JP4880652B2 - Pattern formation method - Google Patents

Description

  The present invention utilizes a pattern forming method in which a pattern is formed by a first exposure, a line pattern is formed by a second exposure in a space portion of the pattern formed at the first time, and a distance between the patterns is reduced. The present invention relates to a method for forming a finer pattern on a substrate.

  In recent years, with the higher integration and higher speed of LSIs, there is a demand for finer pattern rules. In light exposure currently used as a general-purpose technology, the intrinsic resolution limit derived from the wavelength of the light source Is approaching.

  As exposure light used for forming a resist pattern, light exposure using g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source was widely used in the 1980s. As a means for further miniaturization, the method of shortening the exposure wavelength is effective, and mass production after 64 Mbit (process size is 0.25 μm or less) DRAM (Dynamic Random Access Memory) in the 1990s In the process, a KrF excimer laser (248 nm) having a short wavelength was used as an exposure light source instead of i-line (365 nm). However, in order to manufacture DRAMs with a density of 256M and 1G or more that require finer processing technology (processing dimensions of 0.2 μm or less), a light source with a shorter wavelength is required, and an ArF excimer has been used for about 10 years. Photolithography using a laser (193 nm) has been studied in earnest.

Initially, ArF lithography was supposed to be applied from the device fabrication of the 180 nm node, but KrF excimer lithography was extended to 130 nm node device mass production, and full-scale application of ArF lithography is from the 90 nm node. Further, a 65 nm node device is being studied in combination with a lens whose NA is increased to 0.9. For the next 45 nm node device, the shortening of the exposure wavelength was promoted, and F ₂ lithography with a wavelength of 157 nm was nominated. However, the cost of the scanner is increased by using a large amount of expensive CaF ₂ single crystal for the projection lens, the optical system is changed due to the introduction of the hard pellicle because the durability of the soft pellicle is extremely low, and the etching resistance of the resist is reduced. Due to problems, it was proposed that F ₂ lithography be advanced and early introduction of ArF immersion lithography (Non-Patent Document 1).

  In ArF immersion lithography, it has been proposed to impregnate water between the projection lens and the wafer. The refractive index of water at 193 nm is 1.44, and pattern formation is possible even with a lens having an NA (numerical aperture) of 1.0 or more. Theoretically, the NA can be increased to near 1.44. Initially, it was pointed out that the resolution was deteriorated and the focus shifted due to the change in refractive index accompanying the change in water temperature. It was confirmed that the water temperature was controlled within 1/100 ° C. and the influence of the heat generated from the resist due to the exposure was almost no worry, and the problem of refractive index change was solved. It was feared that microbubbles in the water could be transferred to the pattern, but it was confirmed that the water was sufficiently degassed and that there was no worry of bubble formation from the resist due to exposure. In the early stage of immersion lithography in the 1980s, a method of immersing the entire stage in water was proposed, but water was inserted only between the projection lens and the wafer to accommodate the operation of the high-speed scanner, and water was supplied and drained. A partial fill system with a nozzle was adopted. However, in principle, a lens design with an NA of 1 or more became possible by immersion in water. However, the conventional optical system based on the refractive index system has become a huge lens, and the lens is caused by its own weight. There was a problem of deformation. A catadioptric optical system has been proposed for a more compact lens design, and a lens design with NA of 1.0 or more has been accelerated. The possibility of a 45 nm node is shown by the combination of a lens with NA 1.2 or higher and strong super-resolution technology (Non-Patent Document 2), and a lens with NA 1.35 has also been developed.

  As a lithography technique for the 32 nm node, vacuum ultraviolet light (EUV) lithography with a wavelength of 13.5 nm is cited as a candidate. Problems with EUV lithography include high laser output, high resist sensitivity, high resolution, low line edge roughness (LWR), defect-free MoSi laminated mask, and low reflection mirror aberration. There are many problems to be solved.

The resolution that can be reached with the highest NA of water immersion lithography using an NA 1.35 lens is 40 to 38 nm and cannot reach 32 nm. Therefore, development of a high refractive index material for further increasing NA is being carried out. It is the minimum refractive index among the projection lens, liquid, and resist that determines the limit of the NA of the lens. In the case of water immersion, the refractive index of water is the lowest compared to the projection lens (refractive index of 1.5 for synthetic quartz) and resist (refractive index of 1.7 for the conventional methacrylate system). NA was decided. Recently, highly transparent liquids having a refractive index of 1.65 have been developed. In this case, it is necessary to develop a projection lens material having the lowest refractive index and a high refractive index of the projection lens made of synthetic quartz. LUAG (Lu ₃ Al ₅ O ₁₂ ) garnet has a refractive index of 2 or more and is the most promising material, but has a problem of large secondary refractive index and absorption. Even if a projection lens material having a refractive index of 1.8 or higher is developed, the NA of the liquid having a refractive index of 1.65 is only 1.55, and 32 nm cannot be resolved. In order to resolve 32 nm, a liquid having a refractive index of 1.8 or more is required. At present, there is a trade-off between absorption and refractive index, and no such material has yet been found. In the case of alkane compounds, organic cyclic compounds are preferred to linear compounds to increase the refractive index. However, since cyclic compounds have high viscosity, there is a problem that they cannot follow high-speed scanning of the exposure apparatus stage. Yes. In addition, when a liquid having a refractive index of 1.8 is developed, since the minimum refractive index becomes a resist, the resist also needs to have a high refractive index of 1.8 or more.

  Recently, a double patterning process in which a pattern is formed by the first exposure and development, and a pattern is formed just between the first pattern by the second exposure (Non-patent Document 3). . Many processes have been proposed as a double patterning method. For example: (1) Form a photoresist pattern with 1: 3 line and space spacing in the first exposure and development, process the underlying hard mask by dry etching, and lay another hard mask on top of it In this method, a line pattern is formed by exposing and developing a photoresist in the space portion of the first exposure, and a hard mask is processed by dry etching to form a line and space pattern that is half the pitch of the first pattern. (2) First exposure and development form a photoresist pattern with a space and line spacing of 1: 3, and dry etching etches the underlying hard mask and coats the photoresist on it. Then, the second space pattern is exposed to the portion where the hard mask remains, and the hard mask is processed by dry etching. In both methods (1) and (2), it is necessary to process the hard mask by two dry etchings.

  As described above, in the method (1), it is necessary to lay a hard mask twice. In the method (2), only one hard mask is required, but it is necessary to form a trench pattern that is difficult to resolve compared to the line pattern. There is. In the method (2), there is a method in which a negative resist is used to form a trench pattern. In this case, the same high contrast light as that used to form a line with a positive pattern can be used. However, since the dissolution contrast of the negative resist is lower than that of the positive resist, if the trench pattern having the same dimensions is formed with the negative resist as compared with the case of forming the line with the positive resist, the resolution is not obtained with the negative resist. Low.

  On the other hand, after forming a wide trench pattern using a positive resist by the method (2), the substrate is heated to shrink the trench pattern, or a water-soluble film is formed on the developed trench pattern. It is possible to apply the RELAX method in which the trench is shrunk by coating the resist surface by heating and then shrinking the resist surface. Occurs.

  In both methods (1) and (2), etching for substrate processing is required twice, so that there is a problem in that throughput is reduced and pattern deformation and displacement occur due to the two etchings. In order to complete the etching once, there is a method in which a negative resist is used in the first exposure and a positive resist is used in the second exposure. There is also a method in which a positive resist is used in the first exposure, and a negative resist dissolved in a higher alcohol having 4 or more carbon atoms that does not dissolve in the second exposure. In these cases, since a negative resist having low resolution is used, there is a high possibility that degradation of resolution will occur.

