JP2001281858A - Photosensitive resin composition, method for producing pattern and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in suitability to development with an aqueous alkali solution, having good i-line transmittance in a prebaked film, giving a pattern with good resolution and ensuring low residual stress for a cured polybenzoxazole film formed on a silicon wafer and to provide a method for producing a pattern and electronic parts excellent in reliability. SOLUTION: The photosensitive resin composition contains a polybenzoxazole precursor having repeating units of formula (1) (where A is a tetravalent organic group having an aromatic ring, B is a divalent organic group, two OH groups and two NH groups bond to A, one of the OH groups and one of the NH groups are regarded as a set, OH and NH in each set are situated in the ortho- positions of the aromatic ring and the total number of aromatic rings contained in A and B is <=3) and having >=3.35 mol/kg concentration of hydroxyl groups when the composition does not contain a fluorine atom and >=2.00 mol/kg concentration of hydroxyl groups when the composition contains fluorine atoms. The light transmittance of a coating formed from the polybenzoxazole precursor at 365 nm is >=1% per 10 μm thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition using a polybenzoxazole precursor giving high i-line transmittance and low stress, and a semiconductor device using the same.

[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 photosensitivity. In addition, it has advantages such as high film-forming ability, but has disadvantages such as lack of storage stability and chromium ions remaining in polyimide, and thus has not been put to practical use.

[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. Also, a photosensitive resin composition using a polybenzoxazole precursor has been proposed. However, these photosensitive polyimide precursors and polybenzoxazole precursors use a basic skeleton as an aromatic monomer having excellent heat resistance and mechanical properties. Low light
The photochemical reaction in the exposed portion cannot be performed sufficiently effectively, and there is a problem that the sensitivity is low and the pattern shape 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 an ultra-high pressure mercury lamp have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, a stepper to be used is 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: 3).
65 nm).

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.
A decent pattern cannot be obtained with an i-line stepper. 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 composition having a high i-line transmittance and a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
The problem is that the silicon wafer on which polyimide or polybenzoxazole is formed as a surface protection film has a larger warp than before due to a difference in thermal expansion coefficient between polyimide and polybenzoxazole and the silicon wafer. Therefore, there is a strong demand for photosensitive polyimides and polybenzoxazoles having a lower thermal expansion than conventional polyimides and polybenzoxazoles. 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.

[0008]

DISCLOSURE OF THE INVENTION The present invention is excellent in developability with an aqueous alkali solution, has good i-line transmittance in a prebaked film, and has good resolution and pattern.
Another object of the present invention is to provide a photosensitive resin composition in which a cured polybenzoxazole film formed on a silicon wafer has low residual stress.

Further, the present invention provides a polybenzo which exhibits excellent developability in an aqueous alkali solution, can produce a pattern having a high sensitivity, a high resolution and a good shape by i-line exposure, and has a low stress after imidization and exhibits heat resistance and the like. An object of the present invention is to provide a method for producing a pattern capable of forming an oxazole film. Further, the present invention provides a highly reliable electronic component having a polybenzoxazole film with high resolution, good shape, excellent heat resistance, and extremely small residual stress. .

[0010]

The present invention provides a compound represented by the general formula (I):

Embedded image (Wherein, A is a tetravalent organic group having an aromatic ring, B is a divalent organic group, and two OH and two NH bonded to A are one OH and one NH. And each set of O
H and NH are located at the ortho position of the aromatic ring, and the total number of aromatic rings contained in A and B is 3 or less.) When the compound does not contain a fluorine atom, the hydroxyl group concentration is 3. A polybenzoxazole precursor having a hydroxyl group concentration of not less than 35 mol / Kg and not less than 2.00 mol / Kg when containing a fluorine atom, and a film of a coating film formed from the polybenzoxazole precursor The present invention relates to a photosensitive resin composition containing a polybenzoxazole precursor having a transmittance of light of 365 nm per 10 μm thickness of 1% or more.

[0011] The present invention also relates to the photosensitive resin, wherein a residual stress of a silicon wafer having a polybenzoxazole film obtained by forming and curing a coating film using the composition is 25 MPa or less at 25 ° C. Composition. Further, in the present invention, the polybenzoxazole precursor is represented by the general formula (2):

Embedded image (Wherein, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is attached, and R ² , R
³ , R ⁴ and R ⁵ each independently represent a monovalent group, and the bond indicated by two arrows indicates that they may be bonded in reverse order). Which is a photosensitive resin composition.

