JP4758303B2 - Photoresist film rework method - Google Patents

Description

  The present invention relates to a method for reworking a photoresist film on a substrate on which an antireflection silicon resin film and a photoresist film are sequentially formed.

  In recent years, with the increasing integration and speed of LSIs, there is a need for finer pattern rules. In lithography using light exposure, which is currently used as a general-purpose technology, the essence derived from the wavelength of the light source The resolution limit is approaching.

  As a light source for lithography used in forming a resist pattern, light exposure using a g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source is widely used, but as a means for further miniaturization. A method of shortening the wavelength of exposure light has been considered effective. For this reason, for example, in a mass production process of a 64-Mbit DRAM processing method, a short wavelength KrF excimer laser (248 nm) is used as an exposure light source instead of i-line (365 nm). However, in order to manufacture a DRAM having a degree of integration of 1G or more, which requires a finer processing technique (for example, a processing dimension of 0.13 μm or less), a light source with a shorter wavelength is required, particularly an ArF excimer laser (193 nm). Lithography using a material has been studied.

As a method of forming a pattern on a substrate using such a lithography technique, there is a multilayer resist process.
For example, in order to prevent the resist pattern from deteriorating due to the influence of halation or standing waves, a method of providing an anti-reflection coating (Anti-Reflective Coating) between the substrate and the photoresist film is known.

Further, in order to form a pattern with a high aspect ratio on a stepped substrate, a method is known that uses a substrate in which an organic film is formed on the substrate, a silicon-containing film is formed thereon, and a photoresist film is formed thereon. (See, for example, Non-Patent Document 1). From the viewpoint of resolution, a thinner photoresist film is desirable. On the other hand, it is desirable that the photoresist film is thicker from the viewpoint of the embedding characteristics of the substrate step and the resistance to substrate etching. Therefore, by using three layers as described above, it is possible to divide into a layer with high embedding characteristics of substrate steps and high resistance to dry etching and a layer with high resolution, and a pattern with a high aspect ratio is formed on a substrate with steps. can do.
Here, examples of the silicon-containing film include a spion glass (SOG) film, and many SOG films have been proposed.

  In order to form a pattern on the substrate using such a substrate, first, the pattern circuit region of the photoresist film is exposed, and then developed with a developer to form a resist pattern on the photoresist film. Further, a pattern is formed on the antireflection film or the SOG film using the photoresist film as a mask. In this way, the resist pattern is transferred one after another, and finally a pattern is formed on the substrate.

  However, resist pattern formation may fail, for example, due to striations at the time of applying the resist solution or deviations in the resist pattern after exposure. In such a case, if the pattern is transferred to the substrate while the resist pattern is shifted, the substrate itself becomes defective and the time and labor to that point are wasted.

Therefore, in such a case, the photoresist film and the antireflection film or SOG film below it are removed, the antireflection film or SOG film is formed again, and the photoresist is further formed thereon. A so-called photoresist film rework is performed to form a film.
However, such a conventional method of reworking a photoresist film has a problem that it is complicated and costly.

J. et al. Vac. Sci. Technol. , 16 (6), Nov. / Dec. 1979

  The present invention has been made in view of such problems, and an object of the present invention is to provide a method for reworking a photoresist film that can be performed more simply and at low cost.

The present invention has been made to solve the above problems, and is a method of reworking at least a silicon film for antireflection, and a photoresist film of a substrate on which a photoresist film is sequentially formed, and at least, wherein a solvent while leaving the silicon resin film photoresist film is removed, that provide rework method of a photoresist film, and forming again a photoresist film on the silicone resin film.

  Thus, if the photoresist film is removed while leaving the silicon resin film in the solvent, and the photoresist film is formed again on the silicon resin film, the silicon resin film does not need to be removed. Compared to the above, the photoresist film can be reworked more easily and at a lower cost.

In the photoresist film rework method of the present invention, the anti-reflection silicon resin film is either between the side chain of the silicon resin and the side chain of the silicon resin, or between the side chain of the silicon resin and the silanol group of the silicon resin. It is not preferable to those which form the cross-linked with 1 or more. In this case, cross-linking of the silicone resin film is cross-linkable hydroxyl groups of the side chains of the silicone resin, that is assumed to be formed by any one or more epoxy groups have preferred.

  The silicon resin film for antireflection is such that one or more crosslinks are formed between the side chain of the silicon resin and the side chain of the silicon resin, or between the side chain of the silicon resin and the silanol group of the silicon resin. If present, a better resist pattern can be obtained when a resist pattern is formed on the photoresist film re-formed on the silicon resin film.

In the method for reworking a photoresist film of the present invention, the solvent for removing the photoresist film is a propylene glycol alkyl ether derivative, and one of saturated alkyl ketones having 5 or more carbon atoms is 50% by mass or more. including those, or propylene glycol alkyl ether derivative, it has the preferred to as the number of carbon atoms containing a total of two or more of the five or more saturated alkyl ketone 50 mass% or more. In this case, the propylene glycol alkyl ether derivative, propylene glycol methyl ether, Ru can be made any one or more selected from propylene glycol methyl ether acetate. Further, the carbon number of 5 or more saturated alkyl ketone, cyclopentanone, cyclohexanone, Ru can be made any one or more selected from 5-methyl-2-hexanone.

  Propylene glycol alkyl ether derivative, solvent containing 50% by mass or more of one of saturated alkyl ketones having 5 or more carbon atoms, or propylene glycol alkyl ether derivative, two or more of saturated alkyl ketones having 5 or more carbon atoms If a solvent containing a total of 50% by mass or more is used, only the photoresist film can be removed more beautifully without damaging the underlying silicon resin film.

Further, in the rework process of the photoresist film of the present invention, a substrate for rework of the photoresist film, under the silicone resin film, Ru can be obtained by forming an organic film.

  In recent years, development of a method for forming a pattern on a substrate using a substrate in which a silicon resin film for antireflection on an organic film and a photoresist film on the organic film are sequentially formed has been advanced. The method of reworking a photoresist film of the present invention can be used to rework the photoresist film of such a substrate.

Further, the present invention provides a photoresist in which a resist film is formed on the photoresist film after forming a photoresist film again on the silicon resin film by at least the rework method of the present invention, and the resist pattern is formed. film forming a pattern on the silicone resin film as a mask, that provides a pattern forming method of a silicon resin film having the pattern formed in the mask and forming a pattern on the substrate. In the case where there is an organic film, the present invention at least forms a photoresist film on the silicon resin film again by the rework method of the present invention, and then forms a resist pattern on the photoresist film. A pattern was formed on the silicon resin film using the photoresist film on which the pattern was formed as a mask, and a pattern was formed on the organic film using the silicon resin film on which the pattern was formed as a mask. that provides a pattern forming method of the organic film as a mask and forming a pattern on the substrate.