  A method in which PEB and development are not performed between the first exposure and the second exposure is the simplest method. For example, after performing the first exposure, the mask is drawn with a shifted pattern and the second exposure is performed, and PEB, development, and dry etching are performed. If the mask is changed for each exposure, the throughput is greatly reduced. Therefore, the second exposure is performed after the first exposure is performed to some extent. Then, depending on the standing time between the first exposure and the second exposure, there may be a change in shape such as dimensional variation due to acid diffusion or generation of a T-top shape. In order to suppress the occurrence of such T-top, application of a resist protective film is effective.

  For example, by applying an immersion resist protective film, a process of performing two exposures, one PEB, development, and dry etching can be performed. Two scanners can be arranged side by side to perform the first exposure and the second exposure in succession. In this case, there arises a problem that the positional deviation caused by the lens aberration between the two scanners and the scanner cost is doubled. If the same resist surface is exposed by shifting the first exposure and the second exposure by half the pitch, the first light and the second light cancel each other, and a pattern is not normally formed.

  However, when a contrast enhancement film (CEL) is applied, the contrast is increased by non-linearity of the light incident on the resist, and it is not canceled out even with exposure shifted by half the pitch. It is desirable that the resist protective film for double patterning has a function as a CEL. In addition, when a non-linear acid generator based on two-photon absorption is used, it is theoretically possible to perform the double patterning exposure only with a resist without CEL. However, no two-photon absorption acid generator has been reported yet for exposure at a wavelength of 200 nm or less.

  The most critical problem in double patterning is the alignment accuracy of the first and second patterns. Since the size of the positional deviation is a variation in line dimensions, for example, if it is attempted to form a 32 nm line with an accuracy of 10%, an alignment accuracy within 3.2 nm is required. Since the alignment accuracy of the current scanner is about 8 nm, a significant improvement in accuracy is necessary.

  Further, the problem of line edge roughness of the resist pattern has become serious. The dimensional variation of the gate electrode is a problem that influences the performance of the transistor. However, as the miniaturization progresses, the size of the line edge roughness has become a factor causing the variation in the threshold current of the transistor. The roughness is reduced by improving the resist material, the dry etching technique, or improving the process. Concerning the resist material, the increase in contrast due to the increase in the addition amount of both the acid generator and the quencher, and the reduction in swelling during alkali development due to the introduction of adhesive groups such as fluoroalcohol and lactone contributed to the reduction in roughness. In the photoresist process, a heat flow after development and a flow process such as bromine plasma treatment were effective. However, the flow process has a problem that the dimensions change due to pattern deformation or pattern shrinkage.

Proc. SPIE Vol. 4690xxix Proc. SPIE Vol. 5040p724 Proc. SPIE Vol. 5992, p557 (2005)

  As described above, when a resist pattern created by two exposures and developments is processed into a substrate by two dry etchings, the throughput is reduced by half. In addition, there arises a problem of pattern displacement due to dry etching. An object of the present invention is to propose a pattern forming method that enables a double patterning process in which a substrate is processed by one dry etching.

The present inventors have solved the above problems by a pattern forming method including the following steps.
That is, in the present invention, in a method of forming a pattern on a substrate by lithography, at least an organic underlayer film is formed on the substrate, a first silicon-containing film is formed on the organic underlayer film, and the first Formed on the silicon-containing film is a resist containing no silicon-containing resin as a main component as a first resist film, and a first resist pattern is formed by exposure and development. A second silicon-containing film is formed on the first resist pattern, and a resist that does not contain a silicon-containing resin as a main component is further formed on the second silicon-containing film as a second resist film. Forming a second resist pattern by film formation, exposure and development; and second etching by dry etching using the second resist pattern formed in the step as an etching mask. Etching the silicon-containing film and simultaneously etching the first silicon-containing film using the first resist pattern exposed at the same time as an etching mask to combine the first resist pattern and the second resist pattern Transferring the pattern to the first and second silicon-containing films to form a silicon-containing film pattern, and further transferring the pattern to the organic underlayer film by dry etching using the obtained silicon-containing film pattern as an etching mask. Forming a pattern on the substrate by performing a step of forming the organic underlayer film pattern and further processing the substrate by dry etching using the obtained organic underlayer film pattern as an etching mask. A method is provided (claim 1).

  As described above, according to the pattern forming method of the present invention including the steps as described above, it is possible to process a resist pattern formed by two exposures and developments in double patterning into a substrate by one dry etching. Thus, the resolution and accuracy can be increased without causing a decrease in throughput or pattern shift, and a finer pattern can be formed on the substrate.

  Further, before forming the second silicon-containing film and forming the second resist film on the second silicon-containing film, a third silicon-containing film is formed on the second silicon-containing film. It is preferable to form a silicon-containing film.

  In this way, by forming the third silicon-containing film on the second silicon-containing film, the reflectance control for the film formed by the second silicon-containing film and the first resist pattern can be performed. And a finer pattern can be formed on the substrate.

  As the silicon-containing film forming composition for forming the third silicon-containing film, it is preferable to use a silicon-containing film forming composition for forming the first silicon-containing film (Claim 3). .

  Thus, by using the silicon-containing film forming composition for forming the first silicon-containing film as the silicon-containing film forming composition for forming the third silicon-containing film, in the pattern forming step, Since the number of materials used can be reduced, it is economical.

  Further, as a silicon-containing film-forming composition for forming the first, second and third silicon-containing films, silicon obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst It is preferable to use a containing compound (claim 4).

  As described above, the silicon-containing film forming composition for forming the first, second and third silicon-containing films is obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst. By using the silicon-containing compound, it is possible to effectively prevent dimensional variation and shape change such as T-top shape generation, and to form a finer pattern on the substrate with high resolution. it can.

  Moreover, it is preferable to use at least one compound selected from inorganic acids and sulfonic acid derivatives as the hydrolysis-condensation catalyst for the silicon-containing compound.

  Thus, when one or more kinds of compounds selected from inorganic acids and sulfonic acid derivatives are used as the hydrolysis catalyst for the silicon-containing compound, a good rectangular resist pattern can be formed.

  The silicon-containing film-forming composition preferably further comprises at least a thermal crosslinking accelerator and an organic solvent in the silicon-containing compound.

  Thus, if the silicon-containing compound is further blended with a thermal crosslinking accelerator and an organic solvent as the silicon-containing film forming composition, the coating properties can be improved, baking after coating, etc. Thus, the crosslinking reaction in the silicon-containing film can be promoted. Therefore, a silicon-containing film formed from such a composition should have good film thickness uniformity, less risk of intermixing with a resist film, and less diffusion of low molecular components into the resist film. it can.

The thermal crosslinking accelerator is preferably at least one compound represented by the following general formula (1) or (2) (Claim 7).
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, b is 0 or 1 In the above integers, a + b is a valence of a hydroxyl group or an organic acid group.)
MA (2)
(Wherein M is sulfonium, iodonium or ammonium, and A is a non-nucleophilic counterion.)

  As described above, when at least one compound represented by the general formula (1) or (2) is used as the thermal crosslinking accelerator, the crosslinking reaction during the formation of the silicon-containing film can be more effectively promoted. And can effectively prevent intermixing with the resist film. Further, when forming the second and third silicon-containing films, low-temperature curing is necessary to prevent shrinking of the patterned photoresist. However, the addition of this crosslinking accelerator reduces the curing temperature. Can be achieved.

