JP5691679B2 - Laminated body and method for producing the same - Google Patents

Description

  The present invention is a laminate used for electronic device creation, etc., and an electric circuit and a semiconductor element are formed on an inorganic layer having a low linear expansion coefficient in a specific range and excellent in heat resistance and insulation. After that, a polyimide layer having an approximately the same linear expansion coefficient as that surface and an electric circuit layer are laminated, and a laminate excellent in dimensional stability, heat resistance and insulation, and a semiconductor element using the laminate are formed. The present invention relates to a semiconductor additional laminate.

In the electric power field, inorganic layers, particularly ceramic substrates, have been used as circuit boards that require heat resistance. By using ceramics, it has much higher heat resistance and mechanical strength than conventional glass fiber reinforced epoxy substrates, and also has good thermal conductivity. It was. However, in the formation of microcircuits on ceramics, in combination with different materials, especially polymer materials, the low coefficient of linear expansion of ceramics causes stress generation due to temperature due to the difference in coefficient of linear expansion. It has been considered that this may cause damage to elements and wiring due to the application of stress and warpage of the substrate.
And in order to effectively use the heat resistance of ceramics, the combined materials cannot be maintained unless the combined materials are also excellent in heat resistance. Limited.
In addition, ceramics and polymers often have poor adhesion and cannot always be used as a good combination.
Another problem with ceramics is that it is difficult to miniaturize wiring. It is necessary to reduce the surface roughness in order to promote finer wiring, but it is known that reducing the surface roughness of ceramics in processes such as polishing is time-consuming and expensive. Yes.
Heating and cooling are repeated when it is necessary to pass through a process where high temperature is applied, when using elements that generate heat, or when used in a high temperature environment such as in an engine room or in direct sunlight. In order to reduce the stress applied to the semiconductor element and the electric circuit, it is a well-known fact that the stress due to heat can be reduced by using a material with a combined linear expansion coefficient. In particular, by using a combination with a small coefficient of linear expansion, even if it is subsequently passed through a manufacturing process with temperature changes and even when temperature is applied during use, there is little expansion and contraction, so stress is applied to electric circuits and semiconductor elements. Therefore, stable electrical wiring and electrical elements can be produced because warpage is unlikely to occur. However, in order to make a laminated board with these combinations, the adhesiveness must be good. However, in the case where only a material having these low linear expansion coefficients is used, the adhesiveness is not good. It was difficult to create.
Alkaline treatment has been mentioned as a means for improving adhesiveness (see Patent Document 1), but in the case of inorganic alkali treatment, a salt is formed, so that metal ions remain in the polyimide film. After that, it was adversely affected by heating, etc., and on the contrary, this treatment sometimes made it vulnerable. Especially from aromatic tetracarboxylic acid component and aromatic diamine component mainly composed of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, whose surface is difficult to chemically modify sufficiently In the polyimide film obtained by the reaction of the aromatic polyimide obtained and the aromatic tetracarboxylic acid and the aromatic diamine having a benzoxazole structure (skeleton), in general alkali treatment, the adhesive strength after heating and humidification after heating Maintenance was difficult.
In addition, the imide ring in the polyimide molecule is hydrolyzed by the modification treatment with inorganic alkali KOH, and a potassium carboxylate salt in which potassium ions are coordinated to carboxyl groups is formed on the modified layer on the polyimide surface. Although a method for adsorbing ions is also proposed (see Patent Documents 1 and 2), these are merely means for forming a metal layer and cannot be easily converted from a method for closely attaching polyimide onto polyimide. .

JP-A-5-283858 JP 2008-34430 A

When it is necessary to pass a process in which a high temperature is applied, such as a circuit formed on thin polyimide with a linear expansion coefficient that is insulating and heat resistant on an inorganic substrate and has a value close to that of both an inorganic layer and a semiconductor element The present invention provides a laminate and a laminate circuit board for producing an electronic device that can be used well even in a high temperature environment such as when an element that generates heat is used, in an engine room, or in a place exposed to direct sunlight.

As a result of intensive studies, the present inventors have found that a laminate having at least an electric circuit between a polyimide layer A on an inorganic layer and at least another polyimide layer B, wherein the polyimide layers A and B are aromatic tetra It consists of a polyimide obtained by the reaction of carboxylic acids and aromatic diamines having a benzoxazole structure (skeleton), and the linear expansion coefficient of the inorganic layer of the laminate is -3 pm / ° C as measured in two orthogonal directions. ~ + 10ppm / ° C, and the linear expansion coefficient of the polyimide layers A and B of the laminate is -5pm / ° C to + 8ppm / ° C when measured in two orthogonal directions, and the polyimide layer A is subjected to electric circuit processing. The side on which the electrical circuit is located is not treated in general with alkali treatment, but in particular after treatment with organic alkali solution, polyamic acid varnish is applied, and polyimide is baked And it has excellent heat resistance and insulation properties, characterized in that, the laminate with small polyimide layer having a surface roughness has been found to be quite significant when used for electronic device fabrication.
That is, the present invention has the following configuration.
1. A method for producing a laminate having an inorganic layer, an electric circuit, a polyimide layer, and a silane coupling agent layer, wherein at least an electric circuit wiring is formed on one side of the inorganic layer, and then the surface side on which the electric circuit is formed After the silane coupling agent treatment, the polyamic acid solution is coated on the silane coupling agent treated surface, dried and then heat treated to form the polyimide layer A, and at least the polyimide layer A is electrically The polyimide layer is formed by forming a circuit wiring, and then applying an organic alkali solution treatment to the surface side on which the electric circuit is formed, then applying a polyamic acid solution on the organic alkali solution treatment surface, drying and then heat-treating. A method for producing a laminate that forms B.
2. Both the polyimide layer A and the polyimide layer B are mainly composed of polyimide obtained by a reaction between an aromatic tetracarboxylic acid and an aromatic diamine having a benzoxazole structure (skeleton). The manufacturing method of the laminated body as described in 2.
3. 1. Each polyimide layer has a thickness of 0.5 μm to 50 μm, and each polyimide layer has a linear expansion coefficient in the in-plane orthogonal two directions of −5 ppm / ° C. to +8 ppm / ° C. Or 2. The manufacturing method of the laminated body as described in any one of.
4). 1. A semiconductor element is formed in the electric circuit. ~ 3. The manufacturing method of the laminated body in any one of.
5. 3. The semiconductor element includes any one of a power semiconductor element, a thin film transistor, a sensor, a MEMS, a solar cell, and a logic circuit. The manufacturing method of the laminated body as described in 2.
6). The organic alkali solution treatment is treatment with a dimethylsulfoxide solution of tetramethylammonium hydroxide. ~ 5. The manufacturing method of the laminated body in any one of.

