JPH11282160A - Photosensitive polyimide composition and pattern forming method and semiconductor device using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive polyimide compsn. which can be treated at a low temp. and which has excellent storage stability and film forming property for desired thickness of the compsn. and good adhesion strength of a polyimide film to a silicon substrate and good heat resistance by incorporating a specified polyimide precursor. SOLUTION: A photosensitive resin compsn. containing a polyimide having a recurrent unit expressed by the formula is used. In the formula, X is a quadrivalent org. group containing silicon and all silicon atoms are included in a structure with four bonding positions of each atom bonded to carbon atoms or other silicon atoms, Y is a, tervalent or quadrivalent org. group, R<1> is a univalent org. group containing a photopolymerizable group, and m is an integer 1 or 2. Namely, the polyimlde compsn. contains the polyimide which has the recurrent unit expressed by the formula and is soluble with an org. solvent. Thereby, the obtd. photosensitive resin compsn. can be treated at a low temp. and has excellent storage stability, excellent film forming property for desired thickness with little reduction of the film thickness, and good adhesion strength of the polyimide film to a silicon substrate and heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide which is used as a material for forming a surface protective film and an interlayer insulating film of a semiconductor device and an interlayer insulating film of a multilayer wiring board and which can be formed on a silicon wafer at a low temperature. The present invention relates to a composition, a pattern manufacturing method using the same, and a semiconductor device.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been. However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is complicated and diversified, such as forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, and cleaning the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. Particularly, photosensitive polyimide has excellent heat resistance and elimination of impurities. Has attracted particular attention because of its ease of use. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed, but this material has practical light sensitivity and a film thickness. Although it has the advantages of high formability and the like, it lacks storage stability and has drawbacks such as chromium ions remaining in polyimide, making it impractical.

[0004] In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Unexamined Patent Publication No. 60-100143)
And so on. However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties.Because of the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low and the exposure is low. However, the photochemical reaction in the portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low and the shape of the pattern is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

For this reason, a conventional contact / proximity exposure apparatus using parallel rays has been replaced by a 1: 1 projection exposure apparatus called a mirror projection and a reduction projection exposure apparatus called a stepper. The stepper utilizes a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of ultra-high pressure mercury lamps have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, the stepper used has been used. Needs to be shortened. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 365 n).
m).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines, and g-line steppers have low transparency due to the above-mentioned reasons, especially i-line. (Wavelength: 365 nm) because there is almost no transmittance.
With a line stepper, a decent pattern cannot be obtained. In addition, a polyimide film for surface protection is required to be a thicker film corresponding to LOC (lead-on-chip), which is a high-density mounting method of a semiconductor element. The problem gets worse. Therefore, there is a strong demand for a photosensitive polyimide having a high i-line transmittance and a polyimide pattern having a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
It has been increasing year by year, and there has been a problem that the warpage of the silicon wafer on which the polyimide as the surface protective film is formed becomes larger than before due to the difference in thermal expansion coefficient between the polyimide and the silicon wafer. Therefore, there is a strong demand for a photosensitive polyimide having a lower thermal expansion property than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, almost no i-line is transmitted, so that the photosensitive characteristics deteriorate. As a method for improving the i-line transmittance, a polyimide into which fluorine has been introduced (Japanese Patent Laid-Open No. 8-234433) and a polyimide having a bent molecular chain (Japanese Patent Laid-Open No. 8-36264) have been proposed. However, the fluorine-introduced polyimide described in the above publication has a weak adhesive force to a silicon wafer, and has low reliability when used for a semiconductor device. In addition, since polyimide having a bent molecular chain has weak intermolecular interaction, heat resistance is reduced and a thermal expansion coefficient is increased, resulting in low reliability in a semiconductor device.

[0008]

The inventions according to claims 1 to 3 can be processed at a low temperature by using a specific polyimide soluble in an organic solvent, and have excellent storage stability of the composition.
An object of the present invention is to provide a photosensitive polyimide composition which is excellent in forming a thick film due to small film loss, and has good adhesion and heat resistance of a formed polyimide film to a silicon substrate. The invention described in claim 4 has the object of the invention described in claim 1,
Further, the present invention provides a photosensitive polyimide composition having good photosensitive characteristics. The invention according to claims 5 to 7 is the invention according to claim 1.
In addition to the objects of the invention described above, an object of the present invention is to provide a photosensitive composition which has improved solubility in an organic solvent, has high i-line transmittance, and has good photosensitive characteristics and heat resistance.