  The silicon-containing film-forming composition is preferably formed by further blending the silicon-containing compound with a monovalent or divalent organic acid having 1 to 30 carbon atoms (claims). 8).

  Thus, a silicon-containing compound with good storage stability can be obtained by adding a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms.

  Moreover, it is preferable to use the silicon-containing compound obtained by substantially removing the acid catalyst from the reaction mixture of the silicon-containing compound obtained by the hydrolysis condensation.

  By removing the reaction catalyst in this way, a silicon-containing compound with good storage stability can be obtained.

  In the pattern forming method of the present invention, it is preferable to use a positive chemically amplified resist as the resist not containing the silicon-containing resin.

  Thus, using a positive chemically amplified resist as a resist that does not contain a silicon-containing resin as a main component, that is, the first and second resist films described above are used as positive chemically amplified resist films. Thus, the resolution can be effectively increased and a finer pattern can be formed on the substrate.

  Furthermore, the organic underlayer film is preferably an organic film having an aromatic skeleton.

  Thus, if the organic underlayer film formed between the substrate and the silicon-containing film is an organic film having an aromatic skeleton, the silicon-containing film can be etched under etching conditions exhibiting high etching resistance. In addition, the organic underlayer film having high etching resistance to the conditions for etching the substrate can be obtained, the resolution is high, and a finer pattern can be formed on the substrate.

  If the double exposure process of the present invention is used, it is possible to double the resolution (half the pattern width) by two exposures and one etching. Therefore, the resolution and accuracy can be increased without lowering throughput or pattern deviation, and a finer pattern can be formed on the substrate.

  The present invention provides a method for forming a pattern on a substrate by lithography, wherein at least an organic underlayer film is formed on the substrate, a first silicon-containing film is formed on the organic underlayer film, and the first silicon Forming a resist containing no silicon-containing resin as a main component on the containing film as a first resist film, forming a first resist pattern by exposure and development, and the step formed in the step A second silicon-containing film is formed on the first resist pattern, and a resist that does not contain a silicon-containing resin as a main constituent component is further formed on the second silicon-containing film as a second resist film. Forming a second resist pattern by exposure, development, and dry etching using the second resist pattern formed in the step as an etching mask. Etching the film and simultaneously etching the first silicon-containing film using the first resist pattern exposed at the same time as an etching mask to form a pattern combining the first resist pattern and the second resist pattern. A step of transferring the first and second silicon-containing films to form a silicon-containing film pattern, and further transferring the pattern to the organic underlayer film by dry etching using the obtained silicon-containing film pattern as an etching mask. A pattern forming method characterized in that a pattern is formed on a substrate by performing a step of forming a lower layer film pattern and a step of processing the substrate by dry etching using the obtained organic lower layer film pattern as an etching mask. is there.

One embodiment of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view showing an example of a pattern forming method according to the present invention.
First, as shown in FIGS. 1A to 1F, an organic underlayer film 2 is formed on a substrate 1, a first silicon-containing film 3 is formed on the organic underlayer film 2, and the first On the silicon-containing film 3, a resist containing no silicon-containing resin as a main constituent is formed as a first resist film 4, and a first resist pattern 4 ′ is formed by exposure and development.
Next, as shown in FIGS. 1G to 1J, a second silicon-containing film 5 is formed on the first resist pattern 4 ′ formed in the above step, and the second A step of forming a second resist film 6 on the silicon-containing film 5 and forming a second resist pattern 6 ′ by exposure and development is performed.
Next, as shown in FIG. 1 (k), the second silicon-containing film 5 is etched by dry etching using the second resist pattern 6 ′ formed in the above step as a mask, and the first exposed at the same time. Using the resist pattern 4 ′ as an etching mask, the first silicon-containing film 3 is etched, and a pattern in which the first resist pattern 4 ′ and the second resist pattern 6 ′ are combined is transferred to the first and second silicon-containing films. Then, a step of forming the silicon-containing film pattern 7 is performed.
Further, as shown in FIG. 1L, the organic underlayer film pattern 8 is formed by transferring the pattern to the organic underlayer film 2 by dry etching using the silicon-containing film pattern 7 obtained in the above step as an etching mask. I do.
Then, as shown in FIGS. 1L to 1N, a process of processing the substrate 1 by dry etching using the organic underlayer film pattern obtained in the above process as an etching mask is performed, and a pattern 1 ′ is formed on the substrate. Form. Note that after the pattern is formed on the substrate by the above steps, the organic underlayer film 2 ′ finally remaining on the substrate can be removed by, for example, oxygen gas plasma or etching with hydrogen-nitrogen.

Hereafter, each process is demonstrated concretely.
1 (a) → (b) A step of forming an organic underlayer film 2 on a substrate 1 by spin coating and baking.
1 (b) → (c) A step of forming the first silicon-containing film 3 by spin coating and baking.
1 (c) → (d) A step of forming a first photoresist film 4 by spin coating.
FIG. 1 (d) → (e) First exposure step.
FIG. 1 (e) → (f) A step of forming a first resist pattern 4 ′ by first development.
FIG. 1 (f) → (g) Step of filling the first resist pattern 4 ′ with the second silicon-containing film forming material by spin coating and forming the second silicon-containing film 5 by baking.
FIG. 1 (g) → (h) A step of forming a second photoresist film 6 by spin coating.
FIG. 1 (h) → (i) Step of performing second exposure.
FIG. 1 (i) → (j) Step of forming a second resist pattern 6 ′ by second development.
1 (j) → (k) Using the first resist pattern 4 ′ and the second resist pattern 6 ′ as an etching mask, the first and second silicon-containing films 3 and 5 are processed by reactive etching to contain silicon. Forming the film pattern 7;
FIG. 1 (k) → (l) A step of forming the organic underlayer film pattern 8 by processing the organic underlayer film 2 by reactive etching using the silicon-containing film pattern 7 formed in the above step as an etching mask.
FIG. 1 (l) → (m) A step of etching the substrate using the organic underlayer film pattern 8 formed in the above step as an etching mask to form a pattern 1 ′ on the substrate.
FIG. 1 (m) → (n) A step of removing the remaining organic underlayer film 2 ′.

  As described above, in the present invention, it is possible to process a resist pattern produced by two exposures and developments into a substrate by one dry etching, and resolution and accuracy without causing a decrease in throughput and pattern deviation. And a finer pattern can be formed on the substrate.

Further, the second silicon-containing film is formed, and the third silicon-containing film is formed on the second silicon-containing film before the second resist film is formed on the second silicon-containing film. By forming a film, a finer pattern can be formed. FIG. 2 is an explanatory view showing an example of a pattern forming method including a step of forming a third silicon-containing film, and the steps will be described below.
First, as shown in FIGS. 2A to 2F, an organic underlayer film 2 is formed on a substrate 1, a first silicon-containing film 3 is formed on the organic underlayer film 2, and the first On the silicon-containing film 3, a resist containing no silicon-containing resin as a main constituent is formed as a first resist film 4, and a first resist pattern 4 ′ is formed by exposure and development.
Next, as shown in FIGS. 2G to 2J, a second silicon-containing film 5 is formed on the first resist pattern 4 ′ formed in the above-described process, and the second silicon is formed. A third silicon-containing film 9 is formed on the containing film 5, and a resist film that does not contain a silicon-containing resin as a main component is formed on the third silicon-containing film 9 as a second resist film 6. Then, a step of forming a second resist pattern 6 ′ by exposure and development is performed.
Next, as shown in FIG. 2 (k), the second silicon-containing film 5 and the third silicon-containing film 9 are etched by dry etching using the second resist pattern 6 ′ formed in the above step as a mask. At the same time, the first silicon-containing film 3 is etched using the first resist pattern 4 ′ exposed at the same time as an etching mask, and a pattern obtained by combining the first resist pattern 4 ′ and the second resist pattern 6 ′ is first and A step of transferring to the second silicon-containing film to form the silicon-containing film pattern 7 is performed.
Further, as shown in FIG. 2 (l), a process of transferring the pattern to the organic underlayer film 2 by dry etching using the silicon-containing film pattern 7 obtained in the above step as an etching mask to form an organic underlayer film pattern 8 I do.
Then, as shown in FIGS. 2L to 2N, a step of processing the substrate 1 by dry etching using the organic underlayer film pattern obtained in the above step as an etching mask is performed, and the pattern 1 ′ is formed on the substrate. Form. Note that after the pattern is formed on the substrate by the above steps, the organic underlayer film 2 ′ finally remaining on the substrate can be removed by, for example, oxygen gas plasma or etching with hydrogen-nitrogen.

