JP3361636B2 - Radiation-sensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises a mixture of a water-insoluble alkali-soluble novolak resin and a specific quinonediazide compound and a water-insoluble alkali-soluble low-molecular compound additive, and ultraviolet rays, far ultraviolet rays, X-rays, electron beams and molecular beams. , Γ
Line, a positive photoresist composition sensitive to radiation such as synchrotron radiation, and more specifically, high resolution can be obtained irrespective of fluctuations in film thickness, less development residue is generated, and development latitude is improved. Also relates to an excellent photoresist composition for microfabrication.

The positive photoresist according to the present invention is applied on a semiconductor wafer or a substrate such as glass, ceramics, metal or the like by a spin coating method, a roller coating method or another coating method to a thickness of about 0.5 to 3 μm. It afterwards,
A positive image is obtained by heating and drying, baking a circuit pattern or the like through an exposure mask by irradiation with ultraviolet rays, baking if necessary after exposure, and developing. Further, by etching this positive image as a mask, the substrate can be patterned. Typical fields of application are manufacturing of semiconductors such as ICs, manufacturing of circuit boards such as liquid crystal and thermal heads, manufacturing of magnetic bubble memory devices, and other photo-ablation processes.

[0003]

2. Description of the Related Art Conventionally, a radiation sensitive resin composition has been used in the photofabrication process such as the manufacture of semiconductor devices such as ICs and the manufacture of magnetic bubble memory elements. Among them, a positive photoresist composition having a particularly high resolution is used. As a positive photoresist composition, a composition containing an alkali-soluble resin binder such as novolak and a naphthoquinonediazide compound as a photosensitive material is generally used. For example, "Novolak type phenol resin / naphthoquinone diazide substituted compound"
USP-3, 666, 473, 4,115,
No. 128 and No. 4,173,470, etc., and "the novolak resin consisting of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinone diazide sulfonate" as the most typical composition.
Is an example of Thompson "Introduction to Microlithography" (LF Thompson "In
troduction to Microlithhog
“Raphy”) (ACS Publishing, No. 219, P11)
2-121).

The novolak resin as a binder can be dissolved in an alkaline aqueous solution without swelling, and when the produced image is used as a mask for etching, it gives high resistance to plasma etching, so that it is used in this application. Especially useful for. Further, the naphthoquinonediazide compound used for the photosensitive material acts as a dissolution inhibitor which lowers the alkali solubility of the novolak resin by itself, but when it is decomposed by light irradiation, an alkali-soluble substance is produced and rather the alkali solubility of the novolak resin is reduced. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large change in properties with respect to light.

From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide type photosensitive material have been developed and put into practical use. In particular, the progress of resist materials toward higher resolution has been remarkable, and sufficient results have been achieved in line width processing down to submicrons.

Conventionally, it has been considered advantageous to use a resist having a high contrast (γ value) in order to enhance the resolution and obtain an image having a good pattern shape, and technical development of a resist composition suitable for such a purpose has been carried out. Came. There are a great number of patents and reports disclosing such technology, and many patent applications have been made regarding the technology of the novolac resin, which is the main component of the positive photoresist, regarding its monomer composition, molecular weight distribution, synthetic method, etc. , Has achieved certain results.

Attempts to improve the properties of the resist by giving the novolak resin a specific molecular weight distribution are already known. For example, Japanese Patent Laid-Open No. 1-105243
It is described in the publication that a novolac resin having a distribution in which the molecular weight is in the range of 500 to 5000 is 30% or less is preferable. Also, JP-A-62-227144
No. 63-2044 and No. 63-2044 show that the ratio of the specific molecular weight region in the molecular weight distribution has a preferable range. Furthermore, No. 60-97347 and No. 60-1.
No. 89739 describes a novolak resin from which low-molecular weight components have been separated and removed, and especially No. 60-45238 describes the use of a resin having a dispersity of 3 or less as used in the present invention.

With respect to the photosensitive material which is another main component, many structures which are effective for increasing the contrast have been disclosed. For example, in SPIE Proceedings Vol. 1672, p. 231 and p. 262 (1992), it is described that a photoresist having a specific structure can provide a photoresist having a high contrast. If a positive photoresist is designed by utilizing such knowledge, it has become possible to develop an ultrahigh resolution resist capable of resolving a pattern having a size comparable to the wavelength of light.

However, integrated circuits are becoming more and more integrated, and in the manufacture of semiconductor substrates such as VLSI,
It has become necessary to process an ultrafine pattern having a line width of 0.5 μm or less. In such applications, there is a demand for a photoresist having a wide development latitude in which a stable and high resolution can be obtained and a constant processing line width is always ensured. Further, in order to prevent processing defects in the circuit, it is required that no resist residue is generated in the resist pattern after development.

The low molecular weight compound having an aromatic hydroxyl group is usually used as a dissolution accelerator for the purpose of improving sensitivity, and many examples of inclusion in a resist composition have been disclosed. However, when such a compound is added, the film slippage in the unexposed area usually increases, and as a result, the shape of the resist is deteriorated. Further, since the developing speed is increased, the developing latitude is generally lowered. Therefore, structural selection of preferred compounds has been carried out in a manner that minimizes these.

On the other hand, in order to increase the degree of integration of integrated circuits, the conventional wet etching method has been changed to a dry etching method. However, during dry etching, the resist temperature rises, so that thermal deformation or the like occurs. The resist is required to have high heat resistance so as not to cause this. In order to improve the heat resistance of the resist, a resin containing no component having a weight average molecular weight of 2000 or less is used (JP-A-60-97347), and a resin having a total content of monomers to trimers of 10% by weight or less is used. The technology used (Japanese Patent Laid-Open No. 60-189739) has been disclosed.

However, when the above-mentioned resin in which the low molecular weight component is removed or reduced is used, the sensitivity is usually lowered,
There is a problem that throughput in device manufacturing is lowered.

Attempts have also been made to improve the sensitivity and developability of the resist by incorporating a specific compound into the resist composition. For example, JP-A-61-141441 discloses a positive photoresist composition containing trihydroxybenzophenone. The positive photoresist containing this trihydroxybenzophenone has improved sensitivity and developability, but the addition of trihydroxybenzophenone deteriorates the heat resistance and causes a problem that the film slippage in the unexposed area increases.

Therefore, it has been desired to develop a resist having a wide development latitude, high sensitivity, good resolution and high heat resistance.

Further, particularly in the formation of an ultrafine pattern of 0.5 μm or less, even if a constant resolution can be obtained with a certain coating film thickness, it can be obtained by slightly changing the coating film thickness. It has been found that there is a phenomenon (hereinafter referred to as film thickness dependency) that the obtained resolution deteriorates. Surprisingly, the resolution changes greatly even if the film thickness changes by only a few hundredths of μ, and moreover, there is such a tendency in any of the typical positive photoresists currently on the market. There was found. Specifically, if the thickness of the resist film before exposure changes with respect to the predetermined film thickness within the range of λ / 4n (λ is the exposure wavelength, n is the refractive index of the resist film at that wavelength) Therefore, the resolution obtained is changed.

In particular, it has been found that when the contrast of the resist is increased so as to obtain a pattern having a high resolution and a rectangular cross-sectional shape, the film thickness dependency is often increased. When actually processing a semiconductor substrate, a pattern is formed by using a resist film applied with a film thickness slightly different for each location due to unevenness on the substrate surface or unevenness of the application film thickness. Therefore, this film thickness dependence will be one obstacle in carrying out microfabrication near the limit of its resolution using a positive photoresist. The problem of the film thickness dependence is, for example, SPIE Proceedin
Its existence is pointed out in gs 1925, p. 626 (1993), and it is caused by the multiple reflection effect of light in the resist film, and it is said that it also correlates with the insolubilization phenomenon of the resist surface. Has been.

However, in order to reduce the film thickness dependency and obtain a high resolution regardless of the film thickness, it has not been known at all until now how to design the composition of the resist material. Since the film thickness dependence is caused by multiple reflection of light, the present inventors tried to improve this by adding a dye into the resist, but the resolution was eventually decreased due to the increased light absorption by the dye. However, the cross-sectional shape of the pattern became trapezoidal and could not be a resist suitable for fine processing.

[0018]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a positive photoresist for ultrafine processing which has a high resolution and a small "film thickness dependency". The term "thickness dependency" as used in the present invention means the magnitude of variation in resolution obtained when the resist film thickness before exposure changes in the range of λ / 4n.

