TW201718711A - Positive-type photosensitive resin composition, uncured resin pattern formed with said resin composition, cured resin pattern, semiconductor device in which same is used, and method for manufacturing same - Google Patents

Abstract

The purpose of the present invention is: to provide a positive-type photosensitive resin composition with which it is possible to obtain a cured resin pattern having high sensitivity to the i-line of a mercury lamp, excellent chemical resistance to strongly acidic aqueous solutions and strongly alkaline aqueous solutions, and, in particular, highly reliable adhesion to aluminum pads even in an electroless plating step after O2 ashing; and to provide a resin pattern using the composition, and a method for manufacturing a semiconductor device in which the same is used. The positive-type photosensitive resin composition contains (a) an alkali-soluble resin and (b) a quinonediazide compound, the alkali-soluble resin (a) including: (a1) a polyimide precursor in which the residue of a tetracarboxylic acid represented by general formula (1) is present in an amount of 5-50 mol% in relation to the total tetracarboxylic acid residue, the residue of a diamine represented by general formula (2) is present in an amount of 10-80 mol% in relation to the total diamine residue, and the residue of a diamine represented by general formula (3) is present in an amount of 10-90 mol% in relation to the total diamine residue; and/or (a2) a polyimide corresponding to (a1). (In general formula (1), A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group free of heteroatoms, and two or more types may be used.) (In general formula (2), B represents a group selected from among O, S, SO2, CH2, CH(CH3), C(CH3)2, and C(CF3)2, and two or more types of these may be used).

Description

Positive photosensitive resin composition, uncured resin pattern formed by the resin composition, cured resin pattern, semiconductor device using the same, and method for producing the same

The present invention relates to a positive photosensitive resin composition, an uncured resin pattern formed by the resin composition, a cured resin pattern, and a semiconductor device using the same and a method for producing the same. More specifically, the present invention relates to a positive photosensitive resin composition which can be suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic light-emitting element, and the like.

In the surface protective film or the interlayer insulating film of the semiconductor element, the insulating layer of the organic light-emitting element, or the flattening film of the TFT substrate, a polyimide resin or a polybenzoic acid having excellent heat resistance or mechanical properties is widely used. An azole resin or a polyamidoximine resin. In the past, a coating film was first formed in a state of a heat-resistant resin precursor having high solubility in an organic solvent, and a phenol resin or the like was used as a base resist to form a desired pattern, and the precursor was formed. A method in which the material is heat-hardened, thereby becoming an insoluble or infusible heat-resistant resin.

In recent years, it has been attempted to simplify the photoresist step by using a negative-type, positive-type photosensitive resin composition which can process a pattern required for its own formation.

In addition, from the viewpoints of miniaturization, weight reduction, high performance, and low cost of electronic equipment, the surface of the electroless plating step is introduced by electroless plating to form nickel and gold layers in the pad portion of the semiconductor wafer. Mounting semiconductor wafers. In the electroless plating step, there is a zincate treatment which is treated with a strong alkaline aqueous solution having a pH of 12 or more, and a positive photosensitive resin composition which is excellent in resistance to a strong alkaline aqueous solution is required.

In the conventional positive-type photosensitive resin composition, it is difficult to achieve high sensitivity to the i-ray of the mercury lamp and further satisfy the performance of the strong alkaline aqueous solution. In particular, in the structure in which the periphery of the aluminum pad is covered with the cured resin pattern, peeling occurs between the aluminum pad and the cured resin pattern, and the reliability is lowered.

In the above-mentioned problem, a positive photosensitive resin composition containing an alkali-soluble resin, a photosensitive agent, and a hot alkali generating agent is proposed (see Patent Document 1), and a hydroxystyrene resin, a specific phenol resin, and a photoacid are produced. A positive photosensitive resin composition of a solvent and a solvent (refer to Patent Document 2), a positive type containing an alkali-soluble resin, a photoacid generator, and a solvent, and a glass transition temperature after curing of 200 ° C or more and an internal stress of 40 MPa or less A photosensitive resin composition (refer patent document 3).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2013-152381 (page 1-2)

Patent Document 2 Japanese Patent Laid-Open Publication No. 2014-211517 (page 1-3)

Patent Document 3 Japanese Patent Laid-Open Publication No. 2015-7674 (page 1-3)

However, in actual manufacturing, in order to improve the yield of the zincate treatment, an O ₂ ashing step is performed before the electroless plating step to remove the residue of the opening of the pad.

In the prior art, since the O ₂ ashing resistance of the resin is not sufficient, there is a problem that the zincate treatment by the electroless plating step after the use causes peeling between the aluminum pad and the cured resin pattern.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a positive photosensitive resin composition which is highly sensitive to i-rays of a mercury lamp and excellent in chemical resistance with respect to a strongly acidic aqueous solution or a strong alkaline aqueous solution. In particular, in the electroless plating step of ashing by O ₂ , a cured resin pattern excellent in adhesion reliability to an aluminum pad, a resin pattern using the resin composition, and a method of manufacturing a semiconductor using the same can be obtained. .

In order to solve the above problems, the positive photosensitive resin composition of the present invention has the following constitution.

[1] A positive photosensitive resin composition comprising (a) an alkali-soluble resin and (b) a quinonediazide compound, wherein the (a) alkali-soluble resin comprises (a1) a polyimide precursor, It has 5 to 50 mol% of a residue of a tetracarboxylic acid represented by the general formula (1) in a tetracarboxylic acid residue, and has a diamine represented by the general formula (2) in a total diamine residue. a residue having a residue of 10 to 80 mol% and having a residue of 10 to 90 mol% of a residue of the diamine represented by the general formula (3) in the total diamine residue, and/or ( A2) corresponds to the polyimine of (a1).

(In the formula (1), A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group which does not contain a hetero atom, and two or more kinds thereof may be used.)

(In the formula (2), B represents a group selected from O, S, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , and C(CF ₃ ) ₂ , and may also be used. These two or more.)

[2] The positive photosensitive resin composition according to [1], which comprises the polyazonia precursor of (a1) as the (a) alkali-soluble resin, and the ring closure ratio of the ruthenium ring is 5 to 25 %.

[3] The positive photosensitive resin composition according to [1] or [2], further comprising (c) a thermal crosslinking agent.

[4] An unhardened resin pattern formed of the positive photosensitive resin composition according to any one of [1] to [3].

[5] A cured resin pattern obtained by curing an unhardened resin pattern as described in [4].

[6] A semiconductor device in which a cured resin pattern as described in [5] is disposed on a semiconductor element.

[7] The semiconductor device according to [6], wherein the cured resin pattern has an opening, and at least one of the openings is disposed on an upper portion of the pad having aluminum or an aluminum alloy.

[8] The semiconductor device according to [7], wherein the under bump metal is disposed on the upper portion of the pad having aluminum or an aluminum alloy.

[9] The semiconductor device according to [8], wherein the under bump metal has a nickel element content of 60% by mass or more and 99.9% by mass or less.

[10] The semiconductor device according to [8] or [9], which is a protective layer having a gold element on a surface of the metal under the bump.

[11] The semiconductor device according to any one of [8] to [10] wherein the pad having aluminum or aluminum alloy and the external electrode are interposed between the under bump metal, by solder bumps, gold wires, And connected to any of the copper wires.

[12] The semiconductor device according to any one of [6] to [11] wherein the thickness of the cured resin pattern is from 3.0 μm to 15.0 μm.

[13] A method of manufacturing a semiconductor device according to any one of [6] to [12], comprising a step of one or more of the following: a step of treating the semiconductor element having the cured resin pattern with a strongly acidic liquid having a pH of 2 or less; a step of treating with a strong alkaline liquid having a pH of 12 or more; a step of treating with a flux liquid; a step of treating the plating solution; and a step of one or more steps of the step of treating the electroless plating solution.

[14] The method for producing a semiconductor device according to [13], wherein the liquid is an electrolytic plating solution or an electroless plating solution, further comprising a step of growing a first metal or alloy; and different from the first The second metal or alloy plating step is grown.

The positive photosensitive resin composition of the present invention is highly sensitive to i-rays, and is excellent in chemical resistance with respect to a strongly acidic aqueous solution or a strongly alkaline aqueous solution, particularly in an electroless plating step after O ₂ ashing. A resin pattern excellent in adhesion reliability to an aluminum pad and a semiconductor using the same can be obtained.

