JP2007164148A - Silicon-containing film forming composition for etching mask, silicon-containing film for etching mask, and substrate processing intermediate and processed substrate processing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon-containing film for an etching mask, a silicon-containing film forming composition for an etching mask which can form a film by spin coating, forms a resist film thereon with an excellent resist pattern, and has a high etching selectivity relative to organic films because of its relatively high silicon content, and to provide a substrate processing intermediate and a processed substrate processing method using the same. <P>SOLUTION: The silicon-containing film forming composition for an etching mask is used for an intermediate film in a multilayer resist process for forming in sequence an undercoat film, a silicon-containing film and a photoresist film on a processed substrate, and applying etching in multiple stages, wherein the silicon-containing film forming composition comprises a silicon-containing polymer obtained through hydrolytic condensation of one or a mixture of hydrolyzable silanes including an Si-Si bond-containing silane compound represented by the formula (1): R<SB>(6-m)</SB>Si<SB>2</SB>X<SB>m</SB>, wherein R is a monovalent hydrocarbon group; X is alkoxy, alkanoyloxy or halogen; and m is 3-6. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silicon-containing film-forming composition suitable for a silicon-containing film used as an intermediate layer of a multilayer resist method used for microfabrication in a manufacturing process of a semiconductor element, etc., a silicon-containing film, and a workpiece to be processed using the same The present invention relates to a substrate processing method.

  With the higher integration and higher speed of LSIs, pattern dimensions are rapidly becoming finer. Along with this miniaturization, the lithography technology has achieved the formation of a fine pattern by shortening the wavelength of the light source and appropriately selecting the resist composition corresponding thereto. At the center of this is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition should have a resist structure in which the resist resin has a skeleton that is resistant to etching by chlorine-based or fluorine-based gas plasma, and the exposed portion is dissolved. Thus, the exposed portion is dissolved to form a pattern, and the substrate to be processed to which the resist composition is applied is etched using the remaining resist pattern as an etching mask.

  However, when the film thickness of the photoresist film to be used is made finer as it is, that is, when the pattern width is made smaller, the resolution performance of the photoresist film is lowered, and when trying to pattern develop the photoresist film with a developer, The so-called aspect ratio becomes too large, resulting in pattern collapse. For this reason, the photoresist film thickness has been reduced with the miniaturization.

On the other hand, a method of processing a substrate by dry etching using a patterned photoresist film as an etching mask is usually used for processing a substrate to be processed. However, in reality, the substrate is processed between the photoresist film and the substrate to be processed. Since there is no etching method that can achieve complete etching selectivity, the resist film is damaged during the processing of the substrate, the resist film collapses during the processing of the substrate, and the resist pattern cannot be accurately transferred to the substrate to be processed. . Therefore, with the miniaturization of the pattern, higher etching resistance is required for the resist material.
On the other hand, since the resin used for the photoresist composition by shortening the exposure wavelength is required to be a resin having low light absorption at the exposure wavelength, novolak resin, polyhydroxystyrene is used against changes to i-line, KrF, and ArF. However, it has been changed to a resin having an aliphatic polycyclic skeleton, but in reality, the etching rate under the above etching conditions has become faster, and a recent photoresist composition with high resolution is high. Rather, the etching resistance tends to be low.
For this reason, it is necessary to etch the substrate to be processed with a thinner and less resistant photoresist film, and it is an urgent task to secure materials and processes in this processing step.

  One method for solving such problems is a multilayer resist method. In this method, a photoresist film, that is, an intermediate film having etching selectivity different from that of the resist upper layer film is interposed between the resist upper layer film and the substrate to be processed to obtain a pattern on the resist upper layer film, and then the upper resist pattern is etched into the etching mask. In this method, the pattern is transferred to the intermediate film by dry etching, and further the pattern is transferred to the substrate to be processed by dry etching using the intermediate film as an etching mask.

  In the two-layer resist method, which is one of the multilayer resist methods, for example, there is a method in which a silicon-containing resin is used for the upper layer resist material and a novolac resin is used as the intermediate film (for example, Patent Document 1: Japanese Patent Laid-Open No. 6-1994). -95385). Silicon resin exhibits good etching resistance against reactive etching by oxygen plasma, but is easily removed by etching using fluorine-based gas plasma. On the other hand, novolak resin is easily removed by reactive etching using oxygen gas plasma, but exhibits good etching resistance against etching using fluorine-based gas plasma or chlorine-based gas plasma. Therefore, after forming a novolac resin film as a resist intermediate film on the substrate to be processed and forming a resist upper layer film using a silicon-containing resin thereon, the silicon-containing resist film is irradiated with energy rays and developed. The pattern is formed by treatment, and the pattern is transferred to the novolac film by etching away the novolac resin where the resist pattern has been removed by reactive etching with oxygen plasma using the etching mask as an etching mask. Using the pattern as an etching mask, pattern transfer can be performed on the substrate to be processed by dry etching using fluorine-based gas plasma or chlorine-based gas plasma.

  Also, in dry etching, when the etching resistance of the etching mask is sufficient, a transfer pattern with a relatively good shape can be obtained, and problems such as pattern collapse due to friction caused by a developing solution during resist development occur. Since it is difficult, a pattern with a relatively high aspect ratio can be obtained. For this reason, for example, when a resist film using a novolac resin is made to have a thickness corresponding to the film thickness of the intermediate film, it has a fine pattern that could not be directly formed due to a pattern collapse during development due to an aspect ratio problem. On the other hand, according to the above two-layer resist method, a novolak resin pattern having a sufficient thickness as an etching mask for a substrate to be processed can be obtained.

  Further, as a multilayer resist method, there is a three-layer resist method that can be performed using a general resist composition used in a single layer resist method. In this case, for example, an organic film made of novolak or the like is formed as a resist underlayer film on a substrate to be processed, and a silicon-containing film such as SOG (spin-on-glass) is formed thereon as an intermediate film, and is usually formed thereon. The organic resist film is formed as a resist upper layer film. For dry etching with fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity with respect to SOG. Therefore, the resist pattern is formed on the SOG film by using dry etching with fluorine-based gas plasma. Transcribed. According to this method, it is difficult to form a pattern having a sufficient film thickness for directly processing a substrate to be processed, or a resist composition having insufficient etching resistance for processing a substrate. Even if it is used, if the pattern can be transferred to the SOG film, a pattern of a novolak film having sufficient etching resistance for processing can be obtained as in the case of the two-layer resist method.

As described above, in the three-layer resist method, a silicon-containing film is used as an intermediate film. As the intermediate film, a silicon-containing inorganic film formed by CVD, for example, an SiO ₂ film (for example, Patent Document 2: JP-A-7-183194). Etc.), SiON films (for example, Patent Document 3: JP-A-7-181688, etc.), and SOG films (for example, Patent Document 4: JP-A-5-291208) can be obtained by spin coating. Etc.) and crosslinkable silsesquioxane films (for example, Patent Document 5: JP 2005-520354 A) are used, and polysilane films (for example, Patent Document 6: Japanese Patent Laid-Open No. 11-60735) are used. Etc.) could also be used. Among these, the SiO ₂ film and the SiON film have a high performance as an etching mask when dry etching a lower organic film, but require a special apparatus for film formation. On the other hand, the SOG film, the crosslinkable silsesquioxane film, and the polysilane film can be formed only by spin coating and heating, and high process efficiency can be obtained.

  The application range of the multilayer resist method is not limited to an attempt to increase the resolution limit of the resist film. Like the via-first method, which is one of the substrate processing methods, if the processed intermediate substrate has a large level difference, there is a large difference in resist film thickness when trying to form a pattern with a single resist film. There arises a problem that the focus cannot be accurately adjusted during exposure. In such a case, the step is filled with a sacrificial film and planarized, and then a resist film is formed thereon to form a resist pattern. In this case, however, the above-described multilayer resist method is inevitably required. (For example, Patent Document 7: Japanese Patent Application Laid-Open No. 2004-349572, etc.).