The laminate of the present invention has little expansion or contraction even in an environment where the temperature changes, so that stress is hardly applied to the electric circuit and semiconductor element, and there is little difference in the coefficient of linear expansion from the inorganic substrate. Therefore, it is possible to produce stable electrical wiring and electrical elements because warpage is unlikely to occur, and because it is easy to create a surface that is flat and has a small surface roughness compared to inorganic layers, fine wiring can be created. This is extremely useful for making an electronic device in which a circuit or the like is formed on a thin polyimide layer that is easy to be insulated, flexible, and heat resistant.

Sectional drawing of the laminated body example which created the polyimide layer on the polyimide layer further on the polyimide layer further on the inorganic layer. Sectional drawing of the polyimide layer on an inorganic layer at the time of creating an electrical circuit and a semiconductor element on a polyimide layer, and a polyimide layer laminated body example. Sectional drawing illustration of the polyimide layer on an inorganic layer at the time of creating an electrical circuit and a semiconductor element on a polyimide layer, and a polyimide layer laminated body example.

The polyimide layer in the laminate of the present invention has at least polyimide layers A and B, both of which are preferably self-supporting polyimides, and the types of polyimide are aromatic tetracarboxylic acids and aromatic diamines. There is no particular limitation as long as the polyimide has a linear expansion coefficient (both in the film length direction and width direction) of −3 ppm / ° C. to +20 ppm / ° C. Carboxylic acids (anhydrides, acids, and amide bond derivatives are collectively referred to as classes) and aromatic diamines (amines and amide bond derivatives are collectively referred to as classes) are reacted. It is a polyimide obtained by casting, drying, and heat treatment (imidization) to obtain a film shape Preferred. Examples of the solvent used in these solutions include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

The molecular structure of aromatic diamines having a benzoxazole structure used in the present invention is not particularly limited, and specific examples include the following.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.

In the present invention, one or two or more diamines exemplified below may be used in combination as long as they are 30 mol% or less of the total diamine. Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy) phenyl]. Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dia Nodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4 , 4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4, 4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-amino) Phenoxy) phenyl] ethane, 1,1-bis [4- 4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, , 4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl ] Butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-a Minophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2- Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-amino) Enoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1, 3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] Benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) ) Phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} fe Sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluoro) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4 -Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-dipheno Cibenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino- 4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4 -Biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) Benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-bi) Phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- ( 4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, 1,3- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and And some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or some or all hydrogen atoms of alkyl groups or alkoxyl groups. Are aromatic diamines substituted with a halogenated alkyl group having 1 to 3 carbon atoms substituted with a halogen atom or an alkoxyl group.

<Aromatic tetracarboxylic acid anhydrides>
Specific examples of the aromatic tetracarboxylic acid anhydrides used in the present invention include the following.

  These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  The solvent used when the polyamic acid is obtained by reacting (polymerizing) the aromatic tetracarboxylic acid and the aromatic diamine is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. Is preferably a polar organic solvent, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Examples include hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by weight, The amount is preferably 10 to 30% by weight.

  Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for minutes to 30 hours. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The weight of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and the viscosity of the solution is measured with a Brookfield viscometer (25 ° C.). In order to obtain the polyimide layer, it is 0.1 to 1000 Pa · s, more preferably 0.5 to 500 Pa · s from the embedding property of the unevenness. From the viewpoint of liquid feeding stability, it is preferably 10 to 2000 Pa · s, more preferably 100 to 1000 Pa · s.

Vacuum defoaming during the polymerization reaction is effective for producing a good quality polyamic acid solution. Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (self-supporting precursor film) is obtained by applying the polyamic acid solution on a support and drying, and then There is a method of imidizing the green film by subjecting it to a heat treatment. Application of the polyamic acid solution to the support includes, for example, casting from a die with a slit and extrusion by an extruder, but is not limited thereto, and conventionally known solution application means can be appropriately used.