The invention described in claim 8 provides a pattern manufacturing method which is excellent in forming a thick film due to small film reduction, and has good adhesion and heat resistance of a formed polyimide film to a silicon substrate. is there. According to a ninth aspect of the present invention, there is provided a semiconductor device having a good adhesive strength of a polyimide film to a silicon substrate and excellent reliability.

[0010]

According to the present invention, there is provided a compound represented by the general formula (1):

Embedded image (Wherein, X is a tetravalent organic group containing a silicon atom, and all of the silicon atoms are included in a structure in which four bonding sites are bonded to a carbon atom or another silicon atom, and Y is 3 to 4 A monovalent organic group, R ¹ is a monovalent organic group containing a photopolymerizable group,
m is an integer of 1 to 2). Further, in the present invention, X is represented by the general formula (2)

Embedded image (Wherein, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, L is an oxygen atom, a sulfur atom, a carbonyl group, a methylene group, a 2,2-propylene group, a sulfinyl group, A sulfoxy group or a single bond, n and u are 1 to
(An integer of 3).

In the present invention, X is represented by the general formula (3):

Embedded image (Wherein, R ² and R ³ are each independently an alkyl or phenyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3). About. The present invention also relates to a photosensitive polyimide composition wherein the photopolymerizable monovalent organic group represented by R ¹ is a group containing a carbon-carbon double bond.

In the present invention, the polyimide may be a compound represented by the general formula (4):

Embedded image (Wherein X ′ is a tetravalent organic group, Y ′ is a divalent organic group, and at least one of X ′ and Y ′ contains a fluorine atom). The present invention relates to a functional polyimide composition. In the present invention, X ′ in the general formula (4) is

Embedded image (Wherein, R ² and R ³ are an alkyl group or a phenyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3), and Y ′ contains a fluorine atom. The present invention relates to a polyimide composition.

[0013] The present invention also relates to the above-mentioned general formula (4).
But,

Embedded image And a photosensitive polyimide composition selected from the group consisting of: Further, the present invention provides a method for producing a pattern, characterized in that a coating film of the photosensitive polyimide composition according to any of the above is irradiated with an actinic ray from a mask on which the pattern is drawn, and an unirradiated portion is developed and removed. About the law. Furthermore, the present invention
A semiconductor device having a polyimide film obtained by using the photosensitive polyimide composition according to any one of the above.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive polyimide composition of the present invention comprises a polyimide having a repeating unit represented by the above general formula (1) and soluble in an organic solvent. The tetravalent organic group represented by X in the general formula (1) is a tetravalent organic group containing a silicon atom, and all of the silicon atoms have four bonding sites bonded to a carbon atom or another silicon atom. I do. As a result, a photosensitive polyimide composition that can be processed at a low temperature, has excellent storage stability, has a small film loss, is excellent in forming a thick film, and has good adhesion and heat resistance of a formed polyimide film to a silicon substrate is obtained. Can be

As the tetravalent organic group represented by X,
It is preferable that the silicon atom be an aromatic group having a structure represented by the general formula (2) because of excellent heat resistance and the like. Examples of such an aromatic group include the following.

Embedded image

Embedded image

Embedded image

In the above, X represents the general formula (3)
The photosensitive polyimide composition which is a tetravalent organic group represented by is preferred because it is relatively easy to produce and is excellent in the above-mentioned effects. Y in the general formula (1) is a trivalent to tetravalent organic group, and generally an amine having two or more amino groups capable of forming a polyimide by reacting with a tetracarboxylic acid or a derivative thereof (an acid anhydride, a diester, or the like). The residue of a compound,
Examples thereof include an aromatic group containing an aromatic ring, a chain aliphatic group, and a cycloaliphatic group containing an aliphatic ring. An aromatic group is preferred in terms of heat resistance and the like. When the aromatic group is a group containing two or more aromatic rings, the number of the aromatic rings is preferably 2 to 4. Specifically, these aromatic rings are a single bond, an ether bond, a carbonyl group, a methylene group. , A 2,2-propylene group, a sulfonyl group, a sulfinyl group, a thioether group and the like. Y is preferably from 4 to 24 from the viewpoint of the number of carbon atoms. Here, as the aromatic group, the two bonding sites forming an amide bond with tetracarboxylic acid are preferably present on an aromatic ring, and even if they are present on the same aromatic ring, It may be present on different aromatic rings present through various bonds.
Also, the site to which R ¹ is bonded is preferably on the aromatic ring.

