in which a substrate 2 having a plurality of recesses 3a is formed by embossing the surface (surface on the undercoat layer 3 side) of the substrate 2 in the same configuration as FIG. . FIG. 3 shows an example in which the undercoat layer 3 is removed and the entirety of each layer is covered with a protective layer (overcoat) 8 in the configuration of FIG. FIG. 4 is an example in which the entire layer is covered with the protective layer 8 without removing the undercoat layer 3 in the configuration of FIG.

  When such a thin film secondary battery 1 is charged, lithium is separated from the positive electrode active material layer 7 as ions, and is inserted into the negative electrode active material layer 5 through the solid electrolyte layer 6. At this time, electrons are emitted from the positive electrode active material layer 7 to the outside. At the time of discharge, lithium is separated from the negative electrode active material layer 5 as ions, and is inserted into the positive electrode active material layer 7 through the solid electrolyte layer 6. At this time, electrons are emitted from the negative electrode active material layer 5 to the outside.

  Although such a thin film secondary battery may be independent as shown in FIGS. 1 to 4, other thin film devices such as an organic thin film transistor (refer to a second embodiment described later), a thin film solar cell, and the like have been described above. It is good also as a composite thin film device laminated | stacked on the thin film secondary battery. Alternatively, the above-described thin film secondary battery (or a thin film secondary battery having a different configuration) may be stacked in a plurality of stages, or a stacked device in which the above-described thin film secondary battery and other circuits are stacked. In these cases, a secondary battery layer is formed on the uppermost layer of an organic thin film transistor or a thin film solar cell via an undercoat layer (in this case, an intermediate insulating layer), or the uppermost layer of the secondary battery In addition, another thin film device can be formed through a protective film (in this case, an intermediate insulating layer).

(1-2) Substrate, Current Collector Layer, Active Material Layer, and Electrolyte Layer The substrate 2 can be formed using a material such as glass, silicon, ceramic, stainless steel, or resin. . When resin is used as a material, for example, polyimide, PET, or the like can be used. The substrate 2 may be either a relatively thick hard substrate or a relatively thin film-like substrate having flexibility or flexibility. Among them, a film-like substrate having a flexibility or flexibility having a thickness of 10 to 200 μm is preferable for forming a thin film device.

  The current collector layer 4 is formed of a conductive material having good adhesion to the negative electrode active material layer 5, the positive electrode active material layer 7, or the solid electrolyte layer 6 adjacent thereto. As the current collector layer 4, a metal thin film having a low electric resistance, for example, a thin film made of vanadium, aluminum, copper, nickel, gold, or the like can be used. The current collector layer 4 is preferably as thin as possible and has a low electrical resistance.

As the positive electrode active material layer 7, a metal oxide thin film containing lithium and any one or more of manganese, cobalt, and nickel, which are transition metals capable of detaching and inserting lithium ions, can be used. For example, lithium-manganese oxide (LiMn ₂ O ₄ , Li ₂ Mn ₂ O _4, etc.), lithium-cobalt oxide (LiCoO ₂ , LiCo ₂ O _4, etc.), lithium-nickel oxide (LiNiO ₂ , LiNi ₂ O, etc.) ₄ ), lithium-manganese-cobalt oxide (LiMnCoO ₄ , Li ₂ MnCoO _4, etc.) and the like can be used. Among these, lithium-manganese oxide (LiMn ₂ O ₄ , Li ₂ Mn ₂ O ₄ ) can be preferably used.

For the solid electrolyte layer 6, lithium phosphate (Li ₃ PO ₄ ) having a good lithium ion conductivity, a substance obtained by adding nitrogen to the lithium phosphate (LiPON), or the like can be used.

Negative electrode active material layer 5 is a silicon - manganese alloy (Si-Mn), silicon - cobalt alloy (Si-Co), silicon - nickel alloy (Si-Ni), lithium - titanium oxide (LiTi ₂ O _4, Li ₄ Ti ₅ O ₁₂ etc.), niobium pentoxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), nickel oxide (NiO) ), Indium oxide added with tin (ITO), zinc oxide added with aluminum (AZO), zinc oxide added with gallium (GZO), tin oxide added with antimony (ATO), fluorine added In addition, tin oxide (FTO), nickel oxide to which lithium is added (NiO-Li), or the like can be used. Among these, niobium pentoxide (Nb ₂ O ₅ ) can be preferably used.

  As the method for forming each thin film, any film can be used as long as the thin film can be formed as uniformly as possible. For example, a vacuum film forming method such as a sputtering method, an electron beam vapor deposition method, a heat vapor deposition method, a coating method, etc. Can be used.

(1-3) Undercoat layer, protective layer (or intermediate insulating layer)
In this embodiment, the undercoat layer 3 and the protective layer 8 (in the case where there is an intermediate insulating layer, the intermediate insulating layer) are formed in the same manner (film formation) using the following resin composition suitable for both of them. ) Formed by the method. Thereby, it is not necessary to prepare a resin composition as a resin film forming material for each, and it is possible to form a film using the same resin film forming apparatus, so that manufacturing cost and manufacturing man-hour can be reduced. . However, the undercoat layer 3 and the protective layer 8 (or the intermediate insulating layer) may be formed using different resin compositions, and different formation methods may be used.

  This resin composition comprises an alicyclic olefin resin (polymer), a curing agent, and a solvent, the alicyclic olefin resin has a protic polar group, and the curing agent has an alicyclic structure portion. It is comprised from the compound which has 3 or more epoxy groups. The alicyclic olefin polymer preferably has a structural unit (a) represented by the following formula (1) or (2).

  However, in Formula (1) and Formula (2), R1-R4 are respectively independently a hydrogen atom, a C1-C10 hydrocarbon group, or a polar group, and n is an integer of 0-2.

  As a C1-C10 hydrocarbon group in Formula (1)-Formula (2), an alkyl group, a cycloalkyl group, an aryl group etc. can be mentioned, for example. Examples of the alkyl group include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a hexyl group, and a heptyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a cyclooctyl group, and the like. Examples of the aryl group include a phenyl group, a 2-methylphenyl group, and a benzyl group. Among these, the hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and an ethyl group. Is more preferable.

  Examples of the polar group in the formula (1) and the formula (2) include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, a primary amino group, a secondary amino group, a primary amide group, and a secondary group. Protic polar groups such as secondary amide groups (N-alkylamide groups) and thiol groups; ester groups (referred to collectively as alkoxycarbonyl groups and aryloxycarbonyl groups), epoxy groups, halogen atoms, nitrile groups, alkoxyl groups, Aprotic polar groups such as acryloyl group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid) composed of R3 and R4, N-substituted imide group, carbonyl group, tertiary amino group, sulfone group, etc. And the like.

  Among these, the protic polar group has an advantage that a polymer having high adhesion to other materials and high heat resistance can be obtained. Moreover, what has a protic polar group is alkali-soluble, and these alkali-soluble things are useful for a radiation sensitive resin composition. Moreover, what has a protic polar group can give a crosslinkable resin, when a crosslinking agent is mix | blended with a composition.

  When the number of polar groups is one or two, the compatibility when the curing agent is blended in the resin composition is good, which is preferable. A resin film formed from this resin composition is preferable because it exhibits a high balance between high adhesion to a substrate and the like and low water vapor permeability. More preferably, there is one polar group.

  The proportion of the structural unit (a) is preferably 65 mol% or more in all the structural units of the alicyclic olefin polymer. Such an alicyclic olefin polymer is suitable as an alicyclic olefin polymer for constituting a resin film for forming an undercoat layer, a protective layer or the like.

  The ratio of the structural unit represented by the formula (2) to the structural unit (a), that is, the hydrogenation rate of the main chain unsaturated bond is preferably 90 mol% or more from the viewpoint of obtaining high heat resistance, 95 It is more preferably at least mol%, and even more preferably at least 98 mol%. High heat resistance has an advantage that its characteristics are prevented or suppressed from being deteriorated by heating during the formation of the resin film.

  In this specification, the alicyclic olefin polymer refers to a polymer having an alicyclic structure. The alicyclic olefin refers to a compound having an alicyclic structure and a carbon-carbon double bond in the ring.

  As the alicyclic olefin polymer used in the resin composition, a ring-opening polymer or an addition polymer can be used. Among these, a ring-opening polymer is preferable. The alicyclic olefin polymer can be obtained by ring-opening polymerization of an alicyclic olefin having a protic polar group represented by the following formula (3) in the presence of a metathesis catalyst. Furthermore, after the polymerization reaction, a hydrogenation reaction can be performed as necessary. Moreover, after obtaining an alicyclic olefin polymer having a polar group that generates a carboxyl group by hydrolysis of a nitrile group, ester group, amide group, acid anhydride group, etc., this is hydrolyzed and converted to a carboxyl group You can also

  However, in Formula (3), R1 to R4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a protic polar group, and only one of R3 and R4 is a polar group. Yes, n is an integer of 0-2. Examples of the hydrocarbon group having 1 to 10 carbon atoms and the protic polar group in the formula (3) include the same groups as those described for the formulas (1) to (2).

Ring-opening polymerization can be carried out in the presence of a metathesis catalyst. Examples of the metathesis catalyst include platinum group compounds such as ruthenium, rhodium, palladium, iridium, osmium, and platinum; tungsten, molybdenum, or rhenium, and periodic groups 1, 2, 4, 12, 13, or 14. A compound comprising an element having the element-carbon bond or the element-hydrogen bond; a catalyst comprising a halide or acetylacetonide such as titanium, vanadium, zirconium, tungsten, molybdenum, and an organoaluminum compound; Ruthenium compounds having an organic compound such as (cyclopentadienyl) ruthenium, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, [(p-cymene) (CH ₃ CN) ₃ Ru] (BF ₄ ) ₂ as a ligand, etc. Can be mentioned. Among these, metathesis catalysts containing molybdenum, ruthenium, osmium, etc. are relatively stable to oxygen and moisture in the air and are not easily deactivated, so they can be produced even in the atmosphere. Among these, a metathesis catalyst containing ruthenium is particularly preferable because of its high polymerization activity.

