JP4911116B2 - Semiconductor device and manufacturing method thereof, photosensitive resin composition, and electronic component - Google Patents

Description

  The present invention relates to a semiconductor device coated with an organic insulating film, a manufacturing method thereof, a photosensitive resin composition, and an electronic component. More specifically, in the step of forming the opening portion of the laminated passivation film composed of the organic insulating film and the inorganic insulating film layer on the metal wiring of the semiconductor substrate, the generation and corrosion of the residue of the pad electrode portion are prevented, and further, copper and The present invention relates to a semiconductor device having a highly reliable organic insulating film having excellent rust prevention effect, residual film prevention effect, and film adhesion hardening with respect to a copper alloy, and a manufacturing method thereof, a photosensitive resin composition, and an electronic component. .

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. However, as the integration and size of semiconductor elements have increased in recent years, the mechanical properties, heat resistance, etc. have been improved more than ever due to the reduction in thickness and size of encapsulating resin packages and the transition to surface mounting by solder reflow. A polyimide resin has been required.

  In recent years, a photosensitive polyimide having a photosensitive property imparted to a polyimide resin itself has been used. However, when this is used, a pattern forming process can be simplified, and a complicated pattern manufacturing process can be shortened (for example, Patent Literatures 1 to 3).

  Conventionally, an organic solvent such as N-methylpyrrolidone has been used for developing the photosensitive polyimide. Recently, however, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been proposed from the viewpoint of environment and cost. ing. As such a positive photosensitive resin, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a soluble hydroxylimide or a polybenzoxazole precursor with naphtho There is a method of mixing a quinonediazide compound (for example, see Patent Documents 4 and 5), and photosensitive polybenzoxazole is attracting attention together with photosensitive polyimide from the viewpoint of expecting low dielectric constant.

  Such photosensitive resins have been widely used in recent years as surface protective films or interlayer insulating films of semiconductor elements, and in particular, naphthoquinonediazide compounds are added to soluble hydroxylimide or polybenzoxazole precursors having high resolution. In the case of a positive photosensitive resin configured by mixing, a method of dry etching through a positive photosensitive resin can be applied when processing an inorganic insulating film formed on a wiring.

The dry etching method is a method in which a reactive gas is injected into a vacuum and is etched by a chemical reaction. Generally, a fluorine element is used for dry etching of a silicon oxide film (including an impurity doped film) or a silicon nitride film. Gas containing is used.
However, this active dry etching gas also reacts with components in the organic insulating film in the plasma to form etching residues. Since this residue contains a large amount of fluorine atoms, it is presumed to be a reaction product of a dry etching gas and a fluorine-containing component in the organic insulating film.

  This residue not only forms a deposited layer on the surface of the organic insulating film but also deposits on the pad electrode in the opening. If this residue is present on the organic insulating film and the pad electrode, the following problems occur. The first problem is that after etching, moisture in the atmosphere and moisture newly entered in the sealing resin react with fluorine in the residue to form hydrofluoric acid, resulting in wiring corrosion due to corrosion of the pad electrode part. It is a point to end up. Corrosion of the wiring not only lowers the yield of the semiconductor element, but also significantly reduces the reliability life of the wiring and shortens the life of the semiconductor element. There is a problem that the reliability life by the pressure cooker test (high temperature / high pressure steam test, one of the items of reliability evaluation, hereinafter abbreviated as PCT) is short, and the variation between lots becomes large.

  The second problem is that due to the presence of the residual layer generated by dry etching on the organic insulating film, the adhesion with the sealing resin is reduced, and the temperature cycle test (one of the reliability evaluation items. (Abbreviated as TCT), peeling from the sealing resin occurs. For this reason, moisture enters from the outside, and this causes the occurrence of problems such as wiring corrosion due to the formation of hydrofluoric acid, thereby reducing the reliability level. The residue deposits are difficult to remove, and removal steps such as oxygen plasma treatment and chemical treatment are required.

  In recent years, due to miniaturization of semiconductor devices, multilayer wiring by high integration, shift to chip size package (CSP), wafer level package (WLP), etc., the dielectric constant has been reduced, and copper, aluminum, gold, and titanium have been reduced. In view of the demand for improved adhesion to wiring or wiring metal such as the above, higher performance polybenzoxazole resins and polyimide resins are required.

  Regarding adhesion, it is generally known that by using an organic silicon compound, adhesion with a substrate such as silicon or a nitride film can be improved (Patent Document 9). However, the adhesion of the resin tends to be insufficient with respect to the material constituting the rewiring represented by copper or the like.

  Furthermore, the conventional polyimide resin has a problem that it is corrosive to metals such as copper and copper alloys. When the polyamic acid of the polyimide precursor contains carboxyl groups in the main chain and terminal groups, and when the carboxyl groups remain even after being polyimideized, corrosion of copper and copper alloys is often caused. This is because a carboxyl group which is an acidic functional group contained in the structure of the polyimide precursor reacts with copper and a copper alloy. Therefore, for example, when an interlayer insulating film for a multilayer wiring board is formed using a varnish containing a polyimide precursor, the copper that comes into contact with the coating film after the varnish drying process or the heat curing (polyimidization) process or after curing. Alternatively, the copper alloy is corroded and copper ions are generated, causing various problems such as poor insulation, disconnection, short-circuiting, rusting of metal parts, deterioration of film adhesion, and film physical properties.

  In addition, when a polyimide film is formed using a varnish of a photosensitive polyimide precursor, it remains at the time of development due to a reaction between a carboxyl group present in the main chain and terminal group in the polyimide precursor and copper or a copper alloy. A film is likely to be formed, resulting in a significant decrease in sensitivity and a poor pattern. That is, when the carboxyl group in the polyimide precursor reacts with copper, carboxyl copper (copper salt) is generated. The polyimide precursor produced by carboxyl copper has a reduced solubility in its own developer, and if it is a positive photosensitive resin composition when it is developed using the developer after the exposure step, it is exposed. A residual film is generated in the portion, and if it is a negative photosensitive resin composition, the residual film is generated in the unexposed portion. Copper ions cause not only a decrease in electrical insulation, but also a decrease in polyimide molecular weight, a decrease in film properties, a decrease in adhesion, and the like.

  In the method of forming a polyimide pattern on a copper wiring using a photosensitive polyimide precursor varnish, a residual film is generated after development due to migration of copper ions resulting from a reaction between a carboxyl group in the polyimide precursor and copper. In some cases, the adhesion between the polyimide film and the copper wiring after PCT may decrease. Therefore, a method of performing a plating process such as chromium plating on the copper wiring layer is generally performed before applying the varnish of the photosensitive polyimide precursor. In addition, a method of treating the surface of the copper layer with a silicon compound having an amino group (Patent Document 10), a method of treating the surface of the copper layer with oxygen or a chemical to produce a copper oxide film (Patent Document 11), etc. A method for patterning a polyimide precursor film after performing surface treatment on a layer has been proposed. A method of treating the copper layer surface with a rust inhibitor is also known. However, a method of forming a film by plating the surface of the copper layer or chemical treatment increases the number of manufacturing steps, which is not preferable in terms of workability and economy.

JP-A-49-115541 JP 59-108031 A JP 59-219330 A JP-A 64-60630 US Pat. No. 4,395,482 Japanese Patent No. 2587148 Japanese Patent No. 3031434 US Pat. No. 5,739,915 JP-A 63-001584 JP-A-6-242613 Japanese Patent Laid-Open No. 5-198559 J. Macromol. Sci. Chem., A24, 12, 1407, 1987

  In the above-described conventional method for manufacturing a semiconductor device, a fluorine-containing gas used for dry etching when forming an opening in a laminated passivation film composed of an organic insulating film and an inorganic insulating film, and a fluorine-containing component in the organic insulating film There is a problem that a residue is formed by the reaction, and the yield and reliability of the semiconductor device are significantly reduced. In addition, when a polyimide precursor varnish is applied to a substrate on which a metal wiring or metal layer made of copper and copper alloy is formed to form an insulating film for a multilayer wiring board, the polyimide precursor has a corrosive action on copper or copper alloy. This causes problems such as defective insulation, disconnection, and short circuit.