In the present invention, the method for applying the polyimide resin solution on the substrate is not particularly limited, but for example, a spin coating method such as spin coating, a doctor blade or applicator, a bar coater, a baker type applicator, a film applicator with a micrometer, Examples include a method using a squeegee such as a comma coater, and a screen printing method.
In the present invention, the drying temperature condition for removing the solvent from the polyimide resin solution applied on the substrate is not particularly limited as long as it is a temperature at which the solvent can be removed. More preferably, it is not more than 250 ° C., more preferably not more than 250 ° C. When the drying temperature is higher than 350 ° C., it takes about time to volatilize the silicon wafer and the functional element due to thermal deterioration, and therefore it is preferably approximately 80 ° C. or higher.
When the film is attached with an adhesive, if the heat resistance of the adhesive layer is inferior to that of the polyimide layer, the heat resistance of the seat relative to the whole is limited by the heat resistance of the adhesive layer. There is virtually no adhesive with higher heat resistance. If this system does not use an adhesive, it will have the highest heat resistance of polyimide, which is the highest level among polymers.

In the polyimide layer in the present invention, it is preferable to add and contain a lubricant in the polyimide to give fine irregularities on the surface of the layer (film) to improve the adhesiveness of the layer (film). As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 μm to 0.8 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, pyrophosphoric acid. Examples include calcium, magnesium oxide, calcium oxide, and clay minerals.
These fine particles are preferably contained in the range of 0.20 to 2.0% by mass with respect to the polyimide. When the content of the fine particles is less than 0.20% by mass, there is not so much improvement in adhesion, which is not preferable. On the other hand, if it exceeds 2.0% by mass, the surface unevenness becomes too large, and even if the adhesiveness is improved, problems such as a decrease in smoothness remain, which is not preferable.
When the wiring width of the electric circuit becomes finer, it is desirable that the particle diameter of the lubricant is sufficiently smaller than the wiring width. For this reason, what does not contain particles having a major axis of 20 nm or more in the portion of the polyimide layer thickness direction at least 3 μm on the side where the electric circuit is formed is also desired. As a result, the polymer layer on the side in contact with the electric circuit layer becomes smooth, and the probability of contact with the smooth electric circuit layer at the atomic level increases, making it suitable for bonding. Preferably, the polymer layer on the side in contact with the electric circuit layer does not contain particles having a major axis of 20 nm or more in a portion of 5 μm or more.

In the present invention, the thickness of the polyimide layers A and B has sufficient insulating properties, and if it is thicker than maintaining the electrical characteristics and other characteristics, it takes time for drying affirmation and is difficult to create, and the cost for film formation is high. This is time consuming and undesirable. For this reason, the realization range is 0.5 μm to 50 μm, and more preferably 1 μm to 15 μm.

The inorganic layer in the laminate of the present invention includes a ceramic and glass layer, a glass plate, a composite of the ceramic plate, a laminate of these, a dispersion of these, and a fiber thereof. The things that are being raised are raised.

The ceramic layer in the laminate of the present invention is AL ₂ O ₃ , Mullite, AlN, SiC, Si ₃ N _4, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO3 + Al2O3, Crystallized glass + Al2O3, Crystallized Ca-BSG, BSG + Quartz, BSG + Quartz, BSG + Al2O3, Pb-BSG + Al2O3, Glass-ceramic, Zero-dura materials, etc., TiO2, strontium titanate, calcium titanate, magnesium titanate. Capacitor materials such as alumina, MgO, steatite, BaTi4O9, BaTi03, BaTi03 + CaZrO3, BaSrCaZrTio3, Ba (TiZr) O3, PMN-PT PFN-PFW, PbNb2O6, Pb0.5Be0.5Nb2O6, PbTiO3, BaTiO3, PZT. This includes piezoelectric materials such as 95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, PLZT.

The glass layer in the laminate of the present invention is quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass ( Alkali-free), borosilicate glass (microsheet), and aluminosilicate glass. Among them, those having a linear expansion coefficient of 5 ppm / ° C. or less are desirable, and liquid crystal glass Corning 1753, Eagle XG, Nippon Electric Glass OA-10G, Asahi Glass AN100, and the like are desirable.

With the linear expansion coefficient in this invention, the average value measured between 30 to 300 degreeC is computed as CTE. Metals and ceramics often do not change within this temperature range, but polyimide layers may change CTE within this temperature range, but the lower limit of measurement can be replaced with 0 ° C, 30 ° C, or 50 ° C. It is possible to replace the upper limit of measurement with 200 ° C, 300 ° C, or 400 ° C.

The linear expansion coefficient of the inorganic layer in the laminate of the present invention is −3 ppm / ° C. to +10 ppm / ° C., more preferably −2 ppm / ° C. to +8 ppm / ° C. If it is larger than this, a stress may be partially applied due to the thermal history, and the occurrence of warping and the peeling of the polyimide layer are likely to occur.

The linear expansion coefficient of the polyimide layer in the laminate of the present invention is −5 ppm / ° C. to +8 ppm / ° C., more preferably −2 ppm / ° C. to +3 ppm / ° C. When the difference between the linear expansion coefficient and the inorganic layer is large, a stress is generated when heat is applied, and defects are easily generated in the circuit.

The 180 degree peel strength in the present invention is 1.5 N / cm or more and 18 N / cm or less, more preferably 3 N / cm or more and 8 N / cm or less. If it is 1.5 N / cm or less, it is difficult to use it as a practical device, and it is technically difficult to realize 18 N / cm or more.