  When the resist pattern is shifted, etc., the photoresist film is removed while leaving the silicon resin film with a solvent by the rework method of the present invention, and a photoresist film is formed again on the silicon resin film, and then the pattern is formed on the substrate. If the pattern is formed, it is possible to avoid transferring the pattern to the substrate while the resist pattern remains shifted. As a result, a high-quality substrate can be obtained, and the time and labor up to that time can be avoided and the cost can be kept low.

Further, the present invention is that provides a substrate on which a pattern was formed in the pattern forming method of the present invention.

  If a pattern is formed on a substrate by the pattern forming method of the present invention, a substrate on which a highly accurate pattern is formed can be manufactured with high yield.

Furthermore, the present invention is a stripping solvent for dissolving and removing a photoresist film, and at least removes the photoresist film on the antireflection silicon resin film while leaving the silicon resin film. that provides solvent characterized by.

  If the photoresist film is removed while leaving the silicon resin film in such a solvent, and the photoresist film is formed again on the silicon resin film, the photoresist film can be reworked more easily and at a lower cost. Can do.

In this case, the solvent is a propylene glycol alkyl ether derivative, one containing 50 mass% or more of a saturated alkyl ketone having 5 or more carbon atoms, or a propylene glycol alkyl ether derivative, saturated having 5 or more carbon atoms. the in total of two or more of the alkyl ketones is intended to include at least 50 mass% is not preferable. In this case, the propylene glycol alkyl ether derivative of propylene glycol methyl ether, have good based on any one or more selected from propylene glycol methyl ether acetate. Further, the carbon number is 5 or more saturated alkyl ketone, cyclopentanone, cyclohexanone, have good based on any one or more selected from 5-methyl-2-hexanone.

  Thus, among the propylene glycol alkyl ether derivatives, the solvent containing 50% by mass or more of one of the saturated alkyl ketones having 5 or more carbon atoms, or the propylene glycol alkyl ether derivatives and the saturated alkyl ketones having 5 or more carbon atoms By using a solvent containing two or more in total of 50% by mass or more, the photoresist film can be removed more beautifully without damaging the silicon resin film.

  As described above, according to the present invention, the photoresist film is removed while leaving the silicon resin film in the solvent, and the photoresist film is formed again on the silicon resin film. The photoresist film can be reworked at a low cost.

Hereinafter, the present invention will be described in more detail.
As described above, conventionally, when a shift occurs in the resist pattern, in order to rework the photoresist film, all of the photoresist film and the antireflection film under it are removed and an antireflection film is formed again. Further, a photoresist film is formed thereon. In accordance with this, in the case of a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed thereon, in order to rework the photoresist film, both the silicon resin film and the photoresist film are removed, and then again. The common practice is to re-form the silicon resin film and the photoresist film.
The inventors of the present invention have intensively studied to develop a method capable of performing such complicated and expensive reworking of the photoresist film more simply and at a lower cost.
Compared result, the present inventors found that only the photoresist film leaving the antireflection silicone resin film by the solvent is removed, if so as to form again the photoresist film on the silicone resin film, the conventional The present invention has been completed by conceiving that the photoresist film can be reworked more easily and at a lower cost.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
FIG. 1 is an explanatory diagram showing an example of a method for reworking a photoresist film according to the present invention.
First, the substrate used for the rework of the photoresist film is one that failed to form a resist pattern (see FIG. 1A). A substrate 10 in FIG. 1A is a substrate in which an antireflection silicon resin film 12 and a photoresist film 13 are sequentially formed on an organic film 11, but the formation of the resist pattern has failed. .
The failure in forming the resist pattern means, for example, a case where the pattern dimension is out of the standard range or a pattern deviation occurs.
For example, the dimension variation of the resist pattern is managed by, for example, placing a dummy pattern for checking dimensions with a scanning electron microscope (SEM) or a dummy wafer for dimension measurement in one cassette. Then, those that fail to form the resist pattern, such as those whose pattern dimensions are out of the standard range or in which pattern deviation has occurred, are extracted, and the photoresist film is reworked.

Next, the photoresist film 13 is removed with the solvent leaving the silicon resin film 12 (see FIG. 1B).
The stripping solvent for dissolving and removing the photoresist film may be any solvent that can remove at least the photoresist film on the antireflection silicon resin film while leaving the silicon resin film. Examples of such solvents include ketones such as cyclopentanone, cyclohexanone, 5-methyl-2-hexanone, ethyl 2-n-amyl ketone, 4-hydroxy-4-methyl-2-pentanone, and 3-methoxybutanol. , Alcohols such as 3-ethyl 3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol ethyl ether, ethylene glycol monoethyl ether, Ethers such as propylene glycol diethyl ether and diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactic acid ester , Ethyl pyruvate, butyl acetate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, γ-butyrolactone, etc. These lactones can be mentioned, and one of these can be used alone or in admixture of two or more.

Among them, a propylene glycol alkyl ether derivative, a solvent containing 50% by mass or more of one of saturated alkyl ketones having 5 or more carbon atoms, or a propylene glycol alkyl ether derivative or 2 of saturated alkyl ketones having 5 or more carbon atoms. By using a solvent containing at least 50% by mass of one or more, the photoresist film can be removed more neatly with almost no damage to the underlying silicon resin film. In this case, the propylene glycol alkyl ether derivative may be any one or more selected from propylene glycol methyl ether (1-methoxy-2-propanol) and propylene glycol methyl ether acetate. Further, the saturated alkyl ketone having 5 or more carbon atoms may be any one or more selected from cyclopentanone, cyclohexanone, and 5-methyl-2-hexanone.
In addition, it is preferable that a solvent has a flash point of 40 degree | times or more from a viewpoint of the ease of handling. Further, alone even less flash point 40 °, if the flash point when a mixture of two or more of 40 degrees or preferably be used for easier handling.

Next, a photoresist film 13 is formed again on the silicon resin film 12 (see FIG. 1C).
In this way, the photoresist film 13 is removed while leaving the silicon resin film 12 with a solvent, and the photoresist film is formed again on the silicon resin film, so that the silicon resin film need not be removed. Therefore, the photoresist film can be reworked more easily and at a lower cost than in the past.

Here, the substrate 10, the organic film 11, the antireflection silicon resin film 12, and the photoresist film 13 will be described.
The organic film 11 is formed on the substrate 10 by a spin coat method or the like. Since this organic film acts as a mask when etching the substrate 10, it is desirable that the etching resistance is high, and it is required not to mix with the antireflection silicon resin film 12 on the upper layer. It is desirable to crosslink later with heat or acid.