The structural unit (a) is a structural unit represented by the formula (1) or (2), and can be obtained by ring-opening polymerization of an alicyclic olefin having a polar group represented by the formula (3). it can. Examples of the alicyclic olefin having a protic polar group include 5-carboxybicyclo [2.2.1] hept-2-ene and 5-methyl-5-carboxybicyclo [2.2.1] hept-2. -Ene, 5-carboxymethyl-5-carboxybicyclo [2.2.1] hept-2-ene, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . Alicyclic olefins having a carboxyl group (hydroxycarbonyl group) such as ^{17, 10} ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5- Methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And alicyclic olefins having a hydroxy group, such as ^{17, 10} ] dodec-3-ene. In these, the alicyclic olefin which has a carboxyl group can be used conveniently.

Examples of the alicyclic olefin having an aprotic polar group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . Alicyclic olefin having an ester group such as 1 ^7,10 ] dodec-3-ene; 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . Alicyclic olefins having a nitrile group such as 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene; N- (4-phenyl)-(5-norbornene And cyclic olefins having an N-substituted imide group such as -2,3-dicarboximide). An alicyclic olefin having an ester group or a nitrile group as an aprotic polar group can generate a protic polar group by hydrolysis.

Examples of the alicyclic olefin having no polar group include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylbicyclo [2.2.1] hept-2-ene. 5-butylbicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-methylidenebicyclo [2.2.1] hept-2 -Ene, ^5- vinylbicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,11,12-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl-tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like.

  The weight average molecular weight (Mw) of this alicyclic olefin polymer is 2,500 or more and less than 60,000, more preferably 3,000 or more and less than 55,000. The weight average molecular weight of the alicyclic olefin polymer can be determined as a polystyrene-converted weight average molecular weight by gel permeation chromatography using tetrahydrofuran at 40 ° C. as a solvent. When the weight average molecular weight of the alicyclic olefin polymer is 2,500 or more and less than 60,000, a resin film excellent in transparency, in-plane film thickness uniformity, and adhesion can be obtained.

  The glass transition temperature of the alicyclic olefin polymer is preferably 20 to 250 ° C, more preferably 50 to 200 ° C, and further preferably 70 to 170 ° C. The glass transition temperature of the alicyclic olefin polymer can be measured using a differential scanning calorimeter (DSC). In ring-opening polymerization of alicyclic olefins, vinyl compounds such as allyl chloride, allyl alcohol and acrylamide; diene compounds such as 1,5-hexadiene and 1,6-heptadiene; α-olefin compounds such as 1-hexene; When the molecular weight modifier is added in an amount of 0.1 to 10 mol% based on the total amount of the monomers, the molecular weight of the ring-opening polymer can be easily adjusted. When the amount of the molecular weight modifier used is small, a polymer having a relatively high weight average molecular weight is obtained, and conversely, when the amount is large, a polymer having a relatively low weight average molecular weight is obtained.

  As the curing agent, a polyfunctional epoxy compound having an alicyclic structure and having three or more epoxy groups is used as a functional group that can react suitably with the protic polar group of the alicyclic olefin polymer. As a specific example of a polyfunctional epoxy compound having an alicyclic structure and having 3 or more epoxy groups, a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”. Nippon Kayaku Co., Ltd.) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) 1-butanol (15-functional alicyclic having a cyclohexane skeleton and a terminal epoxy group) Epoxy resin, trade name “EHPE3150” manufactured by Daicel Chemical Industries, Ltd., epoxidized 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin) Trade name “Epolide GT301” (manufactured by Daicel Chemical Industries), epoxidized butanetetracarboxylic acid tetrakis ( -.. Cyclohexenyl methyl) modified ε- caprolactone (aliphatic cyclic tetrafunctional epoxy resin trade name "EPOLEAD GT401" manufactured by Daicel Chemical Industries, Ltd.) and the like.

  The molecular weight of the curing agent is preferably 100 to 100,000, more preferably 500 to 50,000, more preferably 1,000 to 10,000, from the viewpoint of stability during heating and gelation efficiency. More preferably. The blending amount of the curing agent can be selected according to the purpose of use, and is preferably 1 to 1,000 parts by weight, and preferably 5 to 500 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. It is more preferable that the amount is 10 to 100 parts by weight. When the blending amount of the curing agent is 1 to 1,000 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer, the heat resistance of the formed resin film can be highly improved.

  The resin composition can contain a radiation sensitive compound, an antioxidant, and other additives as necessary.

  A radiation sensitive compound can be used when patterning a resin film using actinic radiation. A radiation-sensitive compound is a compound that can absorb actinic radiation such as ultraviolet rays and electron beams and cause a chemical reaction. In the present invention, when an alicyclic olefin polymer having a protic polar group is used, it is preferably a compound capable of controlling its alkali solubility. Examples of radiation sensitive compounds include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds that are widely used as photoacid generators in radiation sensitive resin compositions for photolithography. . Of these, azide compounds are preferable, and quinonediazide compounds are particularly preferable. The compounding amount of the radiation sensitive compound is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, and 10 to 40 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. More preferably it is. When the amount of the radiation sensitive compound is 1 to 100 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer, when the resin film formed on the substrate is patterned, the radiation irradiated part and the radiation unirradiated The difference in solubility with the part becomes large, patterning by development is easy, and radiation sensitivity is also high.

  Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-tert. -Butyl-4'-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3'-tert-butyl-5'-methyl- 2 ' -hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), alkyl Bisphenol and the like can be mentioned. Examples of phosphorus antioxidants include triphenyl phosphite and tris phosphite (nonylphenyl). Examples of the sulfur-based antioxidant include dilauryl thiodipropionate. Among these, from the viewpoint of maintaining transparency during heating, a phenol-based antioxidant is preferable, and pentaerythritol tetrakis (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate) [Irganox] (Registered trademark) 1010] is particularly preferable.

  Examples of other additives include sensitizers, surfactants, latent acid generators, adhesion assistants, antistatic agents, antifoaming agents, pigments, and dyes. Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4- Examples thereof include benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  Surfactants are used for the purpose of preventing striations and improving coating properties. For example, nonionic surfactants; fluorosurfactants; silicone surfactants; (meth) acrylic Examples include acid copolymer surfactants.

  The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin film obtained from the resin composition. For example, the latent acid generator is a cationic polymerization catalyst that generates an acid by heating. Examples include zolium salts, ammonium salts, phosphonium salts, and the like. Of these, sulfonium salts and benzothiazolium salts can be suitably used.

  Examples of the adhesion assistant include a functional silane coupling agent, and specific examples thereof include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyl Examples thereof include trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among these, γ-glycidoxypropyltrimethoxysilane can be preferably used.

  The undercoat layer or the protective layer is formed by performing the following steps. First, when the undercoat layer is formed, an application step of applying the above-described resin composition is performed on the substrate by using a spin coating method or a dipping method. Next, a first heat treatment step for heat treatment for drying the applied resin composition and a second heat step for heat treatment for firing the resin composition are performed. Both the undercoat layer and the protective layer are preferably formed by having the above steps.

  When forming the protective layer, the same steps as the formation of the undercoat layer should be performed after the formation of each of the above-described layers (current collector layer, positive electrode active material layer, solid electrolyte layer, and negative electrode active material layer). Formed by.

  Further, when another thin film device is formed on the uppermost layer of the secondary battery via a protective film (in this case, an intermediate insulating layer), it is formed by performing the same steps.

  The first heat treatment step for drying the resin solution is preferably performed in an environment of 30 to 150 ° C., more preferably 60 to 100 ° C., preferably 0.5 to 90 minutes, more preferably 1 to 60 minutes. More preferably, it can be carried out by leaving for 1 to 30 minutes.

  The second heat treatment step for firing the dried resin composition can be performed using, for example, a hot plate or an oven. The heating temperature is preferably 150 to 250 ° C., and the heating time can be appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, it is preferably 5 to 60 minutes, and when an oven is used, it is preferably 10 to 90 minutes. Heating can be performed in an inert gas (for example, Ar gas) atmosphere as necessary.

Example 1
Resin composition solutions used in the examples described below were produced as follows. 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts, N- (4-phenyl)-(5-norbornene-2,3-dicarboximide) 40 parts, 1,5-hexadiene 2.8 parts, (1, 3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol ethyl methyl ether 400 parts were charged into a nitrogen-substituted pressure-resistant glass reactor and stirred at 80 ° C. for 2 hours. A polymerization reaction solution containing a ring-opening metathesis polymer 1A was obtained by performing a polymerization reaction for a period of time. The polymerization conversion rate was 99.9% or more. The polymer 1A had a weight average molecular weight of 3,200 and a molecular weight distribution of 1.68.

  Next, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added to the polymerization reaction solution, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to proceed the hydrogenation reaction. 1 part of the powder was added, and the mixture was placed in an autoclave and stirred, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of a hydrogenation reaction solution containing the hydride 1B of the ring-opening metathesis polymer 1A. Filtration was performed without any delay. The hydrogenation reaction solution containing hydride 1B obtained here had a solid content concentration of 20.6%, and the yield of hydride 1B was 98.1 parts. The obtained hydride 1B had a weight average molecular weight of 4,430 and a molecular weight distribution of 1.72. The hydrogenation rate was 99.9%.

  The hydrogenated reaction solution of hydride 1B thus obtained was concentrated with a rotary evaporator to adjust the solid content concentration to 35.0% to obtain a solution of hydride 1C. There was no change in yield, weight average molecular weight, molecular weight distribution of hydride before and after concentration. In the above description, the hydride 1B and the hydride 1C are distinguished from each other. However, such a division is convenient, and both hydrides are the same.