Another object of the present invention is to provide a positive photoresist which has a wide development latitude and hardly develops a development residue. Here, the development latitude can be expressed by the development time dependency of the resist line width or sensitivity obtained by development, or the temperature dependency. The development residue refers to a trace amount of resist insoluble matter that remains between fine patterns after development, which can be observed with a scanning electron microscope or the like.

Still another object of the present invention is to provide a photoresist having high heat resistance and high resistance to dry etching.

[0021]

Means for Solving the Problems The inventors of the present invention have paid careful attention to the above-mentioned various characteristics and have conducted diligent studies. In the composition, the radiation-sensitive compound has a phenolic hydroxyl group of 3
And / or 4 water-insoluble alkali-soluble low molecular weight compound naphthoquinone diazide sulfonic acid diester compound (A) and water-insoluble alkali-soluble low molecular weight compound naphthoquinone diazide sulfonic acid ester compound having 5 to 7 phenolic hydroxyl groups The inventors have found that the above object can be achieved by using a radiation-sensitive resin composition characterized by containing a mixture with (B) in an amount of 30% or more of the radiation-sensitive compound, and have completed the present invention.

Here, the relation between the known technology forming part of the constituent features of the present invention and the present invention will be described. A part of the skeletal compound of the radiation-sensitive compound (A) used in the present invention is described, for example, in USP-51789886 and JP-A-2-296.
249, JP-A-2-296248 and the like.
However, the photosensitive compounds described are essentially based on a complete naphthoquinonediazidosulfonic acid ester of a phenolic hydroxyl group. In a positive photoresist using these as a composition of a water-insoluble alkali-soluble resin and a water-insoluble alkali-soluble low-molecular compound, the development residue is likely to occur, the development latitude is narrow, and the film thickness dependency is large. There was a problem that the heat resistance was low.

However, the effect of the present invention is that in a radiation-sensitive resin composition containing a water-insoluble alkali-soluble resin, a water-insoluble alkali-soluble low molecular weight compound and a radiation-sensitive compound, the radiation-sensitive compound contains a phenolic hydroxyl group. A specific water-insoluble alkali-soluble low-molecular compound having 3 and / or 4 naphthoquinone diazide sulfonic acid diester compound (A) and a specific water-insoluble alkali-soluble low-molecular compound having 5 to 7 phenolic hydroxyl groups Mixture with naphthoquinone diazide sulfonic acid ester compound (B) accounts for 30% of total radiation sensitive compound
This is a unique effect that is exhibited only when the above is the case.

That is, when a mixture of such radiation-sensitive compounds is combined with the water-insoluble alkali-soluble resin and the water-insoluble alkali-soluble low molecular weight compound defined in the present invention, the expected alkali dissolution inhibiting action of the radiation-sensitive compounds and their photodegradation products are expected. While an appropriate balance of the action of promoting alkali dissolution enhances the resolution of the resist, it is quite surprising that it gives a broader development latitude and good film thickness dependence than either of them alone. Moreover, when the radiation-sensitive compound is a naphthoquinone diazide sulfonic acid diester compound which is a specific water-insoluble alkali-soluble low molecular weight compound having 3 and / or 4 phenolic hydroxyl groups, the low heat resistance, which was a problem, is significantly increased. We have found improvements.

The embodiments of the present invention will be described in detail below.

The radiation-sensitive compound (A) of the present invention is a water-insoluble alkali-soluble compound having a phenolic hydroxyl group and three and / or four phenol rings represented by the following general formulas (A ₁ ) and / or (A ₃ ). It is a low molecular weight compound.

[0027]

[Chemical 7]

Where R _{1 to} R ₈ are hydrogen atoms,
It represents -CN, -X-R _a1 or a halogen atom. In the case of a large alkyl group-containing group, the film thickness dependency and the development residue tend to be deteriorated. Therefore, among these, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or A cycloalkyl group having 5 to 7 carbon atoms is preferable. Particularly, a hydrogen atom, a methyl group, an ethyl group or a methoxy group is preferable.

X _{1 to} X ₂ : a single bond, a carbonyl group, a sulfide group, a sulfonyl group or --C (R _b1 ).
_Represents (R _b2 )-. However, when 1 = 0, X ₁ represents a group represented by the following general formula A ₁₁ or A ₁₂ .

[0030]

[Chemical 8]

[0031]

[0032]

[0033]

R ₉ , R _{12 to} R ₁₇ , R _b1 and R _b2 : each represents a hydrogen atom, a methyl group, an ethyl group or a haloalkyl group having 1 to 2 carbon atoms. R _b1 and R _b2 may combine together to form an alicyclic hydrocarbon residue. Among these,
A hydrogen atom or a methyl group is preferred in terms of film thickness dependence and performance of development residue.

R ₁₀ , R ₁₁ , R _a3 , R _a4 , R ₁₈ and R ₁₉ each represent a hydrogen atom, --X--R _a1 , --CN or a halogen atom, each of which is a hydrogen atom or a carbon number of 1 to 4; An alkyl group or an alkoxy group having 1 to 4 carbon atoms is preferable.
Particularly, a hydrogen atom, a methyl group, an ethyl group or a methoxy group is preferable.

X: single bond, --O--, --S--, --CO--,
_{-OCO-, N (R a1) CO-} ,

Xa represents a carbonyl group, a sulfide group, a sulfonyl group or --C (R _b1 ) (R _b2 )-.

X _{1 to} X ₂ and Xa are sulfide groups, sulfone groups, --C (Rb1) because of the solubility of the radiation-sensitive compound (A) in the coating solvent, the cost, and the ease of industrial production.
A group represented by (Rb2)-, or when 1 = 0, X1 is preferably a group represented by the above general formula A11 or A12.

R _{a1 is} an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group,

Z ₁ : represents a single bond or a trivalent alicyclic hydrocarbon group formed together with CR ₉ , and more preferably a single bond.

[0041]

K and l are each 0 or 1, m and n are each 1 or 2, q is an integer of 1 to 8, and k and l are 1 respectively,
Each of m, n and q is preferably 1.

[0043]

D _{1 to} D ₅ : each represents a hydrogen atom or a naphthoquinonediazide-4 or 5-sulfonyl group.

R _{32 to} R ₄₃ : hydrogen atom, --CN,
-X-R _a1 or a halogen atom is represented, but in the case of a large alkyl group-containing group, the film thickness dependence and the development residue tend to be deteriorated. The alkoxy groups of formulas 1 to 4 and chloro atoms are preferred. Particularly, a hydrogen atom, a methyl group, an ethyl group or a methoxy group is preferable.

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

X _{4 to} X ₆ : a single bond, a carbonyl group, a sulfide group, a sulfonyl group or --C (R _b1 ).
(R _b2 )-, which is a single bond, a sulfide group, a sulfonyl group or -C (R) in view of solubility of the radiation-sensitive compound (A) in a coating solvent, cost, and ease of industrial production.
A group represented by _b1 ) ( _Rb2 ) _-is preferable.

[0054]

[0055]

[0056]

[0057]

D _{8 to} D ₁₁ : each represents a hydrogen atom or a naphthoquinonediazide-4 or 5-sulfonyl group.

[0059]

[0060]

However, in each of the radiation-sensitive compounds represented by the general formulas (A ₁ ) and (A ₃ ) among D _{1 to} D ₃ and D _{8 to} D ₁₁ , two in one molecule are naphthoquinonediazide.
4 or 5-sulfonyl group. R _{a5 to} R _a7 : each independently represents a hydrogen atom, —CN, —X—R _a1 or a halogen atom. R _{a5 to} R _a7 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

Among these, the radiation-sensitive compound (A)
Is preferably a radiation-sensitive compound represented by formula (A1) or (A3), and particularly preferably l = 1.

Radiation-sensitive compound (A) useful in the present invention
Specific examples of the above are shown below, but of course the invention is not limited thereto. D represents a hydrogen atom or a naphthoquinonediazide-4 or 5-sulfonyl group, respectively.

[0064]

[Chemical 12]

[0065]

[Chemical 13]

[0066]

[Chemical 14]

[0067]

[Chemical 15]

[0068]

[0069]

[Chemical 17]

[0070]

[Chemical 18]

[0071]

The radiation-sensitive compound (B) of the present invention is a naphthoquinone diazide sulfonic acid ester compound which is a water-insoluble alkali-soluble low molecular weight compound having 5 to 7 phenolic hydroxyl groups, and is preferably of the general formula (B
The naphthoquinone diazide sulfonic acid ester compound represented by 1) is preferable.