1‧‧‧ hardened resin pattern

2‧‧‧Semiconductor components

3A‧‧‧Under bump metal (main material)

3B‧‧‧Under bump metal (surface material)

4‧‧‧Electrode pads

5‧‧‧ solder bumps

6‧‧‧Metal wire

Fig. 1 is a schematic view showing a cross section of an example of a semiconductor device of the present invention.

Fig. 2 is a schematic view showing a cross section of another example of the semiconductor device of the present invention.

Form of implementing the invention

The positive photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, and (b) a quinonediazide compound, the (a) alkali-soluble tree The lipid comprises (a1) a polyimine precursor which has a residue of 5 to 50 mol% of the tetracarboxylic acid represented by the above formula (1) in the tetracarboxylic acid residue, and is present in the total diamine residue. The residue having the diamine represented by the above formula (2) has a residue of 10 to 80 mol%, and has a residue of 10 to 90 of the diamine represented by the above formula (3) in the entire diamine residue. The mol% of the polyimide precursor and/or (a2) corresponds to the polyimine of (a1). Here, the polyimine corresponding to (a1) is a closed ring of (a1) and is a polyimine. Conveniently, the following is a description of "polyimine precursor of structure (a1) and / or polyimine of structure of (a2)" as "polyamide (precursor) of (a1,2)" "Polyimide precursor and/or polyimine" is labeled as "polyimine (precursor)" and will constitute "(a1,2) polyimine (precursor)" The residue of the tetracarboxylic acid and the residue of the diamine are labeled as "monomer residues of the polyethylenimine (precursor) of (a1,2)".

In the present invention, the ratio of the monomer residue of the polyazinamide (precursor) of (a1, 2) contained in (a) the alkali-soluble resin is important, and the mechanism and ratio of the estimation are as follows. Good ratio.

The polycarboxylic acid (precursor) of (a1, 2) contains a residue of the tetracarboxylic acid represented by the above formula (1) which is rigid and does not contain other functional groups, and can be inhibited when O _{2 is} ashed. The surface of the resin film is oxidized, and deterioration of chemical resistance after ashing of O ₂ can be suppressed according to the foregoing.

The residue of the tetracarboxylic acid represented by the above formula (1) is preferably 5 mol% or more in the total tetracarboxylic acid residue from the viewpoint of exhibiting the surface oxidation inhibiting effect of the resin film when O _{2 is} ashed. It is more preferably 7 mol% or more, and more preferably 9 mol% or more. On the other hand, from the viewpoint of maintaining high sensitivity, 50 mol% or less of the total tetracarboxylic acid residue is preferable, 45 mol% or less is more preferable, and 40 mol% or less is further more preferable. Any other than the above-described tetracarboxylic acid residue may be used in any of the formula (1).

The polyamine imine (precursor) of (a1, 2) contains a residue of the diamine represented by the above formula (2) which is a relatively low molecule of the dinuclear body, but is larger than the molecular weight of the second In the case of an amine, the ratio of the quinone imine (precursor) unit of the entire polyimine (precursor) resin of (a1, 2) can be maintained high, which is similar to the residue of the above formula (1). O ₂ ashing suppresses surface oxidation of the resin film, and according to the above, chemical resistance deterioration after O ₂ ashing can be suppressed. Further, among the residues of the diamine represented by the above formula (2), there is also an effect of suppressing light absorption by the π-conjugated system of two benzene rings in the blocking molecule, and suppressing a decrease in sensitivity at the time of exposure. The same can affect the chemical resistance and high sensitivity after the O ₂ ashing.

The residue of the diamine represented by the above formula (2) is preferably contained in the total diamine residue in an amount of 10 mol% or more from the viewpoint of exhibiting the surface oxidation inhibiting effect of the resin film when O _{2 is} ashed. 12% or more is more preferable, and more than 15% by mole is particularly good. On the other hand, from the viewpoint of maintaining high sensitivity, 80 mol% or less of the total diamine residue is preferable, 70 mol% or less is more preferable, 60 mol% or less is further more preferable, and 50 mol% or less is particularly preferable. .

The polyamine (precursor) of (a1, 2) contains the residue of the diamine represented by the above formula (3), and the polyethylenimine (precursor) of the resin (a1, 2) is appropriately given. The alkali developability and the organic solvent are soluble, and the positive photosensitive resin composition can be highly sensitive and the storage stability can be improved. The residue of the diamine represented by the formula (3) contains 10 mol% or more, and 15 mol% in the total diamine residue from the viewpoint of exhibiting high sensitivity and improvement in storage stability. More preferably, it is further preferably 20 mol% or more, and more preferably 25 mol% or more. On the other hand, from the viewpoint of suppressing deterioration of chemical resistance after O ₂ ashing, 90 mol% or less of the total diamine residue is preferable, 85 mol% or less is more preferable, and 80 mol% or less is further more preferable. , 75 mol% or less is particularly good.

In the polyimine (precursor) of (a1, 2), the total amount of the residue of the diamine represented by the above formula (2) and the residue of the diamine represented by the above formula (3) is 20 to 100 mol% of the diamine residue. When it is 20 mol% or more, the high sensitivity and the deterioration of the chemical resistance after the ashing of O ₂ can be suppressed. From this viewpoint, it is preferably 30 mol% or more, more preferably 35 mol% or more, and further preferably. It is 40% or more.

In the structure of the above formula (1) contained in the polyimine (precursor) of (a1, 2), A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group which does not contain a hetero atom. Examples of the aromatic hydrocarbon group include a group derived from a benzene ring, a cyclotetradecene ring, a cyclooctadecene ring, a naphthalene ring, and an anthracene ring, but are not limited thereto. Among them, a group derived from a benzene ring, a naphthalene ring, and an anthracene ring can be used from the viewpoint of chemical stability.

The preferred embodiment of the above-mentioned general formula (1) is, for example, the following (A-1) group, but it is not limited thereto, and two or more of these may be used.

Among these, as a particularly preferable structure, the following (A-2) group structure can be mentioned, and these two types or more can also be used.

In the structure of the above formula (2) contained in the polyimine (precursor) of (a1, 2), B represents a group selected from O, S, SO ₂ , CH ₂ , CH(CH ₃ ), C (CH ₃ ) ₂ and C(CF ₃ ) ₂ may be used, and two or more of these may be used. Preferred examples of B include O, S, SO ₂ , CH ₂ and C(CF ₃ ) ₂ , and particularly preferred examples thereof include O, S, SO ₂ and CH ₂ .

The (a) alkali-soluble resin which is the alkali-soluble resin of the present invention may, for example, be a polyimine or a polybenzoate. An azole, a polyamidamine, or a precursor thereof, or a copolymer of the same, a carboxyl group-containing resin, or even a phenolic resin such as phenolic, polyhydroxystyrene, or soluble phenolic, but is not limited thereto. These are the same. Polyimine (precursor) of (a1, 2) is also included in these. The polyimine (precursor) of (a1, 2) may also be a copolymer of the resins. Further, two or more kinds of these resins may be contained.

When an alkali-soluble resin which is not equivalent to (a1, 2) polyimine (precursor) is used, it is premised on maintaining the chemical resistance after ashing of O ₂ , and the content thereof is (a) 60% of the total alkali-soluble resin. The mass % or less is more preferably 50% by mass or less, and more preferably 45% by mass or less. Among them, a phenol resin such as a carboxyl group-containing resin, a phenol resin, a polyhydroxystyrene, or a soluble phenolic resin has a lower chemical resistance after ashing with O ₂ than the others, and therefore a preferred use amount is (a) an alkali-soluble resin. It is 45 mass% or less, more preferably 40 mass% or less, and particularly preferably 35 mass% or less.

The polyamidene precursor which is particularly useful as the (a) alkali-soluble resin of the present invention may, for example, be a poly-proline, a polyphthalate, a polyamidamine or a polyisosine. Wait. For example, polylysine can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, or the like with a diamine, a corresponding diisocyanate compound, or trimethyldecaneated diamine. In order to obtain a suitable molecular weight, a part of the diamine may be substituted with a monoamine as a blocking agent, or a part of the tetracarboxylic dianhydride may be similarly used as an acid anhydride, a monoacid chlorine compound, or a monoactive ester as a blocking agent. Compound substitution. Further, the polyphthalate may be a method in which a tetracarboxylic acid diester is used in place of the tetracarboxylic acid by the above method; or, in the above manner, N, N- is used for the obtained polylysine. A conventional alkylating agent such as dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal is obtained by esterifying a part or all of a carboxylic acid. The polyimine can be obtained, for example, by subjecting the polyamic acid obtained by the above method to dehydration ring closure by heating or chemical treatment such as acid or alkali.