  100 parts of hydrogenation reaction solution (solid content 35.0%) containing hydride 1C obtained above, epoxidized butanetetracarboxylic acid tetrakis (3- Cyclohexenylmethyl) -modified ε-caprolactone (trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.) 60 parts, glycidoxypropyltrimethoxysilane (trade name “SH6040”, manufactured by Toray Dow Corning Silicone Co., Ltd.) ) 1 part, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals) 2 as an antioxidant Parts, diethylene glycol ethyl methyl ether 516 parts, silicone Surfactant (product name "KP341", manufactured by Shin-Etsu Chemical Co., Ltd.) was 0.2 parts were mixed and stirred. This solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a resin composition (1D). In addition, the resin composition adjusted in this way may be called ZOP3 solution.

(Example 1-1)
In order to manufacture the thin film secondary battery having the configuration shown in FIG. 1, an undercoat layer is formed on a substrate using a resin composition (ZOP3 solution), and a negative electrode side current collector layer, A negative electrode active material layer, an electrolyte layer, a positive electrode active material layer, and a positive electrode side current collector layer were formed in this order. As the substrate, a thin stainless steel substrate made of stainless steel was used. Instead of the negative electrode side current collector layer described above, or between the undercoat layer and the negative electrode side current collector layer, a metal film having a thickness of about 200 nm made of aluminum (Al) or the like is formed by, for example, vacuum deposition, You may make it form.

  1 ml of this ZOP3 solution was dropped on the substrate, and spin coating was performed at a rotation speed of 1000 rpm for 30 seconds. Next, heat treatment is performed at 90 ° C. for 5 minutes in an air atmosphere (first heat treatment step), and further, heat treatment is performed at 180 ° C. for 60 minutes in an Ar gas atmosphere (second heat treatment step). An organic coating as a layer was formed. The thickness of this undercoat layer was about 500 nm.

  The negative electrode side current collector layer was formed by using a DC magnetron sputtering method using vanadium (V) as a forming material. The DC power was 110 [W], the sputtering gas was Ar gas, and the gas pressure was 4 [mTorr]. The film thickness of this negative electrode current collector layer was 160 nm.

The negative electrode active material layer was formed by RF magnetron sputtering using niobium pentoxide (Nb ₂ O ₅ ) as a forming material. The RF power was 100 [W], the sputtering gas was a mixed gas of Ar and O ₂ (Ar: O ₂ = 9: 1), and the gas pressure was 10 [mTorr]. The film thickness of this negative electrode active material layer was 200 nm.

The electrolyte layer was formed by using RF 3 magnetron sputtering method using Li ₃ PO ₄ as an electrolyte. The RF power was 100 [W], the sputtering gas was N ₂ gas, and the gas pressure was 10 [mTorr]. The thickness of this electrolyte layer was 400 nm.

The positive electrode active material layer was formed using an RF magnetron sputtering method using lithium manganate (LiMn ₂ O ₄ ) as a forming material. The RF power was 100 [W], the sputtering gas was Ar gas, and the gas pressure was 10 [mTorr]. The film thickness of this positive electrode active material layer was 400 nm.

  The positive electrode side current collector layer was formed by DC magnetron sputtering using vanadium (V) as a forming material. The DC power was 60 [W], the sputtering gas was Ar gas, and the gas pressure was 50 [mTorr]. The film thickness of the positive electrode current collector layer was 160 nm.

  About the obtained thin film secondary battery, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that the current during charging and discharging was 100 μA, and charging and discharging were repeated 15 times. The results are shown in FIGS. In FIG. 5, the horizontal axis represents charge / discharge capacity (Capacity) [μAh], and the vertical axis represents cell voltage (Cell Voltage) [V]. In FIG. 6, the horizontal axis represents the cycle number (Cycle Number), and the vertical axis represents the charge / discharge capacity (Capacity) [μAh]. In FIG. 5, the curve rising to the right is the characteristic during charging, and the curve falling to the right is the characteristic during discharging. As can be seen from these measurement results, it was confirmed that a stable and substantially constant charge / discharge curve and charge / discharge capacity were exhibited.

(Example 1-2)
In order to manufacture the thin film secondary battery having the configuration shown in FIG. 1, an undercoat layer is formed on the substrate using the same resin composition as in Example 1-1, and a secondary battery layer is formed thereon. Formed. A substrate made of a polyimide film was used as the substrate. Other than the material of the substrate, it is the same as (Example 1-1) described above.

  About the obtained thin film secondary battery, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that the current during charging and discharging was 50 μA, and charging and discharging were repeated 15 times. The result is shown in FIG. In FIG. 7, the horizontal axis represents charge / discharge capacity (Capacity) [μAh], and the vertical axis represents cell voltage (Cell Voltage) [V]. In FIG. 7, the curve that rises to the right is the characteristic during charging, and the curve that falls to the right is the characteristic during discharging. As can be seen from this measurement result, it was confirmed that a stable and substantially constant charge / discharge curve and charge / discharge capacity were exhibited.

(Example 1-3)
In order to manufacture the thin film secondary battery having the configuration shown in FIG. 2, an undercoat layer is formed on the substrate using the same resin composition as in Example 1-1, and a secondary battery layer is formed thereon. Formed. As the substrate, as shown in FIG. 9, a resin film substrate whose surface was embossed was used. Except for the configuration and the material of the substrate, it is the same as Example (1-1) described above. In addition, this (Example 1-3) assumed manufacturing the composite thin film device which forms a thin film secondary battery on a solar cell (Solar Cell) as a board | substrate through an undercoat layer on it. Is.

  About the obtained thin film secondary battery 1, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that the current during charging and discharging was 50 μA, and charging and discharging were performed twice. The result is shown in FIG. In FIG. 8, the horizontal axis represents the charge / discharge capacity (Capacity) [μAh], and the vertical axis represents the cell voltage (Cell Voltage) [V]. In FIG. 8, the curve rising to the right is a characteristic during charging, and the curve falling to the right is a characteristic during discharging. For reference, the case where the current during charging is 100 μA is also shown. As can be seen from this measurement result, it was confirmed that a stable and substantially constant charge / discharge curve and charge / discharge capacity were exhibited. Thus, even when a substrate having an uneven surface is used, the surface of the undercoat layer is smooth, and the characteristics of the thin-film secondary battery formed on the undercoat layer are good. Recognize.

(Example 1-4)
In order to manufacture the thin film secondary battery having the configuration shown in FIG. 3, the secondary battery layer is formed on the substrate without forming the undercoat layer, and the same as (Example 1-1) is formed thereon. A protective layer was formed using the resin composition. A glass substrate was used as the substrate. In order to form a protective layer, this resin composition solution was applied by spin coating on a substrate including a secondary battery layer. Next, this resin composition solution is heated at 90 ° C. for 5 minutes (first heat treatment step), and further heated at 250 ° C. for 60 minutes (second heat treatment step) to form an organic film as a protective layer. Formed. The thickness of this protective layer was 500 nm. Except for these, the procedure is the same as the above-described (Example 1-1).

  About the obtained thin film secondary battery, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that current during charging and discharging was 50 μA, and charging and discharging were performed 15 times. The result is shown in FIG. In FIG. 11, the horizontal axis represents charge / discharge capacity (Capacity) [μAh], and the vertical axis represents cell voltage (Cell Voltage) [V]. In FIG. 11, a curve that rises to the right is a characteristic during charging, and a curve that falls to the right is a characteristic during discharge. As can be seen from this measurement result, it was confirmed that a stable and substantially constant charge / discharge curve and charge / discharge capacity were exhibited. Thus, even when the secondary battery layer is covered with the protective layer, it can be seen that the characteristics of the thin film secondary battery are good.

(Example 1-5)
In order to manufacture the thin film secondary battery having the configuration shown in FIG. 4, an undercoat layer is formed on the substrate using the same resin composition as in Example 1-1, and a secondary battery layer is formed thereon. Further, a protective layer was formed thereon using the same resin composition as in (Example 1-1). A glass substrate was used as the substrate. The treatment for forming the protective layer is the same as in (Example 1-4). Except for these, the procedure is the same as the above-described (Example 1-1).

  About the obtained thin film secondary battery, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that the current during charging and discharging was 100 μA, and charging and discharging were repeated 20 times. The results are shown in FIGS. In FIG. 12, the horizontal axis represents the charge / discharge capacity (Capacity) [μAh], and the vertical axis represents the cell voltage (Cell Voltage) [V]. In FIG. 13, the horizontal axis represents the number of cycles (Cycle Number), and the vertical axis represents the charge / discharge capacity (Capacity) [μAh]. In FIG. 12, a curve that rises to the right is a characteristic during charging, and a curve that falls to the right is a characteristic during discharge. As can be seen from these measurement results, it was confirmed that a stable and substantially constant charge / discharge curve and charge / discharge capacity were exhibited. Thus, even when the secondary battery layer formed on the undercoat layer is covered with the protective layer, it can be seen that the characteristics of the thin film secondary battery are good. In particular, in this (Example 1-5), since the undercoat layer and the protective layer are formed of the same material and by the same film forming method, the number of manufacturing steps can be maintained while maintaining the characteristics of the thin film secondary battery. The manufacturing cost could be reduced.

(Comparative Example 1)
In order to compare with the above (Example 1-1) to (Example 1-5), a secondary battery layer was formed on the substrate. A glass substrate was used as the substrate. No undercoat layer or protective layer was provided. Except for these, the procedure is the same as the above-described (Example 1-1).

  About the obtained thin film secondary battery, in order to evaluate the battery performance, the charging / discharging characteristic was measured using the charging / discharging measuring device. Measurement conditions were such that the current during charging and discharging was 50 μA, and charging and discharging were repeated 15 times. The result is shown in FIG. In FIG. 10, the horizontal axis represents the charge / discharge capacity (Capacity) [μAh], and the vertical axis represents the cell voltage (Cell Voltage) [V]. In FIG. 10, a curve that rises to the right is a characteristic during charging, and a curve that falls to the right is a characteristic during discharge.

  As can be seen by comparing the measurement results of (Comparative Example 1) with the measurement results of (Example 1-1) to (Example 1-5) described above, the undercoating layer and / or the resin composition described above were used. Alternatively, it can be understood that when the protective layer is formed, a substantially constant charge / discharge curve and charge / discharge capacity can be realized stably without adversely affecting the characteristics of the obtained thin film secondary battery.