[0073]

[Chemical 20]

Here, R62 to R82: hydrogen atom,-
It represents CN, -X-Ra1 or a halogen atom, but in the case of a large alkyl group-containing group, the film thickness dependence and the development residue tend to be deteriorated, so that a hydrogen atom and a carbon number of 1 respectively.
An alkyl group having 4 to 4 or an alkoxy group having 1 to 4 carbon atoms,
Chlorine atoms are preferred. Particularly, a hydrogen atom, a methyl group, an ethyl group or a methoxy group is preferable.

X9 to X14: single bond, carbonyl group, sulfide group, sulfonyl group or --C (Rb1) (Rb
2) -is represented by a single bond, a sulfide group, a sulfonyl group, -C (Rb1) (R) in view of solubility of the radiation-sensitive compound (B) in a coating solvent, cost, and ease of industrial production.
The group represented by b2)-is preferable.

D17 to D23: each represents a hydrogen atom or a naphthoquinonediazide-4 or 5-sulfonyl group. The proportion of the naphthoquinonediazide-4 or 5-sulfonyl group in all the substituents of D17 to D23 is 10 to 60% because if it is too much, sensitivity deterioration and development residue, shape deterioration and the like are likely to occur. preferable. Especially 20 ~
50% is preferable.

Ra1: represents an alkyl group having 1 to 10 carbon atoms, an aryl group or aralkyl.

Rb1 and Rb2: each represents a hydrogen atom, a methyl group, an ethyl group or a haloalkyl group having 1 to 2 carbon atoms.
Rb1 and Rb2 may be bonded together to form an alicyclic hydrocarbon residue.

I and j: represent 0 or 1, respectively, i
+ J = 1 or 0 is preferable.

The radiation-sensitive compound of the present invention has a naphthoquinone diazide sulfonic acid ester group as the radiation-sensitive compound molecular chain from the viewpoints of the dissolution inhibiting action of the water-insoluble alkali-soluble resin, the development residue of the radiation-sensitive composition, and the high resolution performance. Radiation sensitive compounds that are terminally located are particularly preferred.

Radiation-sensitive compounds (B) useful in the present invention
Specific examples of the above are shown below, but of course the invention is not limited thereto. D represents a hydrogen atom or a naphthoquinonediazide-4 or 5-sulfonyl group, respectively.

[0082]

[Chemical 21]

[0083]

[Chemical formula 22]

[0084]

[Chemical formula 23]

[0085]

[Chemical formula 24]

[0086]

[Chemical 25]

[0087]

[Chemical formula 26]

[0088]

[Chemical 27]

[0089]

[Chemical 28]

[0090]

[Chemical 29]

[0091]

[Chemical 30]

[0092]

[Chemical 31]

[0093]

[Chemical 32]

[0094]

[Chemical 33]

[0095]

[Chemical 34]

[0096]

[Chemical 35]

[0097]

[Chemical 36]

The ratio of the radiation-sensitive compound (A) to the radiation-sensitive compound (B) in the mixture of the radiation-sensitive compounds of the present invention depends on the film thickness and the development residue when the radiation-sensitive compound (A) is too much. , The performance such as heat resistance tends to deteriorate, and when the radiation-sensitive compound (B) is too much, the development latitude during development, high resolution performance,
Since the shape and the like tend to deteriorate, it is in the range of 0.02 to 20, preferably 0.1 to 10. The range of 0.2 to 4 is particularly preferable.

The mixture of the radiation-sensitive compound (A) and the radiation-sensitive compound (B) of the present invention is preferably used as a composition of a specific water-insoluble alkali-soluble resin and a specific water-insoluble alkali-soluble low molecular compound. As the specific water-insoluble alkali-soluble resin, a water-insoluble alkali-soluble novolak resin having a weight average molecular weight to number average molecular weight ratio of 1.2 to 5 is preferable. A water-insoluble alkali-soluble novolac resin having a weight-average molecular weight to number-average molecular weight ratio of less than 1.2 is difficult to produce industrially, and if the ratio exceeds 5, the development latitude becomes narrow and the development latitude becomes low. It is not desirable because it tends to have a large amount of residue. Those skilled in the art can manufacture the water-insoluble alkali-soluble resin having a small ratio of the weight average molecular weight and the number average molecular weight by referring to, for example, JP-A-4-122938.

Among them, at least one kind of the water-insoluble alkali-soluble resin synthesized by a condensation reaction of phenol, cresol, xylenol, trimethylphenol or a mixture of two or more kinds thereof with an aldehyde compound is used. It is a novolac resin, the ratio of the weight average molecular weight to the number average molecular weight is 1.2 to 5, and the weight average molecular weight is 550.
0-25000, or the water-insoluble alkali-soluble resin is p-cresol, o-cresol, 2,
At least one novolak resin synthesized by a condensation reaction of a mixture of 3-xylenol, 2,6-xylenol, and trimethylphenol with an aldehyde compound, the ratio of the weight average molecular weight to the number average molecular weight being 1.2-4.0
And a water-insoluble alkali-soluble novolak resin having a weight average molecular weight of 1500 to 5000 is more preferable.

However, the value of the molecular weight of the novolak resin refers to a value obtained by GPC (gel permeation chromatography) defined with standard polystyrene as a reference value.

The specific water-insoluble alkali-soluble low molecular weight compound has a total carbon number of 60 or less in one molecule and has 2 to 10 phenolic hydroxyl groups in one molecule. Molecular compounds are preferred. Further, the water-insoluble alkali-soluble low molecular weight compound has a ratio of phenolic hydroxyl groups to aromatic rings of 0.5 to 1.4 and a total number of carbon atoms in one molecule of 12 to 50,
Moreover, it is preferable that it is at least one water-insoluble alkali-soluble low-molecular compound having 2 to 10 phenolic hydroxyl groups in one molecule. Among such compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the water-insoluble alkali-soluble resin are particularly desirable. Further, when the carbon number of the compound is more than 60, the effect of the present invention is reduced. On the other hand, if it is less than 12, a new defect such as a decrease in heat resistance occurs. In order to exert the effect of the present invention, it is necessary to have at least two hydroxyl groups in the molecule.
When it exceeds 0, the effect of improving the development latitude is lost. Further, the ratio of the phenolic hydroxyl group to the aromatic ring is 0.5.
Below, there is a large dependence on film thickness, and the development latitude tends to be narrowed. When this ratio is 1.4 or more, the stability of the composition is deteriorated, and it is difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The amount of the low molecular weight compound added is preferably 2 to 100% by weight, more preferably 10 to 70% by weight, based on the alkali-soluble resin. If the amount added exceeds 100% by weight, the development residue deteriorates and a new defect that the pattern is deformed during development is not preferable.

The water-insoluble alkali-soluble low molecular weight compound having an aromatic hydroxyl group of the present invention is described in, for example, JP-A-4-12.
2938, JP-A-2-28531, and US Pat. No. 4,916.
210, European Patent No. 219294, etc., and can be easily synthesized by those skilled in the art with reference to the method. Specific examples of the low molecular weight compound having an aromatic hydroxyl group useful in the present invention are shown below, but it goes without saying that they are not limited thereto.

[0105]

[Chemical 37]

[0106]

[Chemical 38]

[0107]

[Chemical Formula 39]

[0108]

[Chemical 40]

[0109]

[Chemical 41]

As the water-insoluble alkali-soluble resin used in the present invention, novolac resin, vinylphenol resin, acetone-pyrogallol resin, acetone-resole resin,
Maleimide copolymer, N- (hydroxyphenyl) maleimide (co) polymer, styrene-maleic anhydride copolymer, polymer containing carboxyl group, sulfonyl group, lactone group, phosphonic acid group or the like is used. You can

The water-insoluble alkali-soluble novolac resin that can be used in the present invention is a substituted phenol alone or in the form of a mixture of plural kinds thereof in the presence of an acidic catalyst.
It is obtained by condensing 0.6 to 1.2 moles of aldehydes with respect to moles. The substituted phenols used here include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol,
2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4
-Trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4
5-trimethylphenol, methylenebisphenol,
Methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o
-Chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, p-methoxyphenol, m-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol , 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, p-tert-butylphenol, α
-Naphthol, β-naphthol, 4-phenylphenol and the like can be used alone or as a mixture of two or more. Among these, it is particularly preferable to use a mixture of a plurality of alkylphenols such as cresol, dimethylphenol and trimethylphenol. Further, monomethylolated products and dimethylolated products of these phenols can also be used as the substituted phenols.