  The present invention has been made in view of the above, and relates to a semiconductor device coated with an organic insulating film, a manufacturing method thereof, a photosensitive resin composition, and an electronic component, and more particularly, an inorganic insulating film coated with an organic insulating film. In the etching of the film, dry etching treatment is performed without generating a residue, and excellent corrosion prevention effect, residual film prevention effect, and film adhesion effect are obtained without corroding copper and copper alloy such as metal wiring and metal layer. It is an object of the present invention to provide a highly reliable semiconductor device and a method for manufacturing the same, a photosensitive resin composition used in the method for manufacturing the semiconductor device, and an electronic component.

  In order to solve the above problems, the present invention provides an inorganic insulating film formed on a semiconductor substrate, an organic insulating film formed on the inorganic insulating film, and the inorganic insulating film exposed after patterning the organic insulating film. In the method of manufacturing a semiconductor device in which an insulating film is dry-etched, the semiconductor device is manufactured using a resin film that does not contain fluorine in its structure as an organic insulating film. Specifically, this resin film is composed of a polyimide precursor or polybenzoxazole precursor that does not contain a fluorine atom in its structure, a photosensitizer, a heterocyclic compound, a thiourea, and a compound having a mercapto group. It is obtained by heat-treating a photosensitive resin composition containing at least one compound selected from the group consisting of: Such a semiconductor device and its manufacturing method have an excellent rust prevention effect, residual film prevention effect, and film adhesion effect without corroding copper and copper alloys such as metal wirings and metal layers. Furthermore, by using a fluorine-free resin film obtained by heat-treating this photosensitive resin composition as an organic insulating film, no residue is formed on the organic insulating film and the pad electrode after dry etching. The present invention provides a highly reliable semiconductor device, a manufacturing method thereof, and a photosensitive resin composition used in the manufacturing method of the semiconductor device without a removal step.

  In addition, the fluorine-free resin film organic insulating film exhibits high breaking elongation, low dielectric constant, and excellent chemical resistance, so damage to the device during sealing can be avoided, and highly reliable electronic components can be manufactured. Provide high yield. The present invention provides an electronic component that can be developed with an alkaline aqueous solution by using the photosensitive resin composition, has a sensitivity and resolution, and has a well-shaped pattern cured film.

  That is, the method for manufacturing a semiconductor device according to the present invention includes a step of forming an inorganic insulating film on at least a pad electrode and a metal wiring formed on a semiconductor substrate, and forming a fluorine-free organic insulating film on the inorganic insulating film. A step of patterning the fluorine-free organic insulating film, and a step of dry-etching the inorganic insulating film exposed by the pattern processing with a fluorine-containing gas to expose the pad electrode portion. A method for manufacturing an apparatus, wherein the fluorine-free organic insulating film comprises (A) a resin that does not contain fluorine in the resin structure, and (B) a heterocyclic compound, a thiourea, and a compound having a mercapto group. It is formed from the resin composition containing the at least 1 sort (s) of compound selected from these.

  In the method for manufacturing a semiconductor device according to the present invention, the resin (A) contained in the resin composition for forming the fluorine-free organic insulating film is a polyimide precursor containing no fluorine in the resin structure. Or it is the film | membrane obtained by heat-processing the resin composition which consists of a polybenzoxazole precursor, It is characterized by the above-mentioned.

  Moreover, in the method for manufacturing a semiconductor device according to the present invention, the resin composition for forming the fluorine-free organic insulating film is a polyimide precursor or poly (polyester) containing no fluorine in the resin structure as a resin (A). A photosensitive resin composition comprising a benzoxazole precursor, (B) at least one compound selected from the group consisting of heterocyclic compounds, thioureas, and compounds having a mercapto group, and a photosensitive agent (C) It is characterized by being.

  In the method for manufacturing a semiconductor device according to the present invention, the photosensitive resin composition can be developed and patterned with an alkaline aqueous solution.

  In the method for producing a semiconductor device according to the present invention, the component (B) is a heterocyclic compound, and the compound is composed of a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring, and a tetrazole ring. It is a compound having at least one structure selected from the group.

  In the method for manufacturing a semiconductor device according to the present invention, the heterocyclic compound is at least one selected from the group consisting of 1H-tetrazole, 5 substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof. It is a seed.

  In the method for manufacturing a semiconductor device according to the present invention, the heterocyclic compound may be 1,2,3-triazole, 1,2,4-triazole and derivatives thereof, 1,2,3-benzotriazole, 5 It is at least one selected from the group consisting of substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and derivatives thereof.

  In the method of manufacturing a semiconductor device according to the present invention, as a further step, a step of forming a second metal wiring pattern layer on the fluorine-free organic insulating film and the exposed pad electrode part, and further Forming a second fluorine-free organic insulating film, the second fluorine-free organic insulating film also comprising: (A) a resin that does not contain fluorine in the resin structure; and (B) a heterocyclic compound. And a resin composition containing at least one compound selected from the group consisting of thioureas and a compound having a mercapto group.

  The semiconductor device according to the present invention is manufactured by the method for manufacturing a semiconductor device.

  The electronic component according to the present invention has the structure of the semiconductor device.

  The electronic component according to the present invention is a chip size package or a wafer level package.

  Further, in the photosensitive resin composition according to the present invention, a step of forming an inorganic insulating film on at least the pad electrode and the metal wiring formed on the semiconductor element, and a fluorine-free organic insulating material on the inorganic insulating film Forming a film, patterning the fluorine-free organic insulating film, and exposing the pad electrode by dry etching the inorganic insulating film exposed by the patterning with a fluorine-containing gas. A photosensitive resin composition for forming the fluorine-free organic insulating film, comprising: (A) a resin not containing fluorine in a resin structure; (B) a heterocyclic compound; And at least one compound selected from the group consisting of ureas and compounds having a mercapto group, (C) a photosensitizer, and (D) a solvent, Characterized in that it does not contain iodine.

  Further, in the photosensitive resin composition according to the present invention, the resin (A) contained in the photosensitive resin composition for forming the fluorine-free organic insulating film is a polyimide containing no fluorine in the resin structure. It is a precursor or a polybenzoxazole precursor.

  In the photosensitive resin composition according to the present invention, the photosensitive resin composition can be developed and patterned with an aqueous alkaline solution.

  Moreover, in the photosensitive resin composition by this invention, the said (B) component is a heterocyclic compound, The compound consists of a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring, and a tetrazole ring. It is a compound having at least one structure selected from the group.

  In the photosensitive resin composition according to the present invention, the heterocyclic compound is at least one selected from the group consisting of 1H-tetrazole, 5 substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof. It is a seed.

  Moreover, in the photosensitive resin composition by this invention, the said heterocyclic compound is 1,2,3-triazole, 1,2,4-triazole and its derivative (s), 1,2,3-benzotriazole, 5 It is at least one selected from the group consisting of substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and derivatives thereof.