(Example 1-6)
In order to evaluate the surface smoothness of the film formed of the above-described resin composition formed on the substrate, the resin composition solution is applied onto the substrate by a spin coating method, dried, and baked. Observation was performed at 450 times using a product of KEYENCE, trade name: VHX-600).

  As the resin composition solution, the ZOP3 solution shown in (Example 1-1) and the ZNX-480 (trade name) manufactured by Nippon Zeon Co., Ltd., which is a COP solution, were used. In the film formation using the ZOP3 solution, 1 ml (milliliter) of the solution was dropped on the substrate, and spin coating was performed by rotating for 30 seconds at a rotation speed of 1000 rpm with a spin coater. Subsequently, it heat-processed for 5 minutes at 90 degreeC, and also baked for 60 minutes in 180 degreeC Ar gas atmosphere. The film thickness of the obtained resin film was about 500 nm. In the film formation using the COP solution, 1 ml (milliliter) of the solution was dropped on the substrate, and spin coating was performed by rotating for 30 seconds at a rotation speed of 1000 rpm with a spin coater. Subsequently, it heat-processed for 5 minutes at 100 degreeC. The film thickness of the obtained resin film was about 450 nm.

As the substrate, a glass substrate, an aluminum vapor-deposited glass substrate, and a stainless steel substrate were used. The aluminum-deposited glass substrate was formed by evaporating aluminum on the glass substrate so that the degree of vacuum was less than 1 × 10 ⁻² Pa, the substrate temperature was RT (room temperature), and the film thickness was about 200 nm.

  14 shows an optical image in which a ZNX480 film is formed on a glass substrate, FIG. 15 shows an optical image in which a ZOP3 film is formed on the glass substrate, and FIG. 16 shows an optical image in which a ZOP3 film is formed on an aluminum-deposited glass substrate. FIG. 17 shows an optical image in which a ZOP3 film is formed on a stainless steel substrate, and FIG. 18 shows an optical image in which a ZNX480 film is formed on a stainless steel substrate.

  The ZOP3 film formed on the glass substrate of FIG. 15, the ZOP3 film formed on the aluminum-deposited glass substrate of FIG. 16, and the ZOP3 film formed on the stainless steel substrate of FIG. 17 are excellent in surface smoothness. I understand that. This is more apparent by comparing the ZNX480 film formed on the glass substrate of FIG. 14 and the ZNX480 film formed on the stainless steel substrate of FIG.

(2) Second embodiment (organic thin film transistor)
Hereinafter, a second embodiment according to an organic thin film transistor will be described as an example of a thin film device.

(2-1) Overall Configuration of Organic Thin Film Transistor The organic thin film transistor of this embodiment includes an organic semiconductor film, a gate electrode, a source electrode, a drain electrode, and a gate insulating film on a substrate. The structure of the organic thin film transistor includes a top gate stagger type, a top gate coplanar type, a bottom gate stagger type, a bottom gate coplanar type, and a bottom gate coplanar type. Gate Coplanar type), and any of these types may be used.

  FIG. 19 is a diagram showing a configuration of a bottom gate / stagger type organic thin film transistor as an example. This organic thin film transistor has an undercoat layer 12 on a substrate 11. A gate electrode 18 and a gate insulating film 17 are provided in contact with the undercoat layer 12. An organic semiconductor film 16, a drain electrode 14, and a source electrode 15 are provided on the gate insulating film 17. Further, a protective film (sealing film) 23 is provided thereon as an outermost layer. In FIG. 20, the gate insulating film 17 has a two-layer structure of a low dielectric layer 17a and a ferroelectric layer 17b. In this case, the low dielectric film 17a is interposed and disposed between the organic semiconductor film 16 and the ferroelectric film 17b.

  The configuration of FIG. 19 or FIG. 20 is an example, and is not limited to the top contact type, may be a bottom contact type, is not limited to the bottom gate type, and may be a top gate type.

  Such an organic thin film transistor may be used alone as shown in FIG. 19 or FIG. 20, but other thin film devices such as a thin film secondary battery (see the first embodiment described above), a thin film solar cell, and the like have been described above. It is good also as a composite thin film device laminated | stacked on the organic thin-film transistor. Further, the above-described organic thin film transistor (or a thin film transistor having a different structure) may be stacked in a plurality of stages, or a stacked device in which the above-described organic thin film transistor and other circuits are stacked. In these cases, each layer constituting the organic thin film transistor is formed on the uppermost layer of the thin film secondary battery, the thin film solar battery or the like via an undercoat layer (in this case, an intermediate insulating layer), or the organic thin film transistor Another thin film device is formed on the uppermost layer via a protective film (in this case, an intermediate insulating layer).

(2-2) Organic Semiconductor Film An organic semiconductor material is used for forming the organic semiconductor film. Examples of the organic semiconductor material include π-conjugated materials. Examples of π-conjugated materials include polypyrroles such as polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), and poly (3,4-disubstituted pyrrole); polythiophene and poly (3-substituted thiophene) , Polythiophenes such as poly (3,4-disubstituted thiophene) and polybenzothiophene; polyisothianaphthenes such as polyisothianaphthene; polychenylene vinylenes such as polychenylene vinylene; poly (p-phenylene vinylene) Poly (p-phenylene vinylenes) such as polyaniline; polyanilines such as polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2,3-substituted aniline); polyacetylenes such as polyacetylene; Polydiacetylenes such as polydiacetylene; Polyazule such as polyazulene Polypyrenes such as polypyrene; polycarbazoles such as polycarbazole and poly (N-substituted carbazole); polyselenophenes such as polyselenophene; polyfurans such as polyfuran and polybenzofuran; poly (p-phenylene) and the like Poly (p-phenylene) s; polyindoles such as polyindole; polypyridazines such as polypyridazine; naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, pyrene, dibenzopyrene, chrysene, perylene, coronene , Terylene, Ovalene, Quoterylene, Circumanthracene, and other polyacenes; and derivatives in which a part of carbon of the polyacenes is substituted with a functional group such as an atom such as N, S, or O, or a carbonyl group (triphenodioxazine, Riphenodithiazine, hexacene-6,15-quinone, etc.), polymers such as polyvinyl carbazole, polyphenylene sulfide, polyvinylene sulfide, and polycyclic condensates described in Japanese Patent Application Laid-Open No. 11-195790. it can.

  In addition, α-sexual thiophene, α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-, which are the same repeating units as those polymers, for example, which are thiophene hexamers Examples thereof include oligomers such as bis (3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives.

  Further, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A-11-251601; naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4- Trifluoromethylbenzyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (1H, 1H-perfluorooctyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N '-Bis (1H, 1H-perfluorobutyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide and N, N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimide, naphthalene 2,3 Naphthalenetetracarboxylic acid diimides such as 6,7-tetracarboxylic acid diimide; and anthracene 2, Condensed ring tetracarboxylic acid diimides such as anthracene tetracarboxylic acid diimides such as 1,6,7-tetracarboxylic acid diimide; fullerenes such as C60, C70, C76, C78, C84, carbon nanotubes such as SWNT, merocyanine dyes And pigments such as hemicyanine pigments.

  Among these π-conjugated materials, thiophene, chelenylene vinylene, phenylene vinylene, p-phenylene, and at least one of these substituents are used as repeating units, and the number n of the repeating units is 4 to 10. At least one selected from the group consisting of oligomers and polymers in which the number n of repeating units is 20 or more; condensed polycyclic aromatic compounds such as pentacene; fullerenes; condensed ring tetracarboxylic acid diimides; and metal phthalocyanines preferable.

  Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. , And the like. Further examples include σ conjugated polymers such as polysilane and polygermane, and organic / inorganic hybrid materials described in Japanese Unexamined Patent Publication No. 2000-260999.

  For the organic semiconductor film, for example, materials having functional groups such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, nitro group; benzoquinone derivatives, tetracyanoethylene, tetracyanoquinodimethane, and derivatives thereof A material that serves as an acceptor for accepting electrons, such as: a material having a functional group such as an amino group, a triphenyl group, an alkyl group, a hydroxyl group, an alkoxy group, or a phenyl group; a substituted amine such as phenylenediamine, anthracene, or benzoanthracene Further, a material which becomes a donor which is an electron donor, such as substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and derivatives thereof, and tetrathiafulvalene and derivatives thereof may be contained.

  Organic semiconductor film deposition (formation) methods include vacuum deposition, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, plasma polymerization, electrolytic weight Examples thereof include a combination method, a chemical polymerization method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and an LB method.

  When a resin composition mainly composed of an alicyclic olefin polymer using limonene as a solvent is used for forming a gate insulating film, which will be described later, an organic semiconductor film formed on the gate insulating film is formed by a vacuum deposition method. Alternatively, it is preferable to use a crystal growth method, and when forming a film by crystal growth, it is preferable to control the crystal grain size in the range of 1 μm to 0.1 μm.

  The film thickness of the organic semiconductor film varies depending on the organic semiconductor material used, but is usually 1 μm or less, preferably from a monolayer thickness to 400 nm.

(2-3) Electrodes Each electrode (gate electrode, source electrode and drain electrode) constituting the organic thin film transistor is formed of a conductive material. Examples of conductive materials include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, and oxide. Tin antimony, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, Gallium, Niobium, Sodium, Sodium-potassium alloy, Magnesium / copper mixture, Magnesium / silver mixture, Magnesium / aluminum mixture, Magnesium / indium mixture, Aluminum / Al oxide Bromide mixture, lithium / aluminum mixture and the like. In addition, known conductive polymers whose conductivity is improved by doping or the like, such as conductive polyaniline, conductive polypyrrole, and conductive polythiophene (polyethylenedioxythiophene and polystyrenesulfonic acid complex, etc.) can be mentioned.

  In particular, the material for forming the source electrode and the drain electrode is preferably a material having a low electrical resistance at the contact surface with the organic semiconductor film among the materials listed above. In the case of a p-type semiconductor, in particular, platinum, gold, silver ITO, conductive polymer and carbon are preferred.