In the present invention, the silane coupling agent layer refers to a layer formed by a treatment using a silane coupling agent, a method of applying and drying a solution of a silane coupling agent on an inorganic layer, and heat treatment, and a solution of the silane coupling agent. Examples include a method in which the polyimide layer is immersed in the substrate and dried and heat-treated, and a method in which the polyimide layer is added at the time of forming the polyimide layer and treated with a coupling agent simultaneously with the film formation. In addition, it is known that the pH during the treatment greatly affects the performance, and the pH may be adjusted as appropriate.
No adhesive layer made of an organic polymer is interposed between the inorganic layer of the present invention and the polyimide layer A. Here, the adhesive layer made of an organic polymer referred to in the present invention refers to an Si component having a weight ratio of less than 10%. There are only those containing 10% by weight or more of Si derived from the silane coupling agent. By using the silane coupling agent layer, the intermediate layer can be made thin, so that there are few degassing components during heating, it is difficult to elute even in the wet process, and even if the elution occurs, there is an effect that it remains in a very small amount.

The thickness of the silane coupling agent layer in the present invention is 50 nm or less, more preferably 20 nm or less. If it is thicker than this, the polyimide layer may be altered, and a rough film is likely to be formed, which causes a drop in peel strength. However, if the thickness is 5 nm or less, the amount is less than the effective amount for adhesion, and the effect of improving the peel strength is reduced.

The organic alkali solution treatment in the present invention is a treatment of immersing a polyimide layer having an electric circuit in an organic solvent solution of an organic compound selected from amines such as ethylenediamine and tetramethylammonium hydroxide (TMAH) and / or an aqueous solution. Is mentioned. As a deformation of immersion, an organic alkali solution may be coated. Examples of these organic solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexa Examples include methylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents can be used alone or mixed and further mixed with water. Desirably, a dimethyl sulfoxide solution of tetramethylammonium hydroxide is raised. The amount of the solvent used may be an amount sufficient to dissolve the amines. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 0.01 to 40% by weight, The amount is preferably 0.5 to 10% by weight. The treatment temperature can be around room temperature. The processing time is preferably about 0.1 min to 20 min, more preferably about 0.3 min to 5 min. If it is longer than this, the process cost increases, and if it is shorter than this, time control becomes difficult. In addition, it is possible to use an aqueous solution, ethanol, methanol, isopropyl alcohol solution, or the like that does not use an organic solvent, but in this case, the same effect can be obtained by immersing in the solution for several hours to several tens of hours in batch processing. Can be obtained.
If this polyimide layer is formed by applying a polyamic acid solution to the polyimide layer without performing this treatment, followed by heat treatment and then forming the polyimide layer, the 180 degree peel strength between the polyimide layer and the polyimide layer is 1 N / cm or less, Although it peels off, a 180 degree peel strength of 5 N / cm or more is obtained by performing the above treatment, and this peel strength is little reduced by performing the PCT process, and after the PCT process is 180 degrees of 4 N / cm or more. Peel strength is obtained. When the polyimide layer is formed by applying a polyamic acid solution after the plasma treatment to the polyimide layer and then drying and then heat-treating, the initial 180 degree peel strength is 5 N / cm or more. The 180 degree peel strength after the PCT treatment is 1 N / cm or less. When the 180 degree peel strength is 1 N / cm or less, it peels easily and there is a problem in practical use. If it is 4 N / cm or more, there is no problem in normal handling. Moreover, if this treatment is properly performed, a 180 degree peel strength of 10 N / cm or more can be obtained, and in this case, it can be used without any problem in most electric circuit applications. In combination with this organic alkali treatment, plasma treatment, UV treatment, silane coupling agent treatment, grafting treatment and the like may be carried out as auxiliary surface treatments.

The plasma treatment in the present invention is not particularly limited, and includes RF plasma treatment in a vacuum, microwave plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., using fluorine-containing gas treatment, an ion source Includes ion implantation treatment, treatment using PBII method, frame treatment, intro treatment, etc. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

The electric circuit in the present invention is mainly composed of copper, Al, Ni, Au, Ag, Cr, Mo, Ti and the like. This refers to metal wiring. Desirably, the thing which contains NiCr alloy and Ti alloy as a barrier layer between a copper wiring and a polyimide film is mentioned.

The semiconductor element in the present invention includes a power semiconductor element, a thin film transistor, a sensor, a solar cell or a logic circuit, a MEMS element, a light emitting element, a light receiving element, an actuator element, and a device to which a commercially available semiconductor element chip is attached. .

The power semiconductor element in the present invention is a semiconductor optimized for power conversion and control, and has a higher breakdown voltage, higher current, higher speed and higher frequency than a normal semiconductor element. Includes rectifier diodes, power transistors, power MOSFETs, insulated gate bipolar transistors (IGBT), thyristors, gate turn-off thyristors (GTO), and triacs.

The thin film transistor in the present invention refers to a semiconductor layer in which a transistor and an insulating film, an electrode, a protective insulating film, and the like constituting an element are formed by depositing a thin film. It is usually distinguished from silicon wafers that use silicon as the semiconductor layer. Usually, a thin film is produced by a method using a vacuum such as PVD (physical vapor deposition) such as vacuum vapor deposition or CVD (chemical vapor deposition) such as plasma CVD. For this reason, what is not a single crystal like a silicon wafer is included. Even if Si is used, it includes microcrystalline silicon TFT, high-temperature polysilicon TFT, low-temperature polysilicon TFT, oxide semiconductor TFT, organic semiconductor TFT, and so on.