Hereafter, each process is demonstrated concretely.
2 (a) → (b) A step of forming the organic underlayer film 2 on the substrate 1 by spin coating and baking.
2 (b) → (c) A step of forming the first silicon-containing film 3 by spin coating and baking.
FIG. 2 (c) → (d) A step of forming the first photoresist film 4 by spin coating.
FIG. 2 (d) → (e) First exposure step.
FIG. 2 (e) → (f) A step of forming a first resist pattern 4 ′ by first development.
2 (f) → (g) a step of filling the first resist pattern 4 ′ with the second silicon-containing film forming material by spin coating and forming the second silicon-containing film 5 by baking; A step of forming the containing film 9 by spin coating baking.
2 (g) → (h) Step of forming the second photoresist film 6 by spin coating.
FIG. 2 (h) → (i) Step of performing second exposure.
FIG. 2 (i) → (j) Step of forming a second resist pattern 6 ′ by second development.
2 (j) → (k) The first, second, and third silicon-containing films 3, 5, and 9 are reactively etched using the first resist pattern 4 ′ and the second resist pattern 6 ′ as an etching mask. Processing to form a silicon-containing film pattern 7;
2 (k) → (l) A step of forming the organic underlayer film pattern 8 by processing the organic underlayer film 2 by reactive etching using the silicon-containing film pattern 7 formed in the above step as an etching mask.
2 (l) → (m) A step of etching the substrate using the organic underlayer film pattern 8 formed in the above step as an etching mask to form a pattern 1 ′ on the substrate.
2 (m) → (n) A step of removing the remaining organic lower layer film 2 ′.

  As described above, by forming the third silicon-containing film on the second silicon-containing film, the reflectance control for the film formed by the second silicon-containing film and the first resist pattern can be performed. Therefore, a finer pattern can be formed. Note that the number of materials can be reduced by using the silicon-containing composition for forming the first silicon-containing film as the silicon-containing composition for forming the third silicon-containing film.

  In the method of forming a pattern on a substrate by lithography according to the present invention, a silicon-containing film effective as an etching mask is formed on the substrate from the silicon-containing film-forming composition by spin coating or the like, similar to a photoresist film. It is possible. 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. The particularly preferable temperature range is preferably 300 ° C. or lower in order to reduce thermal damage to the lower organic underlayer film in the first silicon-containing film. In the second and third silicon-containing films, since a photoresist film having poor heat resistance is formed, a particularly preferable temperature range is 200 ° C. or less.

Here, in the present invention, the silicon-containing film can be formed on the processed portion of the substrate via the organic underlayer film, and a photoresist film can be formed thereon to perform pattern formation. .
In this case, examples of the processed portion of the substrate include 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. .

More specifically, the substrate can be a substrate in which a layer to be processed (processed portion) is formed on a base substrate. The base substrate is not particularly limited, and may be made of Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, or the like, which is different from the layer to be processed. May be used. The layer to be _{processed, Si, SiO 2, SiN,} SiON, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. and various low dielectric films and etching stopper film is used In general, it can be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

  In the present invention, a commercially available organic antireflection film may be formed between the silicon-containing film and the upper resist film. At this time, the structure of the antireflection film is a compound having an aromatic substituent. It is preferable that the antireflection film does not cause an etching load on the upper resist film when the pattern of the upper resist film is transferred by dry etching. For example, if the thickness is 80% or less, preferably 50% or less of the upper resist film, the load during dry etching becomes very small. In this case, the antireflection film is preferably adjusted so that the minimum reflection is 2% or less, preferably 1% or less, more preferably 0.5% or less.

  As the resist used in the present invention, a general organic resist can be used except for a silicon-containing resist. Basically, a negative type or a positive type may be used, and a chemical amplification type or not. However, the resist used in the method of forming a pattern on the substrate by lithography according to the present invention is preferably a chemically amplified resist, and more preferably a positive chemically amplified resist. As the chemically amplified resist, any one having an aromatic skeleton used for exposure by a KeF excimer laser in a resin or one having an aliphatic polycyclic compound skeleton used for exposure by an ArF excimer laser in any of the resins is used. Although many are disclosed, any resist can be used in the pattern forming method of the present invention, but in order to use it with a pattern rule of 100 nm or less, ArF exposure is actually required.

  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. However, there are differences in characteristics depending on what kind of resin is used. Already known resins can be broadly classified into poly (meth) acrylic, COMA (CycloOlefin Maleic Anhydride), COMA- (meth) acrylic hybrid, ROMP (RingOpeningMethationPolymerization), polynorbornene, and the like. Since a resist composition using a (meth) acrylic resin ensures 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 acid, (meth) acrylic acid ester having an acid labile group having an adamantane skeleton (Japanese Patent Laid-Open No. 9-73173), norbornane or tetracyclododecane skeleton is used. A (meth) acrylic acid ester having an acid labile group (Japanese Patent 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 (WO 00/01684 pamphlet), (meth) acrylic acid having an oxanorbornane side chain An ester (Japanese Patent Laid-Open No. 2000-159758) and a (meth) acrylic acid ester having a hydroxyadamantyl side chain (Japanese Patent Laid-Open No. 8-12626) are particularly preferred because they provide good etching resistance and high resolution. it can. Further, a polymer containing a unit (for example, 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 swells in the polymer. In particular, it has been attracting attention as a resist polymer corresponding to the immersion method, which has been attracting attention in recent years, because it has high resolving properties. Decreasing is a problem. 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. A large number of basic substances are also known and exemplified in 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 a 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 film of the present invention, an organic underlayer film is provided between the silicon-containing film of the present invention and the substrate. When the organic underlayer film is used as an etching mask for the substrate, the organic underlayer film is preferably an organic film having an aromatic skeleton. A silicon-containing material may be used as long as the silicon content is 15% by mass or less.

  In the case of a multilayer resist method using an organic film as an etching mask for a substrate as an organic underlayer film, the organic film is a film that transfers a patterned resist pattern to a silicon-containing film and then transfers the pattern once again. In addition, the silicon-containing film has 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 is required for the condition for etching the substrate.

  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, and disclosed in JP-A-2005-128509. In addition to 4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin (molecular weight 11,000), a number of resins including novolak resin are used as resist underlayer film materials for two-layer resist method and three-layer resist method. Any of them can be used. In addition, when it is desired to increase the heat resistance as compared with a normal novolac, a polycyclic skeleton such as 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin can be added. Can also be selected (for example, JP-A-2004-153125). Further, if the organic film is formed at a low temperature, a hydroxystyrene-based resin can also be selected, but there is also an effect of introducing a polycyclic skeleton in order to increase the etching resistance thereof, for example, indene, fluorene, etc. Can be copolymerized. Further, in a case where heat resistance is particularly required for forming an organic film, a polyimide resin can be used (Japanese Patent Laid-Open No. 2004-153124).