Moreover, in the photosensitive resin composition by this invention, the said resin (A) is selected from the group which consists of a polyimide precursor which mainly has the structural unit represented by following General formula (1)-(3). It is characterized by being at least one kind.
General formula (1):

(式中、Ｒ¹は四価の有機基、Ｒ²は二価の有機基、Ｒ³は水素原子又は一価の有機基であり、ａは繰り返し数を示す整数であり、２〜１００,０００である。)
一般式（２）：

(Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, a is an integer indicating the number of repetitions, 2 to 100, 000.)
General formula (2):

(式中、Ｒ¹は四価の有機基、Ｒ⁴は四価の有機基、Ｒ⁵とＲ⁶は水素原子又は一価の有機基でありこれらは同一であっても異なっていてもよく、ｂは繰り返し数を示す整数であり、２〜１００,０００である。)
一般式（３）：

(Wherein R ¹ is a tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, and these may be the same or different. And b is an integer indicating the number of repetitions, and is 2 to 100,000.)
General formula (3):

(式中、Ｒ⁷は二価又は四価の有機基、Ｒ⁴は四価の有機基、Ｒ⁸は二価の有機基、Ｒ⁵とＲ⁶は水素原子又は一価の有機基でありこれらは同一であっても異なっていてもよく、ｃ及びｄは繰り返し数を示す整数であってそれぞれ２〜１００,０００であり、２つの繰り返し単位はブロック又はランダムに存在する。)

(Wherein R ⁷ is a divalent or tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁸ is a divalent organic group, and R ⁵ and R ⁶ are hydrogen atoms or monovalent organic groups. These may be the same or different, and c and d are integers indicating the number of repeats, each being 2 to 100,000, and the two repeat units are present in blocks or randomly.)

  Conventionally, when an organic insulating film is used as a coating material for an inorganic insulating film on a semiconductor element, the organic insulating film patterned as a mask is used as a semiconductor manufacturing method. When the inorganic insulating film is dry-etched, the organic insulating film or pad electrode In some cases, a residue is generated and the residue corrodes, resulting in poor insulation of the pad electrode part and poor adhesion to the mold resin. However, when the fluorine-free resin film according to the present invention is used, a residue removal process is not required because a residue is not generated, and further, reliability is ensured without corroding copper and a copper alloy such as a metal wiring or a metal layer. A semiconductor device having a high level can be obtained.

  Further, the resin film containing no fluorine atom in the structure is preferably a polyimide precursor or polybenzoxazole precursor capable of alkali development that does not contain a fluorine atom in the structure, a photosensitizer, a heterocyclic compound, a thiol compound, It is obtained by applying a photosensitive resin composition containing at least one compound selected from the group consisting of ureas and a compound having a mercapto group, followed by heat treatment after drying and development. By using this photosensitive resin composition, it is possible to obtain a patterned cured film having a good shape that is excellent in sensitivity, resolution, adhesiveness, heat resistance and low water absorption.

  Further, the electronic component of the present invention has a good shape, a pattern excellent in adhesiveness and heat resistance, avoids damage to the device, and has high reliability. In addition, since the damage to the device is small, the yield is high.

  Hereinafter, the semiconductor device and the manufacturing method thereof, the photosensitive resin composition, and the electronic component according to the present invention will be described in detail. In addition, this invention is not limited by the following embodiment. In the present invention, “fluorine” means a fluorine atom unless otherwise specified.

  The present invention is a semiconductor device manufacturing method using a fluorine-free heat-resistant polymer film as an organic insulating film in a semiconductor device having a process of etching an inorganic insulating film having an organic insulating film. Examples of the heat-resistant polymer film include fluorine-free polyimide resin, polybenzoxazole resin, polyamide resin, polyamideimide resin, and the like. Polyimide resin and polybenzoxazole resin are preferable, and polyimide resin is particularly preferable. Used as For example, the polyimide has a repeating unit represented by the following general formula (4).

  In the general formula (4), the linking groups X and Y are mere bonds or represent a divalent group having an arbitrary molecular structure that can be synthesized as a polyimide, and do not contain a fluorine atom. e represents the number of repetitions of 2 to 100,000.

  This polyimide resin can be obtained in the form of a high heat-resistant film by heat-treating a film formed from a resin composition of a polyimide precursor such as fluorine-free polyamic acid or polyamic acid ester. The heating temperature in the heat treatment step is usually 120 to 450 ° C, more preferably 250 to 400 ° C.

  In addition, this polyimide resin can be obtained by heat treatment after patterning a fluorine-free photosensitive resin composition in which a photosensitive agent is blended with a polyimide precursor such as fluorine-free polyamic acid or polyamic acid ester. desirable.

Here, in order to obtain a fluorine-free photosensitive resin composition, as described above, the polyimide precursor as a main component does not contain fluorine, and as other additive components such as a photosensitizer, It can carry out by using what does not contain a fluorine in the structure of a component.
The photosensitive resin composition according to the present invention preferably contains no fluorine atoms at all, but the composition contains some components due to being contained as impurities in each component contained in the composition. What exists is insignificant, and in the present invention, fluorine is not substantially contained so as to affect the effect of the present invention.

[Resin composition used in semiconductor device manufacturing method]
Hereinafter, the resin composition used for the manufacturing method of the semiconductor device by this invention is demonstrated. The resin composition comprises (A) a resin that does not contain a fluorine atom in the resin structure, and (B) at least one compound selected from the group consisting of heterocyclic compounds, thioureas, and compounds having a mercapto group. It contains. In order to impart photosensitivity to the resin composition, it is preferable to further contain (C) a photosensitizer, and further to contain (D) a solvent for further dissolving each component. Hereinafter, each component will be described.

[(A) component]
The resin (A) resin structure that does not contain a fluorine atom in the resin composition (hereinafter referred to as component (A)) must not contain fluorine in the molecular structure. Polyimide precursors such as polyamic acid and polyamic acid ester that can be cyclized to form an imide ring, polybenzoxazole precursors such as polyhydroxyamide that can be cyclized to form a benzoxazole ring, and polyamide resins other than the above , Polyamideimide resin, polyimide resin and the like, among which a polyimide precursor and a polybenzoxazole precursor are preferable, and a polyimide precursor is more preferable. The component (A) is preferably soluble in an alkaline aqueous solution used as a developer. This can be achieved by having an alkali-soluble group in the resin molecule, and examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Those having a hydroxyl group are preferred.
In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution.

  Among these, a polyimide precursor mainly composed of a structural unit represented by any one of the following general formulas (1) to (3) can become a polyimide having an imide ring by heating or an appropriate catalyst. . Since it has a ring structure, heat resistance and solvent resistance are remarkably improved, which is preferable.

(式中、Ｒ¹は四価の有機基、Ｒ²は二価の有機基、Ｒ³は水素原子又は一価の有機基であり、ａは繰り返し数を示す整数であり、２〜１００,０００である。)

(Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, a is an integer indicating the number of repetitions, 2 to 100, 000.)

(式中、Ｒ¹は四価の有機基、Ｒ⁴は四価の有機基、Ｒ⁵とＲ⁶は水素原子又は一価の有機基でありこれらは同一であっても異なっていてもよく、ｂは繰り返し数を示す整数であり、２〜１００,０００である。)

(Wherein R ¹ is a tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, and these may be the same or different. And b is an integer indicating the number of repetitions, and is 2 to 100,000.)

(式中、Ｒ⁷は二価又は四価の有機基、Ｒ⁴は四価の有機基、Ｒ⁸は二価の有機基、Ｒ⁵とＲ⁶は水素原子又は一価の有機基でありこれらは同一であっても異なっていてもよく、ｃ及びｄは繰り返し数を示す整数であってそれぞれ２〜１００,０００であり、２つの繰り返し単位はブロック又はランダムに存在する。)

(Wherein R ⁷ is a divalent or tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁸ is a divalent organic group, and R ⁵ and R ⁶ are hydrogen atoms or monovalent organic groups. These may be the same or different, and c and d are integers indicating the number of repeats, each being 2 to 100,000, and the two repeat units are present in blocks or randomly.)

In the polyimide precursor, R ^{1 in} the structure represented by the general formulas (1) and (2) and R ⁷ in the structure represented by the general formula (3) are specifically benzene, naphthalene, Divalent or tetravalent aromatic hydrocarbon residues having a skeleton such as perylene, biphenyl, dimethylbiphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylpropane, and benzophenone, or a skeleton such as butane, cyclobutane, cyclohexane, and adamantane A divalent or tetravalent aliphatic hydrocarbon residue is exemplified as a typical example, but is not limited thereto.