  These gate electrodes, source electrodes, and drain electrodes are formed using fluid electrode materials such as solutions, pastes, inks, and dispersions containing the above conductive materials, in particular, conductive polymers or platinum. It is preferable to use a fluid electrode material containing metal fine particles containing gold, silver and copper.

  As the fluid electrode material containing metal fine particles, for example, a known conductive paste may be used. Preferably, metal fine particles having an average particle diameter of 1 to 50 nm, preferably 1 to 10 nm are used as necessary. Using a dispersion stabilizer, a material dispersed in a dispersion medium that is water or an arbitrary organic solvent is used. The average particle diameter can be measured by a photon correlation method.

  As the material of the metal fine particles, in addition to the above-described platinum, gold, silver, copper, nickel, chromium, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, Tungsten, zinc or the like may be used.

  As a method for producing such a dispersion of fine metal particles, metal ions are reduced in the liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, metal vapor synthesis method, colloidal method, coprecipitation method, etc. And a chemical production method for producing metal fine particles. After forming an electrode using these metal fine particle dispersions and drying the solvent, the metal fine particles are thermally fused by heating in the range of 100 to 300 ° C., preferably 150 to 200 ° C. as necessary. To form an electrode pattern having a desired shape.

  As a method for forming an electrode, a conductive thin film is formed by sputtering or vapor deposition using the conductive material as a raw material, then a pattern is formed with a photoresist, and then an unnecessary thin film is removed by etching to form an electrode pattern. Lithographic method; metal mask method in which a metal mask is placed on a substrate and sputtering or vapor deposition is performed to form an electrode pattern; after a photoresist pattern is formed on a metal foil such as aluminum or copper by thermal transfer or ink jet Known methods such as a method of forming an electrode pattern by removing an unnecessary thin film by etching may be used. Alternatively, a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink jet method, or may be formed from a coating film by lithography or laser ablation. Further, a method of patterning a conductive ink or conductive paste containing a conductive polymer or metal fine particles by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used. The thickness of the electrode is not particularly limited, but is usually 20 to 500 nm, preferably 50 to 200 nm.

(2-4) Gate insulating film The gate insulating film of this embodiment is a film comprising an organic polymer compound. The organic polymer compound contained in the gate insulating film has a small relative dielectric constant and is usually 3 or less. In this embodiment, the relative dielectric constant can be measured by a capacitance method using an LCR meter (product number 4284A manufactured by Agilent Technologies). Examples of such organic polymer compounds include polyolefins such as polyethylene, polypropylene, and polybutene; alicyclic olefin polymers; polyamines; polyethers; Of these, alicyclic olefin polymers can be suitably used from the viewpoint that the frequency dependence of the dielectric constant is small.

  As an alicyclic olefin polymer, the thing similar to what was demonstrated about the undercoat layer and protective layer of 1st Embodiment mentioned above can be used. The resin composition in the case where the resin composition mainly composed of the alicyclic olefin polymer is used for forming the gate insulating film preferably contains an aliphatic hydrocarbon compound. In this case, the aliphatic hydrocarbon compound is preferably an alicyclic hydrocarbon having a boiling point of 150 ° C. or more, more preferably an alicyclic hydrocarbon having a boiling point of 150 to 250 ° C., and a boiling point of 160 to 230 ° C. The alicyclic hydrocarbon is more preferably, and an alicyclic hydrocarbon having a boiling point of 170 to 200 ° C. is particularly preferable. If the boiling point of the alicyclic hydrocarbon is too high, the volatility at the time of forming the resin film is inferior. For this reason, if sufficient volatilization is performed, the resin film may be oxidatively deteriorated.

  Examples of alicyclic hydrocarbons having a boiling point of 150 ° C. or higher include cyclooctane (boiling point 151 ° C.), cyclononane (boiling point 171 ° C.), cyclodecane (boiling point 201 ° C.), cycloundecane (boiling point 91 ° C. (1.6 kPa)), etc. Such as cyclononene (boiling point 168 ° C.), cyclooctadiene, 1,4,7-cyclodecatriene, 1,5,9-cyclodecatriene (boiling point 231 ° C.), cyclooctyne (boiling point 157 ° C.), etc. Saturated alicyclic monocyclic hydrocarbons; saturated alicyclic polycyclic hydrocarbons such as decahydronaphthalene (common name: decalin, boiling point 190 ° C, cis-trans mixture), and unsaturated such as dicyclopentadiene (boiling point 170 ° C) Alicyclic polycyclic hydrocarbons; limonene (boiling point 176 ° C.), m-menthane (boiling point 167 ° C.), p-menthane (boiling point 171 ° C.), 3- -Mentene (boiling point 169 ° C.), α-ferrandolene (boiling point 67 ° C. (2.1 kPa)), β-ferrandolene (boiling point 180 ° C.), α-pinene (boiling point 156 ° C.), β-pinene (boiling point 165 ° C.) And monoterpenes such as α-serinene (boiling point 143 ° C. (2.7 kPa)), β-selinene (boiling point 134 ° C. (17.8 kPa)), and the like.

Among these, limonene can be preferably used. Limonene is a kind of monocyclic monoterpene and has a chemical formula of C ₁₀ H ₁₆ and a molecular weight of 136.23. When such limonene is used as the solvent for the alicyclic olefin polymer, the surface smoothness of the resin film (gate insulating film) formed using this resin composition can be obtained satisfactorily. In the case of using such a resin composition mainly composed of an alicyclic olefin polymer containing limonene as a solvent, according to experiments by the present inventors, the surface smoothness of the gate insulating film is expressed by root mean square roughness (RMS). It was found that control was possible to 1 nm or less.

  In the present invention, after the ring-opening metathesis polymerization of the alicyclic olefin, the resin composition is prepared without separating the polymer from the polymerization reaction solution. Therefore, the same solvent used for the resin composition is polymerized. It is preferable to use it as a solvent. Thereby, environmental pollution resulting from solvent removal can be suppressed, and since the steps of polymer isolation, drying and re-dissolution in a solvent can be omitted, the productivity of the resin composition is improved.

  Specific examples of such solvents may include monoalkylene glycol solvents; polyalkylene glycol solvents; monoalkylene glycol alkyl ester solvents; polyalkylene glycol alkyl ester solvents; monoalkylene glycol diester solvents; polyalkylene glycol diester solvents. .

  Examples of monoalkylene glycol solvents include monoalkylene glycols such as ethylene glycol and propylene glycol; monoalkylene glycol monoethers such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; ethylene And monoalkylene glycol dialkyl ethers such as glycol diethyl ether and propylene glycol dimethyl ether.

  Examples of polyalkylene glycol solvents include polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl Polyalkylene glycol monoalkyl ethers such as ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol Polyalkylene glycol dialkyl ethers such as methyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether; Can be mentioned.

  Specific examples of the monoalkylene glycol alkyl ester solvent include propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono i- Examples thereof include butyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol mono t-butyl ether acetate and the like.

  Specific examples of the polyalkylene glycol alkyl ester solvent include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate and the like.

  Specific examples of the monoalkylene glycol diester solvent include ethylene glycol diacetate and propylene glycol diacetate. Specific examples of the polyalkylene glycol diester solvent include diethylene glycol diacetate, dipropylene glycol diacetate, and triethylene glycol diacetate.

  In addition to these, high-boiling ketone solvents such as 2-heptanone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; high-boiling alcohol solvents such as 3-methoxy-3-methylbutanol and 3-methoxybutanol; ethyl lactate , N-propyl lactate, isopropyl lactate, 3-methoxybutyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, ethyl 3-ethoxypropionate, γ-butyllactone, etc. Solvent; Amide solvent such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylacetamide; Dimethyl sulfoxide;

  Among these, preferred solvents are polyalkylene glycol solvents, monoalkylene glycol alkyl ester solvents and polyalkylene glycol alkyl ester solvents, among which those having a boiling point of 150 ° C. or higher are preferred, and boiling points of 150 to 250 ° C. are preferred. Those are more preferred.

  In the present invention, the polymerization conditions are not particularly limited for ring-opening metathesis polymerization of an alicyclic olefin. The polymerization temperature is not particularly limited, but is usually −50 to + 150 ° C., preferably 0 to 100 ° C. The polymerization time may be appropriately determined according to the polymerization temperature, the amount of catalyst used, etc., but is usually from 1 minute to 24 hours. The polymerization atmosphere is not particularly limited, and may be performed in air or the like when the ring-opening metathesis polymerization catalyst is stable, but it is preferably performed in an inert gas atmosphere such as nitrogen, carbon dioxide gas, or rare gas.

  The alicyclic olefin ring-opening metathesis polymer thus obtained is preferably a weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as an eluent from the viewpoint of patternability and developability. The content of oligomer components having an average molecular weight of 2,000 to 10,000 and a number average molecular weight of 1,000 or less is 2% by weight or less. The ring-opening metathesis polymer preferably has a weight average molecular weight / number average molecular weight ratio of 1.80 or less. In the present invention, the oligomer content is a value calculated from a peak area ratio measured by gel permeation chromatography-low angle laser light scattering light intensity (GPC-LALLS) method.

  After the polymerization step, the polymer composition can be used as a mixture of a resin and a solvent to adjust the resin composition without performing operations such as separation, drying, and re-dissolution of the polymer from the polymerization reaction solution. According to this method, it is not necessary to separate the polymer once and redissolve it in a solvent, which is advantageous in terms of equipment, environmental safety and energy.

  The resin composition of the present invention contains an alicyclic olefin ring-opening metathesis polymer obtained by ring-opening metathesis polymerization of an alicyclic olefin instead of a polymerization reaction solution containing a ring-opening metathesis polymer. A hydrogenation reaction solution containing a hydride of a ring-opening metathesis polymer obtained by introducing hydrogen into the polymerization reaction solution and hydrogenating the alicyclic olefin ring-opening metathesis polymer can also be used. That is, the hydrogenation reaction of the alicyclic olefin ring-opening metathesis polymer is carried out with the polymerization reaction solution obtained by the ring-opening polymerization.