  As the solvent used for dissolving the resin, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether, and mixed solvents thereof can be used in addition to propylene glycol monomethyl ether acetate. On the other hand, it is dissolved and applied in an amount of about 200 to 10,000 parts, particularly about 300 to 5,000 parts.

  The organic underlayer film can be formed on a substrate by spin coating or the like, similar to the photoresist composition, using a composition solution. After forming the resist underlayer film by spin coating or the like, it is desirable to bake to evaporate the organic solvent. 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 organic underlayer film is 10 nm or more, particularly 50 nm or more, and preferably 50,000 nm or less, although it varies depending on etching processing conditions. Although it is an advantage of a general multilayer resist method that the film thickness width of the organic underlayer film can be increased, it is 30 to 20000 nm, particularly 50 to 15000 nm, depending on the material of the substrate, processing conditions, etc. in the pattern forming method of the present invention. Good results are obtained in the range of. The thickness of the silicon-containing film according to the present invention is preferably 1 nm to 200 nm, and the thickness of the photoresist film is preferably 1 nm to 300 nm.

The silicon-containing compound contained in the composition for forming a silicon-containing film used in the present invention can be obtained, for example, by hydrolytic condensation of a monomer (hydrolyzable silicon compound) with an acid catalyst. Although the following method can be illustrated as a manufacturing method of a preferable silicon-containing compound, it is not restricted to this method.
The monomer used as a starting material can be represented by the following general formula (3).
R ¹ _m1 R ² _m2 R ³ _m3 Si (OR) _(4-m1-m2-m3) (3)
(R is an alkyl group having 1 to 3 carbon atoms, R ¹ , R ² , and R ³ are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, m1, m2, m3 Are independently 0 or 1.)
As the silicon-containing compound contained in the silicon-containing film-forming composition used in the present invention, one obtained by hydrolytic condensation of one or two or more mixtures selected from the monomers represented by the general formula (3) is used. be able to.

Here, the organic group means a group containing carbon, further contains hydrogen, and may contain nitrogen, oxygen, sulfur, silicon and the like. Examples of the organic group for R ¹ , R ² , and R ³ include linear, branched, and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and other unsubstituted monovalent hydrocarbon groups, and these A group in which one or more hydrogen atoms of the group are substituted with an epoxy group, an ester group, an alkoxy group, a hydroxy group, or the like, -O-, -CO-, -OCO-, -COO-, -OCOO- And a group represented by the following general formula (4), such as a group having an intervening group, an organic group containing a silicon-silicon bond, and the like.

Preferred as R ¹ , R ² , R ³ of the monomer represented by the general formula (3) are hydrogen atom, 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, Examples thereof include alkenyl groups such as vinyl groups and allyl groups, alkynyl groups such as ethynyl groups, and aryl groups such as phenyl groups and tolyl groups as light absorbing groups, and aralkyl groups such as benzyl groups and phenethyl groups.

  For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxysilane can be exemplified as monomers as the tetraalkoxysilane in which m1 = 0, m2 = 0, and m3 = 0. Tetramethoxysilane and tetraethoxysilane are preferable.

  For example, as trialkoxysilane in which m1 = 1, m2 = 0, m3 = 0, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i o-propoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, n-butyltrimethoxysilane, n-butyltri Ethoxysilane, n-butyltri-npropoxysilane, n-butyltri-iso-propoxysilane, sec-butyltrimethoxysilane, sec-butyl-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl- Tri-iso-propoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-npropoxysilane, t-butyltri-iso-propoxysilane, cyclopropyltrimethoxysilane, cyclopropyltrieth Sisilane, cyclopropyl-tri-n-propoxysilane, cyclopropyl-tri-iso-propoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyl-tri-n-propoxysilane, cyclobutyl-tri-iso-propoxy Silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl-tri-n-propoxysilane, cyclopentyl-tri-iso-propoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyl-tri-n-propoxysilane, cyclohexyl -Tri-iso-propoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyl-to Ri-n-propoxysilane, cyclohexenyl-tri-iso-propoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyl-tri-n-propoxysilane, cyclohexenylethyltri-iso-propoxy Silane, cyclooctanyltrimethoxysilane, cyclooctanyltriethoxysilane, cyclooctanyl-tri-n-propoxysilane, cyclooctanyl-tri-iso-propoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadi Enylpropyltriethoxysilane, cyclopentadienylpropyl-tri-n-propoxysilane, cyclopentadienylpropyl-tri-iso-propoxysilane, bicyclohepteni Trimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyl-tri-n-propoxysilane, bicycloheptenyl-tri-iso-propoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyl-tri- Examples thereof include n-propoxysilane, bicycloheptyl-tri-iso-propoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyl-tri-n-propoxysilane, adamantyl-tri-iso-propoxysilane and the like. Further, as a light absorbing monomer, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane Benzyltri-iso-propoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltri-n-propoxysilane, tolyltri-iso-propoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltri-n-propoxysilane, Phenethyl tri-iso-propoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltri-n-propoxysilane, naphthyltri-i It can be exemplified o- propoxy silane.

  Preferably, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyl Trimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltrimethoxysilane, iso-butyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyl Trimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohex Cycloalkenyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, benzyl trimethoxysilane, benzyl triethoxysilane, phenethyl trimethoxysilane, phenethyl triethoxysilane.

  For example, as dialkoxysilane in which m1 = 1, m2 = 1, m3 = 0, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl -Di-iso-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxy Silane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, diiso-propyl- Di-n-propoxysilane, -Iso-propyl-di-iso-propoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyl-di-iso- Propoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-t- Butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyl-di-n-propoxysilane, di-t-butyl-di-iso-propoxysilane, di-cyclopropyldimethoxysilane, di-cyclopropyl Diethoxysilane, di-cyclopropyl-di-n-propoxysilane, di-cyclopropyl-di-i o-propoxysilane, di-cyclobutyldimethoxysilane, di-cyclobutyldiethoxysilane, di-cyclobutyl-di-n-propoxysilane, di-cyclobutyl-di-iso-propoxysilane, di-cyclopentyldimethoxysilane, di- Cyclopentyldiethoxysilane, di-cyclopentyl-di-n-propoxysilane, di-cyclopentyl-di-iso-propoxysilane, di-cyclohexyldimethoxysilane, di-cyclohexyldiethoxysilane, di-cyclohexyl-di-n-propoxysilane Di-cyclohexyl-di-iso-propoxysilane, di-cyclohexenyl dimethoxysilane, di-cyclohexenyl diethoxysilane, di-cyclohexenyl-di-n-propoxysilane, di-cyclohexenyl-di -Iso-propoxysilane, di-cyclohexenylethyldimethoxysilane, di-cyclohexenylethyldiethoxysilane, di-cyclohexenylethyl-di-n-propoxysilane, di-cyclohexenylethyl-di-iso-propoxysilane, di -Cyclooctanyldimethoxysilane, di-cyclooctanyldiethoxysilane, di-cyclooctanyl-di-n-propoxysilane, di-cyclooctanyl-di-iso-propoxysilane, di-cyclopentadienylpropyldimethoxy Silane, di-cyclopentadienylpropyldiethoxysilane, di-cyclopentadienylpropyl-di-n-propoxysilane, di-cyclopentadienylpropyl-di-iso-propoxysilane, bis-bicycloheptenyl dimethoxysila Bis-bicycloheptenyldiethoxysilane, bis-bicycloheptenyl-di-n-propoxysilane, bis-bicycloheptenyl-di-iso-propoxysilane, bis-bicycloheptyldimethoxysilane, bis-bicycloheptyldiethoxysilane Bis-bicycloheptyl-di-n-propoxysilane, bis-bicycloheptyl-di-iso-propoxysilane, bis-adamantyldimethoxysilane, bis-adamantyldiethoxysilane, bis-adamantyl-di-n-propoxysilane, bis -Adamantyl-di-iso-propoxysilane etc. can be illustrated. Examples of the light absorbing monomer include diphenyldimethoxysilane, diphenyl-di-ethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyl-di-npropoxysilane, diphenyl-di-iso-propoxysilane, and the like. .