As aldehydes, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, chloroacetaldehyde, dichloroacetaldehyde, bromoacetaldehyde, acrolein, methacrolein, crotonaldehyde, acrolein dimethyl acetal. , Furfural, etc. can be used alone or in combination of two or more.

As the acidic catalyst, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid or the like can be used. The water-insoluble alkali-soluble resin of the present invention has an average molecular weight defined by Mw value of 100.
Those in the range of 0 to 25,000 are preferable, and further 20
The range of 00 to 15000 is particularly preferable. If the Mw value is too large, the effect of the present invention for obtaining a wide development latitude and the like cannot be obtained.

As the radiation-sensitive compound used in the present invention, a mixture of the radiation-sensitive compound (A) and the radiation-sensitive compound (B) can be used by further mixing with another radiation-sensitive compound. Other radiation-sensitive compounds include radiation-sensitive alkaline dissolution inhibitor compounds and radiation-sensitive acid generator compounds. When a radiation-sensitive acid generator compound is used, it is preferable to further use an acid labile group-containing alkali dissolution inhibitor compound in combination.

Examples of the radiation-sensitive alkali dissolution inhibitor compounds include quinonediazide compounds, diazoketone compounds, azide compounds, orthonitrobenzyl compounds, orthonitroarylsulfonyl ester compounds and polyolefin sulfone compounds. .

The quinonediazide compounds include 1,2
-Naphthoquinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-
Esters of benzoquinonediazide-4-sulfonic acid and polyhydroxyaromatic compounds are used. Examples of the polyhydroxy aromatic compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and 2,3. , 4,4'-Tetrahydroxybenzophenone, 2,2 ', 4,4'-Tetrahydroxybenzophenone, 2,4,6,3', 4 ', 5'-Hexahydroxybenzophenone, 2 , 3,4,3 ', 4', 5'-Polyhydroxybenzophenones such as hexahydroxybenzophenone, 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenone Polyhydroxyphenylalkylketones such as ruhexylketone, bis
(2,4-dihydroxyphenyl) methane, bis (2,4-
3,4-trihydroxyphenyl) methane, bis
Bis ((poly) hydroxyphenyl) alkanes such as (2,4-dihydroxyphenyl) propane-1 3,
Propyl 4,5-trihydroxybenzoate 3,4,5
-Polyhydroxybenzoic acid esters such as phenyl trihydroxybenzoate, bis (polyhydroxybenzoyl) such as bis (2,3,4-trihydroxybenzoyl) methane and bis (2,3,4-trihydroxybenzoyl) benzene Alkanes or bis (polyhydroxybenzoyl) aryls, alkylene-di (polyhydroxybenzoates) such as ethylene glycol-di (3,5-dihydroxybenzoate), 3,5,3 ', 5'-biphenyl tetrol, 2,4,2 ', 4'-biphenyl tetrol, 2,4,6,3', 5'-biphenyl pentol,
Polyhydroxybiphenyls such as 2,4,6,2 ', 4', 6'-biphenylhexol, 4,4 ', 3'',4''-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4 ', 2'',3'',4''-pentahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 2,3,4 , 2 ', 3', 4 ', 3 ", 4"-octahydroxy-5,5'-dihydroxytriphenylmethane and other polyhydroxytriphenylmethanes 3,3,3,
3 ', 3'-Tetramethyl-1,1'-spirobi-indan-5,6,5', 6'-tetrol, 3,3,3 ', 3'
-Tetramethyl-1,1'-spirobi-indane-5,
6,7,5 ', 6', 7'-hexool, 3,3,3 ',
3'-tetramethyl-1,1'-spirobiindane-
4,5,6,4 ', 5', 6'-hexool, 3,3,
Polyhydroxyspirobi-indanes such as 3 ′, 3′-tetramethyl-1,1′-spirobi-indane-4,5,6,5 ′, 6 ′, 7′-hexool, 3,3-bis ( Three,
4-dihydroxyphenyl) phthalide, 3,3-bis (2,3,4-trihydroxyphenyl) phthalide,
Polyhydroxyphthalides such as 3 ', 4', 5 ', 6'-tetrahydroxyspiro [phthalide-3,9'-xanthene], 2- (3,4-dihydroxyphenyl) -3,5,
7-trihydroxybenzopyran, 2- (3,4,5-
Trihydroxyphenyl) -3,5,7-trihydroxybenzopyran, 2- (3,4-dihydroxyphenyl) -3- (3,4,5-trihydroxybenzoyloxy) -5,7-dihydroxybenzopyran, 2-
(3,4,5-trihydroxyphenyl) -3- (3,
4,5-Trihydroxybenzoyloxy) -5,7-
Polyhydroxybenzopyrans such as dihydroxybenzopyran, 2,4,4-trimethyl-2- (2 ', 4'-
Dihydroxyphenyl) -7-hydroxychroman,
2,4,4-trimethyl-2- (2 ', 3', 4'-trihydroxyphenyl) -7,8-dihydroxychroman,
Polyhydroxyphenyl chromanes such as 2,4,4-trimethyl-2- (2 ', 4', 6'-trihydroxyphenyl) -5,7-dihydroxychroman, 2,6-bis (2,3,4) -Trihydroxybenzyl) -4-methylphenol, 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenol, 2,6-bis (5-chloro-2,4-dihydroxybenzyl) -4- Methylphenol, 2,6-bis (2,4,6-trihydroxybenzyl) -4-methylphenol, 2,6-bis (2
-Acetyl-3,4,5-trihydroxybenzyl)-
4-methylphenol, 2,4,6-tris (2,3,
4-trihydroxybenzyl) phenol, 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) -4
-Methylphenol, 2,4,6-tris (3,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, 4,6-bis (3,5-dimethyl-4-hydroxybenzyl) pyrogallol, 2, 6-bis (3,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, hydroxybenzylphenols such as 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) phloroglucinol, or quercetin Flavonoid pigments such as rutin, rutin, etc., as well as a low-nuclear body of novolac or an analogue thereof can be used.

Further, a polymer containing an aromatic hydroxyl group such as an acetone pyrogallol condensation resin or polyvinyl phenol can be used instead of these low molecular weight compounds. Further, it is possible to substitute the hydroxyl group of novolac itself with quinonediazide in an appropriate amount so that it also functions as a photosensitive material or as a binder. Among these, those having a structure containing a portion having two or more aromatic hydroxyl groups on the same aromatic ring and having a total of three or more hydroxyl groups are preferable.

Examples of the diazoketone compounds include 5
-Diazomeldrum acid, 2-diazo-1-phenylbutane-1,3-dione, 1,3-diphenyl-2-diazopropane-1,3-dione, 2-diazomethylphenylmalonate, 2-diazo- 1- (3'-chlorosulfonylphenyl) -1-trimethylsilylpropane-
1,3-dione, or JP-A-60-14235, 62-47296, 63-253938, 63-2.
53940 and the like diazoketone compounds.

Examples of the azide compounds include 1-azidopyrene, p-azidobenzophenone, 4'-methoxy-4-azidodiphenylamine and 4-azidobenzal-.
2'-methoxyacetophenone, 4-azido-4'-nitrophenylazobenzene, 1- (p-azidophenyl) -1-cyano-4- (p-diethylaminophenyl) -1,3-butadiene, 4- Monoazide compounds such as azidochalcone, 4,4′-diazidobenzophenone,
4,4'-diazidodiphenylmethane, 4,4'-diazidostilbene, 4,4'-diazidochalcone, 4,
4'-diazidobenzalacetone, 4,4'-diazidodiphenyl ether, 4,4'-diazidodiphenyl sulfide, 4,4'-diazidodiphenyl sulfone,
2,6-di (4'-azidobenzal) cyclohexanone, 2,6-di (4'-azidobenzal) -4-methylcyclohexanone, 1,8-diazidonaphthalene,
3-azido-4'- (3'-azidobenzalmethyl)
Stilben, or Japanese Patent Publication No. 35-49295, 4
8-31841, 44-26047, 44-260
48, ibid 45-7328, ibid 47-30204, ibid 49
-12283, 51-29932, 53-325,
JP-A-48-14316, 48-93623, 49
-81103, 55-57538, 56-3953
8, the same 58-68036, the same 58-203438, the same 6
0-107644, 62-2249, 63-305.
347, USP2852379, the same 2940853, the same 3092494, GB892811, FR151148.
5, azide compounds described in DE514057 and the like.