From the viewpoint of low thermal expansion and the like, it is particularly preferable to select Y- (R ¹ ) m from the following.

Embedded image

In the general formula (1), R ¹ is a monovalent organic group containing a photopolymerizable group. R ¹ is a group directly bonded to an aromatic ring when Y is an aromatic group, and a group directly bonded to an alicyclic ring when Y is an aliphatic group containing an alicyclic ring; When it is an aliphatic group in the form of a chain, it is defined as a group directly bonded to a carbon atom constituting the main chain. Examples of the photopolymerizable group include a photopolymerizable carbon-carbon double bond, for example,

Embedded image And a group containing a terminal structure represented by As the monovalent organic group containing a photopolymerizable group, specifically, a group having the following structure is preferable.

Embedded image (Wherein A is a hydrocarbon group having 2 to 10 carbon atoms containing a double bond, A ′ is a hydrocarbon group having 1 to 10 carbon atoms, A ″
Is an acryloxy group or a methacryloxy group)

Preferred examples are shown below.

Embedded image

Embedded image

Embedded image (Wherein, p represents an integer of 1 to 10).

The polyimide used in the present invention, which has a repeating unit represented by the general formula (4) together with a repeating unit represented by the general formula (1), has excellent i-line transmittance and low It is preferable because of its excellent stress, heat resistance and adhesiveness. In the general formula (4), at least one of X ′ and Y ′ contains a fluorine atom. The tetravalent organic group represented by X ′ containing no fluorine atom is generally a residue of a tetracarboxylic acid or a derivative thereof which forms a polyimide precursor by reacting with a diamine, and specifically, an aromatic ring (benzene ring , A naphthalene ring, etc.), a chain aliphatic group, a cycloaliphatic group containing an aliphatic ring, and the like. An aromatic group is preferred in terms of heat resistance and the like. When the aromatic group is a group containing two or more aromatic rings, the number of the aromatic rings is preferably 2 to 4. Specifically, these aromatic rings are a single bond, an ether group, a carbonyl group, a methylene group. , A 2,2-propylene group, a sulfonyl group, a sulfinyl group, a thioether group and the like. X preferably has 4 to 24 carbon atoms.

In the aromatic group, all four binding sites are preferably present on the aromatic ring, and these binding sites are divided into two sets of two each. It is preferably located at the ortho or peri position of the aromatic ring. The above two sets may be present on the same aromatic ring, or may be present on separate aromatic rings linked via various bonds.

Among them, in terms of low thermal expansion and / or i-line transmittance, etc.

Embedded image Are particularly preferred.

X ′ containing a fluorine atom is preferably an aromatic group containing an aromatic ring. In the aromatic group containing an aromatic ring exemplified in the above description, instead of one or more hydrogen atoms on the aromatic ring, , A fluorine atom, a trifluoromethyl group, a fluoroalkyl group such as a perfluoroethyl group, a fluorine-containing group such as a fluoroalkyloxy group bonded directly or indirectly through various groups, or two or more Examples of the group connecting an aromatic ring include a group having a fluorine-containing group such as a hexafluoro-2,2-propenyl group.

More specific examples of X 'containing a fluorine atom are described below.

Embedded image

Preferred examples of these are:

Embedded image And the like.

In the general formula (4), Y ′ is 2
And a valence organic group, wherein Y and R ¹ in the general formula (1) are
Does not include the group consisting of Y ′ which does not contain a fluorine atom is generally a residue of a diamine capable of forming a polyimide precursor by reacting with a tetracarboxylic acid or a derivative thereof (an acid anhydride, a diester or the like), and has an aromatic ring containing an aromatic ring. Group, a chain aliphatic group, a cyclic aliphatic group containing an aliphatic ring, and the like. An aromatic group is preferred in terms of heat resistance and the like. When the aromatic group is a group containing two or more aromatic rings, the number of the aromatic rings is preferably 2 to 4. Specifically, these aromatic rings are a single bond, an ether group, a carbonyl group, a methylene group. , A 2,2-propylene group, a sulfonyl group, a sulfinyl group, a thioether group and the like. Y is 4 to 4 in terms of the number of carbon atoms.
30 are preferred. Here, as the aromatic group, two bonding sites forming an amide bond with a tetracarboxylic acid are preferably present on an aromatic ring.
They may be present on the same aromatic ring or on different aromatic rings present through various bonds. Also, instead of one or more hydrogen atoms on the aromatic ring, C 1 -C 10
May have a substituent such as an alkyl group, an alkoxy group, an amide group, a carboxyl group, a phenolic hydroxyl group, and a group having a carbon-carbon double bond.