Further, R ¹ in the structure represented by the above general formula (1) and (2), and as the number of carbon atoms of R ⁷ in the structure represented by the general formula (3), 4-30 is preferred. Preferred groups are phenyl, biphenyl, dimethylbiphenyl, diphenyl ether, cyclohexane and adamantane. In addition, two or more types can be contained as required.

R ² , R ⁴ and R ⁸ in the structures represented by the general formulas (1) to (3) are specifically diphenyl, dimethylbiphenyl, diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenyl sulfoxide, A divalent or tetravalent aromatic hydrocarbon residue having a skeleton such as diphenylsulfone, biphenyl, or benzene is exemplified as a typical example, but is not limited thereto. Moreover, as these R ^2, R ⁴ and the carbon atoms of R ^8, 6 to 30 is preferable. Preferred groups are diphenyl isopropylidene, diphenyl ether, biphenyl, and diphenyl sulfone. In addition, if necessary, ^two or more kinds of the groups exemplified above can be contained as R ² or R ⁴ .

R ³ , R ⁵ and R ⁶ in the structures represented by the general formulas (1) to (3) can contain not only a hydrogen atom but also a monovalent organic group to such an extent that the alkali solubility is not lowered. . The substitution rate of monovalent organic groups with respect to hydrogen atoms is preferably 0 to 80%, and particularly preferably 0 to 60%. When the substitution rate is higher than this, a decrease is observed in the adhesion to the substrate and the solubility of the resin in the developer. Specific examples of R ³ , R ⁵ and R ⁶ include alkyl groups, aryl groups, alkoxyalkyl groups, alkylsilyl groups, groups constituting acetals or ketals, groups constituting esters, acryloyl groups, methacryloyl groups, and the like. Can be mentioned. Especially, a C1-C10 alkyl group and an aryl group are excellent in the storage stability of a varnish, and are preferable.

In addition, in the repeating units of the general formulas (1), (2), and (3), examples of the tetracarboxylic acid used for forming R ¹ or R ⁷ generally include anhydrides thereof. Merit acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 2,2-bis Aromatic tetracarboxylic dianhydrides such as (3,4-dicarboxyphenyl) hexafluoropropane dianhydride are preferred, and these can be used alone or in combination of two or more.

As the diamine component used to form the R ⁴ in the repeating units of the above general formula, dihydroxydiamine Formation (bis-aminophenols) having a phenolic hydroxyl group capable of imparting alkali solubility and the like.
Hydroxydiamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-) Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoro Although propane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

In addition to the above, diamines corresponding to the following can also be used to the extent that the alkali solubility is not lowered. These are not particularly limited, and examples thereof include 4,4 '-(or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl ether, 4,4 '-( Or 3,4'-, 3,3'-, 2,4'-, 2,2 '-) diaminodiphenylmethane, 4,4'- (or 3,4'-, 3,3'-, 2,4 '-, 2,2'-) diaminodiphenylsulfone, 4,4 '-(or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl sulfide, paraphenylene Diamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylene-bis -(2,6-diethylaniline), 4,4'-methylene-bis- ( , 6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4′-benzophenonediamine, bis- {4- (4′-aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, Bis {4- (3'-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane and the like can be mentioned, and these are used alone or in combination of two or more. Moreover, it is preferable that content of the diamine which does not correspond to the structure of these general formula (2)-(4) is 50% or less of all the diamine, in order not to reduce i line | wire transmittance.
Moreover, aliphatic diamines, such as diaminopolysiloxane, can also be used similarly.

  The polyimide precursor represented by the general formula (1) can be obtained, for example, by the following method. That is, tetracarboxylic dianhydride is reacted with diamine in an organic solvent such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide.

The reaction product obtained by the above method is crystallized in a poor solvent such as water, methanol, ethanol, propyl alcohol, acetone, etc., filtered and dried to obtain the purified general formula (1). Polyamide resins having the structural units shown can be obtained. Further, the obtained polyamide resin is used as a protective agent for a hydroxyl group having R ⁵ in an aprotic organic solvent such as tetrahydrofuran, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, and the like. In accordance with the reaction, a reaction catalyst is added to carry out a protection reaction, whereby a polyimide precursor having a structural unit represented by the general formula (1) can be obtained.

  The polyimide precursor represented by the general formula (2) can be obtained, for example, by the following method. That is, a tetracarboxylic dianhydride or a tetracarboxylic acid diester halide is mixed with bisaminophenol in an organic solvent such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, and the like. And react with the reaction catalyst. As a method for synthesizing a tetracarboxylic acid diester compound, for example, the tetracarboxylic dianhydride and the alcohol compound are mixed in an organic solvent in the presence of a base.

The reaction product obtained by the above method is crystallized in a poor solvent such as water, methanol, ethanol, propyl alcohol, acetone, etc., filtered and dried, and purified by the general formula (2). A polyimide precursor having the structural units shown can be obtained. Further, the obtained polyimide precursor is protected with a hydroxyl group-protecting agent having R ³ in an aprotic organic solvent such as tetrahydrofuran, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, A polyimide precursor having a structural unit represented by the general formula (2) can be obtained by adding a reaction catalyst as necessary to carry out a protection reaction.

  The polyimide precursor represented by the general formula (3) is a structural unit (preferably formed by reaction of a dicarboxylic acid or derivative thereof with bisaminophenol together with the structure represented by the general formula (1). Is a structural unit of a polybenzoxazole precursor. In this case, the proportion of the structure represented by the general formula (1) is preferably 50% or less in all repeating units.

(式中、Ｒ⁹は二価の有機基、Ｒ⁴は四価の有機基、Ｒ⁶は水素原子又は一価の有機基でありこれらは同一であっても異なっていてもよく、ｆは繰り返し数を示す整数であり、２〜１００,０００である。)で表される構造単位を主とするポリベンゾオキサゾール前駆体が好ましいものとして挙げられる。 In addition, polybenzoxazole precursors such as polyhydroxyamide that can be cyclized to form a benzoxazole ring include the following general formula (5):

(Wherein R ⁹ is a divalent organic group, R ⁴ is a tetravalent organic group, R ⁶ is a hydrogen atom or a monovalent organic group, which may be the same or different, and f is A preferred example is a polybenzoxazole precursor mainly composed of a structural unit represented by an integer indicating the number of repetitions and 2-100,000.

Similarly with R ⁷ in the general formula (3) as R ^6, R ⁹ in the general formula (3) as R ^4, R ⁶ in the general formula (3) as R ⁴ in formula (5) Each of these structures is given as a specific example.

Examples of the dicarboxylic acid used to form R ^{7 in} the general formula (3) and R ⁹ in the general formula (5) include isophthalic acid, terephthalic acid, and 2,2-bis (4-carboxyphenyl). -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4- Carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic Aromatic dicarboxylic acids such as acids, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclope Tanji carboxylic acid, oxalic acid, malonic acid, such as aliphatic dicarboxylic acids such as succinic acid but is not limited thereto.
These compounds can be used alone or in combination of two or more.

In addition to the above, as the component (A), other polyamide resins, polyamideimide resins, polyamideimide resins, etc. can be used. From the viewpoint of various properties, the polyimide precursor or polybenzoxazole precursor is used. It is preferable.
In order to impart alkali solubility to any resin, the resin preferably has a functional group capable of imparting alkali solubility such as a carboxyl group or a phenolic hydroxyl group, and the characteristics are improved by using a resin having such a functional group. The photosensitive resin composition and the method for producing a semiconductor device of the present invention can solve the problems in the case of doing so.

  Although there is no restriction | limiting in particular in the molecular weight of (A) component, Generally it is preferable that it is 10,000-200,000 by a weight average molecular weight (Mw). The molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of standard polystyrene.

[(B) component]
The resin composition of the present invention comprises (B) at least one compound selected from the group consisting of a heterocyclic compound, a thiourea and a compound having a mercapto group (hereinafter referred to as component (B)). The heterocyclic compound refers to a cyclic compound in which a ring is composed of atoms of two or more elements (carbon, nitrogen, oxygen, sulfur, etc.). Heterocyclic compounds include pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimididine ring, pyrazine ring , A piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a compound having a triazine ring, and the like. Compounds having a thiazole ring, an imidazole ring and a tetrazole ring are preferred.