The ortho-nitrobenzyl compounds include
For example, stearic acid ortho-nitrobenzyl ester, cholesteric acid ortho-nitrobenzyl ester, ortho-nitrobenzyloxytriphenylsilane, 5-methyl-2-nitrobenzyltriphenylsilane, di (5-chloro-2-nitrobenzyloxy) diphenylsilane,
Poly-ortho-nitrobenzyl methacrylate, poly-ortho-nitrobenzyl acrylate, ortho-nitrobenzaldehyde acetalized polyvinyl alcohol,
Alternatively, JP-A-48-47320 and JP-A-60-19853.
8, the same 61-138255, the same 62-153853, the Japanese Patent Publication No. 56-2696 and the like orthonitrobenzyl compounds.

Examples of orthonitroarylsulfenyl ester compounds include, for example, 2,4-dinitrobenzenesulfenylcholate, orthonitrobenzenesulfenyladamantane carboxylate, orthonitrobenzenesulfenyllutoris (trimethylsilyl) cholate and poly. 2,4-Dinitrobenzenesulfenyl methacrylate, JP-A-61-3141 and 61-3
6741 and the like orthonitroarylsulfenyl ester compounds.

Examples of the polyolefin sulfone compounds include polybutene-1-sulfone, polyhexene-1-sulfone, polycyclopentenesulfone, poly-2-methylpentenesulfone, polyoctene-1-sulfone, polybutene-2-sulfone, and JP-A-62-27.
732 and 63-218949, and the like.

Examples of the radiation-sensitive acid generator compound include those disclosed in JP-A-59-45439 and JP-A-60-362.
5, JP-A-62-229242, JP-A-63-27.
829, JP-A-63-36240, JP-A-63-2.
50642, Polym. Eng. Sce. , 23
Vol., 1012 (1983); ACS. Sym. 242
Vol. 11, p. (1984); Semiductor.
World 1987, November issue, page 91; Mac
romolecules, 21: 1475 (198)
8); SPIE, vol. 920, p. 42 (1988) and the like, and the like, and the like, which generate an acid upon exposure.

Examples of the acid-labile group-containing alkali dissolution inhibiting compounds include, for example, acetal or O, N-acetal compounds described in JP-A-48-89003, ortho compounds described in JP-A-51-120714, and the like. Ester or amide acetal compounds, polymers having an acetal or ketal group in the main chain as described in JP-A-53-133429, enol ether compounds described in JP-A-55-12995, JP-A-55-126236. N-acyliminocarbonic acid compounds described in, for example, JP-A-56-17345
Polymers having an orthoester group in the main chain described in JP-A-59-45439 and JP-A-60-3625.
No. 62-229242, 63-278.
29, JP-A-63-36240, JP-A-63-25
No. 0642, Japanese Patent Application No. 6-63862 and the like, tertiary or secondary alkyl ester compounds, JP-A-60-10
Silyl ester compounds described in JP-A No. 247, etc., JP-A-60
Examples thereof include silyl ether compounds and tetrahydropyranyl ether compounds described in JP-A-60-125446 and the like.

Examples of the tetrahydropyranyl ether compounds include 4,4'-isopropylidene diphenol-bis-2-tetrahydropyranyl ether and 4,4'-isopropylidenephenol
4'-sulfonyldiphenol-bis-tetrahydropyranyl ether, poly-tetrahydropyranyl ether of phenol formaldehyde resin and USP3779.
There are tetrahydropyranyl ether compounds described in 778 and the like.

The content ratio of the mixture of the radiation-sensitive compound (A) and the radiation-sensitive compound (B) in the radiation-sensitive compound of the present invention is such that the mixture is 30% or more of the radiation-sensitive compound, preferably 40%. % Or more.
It is particularly preferably 50% or more. When this ratio is 30% or less, the film thickness dependency is deteriorated and the development residue tends to increase.

The ratio of the radiation-sensitive compound to the water-insoluble alkali-soluble resin used in the present invention is 5 to 100 parts by weight, preferably 20 to 80 parts by weight, relative to 100 parts by weight of the resin. If the usage ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and if it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are lowered. Also,
When the radiation-sensitive acid generator compound is used, 100 parts by weight of the acid labile group-containing alkali dissolution inhibitor compound is used.
0.1 to 200 parts by weight of the radiation-sensitive acid generator compound,
It is preferably used in the range of 1 to 60 parts by weight. If this ratio is less than 0.1 part by weight, the sensitivity will be significantly reduced.

The present invention may further contain a polyhydroxy compound in order to accelerate the dissolution in the developing solution.
Preferred polyhydroxy compounds include polyhydroxy aromatic compounds which are ester residues of the above-mentioned quinonediazide compounds. Typical examples are phenols, resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Examples thereof include tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, polyhydroxytriphenylmethanes, polyhydroxyspirobiindanes, hydroxybenzylphenols, acetone-pyrogallol condensation resin, and phlorogluside.

As a solvent for dissolving the radiation-sensitive compound, the water-insoluble alkali-soluble low molecular weight compound and the water-insoluble alkali-soluble resin of the present invention, methyl ethyl ketone,
Ketones such as methyl amyl ketone and cyclohexanone,
Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, n-propyl alcohol
, Iso-butyl alcohol, n-butyl alcohol
, Cyclohexyl alcohol, alcohols such as diacetone alcohol, ethers such as dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, methyl methoxypropione
, Propyl formate, propyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methoxyethylpropionate, methoxymethylpropionate, ethoxyethylpropionate , Esters such as ethyl pyruvate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 1, 1 , Halogenated hydrocarbons such as 2-trichloroethylene, aromatic hydrocarbons such as toluene and xylene, dimethylacetamide, N-methylpyrrolidone, dimethylformamide,
A highly polar solvent such as dimethyl sulfoxide can be exemplified. These solvents may be used alone or as a mixture of a plurality of solvents.

In the radiation-sensitive resin composition of the present invention, if necessary, a dye, a plasticizer, an adhesion auxiliary agent storage stabilizer, a sensitizer,
Compatible additives such as a striation inhibitor and a surfactant can be blended. Specific examples thereof include dyes such as methyl violet, crystal violet, malachite green, curcumin, tinuvin, thiazolylazophenol, stearic acid, acetal resins, phenoxy resins, plasticizers such as alkyd resins, and hexamethyl. Adhesion aids such as disilazane and chloromethylsilane and polyoxyethylene ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene nonylphenyl ether
Ters, polyoxyethylene polyoxypropylene block copolymers, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan trioleate, polyoxyethylene sorbitan monostearate,
Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan trioleate and other polyoxyethylene sorbitan fatty acid esters, F-top E
F301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.)
Manufactured by), Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluoride FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Gard AG710, Sir.
Freon S-382, SC101, SC102, SC10
3, fluorine-containing surfactants such as SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polymer No. 75, no. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the water-insoluble alkali-soluble resin in the composition of the present invention.

Particularly in dyes, dyes containing an alkali-soluble group such as an aromatic hydroxyl group and a carboxylic acid group in the molecule, for example, curcumin, are particularly advantageously used. When such a compound is added, It is desirable to adjust the amount of the low molecular weight dissolution enhancer of the present invention accordingly to obtain optimum performance.

After applying the above radiation-sensitive resin composition onto a substrate (eg, silicon / silicon dioxide coating) used in the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, a predetermined mask is applied. It is possible to obtain a good resist pattern by exposing through and developing. With the radiation-sensitive resin composition of the present invention, a so-called positive type pattern image in which a portion not normally irradiated with radiation is formed as an image is obtained. However, a method of heat treatment in an amine atmosphere as disclosed in JP-A-63-316429 or the like, or JP-A-62-
Compounds such as 2,6-di-t-butylpyridine, benzimidazole, pyridine, quinoline, acridine, lutidine, 1-methylbenzimidazole and melamine formaldehyde alkyl ether described in 35350 and EP263434A are used for the resin composition of the present invention. It is also possible to effectively obtain a negative pattern by performing so-called image reversal by blending or the like.

The developer of the radiation-sensitive resin composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Inorganic alkalis such as aqueous ammonia, ethylamine, n-
Primary amines such as propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium Hydroxide,
Aqueous solutions of quaternary ammonium salts such as tetraethylammonium hydroxide and choline hydroxide, and alkalis such as cyclic amines such as pyrrole and piperidine can be used. Further, alcohols, surfactants, aromatic hydroxyl group-containing compounds, etc. may be added in appropriate amounts to the aqueous solution of the above alkalis before use. Of these, it is most preferable to use tetramethylammonium hydroxide.