As Y ′ containing a fluorine atom, examples of the aromatic group containing an aromatic ring exemplified in the above description include a fluorine atom or a trifluoromethyl group instead of one or more hydrogen atoms on the aromatic ring. , A fluoroalkyl group such as a perfluoroethyl group, a fluorine-containing group such as a fluoroalkyloxy group bonded directly or indirectly through various groups, or hexafluoro as a group connecting two or more aromatic rings And those in which a group containing fluorine such as -2,2-propenyl group is present.

More specific examples of Y ′ containing a fluorine atom are described below.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Preferred examples of these are:

Embedded image And the like.

In the polyimide of the photosensitive polyimide composition of the present invention, the repeating units represented by the general formula (1) are all repeating units having one unit consisting of one carboxylic acid residue and one amine residue. Medium 10-100
In terms of photosensitive characteristics and heat resistance of the imide film, it is preferably contained in an amount of 15 to 100 mol%, more preferably 15 to 100 mol%, and still more preferably 20 to 90 mol%.

In the case of having a fluorine atom-containing repeating unit represented by the general formula (4), 5 of all repeating units having one unit consisting of one carboxylic acid residue and one amine residue as one unit. The content is preferably from 90 to 90 mol% from the viewpoint of i-line transmittance, and more preferably from 10 to 80 mol%. The polyimide used in the present invention may have a repeating unit other than the repeating units represented by the general formulas (1) and (4), and the proportion is represented by the general formulas (1) and (4). It is preferred that the remainder is within the preferred range of the repeating unit. Examples of such a repeating unit include, for the purpose of improving adhesiveness and development speed, a repeating unit in which a silicon-containing group Z is bonded instead of R ¹ in the general formula (1); In (4), a repeating unit in which neither X ′ nor Y ′ contains fluorine is preferred.

Of these, the repeating unit to which the silicon-containing group Z is bonded is preferable because it can improve the adhesiveness and the developing speed without impairing the stability of the photosensitive resin. It is preferable to have 1 to 20 mol%. Examples of the silicon-containing group represented by Z include an alkylsilyl group, an alkoxysilyl group, and a group containing silicon in the form of a siloxane bond (a bond represented by -Si-O-Si-). Specifically, groups having the following structures are preferred.

Embedded image Wherein Z ′ is

Embedded image (Wherein, a plurality of R ′ are each independently H, OH, R ″ or OR ″, and when a plurality of R ″ are present, each independently represents a hydrocarbon group having 1 to 10 carbon atoms. Yes, p is 1
An integer of 10 and r is an integer of 0 to 10), and when two Z are present, they may be the same or different. ]

Preferred examples are shown below.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image (Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, k is 0)
And m represents an integer of 0 to 3, and p and q each independently represent an integer of 1 to 10.) Of these, those having a structure having an alkoxysilyl group at the terminal are more preferred in terms of adhesiveness. preferable.

The molecular weight of the polyimide used in the present invention is not particularly limited, but is preferably 10,000 to 300,000, more preferably 30,000 to 150,000 in terms of weight average molecular weight. Here, the molecular weight can be determined by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The polyimide of the present invention can be produced according to various known production methods. For example, in an organic solvent, the general formula (5)

Embedded image (Wherein X is the same as in the general formula (1)), after synthesizing a polyamic acid from a tetracarboxylic acid containing a silicon-containing tetracarboxylic dianhydride and a triamine or an amino compound containing a tetraamine, and further adding light. The compound can be synthesized by reacting a compound containing a polymerizable group with an amino group remaining in the synthesized polyamic acid. Thereafter, the polyamic acid is thermally or chemically subjected to a dehydration ring-closing reaction to obtain the polyimide of the present invention.

As the tetracarboxylic dianhydride other than the silicon-containing tetracarboxylic dianhydride, the following general formula (6)

Embedded image (Wherein X ′ is the same as X ′ in the general formula (4)).