  Examples of the thioureas include monomethylthiourea, thiourea, dimethylthiourea, diethylthiourea, dibutylthiourea and the like, but are not limited thereto.

  Specific examples of the heterocyclic compound and the compound having a mercapto group include pyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 2-ethylpyrrole, indole, 5-hydroxyindole, Pyrazole, 4-methylpyrazole, 3-aminopyrazole, 3-methylpyrazole, 3,5-diisopropylpyrazole, 3-amino-5-hydroxypyrazole, indazole, 5-aminoindazole, 6-aminoindazole, imidazole, 2-methyl Imidazole, 2-ethylimidazole, 2-butylimidazole, 4-imidazolecarboxylic acid, 4-methylimidazole, benzimidazole, 5-methylbenzimidazole, 2-aminobenzimidazole, 5,6-dimethylbenzimidazole , 2-mercapto-1,3,4-thiadiazole, 2,5-dimethyl-1,3,4-thiadiazole, 4-phenyl-1,2,3-thiadiazole, 2-amino-1,3,4 -Thiadiazole, 2-amino-5-ethyl-1,3,4-oxadiazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2-methoxythiazole, 2-ethoxythiazole, 2-isobutylthiazole, 2- Trimethylsilylthiazole, 5-trimethylsilylthiazole, 4-methylthiazole, 4,5-dimethylthiazole, 2-ethylthiazole, 2,4-dimethylthiazole, 2-amino-5-methylthiazole, 2-amino-4-methylthiazole, 2,4,5-trimethylthiazole, benzothiazole, 2-methylbenzothiazole 2,5-dimethylbenzothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4 -Triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1 , 2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2 , 4-Tria Sol, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, benzotriazole, 5-methyl-1H-benzo Triazole, 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotriazole-4-sulfonic acid, 1H-tetrazole, 5-methyl-1H-tetrazole, 5- (methylthio) -1H-tetrazole, 5 -(Ethylthio) -1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-nitro-1H-tetrazole 1-methyl-1H-tetrazole, 5,5′-bis-1H-tetrazole However, it is not limited to these. These may be used alone or in combination of two or more.

  Among the above compounds, at least one selected from the group consisting of 1H-tetrazole, 5 substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof is preferable, 1,2,3-triazole, 1,2, Selected from the group consisting of 4-triazole and derivatives thereof, 1,2,3-benzotriazole, 5 substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and derivatives thereof At least one kind is more preferable, and 5-methyl-1H-benzotriazole, 5-methyl-1H-tetrazole, and 5,5′-bis-1H-tetrazole are particularly preferable.

  (B) component in this invention is used in order to prevent the corrosion between resin and a board | substrate (copper and copper alloy), and to improve adhesiveness.

  The blending amount of the component (B) in the present invention is usually 0.1 to 10 parts by weight per one type with respect to 100 parts by weight of the component (A). Part by weight is preferred. More preferably, it is the range of 0.2-5 weight part. When the blending amount of the component (B) is less than 0.1 parts by weight, the effect of improving the adhesion to the metal layer tends to be reduced. Is not expected.

[Component (C)]
The photosensitive resin composition of this invention contains the photosensitive agent which is (C) component with resin which does not contain a fluorine in a structure. The component (C) needs to be a photosensitizer that does not contain fluorine in the structure. The photosensitive agent has a function for a developer of a film formed from the composition in response to light. Although there is no restriction | limiting in particular in a photosensitive agent, It is preferable that it generates an acid or a radical by light.

  In the case of a positive photosensitive resin, it is more preferable that the acid is generated by light (photoacid generator). In the positive photosensitive resin, the photoacid generator has a function of generating an acid by light irradiation and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. Examples of such a photoacid generator include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like, and o-quinonediazide compounds are preferable because of their high sensitivity.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl. Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3 -Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-Amino-4-hydroxyphenyl) hexaph Oropuropan, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound are blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. Is preferred. A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the structure of the resin (A), when there is a group having a photocrosslinkable group such as an acryloyl group or a methacryloyl group, a component that generates a radical, that is, a photopolymerization initiator, is used as the component (C). Therefore, it can be used as a negative photosensitive resin composition. This has a function of reducing the solubility of the light irradiated portion in an alkaline aqueous solution by a crosslinking reaction by light irradiation.

  In the photosensitive resin composition of the present invention, the blending amount of the component (C) is 5 with respect to 100 parts by weight of the component (A) in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable sensitivity range. -100 weight part is preferable, and 8-40 weight part is more preferable.

[Component (D)]
The solvent which is the component (D) used in the resin composition of the present invention must not contain fluorine in the structure, and γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n -Butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene Examples include sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methyl amyl ketone.

  These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, but is generally adjusted so that the ratio of the solvent in the resin composition is 20 to 90% by weight.

[Other additive components]
In the photosensitive resin composition, in addition to the components (A) to (D), (1) a dissolution accelerator, (2) a dissolution inhibitor, (3) an adhesion promoter, (4) a surfactant or You may mix | blend components, such as a leveling agent. However, it is necessary that the structure of these components does not contain fluorine.

((1) dissolution promoter)
In this invention, when making a resin composition alkali-soluble, the solubility promoter which accelerates | stimulates the solubility with respect to the aqueous alkali solution of (A) component, for example, the compound which has a phenolic hydroxyl group can be contained. The compound having a phenolic hydroxyl group can be added to increase the dissolution rate of the exposed area when developing with an aqueous alkaline solution, increasing the sensitivity, and preventing the film from melting when the film is cured after pattern formation. it can.

  The compound having a phenolic hydroxyl group that can be used in the present invention is not particularly limited. Examples of the low molecular weight compound having a phenolic hydroxyl group include o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-[(2-hydroxy-5 -Methylphenyl) methyl] -4-methylphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4'-[ 1- [4- [2- (4-Hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetris 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4′- [(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′-[( 2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3 4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl ] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[(2-hydroxyphenyl) ) Methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3-methyl-1-propanyl-3-ylidine) trisphenol, 4,4 ′, 4 ″, 4 ′ ″- (1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [ (3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -3,5-bis [( Hydroxy-3-methyl And phenyl) methyl] phenyl] -phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) methyl] phenol.

  When the molecular weight is increased, the effect of promoting the dissolution of the exposed area is reduced, and therefore, a compound having a molecular weight of 1,500 or less is preferable. What is listed in the following general formula (6) is particularly preferable because it is excellent in the balance between the effect of promoting the dissolution of the exposed portion and the effect of preventing the melting of the film during curing.

（式中、Ｚは単結合又は２価の有機基を示し、各Ｒは各々独立にアルキル基又はアルケニル基を示し、ｇ及びｈは各々独立に１又は２であり、ｉ及びｊは各々独立に０〜３の整数である。）

(In the formula, Z represents a single bond or a divalent organic group, each R independently represents an alkyl group or an alkenyl group, g and h are each independently 1 or 2, and i and j are each independently It is an integer of 0 to 3).

  The blending amount of the component of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of the development time and the allowable width of the remaining film ratio of the unexposed part. More preferred is 25 parts by weight.

((2) dissolution inhibitor)
In this invention, when making a resin composition alkali-soluble, the dissolution inhibitor which is a compound which inhibits the solubility with respect to the aqueous alkali solution of (A) component can be further contained. Specific examples include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide.

  These dissolution inhibitors effectively cause dissolution inhibition and are useful for controlling the remaining film thickness and development time. The blending amount of the dissolution inhibitor is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the component (A), from the viewpoint of sensitivity and an allowable range of development time. 0.1 to 20 parts by weight is more preferable.