  Preferably, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, di-n-propyl-di-methoxysilane, di-n-butyldi-methoxy Examples include silane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.

  For example, examples of the monoalkoxysilane in which m1 = 1, m2 = 1, and m3 = 1 include trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, and dimethylethylethoxysilane. Examples of the light absorbing monomer include dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, and the like.

  Preferable examples include trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane and the like.

Another example of the organic group represented by R ¹ , R ² , or R ³ is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of an epoxy group, an ester group, an alkoxy group, and a hydroxy group. Examples of the organic group having at least one carbon-oxygen single bond and carbon-oxygen double bond in the general formula (3) include those represented by the following general formula (4).

炭素数１〜４のアルコキシ基、炭素数１〜６のアルキルカルボニルオキシ基、又は炭素数１〜６のアルキルカルボニル基であり、Ｑ_１とＱ_２とＱ_３とＱ_４は各々独立して−ＣｑＨ_{（２ｑ−ｐ）}Ｐ_ｐ−（式中、Ｐは上記と同様であり、ｐは０〜３の整数であり、ｑは０〜１０の整数である。）、ｕは０〜３の整数であり、Ｓ_１とＳ_２は各々独立して−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−又は−ＯＣＯＯ−を表す。ｖ１、ｖ２、ｖ３は、各々独立して０又は１を表す。これらとともに、Ｔは脂環又は芳香環からなる２価の基であり、Ｔの例を以下に示す。ＴにおいてＱ_２とＱ_３と結合する位置は、特に限定されないが、立体的な要因による反応性や反応に用いる市販試薬の入手性等を考慮して適宜選択できる。） _{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 - (4)
(In the above formula, P is a hydrogen atom, a hydroxyl group, a group having an epoxy ring represented by the following formula,

An alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms, and Q _1, Q _2, Q _{3, and} Q ₄ are each independently- CqH _(2q-p) P _p- (wherein P is the same as above, p is an integer of 0 to 3, q is an integer of 0 to 10), u is an integer of 0 to 3 S _{1 and} S ₂ each independently represent —O—, —CO—, —OCO—, —COO— or —OCOO—. v1, v2, and v3 each independently represent 0 or 1. Together with these, T is a divalent group consisting of an alicyclic ring or an aromatic ring, and examples of T are shown below. The position at which Q _{2 and} Q ₃ are bonded to each other in T is not particularly limited, but can be appropriately selected in consideration of reactivity due to steric factors, availability of commercially available reagents used in the reaction, and the like. )

  Preferable examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) include the following. In addition, in the following formula, (Si) is described in order to indicate the bonding site with Si.

Moreover, the organic group containing a silicon- silicon bond can also be used as an example of the organic group of R < ¹ >, R < ² >, R < ³ >. Specifically, the following can be mentioned.

  One or two or more of these monomers can be selected and used as a reaction raw material to form a silicon-containing compound by mixing before or during the reaction.

The silicon-containing compound is preferably produced by hydrolytic condensation of monomers using at least one compound selected from inorganic acids and sulfonic acid derivatives as an acid catalyst.
Preferable examples of the acid catalyst used at this time include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. The catalyst is used in an amount of 10 ⁻⁶ mol to 10 mol, preferably 10 ⁻⁵ mol to 5 mol, more preferably 10 ⁻⁴ mol to 1 mol, relative to 1 mol of silicon monomer.

  The amount of water when obtaining a silicon-containing compound by hydrolysis condensation from these monomers is 0.01 to 100 mol, more preferably 0.05 to 50 mol, per mol of hydrolyzable substituent bonded to the monomer. More preferably, 0.1 to 30 mol is added. Thus, if it adds within the range of 0.01-100 mol, there is no possibility that the apparatus used for reaction may become excessive, and it is economical.

  As an operation method, a monomer is added to an aqueous catalyst solution to start a hydrolysis condensation reaction. At this time, an organic solvent may be added to the catalyst aqueous solution, the monomer may be diluted with the organic solvent, or both may be performed. The reaction temperature is 0 to 100 ° C, preferably 5 to 80 ° C. A method in which the temperature is maintained at 5 to 80 ° C. when the monomer is dropped and then ripened at 20 to 80 ° C. is preferable.

  Examples of organic solvents that can be added to the catalyst aqueous solution or that can dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and acetone. , Acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl 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, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, γ-Butyllactone and mixtures thereof are preferred.

Among these solvents, preferred are water-soluble ones. For example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, Examples thereof include polyhydric alcohol condensate derivatives such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran and the like.
Among these, those having a boiling point of 100 ° C. or less are particularly preferable.

  In addition, the usage-amount of an organic solvent is 0-1,000 ml with respect to 1 mol of monomers, Especially 0-500 ml is preferable. If the amount of the organic solvent used is 1,000 ml or less, there is no fear that the reaction vessel becomes excessive, and it is economical.

  Thereafter, if necessary, a neutralization reaction of the catalyst is performed, and the alcohol generated by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous reaction mixture solution. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. The alkaline substance may be any substance as long as it shows alkalinity in water.

  Subsequently, the alcohol produced by the hydrolytic condensation reaction is removed from the reaction mixture. The temperature at which the reaction mixture is heated at this time depends on the added organic solvent and the type of alcohol generated by the reaction, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and even more preferably 15 to 80 ° C. . The degree of vacuum at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or lower, more preferably absolute pressure of 80 kPa or lower, and still more preferably absolute pressure. Is 50 kPa or less. Although it is difficult to accurately know the amount of alcohol removed at this time, it is desirable to remove approximately 80% by mass or more of the alcohol produced.

  Next, in order to remove the acid catalyst used for the hydrolysis condensation from the reaction mixture, the silicon-containing compound is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the silicon-containing compound and separates into two layers when mixed with water. For example, 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, Butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether , Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Recall monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Examples include acetate, γ-butyl lactone, methyl isobutyl ketone, cyclopentyl methyl ether, and the like, and mixtures thereof.

  It is also possible to use a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent. For example, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol monomethyl ether + ethyl acetate, butane Diol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + Ethyl acetate, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobutyl Ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether + methyl isobutyl ketone, propylene glycol monoethyl ether + methyl isobutyl ketone, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol Monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + Cyclopen Methyl ether, ethylene glycol monomethyl ether + cyclopentyl methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl ether + cyclopentyl Methyl ether, methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl ether acetate, 2-propanol + propylene glycol methyl ether acetate, propylene glycol monomethyl ether + propylene glycol Methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl Combinations of ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate, and the like can be raised.