  Further, the antireflection silicon resin film 12 can also be formed on the organic film 11 by spin coating or the like, as with the organic film 11. After application by spin coating or the like, it is desirable to evaporate the organic solvent and to bake to promote the crosslinking reaction in order to prevent mixing with the upper photoresist film 13. The baking temperature is preferably in the range of 80 to 300 ° C., and the baking time is preferably in the range of 10 to 300 seconds.

  Further, after the antireflection silicon resin film 12 is formed, a photoresist film 13 is formed thereon, and the spin coating method is preferably used as in the formation of the organic film 11 and the antireflection silicon resin film 12. . It is preferable to pre-bake after applying the photoresist film material by spin coating or the like. As prebaking conditions, a time range of 10 seconds to 300 seconds in a temperature range of 80 ° C. to 180 ° C. is preferable.

  Examples of the silicon resin film for antireflection include those in which a cross-linkage is formed by any one or more between the side chain of the silicon resin and the side chain of the silicon resin, or between the side chain of the silicon resin and the silanol group of the silicon resin. . In this case, the silicon resin film is preferably cross-linked by at least one of a cross-linkable hydroxyl group and epoxy group in the side chain of the silicon resin.

  Such a silicon resin can be obtained, for example, by hydrolyzing and condensing one kind or a mixture of two or more kinds of silicon-containing compounds represented by the following general formula (1).

（上記式中、Ｒ^１ａは炭素−酸素単結合、炭素−酸素二重結合のうち少なくとも１つを有する有機基であり、Ｒ^２は光吸収基を有する１価の有機基であり、Ｘは同一又は異種のハロゲン原子、水素原子、ヒドロキシ基、炭素数１〜６のアルコキシ基、又は炭素数１〜６のアルキルカルボニルオキシ基である。ｍとｎは各々０〜３の整数であって、０＜（４−ｍ−ｎ）≦４の関係を満足する。）

(In the above formula, R ^1a is an organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group, and X is The same or different halogen atom, hydrogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, or alkylcarbonyloxy group having 1 to 6 carbon atoms, m and n are each an integer of 0 to 3, (The relationship 0 <(4-mn) ≦ 4 is satisfied.)

  The preferable mass average molecular weight of the silicon resin obtained from the silicon-containing compound represented by the general formula (1) is 500 to 1,000,000, more preferably 1000 to 50 in terms of polystyrene as measured based on GPC (gel permeation chromatography). Ten thousand.

  The organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond in the general formula (1) preferably has 2 to 30 carbon atoms, and more preferably an epoxy group, an ester group, One or more organic groups selected from an alkoxy group and a hydroxy group. The organic group means a group containing carbon and may contain hydrogen, nitrogen, sulfur and the like. Examples of the organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond in the general formula (1) include the following.

_{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 -
(In the above formula, P is a hydrogen atom, a hydroxyl group, an epoxy ring (OCH ₂ CH—), an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkyl having 1 to 6 carbon atoms. Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently —C _q H _{2q -p} P _p — (wherein P is the same as above, p is an integer of 0 to 3) Q is an integer from 0 to 10), u is an integer from 0 to 3, and S ₁ and S ₂ are each independently —O—, —CO—, —OCO—, —COO—. Or v0, v2 and v3 each independently represents 0 or 1. An example of T together with these is shown below, although the position where Q ₂ and Q ₃ are bonded to each other in T is not particularly limited. Select as appropriate considering the reactivity due to steric factors and the availability of commercially available reagents used in the reaction. Kill.)

  Preferable examples of the organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond in the general formula (1) include the following. In addition, in the following formula, (Si) is described in order to indicate the bonding site with Si.

  Next, the light absorbing group in the general formula (1) is a group having absorption at a wavelength of 150 to 300 nm, and preferably contains one or more of an anthracene ring, a naphthalene ring, and a benzene ring. Or these rings may have one or more substituents. The substituent is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, or an acetal group having 1 to 6 carbon atoms, more preferably a methyl group or a methoxy group. Group, t-butoxy group, t-amyloxy group, acetoxy group, 1-ethoxyethoxy group and the like. An example of this can be given below.

The methoxy group, acetoxy group, and acetal group of the light absorbing group can be deprotected during polymerization or after polymerization to form a hydroxy group.
In particular, for lithography with a wavelength of 200 nm or less, the light absorbing group preferably contains a benzene ring.

  In addition to the aromatic light absorbing group, a light absorbing group having a Si—Si bond can also be used. Specifically, the following can be mentioned.

The silicon resin of the silicon resin film for antireflection can be synthesized by co-condensing the silicon-containing compound (monomer) represented by the general formula (1) by hydrolysis.
The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid Acids such as sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide , Bases such as choline hydroxide and tetrabutylammonium hydroxide, tetraalkoxytitanium, trialkoxymono (acetylacetonato) titanium, tetraalkoxyzirconium, trialkoxymono (acetylacetonato) zirconium Which metal chelate compound can be mentioned.

  As a reaction operation, water and a catalyst may be dissolved in an organic solvent, and a monomer may be added thereto. At this time, the monomer may be diluted with an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. when dropping the monomer and then raising the temperature to 40 to 80 ° C. for aging is preferable.

As another operation, a water-free catalyst may be dissolved in an organic solvent, and water or water diluted with an organic solvent may be added thereto. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. when dropping the monomer and then raising the temperature to 40 to 80 ° C. for aging is preferable.
As an organic solvent, a water-soluble thing is preferable, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether and mixtures thereof are preferred.

Thereafter, flame soluble or water below SL is adding an organic solvent insoluble, separating the organic solvent layer, removing the washing to used in hydrolytic condensation catalyst. At this time, the catalyst may be neutralized as necessary.

  As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, Ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate Butyl, tert-butyl propionate, propylene glycol mono tert Butyl ether acetate, γ- butyrolactone, and mixtures thereof.

  Thereafter, the organic solvent layer is separated and dehydrated. It is necessary to sufficiently perform the remaining of water in order to advance the condensation reaction of the remaining silanol. Preferable examples include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.

  As another operation method, an organic solvent that is hardly soluble or insoluble in water can also be used as the organic solvent used for the hydrolysis and condensation of the monomer. For example, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Acetate, γ-butyl lactone and A mixture thereof are preferred.

The monomer is dissolved in the organic solvent, and water is added to initiate the hydrolysis reaction.
The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable.

By adjusting the reaction conditions at this time, it is possible to obtain a silicone resin in which the proportion of silicon atoms whose terminals are Si—OH and / or Si—OR is 0.1 to 50 mol%. The terminal group at this time can be easily obtained by using ²⁹ Si-NMR. When the ratio of silicon atoms whose ends are Si—OH and / or Si—OR is A (mol%), the following formula is obtained.