Specifically, for example, butanetetracarboxylic dianhydride, ethylenebistrimellitate dianhydride,
Triethylene bis trimellitate dianhydride, tetraethylene bis trimellitate dianhydride, pentaethylene bis trimellitate dianhydride, hexaethylene bis trimellitate dianhydride, heptaethylene bis trimellitate dianhydride, octaethylene bis trimellitate Dianhydride,
Decaethylene bistrimellitate dianhydride, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic 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-perylenetetracarboxylic dianhydride, sulfonyldi Phthalic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2 Bis {4 '- (2,3- or 3,
4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,
2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride, a tetracarboxylic acid having a fluorine atom specifically represented by a chemical structural formula in the description of X' Dianhydrides. Further, in some cases, the following general formula (7)

Embedded image (Wherein, R ⁴ and R ⁵ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and s is an integer of 1 to 10). You can also. These can be used alone or in combination of two or more kinds together with the silicon-containing tetracarboxylic dianhydride represented by the general formula (6). Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, m-terphenyl-3, and the like in terms of low stress, heat resistance, i-ray permeability and the like. 3 ', 4,4'
-Tetracarboxylic dianhydride, p-terphenyl-3,
Preferred are 3 ', 4,4'-tetracarboxylic dianhydride, oxydiphthalic dianhydride and the like.

The amine capable of forming Y in the general formula (1) is preferably a triamine or a tetraamine. For example, 4,4'-diaminodiphenyl ether-
3-carbonamide, 3,4′-diaminodiphenylether-4-carbonamide, 3,4′-diaminodiphenylether-3′-carbonamide, 3,3′-diaminodiphenylether-4-carbonamide, 4,
4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-
Triamines such as 3′-sulfonamide and 3,3′-diaminodiphenylether-4-sulfonamide;
3 ′, 4,4′-biphenyltetraamine, 3,3 ′,
And tetraamines such as 4,4'-tetraaminobiphenyl ether.

The compound containing a photopolymerizable group that forms R ¹ in the general formula (1) includes maleic anhydride,
Itaconic anhydride, citraconic anhydride, 5-norbornene-
2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, isobutenylsuccinic anhydride, having the following structural formula

Embedded image (Wherein p represents an integer of 1 to 10), and the like.

These compounds can be reacted with one or two remaining amino groups derived from triamine or tetraamine in the polyimide precursor in an organic solvent. The reaction temperature is preferably in the range of 10 to 100 ° C, and if it is lower than 10 ° C, the reactivity is low and the compound cannot be sufficiently introduced into the side chain. If the temperature exceeds 100 ° C., imidization proceeds, and the dissolution rate during development decreases. The reaction time varies depending on the reaction temperature, but is preferably 5 to 50 hours from the viewpoint of production efficiency.

The silicon-containing compound for introducing the silicon-containing group represented by Z includes a compound represented by the following structural formula.

Embedded image

Embedded image (Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, k is 0)
An integer of 2 to 2, m is an integer of 0 to 3, p and q each independently represent an integer of 1 to 10)

The diamine forming the repeating unit represented by Y 'in the general formula (4) is represented by the following general formula (8)

Embedded image (Wherein Y ′ is the same as Y ′ in the general formula (4)), and these are not particularly limited. For example, 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,
Paraphenylenediamine, metaphenylenediamine, p
-Xylylenediamine, m-xylylenediamine, o-
Trizine, o-tolidine sulfone, 4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diisopropylaniline),
2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis- @ 4
-(4'-aminophenoxy) phenyl} sulfone,
1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 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 fluorine atom-containing diamines such as diamine having a fluorine atom specifically represented by the chemical structural formula in the description of Y ′. These are used alone or in combination of two or more.

In some cases, the following general formula (9)

Embedded image (Wherein, R ⁶ and R ⁷ each represent a divalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different;
⁸ and R ⁹ each represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, and t is 1 to 1
A diamine having a siloxane bond, such as diaminopolysiloxane represented by the formula (1), can also be used.

In the production of the polyimide used in the present invention, the use amount of triamine or tetraamine is preferably in the range of 10 to 100 mol%, more preferably 15 to 100 mol%, of the total amount of the amine component.
More preferably, it is 0 to 90 mol%. If the amount is less than 10 mol%, the photosensitive properties tend to decrease, and the mechanical and thermal properties of the polyimide film tend to decrease. As the organic solvent used for the reaction, a polar solvent that completely dissolves the produced polyimide is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Examples include tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
Examples include tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These organic solvents can be used alone or
Used in combination of more than one type.