The sensor in the present invention is a strain gauge, a load cell, a semiconductor pressure sensor, an optical sensor, a photoelectric element, a photodiode, a magnetic sensor, a contact temperature sensor, a thermistor temperature sensor, a resistance temperature sensor temperature sensor, a thermocouple Temperature sensor, non-contact temperature sensor, radiation thermometer, microphone, ion concentration sensor, gas concentration sensor, displacement sensor, potentiometer, differential transformer displacement sensor, rotation angle sensor, linear encoder, tachometer, rotary encoder, optical position sensor (PSD), ultrasonic distance meter, capacitance displacement meter, laser Doppler vibration velocity meter, laser Doppler velocimeter, gyro sensor, acceleration sensor, earthquake sensor, one-dimensional image, linear image sensor, two-dimensional image, CCD image sensorー, CMOS image sensor, Liquid, Leak sensor (Leak sensor), Liquid sensor (Level sensor), Hardness sensor, Electric field sensor, Current sensor, Voltage sensor, Power sensor, Infrared sensor, Radiation sensor, Humidity sensor, Smell sensor , Flow sensors, tilt sensors, vibration sensors, time sensors, combined sensors that combine these sensors, and sensors that output other physical quantities or sensitivity values based on some calculation formula from the values detected by these sensors including.

The MEMS in the present invention refers to an object created using MEMS technology, such as an inkjet printer head, a probe for a scanning probe microscope, a contactor for an LSI floating bar, an optical spatial modulator for maskless exposure, an optical integrated device, Infrared sensors, flow sensors, acceleration sensors, MEMS gyro sensors, RF MEMS switches, internal and external blood pressure sensors, and video projectors using grating light valves, digital micromirror devices, etc.

The solar cell in the present invention is formed by forming a laminate including a photoelectric conversion layer made of a semiconductor on the polyimide layer of the laminate described above. In this case, it is desirable for the polyimide layer to transmit visible light. The said laminated body has a photoelectric converting layer which converts the energy of sunlight into an electrical energy as an essential structure, and usually further has an electrode layer etc. for taking out the obtained electrical energy.
Hereinafter, a laminated structure in which a photoelectric conversion layer is sandwiched between a pair of electrode layers will be described as a typical example of the laminated body formed so as to constitute a film-like solar cell. However, a structure in which several photoelectric conversion layers are stacked can be regarded as the solar cell of the present invention if it is fabricated by PVD or CVD. The laminated structure formed in the present invention is not limited to the embodiment described below, and the structure of the laminated body of the solar cell of the prior art may be referred to as appropriate, and a protective layer and known auxiliary means may be added. Is.
One electrode layer (hereinafter also referred to as a back electrode layer) of the pair of electrode layers is preferably formed on one main surface of the film substrate. The back electrode layer is obtained by laminating a conductive inorganic material by a method known per se, for example, a CVD (Chemical Vapor Deposition) method or a sputtering method. Examples of conductive inorganic materials include metal thin films such as Al, Au, Ag, Cu, Ni, and stainless steel, and In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (adding Sn to In ₂ O ₃ Oxide semiconductor-based conductive materials and the like. The thickness of the back electrode layer is not particularly limited, and is usually about 30 to 1000 nm. Preferably, the back electrode layer is a metal thin film. Further, even if a film formation that does not use a vacuum such as Ag paste is used for extracting some electrodes, it can be said to be the solar cell of the present invention.

The photoelectric conversion layer for converting the energy of sunlight into electrical energy is a layer made of a semiconductor, and a compound semiconductor thin film (chalcopyrite structure semiconductor thin film) made of a group I element, a group III element, and a group VI element, CuInSe2 ( CIS) film, or a Cu (In, Ga) Se ₂ (CIGS) film in which Ga is dissolved in the same (hereinafter, both are collectively referred to as a CIS film), and a layer made of a silicon-based semiconductor. Examples of the silicon-based semiconductor include a thin film silicon layer, an amorphous silicon layer, and a polycrystalline silicon layer. The photoelectric conversion layer may be a laminate having a plurality of layers made of different semiconductors. Moreover, the photoelectric converting layer using a pigment | dye may be sufficient.
The thin film silicon layer is a silicon layer obtained by a plasma CVD method, a thermal CVD method, a sputtering method, a cluster ion beam method, a vapor deposition method, or the like.
The amorphous silicon layer is a layer made of silicon having substantially no crystallinity. The lack of crystallinity can be confirmed by not giving a diffraction peak even when irradiated with X-rays. Means for obtaining an amorphous silicon layer are known, and examples of such means include a plasma CVD method and a thermal CVD method.
The polycrystalline silicon layer is a layer made of an aggregate of microcrystals made of silicon. The above amorphous silicon layer is distinguished by giving a diffraction peak by irradiation with X-rays. Means for obtaining a polycrystalline silicon layer are known, and such means include means for heat-treating amorphous silicon.
The photoelectric conversion layer used in the present invention is not limited to a silicon-based semiconductor layer, and may be, for example, a thick film semiconductor layer. The thick film semiconductor layer is a semiconductor layer formed from a paste of titanium oxide, zinc oxide, copper iodide or the like.
The means for constituting the semiconductor material as the photoelectric conversion layer may refer to a known method as appropriate. For example, an about 20 nm a-Si (n layer) is formed by performing high-frequency plasma discharge in a gas in which phosphine (PH ₃ ) is added to SiH ₄ at a temperature of 200 to 500 ° C., and then SiH _4. An a-Si (i layer) of about 500 nm can be formed only with gas, and then diborane (B ₂ H ₆ ) can be added to SiH ₄ to form a p-Si (p layer) of about 10 nm. .