As an example of the tetracarboxylic acid corresponding to the preferred tetracarboxylic acid residue contained in the polyethylenimine (precursor) of the (a) alkali-soluble resin, in addition to the structure of the above (A-1) group, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis (2, 3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)anthracene, double An aromatic tetracarboxylic acid or a butane tetracarboxylic acid such as (3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-decanetetracarboxylic acid An aliphatic tetracarboxylic acid such as an acid or 1,2,3,4-cyclopentanetetracarboxylic acid. These tetracarboxylic acids may be used as they are, or as an acid anhydride, an active ester or the like. Further, these two or more kinds of tetracarboxylic acids may be used in combination.

Examples of the diamine corresponding to the preferred diamine residue contained in the polyethylenimine (precursor) of the (a) alkali-soluble resin, in addition to the structures of the above formula (2) and formula (3) In addition to the diamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis (3) can also be used. -Amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, 3,3'-diamino -4,4'-biphenol, 9,9-bis(3-amino-4-hydroxyphenyl)indole, etc., hydroxyl-containing diamine, 3-sulfonic acid-4,4'-diaminodiphenyl a thiol group-containing diamine such as a sulfonic acid group-containing diamine or a dimercaptophenylenediamine such as an ether, 1,4-bis(4-aminophenoxy)benzene, benzidine or m-phenylenediamine , p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)fluorene, bis(3-aminophenoxyphenyl)fluorene , bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 2,2'-dimethyl-4,4'-diamine linkage Benzene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl -4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diamine linkage , 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, etc. The aromatic diamine or a compound in which one of the hydrogen atoms of the aromatic ring is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom or the like, and 2,4-diamino-1. 3,5-three (decylamine), 2,4-diamino-6-methyl-1,3,5-three (acetamide), 2,4-diamino-6-phenyl-1,3,5-three a diamine having a nitrogen-containing heteroaromatic ring such as (benzoguanamine), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane, 1, 3-bis(p-aminophenyl)-1,1,3,3-tetramethyldioxane, 1,3-bis(p-aminophenethyl)-1,1,3,3 - anthrone such as tetramethyldioxane or 1,7-bis(p-aminophenyl)-1,1,3,3,5,5,7,7-octamethyltetraoxane An aliphatic diamine other than an alicyclic diamine such as a diamine, a cyclohexanediamine or a methylene dicyclohexylamine. For example, as a diamine containing a polyethylene oxide group, JEFFAMINE (registered) Trademarks) KH-511, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2003, JEFFAMINE EDR-148, JEFFAMINE EDR-176, D-200 of polyoxypropylenediamine, D-400, D-2000, D-4000 (the above is the trade name, which can be obtained by HUNTSMAN).

These diamines can be used as they are or as a corresponding diisocyanate compound or trimethyldecaneated diamine. Further, these two or more kinds of diamines may be used in combination.

In order not to impair the chemical resistance after the ashing of O ₂ , it is preferred to use the aromatic diamine as 50 mol% or more of the entire diamine.

Further, in order to enhance the storage stability of the positive photosensitive resin composition, (a) the polyisimide (precursor) resin of the alkali-soluble resin has a monoamine, an acid anhydride, a monocarboxylic acid, and a monoacid chloride at the end of the main chain. The blocking agent of the compound, the mono-active ester compound or the like is preferably blocked.

The introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, and particularly preferably 5 mol% or more, based on the total amine component. On the other hand, from the viewpoint of maintaining the molecular weight of the polyimine (precursor) high, it is preferably 60 mol% or less, and particularly preferably 50 mol% or less.

The introduction ratio of the acid anhydride, the monocarboxylic acid, the monoacid chloride compound or the mono-active ester compound used as the terminal blocking agent is preferably 0.1 mol% or more, more preferably 5 mol% or more, based on the diamine component. It is preferably 100 mol% or less, more preferably 90 mol% or less. It is also possible to introduce a plurality of different terminal groups by reacting a plurality of blocking agents.

For the purpose of improving the chemical resistance of the cured resin pattern obtained by firing, a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloro compound or a mono-active ester compound having at least one alkenyl group or alkynyl group may be used as the Wait for the blocking agent.

The blocking agent introduced into the resin can be easily detected by the following method. For example, the resin into which the terminal blocking agent is introduced is dissolved in an acidic solution, and is decomposed into an amine component and an acid component which are constituent units of the resin, and the gas chromatography (GC) or nuclear magnetic resonance (NMR) measurement is performed thereon. The blocking agent can be easily detected by means. Unlike the foregoing, the resin into which the blocking agent is introduced can be directly detected by thermal decomposition gas chromatography (PGC) or infrared spectroscopy and ¹³ C-NMR spectroscopy.

In the polyimine (precursor) used as the (a) alkali-soluble resin, the molar ratio of the unit of the ruthenium ring of the total quinone imine (precursor) unit is defined as the quinone ring. For the closed-loop rate (R _IM (%)), R _IM can be used in the full range of 0% or more and 100% or less. When polyurethane ester is used, R _{IM is} preferably 3% or more, more preferably 5% or more from the viewpoint of improving storage stability, and is preferably 70% or less, more preferably 50% from the viewpoint of improving sensitivity. Hereinafter, it is further preferably 25% or less.

The above-mentioned ruthenium ring closed-loop ratio (R _IM (%)) can be easily determined, for example, by the following method. First, the polymer of the infrared absorption spectrum was measured, it was confirmed absorption peak (vicinity of 1780 cm ^-1, near 1377cm ^-1) acyl imine of the polyimide due to the presence of, and determine the peak intensity in the vicinity of 1377cm ^-1 ( X). Next, the polymer was heat-treated at 350 ° C for 1 hour, and the infrared absorption spectrum was measured to determine the peak intensity (Y) around 1377 cm ^-1 . These peak intensity ratios correspond to the content of the quinone imine group in the polymer before heat treatment, that is, equivalent to the ring closure ratio of the quinone ring (R _IM = X / Y × 100 (%)).

As the polyphthalate used in the (a) alkali-soluble resin, all of the carboxyl groups may be esterified, or only a part of the carboxyl groups may be esterified. Here, the carboxyl group means a carboxyl group other than the carboxyl group residue of the indoleamine constituting the main chain of the polylysine which is neither esterified nor ruthenium imine ring corresponding to the polyphthalate. In order to make the alkali solubility of the resin and the solubility of the organic solvent moderate, when the molar ratio of the carboxyl group esterified to the all carboxyl group is defined as the esterification ratio (R _E (%)), R _{E is} preferably 20% or more. More preferably, it is 25% or more, preferably 100% or less, more preferably 95% or less.

The ester group of the polyphthalate used as the (a) alkali-soluble resin can be labeled as COO-R ₁ . Here, R ₁ represents a monovalent organic group having 1 to 10 carbon atoms. Examples of R ₁ include a methyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a third butoxycarbonyl group, a phenyl group, a benzyl group, a tetrahydrofuranyl group, and a tetrahydropyridyl group. Further, it is not limited to these, and it is also possible to use two or more of the above-mentioned groups, such as a decyl group, a trimethyl decyl group, and a triethyl decyl group.

The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. By containing the quinonediazide compound, an acid is generated in the ultraviolet ray-exposed portion, and the solubility in the alkali aqueous solution with respect to the exposed portion is increased. Therefore, after the ultraviolet ray exposure, a positive pattern can be obtained by alkali development.

The (b) quinonediazide compound used in the present invention may contain two or more kinds of quinonediazide compounds. According to the above, the ratio of the dissolution rate of the exposed portion to the unexposed portion can be made larger, and a high-sensitivity positive photosensitive resin composition can be obtained.