  The alicyclic olefin ring-opening metathesis polymer hydride obtained by this hydrogenation preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of 2,500 to 15,000 (more preferably , 3,000 to 12,000), and the content of the oligomer component having a number average molecular weight of 1,000 or less is 2% by weight or less. The hydride of the ring-opening metathesis polymer preferably has a weight average molecular weight / number average molecular weight ratio of 1.80 or less.

  As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used. Among these hydrogenation catalysts, a carbon-supported palladium catalyst and a noble metal complex catalyst such as rhodium and ruthenium are preferable because they do not cause side reactions such as modification of a functional group such as a protic polar group, and have a high electron donating property. A ruthenium catalyst coordinated with a nitrogen-containing heterocyclic carbene compound or phosphines is particularly preferred.

  The hydrogenation catalyst can be removed by adding a porous solid insoluble in the reaction solution, such as activated carbon, to the hydrogenation reaction solution after the hydrogenation reaction, adsorbing the catalyst to the hydrogenation reaction solution, and then filtering. When the catalyst is adsorbed to the porous solid, the catalyst adsorbs efficiently when hydrogen is dissolved in the hydrogenation reaction solution.

  In the present invention, (1) a resin composition can be obtained by adding a curing agent to a polymerization reaction solution containing an alicyclic olefin polymer obtained by polymerizing an alicyclic olefin, (2) A hydrogenation reaction solution containing an alicyclic olefin polymer hydride obtained by introducing hydrogen into the polymerization reaction solution and hydrogenating the alicyclic olefin polymer contained in the polymerization reaction solution. A resin composition can be obtained by blending a curing agent.

  At this time, excess solvent can be distilled off from the polymerization reaction solution or the hydrogenation reaction solution, or a new solvent can be added.

  The resin composition for forming the gate insulating film may contain other known organic polymer compounds. The content of the organic polymer compound in the gate insulating film is preferably 70 to 100% by weight, more preferably 90 to 100% by weight. In addition, other colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. are added as appropriate. It may be what you did.

  As a method for forming (forming) a gate insulating film, a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, a plasma polymerization method, an electrolytic weight Examples thereof include a combination method, a chemical polymerization method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and an LB method. Of these, the wet method is preferred. The wet method is a method in which the organic polymer compound constituting the low dielectric film and optionally the compounding agent are dissolved in a solvent to obtain a solution, the solution is cast, and then the solvent is removed to form a film. It is. The solvent to be used may be appropriately selected from known solvents according to the organic polymer compound to be used. Examples of the wet method include spin coating, blade coating, dip coating, roll coating, bar coating, die coating, screen printing, and inkjet printing. In addition, a printing method called soft lithography such as microcontact printing or micromolding can be applied. Of these wet methods, the spin coating method is particularly preferable.

(2-4-1) Two-layer gate insulating film The gate insulating film includes a low dielectric film having a relatively low dielectric constant and a ferroelectric film (high dielectric film) having a relatively high dielectric constant. May be a film having a two-layer structure (see FIG. 20). Although a two-layered gate insulating film is described here, a multilayered film having three or more layers may be used. As the low dielectric film, the same resin composition mainly composed of an alicyclic olefin polymer containing limonene as a solvent can be used as in the gate insulating film described above.

  The relative dielectric constant of the low dielectric film is usually set to a value of 4 or less, preferably set to a value of 3.5 or less, and more preferably set to a value of 3 or less. The lower limit of the relative dielectric constant is usually about 2. The film thickness of the low dielectric film is preferably set to 5 nm to 500 nm, more preferably 10 nm to 300 nm. The relative dielectric constant of the ferroelectric film is usually set to a value of 5 or more, preferably 7 or more, and more preferably 10 or more. The upper limit of the relative dielectric constant is usually about 50. The film thickness of the ferroelectric film is preferably set to 5 nm to 500 nm, more preferably 10 nm to 300 nm. By appropriately setting the relative dielectric constant and film thickness of the low dielectric film and the relative dielectric constant and film thickness of the ferroelectric film, the effective dielectric constant of the entire gate insulating film can be adjusted. The thickness of the gate insulating film as a whole of the low dielectric film and the ferroelectric film laminated may be any thickness as long as the insulating property is maintained, but generally 10 to 500 nm is preferably used. More preferably, it is 10 to 300 nm. It is desirable to make it as thin as possible as the size of the organic thin film transistor element is reduced.

(2-4-2) Ferroelectric film The material of the ferroelectric film is not particularly limited, but is usually an insulating organic polymer alone, or an insulating organic polymer and an inorganic metal oxide or a high dielectric insulator. A mixture of these with nanoparticles can be used. The dielectric constant can be adjusted by selecting the insulating organic polymer or adjusting the mass ratio between the insulating organic polymer and the nanoparticles. Using such a material, a ferroelectric film can be formed according to the same formation method as the low dielectric film described above. Also in the formation of the ferroelectric film, the wet method is preferable among the above-described formation methods, and the spin coating method is particularly preferable.

  Examples of the insulating organic polymer include polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyethersulfone, and polyetherketone. , Polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polycarbodiimide, polysiloxane, polymethyl methacrylate, polymethacrylamide, nitrile rubber, acrylic rubber, polyethylene tetrafluoride, epoxy resin, phenol resin, melamine resin , Urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, Butadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated polyisoprene, hydrogenated polybutadiene, and cyanoethylated One or more substances selected from the group consisting of cellulose can be used.

The inorganic metal oxide nanoparticles are not particularly limited, and examples thereof include nanoparticles such as Ta ₂ O ₅ , Y ₂ O ₃ , TiO ₂ , CeO _2, and ZrO ₂ . The nanoparticles of the high dielectric insulator are not particularly limited. For example, Ba _d Sr _1-d TiO ₃ (where d satisfies 0 <d <1; BST), PbZr _e Ti _{1- e} O ₃ (wherein _e satisfies 0 <e <1; PZT), Bi ₄ Ti ₃ O ₁₂ , BaMgF ₄ , SrBi ₂ (Ta _1-f Nb _f ) ₂ O ₉ (where f is 0 <f <1 is satisfied), Ba (Zr _1-g Ti _g ) O ₃ (wherein g satisfies 0 <g <1; BZT), BaTiO ₃ , SrTiO ₃ and Bi ₄ Ti ₃ O. Nanoparticle such as ₁₂ . _{Incidentally, Ba d Sr 1-d TiO} 3 is what is referred to as Barium Strontium Titanate, usually, BaTiO ₃ and SrTiO ₃ in a weight ratio: in _{(BaTiO 3 SrTiO 3) 1:} 9~9: 1 in It is obtained by mixing at a ratio. These nanoparticles can be used alone or in admixture of two or more. As said nanoparticle, a thing with a dielectric constant of 5 or more is preferable, From this viewpoint, the nanoparticle of a highly dielectric insulator is used suitably normally. The average particle diameter of the nanoparticles is usually 50 nm or less, preferably 1 to 50 nm, more preferably 1 to 30 nm. The dielectric constant can be measured according to JIS K 6911, and the average particle diameter can be measured by a dynamic light scattering method.

  The material of the ferroelectric film is at least one organic metal selected from the group consisting of a titanium compound, a zirconium compound, a hafnium compound, and an aluminum compound in place of the above-described nanoparticle instead of the insulating organic polymer as described above. You may use what mixed the compound. Also in this case, it is preferable to use an organometallic compound having a relative dielectric constant of 5 or more.

(2-5) Substrate In the organic thin film transistor of this embodiment, a substrate is used to support the thin film organic thin film transistor. The substrate is not particularly limited, and any material may be used. Generally used as the substrate is polycarbonate, polyimide, polyethylene terephthalate (PET) or other flexible plastic substrate such as alicyclic olefin polymer, but glass such as quartz, soda glass, inorganic alkali glass, etc. A substrate, a silicon wafer, or the like can also be used.

(2-6) Undercoat layer and protective layer The organic thin film transistor of the present embodiment has a protective layer as an outermost layer on the substrate in addition to the undercoat layer. However, the structure which abbreviate | omitted either the undercoat layer or the protective layer may be sufficient.

  Formation of the undercoat layer and / or protective layer in the organic thin film transistor of the present embodiment uses the same resin composition as the undercoat layer and protective layer in the thin film secondary battery of the first embodiment described above, and the same formation method Can be done. Since the description is duplicated, a detailed description thereof is omitted here.

(Example 2-1)
In this example, an organic electronic device including the bottom gate / stagger type organic thin film transistor (TFT) shown in FIG. 19 was manufactured. Although the undercoat layer was formed, the protective film was not formed.

  A glass substrate (25 mm × 10 mm × 1 mm in size) was used as the substrate. As the substrate, a polyethylene terephthalate film substrate (25 mm × 10 mm × 0.5 mm in size) may be used.

  As the resin composition solution for forming the undercoat layer on the substrate, a ZOP3 solution prepared in the same manner as in Example 1-1 for the thin film secondary battery was used. 1 ml of this resin composition solution was dropped on the substrate, and spin coating was performed at a rotation speed of 1000 rpm for 30 seconds. Next, heat treatment was performed at 90 ° C. for 5 minutes (first heat treatment step), and further heat treatment was performed at 180 ° C. for 60 minutes (second heat treatment step) to form an organic film as an undercoat layer. The thickness of this undercoat layer was about 500 nm.

A gate electrode was formed on the undercoat layer by aluminum vapor deposition. The aluminum was deposited such that the degree of vacuum was less than 1 × 10 ⁻² Pa, the temperature of the substrate was RT (room temperature), and the film thickness was about 200 nm.

  A single-layer gate insulating film was formed on the undercoat layer on which the gate electrode was formed. For the gate insulating film, 0.5 ml of a 5% cyclohexane solution of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) was applied at a rotational speed of 2000 rpm for 30 seconds using a spin coating method, and 5% at 100 ° C. It was formed by heat treatment for minutes. The thickness of the gate insulating film was about 350 nm.