Of the pair of electrode layers sandwiching the photoelectric conversion layer, an electrode layer (hereinafter also referred to as a current collecting electrode layer) provided on the side opposite to the film substrate is formed by solidifying a conductive paste containing a conductive filler and a binder resin. It may be an electrode layer or a transparent electrode layer. As the transparent electrode layer, an oxide semiconductor material such as In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ added with Sn) can be preferably used.
Thus, a film-like solar cell in which transparent electrode / p-type a-Si / i-type a-Si / n-type a-Si / metal electrode / polyimide film layer is laminated in this order, which is a preferred embodiment of the present invention. Is obtained.
Alternatively, the p layer may be a-Si, the n layer may be polycrystalline silicon, and a thin and doped a-Si layer may be inserted between them. In particular, when an a-Si / polycrystalline silicon hybrid type is used, the sensitivity to the sunlight spectrum is improved.
In the production of a solar cell, an antireflection layer, a surface protective layer, or the like may be added in addition to the above structure.

The logic circuit in the present invention includes a logic circuit based on NAND and OR and a circuit synchronized by a clock.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.

1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved using N, N-dimethylacetamide and measured.)
2. Thickness of polyimide layer, etc. Measured using a micrometer (Finereuf, Millitron 1245D).
3. The tensile elastic modulus, tensile breaking strength, and tensile breaking elongation of the polyimide layer were applied to a varnish without applying a silane coupling agent on the 8-inch silicon wafer. The coating was adjusted with a spin coater so that the film thickness after firing was 5 μm. After drying at 100 ° C. for 10 minutes, the sample is put in a muffle furnace in which N 2 is flowing, and the temperature is raised from room temperature to 350 ° C. at a rate of 3 ° C./min. The varnish was fired while maintaining. This was measured using a stripped polyimide layer. As the coating and firing conditions, a test piece was prepared by cutting a polyimide layer to be measured into a strip of 100 mm × 10 mm. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph (R) model name AG-5000A), the tensile modulus, tensile breaking strength, and tensile breaking elongation were measured under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm. did.

4. 180 degree peel strength
According to the 180 degree peeling method of JIS C6471, the peeling strength of the sample was determined by performing a 180 degree peeling test under the following conditions. The peel strength measurement sample was measured by applying a polyimide layer to the inorganic layer before patterning in the same manner as in Example 1. Specifically, after attaching polyimide layer B, Nikkan Kogyo SAFW and further, a large commercial polyimide film 25 μm thick is roll-laminated at 100 ° C., then pressed at 160 ° C. for 1 hour, and cooled at room temperature After that, N = 5 was measured and the average value was taken as the measured value, with the commercially available polyimide film and the inorganic layer polyimide layer laminate on both sides sandwiching SAFW as the side where the commercially available polyimide film was bent 180 degrees.
Device name: Autograph AG-IS, manufactured by Shimadzu Corporation
Measurement temperature; Room temperature Peeling speed; 50mm / min
Atmosphere: Air Measurement sample width: 1cm

Since the interfacial peeling between the polyimide layer B and SAFW or the mixed destruction with the SAFW material destruction occurs at around 8 N / cm, the peeling strength between the inorganic layer and the polyimide layer can only be estimated to be higher.

5. Linear expansion coefficient (CTE)
The stretch rate of the polyimide layer to be measured is measured under the following conditions in two orthogonal directions, and the stretch rate / temperature at intervals of 30 ° C. to 45 ° C., 45 ° C. to 60 ° C.,. This measurement was performed up to 300 ° C., and the average value of all measured values was calculated as CTE. The sample is the above-mentioned 3. A sample for measuring the tensile elastic modulus, tensile breaking strength and tensile breaking elongation of the polyimide layer was used.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere; Argon load; 35 g / mm ²
6). Measuring method of silane coupling agent layer thickness The silane coupling layer thickness was determined by measuring the thickness of a Si wafer.
The film thickness was measured by ellipsometry, and the measuring instrument used was FE-5000 manufactured by Hottal. The hardware specifications of this measuring instrument are as follows.
Reflection angle range 45 to 80 °, wavelength range 250 to 800 nm, wavelength resolution 1.25 nm, spot diameter 1 mm, tan Ψ measurement accuracy ± 0.01, cosΔ measurement accuracy ± 0.01, system rotation analyzer method.
Measurement was performed at a deflector angle of 45 ° and an incident angle of 70 °, and the analyzer was measured at 0 to 360 ° and 250 to 800 nm in 11.25 ° increments.
The film thickness was obtained by fitting by a non-linear least square method. At this time, the model is Air / thin film / Si model,
n = C ₃ / λ ⁴ + C ₂ / λ ² + C ₁
k = C ₆ / λ ⁴ + C ₅ / λ ² + C ₄
The wavelength dependence C _{1 to} C ₆ was determined by the following formula.
The coating conditions in both the examples and comparative examples were the same as those in Example 1, and the coating amount under these conditions was 15 nm.