Examples of the (b) quinonediazide compound used in the present invention include a sulfonate bond of a polyhydroxy compound with quinonediazide, a sulfonic acid of a polyamine compound and quinonediazide. Sulfonamide-bonded, sulfonate-bonded and/or sulfonamide-bonded polyhydroxypolyamine compounds to quinonediazide. All of the functional groups of the polyhydroxy compound or the polyamino compound may not be substituted by quinonediazide, but 50 mol% or more of the entire functional group is preferably substituted by quinonediazide. By using the quinonediazide compound as described above, a positive photosensitive resin composition which is sensitive to i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) which are general ultraviolet light lamps can be obtained.

In the present invention, the quinonediazide compound may be any of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl. A compound having both of these groups in the same molecule may be used, and a compound using a different group may also be used in combination.

The (b) quinonediazide compound used in the present invention can be synthesized by a conventional method. For example, a method of reacting 5-naphthoquinonediazidesulfonium chloride with a polyhydroxy compound in the presence of triethylamine can be mentioned.

The content of the (b) quinonediazide compound used in the present invention is preferably from 1 to 60 parts by mass based on 100 parts by mass of the (a) alkali-soluble resin. When the content of the quinonediazide compound is within this range, high sensitivity can be achieved, and mechanical properties such as elongation of the cured resin pattern can be maintained. In order to further improve the sensitivity, it is preferably 3 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and may contain a sensitizer as needed, in order not to impair the mechanical properties of the cured resin pattern. Wait.

The positive photosensitive resin composition of the present invention preferably further contains (c) a thermal crosslinking agent. As the (c) thermal crosslinking agent, a compound having at least two alkoxymethyl groups and/or methylol groups and at least two compounds having an epoxy group and/or an oxetanyl group may be used, but Not limited to these. When these compounds are contained, the (a) alkali-soluble resin is subjected to a condensation reaction at the time of firing after pattern formation to form a crosslinked structure, and mechanical properties such as elongation of the cured resin pattern can be improved. Further, two or more kinds of the thermal crosslinking agents may be used, and further broad design can be carried out according to the above.

Preferred examples of the compound having at least two alkoxymethyl groups and/or hydroxymethyl groups include DML-PC and DML-PEP. DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML- BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML- pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM- TPPHBA, HMOM-TPHAP (above trade name, Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above is a trade name, manufactured by Sanwa Chemical Co., Ltd.) and is available from various companies. These two or more types may be contained.

Further, preferred examples of the compound having at least two epoxy groups and/or oxetane groups include bisphenol A type epoxy resin and bisphenol A type oxetane resin. , bisphenol F type epoxy resin, bisphenol F type oxetane resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidoxypropyl) decane The epoxy group-containing anthrone or the like is not limited thereto. Specifically, EPICLON (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (above trade name, Dainippon Ink Chemical Industry ( ())), RIKARESIN (registered trademark) BEO-60E (trade name, New Japan Physical and Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name, ADEKA (share) system), etc., and can be obtained by each company . These two or more types may be contained.

The content of the (c) thermal crosslinking agent used in the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 10 parts by mass based on 100 parts by mass of the (a) alkali-soluble resin. The above is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less from the viewpoint of maintaining mechanical properties such as elongation.

The positive photosensitive resin composition of the present invention may contain a solvent as needed. Preferable examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, and N,N-dimethylacetamide. a polar aprotic solvent such as dimethyl hydrazine, tetrahydrofuran, two Alkenes such as alkane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone or diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol Esters such as methyl ether acetate, 3-methyl-3-methoxyacetic acid butyl ester, ethyl lactate, methyl lactate, etc., diacetone alcohol, 3-methyl-3-methoxybutanol, etc. An aromatic hydrocarbon such as an alcohol, toluene or xylene. These two or more types may be contained.

The content of the solvent is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of dissolving the resin in 100 parts by mass of the (a) alkali-soluble resin, and from the viewpoint of obtaining an appropriate film thickness, it is preferably It is 1800 parts by mass or less, more preferably 1,500 parts by mass or less.

The positive photosensitive resin composition of the present invention may contain a thermal acid generator as needed. By containing a thermal acid generator, the crosslinking rate, benzo can also be obtained at a relatively low firing temperature of 150 to 300 ° C. A sulfazole ring closure ratio and a hardened resin pattern having a high ruthenium ring closure ratio.

For the purpose of exhibiting the above-mentioned effects, the content of the preferred thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and the elongation, etc., based on 100 parts by mass of the (a) alkali-soluble resin. The viewpoint of maintaining mechanical properties is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.

The positive photosensitive resin composition of the present invention may contain a low molecular compound having a phenolic hydroxyl group in a range that does not cause a shrinkage residual film ratio after curing, if necessary. By containing a low molecular compound having a phenolic hydroxyl group, adjustment of alkali solubility during pattern processing is facilitated.

In order to exhibit the above-described effects, the content of the low molecular compound having a phenolic hydroxyl group is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the (a) alkali-soluble resin. The viewpoint of maintaining mechanical properties such as elongation is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.

The positive photosensitive resin composition of the present invention may contain a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, or the like for the purpose of improving the wettability with the substrate as needed. Ketones such as alcohols, cyclohexanone and methyl isobutyl ketone, tetrahydrofuran, and An ether such as an alkane.

A preferred content of the compound used for the purpose of improving the wettability of the substrate is relative to (a) an alkali-soluble resin 100. The amount is 0.001 parts by mass or more, and from the viewpoint of obtaining an appropriate film thickness, it is preferably 1800 parts by mass or less, more preferably 1,500 parts by mass or less.

The positive photosensitive resin composition of the present invention may further contain inorganic particles. Preferable specific examples include cerium oxide, titanium oxide, barium titanate, alumina, talc, and the like, but are not limited thereto.

The primary particle diameter of the inorganic particles is preferably 100 nm or less, and particularly preferably 60 nm or less.

The primary particle diameter of the inorganic particles, as the number average particle diameter, is a calculation method obtained by determining the specific surface area. The specific surface area is defined as the sum of the surface areas contained in the powder of unit mass. The measurement method of the specific surface area is BET, and can be measured using a specific surface area measuring apparatus (Hrmodel-1201 manufactured by Mountech Co., Ltd.).

Further, in order to improve the adhesion to the ruthenium substrate, trimethoxy propyl decane, trimethoxy epoxide, trimethoxy oxirane, trimethoxy thiol may be contained in a range that does not impair the stability of storage. A decane coupling agent such as propyl decane.

The content of the decane coupling agent to be used for the adhesion to the ruthenium substrate is preferably 0.01 parts by mass or more based on 100 parts by mass of the (a) alkali-soluble resin, from the viewpoint of maintaining mechanical properties such as elongation. It is preferably 5 parts by mass or less.

The positive photosensitive resin composition of the present invention preferably has a viscosity of from 2 to 5,000 mPa ‧ s. The desired film thickness can be easily obtained by adjusting the solid content concentration by setting the viscosity to 2 mPa ‧ s or more. On the other hand, when the viscosity is 5,000 mPa ‧ or less, a coating film having high uniformity can be easily obtained. The resin composition having the viscosity as described above can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.

Next, a method of forming a resin pattern on a substrate using the positive photosensitive resin composition of the present invention will be described. In the present specification, the uncured pattern formed of the positive photosensitive resin composition of the present invention is referred to as an uncured resin pattern, and the pattern obtained by curing the above is referred to as a cured resin pattern. Moreover, when it is simply described as a resin pattern, it is a resin pattern which is collectively called an unhardened, and a hardened resin pattern. The substrate for forming the resin pattern is not particularly limited, but the positive photosensitive resin composition of the present invention is preferably used in a semiconductor device, and when used in this application, a semiconductor such as a germanium forming a circuit as a substrate It is preferable to form a resin pattern on the element.

First, the positive photosensitive resin composition of the present invention is applied onto a substrate. As the substrate, a wafer such as tantalum, ceramic, or gallium arsenide may be used, or a metal may be used as an electrode or a wiring. However, the present invention is not limited thereto. Examples of the metal used for the electrode and the wiring include aluminum (Al), Al-Si, Al-Si-Cu, Cu, etc., but are not limited thereto. The invention provides a hardened resin pattern and a semiconductor using the same, in particular, in the electroless plating step after O ₂ ashing, the adhesion reliability with the aluminum pad is also good, so the substrate formed by using the aluminum pad is better. . As a coating method of applying the positive photosensitive resin composition of the present invention to a substrate, a method using spin coating, spray coating, roll coating, or the like using a spinner can be applied. In addition, the film thickness at the time of application differs depending on the coating method, the solid content concentration of the positive photosensitive resin composition, the viscosity, and the like. However, the film thickness after drying is usually 0.1 to 150 μm, and coating is preferred.