  When the three-layer resist method is used, the silicon-containing film obtained by spin coating can be used as an intermediate film to improve the efficiency of the process. However, the silicon-containing films that have been conventionally used have several problems. is there.

  For example, it is well known that when a resist pattern is formed by photolithography, the exposure light is reflected by the substrate and interferes with the incident light to cause a so-called standing wave problem. In order to obtain a fine pattern with no reflection, it is necessary to insert an antireflection film as an intermediate film. Therefore, in the three-layer resist method, it is necessary to put an organic antireflection film between the resist upper layer film and the silicon-containing intermediate film. However, when it is inserted, organic reflection is performed using the resist upper layer film as an etching mask. The prevention film needs to be patterned, and a load is applied to the resist upper layer film during dry etching. Conventionally, in order not to cause this load, a technique of giving a light-absorbing structure such as an aromatic structure to a silicon-containing intermediate film has been used (Patent Document 8: JP-A-2005-15779).

  However, an organic structure such as anthracene that absorbs light efficiently works to reduce the etching rate by dry etching with fluorine-based gas plasma, and performs dry etching of a silicon-containing film without imposing a load on the resist film. This is a disadvantageous direction. Therefore, it is not preferable to add such a substituent in a large amount.

  Furthermore, the etching rate of the intermediate film with respect to the reactive etching by oxygen gas plasma generally used when processing the resist underlayer film using the silicon-containing intermediate film as an etching mask is the etching selectivity ratio between the resist intermediate film and the underlayer film. In order to increase the thickness, it is preferably smaller, and for that purpose, it is desirable that the silicon content is as high as possible. However, if the side chain is designed to have a function such as a light absorption skeleton, the proportion of the side chain increases, and the silicon content decreases.

  On the other hand, it is disclosed in Patent Document 9 (Japanese Patent Laid-Open No. 2003-140352) that polysilanes can achieve a relatively high silicon content and become a suitable antireflection film material. In addition, the silicon-silicon bond is preferable as a silicon-containing intermediate film having an antireflection function because it absorbs long-wavelength light, whereas the silicon-oxygen-silicon bond is transparent up to light having a considerably short wavelength. It was. However, polysilanes were observed to undergo a phenomenon in which the main chain silicon-silicon bond was cleaved under halogen-based etching conditions, converted to a low molecular component, the film strength was lowered, and the etching pattern was collapsed.

JP-A-6-95385 JP-A-7-183194 JP-A-7-181688 Japanese Patent Laid-Open No. 5-291208 JP 2005-520354 A Japanese Patent Laid-Open No. 11-60735 JP 2004-349572 A JP-A-2005-15779 JP 2003-140352 A Japanese Patent Laid-Open No. 5-310942 JP-A-9-73173 JP 2003-84438 A International Publication No. 00/01684 Pamphlet JP 2000-159758 A JP-A-8-12626 JP 2005-146252 A JP 2005-128509 A JP 2004-153125 A complete organic organic chemistry vol. 2,389 (1982) Polym. Mater. Sci. Eng. 1997. 77. pp449

  Therefore, an object of the present invention is to form a film by spin coating, and when a resist pattern is formed after forming a resist film thereon, a good pattern can be formed and has a relatively high silicon content. Provided are a silicon-containing film for an etching mask and a composition for forming a silicon-containing film for an etching mask, and a substrate processing intermediate using the same and a processing method for a substrate to be processed, which can obtain high etching selectivity with an organic film. It is in.

  Polysilsesquioxane having a Si—Si bond is disclosed in Patent Document 10 (Japanese Patent Laid-Open No. 5-310942), and although the mechanism is not disclosed in detail, it is used as a photoresist composition or a photoreactive material. It has been suggested that it can be used. When the present inventors use such a material for the silicon-containing film for an etching mask of the three-layer resist method as described above instead of the resist film itself, it can be a method for solving the above-mentioned problems. In particular, as a result of intensive studies, a hydrolyzable condensate of a hydrolyzable silane represented by the following general formula (1), including the polysilsesquioxane having a relatively small side chain, It has been found that a cohydrolyzed condensate with a hydrolyzable silane represented by the following general formula (2) is a material suitable for solving the above problems. In particular, when compared with conventional polysilane antireflection coatings, even if silicon-silicon bonds are cleaved under halogen-based etching conditions, there are very many siloxane bonds, which are very strong bonds, so the etching pattern is The present inventors have found that a film can be processed without collapsing, and have made the present invention.

That is, the present invention provides an intermediate layer of a multilayer resist method in which a lower layer film is formed on a substrate to be processed, a silicon-containing film is formed thereon, a photoresist film is further formed thereon, and then a multi-stage etching is performed. In the silicon-containing film-forming composition used for the film, at least one of the following general formula (1)
R _(6-m) Si ₂ X _m (1)
(R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, X is an alkoxy group, an alkanoyloxy group or a halogen atom, R and X may be the same or different substituents, and m is 6 ≧ m ≧ 3.)
A silicon-containing film for an etching mask, comprising a silicon-containing polymer obtained by hydrolytic condensation of a hydrolyzable silane alone or in a mixture containing a silane compound having a silicon-silicon bond represented by A composition is provided.

Further, as one of preferred embodiments, the silicon-containing polymer is further added to the following general formula (2) in addition to the silane compound represented by the general formula (1).
A _a SiB _(4-a) (2)
(A is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, B is an alkoxy group, an alkanoyloxy group or a halogen atom, and A and B may be the same or different substituents, a is 0 or 1.)
A silicon-containing film-forming composition for an etching mask, which is a silicon-containing polymer obtained by hydrolytic condensation of a mixture of hydrolyzable silanes containing the hydrolyzable silane compound represented by

  Moreover, when using the silane compound shown by multiple types of general formula (1), in the silane compound shown by the general formula (1) to be used, if m is 4 or 3, the coating property is Therefore, a polymer excellent in storage stability can be obtained. When m is 5 or 6 as a main component, when hydrolyzing and condensing the silane compound, the amount of residual silanol increases too much, resulting in recombination of silanols during storage, creating foreign matter, and coating In some cases, the film thickness of the liquid increases, resulting in a decrease in coating properties and storage stability.

  Furthermore, when using the multiple types of silane compound shown by General formula (1), among the silane compounds shown by General formula (1), the mixing ratio of the silane compound whose m is 4 and the silane compound whose m is 3 Can be obtained in a molar ratio of 3: 7 to 7: 3. Of course, this depends on the selection of R, but m = 4 gives a polar effect to the surface, makes it difficult for the upper resist film to collapse, and widens the process window. When the number m = 3 increases, the oil repellency, which is a characteristic of the silicone resin, increases, and striation may occur when the upper resist film is applied. On the other hand, when the number of m = 4 is too large, as described above, the residual amount of silanol in the polymer tends to increase, which may cause a decrease in storage stability.

  In addition, when the silicon-containing polymer contained has a weight average molecular weight exceeding 20,000, the coating property tends to be lowered. Depending on the case, foreign matter may be generated or application spots may occur, and the weight average molecular weight may be 20 It is preferable to use a polymer having a weight average molecular weight of 500 or less, and a film having a weight average molecular weight of 500 or less accounts for more than 5% by mass of the entire silicon-containing polymer. A coating film with poor uniformity may be obtained.

  Further, the silicon-containing polymer contained is 0.45 ≦ L / (L + M + N, where L is the number of Si—O bonds in the polymer, M is the number of Si—Si bonds, and N is the number of Si—C bonds. ) When the raw material silane compound is selected so as to satisfy ≦ 0.95, the etching resistance when the substrate is processed by oxygen RIE (oxygen reactive etching) becomes higher.