Further, the present invention further comprises generating an acid by light.
The present invention relates to the above photosensitive resin composition containing the compound.
In the present invention, X and Y in the general formula (1) are each independently
Standing single bond, O, CH ₂, C = O, Si (CH₃)₂,
C (CH₃)₂, C (CF₃)₂, C (CH₃) (CF
₃), Si (OCH₃)₂, C (OCH₃)₂, C (O
CF₃)₂, C (OCH₃) (OCF₃), S, S
O₂, CH (CH₃), CH (CF₃), CH (OCH
₃), CH (OCF₃), SiH (CH₃) And SiH
(OCH₃) Is a group selected from², R³, R
⁴And R⁵Is a hydrogen atom, an alkyl having 1 to 10 carbon atoms
Group, CF₃, Halogen atom, COOH and OH
The present invention relates to the photosensitive resin composition which is a group to be formed.

The present invention also relates to a method for producing a pattern, comprising the steps of applying and drying each photosensitive resin composition on a support substrate, exposing, developing, and heating. The present invention also relates to a method for producing a pattern, wherein the exposing step is performed using i-line as an exposure light source.

Further, according to the present invention, the support substrate has a diameter of 300.
The present invention relates to a method for manufacturing a pattern which is a silicon wafer having a size of at least mm. The present invention also relates to an electronic component having a layer of a pattern obtained by the above-mentioned manufacturing method. Further, according to the present invention, the electronic component is a semiconductor device, and the pattern layer is a surface protective film or an interlayer insulating film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention contains a polybenzoxazole precursor represented by the aforementioned general formula (I). The polybenzoxazole precursor is capable of forming polybenzoxazole by a ring closing reaction, and has a structure represented by the general formula (I) in the present invention.

In the general formula (I), A is a tetravalent organic group having an aromatic ring, and is generally a residue of dihydroxydiamine which reacts with a dicarboxylic acid to form a polybenzoxazole precursor structure. Two OHs that bind to A
And two NHs constitute one set of one OH and one NH,
Each set of OH and NH is located ortho to the aromatic ring. Examples of the tetravalent organic group having an aromatic ring represented by A include a group having at least one aromatic ring (such as a benzene ring or a naphthalene ring) having 6 to 20 carbon atoms, such as an alkyl group or an alkoxy group. It may have various substituents such as a group, a halogen atom and a halogenated alkyl group.

The divalent organic group represented by B is generally a residue of a dicarboxylic acid which reacts with dihydroxydiamine to form a structure of a polybenzoxazole precursor. Examples of the divalent organic group having an aromatic ring represented by B include a group having at least one aromatic ring (such as a benzene ring or a naphthalene ring) having 6 to 20 carbon atoms.
It may have various substituents. It is preferable to have one aromatic ring from the viewpoint of solubility in an alkaline aqueous solution.

In the repeating unit represented by the general formula (1), the total number of aromatic rings contained in A and B is 3 or less. Here, when the number of aromatic rings is four or more, there is a disadvantage that it is difficult to achieve both low wafer stress and solubility in an alkaline aqueous solution. When the polybenzoxazole precursor of the present invention does not contain a fluorine atom, the hydroxyl group concentration is 3.35 mol / Kg or more, preferably 4.0 to 4.0 mol / Kg.
It is 10.0 mol / Kg, and when it contains a fluorine atom, the hydroxyl group concentration is 2.00 mol / Kg or more, preferably 3.0 to 10.0 mol / Kg. If this value is lower than these values, there is a disadvantage that it is not sufficiently dissolved in an aqueous alkaline solution.

The above hydroxyl group concentration can be calculated as the hydroxyl group content per repeating unit mass (number of hydroxyl groups / mass of repeating unit) based on the type and amount of raw materials of the resin.