The polyimide can be synthesized by imide ring closure of the polyimide precursor obtained by the above method. The imide ring closure can be usually performed by heating. The heating conditions are not particularly limited, but the heating temperature is preferably from 80 to 450 ° C. If the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the generated polyimide tends to deteriorate. The heating time is preferably set to 10 to 100 minutes. If the heating time is less than 10 minutes, the ring-closing reaction tends to be slow, and if it exceeds 100 minutes, the resulting polyimide tends to deteriorate and the workability tends to decrease.

The photosensitive polyimide composition of the present invention can contain a photoinitiator, if necessary. Examples of the photoinitiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4, -bis (diethylamino) benzophenone, acetophenone, benzophenone, and thioxanthone , 2,2-dimethoxy-2-
Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio)
Phenyl] -2-morpholino-1-propanone, benzyl, diphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4- Azacyclohexanone, N
-Ethyl-N- (p-chlorophenyl) glycine, N-
Phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl)
Oxyiminopropan-1-one, 3,3,4,4,-
Tetra (t-butylperoxycarbonyl) benzophenone, 3,3, -carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis-
[2,6-difluoro-3- (pyr-1-yl) phenyl] titanium and the like. These are used alone or in combination of two or more.

The amount of the photoinitiator used is 0.1 to 0.1 with respect to the amount of the polyimide containing the repeating unit represented by the general formula (1).
The content is preferably from 0.01 to 30% by weight, and
More preferably, it is 0% by weight. This usage is
If it is less than 0.01% by weight, the light sensitivity tends to be poor,
If it exceeds 0% by weight, the mechanical properties of the film tend to be poor.

The photosensitive polyimide composition of the present invention may contain an addition polymerizable compound, if necessary. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol methacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Data pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyl toluene, 4-vinyl pyridine, N- vinylpyrrolidone, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2
-Hydroxypropane, methylenebisacrylamide,
N, N-dimethylacrylamide, N-methylolacrylamide and the like can be mentioned. These are used alone or in combination of two or more.

The amount of the addition polymerizable compound used is preferably 1 to 200% by weight based on the amount of the polyimide containing a repeating unit represented by the general formula (1). When the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developer tend to be inferior, and when it exceeds 200% by weight, the mechanical characteristics of the film tend to be inferior.

The photosensitive polyimide composition of the present invention may contain an azide compound, if necessary. As azide compounds, for example,

Embedded image

Embedded image

Embedded image And the like. These are used alone or in combination of two or more.

The amount of the azide compound used is based on the amount of the polyimide containing the repeating unit represented by the general formula (1).
The content is preferably 0.01 to 30% by weight, and 0.05
More preferably, the content is set to 10 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

The photosensitive polyimide composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. Examples of the radical polymerization inhibitor or the radical polymerization inhibitor include, for example, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, Examples include N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor is preferably 0.01 to 30% by weight based on the amount of the polyimide containing the repeating unit represented by the general formula (1). More preferably, the content is 0.05 to 10% by weight. If this amount is less than 0.01% by weight, the stability during storage tends to be inferior, and 30% by weight.
When it exceeds, the light sensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive polyimide composition of the present invention is applied onto a substrate such as a silicon wafer, a metal substrate, a ceramic substrate or the like by an immersion method, a spray method, a screen printing method, a spin coating method or the like, and most of the solvent is removed. By heating and drying, a coating film having no tackiness can be obtained. There is no particular limitation on the thickness of this coating film, but from the viewpoint of circuit characteristics and the like, the thickness of
It is preferably 50 μm, more preferably 6 to 40 μm, and particularly preferably 10 to 40 μm. After irradiating actinic rays or actinic rays on the coating film through a mask on which a desired pattern is drawn, for example, by irradiating it with a pattern, the unexposed portion is developed and dissolved with an appropriate developing solution to be removed. Thereby, a desired relief pattern can be obtained.

The photosensitive polyimide composition of the present invention is suitable for i-ray exposure using an i-ray stepper or the like. However, as an actinic ray or actinic ray to be irradiated, light other than i-ray, for example, an ultrahigh pressure mercury lamp Light such as a contact / proximity exposure machine, a mirror projection exposure machine, a g-ray stepper, and other ultraviolet rays, a visible light source, X-rays, and an electron beam can also be used. As the developer, for example, a good solvent (N, N-dimethylformamide, N, N
-Dimethylacetamide, N-methyl-2-pyrrolidone, etc.), the good solvent and the poor solvent (lower alcohol, ketone,
Water, aromatic hydrocarbons, etc.) and basic solutions (tetramethylammonium hydroxide aqueous solution, triethanolamine aqueous solution, etc.).