The silicon content of the silicon-containing polymer is defined as follows.
In the case of the hydrolyzable silicon-containing monomer of the general formula (1), the reaction formula obtained when fully hydrolyzed by adding sufficient water is:
R _(6-m) Si ₂ X _m + (m / 2) H ₂ O → R _(6-m) Si ₂ O _{(m / 2)}
When the formula amount of the R portion is Rw, the silicon content ratio S ₁ (%) of the silicon-containing polymer at this time is
S ₁ = [28.1 × 2 / {Rw × (6-m) + 28.1 × 2 + 16 × (m / 2)}] × 100
It becomes.
Similarly, in the case of the compound of general formula (2):
A _a SiB _(4-a) + {(4-a) / 2} H ₂ O → A _a SiO _{{(4-a) / 2}}
When the formula amount of the A portion is Aw, the silicon content ratio S ₂ (%) of the silicon-containing polymer at this time is
S ₂ = [28.1 / {Aw × a + 28.1 + 16 × (4-a) / 2)}] × 100
It becomes.
The total silicon content can be determined from the molar ratio of each compound.
Accordingly, when (mass derived from silicon / mass of resin) × 100 is set to 30% or more, a silicon-containing film-forming composition for an etching mask that works effectively during etching of the lower layer film can be obtained even at a film thickness of 100 nm or less.

  Further, when the silicon content of the silicon-containing polymer is 40% or more as (mass derived from silicon / mass of resin) × 100, silicon for an etching mask that works effectively during etching of the lower layer film even at a film thickness of 50 nm or less A composition for forming a film is obtained.

  The composition can contain an acid generator and a crosslinking agent in addition to the silicon-containing polymer. In this case, these components are used by dissolving in an organic solvent.

  In addition, the present invention provides a novel silicon-containing film for an etching mask by forming a silicon-containing film on the organic film formed on the substrate to be processed using the above-described composition. .

  In the silicon-containing film of the present invention, the silicon-containing polymer is preferably cross-linked at the time of film formation and is insoluble in the organic solvent.

  In addition, when using the silicon-containing film for an etching mask of the present invention as an etching mask, a photoresist film is further laminated thereon, with or without another film interposed therebetween, and an intermediate substrate to be processed. To do.

  Moreover, in lithography using ArF excimer laser light, a single layer resist film has insufficient etching resistance, but when high resolution is particularly essential, a photoresist layer used for the substrate intermediate to be processed is used. It is preferable to use a photoresist layer that is a poly (meth) acrylic acid-based alkali-soluble resin that is protected with an acid labile group and rendered insoluble in alkali. Furthermore, it is preferable that the photoresist film includes a polymer containing a side chain having an alcohol functional group that exhibits acidity when the adjacent carbon is substituted with fluorine.

  Further, as a preferable pattern transfer method using the substrate intermediate to be processed of the present invention, after forming the resist pattern using the substrate intermediate to be processed, the silicon-containing film is etched using the resist pattern as an etching mask, Next, there is provided a processing method of a substrate to be processed, in which an organic film is etched using a patterned silicon-containing film as an etching mask, and further, the processing substrate is etched using the patterned organic film as an etching mask. In this case, it is preferable to adopt a photolithography method using ArF excimer laser light in forming this resist pattern.

  Furthermore, it is known that the Si—Si bond has sufficient absorption in the vicinity of a wavelength of 193 nm of an ArF excimer laser (Non-patent Document 1: complete organic chemistry vol. 2,389 (1982)), and formation of the resist pattern. When using a photolithography method using ArF excimer laser light, the silicon-containing film for an etching mask of the present invention shows not only an etching mask but also a good antireflection effect.

  The composition for forming a silicon-containing film for an etching mask according to the present invention includes a hydrolytic condensation of a hydrolyzable silane represented by the general formula (1), or a hydrolyzable silane represented by the general formula (1) and the general formula. The material obtained relatively easily by cohydrolysis condensation of the hydrolyzable silane represented by (2) can be used, and by using this, good pattern formation of the photoresist formed thereon can be achieved. In addition, since a high etching selectivity with an organic material can be obtained, the formed photoresist pattern is transferred by dry etching in order to the silicon-containing intermediate film and the organic underlayer film. Pattern transfer can be performed with high accuracy on a processed substrate.

The polymer used in the composition for forming a silicon-containing film for an etching mask of the present invention is obtained by adding a simple substance or a mixture of hydrolyzable silane compounds containing at least one silane compound represented by the following general formula (1). It is a siloxane polymer obtained by decomposition condensation.
R _(6-m) Si ₂ X _m (1)
(R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, X is an alkoxy group, an alkanoyloxy group or a halogen atom, R and X may be the same or different substituents, and m is 6 ≧ m ≧ 3.)

The polymer further contains a hydrolyzable silane compound represented by the general formula (1) and at least one hydrolyzable silane compound represented by the following general formula (2). A silicon-containing polymer obtained by hydrolytic condensation of the above mixture may also be used.
A _a SiB _(4-a) (2)
(A is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, B is an alkoxy group, an alkanoyloxy group or a halogen atom, and A and B may be the same or different substituents, a is 0 or 1.)

  In addition, the use ratio of the disilane compound of the general formula (1) and the monosilane compound of the general formula (2) varies depending on the formula amount of R and A, and is blended so that the silicon content in the polymer is 30% by mass or more. It is preferable to do.

  Preferred as R of the silane compound (1) are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-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 and other alkyl groups, vinyl group, allyl group and other alkenyl groups, ethynyl group and the like Examples thereof include aryl groups such as alkynyl group, phenyl group and tolyl group, aralkyl groups such as benzyl group, and other unsubstituted monovalent hydrocarbon groups. Of these, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and a vinyl group are particularly preferable.

  Moreover, the substituted monovalent hydrocarbon group which substituted one or more of the hydrogen atoms of these groups with the functional group is also used suitably. Examples of such functional groups include a hydroxyl group, an epoxy group, an oxetanyl group, an amino group, a methylamino group, a dimethylamino group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Particularly preferred are a hydroxyl group and an epoxy group.

  Preferred as X are methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, 2-ethyl. Butoxy group, 3-ethylbutoxy group, 2,2-diethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group and other alkoxy groups, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, An alkanoyloxy group such as valeryl group, isovaleryl group, pivaloyl group and cyclohexylcarbonyl group, and a halogen atom such as fluorine, chlorine, bromine and iodine. Of these, methoxy, ethoxy, n-propoxy, iso-propoxy, acetyl, chlorine and the like are particularly preferable.

  When the number of X is small, the silane compound represented by the general formula (1) tends to decrease the condensability. When the condensability is low, the silane compound is co-hydrolyzed with the compound represented by the general formula (2) to form a polymer. Sometimes it doesn't integrate well into the skeleton. Therefore, when a compound represented by a plurality of general formulas (1) is used, it is preferable that the number m of X is 3 or more as a main component. Furthermore, when the main component is X having 5 or more, the amount of silanol remaining after the condensation may be too much, and the storage stability of the obtained silicon-containing polymer may be lowered. Therefore, the number of X possessed by the main component is preferably 3 or 4. Here, the main component means that 40% by mass or more, especially 50% by mass or more is occupied in all silane compounds.

  Furthermore, the condensate having m of 3 tends to have an oil repellency characteristic of a silicone resin, and may repel the upper layer resist coating solution. On the other hand, the condensate due to m = 4 tends to leave silanol, but when used as a hard mask, the selection of R and the selection and addition amount of the monomer of the general formula (2) are also important. In general, when the ratio of m = 4 to m = 3 is between 0.3 and 0.7, a silicon-containing polymer having good physical properties can be obtained.

  In the silane compound (2), A is preferably selected from R in the silane compound (1) and B in the silane compound (2) is selected from the same selection range as X in the silane compound (1). When introducing a group or the like, there are cases where introduction into A is advantageous in purifying a silane compound.

Here, as A, an organic group having at least one of a carbon-oxygen single bond and a carbon-oxygen double bond is preferable. The following can be illustrated as a preferable example. In addition, in the following formula, (Si) is described in order to indicate the bonding site with silicon.