The polybenzoxazole precursor used in the present invention has a wavelength of 36 per 10 μm of a prebaked film formed from the polybenzoxazole precursor.
The light transmittance at 5 nm is preferably 1% or more,
It is more preferably at least 5%, further preferably at least 10%. Here, if this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern having a high resolution and a good shape. Particularly preferred transmittance is 10% to 80%. The polybenzoxazole precursor film can be manufactured by applying the polybenzoxazole precursor in a solvent in a state of being dissolved in a solvent, applying the solution to a substrate, and then drying the film. The transmittance of light having a wavelength of 365 nm of the polybenzoxazole precursor film can be measured with a spectrophotometer (for example, Hitachi U-3410, manufactured by Hitachi, Ltd.). Even when the film thickness at the time of measurement is not exactly 10 μm, it is possible to convert the film thickness per 10 μm according to Lambert's law.

Further, the photosensitive resin composition of the present invention comprises a silicon resin having thereon a polybenzoxazole film obtained by curing (ring-closing to oxazole) a coating film formed on a silicon wafer using the composition. It is preferable that the residual stress of the wafer is 25 MPa or less at 25 ° C. Here, if this value exceeds 25 MPa, there is a disadvantage that the amount of warpage of the silicon wafer and the residual strain inside the silicon chip increase. More preferred residual stress is 0
２０20 MPa. In addition, the residual stress in this invention is 5-8 at normal temperature (25 degreeC) using a composition.
5-20 μm thick film after curing formed on inch wafer,
For a film having a thickness of preferably about 10 μm, a thin film stress measuring device (for example, FLX-2320 manufactured by Tencor Co., Ltd.)
(Type).

The polybenzoxazole precursor used in the photosensitive resin composition of the present invention preferably has a repeating unit having the structure represented by the general formula (2). More preferably, 80% or more of all the repeating units are still more preferable, and about 100%
Is particularly preferred. In the general formula (2), X
And Y are each independently a divalent group that is not conjugated to the benzene ring to which they are attached, and specifically, may have a carbonyl group, an oxy group, a thio group, a sulfinyl group, a sulfonyl group, or a substituent. Examples thereof include an alkylene group having a good carbon number of 1 to 5, an imino group which may have a substituent, a silylene group which may have a substituent, and a group formed by a combination of these groups.

The substituents that may be present in each group described in the description of X and Y include a monovalent substituent and a divalent substituent.
Valent substituents, specifically, an alkyl group having 1 to 10 carbon atoms, which may have a branch, and 1 to 10 carbon atoms.
Halogen (chlorine, fluorine, iodine, bromine, etc.) substituted alkyl group, alkenyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms
Having 6 carbon atoms such as alkynyl, phenyl and benzyl
To 20 aromatic hydrocarbon groups, alkyloxy groups having 1 to 10 carbon atoms, halogens having 1 to 10 carbon atoms (chlorine, fluorine,
Iodine, bromine, etc.) substituted alkyloxy group, cyano group, halogen atom (chlorine, fluorine, iodine, bromine, etc.), hydroxy group, amino group, azide group, mercapto group, trialkyl group having 1 to 5 carbon atoms An alkylsilyl group, an alkylene group having 2 to 5 carbon atoms, a carbonyl group, a carboxyl group,
Examples include an imino group, an oxy group, a thio group, a sulfinyl group, a sulfonyl group, a dialkylsilylene group having 1 to 5 carbon atoms in each alkyl group, and a substituent formed by a combination thereof. Among them, carbon number 1-5
The alkyl group, the halogen-substituted alkyl group, the alkyloxy group, the halogen-substituted alkyloxy group, the aromatic hydrocarbon group, and the alkylene group having 2 to 3 carbon atoms are more preferable.

X and Y each independently represent a single bond,
O, CH₂, C = O, Si (CH₃) ₂, C (CH₃)
₂, C (CF₃)₂, C (CH₃) (CF₃), Si
(OCH ₃)₂, C (OCH₃)₂, C (OC
F₃)₂, C (OCH₃) (OCF₃), S, SO₂,
CH (CH₃), CH (CF₃), CH (OCH₃),
CH (OCF₃), SiH (CH₃) And SiH (OC
H₃) Is a group selected from
C is preferable because stress can be reduced.

The monovalent group represented by R ² , R ³ , R ⁴ and R ⁵ is a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, CF ₃ , a halogen atom, COOH and OH. Is preferred in terms of i-line permeability and solubility in an aqueous alkaline solution.

The polybenzoxazole precursor used in the present invention can be synthesized by reacting dihydroxydiamine with dicarboxylic acid or a derivative thereof in an organic solvent used as required.

Preferred dihydroxydiamine components include, for example,

Embedded image

Embedded image And the like.