In order to improve the adhesion between the substrate and the positive photosensitive resin composition, the substrate may be pretreated with the above-described decane coupling agent. example For example, a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate or the like is used in a concentration of 0.5 to 20% by mass. The solution of the dissolved decane coupling agent is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, heat treatment at 50 to 300 ° C is followed by a reaction between the substrate and the decane coupling agent.

Next, the substrate coated with the positive photosensitive resin composition is dried to obtain an uncured film of a positive photosensitive resin composition (hereinafter also referred to as a prebaked film). The drying system uses an oven, a hot plate, infrared rays, etc., and is preferably carried out in the range of 50 to 150 ° C for 1 minute to several hours.

Next, on the uncured film of the positive photosensitive resin composition, a mask having a desired pattern is passed through, and actinic rays are irradiated and exposed. Examples of the actinic ray used for exposure include ultraviolet light, visible light, electron beam, and X-ray. However, in the present invention, i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp can be used. . After the exposure, the exposed portion is removed using a developing solution to form an uncured resin pattern. As a developing solution, tetramethylammonium hydroxide, choline hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, a compound exhibiting basicity such as dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine or the like An aqueous solution is preferred. Further, depending on the case, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl may be separately added to the aqueous alkali solution. A polar solvent such as arsenic, γ-butyrolactone or dimethyl acrylamide, an alcohol such as methanol, ethanol or isopropanol, or lactate B An ester such as an ester or a propylene glycol monomethyl ether acetate; a ketone such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone; or a combination thereof. After development, it is preferred to carry out a rinse treatment with water. Here, an alcohol such as ethanol or isopropyl alcohol, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, or the like may be added to water to carry out a rinse treatment.

After development, applying a desired temperature for heat treatment, and performing a thermal crosslinking reaction, a ruthenium ring closure reaction, The azole is ring-closed to form a hardened resin pattern. The heat resistance and chemical resistance of the resin pattern can be improved by hardening. In the heat treatment, the temperature may be gradually increased in a stepwise manner, or the temperature may be continuously increased in a certain temperature range, and it is preferably carried out at 5 minutes to 5 hours. As an example, heat treatment was performed for 30 minutes at 150 ° C, 220 ° C, and 320 ° C. Alternatively, a method of heating the temperature linearly from room temperature to 400 ° C for 2 hours may be mentioned.

The thickness of the cured resin pattern formed using the positive photosensitive resin composition of the present invention is preferably 0.1 μm or more and 150 μm or less. However, in order to obtain sufficient chemical resistance, it is preferably 3.0 μm or more, and more preferably 4.0 μm. The above is particularly preferably 4.5 μm or more, and more preferably 15.0 μm or less, further preferably 8.0 μm or less, and particularly preferably 7.0 μm or less, in order to improve sensitivity and resolution.

The cured resin pattern formed by the positive photosensitive resin composition of the present invention can be suitably used for a passivation film of a semiconductor, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, and an insulation for an organic light-emitting element. The use of layers, etc.

When the resin pattern of the cured film has an opening, after the formation of the cured resin pattern, the ashing treatment may be performed using a gas such as O ₂ or Ar. By performing the above, the organic residue of the opening of the cured resin pattern can be removed, and for example, the connection reliability of the electrode pad can be improved. Examples of the ashing treatment include plasma treatment, reactive ion etching (RIE), and reverse sputtering, but are not limited thereto.

Hardening resin pattern according to the present invention, in particular the chemical resistance of O ₂ is excellent in the post-ash, and may be suitably selected for inclusion in a pH of 2 or less in a strong acidic liquid, a pH of 12 or more strongly alkaline liquid, flux The manufacture of a semiconductor in the step of liquid treatment of one or more liquids, electrolytic plating solutions, and electroless plating solutions.

Examples of the strongly acidic liquid having a pH of 2 or less include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, and the like. In the manufacturing step of the semiconductor, for example, as the pre-treatment of electroless plating on the aluminum pad, the zinc plating is divided into two times to perform the double zincate treatment on the surface of the aluminum pad, and the first zincate is removed. When the treated zinc layer is used, a strong acid such as dilute nitric acid can be used.

Examples of the strong alkaline liquid having a pH of 12 or more include sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution, aqueous cesium hydroxide solution, tetramethylammonium hydroxide aqueous solution, and choline hydroxide. An aqueous solution or the like, but is not limited to these. The zincate adjusting solution described later is also widely used as a strong alkaline liquid having a pH of 12 or higher.

Examples of the flux liquid include, for example, a rosin-based flux, an organic water-soluble flux, an inorganic water-soluble flux, and the like, but are not limited thereto.

In the electrolytic plating solution and the electroless plating solution of the present invention, as a pretreatment step thereof, the metal or alloy is temporarily plated. Long liquid. In addition, the alloy described in the present invention refers to a metal such as a solid solution, a eutectic or an intermetallic compound, which is composed of a plurality of metal elements, metal elements and non-metal elements. All of this.

As an example of the pretreatment step as described above, as an example of electroplating a metal or an alloy, for example, a zincate treatment performed before electroless nickel plating on an aluminum surface is exemplified.

Examples of the metal or alloy to be plated with the electrolytic plating solution include copper, nickel, gold, Sn-Ag, and the like, but are not limited thereto.

Examples of the electroless plating solution and the metal or alloy plated with the pretreatment liquid include zinc, nickel, tin, gold, palladium, and the like, but are not limited thereto.

When the metal or alloy is grown by electroplating using an electrolytic plating solution or an electroless plating solution, the first metal or alloy is plated and grown, and then treated with one or more liquids one or more times. It is preferable to electroplate the metal or alloy of the second type different from the first one, and it is possible to grow a metal or an alloy of three or more types by electroplating. By performing the above, considering the plating growth rate of the metal or alloy, the density of the plating film, the ionization tendency, and the like, it is possible to further perform high-reliability electroplating and reduce the amount of expensive gold or palladium used, and Suppress costs.

The cured resin pattern of the present invention, particularly in the electroless plating step after O ₂ ashing, has good adhesion reliability with the aluminum pad, and therefore, when the resin pattern of the cured film has an opening portion, the cured resin pattern It is preferable that at least one of the openings is disposed on the upper portion of the pad having aluminum or aluminum alloy. By performing electroless nickel/displacement gold plating in the above-described configuration, adhesion between the aluminum pad and the cured resin pattern is excellent, and it has excellent wettability with the wire bonding or solder ball, and resistance of the nickel layer. The under bump metal of the solder diffusion effect is formed on the upper portion of the pad having aluminum or aluminum alloy, and can be used as an electrode pad of high connection reliability.

Examples of the metal used as the under bump metal include nickel, a nickel alloy, copper, a copper alloy, chromium, titanium, titanium tungsten, gold, platinum, and palladium, but are not limited thereto. Among these, from the viewpoint of being relatively inexpensive, nickel or a nickel alloy is mainly used, and a preferable content of the nickel element in the under bump metal is 60% by mass or more and 99.9% by mass or less, and more preferably 70% by mass or more. 99.9% by mass or less, particularly preferably 80% by mass or more and 99.9% by mass or less.

Further, from the viewpoint of improving the connection reliability, a protective layer having gold or copper is preferable among the surfaces of the under bump metal, and a protective layer having a gold element is more preferable. From the viewpoint of connection reliability, the metal under the bump has an element other than the nickel element, and the content of the nickel element in the metal under the bump is preferably 99.9% by mass or less, more preferably 99.5% by mass or less. It is 99.0% by mass or less. Examples of the aluminum alloy include Al-Si, Al-Si-Cu, and the like, but are not limited thereto.

From the viewpoint of suppressing metal corrosion of the connection portion and obtaining high connection reliability, the pad having aluminum or aluminum alloy and the external electrode are interposed between the under bump metal and the solder bump, the gold wire, and the copper wire. Either the connection is preferred.

[Examples]

The present invention will now be described by way of examples, but the invention is not limited thereto.