Here, Q ₁ , Q ₂ , Q ₃ , and Q ₄ are the number of siloxane bonds formed by tetrafunctional Si atoms, and T ₁ , T ₂ , and T ₃ are the siloxane bonds formed by trifunctional Si atoms. The numbers D ₁ and D ₂ represent the number of siloxane bonds formed by the bifunctional Si atom. The amount of each bond is calculated by integrating the ²⁹ Si-NMR peak values.

  At this time, when A is 0.1 mol% or less, the number of terminal SiOH and SiOR used for crosslinking of the resin is too small, and the coating film cannot be sufficiently cured, and the resist is used in the next step. Mixing may occur and a resist pattern with good rectangularity may not be obtained. On the other hand, if A is 50 mol% or more, condensation may be insufficient, and only a coating film having a weak strength may be obtained, and a resist pattern may collapse, which may be undesirable.

Furthermore, when A is between 0.1 mol% and 50 mol% and the ratio of Si—OH and Si—OR is a predetermined ratio, a more fully cured coating film can be obtained. That is, more preferably, the ratio is Si—OH / Si—OR = (100/0) to (20/80). At this time, the ratio of —SiOH / —SiOR can be determined using ¹³ C-NMR, using the integrated intensity (B) per one carbon atom at the α-position of the Si atom as an internal standard. That is, determined -SiO C H ₂ -Rx next when the R of -SiOR and Rx-CH _2, Si-OR content from the ratio of integrated intensity of the carbon atoms of the underlined portion (B).

^{In 29} Si-NMR, since the total amount (C) of Si—OH and Si—OR is determined, the ratio of SiOH and SiOR is Si—OH / Si—OR = (C—B) / B.
If the ratio of Si-OR is less than Si-OH / Si-OR = 20/80, condensation between Si-OH and condensation between Si-OH and Si-OR proceed easily and there is sufficient strength. A coating film that hardly generates intermixing can be obtained.

  Further, when an epoxy group is contained in an organic group containing a carbon-oxygen bond, it has an organic group having different types of carbon-oxygen bonds by forming a silicon resin (silicone resin) and then performing a modification reaction. It can be converted into a modified silicon resin (silicone resin). Examples of the repeating unit of the modified silicon resin (silicone resin) are given below.

  Here, Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. Specifically, , Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl Group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, cyclohexylcarbonyl group, methoxy group Examples include carbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, t-butoxycarbonyl group, etc. It can be.

  The conversion from the original silicon resin is possible by a generally known method. For example, it can be easily converted into a modified silicon resin by heating alcohols or carboxylic acids in the presence of an acid, alkali or quaternary ammonium catalyst. In the reaction with carboxylic acids, carboxylic acid itself becomes a catalyst, so there is no need to add a catalyst.

  Acid catalysts used at this time include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, acetic acid, propionic acid Acids such as oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid can be used. Examples of the alkali catalyst include bases such as ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, triethylamine, triethanolamine, benzyldiethylamine, tetraethylammonium hydroxide, choline hydroxide, and tetrabutylammonium hydroxide. Examples of the quaternary ammonium catalyst include benzyltriethylammonium chloride and benzyltriethylammonium bromide.

  The original silicon resin and modified silicon resin thus obtained (hereinafter referred to as silicon resin including both and a blend of both) can also be used by blending. Since the blend ratio at this time greatly affects the performance of the resulting anti-reflection silicon resin film material, it can be blended at an arbitrary ratio so that the performance is maximized. In the obtained mixture, it is more preferable to make the polymer compound into a uniform composition by operations such as heating, stirring, ultrasonic irradiation, and kneading.

  The organic solvent used for the antireflection silicon resin film material may be any organic solvent that can dissolve silicon resin (silicone resin), acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and ethyl 2-n-amyl ketone, 3-methoxybutanol, 3-ethyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2- Alcohols such as propanol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol diethyl ether, ethers such as diethylene glycol diethyl ether, propylene glycol monoethyl ether acetate, Propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, ethyl 3-methoxypropionate, 3-ethoxypropyl Examples include esters such as ethyl pionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. One of these may be used alone or two or more may be used. Although it can be used in mixture, it is not limited to these. Of these organic solvents, diethylene glycol diethyl ether, 1-ethoxy-2-propanol, propylene glycol monoethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used.

  The amount of the organic solvent used is preferably 400 to 10,000 parts by mass, particularly 500 to 5,000 parts by mass with respect to 100 parts by mass of the silicon resin.

  An acid generator can be added to the antireflection silicon resin film in order to further accelerate the crosslinking reaction by heat. The acid generator includes those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added.

As an acid generator to be added,
i. An onium salt of the following general formula (P1a-1), (P1a-2), (P1a-3) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

(In the above formula, R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and having 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, part or all of hydrogen atoms of which may be substituted with an alkoxy group, etc. R ^101b and R ^101c and may form a ring, when they form a ring, R ^101b, .K indicating each is R ^101c alkylene group having 1 to 6 carbon atoms ^- .R ^101d is representative of a non-nucleophilic counter ion R ^101e , R ^101f and R ^101g are represented by adding a hydrogen atom to R ^101a , R ^101b and R ^101c , R ^101d and R ^101e , and R ^101d , R ^101e and R ^101f may form a ring. Well, when forming a ring, R ^101d and R ^101e and R ^101d and R ^101e and R ^101f represent an alkylene group having 3 to 10 carbon atoms.

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylethyl, 4- Examples thereof include an ethylcyclohexyl group, a cyclohexylethyl group, a norbornyl group, an adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Ethylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, diethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like.

Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzene. Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

  (P1a-1) and (P1a-2) have the effects of both a photoacid generator and a thermal acid generator, while (P1a-3) acts as a thermal acid generator.

(In the above formula, R ^102a and R ^102b each independently represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear or branched alkyl group having 1 to 10 carbon atoms. R ^104a and R ^104b each independently represents a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.

Specific examples of R ^102a and R ^102b include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylethyl group, 4-ethylcyclohexyl group, cyclohexylethyl group and the like.

R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like.

^Examples of R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group.

Examples of K ⁻ are the same as those described in the formulas (P1a-1), (P1a-2), and (P1a-3).

(In the above formula, R ¹⁰⁵ and R ¹⁰⁶ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogenated aryl group having 6 to 20 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like.

Examples of the halogenated alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a trifluoroethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, methylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and diethylphenyl group.

Examples of the halogenated aryl group for R ¹⁰⁵ and R ¹⁰⁶ include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group.
^Examples of the aralkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a benzyl group and a phenethyl group.