Further, within the scope of the present invention, for example,
3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2-bis (3-amino-
Diamines such as (4-hydroxyphenyl) hexafluoropropane can also be used.

Preferred dicarboxylic acid components include those having one benzene ring in which two carboxyl groups are bonded to the para position.

Embedded image And the like are specifically preferred.

Further, within the scope of the present invention, for example,
Diphenyl ether-4,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, benzophenone-
4,4'-dicarboxylic acid, benzophenone-3,4'-
Dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenylsulfone-3,4′-dicarboxylic acid, and the like,

[0031]

Embedded image

Embedded image

Embedded image Etc. can also be used.

As the organic solvent used in the above reaction, a polar solvent which completely dissolves the resulting polybenzoxazole precursor is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -Dimethylformamide, dimethylsulfoxide, γ-butyrolactone and the like.

The polybenzoxazole precursor can be obtained, for example, by reacting a dicarboxylic acid dihalide (chloride, bromide, etc.) with a diamine.
In this case, the reaction is preferably performed in an organic solvent in the presence of a dehaloacid catalyst. As the dicarboxylic dihalide, dicarboxylic dichloride is preferable. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride.

The photosensitive resin composition of the present invention can be obtained by imparting photosensitivity to the polybenzoxazole precursor. Examples of the method for imparting photosensitivity include known methods such as mixing a photosensitizer such as a photoacid generator and a photobase generator.

The molecular weight of the polybenzoxazole precursor is not particularly limited, but may be 20,000 in weight average molecular weight.
Preferably it is ~ 100,000. The molecular weight can be measured by a gel permeation chromatography method and converted to standard polystyrene.

The photosensitive resin composition of the present invention, together with the polybenzoxazole precursor, generally comprises a photosensitizing agent such as a compound which generates an acid by light or a compound which generates a base by light in order to make it photosensitive. , But it is preferable to use a compound that generates an acid by light. The compound capable of generating an acid by light has a function of generating an acid by being changed by light irradiation and increasing the solubility of a portion irradiated with light in a developing solution (aqueous alkaline solution). Examples of the type include photosensitive quinonediazide compounds such as o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. There is no particular limitation, but photosensitive quinonediazide compounds are preferable because of their excellent effects. As the photosensitive quinonediazide compound, 1,2-benzoquinonediazide described in U.S. Pat.
Known compounds having a 2-naphthoquinonediazide structure may be mentioned. The compound that generates an acid by light is preferably 5 to 100 parts by weight, based on 100 parts by weight of the polybenzoxazole precursor, in view of the film thickness and sensitivity after development.
More preferably, it is used in an amount of 10 to 40 parts by weight.

The photosensitive resin composition of the present invention may further contain an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid and the like in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate.

The photosensitive resin composition of the present invention can be obtained in the form of a solution by dissolving each component in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-
Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylenesulfone, γ-butyrolactone, cyclohexanone, cyclopentanone are used alone or in combination of two or more. Can be

The photosensitive resin 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. Although there is no particular limitation on the thickness of this coating film, from the viewpoint of circuit characteristics and the like, it is 4 to 50 μm.
m, more preferably 6 to 40 μm, and particularly preferably 10 to 40 μm.

Further, since the photosensitive resin composition of the present invention can form a film having a low residual stress, the photosensitive resin composition has a diameter of 300 mm (12 mm).
It is suitable for application to a large-diameter wafer such as a silicon wafer having a diameter of 2 inches or more. On this coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion or the exposed portion is developed and dissolved with a suitable developing solution, By removing, a desired pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for i-line exposure using an i-line stepper or the like.
A contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, other ultraviolet rays, a visible light source, X-rays, and an electron beam can also be used.