  Furthermore, it is also possible to use a mixture of a higher alcohol having 4 or more carbon atoms and a poorly water-soluble organic solvent. Examples of the higher alcohol having 4 or more carbon atoms include 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1,1-dimethyl-1-propanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2- Hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol 2,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1, -Heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-methyl 2-hexanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 2-methyl-3-hexanol, 3-methyl-3-hexanol, 4-methyl-3 -Hexanol, 5-methyl-3-hexanol, 2,2-dimethyl-1-pentanol, 2,3-dimethyl-1-pentano 2,4-dimethyl-1-pentanol, 2-ethyl-1-pentanol, 3-ethyl-1-pentanol, 2,3-dimethyl-2-pentanol, 2,4-dimethyl-2- Pentanol, 3,3-dimethyl-2-pentanol, 3,4-dimethyl-2-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-2-pentanol, 2,2-dimethyl -3-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 1-octanol, 2-octanol, 3-octanol, 4 -Octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol 2-methyl-2-heptanol, 3-methyl-2-heptanol, 4-methyl-2-heptanol, 5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol, 3-methyl-3-heptanol, 4-methyl-3-heptanol, 5-methyl-3-heptanol, 6-methyl-3-heptanol, 2,2-dimethyl-1-hexanol, 2,3-dimethyl-1- Hexanol, 2,4-dimethyl-1-hexanol, 2,5-dimethyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, 2, 3- Dimethyl-2-hexanol, 2,4-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, 3,3-dimethyl-2 Hexanol, 3,4-dimethyl-2-hexanol, 3,5-dimethyl-2-hexanol, 4,4-dimethyl-2-hexanol, 4,5-dimethyl-2-hexanol, 3-ethyl-2-hexanol, 4-ethyl-2-hexanol, 2,2-dimethyl-3-hexanol, 2,3-dimethyl-3-hexanol, 2,4-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 3- Ethyl-3-hexanol, 4-ethyl-3-hexanol, 2,2,3-trimethyl-1-pentanol, 2,2,4-trimethyl-1-pentanol, 2,3,3-trimethyl-1- Pentanol, 2,3,4-trimethyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 3,3,4-trimethyl-1-pen Nord, 3, 4, 4-trimethyl-1-pentanol, 2-ethyl-2-methyl-1-pentanol, 2-ethyl-3-methyl-1-pentanol, 2-ethyl-4-methyl-1 -Pentanol, 3-ethyl-2-methyl-1-pentanol, 3-ethyl-3-methyl-1-pentanol, 3-ethyl-4-methyl-1-pentanol, 3-ethyl-3-methyl 2-pentanol, 3-ethyl-4-methyl-2-pentanol, 2-propyl-1-pentanol, 1-nonanol, 2-nonanol, 3-nonanol, 3,5,5-trimethyl-1- Hexanol, 2,6-dimethyl-4-heptanol, 3-ethyl-2, 2-dimethyl-3-pentanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 3,7-di Examples include methyl-1-octanol, 3,7-dimethyl-3-octanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol and the like. Is done. A mixed solvent obtained by combining these higher alcohols with ethyl acetate, methyl isobutyl ketone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, and the like is preferable, but is not limited thereto.

  The mixing ratio of the water-soluble organic solvent or higher alcohol and the poorly water-soluble organic solvent is appropriately selected. 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass.

  Subsequently, the acid catalyst can be removed by washing with neutral water. As this water, what is usually called deionized water or ultrapure water may be used. The amount of this water is 0.01 to 100 L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L with respect to 1 L of the silicon-containing compound solution. In this washing method, both may be placed in the same container, stirred, and allowed to stand to separate the aqueous layer. The number of times of washing may be one or more, but it is preferably about 1 to 5 times because the effect of washing only is not obtained even after washing 10 times or more.

  Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of removing the acid catalyst after neutralization with an epoxy compound such as ethylene oxide or propylene oxide. These methods can be appropriately selected according to the acid catalyst used in the reaction.

  In the present invention, the fact that the acid catalyst is substantially removed means that the acid catalyst used in the reaction remains in the silicon-containing compound at 10% by mass or less, preferably 5% by mass or less. Means that.

  The washing operation at this time may cause a part of the silicon-containing compound to escape to the aqueous layer and may have substantially the same effect as the fractionation operation. In view of the fractionation effect, it may be selected as appropriate.

  Thus, a silicon-containing compound with good storage stability can be obtained by substantially removing the acid catalyst.

  The final solvent is added to the silicon-containing compound solution from which the acid catalyst has been removed, and the solvent is exchanged under reduced pressure to obtain a silicon-containing compound solution. The temperature of solvent exchange at this time depends on the type of extraction solvent to be removed, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 15 to 80 ° C. The degree of reduced pressure at this time varies depending on the type of the extraction solvent to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or lower, more preferably 80 kPa or lower, more preferably 50 kPa in absolute pressure. It is as follows.

  At this time, the silicon-containing compound may become unstable by changing the solvent. Although this occurs due to the compatibility between the final solvent and the silicon-containing compound, in order to prevent this, a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms, which will be described later, may be added as a stabilizer. . The amount to be added is 0 to 25 parts by weight, preferably 0 to 15 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the silicon-containing compound in the solution before the solvent exchange. 0.5 parts by mass or more is preferable. If necessary for the solution before the solvent exchange, an acid may be added to perform the solvent exchange operation.

  Preferred as the final solvent to be added to the silicon-containing compound solution is an alcohol solvent, and particularly the solvent used in the second silicon-containing film-forming composition is a solvent that does not dissolve the resist pattern, for example, having 4 carbon atoms. The above higher alcohols are preferred. Specifically, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1- Butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1,1-dimethyl-1-propanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2 -Pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butyl 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3- Heptanol, 4-heptanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-methyl-2-hexanol, 3-methyl- 2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 2-methyl-3-hexanol, 3-methyl-3-hexanol, 4-methyl-3-hexanol, 5-methyl-3- Hexanol, 2,2-dimethyl-1-pentanol, 2,3-dimethyl-1-pentanol, 2,4-dimethyl-1- Butanol, 2-ethyl-1-pentanol, 3-ethyl-1-pentanol, 2,3-dimethyl-2-pentanol, 2,4-dimethyl-2-pentanol, 3,3-dimethyl-2- Pentanol, 3,4-dimethyl-2-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-2-pentanol, 2,2-dimethyl-3-pentanol, 2,3-dimethyl -3-pentanol, 2,4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-methyl-2-heptano 3-methyl-2-heptanol, 4-methyl-2-heptanol, 5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol, 3-methyl-3-heptanol 4-methyl-3-heptanol, 5-methyl-3-heptanol, 6-methyl-3-heptanol, 2,2-dimethyl-1-hexanol, 2,3-dimethyl-1-hexanol, 2,4-dimethyl -1-hexanol, 2,5-dimethyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2 4-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, 3,3-dimethyl-2-hexanol, 3,4-dimethyl Lu-2-hexanol, 3,5-dimethyl-2-hexanol, 4,4-dimethyl-2-hexanol, 4,5-dimethyl-2-hexanol, 3-ethyl-2-hexanol, 4-ethyl-2- Hexanol, 2,2-dimethyl-3-hexanol, 2,3-dimethyl-3-hexanol, 2,4-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 3-ethyl-3-hexanol, 4-ethyl-3-hexanol, 2,2,3-trimethyl-1-pentanol, 2,2,4-trimethyl-1-pentanol, 2,3,3-trimethyl-1-pentanol, 2, 3 4-trimethyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 3,3,4-trimethyl-1-pentanol, 3,4,4-trime 1-pentanol, 2-ethyl-2-methyl-1-pentanol, 2-ethyl-3-methyl-1-pentanol, 2-ethyl-4-methyl-1-pentanol, 3-ethyl- 2-methyl-1-pentanol, 3-ethyl-3-methyl-1-pentanol, 3-ethyl-4-methyl-1-pentanol, 3-ethyl-3-methyl-2-pentanol, 3- Ethyl-4-methyl-2-pentanol, 2-propyl-1-pentanol, 1-nonanol, 2-nonanol, 3-nonanol, 3,5,5-trimethyl-1-hexanol, 2,6-dimethyl- 4-heptanol, 3-ethyl-2, 2-dimethyl-3-pentanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 3, 7-dimethyl-1-octanol, 3 7-dimethyl-3-octanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol and the like.