(In the above formula, R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogen having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ are each independently And represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ¹⁰⁵ is the same as described for P2.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（上記式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

(In the above formula, R ^101a and R ^101b are the same as described above.)

(In the above formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further It may be substituted with a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched group having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or an alkoxy group having 1 to 4 carbon atoms; A phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or substituted with a chlorine atom or a fluorine atom The Even if it is.)

^Examples of the arylene group for R ¹¹⁰ include a 1,2-phenylene group and a 1,8-naphthylene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a phenylethylene group, and a norbornane- 2,3-diyl group etc. are mentioned, As the alkenylene group, 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like can be mentioned.

^Examples of the alkyl group of R ¹¹¹ include the same groups as R ^{101a to} R ^101c, and examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, diethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7 -Octenyl group and the like, and the alkoxyalkyl group includes methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, methoxypropyl group, Ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl , Propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

Examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
Examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, p -Acetylphenyl group, p-nitrophenyl group, etc. are mentioned, As a C3-C5 heteroaromatic group, a pyridyl group, a furyl group, etc. are mentioned.

  Specific examples of onium salts include tetraethylammonium trifluoromethanesulfonate, tetraethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, and p-toluenesulfonic acid. Tetraethylammonium, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoro Triphenylsulfonium lomethanesulfonate, trifluoromethanesulfonic acid (p-tert-butyl) Xylphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (P-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid tri Phenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid triethylsulfonium, p-toluenesulfonic acid Liethylsulfonium, cyclohexylethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, diethylphenylsulfonium trifluoromethanesulfonate, diethylphenylsulfonium p-toluenesulfonate, Dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) ethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ethyl (2- Oxocyclopentyl) sulfonium trifluoromethanesulfona And 1,2′-naphthylcarbonylethyltetrahydrothiophenium triflate.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Etc.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-diethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-ethyl3,4-pentanedione glyoxime, bis -O- (n-butanesulfonyl) -α-diethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n Butanesulfonyl) -2-ethyl 3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-diethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-diethylglyoxime, bis-O -(1,1,1-trifluoroethanesulfonyl) -α-diethylglyoxime, bis-O- (tert-butanesulfonyl) -α-diethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α- Diethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-diethylglyoxime, bis-O- (benzenesulfonyl) -α-diethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-diethylglyoxime Oxime, bis-O- (p-tert-butylbenzenesulfonyl) -α Diethyl glyoxime, bis -O- (xylene sulfonyl)-.alpha.-diethyl glyoxime, bis -O- (camphorsulfonyl)-.alpha.-diethyl glyoxime, and the like.

  Examples of the bissulfone derivative include bisnaphthylsulfonylmethane, bistrifluoroethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.

Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

  Examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Examples include benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-triethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 -Dicarboximide p-toluenesulfonic acid ester etc. are mentioned.

Preferably, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylethyl (2-oxo) (Cyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) ethyl (2-oxocyclohexyl) sulfur Chloride, 1,2'-naphthyl carbonyl ethyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-diethylglyoxime, bis-O- (n-butanesulfonyl) -α-diethylglyoxime,
Bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid A sulfonic acid ester derivative of an N-hydroxyimide compound such as an ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, or N-hydroxynaphthalimide benzenesulfonic acid ester is used.

In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the acid generator is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 40 parts by mass with respect to 100 parts by mass of the silicon resin. If it is 0.1 mass part or more, the amount of acid generation is sufficient, and the crosslinking reaction becomes more sufficient. On the other hand, if the amount is 50 parts by weight or less, the possibility of mixing phenomenon due to the transfer of acid to the upper photoresist film is smaller.

  Moreover, a neutralizing agent can also be added to the silicon resin film for antireflection. The neutralizing agent is a material for preventing the generated acid from diffusing into the photoresist film applied in the next step, for example, at least selected from a methylol group, an alkoxyethyl group, and an acyloxyethyl group. An epoxy compound, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with one group can be exemplified.

  Examples of the neutralizing agent include epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.

  Specific examples of the melamine compound among the neutralizing agents include hexamethylol melamine, hexamethoxyethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxyethylated and a mixture thereof, hexamethoxyethyl melamine, Examples include hexaacyloxyethyl melamine, compounds in which 1 to 5 methylol groups of hexamethylol melamine are acyloxyethylated, or mixtures thereof.

  Among the neutralizing agents, guanamine compounds include tetramethylolguanamine, tetramethoxyethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxyethylated, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine. And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxyethylated, and mixtures thereof.

  Among the neutralizing agents, as the glycoluril compound, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxyethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxyethylated, or its Examples thereof include a mixture, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxyethylated, or a mixture thereof.

Among the neutralizing agents, examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are converted to methoxyethyl group, or a mixture thereof. It is done.
The addition amount of the neutralizing agent is preferably 0 to 50 parts, more preferably 0 to 40 parts with respect to 100 parts (parts by mass) of the silicon resin.

  Next, a known photoresist film material can be used for forming the photoresist film, and for example, a combination of a base resin, an organic solvent, and an acid generator can be used. As the base resin, polyhydroxystyrene and derivatives thereof, polyacrylic acid and derivatives thereof, polymethacrylic acid and derivatives thereof, a copolymer selected from hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof, Three or more copolymers selected from cycloolefin and derivatives thereof and maleic anhydride and acrylic acid and derivatives thereof, three or more copolymers selected from cycloolefin and derivatives thereof and maleimide and acrylic acid and derivatives thereof, polynorbornene And one or more polymers selected from the group consisting of metathesis ring-opening polymers. In addition, the main skeleton remains after the induction, such as acrylic acid derivatives such as acrylic acid esters, methacrylic acid derivatives such as methacrylic acid derivatives, and alkoxystyrenes such as hydroxystyrene derivatives. Means what

  In particular, as a photoresist film material for KrF excimer laser, polyhydroxystyrene (PHS), a copolymer selected from hydroxystyrene, styrene, acrylic acid ester, methacrylic acid ester, and maleimide N carboxylic acid ester Photoresist film materials for ArF excimer laser include polyacrylate ester, polymethacrylate ester, alternating copolymer of norbornene and maleic anhydride, alternating copolymer of tetracyclododecene and maleic anhydride Systems, polynorbornene systems, and metathesis polymerization systems based on ring-opening polymerization, but are not limited to these polymerization polymers.

  In the case of a positive type photoresist film material, it is common to lower the dissolution rate of the unexposed area by replacing the hydroxyl group of the phenol or carboxyl group with an acid labile group. That is, a hydrogen atom of a carboxyl group or a hydrogen atom of a phenolic hydroxyl group is substituted with an acid labile group having an alkali dissolution control ability, and the acid labile group is dissociated by the action of an acid generated by exposure to dissolve in an aqueous alkali solution. Can be used as a positive-type photoresist film material in combination with a base resin that increases the thickness.