((3) Adhesion imparting agent)
The resin composition of the present invention can contain an adhesion-imparting agent such as an organic silane compound and an aluminum chelate compound in order to enhance the adhesion of the cured film to the substrate.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n -Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenyl Silanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4- Bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyl Hydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these adhesion grant agents, 0.1-30 weight part is preferable with respect to 100 weight part of (A) component, and 0.5-20 weight part is more preferable.

((4) Surfactant or leveling agent)
The resin composition of the present invention can be added with an appropriate surfactant or leveling agent in order to prevent coatability, for example, striation (film thickness unevenness) or improve developability. .

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like, and Megafax F171 is a commercially available product. , F173, R-08 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Product made by Shin-Etsu Chemical Co., Ltd.) Name).

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film using the photosensitive resin composition of this invention is demonstrated. The method for producing a patterned cured film according to the present invention includes a step of applying the above-described photosensitive resin composition on a support substrate and drying, and a step of exposing the photosensitive resin film obtained by the drying step to a predetermined pattern; A resin pattern such as a polyimide resin can be obtained through a step of developing the photosensitive resin film after the exposure and a step of heat-treating the photosensitive resin film after the development. Hereinafter, each step will be described.

(Coating / drying (film formation) process)
First, in the step of applying and drying the photosensitive resin composition described above on a support substrate, on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, The photosensitive resin composition is spin-coated using a spinner or the like and then dried using a hot plate, an oven, or the like. Thereby, the photosensitive resin film which is a film of the photosensitive resin composition is obtained.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed on the support substrate with an actinic ray such as an ultraviolet ray, visible ray, or radiation via a mask.

(Development process)
In the development step, a pattern is obtained by removing the exposed portion of the photosensitive resin film exposed to actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

(Heat treatment process)
Next, in the heat treatment step, the pattern obtained after development is heat-treated, for example, in the case of a polyimide precursor, imide ring closure occurs, and a heat-resistant polyimide pattern having an imide ring can be formed. 120-450 degreeC is preferable and the heating temperature in a heat processing process has more preferable 250-400 degreeC.

  The heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the photosensitive resin film can be prevented. Since the said heating temperature range is lower than the conventional heating temperature, the damage to a support substrate or a device can be restrained small. Therefore, by using the pattern manufacturing method of the present invention, devices can be manufactured with high yield. It also leads to energy savings in the process.

[Method for Manufacturing Semiconductor Device]
Next, a method for manufacturing a semiconductor device using the above-described photosensitive resin composition will be described. A method of manufacturing a semiconductor device according to the present invention includes a step of forming an inorganic insulating film on at least a pad electrode and a metal wiring formed on a semiconductor substrate, and a step of forming a fluorine-free organic insulating film on the inorganic insulating film. A step of patterning the fluorine-free organic insulating film, and a step of dry etching the inorganic insulating film exposed by the pattern processing with a fluorine-containing gas to expose the pad electrode portion. The manufacturing method, wherein the fluorine-free organic insulating film is selected from the group consisting of (A) a resin that does not contain fluorine in the resin structure, and (B) a heterocyclic compound, a thiourea, and a compound having a mercapto group It is formed from the resin composition containing the at least 1 sort (s) of compound. Hereinafter, a method for manufacturing a semiconductor device according to the present invention will be described in more detail with reference to the drawings.

1 to 6 are schematic cross-sectional views illustrating the manufacturing process of the semiconductor device of the present invention. In these drawings, a metal element including a circuit element and a pad electrode (first conductor layer) 2 is formed on a semiconductor element such as a Si substrate or the semiconductor substrate 1, and the pad electrode 2 and the semiconductor substrate 1 are oxidized by silicon. It is covered with an inorganic insulating film 3 such as a film. Examples of the target to be coated with the inorganic insulating film 3 include a substrate portion made of Si, SiO ₂ , Si ₃ N ₄ , Ta, Ti, Ta ₂ O ₅ , TaN, Al or the like, a film, a wiring, and the like. On the inorganic insulating film 3 formed on the semiconductor substrate 1, a film such as a polyimide precursor having photosensitivity as the first organic insulating film 4 is formed by a spin coat method or the like (FIG. 1).

  Next, after irradiating light from a mask (not shown) on which a pattern for forming the window 5A is formed on a predetermined portion of the first organic insulating film 4 which is a photosensitive polyimide resin layer, an alkaline aqueous solution is used. Develop to form a pattern. Thereafter, it is heated to form a polyimide film as the first organic insulating film 4 (FIG. 2).

  Next, using this patterned polyimide film (first organic insulating film 4) as a mask, the inorganic insulating film 3 is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to form a window. 5B is opened (FIGS. 3 and 4). Dry etching is preferably performed at a high output. Although the specification of the maximum output that can be set differs depending on the apparatus, the etching process can be performed in a shorter time because the etching rate is improved by performing it under higher output conditions.

  Examples of the fluorine-containing gas used during etching include fluorinated methane. Examples of the fluorinated methane include tetrafluoromethane, trifluoromethane, difluoromethane, and fluoromethane. Of these, tetrafluoromethane, trifluoromethane, and difluoromethane are particularly preferable. These fluorinated methanes may be used alone or in combination.

Furthermore, a mixed gas composed of fluorinated methane and oxygen can be used, and in this case, the proportion of oxygen is preferably 5 to 30% by volume. Moreover, the mixed gas which consists of fluorinated methane and hydrogen can also be used, and the ratio of hydrogen is preferable 10-30 volume% with respect to fluorinated methane in this case. When the ratio of oxygen to fluorinated methane exceeds 30% by volume or the ratio of hydrogen exceeds 30% by volume, the surface of the organic insulating film is rough, which may cause a problem in appearance. For inorganic insulating films such as Si, SiO ₂ , Si ₃ N ₄ , Ta, Ti, Ta ₂ O ₅ , TaN, etc., etching can be performed in a shorter time by selecting the optimum dry etching process conditions. .

  Regarding the process pressure set at the time of etching, the lower one is preferable. By keeping the pressure in the system low, the residue can be discharged without leaving a residue during etching. The process pressure in the system is 0.5 Pa to 25 Pa, preferably 1 Pa to 15 Pa. If it is less than the lower limit value, plasma will not be generated, and there is a possibility that the etching process cannot be performed. As other semiconductor device manufacturing methods, known methods can be used.

  Further, a second conductor layer (second metal wiring pattern layer formed of copper or the like) 6 is formed using a known photolithography technique, and electrical connection with the first conductor layer 2 is completely performed. (FIG. 5).

  Next, a second organic insulating film (surface protective film layer) 7 is formed (FIG. 6). In the examples of FIGS. 1 to 6, the photosensitive resin composition is applied and dried by a spin coating method, and after irradiating light from a mask on which a pattern for forming a window 8 is formed in a predetermined portion, an alkaline aqueous solution is used. Development is performed to form a pattern, and heating is performed to form a second organic insulating film (surface protective film) 7 that is a polyimide resin film. The second organic insulating film 7 as the surface protective film layer protects the conductor layer from external stress, α rays, etc., and the obtained semiconductor device is excellent in reliability.

  In the above example, the first organic insulating film (interlayer insulating layer) 4 and the second organic insulating film (surface protective film layer) 7 are both formed using the photosensitive resin composition of the present invention. In this case, a residue is not generated after the inorganic insulating film is opened by dry etching using the organic insulating film as a mask, and the residue removing step is not required. Therefore, the process can be shortened, and the second layer However, since copper and copper alloys such as metal wiring and metal layers are not corroded and both layers have the same composition, they are strong against heat history and can exhibit excellent reliability. When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

  In the case of using a conventional semiconductor device manufacturing method, in particular, an alkali-soluble photosensitive resin composition, since a photosensitive resin composition containing fluorine is generally used as an organic insulating film, a laminated passivation film made of an inorganic insulating film is used. There is a problem in that the yield and reliability of the semiconductor device are significantly reduced by the reaction between the fluorine-containing gas used for dry etching in forming the opening in the substrate and the fluorine-containing component in the organic insulating film, thereby forming a residue. It was. The residue deposits are difficult to remove, and removal steps such as oxygen plasma treatment and chemical treatment are required. In addition, when a resin composition such as a polyimide precursor varnish is applied on a substrate on which a metal wiring or metal layer made of copper and a copper alloy is formed to form an insulating film for a multilayer wiring board, the polyimide precursor is copper or copper. There has been a problem that the alloy has a corrosive action, resulting in poor insulation, disconnection, short circuit, and the like.