As the developing solution, an alkaline aqueous solution can be used. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium silicate, and the like.
An aqueous solution of 5% by weight or less, such as tetramethylammonium hydroxide, preferably an aqueous solution of 1.5 to 3.0% by weight is used, and a more preferred developer is 1.5 to 3% by weight of tetramethylammonium hydroxide. 0% by weight aqueous solution. Further, a surfactant or the like can be added to the above-mentioned developer for use. Each of these is blended in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

After the development, if necessary, rinsing with water or a poor solvent can be performed to stabilize the pattern. The obtained pattern can be made into a highly heat-resistant polybenzoxazole patterned by heating. The heating temperature at this time is preferably 100 to 500 ° C, more preferably 200 to 400 ° C. When the heating temperature is lower than 100 ° C., the mechanical properties and thermal properties of the film tend to decrease.
If it exceeds, the mechanical and thermal properties of the film tend to decrease. The heating time at this time is preferably set to 0.05 to 10 hours. If the heating time is less than 0.05 hours, the mechanical and thermal properties of the film tend to decrease, and if it exceeds 10 hours, the mechanical and thermal properties of the film tend to decrease.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and more specifically, for surface protection films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. The electronic component 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.

As an example of the electronic component of the present invention, an example of a manufacturing process of a semiconductor device 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 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, a phenol novolak type or the like 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. A window 6A is provided to perform the process (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 the example of this figure, the surface protective film is coated with the photosensitive resin composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to an alkaline aqueous solution. To form a pattern and heat to form a resin film. This resin film causes the conductor layer to
The semiconductor device is protected from α rays and the like, and the obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

The photosensitive resin 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 removes most of the solvent. By heating and drying, a coating film having no tackiness can be obtained. Although there is no particular limitation on the thickness of this coating film, from the viewpoint of circuit characteristics and the like, it is 4 to 50 μm.
m, more preferably 6 to 40 μm, particularly preferably 10 to 30 μm, and particularly preferably 10 to 20 μm. On this coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the exposed portion is developed and dissolved with a suitable alkali developing solution,
By removing, a desired relief pattern can be obtained.

[0050]

The present invention will be described below with reference to examples. Synthesis Examples 1 to 5 (1) In a 200 ml four-necked flask, 0.03 mol of dicarboxylic acid shown in Table 1, 4.75 g (0.06 mol) of pyridine, N, N'-dimethylacetamide (DMAc) 7
0 ml was added and stirred to obtain a uniform solution. The flask containing this solution was cooled with ice and 8.57 g of thionyl chloride was added.
(0.072 mol) was added dropwise in 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain an acid chloride solution.

(2) Synthesis of Polybenzoxazole Precursor In another 200 ml four-necked flask, 0.03 mol of dihydroxydiamine and 5.06 g of pyridine (0.
064 mol) and 50 ml of DMAc, and the acid chloride solution obtained in the above (1) was slowly added dropwise over 1 hour while cooling the flask with ice (10 ° C. or lower) and stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice, and dried in vacuum. This polymer powder was converted to γ-butyrolactone (γ-B
L), and the viscosity was adjusted to 80 poise to obtain a polybenzoxazole precursor solution (P-1 to 5).

The viscosity was measured using an E-type viscometer (EHD type, manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25 ° C. and a rotation speed of 2.5 rpm. The dried solution of the obtained benzoxazole precursor solution (P-1 to 5) was measured for infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.) by the KBr method. both the absorption of C = O of amide group near 1600 cm ^-1, absorption of N-H were observed at around 3300 cm ^-1.

Examples 1 to 3 and Comparative Examples 1 and 2 10 g of the powder of each polybenzoxazole precursor (P-1 to 5) obtained in Synthesis Examples 1 to 5 was converted to 15 g of γ-butyrolactone (γ-BL). After dissolution, 2 g of 1,2-naphthoquinonediazide was added to obtain a uniform photosensitive resin composition solution.

The obtained photosensitive resin composition solution was filtered through a filter, and each solution was spin-coated on a silicon wafer. Next, the coating was heated at 100 ° C. for 150 seconds using a hot plate to form a coating film of 15 μm, then subjected to a pattern mask and exposed with an i-line stepper. After the exposure, paddle development was performed using an aqueous solution of tetramethylammonium hydroxide, and this was heated at 400 ° C. for 60 minutes to obtain a relief pattern of polybenzoxazole.

The transmittance of each of the polybenzoxazole precursors (P-1 to 5) obtained in Synthesis Examples 1 to 5, the residual stress on the silicon wafer, and the resolution of the relief pattern were evaluated by the following methods. Table 2 shows the evaluation results.
The transmittance was measured by spin-coating the resin solution of each of the obtained polybenzoxazole precursors (P-1 to 5) and drying at 85 ° C. for 2 minutes and further at 105 ° C. for 2 minutes. 10 μm) was measured with a spectrophotometer.