The present invention will be described below with reference to its examples, but it goes without saying that the embodiments of the present invention should not be limited to these examples.

[0135]

【Example】

Synthesis Example 1 Synthesis of Photosensitive Material (2A) 50.5 g of 2,6-bis (hydroxymethyl) -p-cresol and 194.7 g of o-cresol were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. The methano
The solution was dissolved in 200 ml of water, and 9.1 g of 36% hydrochloric acid was added. Then, the mixture was reacted under heating under reflux for 7 hours. The reaction mixture was poured into 4 liters of water, the precipitate was washed with water, and then hexane /
The mixture was stirred in dichloromethane (2/1) to remove unreacted raw materials. By recrystallizing with ethanol / water, 54 g of a white solid was obtained. According to NMR, this is 2,6-bis (3'-methyl-4'-hydroxybenzyl) -p-
It was confirmed to be cresol.

8.71 g of 2,6-bis (3'-methyl-4'-hydroxybenzyl) -p-cresol obtained in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping device. And 1,2-naphthoquinonediazide-
13.43 g of 5-sulfonyl chloride and 20 of acetone
0 ml and 10 ml of distilled water were charged and dissolved. To this, a solution of 5.27 g of triethylamine in 25 ml of acetone was added dropwise at room temperature over 35 minutes, and the reaction was further continued for 3 hours. After adding 3.14 g of acetic acid to the reaction mixture, it was poured into 3 l of distilled water. The precipitated yellow precipitate was filtered off, washed with water,
After drying, 19.7 g of a photosensitive material (2A) was obtained. High performance liquid chromatography analysis revealed that the diester form was 59% and the triester form was 24%.

Synthesis Example 2 Synthesis of Photosensitive Material (2B) 2,6-bis (3′-methyl-4′-hydroxybenzyl) -p-cresol 2,6-bis (3′-methyl) instead of 8.71 g -4'-hydroxybenzyl) -p-
17.1 g of photosensitive material (2B) was obtained in the same manner as in Synthesis example (1) except that 5.81 g of cresol was used. High-performance liquid chromatography analysis revealed that the diester form was 2
It was 0% and the content of the triester was 75%.

Synthesis Example 3 Synthesis of Photosensitive Material (3A) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 2,4-bis (hydroxymethyl) -p-cresol 40.4 g and 2,5- 176 g of xylenol was dissolved in 170 ml of methanol, and 7.3 g of 36% hydrochloric acid was added. Then, the mixture was reacted under heating under reflux for 12 hours. The reaction mixture was poured into 3.5 l of water, the precipitate was washed with water, and then stirred in hexane / dichloromethane (2/1) to remove unreacted raw materials. By recrystallizing with ethanol / water, 41 g of a white solid was obtained. By NMR, this is 2,
It was confirmed to be 6-bis (2 ′, 5′-dimethyl-4′-hydroxybenzyl) -p-cresol.

2,6-bis (2 ', 5'-dimethyl-4'-hydroxybenzyl) obtained in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device.
7.34 g of -p-cresol, 10.48 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 160 ml of acetone, and 10 mL of distilled water were charged and dissolved.
Triethylamine 4.11g acetone 20ml
The solution was added dropwise at room temperature over 30 minutes and then reacted for 5 hours. After adding 2.45 g of acetic acid to the reaction mixture, it was added to 2.5 l of distilled water. The deposited yellow precipitate was filtered off, washed with water and dried to obtain 15.5 g of Photosensitive Material (3A). When analyzed by high performance liquid chromatography,
The diester form was 61% and the triester form was 35%.

Synthesis Example 4 Synthesis of Photosensitive Material (3B) 2,6-bis (2 ', 5'-dimethyl-4'-hydroxybenzyl) -p-cresol Instead of 7.34 g of 2,6-bis (2 13.2 g of photosensitive material (3B) was prepared in the same manner as in Synthesis example (3) except that 4.91 g of ', 5'-dimethyl-4'-hydroxybenzyl) -p-cresol was used.
Got High-performance liquid chromatography analysis revealed that the diester form was 18% and the triester form was 77%.

[0141]

[0142]

[0143]

Synthesis Example 7 Synthesis of Photosensitive Material (9A) 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) p-cresol 15 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 30.3 g and Acetone (300 ml) was charged into a three-necked flask and uniformly dissolved. Then triethylamine / acetone = 12.4 g /
30 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 15 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and methanol and dried (40 ° C.) to recover a photosensitive material (9A). When the product was analyzed by HPLC, it was found to be a mixture of 28% triester, 59% diester, and the rest being other low-substituted products.

Synthesis Example 8 Synthesis of Photosensitive Material (9B) 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) p-cresol 10 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 30.3 g and Acetone (300 ml) was charged into a three-necked flask and uniformly dissolved. Then triethylamine / acetone = 12.4 g /
30 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 15 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and methanol, and dried (40 ° C.) to recover a photosensitive material (9B). When the product was analyzed by HPLC, it was a mixture of 78% triester, 12% diester, and the other low-substituted product.

Synthesis Example 9 Synthesis of Photosensitive Material (139A) 50.5 g of 2,6-bis (hydroxymethyl) -p-cresol and o-cresol 194 were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. 0.7 g and methano-
The solution was dissolved in 200 ml of water, and 9.1 g of 36% hydrochloric acid was added. Then, the mixture was reacted under heating under reflux for 7 hours. The reaction mixture was poured into 4 liters of water, the precipitate was washed with water, and then hexane /
The mixture was stirred in dichloromethane (2/1) to remove unreacted raw materials. By recrystallizing with ethanol / water, 54 g of a white solid was obtained. According to NMR, this is 2,6-bis (3'-methyl-4'-hydroxybenzyl) -p-
It was confirmed to be cresol.

The obtained 2,6-bis (3'-methyl-
4'-hydroxybenzyl) -p-cresol 34.9
g, potassium hydroxide 5.7 g in methanol / water (4 /
6) It was dissolved in 300 ml and 81 g of 37% formalin was added. Then, it was made to react at 40 ° C. for 24 hours. The reaction mixture was diluted with 500 ml of water and then neutralized with acetic acid. The precipitated pale yellow solid was filtered and washed with water to obtain 35 g of 2,6-bis (3'-methyl-4'-hydroxy-5'-hydroxymethylbenzyl) -p-cresol.

This 2,6-bis (3'-methyl-4'-
Hydroxy-5'-hydroxymethylbenzyl) -p-
To 20.5 g of cresol, 56.5 g of phenol and 200 ml of methanol were added, 3 g of 36% hydrochloric acid was further added, and the mixture was heated under reflux for 7 hours. Then, the mixture was poured into 3 l of water, and the precipitated light brown solid was subjected to column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 3 /
Purified in 1). 12 g of a white solid was obtained and its structure was confirmed by NMR.

White solid 14.0 obtained in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device.
2 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 13.43 g, acetone 250 ml, and distilled water 10 mL were charged and dissolved. To this, a solution of 5.27 g of triethylamine in 25 ml of acetone was added dropwise at room temperature over 35 minutes, and the reaction was further continued for 3 hours. After adding 3.14 g of acetic acid to the reaction mixture, it was poured into 3 l of distilled water. The deposited yellow precipitate was filtered off, washed with water and dried to obtain 23.2 g of a photosensitive material (139A). High performance liquid chromatography analysis revealed that the diester content was 37%,
The triester content was 21%.

Synthesis Example 10 Synthesis of Photosensitive Material (153A) 4,6-bis (hydroxymethyl) -2-methylpheno was used instead of 50.5 g of 2,6-bis (hydroxymethyl) -p-cresol of Synthesis Example 9. 20.5 g of a yellow solid photosensitive material (153A) was obtained in the same manner as in Synthesis Example 9 except that 50.5 g of the same was used. When analyzed by high performance liquid chromatography, the diester form was 39%,
The triester content was 20%.

Synthesis Example 11 Synthesis of Photosensitive Material (144A) 2,6-bis (hydroxymethyl) -p-cresol 1
6.8 g and 91.8 g of bis (3-methyl-4-hydroxyphenyl) methane (manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 200 ml of methanol, and 6.1 g of 36% hydrochloric acid was added.
Then, the mixture was heated to reflux for 24 hours. 3 l of reaction mixture in water
After washing the precipitated viscous solid with water, column chromatography (filler: silica gel, eluent: hexane /
It was purified with ethyl acetate = 2/1). 28 g of a white solid was obtained and its structure was confirmed by NMR. Stirrer, reflux condenser,
Into a four-necked flask equipped with a thermometer and a dropping device, 14.72 g of the obtained white solid, 13.43 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 250 ml of acetone, and 10 mL of distilled water were charged and dissolved. To this, a solution of 5.27 g of triethylamine in 25 ml of acetone was added dropwise at room temperature over 35 minutes, and the reaction was further continued for 3 hours. After adding 3.14 g of acetic acid to the reaction mixture, it was poured into 3 l of distilled water. The deposited yellow precipitate was separated by filtration, washed with water and dried to obtain 23.8 g of a photosensitive material (144A).
When analyzed by high performance liquid chromatography, the diester form was 32% and the triester form was 25%.