The organic semiconductor film was formed by vapor-depositing pentacene on the gate insulating film. The vapor deposition of pentacene was performed so that the degree of vacuum was less than 2 × 10 ⁻³ Pa, the substrate temperature was RT (room temperature), the deposition temperature was 190 ° C., the deposition rate was 0.06 nm / s, and the film thickness was about 50 nm. . The source electrode and the drain electrode (source-drain shape: W = 80 μm, L = 40 μm) were formed by covering a metal mask on the organic semiconductor film and depositing gold thereon. Gold was deposited such that the degree of vacuum was less than 1 × 10 ⁻² Pa, the temperature of the substrate was RT (room temperature), and the film thickness was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) manufactured in this way were evaluated by measuring a current-voltage curve, and the results are shown in FIG. 21 and FIG. As a measuring device, 2400 (trade name) manufactured by Keithley was used.

FIG. 21 is a VD-ID diagram when VG is constant (−60V, −50V, −40V, −30V) and VD is changed between 0V and −60V. FIG. 22 is a plot of ID square root versus VG in the case of VD = −60 V in FIG. The mobility was ˜0.42 cm ² / Vs. From these results, it can be seen that the organic thin film transistor having the undercoat layer of this example has good characteristics.

(Example 2-2)
In this example, an organic electronic device including the bottom gate / stagger type organic thin film transistor (TFT) shown in FIG. 19 was manufactured. The undercoat layer and the protective film were not formed.

  A glass substrate (25 mm × 10 mm × 1 mm in size) was used as the substrate.

A gate electrode was formed on the substrate by vapor deposition of aluminum. The aluminum was deposited such that the degree of vacuum was less than 1 × 10 ⁻² Pa, the temperature of the substrate was RT (room temperature), and the film thickness was about 200 nm.

  A single-layer gate insulating film was formed on the substrate on which the gate electrode was formed. For the gate insulating film, 1 ml of a 5% limonene solution of an alicyclic olefin polymer (manufactured by ZEON Corporation, trade name: ZNX480) is applied at a rotational speed of 2000 rpm for 30 seconds using a spin coating method, and heat treated at 100 ° C. for 5 minutes. Was formed. The thickness of the gate insulating film was about 130 nm.

The organic semiconductor film was formed by vapor-depositing pentacene on the gate insulating film. The vapor deposition of pentacene was performed so that the degree of vacuum was less than 2 × 10 ⁻³ Pa, the substrate temperature was RT (room temperature), the deposition temperature was 190 ° C., the deposition rate was 0.06 nm / s, and the film thickness was about 50 nm. . The source electrode and the drain electrode (source-drain shape: W = 5000 μm, L = 70 μm) were formed by covering a metal mask on the organic semiconductor film and depositing gold thereon. Gold was deposited such that the degree of vacuum was less than 1 × 10 ⁻² Pa, the temperature of the substrate was RT (room temperature), and the film thickness was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) thus manufactured were evaluated by measuring current-voltage curves, and the results are shown in FIGS. The measuring device is Keithley 2400.

FIG. 23 is a VD-ID diagram when VG is constant (−6V, −5V, −4V, −3V) and VD is changed between 0V and −6V. FIG. 24 is a plot of ID square root versus VG in the case of VD = −6V in FIG. In this example, the mobility was 2.34 × 10 ⁻³ cm ² / Vs, and the threshold voltage VT was −3.2V.

(Example 2-3)
As shown in FIG. 20, the gate insulating film was almost the same as (Example 2-2) except that a two-layer gate insulating film was used. The source-drain shape was W = 80 μm and L = 40 μm.

  As the ferroelectric film, which is the first layer of the gate insulating film having a two-layer structure, polyvinyl alcohol (PVA) was dissolved in high-purity water to produce a solution having a concentration of 5% by weight. This solution was applied by spin coating at a rotational speed of 2000 rpm for 30 seconds and subjected to heat treatment at 100 ° C. for 2 minutes to form a film. The thickness of this ferroelectric film was 240 nm.

  The low dielectric film which is the second layer of the gate insulating film is a spin coating method in which 1 ml of a 2.5% limonene solution of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is rotated at 4000 rpm for 30 seconds. Was formed by heat treatment at 100 ° C. for 5 minutes. The thickness of the low dielectric film was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) manufactured in this way were evaluated by measuring a current-voltage curve, and the results are shown in FIG. 25 and FIG. The measuring device is Keithley 2400.

FIG. 25 is a VD-ID diagram when VG is constant (−6V, −5V, −4V) and VD is changed between 0V and −6V. FIG. 26 is a plot of ID square root versus VG when VD = −6V in FIG. In this example, the mobility was 7.34 × 10 ⁻³ cm ² / Vs, and the threshold voltage VT was −3.34V.

(Example 2-4)
Except that the low dielectric film and the ferroelectric film constituting the gate insulating film were changed, it was almost the same as the above-mentioned (Example 2-3). The source-drain shape was W = 180 μm and L = 40 μm.

  As the ferroelectric film, which is the first layer of the gate insulating film having a two-layer structure, polyvinyl alcohol (PVA) was dissolved in high-purity water to produce a solution having a concentration of 2% by weight. This solution was applied by spin coating at a rotational speed of 2000 rpm for 30 seconds and heat-treated at 100 ° C. for 2 minutes. The thickness of this ferroelectric film was 150 nm.

  The low dielectric film which is the second layer of the gate insulating film is a spin coating method in which 1 ml of a 2.5% limonene solution of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is rotated at 4000 rpm for 30 seconds. Was formed by heat treatment at 100 ° C. for 5 minutes. The thickness of the low dielectric film was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) manufactured in this way were evaluated by measuring a current-voltage curve, and the results are shown in FIGS. The measuring device is Keithley 2400.

FIG. 27 is a VD-ID diagram when VG is constant (−6V, −5V, −4V) and VD is changed between 0V and −6V. FIG. 28 is a plot of ID square root versus VG in the case of VD = −6V in FIG. In this example, the mobility was 1.11 × 10 ⁻¹ cm ² / Vs, and the threshold voltage VT was −3.83V.

(Example 2-5)
Except that the low dielectric film and the ferroelectric film constituting the gate insulating film were changed, it was almost the same as the above-mentioned (Example 2-3). The source-drain shape was W = 80 μm and L = 40 μm.

  As the ferroelectric film, which is the first layer of the gate insulating film having a two-layer structure, polyvinyl alcohol (PVA) was dissolved in high-purity water to produce a solution having a concentration of 5% by weight. This solution was applied by spin coating at a rotational speed of 2000 rpm for 30 seconds and subjected to heat treatment at 100 ° C. for 2 minutes to form a film. The thickness of this ferroelectric film was 240 nm.

  The low dielectric film, which is the second layer of the gate insulating film, is a spin coating method in which 1 ml of a 2.5% limonene solution of an alicyclic olefin polymer (trade name: ZNX480 manufactured by Nippon Zeon Co., Ltd.) is rotated at 4000 rpm for 30 seconds. Was formed by heat treatment at 100 ° C. for 5 minutes. The thickness of the low dielectric film was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) manufactured in this way were evaluated by measuring a current-voltage curve, and the results are shown in FIG. 29 and FIG. The measuring device is Keithley 2400.

FIG. 29 is a VD-ID diagram when VG is constant (−20V, −16V, −12V) and VD is changed between 0V and −20V. FIG. 30 is a plot of ID square root versus VG in the case of VD = −20V in FIG. In this example, the mobility was 1.04 × 10 ⁻² cm ² / Vs, and the threshold voltage VT was −3.83V.

(Example 2-6)
Except that the low dielectric film and the ferroelectric film constituting the gate insulating film were changed, it was almost the same as the above-mentioned (Example 2-3). The source-drain shape was W = 80 μm and L = 40 μm.

  As the ferroelectric film, which is the first layer of the gate insulating film having a two-layer structure, polyvinyl alcohol (PVA) was dissolved in high-purity water to produce a solution having a concentration of 5% by weight. This solution was applied by spin coating at a rotational speed of 2000 rpm for 30 seconds and subjected to heat treatment at 100 ° C. for 2 minutes to form a film. The thickness of this ferroelectric film was 240 nm.

  The low dielectric film which is the second layer of the gate insulating film is a spin coating method in which 1 ml of a 2.5% limonene solution of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is rotated at 4000 rpm for 30 seconds. Was formed by heat treatment at 100 ° C. for 5 minutes. The thickness of the low dielectric film was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) manufactured in this way were evaluated by measuring a current-voltage curve, and the results are shown in FIGS. The measuring device is Keithley 2400.

FIG. 31 is a VD-ID diagram when VG is constant (−20V, −16V, −12V) and VD is changed between 0V and −20V. FIG. 32 is a plot of ID square root versus VG in the case of VD = −20V in FIG. In this example, the mobility was 0.56 cm ² / Vs, and the threshold voltage VT was −7.45V.

(Example 2-7)
Except that the low dielectric film and the ferroelectric film constituting the gate insulating film were changed, it was almost the same as the above-mentioned (Example 2-3). The source-drain shape was W = 180 μm and L = 40 μm.

  As the ferroelectric film, which is the first layer of the gate insulating film having a two-layer structure, polyvinyl alcohol (PVA) was dissolved in high-purity water to produce a solution having a concentration of 5% by weight. This solution was applied by spin coating at a rotational speed of 2000 rpm for 30 seconds and subjected to heat treatment at 100 ° C. for 2 minutes to form a film. The thickness of this ferroelectric film was 240 nm.

  The low dielectric film which is the second layer of the gate insulating film is a spin coating method in which 1 ml of a 2.5% limonene solution of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is rotated at 4000 rpm for 30 seconds. Was formed by heat treatment at 100 ° C. for 5 minutes. The thickness of the low dielectric film was about 100 nm.

  The electrical characteristics of the organic thin film transistor (organic TFT) thus manufactured were evaluated by measuring a current-voltage curve, and the results are shown in FIGS. The measuring device is Keithley 2400.