  Also, when looking at the overall polymer structure, the number of Si-O bonds in the polymer is L, and the number of Si-Si bonds in the polymer is M, depending on the selection of R and A which are organic side chains. Assuming that the number of Si—C bonds in the polymer is N, oxygen RIE resistance is sufficiently practical and preferable when 0.45 ≦ L / (L + M + N) ≦ 0.95 is satisfied. At this time, if it is less than 0.45, there are many bonds that react with oxygen RIE such as Si—C and Si—Si, so that the etching resistance is not high for the high silicon content, and there is no merit. On the other hand, when it exceeds 0.95, the obtained silicon-containing polymer tends to have a large amount of silanol, and the storage stability when it is used as a film-forming composition may be low.

  The selection of the substituent and the mixture of the general formula (2) or other hydrolyzable silane compounds are preferably adjusted based on the silicon content contained in the polymer. The silicon content in the polymer needs to be 15% or more as the silicon-derived mass / resin (silicon-containing polymer) mass, but when this is adjusted to 30% or more, the etching mask is used in the processing step of the lower layer film. Can be used to process the lower layer film with a polymer film thickness of 100 nm or less. As a result, the thickness of the upper resist film can be reduced, and the substrate can be processed with a resist film having a thickness of about 150 to 250 nm. In addition, when the silicon content is adjusted to 40% or more, the lower layer film can be etched even if the thickness of the silicon-containing film is 50 nm or less. In this case, the thickness of the resist film is 100 to 200 nm. can do.

  The amount of water when obtaining a siloxane polymer by cohydrolytic condensation from these silane compounds is preferably 0.02 to 10 moles per mole of monomer. At this time, a catalyst can also be used, such as formic acid, acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, citric acid, Tartaric acid, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid and other acids, tetraalkoxytitanium, trialkoxymono (acetylacetonato) titanium, tetraalkoxyzirconium, trialkoxymono (acetylacetate) Nert) and metal chelate compounds such as zirconium and aluminum triacetylacetonate.

  As the reaction operation, the monomer is dissolved in an organic solvent, and water is added to start 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 20 to 80 ° C. for aging is preferable. Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2- n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl 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, 3-ethoxypropion Ethyl acetate tert- butyl, tert- butyl propionate, propylene glycol mono-tert- butyl ether acetate, γ- butyrolactone, and mixtures thereof.

  Thereafter, a neutralization reaction of the catalyst is performed, and the organic solvent layer is separated and dehydrated. Since the remaining water causes the condensation reaction of the remaining silanol to proceed, it is necessary to perform sufficient dehydration. 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, 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. 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 monoethyl 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, an organic solvent that is hardly soluble or insoluble in the above water is added, the organic solvent layer is separated and washed with water to remove the catalyst used for the hydrolytic condensation. At this time, you may neutralize as needed. Subsequently, the separated organic solvent layer is dehydrated. Since the remaining water causes the condensation reaction of the remaining silanol to proceed, it is necessary to perform sufficient dehydration. 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.

  The molecular weight of the resulting silicon-containing polymer can be adjusted not only by the selection of the monomer but also by controlling the reaction conditions during polymerization, but if a polymer having a weight average molecular weight exceeding 20,000 is used, foreign matter may be generated depending on the case. And application spots may occur, and it is preferable to use those having a density of 20,000 or less. In addition, when the ratio of the weight average molecular weight of 500 or less in the molecular weight distribution exceeds 5% by mass of the entire silicon-containing polymer, it evaporates before causing a crosslinking reaction during firing, and the surface of the coating film The internal uniformity may be deteriorated, and it is preferable to use one having 5% by mass or less. In addition, the data regarding the said weight average molecular weight represent molecular weight in polystyrene conversion, using polystyrene as a standard substance by gel permeation chromatography (GPC) using RI as a detector.

A modifier and an organic solvent can be blended with the composition of the present invention. Examples of the modifier that can be used in the present invention include an acid generator, a crosslinking agent, a surfactant, and a stabilizer.
In order to further accelerate the crosslinking reaction by heat, an acid generator can be added. There are acid generators that generate an acid by thermal decomposition and those that generate an acid by light irradiation, and any of them can be added.

As the acid generator used in the present invention,
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.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０の置換あるいは非置換のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。Ｒ^101d、Ｒ^101e、Ｒ^101f、Ｒ^101gは、Ｒ^101a、Ｒ^101b、Ｒ^101cと同様であるが、水素原子であってもよい。Ｒ^101dとＲ^101e、Ｒ^101dとＲ^101eとＲ^101fとは環を形成してもよく、環を形成する場合には、Ｒ^101dとＲ^101e及びＲ^101dとＲ^101eとＲ^101fは炭素数３〜１０のアルキレン基を示す。）

Wherein 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 a substitution having 6 to 20 carbon atoms. Alternatively, it represents an unsubstituted aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. ^101b and R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion. R ^101d , R ^101e , R ^101f and R ^101g are the same as R ^101a , R ^101b and R ^101c , but may be a hydrogen atom, R ^101d and R ^101e , R ^101d and R ^101e and R ^101f may form a ring. R ^101d and R ^101e and R ^101d , R ^101e and R ^101f each represents 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 an alkyl group, a methyl group, an ethyl group, a 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, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl Group, cyclohexylmethyl group, norbornyl group, 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 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include phenyl group, naphthyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, 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, dimethylphenyl 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, etc. 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 benzenesulfonate. And aryl sulfonates such as 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.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(Wherein R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl 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. K ^- is the formula (P1a-1), can be exemplified the same ones as described in (P1a-2) and (P1a-3).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０の置換あるいは非置換のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

Wherein R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups or aryl halides having 6 to 20 carbon atoms. Group, 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, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. 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-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, 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 in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. Represents a linear or branched alkylene group.)

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.

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

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

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(In the 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 carbon atoms. It may be substituted with a linear or branched alkyl group 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 chain 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 alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group of 4 to 4, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a phenyl group which may be substituted with a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is 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, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, 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. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specific examples include the following acid generators. Tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, trifluoromethanesulfonic acid (P-methoxybenzyl) dimethylphenylammonium, trifluoromethanesulfonic acid (p-methoxybenzyl) trimethylammonium, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid Diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) Enyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p- tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, 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 triphenylsulfonic acid , Triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) ) Sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexyl trifluoromethanesulfonate Methyl (2-Oki Socyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothio Onium salts such as phenium triflate.

  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-amylsulfonyl) diazomethane, B hexylsulfonyl-1-(tert-butylsulfonyl) diazomethane, 1-cyclohexyl sulfonyl-1-(tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl) diazomethane derivatives such as diazomethane.

  Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, 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-methyl-3,4-pentanedione glyoxime, bis-O- ( n-butanesulfonyl) -α-dimethylglyoxime, 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- Til-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,1 , 1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis -O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O -(P-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, Scan -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

Bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.
Β-ketosulfonic acid derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone.
Nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.
Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene .

  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 -Chloroethane sulfonic acid ester, N-hydroxysuccinimide benzene sulfonic acid ester, N- Droxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimide ethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester, N-hydroxyglutarimide benzenesulfonic acid Esters, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimidebenzenesulfonate, N-hydroxyphthalate Imidotrifluoromethanesulfonic 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-toluenesulfonate Sulfonic acid ester derivatives of N-hydroxyimide compounds such as

  Among these, in particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid tri Phenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethylsulfonic acid cyclohexylmethyl ( 2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) Onium salts such as sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) ) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis- Glyoxime derivatives such as O- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime Bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Acid ester derivatives are preferably 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 0.01 to 50 parts, more preferably 0.1 to 40 parts, with respect to 100 parts (parts by mass) of the base polymer. In order to prevent intermixing when a resist composition solution or the like is applied on the film after film formation, it is necessary to form a sufficient bond between the siloxane polymers. It is done.

  In the present invention, a crosslinking agent can be used as a modifier. Here, the cross-linking agent is a material that cross-links with a polymer by an acid, for example, a melamine compound, a guanamine compound, a glycoluril compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples include compounds containing double bonds such as urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups.

  Examples of the epoxy compound among the various compounds include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound obtained by methoxymethylation of 1 to 6 of hexamethylol melamine or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine Or a mixture thereof in which 1 to 5 of the methylol groups are acyloxymethylated. Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. A compound in which ˜4 methylol groups are acyloxymethylated or a mixture thereof may be mentioned. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, and tetramethylolglycoluril methylol. Examples thereof include compounds in which 1 to 4 of the groups are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, tetramethoxyethyl urea, and the like.

  Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, Examples thereof include trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

When an epoxy group is contained as a substituent for R or A, the addition of a compound containing a hydroxy group is effective for increasing the reactivity with the epoxy group and improving the crosslinking efficiency. Particularly preferred are compounds containing two or more hydroxy groups in the molecule. For example, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] -decane, pentaerythritol, 1,2,6-hexanetriol, 4,4 ′, 4 ″ -methylidene Triscyclohexanol, 4,4 ′-[1- [4- [1- (4-hydroxycyclohexyl) -1-methylethyl] phenyl] ethylidene] biscyclohexanol, [1,1′-bicyclohexyl] -4, Alcohol group-containing compounds such as 4′-diol, methylenebiscyclohexanol, decahydronaphthalene-2,6-diol, [1,1′-bicyclohexyl] -3,3 ′, 4,4′-tetrahydroxyl, bisphenol , Methylene bisphenol, 2,2'-methylene bis [4-methylphenol], 4,4'-methylidene-bis [2,6-dimethylphenol 4,4 ′-(1-methyl-ethylidene) bis [2-methylphenol], 4,4′-cyclohexylidenebisphenol, 4,4 ′-(1,3-dimethylbutylidene) bisphenol, 4, 4 ′-(1-methylethylidene) bis [2,6-dimethylphenol], 4,4′-oxybisphenol, 4,4′-methylenebisphenol, bis (4-hydroxyphenyl) methanone, 4,4′-methylenebis [2-Methylphenol], 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′-(1,2-ethanediyl) bisphenol, 4,4 ′-(diethylsilylene) ) Bisphenol, 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol, 4,4 ′, 4 ″ -methylide Trisphenol, 4,4 ′-[1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4- Methylphenol, 4,4 ′, 4 ″ -ethylidenetris [2-methylphenol], 4,4 ′, 4 ″ -ethylidenetrisphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-(1,2 -Ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ′ ″-ethanediylidene) tetrakis [2-methylphenol], 2,2′-methylenebis [6-[(2-hydroxy-5-methylphenyl) ) Methyl] -4-methylphenol], 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris (4-hydroxyphenylmethyl) -1,3-benzenediol, 2,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′, 4 ′ ″-(3-methyl-1-propanyl-3-ylidene) trisphenol, 2, 6-bis [(4-hydroxy-3-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [4-hydroxy-3-fluorophenyl] methyl] -4-fluorophenol, 3,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol P-methylcalix [4] arene, 2,2′-methylenebis [6-[(2,5 / 3,6-dimethyl-4 / 2-hydroxyphenyl) methyl] -4-methylphenol, 2,2 ′ -Methylenebis [6-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-methylphenol, 4,4 ', 4'',4'''-tetrakis [(1-methylethylidene) bis ( 1,4-cyclohexylidene)] phenol, 6,6′-methylenebis [4- (4-hydroxyphenylmethyl) -1,2,3-benzenetriol, 3,3 ′, 5,5′-tetrakis [( And phenolic low nuclei such as 5-methyl-2-hydroxyphenyl) methyl]-[(1,1′-biphenyl) -4,4′-diol].

  On the other hand, when R or A contains a hydroxyl group, the addition of a compound containing an epoxy group is effective for increasing the reactivity with the hydroxyl group and improving the crosslinking efficiency. Particularly preferred are compounds containing two or more epoxy groups in the molecule. For example, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like can be given.

  In the present invention, the amount of the crosslinking agent such as a hydroxyl group-containing additive or an epoxy group-containing additive is preferably 0.1 to 50 parts, particularly preferably 1 to 20 parts, relative to 100 parts of the base polymer. If it is less than 0.1 part, the crosslinking is insufficient and the polymer is hardened, which may cause mixing with the resist upper layer film. On the other hand, if it exceeds 50 parts, the antireflection effect may be reduced, the crosslinked film may be cracked, the silicon content of the entire film may be reduced, and the etching resistance may be reduced.

  In the present invention, a surfactant can be blended as a modifier as required. Here, the surfactant is preferably nonionic, and perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, and fluorine-containing organosiloxane compound are used. Can be mentioned. For example, Florard “FC-430”, “FC-431”, “FC-4430” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “KH-10”, “KH” -20 "," KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS-451 "(all Daikin Industries, Ltd.) ), MegaFuck “F-8151” (Dainippon Ink Industries Co., Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned. Preferably, Florard “FC-4430” (manufactured by Sumitomo 3M Limited), “KH-20”, “KH-30” (all manufactured by Asahi Glass Co., Ltd.), “X-70-093” (Shin-Etsu Chemical Co., Ltd.) Product).

  In the present invention, a stabilizer can be blended as a modifier as required. Here, the stabilizer is added to suppress fluctuations in film thickness when the composition is stored. Stabilizers include carboxylic acids such as oxalic acid, malonic acid, malonic acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, citraconic acid, glutaric acid, glutaric acid anhydride, adipic acid, or carboxylic acid anhydrides. Can be mentioned.

  Furthermore, it is also possible to add a solvent having an effect of improving the stability of the composition as a stabilizer. Such a solvent must have one or more ether bonds, carbonyl bonds and / or ester bonds, and one or more hydroxy groups in the molecule, and can dissolve acid generators and other additives. I must. Examples of the organic solvent include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2- (cyclohexyloxy) ethanol, propylene glycol butyl ether, 1- tert-butyl-2-propanol, 3-ethoxy-1-propanol, propylene glycol propyl ether, di (propylene glycol) -tert-butyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol 1-methoxy-2-propanol, 3-methoxy-1,2-propanediol, 3-ethoxy-1,2-propanediol, 3-allyloxy-1,2-propanediol, di (ethylene glycol), di ( Propire Glycol), di (ethylene glycol) monomethyl ether, di (ethylene glycol) monoethyl ether, di (ethylene glycol) monobutyl ether, di (ethylene glycol) monopropyl ether, di (propylene glycol) monomethyl ether, di (propylene glycol) Monoethyl ether, di (propylene glycol) monobutyl ether, di (propylene glycol) monopropyl ether, ethylene glycol monoacetate, methyl glycolate, ethyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, lactic acid tert-butyl, methyl 2-hydroxybutanoate, ethyl 2-hydroxybutanoate, propyl 2-hydroxybutanoate, butyl 2-hydroxybutanoate, 2 Isobutyl hydroxybutanoate, tert-butyl 2-hydroxybutanoate, methyl 3-hydroxybutanoate, methyl 3-hydroxybutanoate, ethyl 3-hydroxybutanoate, propyl 3-hydroxybutanoate, butyl 3-hydroxybutanoate, 3 -Isobutyl hydroxybutanoate, tert-butyl 3-hydroxybutanoate, hydroxyacetone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- 3-methyl-2-butanone, 3-acetyl-1-propanol, 4-hydroxy-4-methyl-2-pentanone and the like are preferable. These can be used individually by 1 type or in mixture of 2 or more types.

The organic solvent used in the present invention may be any organic solvent that can dissolve the siloxane polymer, the modifier, and the like contained in the composition shown in claims 1 to 4. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Examples thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. Although it can be used in mixture, it is not limited to these.
Also, the solvents indicated as stabilizers can also be used as solvents if they can dissolve the siloxane polymer and modifier.

  In the present invention, among these organic solvents, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, butyl acetate, ethyl lactate, cyclohexanone, γ-butyl lactone and its A mixed solvent is preferably used.

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

  The silicon-containing film for an etching mask of the present invention can be produced on a substrate by a spin coat method or the like from a silicon-containing film-forming composition as in the case of a photoresist film. After spin coating, it is desirable to evaporate the solvent and bake to promote the crosslinking reaction in order to prevent mixing with the upper resist film. The baking temperature is preferably in the range of 50 to 400 ° C. and in the range of 10 to 300 seconds.