  Examples of the organic solvent and acid generator used for the photoresist film material include the same organic solvent and acid generator as those described above for the silicon resin film material. The added amount of each component of the photoresist film material, for example, the added amount of the base resin is the same as the added amount of the silicon resin in the silicon resin film material, and the organic solvent and acid generation used for the photoresist film material The addition amount of the agent is also the same as that of the organic solvent and the acid generator of the silicon resin film material.

  Examples of the resin for the organic film include resins such as cresol novolak, naphthol novolak, catol dicyclopentadiene novolak, amorphous carbon, polyhydroxystyrene, acrylate, methacrylate, polyimide, and polysulfone.

  Further, the substrate 10 used at this time is not particularly limited, and a silicon wafer or the like is used. In the example shown in FIG. 1, the substrate 10 is composed of a layer to be processed 10a on a base layer 10b.

  The thickness of each film is, for example, 50 to 2000 nm for the organic film 11, 10 to 2000 nm for the antireflection silicon resin film 12, and 0.1 to 1 μm (preferably 100 to 500 nm) for the photoresist film 13. It is not limited.

Next, the pattern forming method of the present invention will be described.
FIG. 2 is an explanatory view showing an example of the pattern forming method of the present invention.
As shown in FIG. 1C, after the photoresist film 13 is formed again on the silicon resin film 12 by the rework method of the present invention, first, as shown in FIG. A resist pattern is formed on the photoresist film 13 by exposure, post-exposure baking (PEB), and development with a developer.

Next, as shown in FIG. 2B, the silicon resin film 12 is etched using the patterned photoresist film 13 as a mask, and the resist pattern is transferred to the silicon resin film 12. Form a pattern.
In order to etch the silicon resin film 12 using the photoresist film 13 as a mask, etching is performed using a chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas, or the like. The silicon resin film 12 preferably has a high etching rate with respect to these gases and a small film loss of the upper photoresist film 13.

Next, as shown in FIG. 2C, the pattern formed on the silicon resin film 12 is transferred to the organic film 11 by oxygen plasma etching or the like, and the pattern is formed on the organic film 11. At this time, the photoresist film 13 is also etched away, and the outermost layer becomes the silicon resin film 12.
As the dry etching conditions, in addition to the above-described method using oxygen-containing plasma, a method using hydrogen-nitrogen-containing gas plasma can be used.

Next, as shown in FIG. 2D, the processed layer 10a on the base layer 10b is etched using the organic film 11 on which the pattern is formed as a mask, and the pattern is transferred to the substrate 10. A pattern is formed.
For example, if the layer to be processed 10a is silicon oxide, metal silicon, or the like, fluorine-based dry etching conditions may be used. If fluorine-based dry etching conditions are used, the silicon resin film 12 remaining on the organic film 11 is also removed simultaneously with the etching of the substrate. However, the present invention is not limited to this, and any of the etching conditions used in the single-layer resist method can be used. For example, chlorine-based dry etching may be performed.
Note that after the pattern is formed on the substrate 10 by the above steps, the organic film 11 remaining on the substrate 10 can be removed by, for example, etching with oxygen plasma or hydrogen-nitrogen.

  For example, when the resist pattern is shifted, the photoresist film is removed with the solvent by the rework method of the present invention while leaving the silicon resin film, and a photoresist film is formed again on the silicon resin film. If the pattern is formed on the substrate as described above, it is possible to avoid transferring the pattern to the substrate while the resist pattern is shifted, and it is possible to perform rework at a low cost. Therefore, the time and labor up to that time will not be wasted.

Next, another example of the pattern forming method of the present invention will be described with reference to FIG.
The substrate 30 is formed by sequentially forming an antireflection silicon resin film 32 and a photoresist film 33 thereon, but no organic film is formed between the substrate 30 and the antireflection silicon resin film 32.
After the photoresist film 33 is formed again on the silicon resin film 32 by the photoresist film reworking method of the present invention, first, as shown in FIG. 3A, the pattern circuit region is exposed and post-exposure baking is performed. (PEB) A resist pattern is formed on the photoresist film 33 by development with a developer.

  Next, as shown in FIG. 3B, the silicon resin film 32 is etched using the photoresist film 33 on which the resist pattern is formed as a mask, and the resist pattern is transferred to the silicon resin film 32. Form a pattern. In order to etch the silicon resin film 32 using the photoresist film 33 on which the resist pattern is formed as a mask, etching is performed using a chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas, or the like.

Next, as shown in FIG. 3C, the substrate 30 is etched using the silicon resin film 32 on which the pattern is formed as a mask, the pattern is transferred to the substrate 30, and the pattern is formed on the substrate 30. In order to etch the substrate 30 using the silicon resin film 32 on which the pattern is formed as a mask, if the layer 30a to be processed on the base layer 30b is SiO ₂ or SiN, etching mainly using a fluorocarbon gas, p-Si For (p-type Si), Al, and W, etching is mainly performed using a chlorine-based or bromine-based gas. The silicon resin film 32 is excellent in etching resistance to chlorine and bromine, and is preferably applicable as a hard mask, particularly when the layer 30a to be processed is p-Si, Al, W, or the like. In the case where the layer 30a to be processed is a SiO ₂ or SiN film, the silicon resin film 32 has a higher etching rate than the photoresist film 33 but is slower than the substrate 30 and can function as a hard mask. preferable.

  When a pattern is created by etching away the layer 30a to be processed of the substrate 30, the photoresist film 33 may be used as a mask, or the silicon resin film 32 on which the pattern is formed may be processed as a mask.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these description.
Example 1
[Preparation of silicon resin film material]
A 3000 ml glass flask was charged with 1400 g of ethanol, 700 g of pure water, and 50 g of a 25 mass% tetramethylammonium hydroxide aqueous solution and stirred. To this mixture, a mixture of 139 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 32 g of phenyltrimethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. Under reduced pressure, Polymer 1 was obtained.

The weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.
Subsequently, the ratio of terminal groups was measured by ²⁹ Si-NMR, and A was calculated to be A = 3.2%. Si-OH / Si-OR was calculated by ¹³ C-NMR, and Si-OH / Si-OR = 100/0.

  The polymer 1 synthesized as described above is dissolved in a ratio of polymer 1: 100 parts by mass, organic solvent: 2000 parts by mass, acid generator: 0.3 parts by mass, and surfactant: 0.5 parts by mass. A silicon resin film material was prepared by filtering through a 0.1 μm fluororesin filter.