[Varnish production example 1]
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 5-amino-2- (p-aminophenyl) benzoxazole 22.53 mass, N-methyl-2-pyrrolidone 176.44 mass And then completely dissolved, and then introduced 19.62 parts by mass of pyromellitic dianhydride and 1.96 parts by mass of maleic anhydride and stirred at a reaction temperature of 25 ° C. for 24 hours. A viscous polyamic acid solution A was obtained. This is called varnish A. Table 1 summarizes the measurement results of this varnish and the mechanical properties when a polyimide layer was formed from this varnish.

[Varnish production example 2]
(Preparation of polyamic acid solution B)
The inside of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 20.27 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole, 1,3- (3-aminopropyl) ) -1,1,3,3-tetramethyldisiloxane 2.63 parts by mass and N-methyl-2-pyrrolidone 178.16 parts by mass were introduced and completely dissolved, and then pyromellitic dianhydride 20. When 07 parts by mass and 1.57 parts by mass of maleic anhydride were introduced and stirred for 24 hours at a reaction temperature of 25 ° C., a yellow and viscous polyamide acid solution B was obtained. This is called Varnish B. Table 1 summarizes the measurement results of this varnish and the mechanical properties when a polyimide layer was formed from this varnish.

[Varnish production example 3]
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 20.02 parts by mass of 4,4′-diaminodiphenyl ether and 166.40 parts by mass of N-methyl-2-pyrrolidone were introduced to completely Then, 19.62 parts by mass of pyromellitic dianhydride and 1.96 parts by mass of maleic anhydride are introduced and stirred at a reaction temperature of 25 ° C. for 24 hours. C was obtained. This is called Varnish C. Table 1 summarizes the measurement results of this varnish and the mechanical properties when a polyimide layer was formed from this varnish.

Example 1
Obtain an Al ₂ O ₃ substrate in which a wiring test pattern is printed and baked with a conductive paste in advance, and add 1 wt% of a silane coupling agent (3-aminopropyltrimethoxysilane: trade name KBM903 Shin-Etsu Silicone) 2 The solution diluted with propanol was applied with a spin coater and placed on a hot plate at 100 ° C. for 1 minute. Thereafter, varnish A was applied. The coating was adjusted with a spin coater so that the film thickness after firing was 5 μm. After drying at 100 ° C. for 10 minutes, the atmosphere in the furnace was put into a muffle furnace substituted with nitrogen, and the temperature was raised from room temperature to 350 ° C. at a rate of 3 ° C./min. A polyimide layer A obtained by firing the varnish while maintaining the temperature for a time was formed. When the film thickness was measured after this, it was 5 μm thick. Next, this varnish film was irradiated with a CO 2 laser at a current value of 12 A, a frequency of 200 Hz, an ON time of 24 μsec, and the number of shots of 4 times to form a hole of Φ80 μm.
Thereafter, the Al2O3 substrate was fixed to the substrate holder in the sputtering apparatus with the varnish film side as the sputtered thin film deposition side. The substrate holder and Al ₂ O ₃ are fixed so as to be in close contact with each other. The temperature of Al ₂ O ₃ can be set by flowing a coolant through the substrate holder. The substrate temperature was set at 2 ° C. Next, plasma treatment of the varnish film surface was performed. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 ⁻³ Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, a frequency of 13.56 MHz, an output of 450 W, a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10 wt%) alloy target, and a DC magnetron sputtering method in an argon atmosphere at 1 nm / second. A nickel-chromium alloy film (underlayer) having a thickness of 7 nm is formed at a rate, and then a coolant whose temperature is controlled to 2 ° C. on the back side of the sputter surface of the substrate is flown into the substrate so that the substrate temperature is set to 2 ° C. Sputtering was performed in contact with the SUS plate of the substrate holder. Copper was deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.25 μm. The thickness of the copper and NiCr layers was confirmed by the fluorescent X-ray method.

A thick copper layer having a thickness of 10 μm was formed using a copper sulfate plating bath on a varnish film with a Cu thin film. The electrolytic plating conditions were immersion in an electrolytic plating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, a small amount of brightener), and electricity was passed through 1.5 Adm ² . As a result, a thick copper plating layer (thickening layer) having a thickness of 4 μm was formed, followed by heat treatment and drying at 120 ° C. for 10 minutes to obtain Al 2 O 3 with a varnish film with a metal film.
Using the obtained sample, photoresist: FR-200, manufactured by Shipley Co., Ltd. was applied and dried, and then closely exposed with a glass photomask, and further developed with a 1.2 mass% KOH aqueous solution. Next, etching was performed with a cupric chloride etching line containing HCl and hydrogen peroxide at 40 ° C. and a spray pressure of 2 kgf / cm 2, and a line row of lines / spaces = 50 μm / 50 μm was formed as a test pattern. . When observed with an optical microscope, a good pattern with no pattern residue was obtained.
Next, 200 cc of a mixed solution of TMAH (2.5 wt%), water (7.5 wt%) and DMSO (90 wt%) is prepared, put in a pad, and the laminate having the above pattern formed therein is taken out after being immersed for 1 minute. After the liquid was drained, it was immersed in a pad containing methyl alcohol for 1 minute, taken out, drained, and then immersed in a pad containing pure water for 1 minute, followed by drying. The laminate was fixed to a glass plate with Kapton tape with the copper wiring side up, and varnish XA was applied using an applicator. The thickness of the polyimide layer B was adjusted so that the coating thickness became 5 μm after firing. This time, the applicator gap was 50 μm. Thereafter, the glass plate is put into a muffle furnace at 100 ° C. for 20 minutes and dried. This was taken out, this laminate was removed from the glass plate, then placed in a muffle furnace again, heated from room temperature to 350 ° C. at a rate of 3 ° C./min, held at 350 ° C. for 1 hour after heating over 80 minutes. . After that, the laminate was taken out from the muffle furnace. The evaluation results are shown in Table 2.