After the development, if necessary, it is preferable to rinse with water or a poor solvent and dry at about 100 ° C. to make the pattern stable. In addition, by heating the relief pattern as needed, a patterned high heat-resistant polyimide can be formed. The heating temperature at this time is preferably from 150 to 500C, more preferably from 200 to 400C. If the heating temperature is lower than 150 ° C., the mechanical and thermal properties of the polyimide film tend to decrease, and if it exceeds 500 ° C., the mechanical and thermal properties of the polyimide film tend to decrease.

The heating time at this time is 0.05 to 1
Preferably, it is 0 hours. This heating time is 0.0
If the time is less than 5 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and if the time exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease. Thus, the photosensitive polyimide composition of the present invention can be used for forming a surface protective film and an interlayer insulating film for a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

One example of the manufacturing process of the semiconductor device of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In this example, the surface protective film is formed by applying the photosensitive resin composition by a spin coating method, drying the applied light, and irradiating light from a mask on which a pattern for forming the window 6C is formed on a predetermined portion. And heat to form a polyimide film. This polyimide film protects the conductor layer from external moisture, foreign matter, etc., but in the present invention, the resulting semiconductor is excellent in adhesiveness and can be formed in a good shape and a high-definition pattern. The device is highly reliable. In the above example, the interlayer insulating film can be formed using the photosensitive polyimide composition of the present invention. Thus, the photosensitive polyimide composition of the present invention can be used for a surface protective film for semiconductors, an interlayer insulating film of a multilayer wiring board, and the like.

[0063]

The present invention will be described below with reference to examples. Synthesis Examples 1 to 5 The amine component and N-methyl-2-pyrrolidone (NMP) shown in Table 1 were added to a 100-ml flask equipped with a stirrer and a thermometer, and dissolved by stirring at room temperature.
Was added and stirred for 30 hours to obtain a viscous polyimide precursor solution. Further, a side chain-introducing component was added to this solution, followed by stirring for 30 hours to obtain a target polyimide precursor solution. Acetic anhydride and pyridine were added to this solution,
After stirring at room temperature for 5 hours, this solution was further poured into a large amount of methanol while stirring to reprecipitate the polyimide. This powder was washed several times with methanol and then dried under reduced pressure to obtain a polyimide powder. This polyimide powder was dissolved in NMP to obtain polyimide solutions (PI-1 to PI-5).
The amounts of the amine component, acid component, side chain introduction component and N-methyl-2-pyrrolidone used are shown in Table 1. When the obtained polyimide solutions (PI-1 to PI-5) were dried, the infrared absorption spectrum (manufactured by JEOL Ltd., JIR-100 type) was measured by the KBr method. Characteristic absorption of the imide was confirmed at around 1780 cm ^-1 .

[0064]

[Table 1]

<Abbreviations> SIDA: bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, 6FDA: 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, SXDA: 1,3-bis (3,4-dicarboxyphenyl) tetramethyldisiloxane dianhydride, DECA: 4,4′-diaminodiphenyl ether-3
-Carbonamide, BPTA: 3,3 ', 4,4'-biphenyltetraamine, DFAP: 2,2'-difluorobenzidine, TFDB: 2,2'-bis (trifluoromethyl) benzidine, MLA: maleic anhydride LS-2940: 3-glycidoxypropyltrimethoxysilane GMA: glycidoxypropyl methacrylate

Examples 1 to 3 and Comparative Examples 1 and 2 Each polyimide (PI-1 to PI) obtained in Synthesis Examples 1 to 5
To 10 g of the solution of I-5), 2,6-bis (4′-
0.027 g of azidobenzal) -4-carboxycyclohexanone (CA), 0.027 g of 4,4'-bis (diethylamino) benzophenone (EAB) and 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one (PDO) 0.054 g was added and mixed with stirring to obtain a uniform photosensitive polyimide composition solution used in Examples 1 to 3 and Comparative Examples 1 and 2.

[0067]

Embedded image

The obtained photosensitive polyimide composition solution was
The solution was filtered, and each of them was dropped and spin-coated on a silicon wafer. Then, using a hot plate, 10
After heating at 0 ° C. for 150 seconds to form a coating film having a thickness of 23 μm, the film was masked with a pattern and exposed with an i-line stepper. This was further heated at 100 ° C. for 60 seconds to give N-methyl-2.
Paddle development using a mixed solution of pyrrolidone / water (75/25 (weight ratio)), which was carried out at 100 ° C. for 30 minutes,
Heating was performed at 200 ° C. for 30 minutes and at 350 ° C. for 60 minutes to obtain a polyimide relief pattern.