The residual stress was measured by spin-coating each composition on a 5-inch wafer, drying at 85 ° C. for 2 minutes and 105 ° C. for 2 minutes, and heat-treating at 400 ° C. for 1 hour.
A polybenzoxazole film having a thickness of μm was formed, and the stress was measured at 25 ° C. using a stress measurement device (FLX-2320 type, manufactured by Tencor). The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

The photosensitive resin composition of the present invention is excellent in developability with an aqueous alkali solution, has good i-ray transmittance in a pre-baked film, can obtain a good resolution and pattern, and has a good performance on a silicon wafer. The cured polybenzoxazole film has a low residual stress.

According to the method for producing a pattern of the present invention,
Excellent developability with aqueous alkali solution, high sensitivity, high resolution by i-line exposure, and good shape pattern can be manufactured.
After imidization, a polybenzoxazole film showing low heat resistance and heat resistance can be formed. Further, the electronic component of the present invention has a high-resolution, good-shaped pattern, a polybenzoxazole film with excellent heat resistance, and extremely low residual stress, and thus has excellent reliability.

[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 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window,
7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/075 G03F 7/075 7/40 501 7/40 501 H01L 21/027 H01L 21/30 502R F-term (Ref.) UA122 UA131 UA132 UA231 UA311 UA511 UA621 UB011 UB051 UB061 UB121 UB122 UB131 UB311 UB321 VA012 VA021 VA022 VA051 VA061 YA10 YA28 YB08 YB24 ZA52 ZB22 ZB50

Claims (10)

[Claims] 1. A compound of the general formula (I) (Wherein, A is a tetravalent organic group having an aromatic ring, B is a divalent organic group, and two OH and two NH bonded to A are one OH and one NH. And each set of O
H and NH are located at the ortho position of the aromatic ring, and the total number of aromatic rings contained in A and B is 3 or less.) When the compound does not contain a fluorine atom, the hydroxyl group concentration is 3. A polybenzoxazole precursor having a hydroxyl group concentration of not less than 35 mol / Kg and not less than 2.00 mol / Kg when containing a fluorine atom, and a film of a coating film formed from the polybenzoxazole precursor A photosensitive resin composition comprising a polybenzoxazole precursor having a transmittance of 365% or more at 365 nm per 10 μm thickness. 2. The photosensitive material according to claim 1, wherein a residual stress of a silicon wafer having a polybenzoxazole film obtained by forming and curing a coating film using the composition is 25 MPa or less at 25 ° C. Resin composition. 3. A polybenzoxazole precursor having the general formula (2): (Wherein, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is attached, and R ² , R
³ , R ⁴ and R ⁵ each independently represent a monovalent group, and the bond indicated by two arrows indicates that they may be bonded in reverse order). The photosensitive resin composition according to claim 1 or 2, wherein 4. The photosensitive resin composition according to claim 1, further comprising a compound capable of generating an acid by light. 5. X and Y in the general formula (1) each independently represent a single bond, O, CH ₂ , C ＝ O, Si (CH ₃ ) ₂ , C (C
H ₃ ) ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) (CF ₃ ),
Si (OCH ₃ ) ₂ , C (OCH ₃ ) ₂ , C (OC
F ₃ ) ₂ , C (OCH ₃ ) (OCF ₃ ), S, SO ₂ ,
CH (CH ₃ ), CH (CF ₃ ), CH (OCH ₃ ),
CH (OCF ₃ ), SiH (CH ₃ ) and SiH (OC
H ₃ ), wherein R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, CF
The photosensitive resin composition according to claim 1, 2, 3, or 4, which is a group selected from ₃ , a halogen atom, COOH and OH. 6. A pattern comprising a step of applying the photosensitive resin composition according to claim 1, 2, 3, 4 or 5 on a supporting substrate, drying, exposing, developing and heating. Manufacturing method. 7. The method according to claim 6, wherein the step of exposing is performed using i-line as an exposure light source. 8. The method according to claim 6, wherein the supporting substrate is a silicon wafer having a diameter of 300 mm or more. 9. An electronic component having a layer of a pattern obtained by the method according to claim 6, 7, or 8. 10. The electronic component according to claim 9, wherein the electronic component is a semiconductor device, and the layer of the pattern is a surface protective film or an interlayer insulating film.