Here, in the present invention, the silicon-containing film can be formed on the processed portion of the substrate to be processed via the lower layer film, and the photoresist film can be formed on the silicon-containing film, whereby pattern formation can be performed.
In this case, the processed portion of the substrate to be processed includes a low dielectric constant insulating film having a k value of 3 or less, a primary processed low dielectric constant insulating film, a nitrogen and / or oxygen-containing inorganic film, a metal film, and the like. Can do.

  In the multilayer resist method, the resist film formed on the silicon-containing film of the present invention is not particularly limited, but is particularly advantageous when using a resist composition for ArF excimer laser light for the following reasons. Used for. That is, when very high resolution is required in lithography, it becomes a problem of how to control the standing wave due to reflection of exposure light, and it is essential to use an antireflection film under the resist. . However, a general antireflection film is based on an aromatic group for most of the light absorption function, and the etching causes a considerable load on the resist film. In contrast, in the three-layer resist method using the silicon-containing film of the present invention, the silicon-containing film has strong light absorption based on the Si-Si bond in the vicinity of a wavelength of 190 nm, and even without using an antireflection film. An antireflection film that is better or thinner than usual is sufficient. Therefore, it can be used particularly advantageously in a three-layer resist method using an exposure light of 200 nm or less such as ArF excimer laser, and is particularly advantageous when lithography is performed using a resist having no sufficient etching resistance as described below. Can be used for

  When the silicon-containing film of the present invention is used in an exposure process with ArF excimer laser light, any of the usual resist compositions for ArF excimer laser light can be used as the upper resist film. Many candidates for ArF excimer laser light resist compositions are already known. If the resist composition is positive, a resin, a photoacid generator and an acid, which are soluble in an alkaline aqueous solution due to the action of an acid, the acid labile group decomposes. If the basic substance for controlling the diffusion of the resin is a negative type, it controls the diffusion of the resin, photoacid generator, crosslinking agent and acid that reacts with the crosslinking agent by the action of an acid and becomes insoluble in an alkaline aqueous solution. The basic substance is a main component, but there is a difference in characteristics depending on what kind of resin is used. Already known resins can be broadly classified into poly (meth) acrylic, COMA, COMA- (meth) acrylic hybrid, ROMP, polynorbornene, etc., of which poly (meth) acrylic resin Since the resist composition used has ensured etching resistance by introducing an alicyclic skeleton into the side chain, the resolution performance is superior to other resin systems.

  Many resist compositions for ArF excimer lasers using poly (meth) acrylic resins are known. For positive type resist compositions, a unit for ensuring etching resistance as a main function, an acid, The polymer is composed of a combination of a unit that decomposes by alkalinity to change to alkali-soluble, a unit for ensuring adhesion, or a combination in which one unit also has two or more of the above functions. . Among these, as the unit whose alkali solubility is changed by an acid, (meth) acrylic acid ester having an acid labile group having an adamantane skeleton (Patent Document 11; JP-A-9-73173), norbornane or tetracyclohexane. A (meth) acrylic acid ester having an acid labile group having a dodecane skeleton (Patent Document 12: Japanese Patent Application Laid-Open No. 2003-84438) gives high resolution and etching resistance, and is particularly preferably used. Moreover, as a unit for ensuring adhesiveness, (meth) acrylic acid ester having a norbornane side chain having a lactone ring (Patent Document 13: International Publication No. 00/01684 pamphlet) and an oxanorbornane side chain ( Etching resistance of (meth) acrylic acid ester (Patent Document 14: JP 2000-159758 A) and (meth) acrylic acid ester having a hydroxyadamantyl side chain (Patent Document 15: JP 8-12626 A) And can be particularly preferably used because it provides high resolution. Further, the polymer contains a unit (for example, Non-Patent Document 2: Polym. Mater. Sci. Eng. 1997. 77. pp449) having an alcohol that exhibits acidity by substitution with fluorine at the adjacent position as a functional group. Is attracting attention as a resist polymer corresponding to the immersion method, which has been attracting attention in recent years, because it gives the polymer physical properties that suppress swelling and gives high resolution. However, the polymer contains fluorine. Therefore, there is a problem that the etching resistance is lowered. The silicon-containing film for an etching mask of the present invention can be used particularly effectively for such an organic resist material that is difficult to secure etching resistance.

  The ArF excimer laser resist composition containing the above polymer contains an acid generator, a basic compound, and the like, but the acid generator can be added to the silicon-containing film-forming composition of the present invention. Almost the same ones can be used, and onium salts are particularly advantageous in terms of sensitivity and resolution. Many basic substances are also known, and many examples are disclosed in Patent Document 16: Japanese Patent Application Laid-Open No. 2005-146252 recently published, and can be advantageously selected from them.

  After producing a silicon-containing film layer for an etching mask, a photoresist layer is produced thereon using a photoresist composition solution, and a spin coating method is preferably used in the same manner as the silicon-containing film layer for an etching mask. Pre-baking is performed after spin-coating the resist composition, and a range of 10 to 300 seconds at 80 to 180 ° C. is preferable. Thereafter, exposure is performed, post-exposure baking (PEB), and development is performed to obtain a resist pattern.

  Etching of the silicon-containing film for the etching mask is performed using chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas or the like. The silicon-containing film for an etching mask of the present invention is characterized in that the etching rate with respect to the gas is high and the film loss of the upper resist film is small.

  In the multilayer resist method using the silicon-containing layer of the present invention, a lower layer film is provided between the silicon-containing film of the present invention and the substrate to be processed. When the lower layer film is used as an etching mask for the substrate to be processed, the lower layer film is preferably an organic film having an aromatic skeleton. However, when the lower layer film is a sacrificial film, not only the organic film but also silicon A silicon-containing material may be used as long as the content is 15% by mass or less.

  In the case of a three-layer resist method using an organic film as an underlayer film that serves as an etching mask for a substrate to be processed, the organic film is a film in which a patterned resist pattern is transferred to a silicon-containing film and then the pattern is transferred again. In addition, the silicon-containing film is required to have a characteristic that it can be etched under an etching condition exhibiting high etching resistance, and a characteristic that the silicon-containing film has a high etching resistance with respect to the condition for etching the substrate to be processed.

  Many organic films as such lower layer films are already known as lower layer films for a three-layer resist method or a two-layer resist method using a silicon resist composition. Patent Document 17: JP-A-2005-128509 In addition to the described 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin (molecular weight 11,000), a number of resins including novolak resins are resists of two-layer resist method and three-layer resist method. These are known as lower layer film materials, and any of them can be used. If you want to improve heat resistance compared to normal novolac, you can add a polycyclic skeleton such as 4 '-(9H-fluorene-9-ylidene) bisphenol novolac resin, and select a polyimide resin. (For example, patent document 18: Unexamined-Japanese-Patent No. 2004-153125).

  The organic film can be formed on a substrate by spin coating or the like, similar to the photoresist composition, using a composition solution. It is desirable to bake in order to evaporate the organic solvent after the resist underlayer film is formed by spin coating or the like. The baking temperature is preferably in the range of 80 to 300 ° C. and in the range of 10 to 300 seconds.

  Although not particularly limited, the thickness of the lower layer film is preferably 10 nm or more, and particularly preferably 50 nm or more. The thickness of the silicon-containing film according to the present invention is 200 nm or less, and the thickness of the photoresist film. The thickness is preferably 300 nm or less.