界面活性剤：ＦＣ−４３０（住友スリーエム社製） Each composition in the silicon resin film material is as follows.
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
Acid generator: AG1 (see structural formula below)

Surfactant: FC-430 (manufactured by Sumitomo 3M)

[Preparation of photoresist film material]
The following resin, photoacid generator and basic additive are dissolved in an organic solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Ltd.) and filtered with a 0.1 μm fluororesin filter. By filtering, a photoresist film material for ArF excimer laser light exposure was prepared.

光酸発生剤：トリフェニルスルホニウムノナフルオロブタンスルホネート
０．２質量部
塩基性添加物：トリエタノールアミン ０．０２質量部
有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
２００質量部 Resin: Polymer 2 (see structural formula below) 10 parts by mass

Photoacid generator: Triphenylsulfonium nonafluorobutanesulfonate
0.2 parts by mass Basic additive: Triethanolamine 0.02 parts by mass Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
200 parts by mass

[Preparation of organic film materials]
As an organic film material, a 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin (molecular weight 11000) -containing material (resin 28 parts by mass, solvent 100 parts by mass) was prepared.

[Pattern formation]
First, the above-prepared organic film material was spin-coated on a substrate and heated to 200 ° C. for 1 minute to form an organic film having a thickness of 300 nm.
Next, the prepared silicon resin film material was spin-coated on the organic film and baked at 180 ° C. for 60 seconds to form a silicon resin film having a thickness of 100 nm.
Further, the prepared photoresist film material was applied on the silicon resin film and baked at 130 ° C. for 60 seconds to form a 200 nm-thick photoresist film.
Thus, a substrate was prepared in which an antireflection silicon resin film was formed on an organic film and a photoresist film was formed thereon.

Next, the film was exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 ring illumination, Cr mask), baked at 110 ° C. for 90 seconds (PEB), and 2.38% by mass. Development was performed with an aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a positive pattern.
Observation of the obtained 90 nm L / S resist pattern revealed that the pattern dimension was different from the standard dimension.
At the same time, we observed the presence or absence of skirting, undercut, and intermixing phenomena near the silicon resin film for those with pattern dimensions within the standards, but there was no skirting, undercutting, or intermixing phenomenon, and the resist pattern shape Was confirmed to be good.

Next, the pattern dimension different from the standard dimension was extracted, and the photoresist film was removed while leaving the silicon resin film with a solvent. At this time, the solvent used is a solvent containing 70% by mass of propylene glycol methyl ether and 30% by mass of cyclohexanone.
Then, the prepared photoresist film material was again applied on the silicon resin film, and baked at 130 ° C. for 60 seconds to form a 200 nm-thick photoresist film.
Since it was not necessary to remove the silicon resin film, the photoresist film could be reworked easily and at low cost.

Next, a resist pattern was formed on the reworked photoresist film in the same manner as described above.
When the obtained resist pattern was observed, the pattern dimension was within the standard dimension.
Therefore, the presence or absence of tailing, undercut, and intermixing phenomenon in the vicinity of the silicon resin film was observed. As a result, it was found that the pattern shapes before and after reworking were good without any tailing, undercutting, or intermixing phenomenon.

Next, using this resist pattern as an etching mask, etching was performed under dry etching conditions in which the etching rate of the silicon resin film was superior to the organic material. As conditions, a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd. was used, chamber pressure 40 Pa, RF power 1300 W, gap 9 mm, CHF ₃ gas flow rate 30 ml / min, CF ₄ gas flow rate 30 ml / min, ArF gas flow rate 100 ml / min. used. By etching the antireflection silicon resin film by this dry etching, it was possible to form a pattern on the antireflection silicon resin film with almost no influence of the pattern change due to the side etching of the photoresist film.
Next, the substrate having the silicon resin film to which the pattern was transferred in this manner was further subjected to dry etching in which the etching rate of the lower organic film was significantly higher than the silicon resin film. As conditions, reactive dry etching using oxygen plasma (chamber pressure 60 Pa, RF power 600 W, Ar gas flow rate 40 sccm, O ₂ gas flow rate 60 sccm, gap 9 mm) was used. By this reactive dry etching, the exposure pattern obtained as a resist pattern was transferred to the lower organic film with high accuracy.
Next, the substrate was etched using the organic film having the pattern transferred in this way as an etching mask to form a pattern on the substrate. At this time, since the layer to be processed of the substrate was silicon oxide, fluorine dry etching conditions were used. Under the dry etching conditions, the antireflection silicon resin film on the organic film was removed by etching simultaneously with the processed layer of the substrate.
Thereafter, the organic film remaining on the substrate was removed by etching with oxygen gas plasma.
When the pattern formed on the substrate was observed, it was found that a good pattern was formed.

(Example 2)
In Example 1, as a solvent used for removing the photoresist film at the time of reworking the photoresist film, instead of the solvent containing 70% by mass of propylene glycol methyl ether and 30% by mass of cyclohexanone, propylene glycol methyl ether 30 Rework of photoresist film and formation of resist pattern in the same manner as in Example 1 except that a solvent containing 40% by mass, 40% by mass of cyclohexanone, and 30% by mass of 4-hydroxy-4-methyl-2-pentanone was used. Then, pattern formation on the substrate was performed.
As a result, since it is not necessary to remove the silicon resin film during rework, the photoresist film can be reworked easily and at low cost.
Further, when the obtained resist pattern was observed, it was found that the pattern shapes before and after reworking were all good without any tailing, undercutting, or intermixing phenomenon.
Furthermore, when the pattern formed on the substrate was observed, it was found that a good pattern was formed.

(Example 3)
In Example 1, as a solvent used for removing the photoresist film at the time of reworking the photoresist film, instead of the solvent containing 70% by mass of propylene glycol methyl ether and 30% by mass of cyclohexanone, propylene glycol methyl ether 30 Except for using a solvent containing 40% by mass, 40% by mass of cyclohexanone, and 30% by mass of ethyl lactate, reworking a photoresist film, forming a resist pattern, forming a pattern on a substrate, etc. in the same manner as in Example 1. went.
As a result, since it is not necessary to remove the silicon resin film during rework, the photoresist film can be reworked easily and at low cost.
Further, when the obtained resist pattern was observed, it was found that the pattern shapes before and after reworking were all good without any tailing, undercutting, or intermixing phenomenon.
Furthermore, when the pattern formed on the substrate was observed, it was found that a good pattern was formed.