Example 2
Laminate 2 was obtained in the same manner as in Example 1 except that the varnish used was changed from varnish A to varnish B.

Example 3
A laminate 3 was obtained in the same manner as in Example 1 except that the substrate used was changed from Al2O3 to Si3N4.

Example 4
A laminate 4 was obtained in the same manner as in Example 2 except that the substrate used was changed from Al2O3 to Si3N4.

Example 5
A laminated plate 5 was obtained in the same manner as in Example 1 except that the substrate used was changed from Al2O3 to blue plate glass.

Comparative Example 1
Laminate 6 was obtained in the same manner as in Example 1 except that the varnish used was changed from varnish A to varnish C.

Comparative Example 2
A laminate 7 was obtained in the same manner as in Example 3 except that the substrate to be used was changed from Al2O3 to Si3N4.

Comparative Example 3
A laminate 8 was obtained in the same manner as in Example 1 except that the silane coupling agent treatment was not performed before the varnish application.

Comparative Example 4
A laminate 9 was obtained in the same manner as in Example 3 except that the treatment with the solution containing TMAH was not performed before the varnish application.

上段、下段は直交２方向の測定値
（＊）はＳＡＦＷとポリイミド層Ｂの界面剥離

Upper row and lower row are measured in two orthogonal directions (*) is the interface peeling between SAFW and polyimide layer B

上段、下段は直交２方向の測定値
（＊）はＳＡＦＷとポリイミド層Ｂの界面剥離

Upper row and lower row are measured in two orthogonal directions (*) is the interface peeling between SAFW and polyimide layer B

The multilayer laminate of the present invention is a multilayer substrate in which a heat-resistant polyimide layer having specific physical properties and a ceramic layer are laminated, and an impedance element or the like is formed on the ceramic layer, and the heat-resistant polyimide layer includes A multilayer circuit board on which conductor circuits and electronic components are mounted. Since impedance elements are formed on the ceramic layer, it is stable against temperature changes and can maintain accurate values. Since a fine circuit can be formed, the mounting density of the substrate can be improved and downsizing is possible, and since the ceramic layer is included therein, the bending as a multilayer substrate can be suppressed, and the ceramic layer and the polyimide layer can be suppressed. Is very useful as a multilayer board because there is no deviation in the linear expansion coefficient from the A.
Produces a multilayer substrate for interposers that has good adhesion reliability under high temperature and high humidity even after a temperature cycle is applied, and has a small difference in linear expansion coefficient from the ceramic layer and high connection reliability when mounting bare chips. It is possible to do, and it is a very meaningful thing in the industry.

(Figure 1)
1: Inorganic layer 2: Electric circuit part 3: Polyimide layer 4: Polyimide layer 5: Electric circuit part (FIG. 2)
1: Inorganic layer 2: Electric circuit portion 3 on the inorganic layer 3: Through electrode 4: Polyimide layer 5: Electric circuit portion 6: Semiconductor element 7: Polyimide layer (FIG. 3)
1: Inorganic layer 2: Electric circuit part 3 on the inorganic layer 3: Through electrode 4: Polyimide layer 5: Electric circuit part 6: Semiconductor element 7: Polyimide layer

Claims (6)

A method for producing a laminate having an inorganic layer, an electric circuit, a polyimide layer, and a silane coupling agent layer, wherein at least an electric circuit wiring is formed on one side of the inorganic layer, and then the surface side on which the electric circuit is formed After the silane coupling agent treatment, the polyamic acid solution is coated on the silane coupling agent treated surface, dried and then heat treated to form the polyimide layer A, and at least the polyimide layer A is electrically The polyimide layer is formed by forming a circuit wiring, and then applying an organic alkali solution treatment to the surface side on which the electric circuit is formed, then applying a polyamic acid solution on the organic alkali solution treatment surface, drying and then heat-treating. Form B A manufacturing method of a layered product. The polyimide layer A and the polyimide layer B are both made of polyimide obtained mainly by a reaction between an aromatic tetracarboxylic acid and an aromatic diamine having a benzoxazole structure (skeleton). The manufacturing method of the laminated body of description. 3. The thickness of each polyimide layer is 0.5 μm to 50 μm, and the linear expansion coefficient in each of the two in-plane orthogonal directions of each polyimide layer is −5 ppm / ° C. to +8 ppm / ° C. 3. The manufacturing method of the laminated body. The manufacturing method of the laminated body in any one of Claims 1-3 by which a semiconductor element is formed in the said electric circuit. The method for producing a laminate according to claim 4, wherein the semiconductor element includes any one of a power semiconductor element, a thin film transistor, a sensor, a MEMS, a solar cell, and a logic circuit. The method for producing a laminate according to any one of claims 1 to 5, wherein the organic alkali solution treatment is treatment with a dimethyl sulfoxide solution of tetramethylammonium hydroxide.

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