The three-layer resist method using the silicon-containing film for an etching mask of the present invention is as follows. In this process, an organic layer is first formed on a substrate to be processed by a spin coating method or the like. Since this organic layer acts as a mask when etching the substrate to be processed, it is desirable that the etching resistance is high, and it is required not to mix with the silicon-containing film for the upper etching mask. It is desirable to crosslink with an acid. A silicon-containing film and a photoresist film for an etching mask of the present invention are formed thereon by the above method. The resist film is subjected to pattern exposure using a light source corresponding to the resist film, for example, KrF excimer laser light, ArF excimer laser light, or F ₂ laser light, according to a conventional method, and heat treatment is performed according to conditions suitable for each resist film. Thereafter, a resist pattern can be obtained by performing a developing operation with a developer. Next, using this resist pattern as an etching mask, the organic material is etched by dry etching conditions in which the etching rate of the silicon-containing film is predominantly high, for example, dry etching using fluorine-based gas plasma. When the antireflection film and the silicon oxide film are etched, a silicon oxide film pattern can be obtained with almost no influence of the pattern change due to the side etching of the resist film. Next, for the substrate having a silicon-containing film pattern to which the resist pattern obtained above is transferred, dry etching conditions where the etching rate of the lower organic film is significantly higher than that of silicon oxide, for example, gas plasma containing oxygen The lower layer organic material is etched by performing reactive dry etching with, or reactive dry etching with gas plasma containing hydrogen-nitrogen. Although this etching process gives a pattern of the lower organic film, the uppermost resist layer is usually lost at the same time. Furthermore, by using the lower organic film obtained here as an etching mask, the substrate to be processed can be precisely etched by using dry etching of the substrate to be processed, for example, fluorine-based dry etching or chlorine-based dry etching. it can.

  EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

[Synthesis Example 1]
A 300 ml glass flask was charged with a mixture of 27 g of tetraethoxydimethyldisilane and 23 g of triethoxytrimethyldisilane and 10 g of ethanol, and 15 g of 0.5N hydrochloric acid aqueous solution was slowly added at room temperature with stirring, and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of propylene glycol monomethyl ether (PGME) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain a PGME solution of polymer 1 It was. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. The physical properties of Polymer 1 are shown in Table 1.

[Synthesis Example 2]
A 300 ml glass flask was charged with 27 g of tetraethoxydimethyldisilane, 23 g of triethoxytrimethyldisilane, 21 g of tetraethoxysilane, 7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 10 g of ethanol, and stirred with stirring. 30 g of a 5N aqueous acetic acid solution was slowly added at room temperature and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of ethyl lactate (EL) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain an EL solution of polymer 2. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. Table 1 shows the physical properties of Polymer 2.

[Synthesis Example 3]
A 300 ml glass flask was charged with 27 g of tetraethoxydimethyldisilane, 23 g of triethoxytrimethyldisilane, 14 g of methyltrimethoxysilane, 48 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 75 g of ethanol while stirring. 50 g of 0.5N aqueous oxalic acid solution was slowly added at room temperature and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 600 g of γ-butyrolactone (GBL) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain a GBL solution of polymer 3 . In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. Table 1 shows the physical properties of Polymer 3.

[Synthesis Example 4]
A 300 ml glass flask was charged with 53 g of tetraethoxydimethyldisilane and 10 g of ethanol, and 15 g of a 0.5N aqueous hydrochloric acid solution was slowly added at room temperature while stirring, and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of propylene glycol monomethyl ether (PGME) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain a PGME solution of polymer 4 It was. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. The physical properties of polymer 4 are shown in Table 1.

[Synthesis Examples 5 to 9]
In a 300 ml glass flask, 12 g, 17 g, 27 g, 37 g, 41 g of tetraethoxydimethyldisilane, 42 g, 35 g, 24 g, 14 g, 9 g of triethoxytrimethyldisilane, respectively, 21 g of tetraethoxysilane, 7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 10 g of ethanol were charged, and 30 g of 0.5N oxalic acid aqueous solution was slowly added at room temperature while stirring, and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of ethyl lactate (EL) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain an EL solution of polymers 5-9. It was. In order to measure the yield of each polymer solution, a predetermined amount of the solution was dried with a dryer at 150 ° C. for 1 hour and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. Table 1 shows the physical properties of the polymers 5 to 9.
[Synthesis Example 10]
A 300 ml glass flask is charged with 30 g of pentaethoxymethyldisilane, 23 g of triethoxytrimethyldisilane, 21 g of tetraethoxysilane, 7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 10 g of ethanol, and is stirred with stirring. 30 g of a 5N aqueous acetic acid solution was slowly added at room temperature and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of ethyl lactate (EL) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain an EL solution of polymer 10. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. The physical properties of polymer 10 are shown in Table 1.

[Synthesis Example 11]
A 300 ml glass flask was charged with 42 g of tetraethoxylane, 4 g of trimethoxyphenylsilane and 10 g of ethanol, and 25 g of a 0.5N aqueous nitric acid solution was slowly added at room temperature while stirring, and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of PGME was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain a PGME solution of polymer 11. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. The physical properties of polymer 11 are shown in Table 1.

[Synthesis Example 12]
A 300 ml glass flask was charged with 42 g of tetraethoxylane, 13 g of 9-anthracenecarboxymethyltriethoxysilane, and 20 g of methanol. 25 g of 0.5N hydrochloric acid aqueous solution was slowly added at room temperature while stirring, and then stirred for 2 hours. After confirming that the monomer was completely consumed by GC and GPC, 350 g of PGME was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain a PGME solution of polymer 12. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. Table 1 shows the physical properties of the polymer 12.

[Synthesis Example 13]
A 300 ml glass flask was charged with 27 g of tetraethoxydimethyldisilane, 23 g of triethoxytrimethyldisilane, 21 g of tetraethoxysilane, 7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 10 g of ethanol, and stirred with stirring. .60 g of 5N methanesulfonic acid aqueous solution was slowly added at room temperature and then stirred for 20 hours. After confirming that the monomer was completely consumed by GC and GPC, the solvent was distilled off under reduced pressure while heating the liquid temperature to 40 ° C. PGME350g was added to the obtained polymer, and it was made to melt | dissolve completely. In order to measure the yield of the polymer solution, a predetermined amount of the solution was dried at 150 ° C. for 1 hour with a dryer and the evaporation residue was measured. The yield was 100%. From this, all the raw materials charged in the reaction were converted into polymers, and the silicon content and L / (L + M + N) in the polymer were determined from the charged composition. The physical properties of polymer 13 are shown in Table 1.

[Examples and Comparative Examples]
As shown in Table 2, in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M), the resin represented by the above polymers 1 to 13, the acid generator represented by AG1, and the crosslinking agent represented by CL1 The silicon-containing film solutions for etching masks were respectively prepared by dissolving them at the ratios shown in Table 2 and filtering with a filter made of 0.1 μm fluororesin.
Next, the silicon-containing film solution for an etching mask is applied on a silicon substrate, and baked at 250 ° C. for 60 seconds to form a silicon-containing film for an etching mask with a film thickness of 193 nm. It was set to ~ 13. Each membrane is described in J.A. A. Optical constants (refractive index: n, extinction coefficient: k) at a wavelength of 193 nm were determined using a spectroscopic ellipsometer (VASE) with variable incident angle manufactured by Woollam, and the results are shown in Table 2.

First, as a lower layer film material, for example, 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolak resin (molecular weight: 11,000) is formed on a substrate to be processed (Japanese Patent Laid-Open No. 2005-128509: Patent Document 17). A composition (28 parts by mass of resin, 100 parts by mass of solvent) was spin-coated and heated to 200 ° C. for 1 minute to form a lower organic film having a thickness of 300 nm. As the lower layer organic film material, in addition to the above, a number of resins including novolak resins are known as lower layer film materials for the multilayer resist method, and any of them can be used.
Next, a solution (Sol 1-13) of a silicon-containing intermediate film material was spin-coated and baked at 250 ° C. for 60 seconds to form an intermediate layer having a thickness of 100 nm.

１０質量部
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
塩基性化合物：トリエタノールアミン ０．０２質量部 Furthermore, in order to form an upper resist film, PGMEA (propylene glycol monomethyl ether) containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M) as the resist composition for ArF excimer laser light exposure (Resist 1) as follows: Acetate solution was dissolved and filtered through a 0.1 μm fluororesin filter.

10 parts by mass Photoacid generator: Triphenylsulfonium nonafluorobutanesulfonate
0.2 parts by mass Basic compound: Triethanolamine 0.02 parts by mass

This composition was applied onto the intermediate layer and baked at 130 ° C. for 60 seconds to form a 200 nm-thick photoresist layer.
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. A 90 nm L / S pattern shape of the obtained pattern was observed, and skirting, undercut, and intermixing phenomena were observed near the substrate. The results are shown in Table 3.