  In contrast, in the present invention, a resin composition containing a resin that does not contain fluorine in the structure and at least one compound selected from the group consisting of heterocyclic compounds, thioureas, and compounds having a mercapto group is heat-treated. By forming the organic insulating film, fluorine residue due to the reaction between the dry etching gas and the organic insulating film is not generated. For this reason, since a residue removal process is unnecessary, a process can be shortened. Furthermore, since copper and copper alloys such as metal wiring and metal layers are not corroded, by using the organic insulating film according to the present invention, defects can be reduced and a highly reliable semiconductor device can be obtained in high yield. be able to.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The electronic component according to the present invention has a pattern formed by the above-described method for producing a cured pattern film using the photosensitive resin composition described above. Specifically, this pattern can be used for forming a surface protective film, an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component can be manufactured by the method for manufacturing a semiconductor device according to the present invention. The electronic component includes a semiconductor device, a display element such as a liquid crystal display element, a multilayer wiring board, various electronic devices, and the like. In particular, a chip size package or a wafer level package can be cited as a preferred application.

  The electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the photosensitive resin composition, and can take various structures. For example, the photosensitive resin composition of the present invention is suitable for an interlayer insulating film and a surface protective film of a chip size package or a wafer level package.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example. In Examples and Comparative Examples, the organic solvent was dehydrated, and the polymer synthesis operation was performed in a nitrogen atmosphere.

Polymer synthesis
(Synthesis Example 1)
In a 0.2-liter flask equipped with a stirrer and a thermometer, 20.16 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 83.93 g of N-methylpyrrolidone, 7.81 g of isopropyl alcohol Then, 0.30 g of diazabicycloundecene was added, and the mixture was stirred and reacted at room temperature for 120 hours to obtain an N-methylpyrrolidone solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid diisopropyl ester. Next, 103.56 g of an N-methylpyrrolidone solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid diisopropyl ester was placed in a flask and cooled to 0 ° C., and 12.44 g of thionyl chloride was added dropwise for 30 minutes. Reaction was performed to obtain an N-methylpyrrolidone solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid diisopropyl ester dichloride. Next, 53.72 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 13.44 g of 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was added. After adding and dissolving with stirring, 16.32 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., an N-methylpyrrolidone solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid diisopropyl ester dichloride 107 .56 g was added dropwise over 20 minutes, and stirring was continued for 1 hour. The obtained solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then decompressed to obtain a polyimide precursor (hereinafter referred to as polymer I). The weight average molecular weight measured using GPC (column: GL-S300MDT-5 manufactured by Hitachi Chemical Co., Ltd.) was 23,800.

(Synthesis Example 2)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged. After the flask was cooled to 5 ° C., thionyl chloride 12. 64 g was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.31 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. After stirring and dissolving, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, followed by stirring for 30 minutes. Continued. The obtained solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer II). The weight average molecular weight measured using GPC (column: GL-S300MDT-5 manufactured by Hitachi Chemical Co., Ltd.) was 17,900.

(Synthesis Example 3)
Except for replacing 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 with 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, The synthesis was performed under the same conditions as in Synthesis Example 1. The weight average molecular weight calculated | required by standard polystyrene conversion of the obtained polyimide precursor (henceforth polymer III) was 22,000.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring apparatus; Detector: Hitachi Ltd. L4000 UV
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column: Gelpack GL-S300MDT-5 x2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

(Photosensitivity evaluation using synthetic polymer)
Examples 1-7 and Comparative Examples 1-7
(B), (C), (D) component and an additional component were mix | blended with the predetermined amount shown in Table 1 with respect to 100 weight part of said (A) component.

  In Table 1, BLO: γ-butyrolactone, PGMEA: propylene glycol monomethyl ether acetate, NMP: N-methylpyrrolidone, and BLO / NMP represent a mixture of both. Each BLO / NMP was added in an amount of 153 parts by weight at a mixing ratio of 1/1 (weight ratio), and each BLO / PGMEA was added in an amount of 153 parts by weight at a mixing ratio of 4/1 (weight ratio). The amount in parentheses indicates the amount added relative to 100 parts by weight of the polymer in parts by weight. B1 to B3, C1 and C2, and E1 to E4 are compounds represented by the following chemical formulas (7) to (9).

  The obtained photosensitive resin composition solution was formed by sputtering a TiN film having a thickness of about 200 mm on a silicon wafer having a diameter of 5 inches and a silicon wafer having a diameter of 5 inches, and a Cu film having a thickness of about 500 mm was formed thereon. A thin sputter-formed wafer (hereinafter referred to as “Cu wafer”) is spin-coated to form a coating film having a dry film thickness of 3 to 10 μm, and then an ultrahigh pressure mercury lamp is passed through an interference filter. I line (365 nm) exposure was performed through the pattern mask. After exposure, it is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer and Cu wafer are exposed, then rinsed with water and necessary for pattern formation. Minimum exposure and resolution were determined. The results are shown in Table 2.

  From the above results, in the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 4, 5, and 7 containing B1, B2, and B3 which are the components (B) of the present invention, the photosensitive characteristics under the same conditions. In the evaluation, the same sensitivity and resolution were obtained for both the silicon wafer and the Cu wafer. On the other hand, Comparative Examples 1 to 3 and 6 that do not contain the component (B) require a higher minimum exposure amount, and the sensitivity of the Cu wafer is lower than that of the silicon wafer.

(Creation of organic insulating film on inorganic insulating film)
A SiO ₂ film as an inorganic insulating film having a thickness of 1 μm was formed on a silicon wafer having a diameter of 5 inches on which an Al wiring was formed by a plasma CVD method. On this inorganic insulating film, the photosensitive resin composition solutions of Examples 1 to 7 and Comparative Examples 1 to 7 are spin-coated to form a coating film having a dry film thickness of 3 to 10 μm. Then, the pad electrode portion was exposed to i-line (365 nm) through a pattern mask with an ultrahigh pressure mercury lamp. After the exposure, the film was heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide until the exposed inorganic insulating film was exposed, and then rinsed with water to form a pattern. Further, the silicon wafer was heated in a gas oven in a nitrogen atmosphere at 150 ° C. for 30 minutes, and further heated at 350 ° C. for 1 hour to obtain an organic insulating film.

(Inorganic insulating film etching)
Next, a silicon wafer having a patterned organic insulating film is etched using an etching apparatus, and a mixed gas having a volume ratio of oxygen: tetrafluoromethane = 20: 80 is set to 7 at a flow rate of 25 sccm at an output of 100 W and a process pressure of 10 Pa. The inorganic insulating film was etched for a minute. At this time, the decrease in the thickness of the organic insulating film was about 0.8 μm. A 50 μm × 50 μm square pattern opening (pad electrode part) was observed with a scanning electron microscope to evaluate the presence or absence of residues. The results are shown in Table 3.

From the above results, the organic insulating films prepared from the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 using the polymer I containing no fluorine in the structure showed no residue due to dry etching. It was.
On the other hand, in the organic insulating film produced from the photosensitive resin compositions of Comparative Examples 3 to 7 using polymers II and III containing fluorine in the structure, a residue was observed in the pad electrode part after dry etching.

  A photosensitive resin composition solution of Examples 1 to 7 was patterned on a Cu wafer having a diameter of 5 inches, heated in a gas oven in a nitrogen atmosphere at 150 ° C. for 30 minutes, and further heated at 350 ° C. for 1 hour. Thus, an organic insulating film was obtained. Using the cured film on the obtained Cu wafer, a stud pull test was performed as an adhesion test. For the stud pull test, a stud pin (Al with an epoxy adhesive) manufactured by Phototechnica Co., Ltd. was used. Adhesion between the stud pin and the cured film was performed by curing in an oven at 150 ° C. for 1 hour.