The production examples of the novolak resin according to the present invention are shown below. Reference Example 1 Synthesis of novolac resin (a) m-cresol 50 g, p-cresol 50 g, 37%
Formalin aqueous solution 45.5 g and oxalic acid dihydrate 0.0
Charge 5 g into a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, raise the temperature to 100 ° C. with stirring,
The reaction was carried out for 10 hours. After the reaction, the mixture was cooled to room temperature, the reflux condenser was removed, and the pressure was reduced to 25 mmHg. Then gradually 1
The temperature is raised to 60 ° C to remove water and unreacted monomers, and
3 g of novolak resin (a) was obtained. When analyzed by GPC, the Mw was 6540 and the dispersity was 7.4.

Reference Example 2 Synthesis of novolak resin (b) 44 g of the novolak resin (a) was taken, 400 ml of MEK was dissolved, 1600 ml of cyclohexane was added, and the mixture was heated to 60 ° C. with stirring. This solution was allowed to stand at room temperature for 16 hours to obtain a precipitate.
The precipitate was collected, filtered, and dried in a vacuum oven at 50 ° C. to obtain about 15 g of novolak resin (b). This is G
When analyzed by PC, the Mw was 8720 and the dispersity was 4.3.

Reference Example 3 Synthesis of novolak resin (c) m-cresol 456.6 g, p-cresol 295.
8 g and 404.35 g of a 37% aqueous formalin solution were charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and stirred while heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 1.03 g of oxalic acid dihydrate was added. Then, the reaction was continued under reflux for 15 hours, the temperature of the oil bath was further raised to 200 ° C., and water and unreacted monomers were removed under reduced pressure except for the reflux condenser to obtain 565 g of novolac resin (c). When analyzed by GPC, Mw
Was 8860 and the dispersity was 7.7.

Reference Example 4 Synthesis of novolak resin (d) 44 g of the novolak resin (c) was taken and dissolved in 280 ml of acetone and 175 ml of toluene, then 18
0 ml of hexane was added, and the mixture was heated to 40 ° C with stirring. This solution was allowed to stand at room temperature for 16 hours to obtain a precipitate. The precipitate was collected, filtered and dried in a vacuum oven at 50 ° C. to give about 15 g of novolak resin (d).
Got When this is analyzed by GPC, Mw is 1140
The degree of dispersion was 0 and the dispersity was 3.9.

Reference Example 5 Synthesis of novolak resin (e) In a three-necked flask having an internal volume of 500 ml equipped with a stirrer and a reflux condenser, 50 g of m-cresol and 25 parts of p-cresol were prepared.
g, 2,5-xylenol 28 g, formalin (37
% Aqueous solution), and stirred well while heating in an oil bath at 110 ° C., 0.15 g of oxalic acid was added, and the mixture was heated and stirred for 15 hours.

Then, the temperature is raised to 200 ° C. and gradually increased by 1-2.
The pressure was reduced to mmHg and distillation was carried out for 2 hours to remove unreacted monomers, water, formaldehyde, oxalic acid and the like. The temperature was lowered to room temperature to obtain 81 g of novolak resin (e). When this is analyzed by GPC, Mw is 4400 and the degree of dispersion is 6.
It was 5.

Reference Example 6 Synthesis of novolak resin (f) 20 g of novolak resin (e) was dissolved in 60 g of methanol. To this, 30 g of distilled water was gradually added with stirring to precipitate the resin component. The upper layer separated into two layers was removed by decanting. Then, 30 g of methanol was added to and dissolved in this, and 40 g of distilled water was gradually added again with stirring to precipitate the resin component. The separated upper layer was removed by decanting and the recovered resin component was heated to 40 ° C. in a vacuum dryer and
After drying for 4 hours, 7 g of novolak resin (f) was obtained. GP
When analyzed by C, the Mw is 9860 and the dispersity is 2.8.
It was 0.

Reference Example 7 Synthesis of novolak resin (g) 14.4 g of methylenebis-p-cresol, 2.2 g of o-cresol, 70.2 of 2,3-dimethylphenol
g, 2,3,5-trimethylphenol 27.2 g,
9.77 g of 2,6-dimethylphenol was mixed with 50 g of diethylene glycol monomethyl ether and charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. Then, 37% formalin aqueous solution 85.2
g, and stirred with heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 6.2 g of oxalic acid dihydrate was added. Then, the temperature of the oil bath is kept at 130 ° C for 18 hours to continue the reaction, and then the reflux condenser is removed to 200 ° C.
It was distilled under reduced pressure to remove unreacted monomers. The obtained novolak resin had an Mw of 3530 and a dispersity of 2.25.

Reference Example 8 Synthesis of novolak resin (h) p-cresol 8.1 g, o-cresol 6.6 g,
2,3-Dimethylphenol 119.1 g, 2,3,5
-Trimethylphenol 40.8 g and 2,6-dimethylphenol 11 g were mixed with 73.5 g of diethylene glycol monomethyl ether and charged into a three-neck flask equipped with a stirrer, a reflux condenser and a thermometer. Then
Add 133.8 g of 37% formalin aqueous solution, 110
The mixture was stirred with heating in an oil bath at ℃. When the internal temperature reached 90 ° C, 9.3 g of oxalic acid dihydrate was added. After that, the temperature of the oil bath was kept at 130 ° C. for 18 hours to continue the reaction, and then the reflux condenser was removed, followed by vacuum distillation at 200 ° C. to remove unreacted monomers. The obtained novolak resin had an Mw of 3830 and a dispersity of 2.36.

Reference Example 9 Synthesis of Photosensitive Material (A) 2,3,4,4′-Tetrahydroxybenzophenone 1
0 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride (41 g) and γ-butyrolactone (400 ml) were charged into a three-necked flask and uniformly dissolved. Then, a mixed solution of triethylamine / acetone = 17 g / 40 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours. 1% of reaction mixture
The solution was poured into 1000 ml of an aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and methanol, and dried (40 ° C.) to recover the photosensitive material (A). The product was analyzed by high performance liquid chromatography (HPLC) to find that it had a wavelength of 254 nm.
81% of the tetra-ester form and 5% of the triester form were observed by the peak area ratio on the chart detected by the absorbance of
%, The balance being the other low substitution products.

Reference Example 10 Synthesis of Photosensitive Material (B) 3,3,3 ′, 3′-Tetramethyl-1,1′-spirobiindane-5,6,7,5 ′, 6 ′, 7′-hexol 10 g 32.5 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 500 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, a mixed solution of triethylamine / acetone = 13.7 g / 50 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% hydrochloric acid aqueous solution, the resulting precipitate was filtered off, washed with water and methanol and dried (40 ° C.) to recover a photosensitive material (B). When the product was analyzed by HPLC, it was found to be a mixture of 86% hexaester and the other low substitution products.

Reference Example 11 Synthesis of Photosensitive Material (C) 2,6-bis (2,3,4-trihydroxybenzyl)
10 g of -p-cresol, 50.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 500 ml of γ-butyrolactone were charged into a three-necked flask and uniformly dissolved. Then triethylamine / acetone = 20.7
A mixed solution of g / 30 ml was gradually added dropwise and reacted at 20 ° C. for 10 hours. The reaction mixture was 1500m in 1% hydrochloric acid aqueous solution
The resulting precipitate was filtered off, washed with water and methanol, and dried (40 ° C.) to recover a photosensitive material (C). When the product was analyzed by HPLC, it was found to be a mixture of 25% heptaester, 58% hexaester, and the other low-substituted products.

The radiation-sensitive resin composition of the present invention was formulated by using the novolak resin prepared in the above Reference Example and the radiation-sensitive compound defined in the present invention in combination with a predetermined low molecular weight compound. Examples of products and comparative examples of resists for comparison are shown.