Further, in the embodiment, a tantalum wafer is used as a module of a semiconductor element, and a positive photosensitive resin composition is directly applied to a tantalum wafer, or a metal layer is formed by sputtering, and a positive photosensitive property is applied. The resin film was formed into a resin composition and evaluated. In the evaluation of the resin film (including the uncured resin pattern and/or the cured resin pattern), it is not necessary to distinguish between the resin film directly formed on the ruthenium wafer or the resin film formed on the metal layer formed by sputtering. The system is called a germanium wafer formed by a wafer and a metal layer, and is marked as a substrate.

First, the evaluation methods of the respective examples and comparative examples will be described. In the evaluation of the positive photosensitive resin composition (hereinafter referred to as varnish), a varnish which was previously filtered with a filter made of polytetrafluoroethylene (manufactured by Sumitomo Electric Industries Co., Ltd.) of 1 μm was used.

(1) Film thickness measurement

The film thickness of the resin film on the substrate was measured using an optical interference type film thickness measuring device (Lambda Ace VM-1030, manufactured by Dainippon Screen Co., Ltd.). Further, the refractive index was measured by using polydiimine as 1.629.

(2) 醯imine ring closed-loop rate (R _IM (%))

The polyimide (precursor) resin was dissolved in γ-butyrolactone (hereinafter referred to as GBL) at 35 mass%, and a rotator (1H-DX manufactured by MIKASA Co., Ltd.) was used on a 4 矽 矽 wafer. The coating was applied by a spin coating method, and then baked at 120 ° C for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Co., Ltd.) to prepare a prebaked film having a thickness of 4 to 5 μm. The resin film-attached wafer was divided into two halves, and one of them was cured by a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systoms Co., Ltd.) under a nitrogen stream (oxygen concentration of 20 ppm or less) at 140 ° C for 30 minutes, followed by a second half. Further, the temperature was raised and hardened at 320 ° C for 1 hour. An infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.) was used, and the infrared absorption spectrum of the resin film before and after hardening was measured to confirm the absorption peak of the quinone imine structure of the polyimine (1780 cm). after X, hardening:: close to ^-1, near 1377 cm ^-1) of the premise of the presence, intensity of 1377 cm ^-1 peak is obtained near the (uncured Y). The peak intensity ratios of these were calculated, and the content of the quinone imine group in the polymer before the heat treatment, that is, the ruthenium ring ring closure ratio (R _IM = X / Y × 100 (%)) was determined.

(3) Evaluation of photographic characteristics

The varnish was made to have a film thickness of 10 μm after prebaking at 120 ° C for 3 minutes, and the varnish was spin-coated on a 8 矽 矽 wafer using a coating and developing device (ACT-8 manufactured by Tokyo Wealth Co., Ltd.). The method is applied and pre-baked. A screen wire having a pattern is mounted on an exposure machine i-ray stepper (NSR-2005i9C manufactured by Nikon Co., Ltd.), and a wafer having a pre-baked resin film is used, and an exposure amount of 100 to 1000 mJ/cm ² is used. The exposure was performed at 10 mJ/cm ² step. After the exposure, an ACT-8 developing device was used, and a 2.38 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution (ELM-D manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used, and the development was repeated twice by the mixing method. The liquid was discharged for 10 seconds, and the mixing time was 25 seconds. After rinsing with pure water, it was dried and dried to determine the minimum exposure amount at which the exposed portion was completely dissolved. As a result, it is not sufficient to set the minimum exposure amount to 500 mJ/cm ² or more (B), and it is good (A) to be 300 mJ/cm ² or more and less than 500 mJ/cm ² , and to be less than 300 mJ/cm ² . Very good (S).

(4) Evaluation of chemical resistance

Sputtering of Ti and Al was performed continuously on the four wafers in this order, and a sputtering substrate (hereinafter referred to as an Al sputtering substrate) having a thickness of 50 nm and an upper layer of Al of 200 nm was prepared. The Al sputtered substrate is used as a substrate with respect to the chemical resistance of the zincate solution and the electroless Ni/displacement Au treatment, and the 4 吋矽 wafer is used as a substrate with respect to the chemical resistance of the strong acid and the flux liquid. . The varnish was applied to the substrate by a spin coating method using a spinner (manufactured by MIKASA Co., Ltd.), and then baked on a hot plate at 120 ° C for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Co., Ltd.). A prebaking film having a thickness of about 6 to 13 μm was produced. The film thickness after prebaking is appropriately adjusted in accordance with the film thickness after hardening of the target. The substrate with the resin film and the mesh line of the cut pattern were superposed on the mask alignment exposure machine (PEM-6M manufactured by Union Optical Co., Ltd.), and the exposure amount was 500 mJ/cm ² in terms of i-ray, and broadband light was used. Exposure. After the exposure, development was carried out by a dipping method using a 2.38 mass% TMAH aqueous solution (manufactured by Tama Chemical Co., Ltd.), and then rinsed with pure water to obtain a positive resin pattern. The substrate with the resin pattern was cured by a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration: 20 ppm or less) at 140 ° C for 30 minutes, and then further heated at 320. After hardening at ° C for 1 hour, the resin pattern of the polyimide was hardened. Further, O ₂ ashing treatment of O _{2 13} Pa, 200 W, and 5 minutes was carried out using an RIE apparatus (RIE-10N manufactured by Samco Co., Ltd.). The film thickness caused by the O ₂ ashing treatment was reduced to about 0.4 μm. The following chemical resistance evaluation was performed using the processed resin pattern-coated substrate. An optical microscope of an optical interference type film thickness measuring device (Lambda Ace VM-1030 manufactured by Dainippon Screen Co., Ltd.) was used for the observation after the chemical resistance test.

(4-1) Zinc treatment

An Al sputtered substrate with a hardened resin pattern obtained by ashing the O ₂ prepared by the above method (in the description of the evaluation of this item, hereinafter referred to as a substrate), in a zincate solution (Melplate (registered trademark)) FZ-7350 (manufactured by Meltex Co., Ltd.) / Melplate (registered trademark) zincate F-plus (manufactured by Meltex Co., Ltd.) / pure water = 20/1/79 (volume ratio) was immersed at 22 ° C for 5 minutes. It was immersed in pure water for 30 seconds and washed, and dried by air blowing. The edge portion of the square pattern of the 100 μm square was removed from the treated substrate, and the penetration width to the residual pattern was measured. The measurement was carried out at five places, and the average value was 20 μm or more, which was not sufficient (B), and the case of 10 μm or more and less than 20 μm was determined to be good (A), and those having less than 10 μm were determined to be extremely good (S).

(4-2) Strong acid treatment

The ruthenium substrate with the hardened resin pattern (the description of the evaluation of this item, hereinafter referred to as a substrate) obtained by ashing the O ₂ prepared by the above method is immersed in 5 mass % sulfuric acid at 40 ° C for 5 minutes. The pure water was immersed for 30 seconds and washed, and dried by air blowing. The treated substrate was observed, and the presence or absence of cracks on the surface of the resin film was observed, and the occurrence of cracks was determined to be insufficient (B), and those not produced were determined to be good (A).

(4-3) flux treatment

A ruthenium substrate with a hardened resin pattern obtained by ashing the O ₂ prepared by the above method (in the description of the evaluation of this item, hereinafter referred to as a substrate), and a flux solution (WHD manufactured by Arakawa Chemical Industries Co., Ltd.) -001), heated at 250 °C for 1 minute on a hot plate (HHP-170D manufactured by AS ONE), using an ultrasonic cleaning machine (AU-26C manufactured by Aiwa Medical Industries Co., Ltd.) on the premise of immersion in pure water. Washing is carried out and drying is carried out by air blowing. The treated substrate was observed, and the presence or absence of cracks on the surface of the resin film was observed, and the occurrence of cracks was determined to be insufficient (B), and those not produced were determined to be good (A).

(4-4) Electroless Ni/displacement Au treatment

The Al sputtered substrate to which the hardened resin pattern is formed by the O ₂ ashing treatment prepared by the above method (hereinafter, the description of the evaluation of this item is hereinafter referred to as a substrate), and the liquid in Table 1 is in accordance with steps 1 to 8. The immersion treatment is carried out in succession. However, after immersion of each liquid, washing with immersion in pure water and drying by blasting are performed each time. In the table, Mel cleaner and Melplate are registered trademarks and are manufactured by Meltex.

The substrate after the treatment of each of the chemical solutions was observed, and the penetration of the residual pattern at the edge portion of the square pattern in which the square shape of 100 μm was removed and the presence or absence of cracks on the surface of the resin film were observed.