  As a result, cohesive failure of the epoxy adhesive layer occurred, the adhesive strength between the cured films of Examples 1 to 7 and the Cu wafer was larger than the epoxy aggregate density strength, and the adhesiveness was sufficient. Moreover, after processing the Cu wafer in which the cured film was formed at 121 degreeC / 1.2MPa for 100 hours using a pressure cooker, the stud pull test was done similarly. As a result, the cohesive failure of the epoxy adhesive layer occurred, and the adhesive strength between the cured films of Examples 1 to 7 and the Cu wafer hardly deteriorated even after the PCT treatment.

  From these results, Examples 1 to 7 using the polymer containing no fluorine in the structure and the photosensitive resin composition containing the component (B) can be obtained even with a Cu wafer having the same sensitivity and resolution as those on a silicon wafer. The cured film showed sufficient adhesion with the Cu wafer. Furthermore, after dry etching, no residue was found in the pad electrode part, which was good.

  As described above, the semiconductor device and the method for manufacturing the semiconductor device according to the present invention use a resin film that does not contain fluorine as the organic insulating film, thereby opening a residue after the inorganic insulating film is opened by dry etching using the organic insulating film as a mask. Since the residue removal step is unnecessary, the process can be shortened. Further, by forming an organic insulating film using a composition containing at least one compound selected from the group consisting of heterocyclic compounds, thioureas, and compounds having a mercapto group, metal wiring, metal layers, etc. Since copper and copper alloys are not corroded, a highly reliable semiconductor device can be obtained in a high yield and the sensitivity of the composition is excellent. This organic insulating film has a good shape, a pattern with excellent adhesion and heat resistance, avoids damage to the device, and provides a highly reliable electronic component. Therefore, this organic insulating film is suitable for an interlayer insulating film and a surface protective film of a chip size package or a wafer level package.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention.

Explanation of symbols

1 Semiconductor substrate 2 Pad electrode (first conductor layer)
3 Inorganic insulating film 4 First organic insulating film (interlayer insulating layer)
5A, 5B Window 6 Second conductor layer 7 Second organic insulating film (surface protective layer)
8 windows

Claims (18)

Forming an inorganic insulating film on at least the pad electrode and the metal wiring formed on the semiconductor substrate;
Forming a fluorine-free organic insulating film on the inorganic insulating film;
Patterning the fluorine-free organic insulating film;
A step of dry-etching the inorganic insulating film exposed by the pattern processing with a fluorine-containing gas to expose the pad electrode part,
The fluorine-free organic insulating film is at least one selected from the group consisting of (A) a resin that does not contain fluorine in the resin structure, and (B) a heterocyclic compound, a thiourea, and a compound having a mercapto group. A method for manufacturing a semiconductor device, comprising: forming a resin composition containing a compound.   The resin (A) contained in the resin composition for forming the fluorine-free organic insulating film is a heat treatment of a resin composition comprising a polyimide precursor or a polybenzoxazole precursor that does not contain fluorine in the resin structure. The method of manufacturing a semiconductor device according to claim 1, wherein the film is a film obtained by the steps described above.   The resin composition for forming the fluorine-free organic insulating film is a polyimide precursor or polybenzoxazole precursor containing no fluorine in the resin structure as the resin (A), (B) a heterocyclic compound, and thiourea 2. The semiconductor device according to claim 1, wherein the semiconductor device comprises a photosensitive resin composition comprising at least one compound selected from the group consisting of a group and a compound having a mercapto group, and a photosensitive agent (C). Manufacturing method.   4. The method of manufacturing a semiconductor device according to claim 3, wherein the photosensitive resin composition can be developed and patterned with an alkaline aqueous solution.   The component (B) is a heterocyclic compound, and the compound has at least one structure selected from the group consisting of a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring and a tetrazole ring. The method for manufacturing a semiconductor device according to claim 1, wherein:   The semiconductor according to claim 5, wherein the heterocyclic compound is at least one selected from the group consisting of 1H-tetrazole, 5 substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof. Device manufacturing method.   The heterocyclic compound is 1,2,3-triazole, 1,2,4-triazole and derivatives thereof, 1,2,3-benzotriazole, 5 substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 6. The method of manufacturing a semiconductor device according to claim 5, wherein the semiconductor device is at least one selected from the group consisting of 5,6-substituted-1H-benzotriazole and derivatives thereof.   Further, as a step, a step of forming a second metal wiring pattern layer on the fluorine-free organic insulating film and the exposed pad electrode portion, and a step of forming a second fluorine-free organic insulating film thereon And the second fluorine-free organic insulating film is also selected from the group consisting of (A) a resin that does not contain fluorine in the resin structure, and (B) a heterocyclic compound, a thiourea, and a compound having a mercapto group The method of manufacturing a semiconductor device according to claim 1, wherein the semiconductor device is formed from a resin composition containing at least one compound.   A semiconductor device manufactured by the method for manufacturing a semiconductor device according to claim 1.   An electronic component comprising the structure of the semiconductor device according to claim 9.   The electronic component according to claim 10, wherein the electronic component is a chip size package or a wafer level package.   A step of forming an inorganic insulating film on at least the pad electrode and the metal wiring formed on the semiconductor element; a step of forming a fluorine-free organic insulating film on the inorganic insulating film; and the fluorine-free organic insulating film. In the method of manufacturing a semiconductor device, including a pattern processing step and a step of dry etching the inorganic insulating film exposed by the pattern processing with a fluorine-containing gas to expose the pad electrode, the fluorine-free organic insulating film A photosensitive resin composition for forming a resin selected from the group consisting of (A) a resin that does not contain fluorine in the resin structure, and (B) a heterocyclic compound, a thiourea, and a compound having a mercapto group A photosensitive resin composition comprising at least one compound, (C) a photosensitive agent, and (D) a solvent, and not containing fluorine.   The resin (A) contained in the photosensitive resin composition for forming the fluorine-free organic insulating film is a polyimide precursor or a polybenzoxazole precursor containing no fluorine in the resin structure. The photosensitive resin composition of Claim 12.   The photosensitive resin composition according to claim 12 or 13, wherein the photosensitive resin composition can be developed and patterned with an alkaline aqueous solution.   The component (B) is a heterocyclic compound, and the compound has at least one structure selected from the group consisting of a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring and a tetrazole ring. The photosensitive resin composition of any one of Claims 12-14 characterized by the above-mentioned.   The photosensitive compound according to claim 15, wherein the heterocyclic compound is at least one selected from the group consisting of 1H-tetrazole, 5-substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof. Resin composition.   The heterocyclic compound is 1,2,3-triazole, 1,2,4-triazole and derivatives thereof, 1,2,3-benzotriazole, 5 substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 16. The photosensitive resin composition according to claim 15, wherein the photosensitive resin composition is at least one selected from the group consisting of 5,6-substituted-1H-benzotriazole and derivatives thereof. 13. The resin (A) is at least one selected from the group consisting of polyimide precursors mainly composed of structural units represented by the following general formulas (1) to (3). The photosensitive resin composition of any one of -17.
General formula (1):

(Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, a is an integer indicating the number of repetitions, 2 to 100, 000.)
General formula (2):

(Wherein R ¹ is a tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, and these may be the same or different. And b is an integer indicating the number of repetitions, and is 2 to 100,000.)
General formula (3):

(Wherein R ⁷ is a divalent or tetravalent organic group, R ⁴ is a tetravalent organic group, R ⁸ is a divalent organic group, and R ⁵ and R ⁶ are hydrogen atoms or monovalent organic groups. These may be the same or different, and c and d are integers indicating the number of repeats, each being 2 to 100,000, and the two repeat units are present in blocks or randomly.)

Images