Each of the polyimides (P) obtained in Synthesis Examples 1 to 5
The resolution and adhesion rate of the relief patterns of I-1 to PI-5) were evaluated by the following methods.
It was shown to. The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

Next, the above Examples 1 to 3 and Comparative Examples 1 to
The relief pattern obtained in 2 at 100 ° C. for 30 minutes,
The polyimide pattern was obtained by heating at 200 ° C. for 30 minutes and under a nitrogen atmosphere at 350 ° C. for 60 minutes. The polyimide patterns obtained from the relief patterns of Examples 1 to 3 were almost the same as the mask dimensions and had good dimensional accuracy. The polyimide patterns obtained from the relief patterns of Comparative Examples 1 and 2 had openings larger than the mask dimensions and had poor dimensional accuracy.

[0071]

[Table 2]

[0072]

The photosensitive polyimide composition according to any one of claims 1 to 3 can be processed at a low temperature by using a specific polyimide soluble in an organic solvent, has excellent storage stability of the composition, and has a reduced film thickness. Since it is small, it is excellent in forming a thick film, and the adhesiveness and heat resistance of the formed polyimide film to a silicon substrate are also good. The photosensitive polyimide composition according to the fourth aspect has the effects of the invention according to the first aspect, and further has good photosensitive characteristics. The photosensitive polyimide composition according to claims 5 to 7 has the effects of the invention according to claim 1,
It has improved solubility in organic solvents, has high i-line transmittance, and can provide better photosensitive characteristics and heat resistance.

According to the manufacturing method of the eighth aspect, a pattern having excellent thin film forming property due to small film reduction and excellent adhesion and heat resistance of the formed polyimide film to the silicon substrate can be obtained. In the semiconductor device according to the ninth aspect, the adhesive strength of the polyimide film to the silicon substrate is good and the reliability is excellent.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1: Semiconductor substrate, 2: Protective film, 3: 1st conductor layer,
4 ... interlayer insulating film layer, 5 ... photosensitive resin layer, 6A, 6B,
6C: window, 7: second conductor layer, 8: surface protective film layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/312 B 21/312 H05K 3/46 T H05K 3/46 H01L 21/30 502R

Claims (9)

[Claims] 1. A compound of the general formula (1) (Wherein, X is a tetravalent organic group containing a silicon atom, and all of the silicon atoms are included in a structure in which four bonding sites are bonded to a carbon atom or another silicon atom, and Y is 3 to 4 A monovalent organic group, R ¹ is a monovalent organic group containing a photopolymerizable group,
m is an integer of 1 to 2). A photosensitive polyimide composition containing a polyimide having a repeating unit represented by the following formula: 2. X is a compound represented by the general formula (2). (Wherein, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, L is an oxygen atom, a sulfur atom, a carbonyl group, a methylene group, a 2,2-propylene group, a sulfinyl group, A sulfoxy group or a single bond, n and u are 1 to
It is an integer of 3. Any one of the four structures shown by
The photosensitive polyimide composition according to claim 1, wherein (3) X is a compound represented by the general formula (3): (Wherein, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, and n is an integer of 1 to 3). Photosensitive polyimide composition. 4. The photosensitive polyimide composition according to claim 1, wherein the monovalent organic group containing a photopolymerizable group represented by R ¹ is a group containing a carbon-carbon double bond. 5. A polyimide comprising a repeating unit represented by the general formula (4) together with a repeating unit represented by the general formula (1): Wherein X ′ is a tetravalent organic group, Y ′ is a divalent organic group, and at least one of X ′ and Y ′ contains a fluorine atom. Item 3. The photosensitive polyimide composition according to Item 1 or 2. 6. X ′ in the general formula (4) is (Wherein, R ² and R ³ are an alkyl group or a phenyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 3), and Y ′ contains a fluorine atom. 3. The photosensitive polyimide composition according to 3. (7) Y ′ in the general formula (4) is The photosensitive polyimide composition according to claim 5, which is selected from the group consisting of: 8. A method of irradiating a coating film of the photosensitive polyimide composition according to claim 1 with an actinic ray from a mask on which a pattern is drawn, and developing and removing an unirradiated portion. The method of manufacturing the pattern. 9. A semiconductor device comprising a polyimide film obtained by using the photosensitive polyimide composition according to claim 1.