Next, a dry etching resistance test was performed. First, the same silicon-containing film for an etching mask (Film 1 to 13) as that used for the optical constant measurement was prepared. These films, the lower layer film and the photoresist film were subjected to an etching test under the following etching conditions (1).
(1) Etching test apparatus with CHF ₃ / CF ₄ gas: Tokyo Electron Limited dry etching apparatus TE-8500P
Etching conditions (1):
Chamber pressure 40.0Pa
RF power 1,300W
Gearup 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
Processing time 10 sec

Next, the resist pattern obtained after the ArF exposure and development was transferred to the silicon-containing intermediate film under the following etching condition (2).
Etching conditions (2):
Chamber pressure 40.0Pa
RF power 1,000W
Gearup 9mm
CHF ₃ gas flow rate 20ml / min
CF ₄ gas flow rate 60ml / min
Ar gas flow rate 200ml / min
Processing time 30 sec

Next, the pattern transferred to the intermediate film was transferred to the lower layer film under the etching condition (3) mainly composed of the following oxygen gas.
Etching conditions (3):
Chamber pressure 60.0Pa
RF power 600W
Ar gas flow rate 40ml / min
O ₂ gas flow rate 60ml / min
Gearup 9mm
Processing time 20 sec

ＡＧ１；ジ（４−ｔ−ブチルフェニル）ヨードニウムパーフルオロブタンスルホネート
ＣＬ１；セロキサイド２０２１（ダイセル化学工業（株）製）
ＰＧＭＥ；プロピレングリコールモノメチルエーテル
ＥＬ ；乳酸エチル
ＧＢＬ ；γ−ブチロラクトン

AG1; Di (4-t-butylphenyl) iodonium perfluorobutanesulfonate CL1; Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.)
PGME; propylene glycol monomethyl ether EL; ethyl lactate GBL; γ-butyrolactone

  Since the intermediate layer film obtained in the present invention has good resist compatibility, a pattern shape having good rectangularity was obtained, but in the intermediate layer film using the polymer obtained in the comparative example, the upper layer resist shape was It was not good.

Next, as shown in Table 4, the rate of dry etching of CF ₄ / CHF ₃ gas was examined. Compared to the lower layer film and the upper layer resist film, the pattern can be transferred by etching using the upper layer film as a mask sufficiently fast. Moreover, it has a sufficient function as a hard mask in the lower layer film etching.

Subsequently, as shown in Table 5, the rate of dry etching of O ₂ gas was examined. Compared to the lower layer film and the upper layer resist film, it is sufficiently slow, and the pattern can be transferred to the lower layer using the intermediate layer as an etching mask.

  Moreover, it was recognized that the shape of the lower layer film after pattern transfer was also good.

Further, a storage stability test was conducted. Whether the silicon-containing film-forming composition (Sol 1-4, Sol 10-12) obtained above is stored at 30 ° C. for 1 month, and then re-applied by the above-described method, so that the film formability does not change. Was tested.

  According to the present invention, a silicon-containing film for an etching mask having a high etching selectivity with respect to the resist film, that is, a high etching speed was obtained. This silicon-containing film for an etching mask had an absorption coefficient sufficient to exhibit a sufficient antireflection effect, and the resist shape after patterning was a vertical shape without occurrence of reverse taper or skirting.

Claims (18)

A silicon-containing film used as an intermediate film in a multilayer resist method in which a multi-step etching is performed after forming a lower layer film on a substrate to be processed, forming a silicon-containing film thereon, and further forming a photoresist film thereon. In the film-forming composition, at least one of the following general formula (1)
R _(6-m) Si ₂ X _m (1)
(R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, X is an alkoxy group, an alkanoyloxy group or a halogen atom, R and X may be the same or different substituents, and m is 6 ≧ m ≧ 3.)
A silicon-containing film for an etching mask, comprising a silicon-containing polymer obtained by hydrolytic condensation of a hydrolyzable silane alone or in a mixture containing a silane compound having a silicon-silicon bond represented by Composition. In addition to the silane compound represented by the general formula (1), the silicon-containing polymer is further represented by the following general formula (2)
A _a SiB _(4-a) (2)
(A is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, B is an alkoxy group, an alkanoyloxy group or a halogen atom, and A and B may be the same or different substituents, a is 0 or 1.)
The silicon-containing film-forming composition for an etching mask according to claim 1, which is a silicon-containing polymer obtained by hydrolytic condensation of a mixture of hydrolyzable silanes containing the hydrolyzable silane compound represented by formula (1). object.   Using the silane compound represented by the general formula (1), the silane compound represented by the general formula (1) is obtained by hydrolytic condensation of a silane mixture whose main component is m or 4 or 3. The composition for forming a silicon-containing film for an etching mask according to claim 1 or 2, comprising the obtained silicon-containing polymer.   The mixing ratio of the silane compound in which m is 4 and the silane compound in which m is 3 among the silane compounds represented by the general formula (1) is 3: 7 to 7: 3 in a molar ratio. Item 4. A silicon-containing film forming composition for an etching mask according to Item 3.   5. The silicon-containing polymer contained has a weight average molecular weight of 20,000 or less, and a weight-average molecular weight of 500 or less is 5% by mass or less of the entire silicon-containing polymer. The composition for forming a silicon-containing film for an etching mask according to claim 1.   The silicon-containing polymer to be contained is 0.45 ≦ L / (L + M + N, where L is the number of Si—O bonds per unit mass of the polymer, M is the number of Si—Si bonds, and N is the number of Si—C bonds. 6) The composition for forming a silicon-containing film for an etching mask according to any one of claims 1 to 5, wherein ≦ 0.95 is satisfied.   7. The silicon-containing film formation for an etching mask according to claim 1, wherein the silicon content of the silicon-containing polymer is 30% or more as (mass derived from silicon / mass of resin) × 100. Composition.   8. The silicon-containing film forming composition for etching mask according to claim 7, wherein the silicon content of the silicon-containing polymer is 40% or more as (mass derived from silicon / mass of resin) × 100.   Furthermore, the composition for silicon-containing film formation for etching masks of any one of Claim 1 thru | or 8 containing an acid generator.   Furthermore, the composition for silicon-containing film formation for etching masks of any one of Claim 1 thru | or 9 containing a crosslinking agent.   A silicon-containing film for an etching mask, which is formed using the composition for forming a silicon-containing film according to any one of claims 1 to 10.   An etching mask characterized in that the silicon-containing film-forming composition according to any one of claims 1 to 10 is used to form a film, and the silicon-containing polymer is crosslinked to suppress dissolution in an organic solvent. Silicon-containing film.   The silicon-containing film for an etching mask according to claim 11 or 12, wherein the silicon-containing film for an etching mask is formed on a substrate to be processed with or without another film interposed between the lower layer film and the resist film.   A substrate processing intermediate comprising a lower layer film, a silicon-containing film according to claim 11 or 12 and a photoresist film laminated on a substrate to be processed.   15. The substrate processing intermediate according to claim 14, wherein the resin constituting the photoresist layer is a poly (meth) acrylic acid-based alkali-soluble resin protected with an acid labile group and rendered insoluble in alkali.   16. The intermediate for processing a substrate according to claim 14, wherein the photoresist film contains a polymer containing a side chain having an alcohol functional group that exhibits acidity when the adjacent carbon is substituted with fluorine.   After forming a resist pattern using the substrate processing intermediate according to claim 14, 15 or 16, the silicon-containing film is etched using the resist pattern as an etching mask, and then the patterned silicon-containing film is used as an etching mask. A method of processing a substrate to be processed, comprising: etching the lower layer film; and further etching the substrate to be processed using the patterned lower layer film as an etching mask.   18. The method for processing a substrate to be processed according to claim 17, wherein a photolithography method using ArF excimer laser light is used in forming the resist pattern.