Examples 1 to 49 and Comparative Examples 1 to 37 The novolac resins (a) to ((a) obtained in Reference Examples 1 to 8 above.
h) and the photosensitive materials (A) obtained in Reference Examples 9 to 11
(C), and further the radiation-sensitive compound (A), the radiation-sensitive compound (B) and the low molecular weight compound defined in the present invention are mixed in the types and amounts shown in Table 1, and this is mixed with ethyl lactate 18
g and ethoxyethyl propionate 4.5 g,
A radiation-sensitive resin composition was prepared by filtration using a 0.1 μm microfilter. The compositions of the radiation-sensitive compounds (A) and (B) such as diesters and triesters of naphthoquinonediazide-5-sulfonic acid in Table 1 are the content values shown in Table 2. This radiation-sensitive resin composition was applied to a silicon wafer using a spinner and dried on a vacuum adsorption type hot plate at 90 ° C. for 60 seconds to obtain a resist film having a film thickness of 0.98 μm. A reduced projection exposure apparatus (NSR-2005i9C manufactured by Nikon Corporation) on this film.
After being exposed to light for 90 seconds, it was heated on a vacuum adsorption type hot plate at 110 ° C. for 90 seconds, developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, washed with water for 30 seconds and dried.

The resist pattern of the silicon wafer thus obtained was observed by a scanning electron microscope to evaluate the radiation-sensitive resin composition. The results are shown in Table 1. Sensitivity was defined as the exposure dose for reproducing a 0.5 μm mask pattern. To evaluate the development latitude, the development time was changed to 40 seconds and 90 seconds, and the same evaluation was performed. The ratio of the sensitivities defined above in both cases was used as an index of the development latitude. The closer this value is to 1.0, the wider the development latitude and the more desirable the result.

The resolving power represents a limiting resolving power in an exposure amount for reproducing a mask pattern of 0.5 μm. In order to evaluate the film thickness dependence, a silicon wafer coated with a film thickness of 1.00 μm for each sample was similarly exposed,
Developed. Film thickness of 0.98 μm and film thickness of 1.00 μm
The ratio of the resolving power of m was used as an index of the film thickness dependence. The closer this ratio is to 1.0, the smaller the film thickness dependency, which is a desirable result.

The development residue was evaluated by observing it with a scanning electron microscope. When the development residue was observed between the resist patterns, it was indicated by x, and when it was not observed, it was indicated by ◯. The heat resistance was shown at a temperature at which a silicone wafer having a resist pattern formed thereon was heated on a hot plate for 4 minutes and the pattern was not deformed.

[0169]

[Table 1]

[0170]

[Table 2]

[0171]

[Table 3]

[0172]

[Table 4]

[0173]

[Table 5]

[0174]

[Table 6]

[0175]

[Table 7]

[0176]

[Table 8]

As described above, the resist samples satisfying the requirements of the present invention exhibit a high film resolving power with less film thickness dependency and development residue, and are superior in development latitude and heat resistance to the resists of Comparative Examples. You can see that

[0178]

The radiation-sensitive resin composition of the present invention is characterized in that it is excellent in film thickness dependence, has a small development residue, and has a high resolution, and has a wide development latitude and high heat resistance. Therefore, it is most preferably used for mass production of semiconductor devices having an ultrafine circuit.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-4-122938 (JP, A) JP-A-5-34917 (JP, A) JP-A-2-103543 (JP, A) JP-A-6- 202321 (JP, A) JP-A-7-28235 (JP, A) JP-A-6-250386 (JP, A) JP-A-6-258827 (JP, A) JP-A-7-175213 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (4)

(57) [Claims] 1. A radiation-sensitive resin composition containing a water-insoluble alkali-soluble resin, a water-insoluble alkali-soluble low molecular weight compound and a radiation-sensitive compound, wherein the radiation-sensitive compound is represented by the following general formula (A ₁ ) and / or ( A ₃ )
Represented by a naphthoquinone diazide sulfonic acid diester compound (A) which is a water-insoluble alkali-soluble low-molecular compound having a phenolic hydroxyl group and three and / or four phenol rings , and the following general formula (B ₁ )
Radiation sensitivity characterized by containing a mixture of a water-insoluble alkali-soluble low molecular weight compound having a phenolic hydroxyl group and 5 to 7 phenol rings with a naphthoquinone diazide sulfonic acid ester compound (B) in an amount of 30% or more of the radiation sensitive compound. Resin composition. [Chemical 1] Here, R _{1 to} R ₈ are each a hydrogen atom, —CN, and —X.
—R _a1 or halogen atom, X _{1 to} X ₂ : single bond,
Rubonyl group, sulfide group, sulfonyl group or-
_Represents C (R _b1 ) (R _b2 )-. However, when 1 = 0, X ₁
Represents a group represented by the following general formula A ₁₁ or A ₁₂ . [Chemical 2] R ₉ , R _{12 to} R ₁₇ , R _b1 , R _b2 : a hydrogen atom and a me
Cyl group, ethyl group or haloalkyl having 1 to 2 carbon atoms
The groups R _b1 and R _b2 are joined together to form an alicyclic hydrocarbon residue.
You may form. R ₁₀ , R ₁₁ , R _a3 , R _a4 , R ₁₈ ,
R ₁₉ : each is a hydrogen atom, —X—R _a1 , —CN or
Halogen atom, X: single bond, -O-, -S-, -CO
-, -OCO-, N ( _Ra1 ) CO-, Xa: carbonyl
Group, sulfide group, sulfonyl group, -C (R _b1 ) (R
_b2 ) -represents. R _a1 : an alkyl group having 1 to 10 carbon atoms,
Aryl group or aralkyl group, Z ₁ : single bond, or
Is a trivalent alicyclic hydrocarbon formed with CR _9.
Group, k, l: 0 or 1, m, n: 1 each
Or 2, q: an integer of _{1 to} 8, D _{1 to} D ₅ : water, respectively
Elemental atom or naphthoquinonediazide-4 or 5-sulfur
Represents a phenyl group. R _{a5 to} R _a7 : each independently hydrogen
Atom, --CN, --X--R _a1 or halogen atom, R ₃₂
To R ₄₃ : each is a hydrogen atom, —CN, —X—R _a1 or
Is a halogen atom, X _{4 to} X ₆ : a single bond, a carbonyl group,
Sulfide group, sulfonyl group or -C (R _b1 ).
_Represents (R _b2 )-. D _{8 to} D ₁₁ : hydrogen atom,
Or naphthoquinonediazide-4 or 5-sulfo
Represents a nyl group. However, the general formula among D _{1 to} D ₃ and D _{8 to} D ₁₁
The radiation-sensitive compounds represented by (A ₁ ) and (A ₃ )
In each case, two in one molecule are naphthoquinonediazide-
4 or 5-sulfonyl group. [Chemical 3] R ₆₂ to R _82: each a hydrogen atom, -CN, even -X-R _a1
Or halogen atom, X _{9 to} X ₁₄ : single bond, carbonyl
Group, sulfide group, sulfonyl group or -C
(R _b1 ) (R _b2 ) _-is represented. D _{17 to} D ₂₃ : Water respectively
Elementary atom, or naphthoquinonediazide-4 or 5-
Represents a sulfonyl group. R _a1 : Alky having 1 to 10 carbon atoms
Represents an alkyl group, an aryl group or an aralkyl. R _b1 , R
_b2 : hydrogen atom, methyl group, ethyl group, carbon number 1 respectively
2 represents a haloalkyl group. R _b1 and R _b2 are each 1
May be bonded to each other to form an alicyclic hydrocarbon residue.
i and j: represent 0 or 1, respectively. 2. The water-insoluble alkali-soluble resin according to claim 1, wherein the resin is phenol, cresol, xylenol,
At least one novolak resin synthesized by condensation reaction of trimethylphenol or a mixture of two or more of these with an aldehyde compound, wherein the weight average molecular weight is 5500 to 25,000. Composition. 3. The water-insoluble alkali-soluble resin according to claim 1, wherein p-cresol, o-cresol, and 2,3.
A radiation-sensitive resin composition, which is at least one novolak resin synthesized by a condensation reaction of a mixture of xylenol, 2,6-xylenol and trimethylphenol with an aldehyde compound. 4. The ratio according to claim 1, wherein the ratio of the phenolic hydroxyl group to the aromatic ring of the water-insoluble alkali-soluble low molecular weight compound is 0.5 to 1.4 and the total number of carbon atoms in one molecule. Is 12 to 50 and is at least one water-insoluble alkali-soluble low molecular weight compound having 2 to 10 phenolic hydroxyl groups in one molecule.