[Synthesis Example 1] Synthesis of diamine compound (HA)

164.8 g (0.45 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 900 mL of acetone and 156.8 g (2.7 mol) of propylene oxide. Cool to -15 °C. Here, a solution of 183.7 g (0.99 mol) of 3-nitrobenzidine chloride dissolved in 900 mL of acetone was added dropwise. After completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered and dried under vacuum at 50 °C.

270 g of solid was placed in a 3 L stainless steel autoclave and dispersed in 2400 mL of methyl sarsus, and 5 g of 5% palladium-carbon was added. Hydrogen was introduced here as a balloon and the reduction reaction was carried out at room temperature. After 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated by a rotary evaporator to obtain a diamine compound (hereinafter referred to as HA) represented by the following formula.

[Synthesis Example 2] Synthesis of alkali-soluble polyimine precursor resin (A-1)

Under dry nitrogen flow, pyromellitic dianhydride (hereinafter referred to as PMDA) 1.09 g (0.005 mol) and bis(3,4-dicarboxyphenyl)ether dianhydride (hereinafter referred to as ODPA) 13.96 g (0.045) Mohr) was dissolved in 120 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Here, HA 18.14 g (0.03 mol), 4,4'-diaminodiphenyl ether (hereinafter referred to as DAE) 2.80 g (0.014 mol) and 1,3-bis(3-aminopropyl) four Methyldioxane (hereinafter referred to as SiDA) 0.50g (0.002 mole) was added simultaneously with NMP40g at 20 ° C The reaction was carried out for 1 hour, and then, the reaction was carried out at 50 ° C for 2 hours. Next, 0.87 g (0.008 mol) of 3-aminophenol (hereinafter referred to as MAP) as a blocking agent was added together with NMP 10 g, and the reaction was carried out at 50 ° C for 2 hours. Thereafter, a solution of 10.72 g (0.09 mol) of N,N-dimethylformamide dimethyl acetal (hereinafter referred to as DMFDMA) diluted with NMP 20 g was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and the solution was poured into 1 L of water to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C for 20 hours to obtain a powder of an alkali-soluble polyimine precursor resin (A-1).

[Synthesis Example 3] Synthesis of alkali-soluble polyimine precursor resin (A-2)

The amount of the acid dianhydride added was changed to 2.34 g (0.01 mol) of PMDA and 12.41 g (0.04 mol) of ODPA, and the polymerization reaction was carried out in the same manner as in Synthesis Example 2 to obtain an alkali-soluble polyimine precursor. Powder of the resin (A-2).

[Synthesis Example 4] Synthesis of alkali-soluble polyimine precursor resin (A-3)

The amount of acid dianhydride added was changed to PMDA 4.36 g (0.02 mol) and ODPA 9.31 g (0.03 mol), and the amount of DMFDMA added was changed to 9.53 g (0.08 mol), and the synthesis example 2 was used. The polymerization was carried out in the same manner to obtain a powder of an alkali-soluble polyimine precursor resin (A-3).

[Synthesis Example 5] Synthesis of alkali-soluble polyimine precursor resin (A-4)

The amount of acid dianhydride added was changed to 2.103 g (0.01 mol) of PMDA and 12.41 g (0.04 mol) of ODPA, and the amount of diamine added other than SiDA was changed to HA 22.67 g (0.0375 mol) and DAE 1.30 g ( 0.0065 In the same manner as in Synthesis Example 2, a polymerization reaction was carried out to obtain a powder of an alkali-soluble polyimine precursor resin (A-4).

[Synthesis Example 6] Synthesis of alkali-soluble polyimine precursor resin (A-5)

The addition amount of the diamine other than SiDA was changed to HA 6.05 g (0.01 mol) and DAE 6.01 g (0.03 mol), and the amount of DMFDMA added was changed to 9.53 g (0.08 mol), and other methods were employed and synthesized. In the same manner as in Example 2, a polymerization reaction was carried out to obtain a powder of an alkali-soluble polyimine precursor resin (A-5).

[Synthesis Example 7] Synthesis of alkali-soluble polyimine precursor resin (A-6)

The acid dianhydride was changed to 1.34 g (0.005 mol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 13.96 g (0.045 mol) of ODPA, and the amount of diamine added other than SiDA was changed to HA17. In the same manner as in Synthesis Example 2, 53 g (0.029 mol) and DAE 2.40 g (0.012 mol) were added, and the amount of DMFDMA was changed to 9.53 g (0.08 mol), and alkali polymerization was carried out in the same manner as in Synthesis Example 2. A powder of polyimine precursor resin (A-6).

[Synthesis Example 8] Synthesis of alkali-soluble polyimine precursor resin (A-7)

The alkali-soluble polyimine precursor resin (A-7) was obtained by the same method as in Synthesis Example 3 except that the DAE was changed to 4,4'-diphenylamine (3.03 g (0.014 mol)). ) powder.

[Synthesis Example 9] Synthesis of alkali-soluble polyimine precursor resin (A-8)

The polymerization reaction was carried out in the same manner as in Synthesis Example 3 except that the reaction after the addition of DMFDMA was changed to 80 ° C for 3 hours to obtain a powder of an alkali-soluble polyimine precursor resin (A-8).

[Synthesis Example 10] Synthesis of alkali-soluble polyimine resin (A-9)

Under dry nitrogen flow, HA 4.53g (0.0075 mol), DAE 1.50g (0.0075 mol), BAHF 10.26g (0.028 mol), SiDA 0.50g (0.002 mol), MAP 1.09g as the blocking agent (0.01 mol) dissolved in NMP 140 g. Here, PMDA 1.09 g (0.005 mol) and ODPA 13.96 g (0.045 mol) were simultaneously added with NMP 20 g, and the reaction was carried out at 20 ° C for 1 hour, and then, the reaction was carried out at 50 ° C for 4 hours. Thereafter, 10 g of xylene was added, and while water and xylene were simultaneously azeotroped, the mixture was stirred at 150 ° C for 5 hours. After the completion of the stirring, the mixture was allowed to cool, and the solution was poured into 1 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C for 20 hours to obtain a powder of an alkali-soluble polyimine resin (A-9).

[Synthesis Example 11] Synthesis of alkali-soluble polyimine precursor resin (A'-10)

The amount of acid dianhydride added was changed to PMDA 6.54 g (0.03 mol) and ODPA 6.20 g (0.02 mol), and the amount of diamine added other than SiDA was changed to HA 17.53 g (0.029 mol) and DAE 2.40 g ( In the same manner as in Synthesis Example 2, the amount of the blocking agent was changed to MAP 1.53 g (0.014 mol), and the amount of DMFDMA added was changed to 9.53 g (0.08 mol). The polymerization was carried out to obtain a powder of an alkali-soluble polyimine precursor resin (A'-10).

[Synthesis Example 12] Synthesis of alkali-soluble polyimine precursor resin (A'-11)

A polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the acid dianhydride was changed to 15.51 g (0.05 mol) of ODPA to obtain a powder of an alkali-soluble polyimine precursor resin (A'-11).

[Synthesis Example 13] Synthesis of alkali-soluble polyimine precursor resin (A'-12)

The polymerization reaction was carried out in the same manner as in Synthesis Example 3 except that the diamine other than SiDA was changed to HA 26.60 g (0.044 mol), and an alkali-soluble polyimine precursor resin (A'-12) was obtained. powder.

[Synthesis Example 14] Synthesis of alkali-soluble polyimine precursor resin (A'-13)

The polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the acid dianhydride was changed to 15.51 g (0.05 mol) of ODPA, and the diamine other than SiDA was changed to HA 26.60 g (0.044 mol). A powder of an alkali-soluble polyimine precursor resin (A'-13).

[Synthesis Example 15] Synthesis of phenol resin (A'-14)

Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of a 37% by mass aqueous formaldehyde solution (formaldehyde 0.93 mol), and 0.63 g of oxalic acid dihydrate were added. After 264 g of methyl isobutyl ketone (0.005 mol) and immersed in an oil bath, the polycondensation reaction was carried out for 4 hours while refluxing the reaction liquid. Thereafter, the temperature of the oil bath was raised for 3 hours to increase the temperature, and then the pressure in the flask was reduced to 40 to 67 hPa, the volatile matter was removed, and the dissolved resin was cooled to room temperature to obtain an alkali-soluble phenol resin (A'- 14) polymer solids.