Example 4
In Example 1, as a solvent used for removing the photoresist film during rework of the photoresist film, instead of a solvent containing 70% by mass of propylene glycol methyl ether and 30% by mass of cyclohexanone, propylene glycol methyl ether acetate Except for using a solvent containing 70% by mass and 30% by mass of cyclohexanone, rework of a photoresist film, formation of a resist pattern, pattern formation on a substrate, and the like were performed in the same manner as in Example 1.
As a result, since it is not necessary to remove the silicon resin film during rework, the photoresist film can be reworked easily and at low cost.
Further, when the obtained resist pattern was observed, it was found that the pattern shapes before and after reworking were all good without any tailing, undercutting, or intermixing phenomenon.
Furthermore, when the pattern formed on the substrate was observed, it was found that a good pattern was formed.

(Comparative Example 1)
On the substrate, ARC29A (manufactured by Brewer Science), which is a commercially available antireflection film material that is not a silicon resin, was spin-coated and baked at 200 ° C. for 60 seconds to form an antireflection film having a thickness of 80 nm. ARC29A is a product that has been frequently used as an antireflection film for ArF photoresist.
Next, the same photoresist film material as used in Example 1 was applied on the antireflection film, and baked at 130 ° C. for 60 seconds to form a 200 nm-thick photoresist film.
In this way, a substrate on which an antireflection film and a photoresist film were sequentially formed thereon was prepared.

Next, the film was exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 ring illumination, Cr mask), baked at 110 ° C. for 90 seconds (PEB), and 2.38% by mass. Development was performed with an aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a positive pattern.
Observation of the obtained 90 nm L / S resist pattern revealed that the pattern dimension was different from the standard dimension.

Next, a pattern having a pattern size different from the standard size was extracted, and both the antireflection film and the photoresist film were removed.
Then, an antireflection film and a photoresist film were formed again on the substrate.
This method removes even the antireflection film to rework the photoresist film, and is complicated and expensive.

A part of the pattern having a pattern size different from the standard size was extracted, and only the photoresist film was removed with cyclohexanone.
Then, a photoresist film was formed again on the antireflection film.
Next, a resist pattern was formed on the reworked photoresist film in the same manner as described above.
When the shape of the obtained resist pattern was observed, it was observed that the footing near the antireflection film was severe.
For this reason, it was found that in the case of an antireflection film formed using ARC29, it is necessary to remove both the antireflection film and the photoresist film in order to form a good pattern on the substrate.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

It is explanatory drawing which shows an example of the rework method of the photoresist film of this invention. It is explanatory drawing which shows an example of the pattern formation method of this invention. It is explanatory drawing which shows another example of the pattern formation method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 30 ... Board | substrate, 10a, 30a ... Processed layer, 10b, 30b ... Underlayer 11 ... Organic film | membrane 12, 32 ... Silicon resin film for reflection prevention,
13, 33 ... Photoresist film.

Claims (5)

At least a method of reworking a photoresist film on a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed thereon,
The antireflection silicon resin film has a cross-link formed between any one side chain of the silicon resin and the side chain of the silicon resin, between the side chain of the silicon resin and the silanol group of the silicon resin, and A silicon resin is obtained by hydrolyzing and condensing a mixture of one or more of the silicon-containing compounds represented by the following general formula (1),

(In the above formula, R ^1a is an organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group, and X is The same or different halogen atom, hydrogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, or alkylcarbonyloxy group having 1 to 6 carbon atoms, m and n are each an integer of 0 to 3, (The relationship 0 <(4-mn) ≦ 4 is satisfied.)
The photoresist film is made of polyhydroxystyrene and derivatives thereof, polyacrylic acid and derivatives thereof, polymethacrylic acid and derivatives thereof, a copolymer formed by hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof, Three or more copolymers selected from olefins and derivatives thereof and maleic anhydride and acrylic acid and derivatives thereof, three or more copolymers selected from cycloolefin and derivatives thereof and maleimide and acrylic acid and derivatives thereof, polynorbornene, And a photo resist film material which is a combination of a base resin consisting of one or more polymers selected from the group consisting of a metathesis ring-opening polymer, an organic solvent and an acid generator,
At least one propylene glycol alkyl ether derivative selected from propylene glycol methyl ether, propylene glycol methyl ether acetate, and one or more carbons selected from cyclopentanone, cyclohexanone, and 5-methyl-2-hexanone. The photoresist film is removed while leaving the silicon resin film in a solvent composed of a saturated alkyl ketone having 5 or more, and a photoresist film is formed again on the silicon resin film. Membrane rework method. The method for reworking a photoresist film according to claim 1 , wherein an organic film is formed under the silicon resin film on the substrate on which the photoresist film is reworked. At least after forming a photoresist film again on the silicon resin film by the rework method according to claim 1 , a resist pattern is formed on the photoresist film, and the photoresist film on which the resist pattern is formed is used as a mask. Forming a pattern on the silicon resin film, and forming the pattern on the substrate using the silicon resin film on which the pattern is formed as a mask. At least after forming a photoresist film again on the silicon resin film by the rework method according to claim 2, a resist pattern is formed on the photoresist film, and the photoresist film on which the resist pattern is formed is used as a mask. A pattern is formed on the silicon resin film, a pattern is formed on the organic film using the silicon resin film on which the pattern is formed as a mask, and a pattern is formed on the substrate using the organic film on which the pattern is formed as a mask. A pattern forming method comprising forming the pattern. Polyhydroxystyrene and its derivatives, polyacrylic acid and its derivatives, polymethacrylic acid and its derivatives, copolymers formed from hydroxystyrene, acrylic acid, methacrylic acid and their derivatives, cycloolefin and its derivatives and anhydrous Three or more copolymers selected from maleic acid and acrylic acid and derivatives thereof, cycloolefin and derivatives thereof and three or more copolymers selected from maleimide and acrylic acid and derivatives thereof, polynorbornene, and metathesis ring-opening polymers A stripping solvent for dissolving and removing a photoresist film obtained from a photoresist film material that is a combination of a base resin composed of one or more polymers selected from the group consisting of: an organic solvent and an acid generator ,
At least one of the side chains of the silicon resin and the side chains of the silicon resin, or between the side chain of the silicon resin and the silanol group of the silicon resin forms a cross-link. A photoresist film on an antireflective silicon resin film obtained by hydrolysis and condensation of one or a mixture of two or more silicon-containing compounds represented by (1), leaving the silicon resin film intact Any one or more of propylene glycol alkyl ether derivatives selected from propylene glycol methyl ether and propylene glycol methyl ether acetate and selected from cyclopentanone, cyclohexanone and 5-methyl-2-hexanone and characterized in that the one or more carbon atoms composed of 5 or more saturated alkyl ketones Solvents that.

(In the above formula, R ^1a is an organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group, and X is The same or different halogen atom, hydrogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, or alkylcarbonyloxy group having 1 to 6 carbon atoms, m and n are each an integer of 0 to 3, (The relationship 0 <(4-mn) ≦ 4 is satisfied.)

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