FIG. 33 is a VD-ID diagram when VG is constant (−20V, −16V, −12V) and VD is changed between 0V and −20V. FIG. 34 is a plot of ID square root vs. VG in the case of VD = −20V in FIG. In this example, the mobility was 0.929 cm ² / Vs, and the threshold voltage VT was −6.93 V.

(Example 2-8)
In order to evaluate the surface smoothness of the film formed from the resin composition (using limonene as a solvent) for forming the gate insulating film or the low dielectric film described above, the resin composition solution is formed on the substrate. Was applied by a spin coat method, dried and fired, and then observed using a digital microscope (manufactured by Keyence Corporation, trade name: VHX-600).

As the resin composition solution, an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is dissolved in limonene to obtain a solution having a concentration of 5% by weight, and 1 ml of the solution is rotated at 2000 rpm for 30 seconds. Using a spin coating method, it was applied onto a SiO ₂ (or Si) substrate and heat-treated at 100 ° C. for 5 minutes. The film thickness of the obtained organic coating was about 130 nm.

  FIG. 35 to FIG. 37 show optical images of a film formed on a substrate and made of an alicyclic olefin polymer using limonene as a solvent. As can be seen from these figures, the surface smoothness of the obtained resin coating was extremely good, and the root mean square roughness (RMS) was 1 nm or less.

  FIG. 42 shows an optical image in which an organic semiconductor film (pentacene) is further formed on the above-described resin film formed on the substrate and the surface thereof is observed with a digital microscope. It was found that the surface smoothness of the organic semiconductor film was also improved.

(Comparative Example 2)
In order to evaluate the surface smoothness of a film formed from a resin composition using cyclohexane as a solvent, the resin composition solution is applied onto a substrate by a spin coating method, dried and baked, and then a digital microscope (stock) It was observed using a product of Keyence Co., Ltd. (trade name: VHX-600).

As the resin composition solution, an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: ZNX480) is dissolved in cyclohexane to obtain a solution having a concentration of 5% by weight, and 1 ml of the solution is rotated at 3000 rpm for 30 seconds. Using a spin coating method, it was applied onto a SiO ₂ or Si substrate and heat-treated at 60 ° C. for 5 minutes. The film thickness of the obtained organic coating was about 450 nm.

  38 to 40 show optical images of a film formed of an alicyclic olefin polymer using cyclohexane as a solvent formed on a substrate. As can be seen from these figures, the surface smoothness of the obtained resin film is considerably inferior to the surface smoothness of the resin film obtained in (Example 2-8). The superiority of the film made of the resin composition was confirmed.

  FIG. 41 shows an optical image in which an organic semiconductor film (pentacene) is further formed on the resin film formed on the substrate described above and the surface thereof is observed with a digital microscope. The surface smoothness of the organic semiconductor film is considerably inferior to the surface smoothness of the organic semiconductor film obtained in (Example 2-8), and a film made of a resin composition containing limonene as a solvent is used. The superiority of using it was confirmed.

(Example 2-9)
FIG. 43 shows measured values of the change characteristics of dielectric constant (frequency dependence of dielectric constant) with respect to the frequency of each insulating film when the configuration and composition of the insulating film are changed. In the figure, the horizontal axis is the frequency f [Hz], and the vertical axis is the dielectric constant Cf [nF / cm ² ].

  In the figure, symbol a represents the characteristics of an insulating film (film thickness = 240 nm) formed of a single layer PVA 5 wt% solution, and symbol b represents an insulating film (film thickness = 130 nm) formed of a single layer COP 5 wt% limonene solution. ) Characteristics. The symbol c is a two-layer insulating film consisting of a ferroelectric film (film thickness = 240 nm) made of PVA 5 wt% solution and a low dielectric film (film thickness = 100 nm) made of COP 5 wt% limonene solution as a ferroelectric film. The symbol d is a ferroelectric film made of a PVA 5 wt% solution (film thickness = 240 nm) and a low dielectric film (film thickness = 100 nm) made of a COP 2.5 wt% limonene solution. The symbol e denotes a ferroelectric film made of a 2 wt% PVA solution (film thickness = 150 nm) and a low dielectric film made of a COP 2.5 wt% limonene solution (film thickness = The characteristics of a two-layer insulating film of 100 nm) are shown.

Dielectric constant Cf of the insulating film at a frequency f = 1 kHz, for symbol a is 25.4nF / cm ^2, for the symbol a is a 15.9nF / cm ^2, for code c is 8.17nF / cm ² The sign d was 19.3 nF / cm ² and the sign e was 33.2 nF / cm ² .

  Compared with the curve of the symbol a, it can be seen that the curves of the symbols b, c and e have a substantially constant dielectric constant even when the frequency changes. From the viewpoint of the curve with the symbol d, no superiority was found.

(3) Third embodiment (composite thin film device)
Using the technique of the present invention, a composite comprising an organic thin film formed on the upper surface of a first thin film device fabricated on a substrate by the organic film forming step described above, and a second thin film device fabricated on the upper surface. Thin film devices can be fabricated. Here, for example, the thin film secondary battery of the first embodiment is formed as the first thin film device, the organic thin film transistor of the second embodiment is formed as the second thin film device, and the thin film secondary battery is organic. It is also possible to operate the thin film transistor, further form the organic thin film on the upper surface thereof, and drive the third thin film device formed on the upper surface.

  Hereinafter, a third embodiment according to a composite thin film device in which an organic thin film transistor is stacked on another circuit will be described. As another circuit, a dielectric memory etc. can be illustrated, for example. In this case, an organic thin film transistor can be used as a drive circuit for the dielectric memory.

  44a to 44f are views showing manufacturing steps (No. 1 to No. 6) of a laminated device in which a coplanar / bottom contact type organic thin film transistor is laminated on another circuit layer (organic thin film transistor). First, as shown in FIG. 44a, an organic semiconductor film 39 ′ is formed on a substrate 31 made of alicyclic olefin resin, polytetrafluoroethylene (PTFE), Si wafer or the like, and gold (Au) is formed thereon. As shown in FIG. 44b, an insulating layer 33 made of an alicyclic olefin resin or the like is formed.

  Next, as shown in FIG. 44c, an electrode 34 made of aluminum (Al) or the like is formed, and as shown in FIG. 44d, an insulating layer 35 is formed. As the insulating layer 35, for example, an epoxy resin other than the alicyclic olefin resin can be used.

  Thereafter, as shown in FIG. 44e, an electrode (gate electrode) made of Al or the like is formed, and an insulating layer (gate insulating layer) 37 is formed thereon, and further an electrode (source electrode, drain electrode) is formed thereon. To do. Thereafter, as shown in FIG. 44f, an organic semiconductor layer 39 is formed. Thereby, a composite thin film device is manufactured.

  The material of each layer described above is an example, and each layer can be formed by appropriately using the material and the forming method described in the second embodiment. In particular, when a resin composition mainly composed of an alicyclic olefin resin containing limonene as a solvent is used as the gate insulating layer 37, the surface thereof is smooth, which adversely affects the characteristics of the thin film transistor laminated thereon. It is possible to manufacture a composite thin film device having a good characteristic with a small amount. The organic thin film transistor layer is not limited to the bottom contact type, and may be a top contact type.

  The embodiments and examples described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Accordingly, each element disclosed in the above embodiment or example is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  The present invention relates to the subject matter included in Japanese Patent Application No. 2008-26419 filed on Feb. 6, 2008, the entire disclosure of which is expressly incorporated herein by reference.

Claims (10)

  In a method for manufacturing a thin film device having an organic film forming step of forming an organic film on a substrate using a resin composition comprising a resin, a curing agent, and a solvent, the resin has a protic polar group A method for producing a thin film device, which is an alicyclic olefin resin, and wherein the curing agent is a compound having an alicyclic structure portion and three or more epoxy groups.   The method of manufacturing a thin film device according to claim 1, wherein the organic film forming step is performed at least once before and after the step of forming an electrode.   At least one of the organic film forming steps includes an application step of applying the resin composition on the substrate, a first heat treatment step of heat-treating at 130 ° C. or less after the application step, and the first The method for manufacturing a thin film device according to claim 1, further comprising a second heat treatment step in which heat treatment is performed at 150 ° C. or higher after the heat treatment step. In the method for forming a thin film device, the method for forming an electrode, and the organic film forming step for forming an organic film by using a resin composition containing a resin and a solvent before and after the step, respectively, at least once. The manufacturing method of the thin film device whose said resin used in at least 1 of a thin film formation process is alicyclic olefin resin which has the structural unit (a) represented by following formula (1) or Formula (2).

(However, in formula, R1-R4 is respectively independently a hydrogen atom, a C1-C10 hydrocarbon group, or a polar group, and n is an integer of 0-2.) In a thin film device having a first organic film, a first electrode group, a second organic film, and a second electrode group in this order on a substrate, the first organic film and the second organic film Is a thin film device comprising an alicyclic olefin resin having a structural unit (a) represented by the following formula (1) or formula (2).

(However, in formula, R1-R4 is respectively independently a hydrogen atom, a C1-C10 hydrocarbon group, or a polar group, and n is an integer of 0-2.)   The thin film device according to claim 5, wherein the first organic film or the second organic film is an organic film formed using a resin composition containing a resin and a solvent.   The thin film device according to claim 6, wherein the resin composition further comprises a curing agent having an alicyclic structure portion and three or more epoxy groups. In the method for manufacturing a thin film transistor including a step of forming a gate insulating film using a resin composition containing a resin and a solvent, the resin is a structural unit represented by the following formula (1) or formula (2) ( A method for producing a thin film transistor, wherein the solvent is an aliphatic hydrocarbon compound having a boiling point of 150 ° C. or higher.

(However, in formula, R1-R4 is respectively independently a hydrogen atom, a C1-C10 hydrocarbon group, or a polar group, and n is an integer of 0-2.)   An electronic component comprising the thin film device according to claim 5, 6 or 7.   The electronic component which uses the thin film device manufactured using the manufacturing method in any one of Claims 1-4.

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