[Synthesis Example 16] Synthesis of polyhydroxystyrene resin (A'-15)

2400 g of tetrahydrofuran, a mixed solution of 2.6 g (0.04 mol) of a second butyllithium as a starter, and 63.5 g (0.36 mol) of p-t-butoxystyrene and styrene were added. 25.0 g (0.24 mol), while stirring for 3 hours, after polymerization, 12.8 g (0.4 mol) of methanol was added and polymerization was terminated to terminate the reaction. Next, in order to purify the polymer, the reaction mixture is poured into 3 L of methanol to dry the precipitated polymer and dissolve. After adding 1.6 g of concentrated hydrochloric acid to acetone at 1.6 ° C and stirring for 7 hours, water was poured to precipitate the polymer, and p-t-butoxy styrene was deprotected to be converted into hydroxystyrene, and washed with water three times. It was dried in a vacuum dryer at 50 ° C for 24 hours to obtain an alkali-soluble polyhydroxystyrene resin (A'-15).

[Synthesis Example 17] Synthesis of phenol resin (A'-16)

61.1 g (0.5 mol) of 2,3-xylenol, 58.0 g (0.475 mol) of salicylaldehyde, and 1.7 g (0.01 mol) of p-toluenesulfonic acid were reacted in an oil bath under a stream of dry nitrogen. The liquid was refluxed while carrying out a polycondensation reaction at 100 ° C for 4 hours. Thereafter, the mixture was cooled to room temperature, and 50 g of acetone and 1.0 g (0.01 mol) of triethylamine were added and stirred for 30 minutes, and then 150 g of pure water was further added and stirred for 30 minutes. After removing the separated aqueous layer, 10 g of GBL was added, and the temperature was raised to 200 ° C. Thereafter, the pressure in the flask was reduced to 40 hPa or less, and the volatile matter was removed, and then cooled to room temperature to obtain an alkali-soluble phenol resin (A'-16). .

[Synthesis Example 18] Synthesis of quinonediazide compound (B-1)

Under dry nitrogen flow, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 42.45g (0.1m) and 5-naphthoquinonediazidesulfonium chloride (NAC-5, Toyo Synthetic Co., Ltd.) ) 75.23g (0.28 moles) dissolved in 1,4-two Alkane 1000g. The reaction vessel is chilled while the inside of the system does not become above 35 ° C and the addition of 1,4-two 150 g of a liquid mixed with triethylamine 30.36 g (0.3 mol). After the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into 7 L of pure water to obtain a precipitate. The precipitate was collected by filtration and washed with 2 L of 1% by mass hydrochloric acid. Thereafter, it was further washed twice with 5 L of pure water. The precipitate was dried in a vacuum dryer at 50 ° C for 24 hours, and an average of 2.8 of Q was a quinonediazide compound (B-1) represented by the following formula of 5-naphthoquinonediazidesulfonate.

The thermal crosslinking agent (C-1) HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) used in the examples is shown below.

The hot base generator (D-1) (R)-t-butyl-2-(hydroxymethyl)pyrrolidine-1-carboxylate (manufactured by Wako Pure Chemical Industries, Ltd.) used in the comparative example is shown below. .

In the alkali-soluble polyimine (precursor) resin obtained in Synthesis Examples 2 to 14, the tetracarboxylic acid residue represented by the above formula (1), which is the total tetracarboxylic acid residue calculated from the added amount, The ratio of the diamine residue represented by the above formula (2) and the diamine residue represented by the above formula (3) in the total diamine residue to the total diamine residue (% by mole) The ring closure ratio (R _IM (%)) of the imide ring obtained by the above method, the polyimine precursor of the structure of the above (a1) or the polyimine of the structure of (a2) or the like A related classification is shown in Table 2. Further, the alkali-soluble resins (A'-14 to 16) described in Synthesis Examples 15 to 17 of the non-polyimine (precursor) are classified as others.

[Production of varnish]

In a polypropylene bottle having a capacity of 32 mL, each component was added in the composition of Table 3, and a stirring defoaming device (ARE-310 manufactured by THINKY Co., Ltd.) was used, and the mixture was stirred for 10 minutes, and mixed under the conditions of defoaming for 1 minute. The method is filtered to remove minute foreign matter, and a varnish (W-1 to 21) is produced. In addition, in Table 3, "GBL" represents γ-butyrolactone.

[Examples 1 to 12, Comparative Examples 1 to 9]

Table 4 shows the results of evaluation of chemical resistance with respect to photosensitivity and zincate treatment using the produced varnish. In Comparative Example 1, the photosensitive characteristics were insufficient. In Comparative Examples 2 to 9, the penetration into the residual pattern during the zincate treatment was broad, and the chemical resistance was insufficient.

[Examples 13 to 21, Comparative Examples 10 to 11]

Table 5 shows the results of chemical resistance evaluation using the varnishes W-1 to 7, 11, 12, 16, and 21 with respect to the strong acid treatment and the flux treatment by the above method. In Comparative Example 11, any treatment caused cracks on the surface of the resin.

[Examples 22 and 23]

Using varnishes W-4 (Example 22) and W-11 (Example 23), the chemical resistance evaluation with respect to the electroless Ni/displacement Au treatment was performed by the above method. All of them were passed through the entire step without permeating the residual pattern of the edge portion of the square pattern of 100 μm square, and cracks on the surface of the resin film were not generated, and the chemical resistance was good.

Claims (14)

A positive photosensitive resin composition comprising (a) an alkali-soluble resin and (b) a quinonediazide compound, wherein the (a) alkali-soluble resin comprises (a1) a polyimine precursor, which is The residue of the tetracarboxylic acid represented by the general formula (1) in the total tetracarboxylic acid residue is 5 to 50 mol%, and the residue of the diamine represented by the general formula (2) in the total diamine residue 10 to 80 mol%, and having a polyamine imine precursor having a residue of 10 to 90 mol% of the diamine represented by the general formula (3) in the total diamine residue, and/or (a2) corresponding Polyimine of the (a1); (In the formula (1), A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group which does not contain a hetero atom, and two or more kinds thereof may be used; (In the formula (2), B represents a group selected from O, S, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , and C(CF ₃ ) ₂ , and may also be used. 2 or more); The positive photosensitive resin composition of claim 1, which comprises the polyazonia precursor of (a1) as the (a) alkali-soluble resin, and the ring closure ratio of the quinone ring is 5 to 25%. The positive photosensitive resin composition of claim 1 or 2 further comprising (c) a thermal crosslinking agent. An uncured resin pattern formed of the positive photosensitive resin composition according to any one of claims 1 to 3. A hardened resin pattern obtained by hardening an uncured resin pattern of claim 4. A semiconductor device in which a hardened resin pattern as claimed in claim 5 is disposed on a semiconductor element. The semiconductor device of claim 6, wherein the hardened resin pattern has an opening, and at least one of the openings is disposed on an upper portion of the pad having aluminum or an aluminum alloy. The semiconductor device of claim 7, wherein the Under Bump Metal is disposed on the upper portion of the pad having aluminum or an aluminum alloy. The semiconductor device according to claim 8, wherein the under bump metal has a nickel element content of 60% by mass or more and 99.9% by mass or less. A semiconductor device according to claim 8 or 9, which is a protective layer having a gold element on a surface of the metal under the bump. The semiconductor device according to any one of claims 8 to 10, wherein the pad having aluminum or aluminum alloy and the external electrode are interposed between the under bump metal, by solder bump, gold wire, and copper wire Connected in one. The semiconductor device according to any one of claims 6 to 11, wherein the hardened resin pattern has a thickness of 3.0 μm or more and 15.0 μm or less. A method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device according to any one of claims 6 to 12, which comprises one selected from the group consisting of The above steps: a step of treating the semiconductor element having the cured resin pattern with a strongly acidic liquid having a pH of 2 or less; a step of treating with a strong alkaline liquid having a pH of 12 or more; and treating with a flux liquid a step of treating with an electrolytic plating solution; and a step of treating with an electroless plating solution. The method of manufacturing a semiconductor device according to claim 13, wherein the liquid is an electrolytic plating solution or an electroless plating solution, further comprising a step of growing the first metal or alloy; and a second species different from the first The step of growing the metal or alloy plating.