On the other hand, alcohol solvents are preferable as the final solvent added to the first and third silicon-containing film forming compositions, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol are particularly preferable. And monoalkyl ether derivatives such as butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, Ethylene glycol monopropyl ether and the like are preferable. Any one of these solvents that does not dissolve the first resist pattern may be used as the final solvent of the second silicon-containing film-forming composition.

  Moreover, as another reaction operation, water or a water-containing organic solvent is added to a monomer or an organic solution of the monomer to start a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to water or a water-containing 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.

  When an organic solvent is used, water-soluble ones are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butane Diol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl Chromatography ether acetate, propylene glycol monoethyl ether acetate, a polyhydric alcohol condensate derivatives such as propylene glycol monopropyl ether and the like can be given a mixture thereof.

  The amount of the organic solvent used may be the same as the above amount. The resulting reaction mixture is post-treated in the same manner as described above to obtain a silicon-containing compound.

  The molecular weight of the obtained silicon-containing compound can be adjusted not only by the selection of the monomer but also by controlling the reaction conditions during the polymerization. Is less likely to occur. Therefore, it is preferable to use a material having 100,000 or less, more preferably 200 to 50,000, and still more preferably 300 to 30,000. The data relating to the mass average molecular weight represents molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using RI as a detector and polystyrene as a standard substance.

  The silicon-containing film-forming composition of the present invention may contain two or more types of silicon-containing compounds having different compositions and / or reaction conditions as long as they are produced under acidic conditions.

  A silicon-containing film-forming composition can be prepared by further blending the silicon-containing compound with a thermal crosslinking accelerator, a monovalent or divalent organic acid having 1 to 30 carbon atoms, and an organic solvent.

In the present invention, it is preferable to contain a thermal crosslinking accelerator in order to further accelerate the crosslinking reaction during the formation of the silicon-containing film. As such a thing, the compound shown by General formula (1) and (2) can be mentioned.
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, and b is 0 or an integer of 1 or more, and a + b is a valence of a hydroxyl group or an organic acid group.)
MA (2)
(Wherein M is sulfonium, iodonium or ammonium, and A is a non-nucleophilic counterion.)

  Examples of the compound represented by the general formula (1) include alkali metal organic acid salts. For example, lithium, sodium, potassium, rubidium, cesium hydrochloride, formate, acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, Decanoate, oleate, stearate, linoleate, linolenate, benzoate, phthalate, isophthalate, terephthalate, salicylate, trifluoroacetate, monochloroacetate, dichloroacetate Salt, monovalent salt such as trichloroacetate, monovalent or divalent oxalate, malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate , Diethyl malonate, succinate, methyl succinate, glutarate, adipate, itaconate, maleate, fumarate, citraco Salt, citric acid, and carbonic acid.

  Specifically, lithium formate, lithium acetate, lithium propionate, lithium butanoate, lithium pentanoate, lithium hexanoate, lithium heptanoate, lithium octanoate, lithium nonanoate, lithium decanoate, lithium oleate, lithium stearate , Lithium linoleate, lithium linolenate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate , Lithium hydroxide, lithium hydrogen oxalate, lithium hydrogen malonate, lithium methyl malonate, lithium hydrogen ethylmalonate, lithium hydrogen propylmalonate, Lithium hydrogen phosphate, lithium dimethyl malonate, lithium diethyl malonate, lithium hydrogen succinate, lithium hydrogen methyl succinate, lithium hydrogen glutarate, lithium hydrogen adipate, lithium hydrogen itaconate, lithium hydrogen maleate, hydrogen fumarate Lithium, lithium hydrogen citrate, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium methylmalonate, lithium ethylmalonate, lithium propylmalonate, lithium butylmalonate, lithium dimethylmalonate, diethyl Lithium malonate, lithium succinate, lithium methyl succinate, lithium glutarate, lithium adipate, lithium itaconate, lithium maleate, lithium fumarate, lithium citraconic acid, que Lithium acid, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butanoate, sodium pentanoate, sodium hexanoate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium oleate, stearic acid Sodium, sodium linoleate, sodium linolenate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, trichloroacetic acid Sodium, sodium hydroxide, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen malonate Sodium hydrogen ethylmalonate, sodium propylmalonate, sodium butylmalonate, sodium dimethylmalonate, sodium diethylmalonate, sodium succinate, sodium methylsuccinate, sodium hydrogenglutarate, hydrogen adipate Sodium, sodium hydrogen itaconate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citraconic acid, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium methylmalonate, sodium ethylmalonate, propyl Sodium malonate, sodium butylmalonate, sodium dimethylmalonate, sodium diethylmalonate, sodium succinate, sodium methylsuccinate, Sodium oxalate, sodium adipate, sodium itaconate, sodium maleate, sodium fumarate, sodium citraconic acid, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, hexane Potassium acetate, potassium heptanoate, potassium octanoate, potassium nonanoate, potassium decanoate, potassium oleate, potassium stearate, potassium linoleate, potassium linolenate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate , Potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, water Potassium hydrogen oxalate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen methyl malonate, potassium hydrogen ethyl malonate, potassium hydrogen propylmalonate, potassium hydrogen butylmalonate, potassium hydrogen dimethylmalonate, potassium hydrogen diethylmalonate, succinic acid Potassium hydrogen hydrogen, potassium hydrogen succinate, potassium hydrogen glutarate, hydrogen hydrogen adipate, potassium hydrogen itaconate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium hydrogen carbonate, oxalic acid Potassium, potassium malonate, potassium methylmalonate, potassium ethylmalonate, potassium propylmalonate, potassium butylmalonate, potassium dimethylmalonate, potassium diethylmalonate, potassium succinate Examples thereof include potassium methyl succinate, potassium glutarate, potassium adipate, potassium itaconate, potassium maleate, potassium fumarate, potassium citraconic acid, potassium citrate, potassium carbonate and the like.

  Examples of the compound represented by the general formula (2) include sulfonium compounds, iodonium compounds, and ammonium compounds represented by (Q-1), (Q-2), and (Q-3).

（式中、Ｒ^２０４、Ｒ^２０５、Ｒ^２０６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^２０５とＲ^２０６とは環を形成してもよく、環を形成する場合には、Ｒ^２０５、Ｒ^２０６はそれぞれ炭素数１〜６のアルキレン基を示す。Ａ^‐は非求核性対向イオンを表す。Ｒ^２０７、Ｒ^２０８、Ｒ^２０９、Ｒ^２１０は、Ｒ^２０４、Ｒ^２０５、Ｒ^２０６と同様であるが、水素原子であってもよい。Ｒ^２０７とＲ^２０８、Ｒ^２０７とＲ^２０８とＲ^２０９とは環を形成してもよく、環を形成する場合には、Ｒ^２０７とＲ^２０８及びＲ^２０７とＲ^２０８とＲ^２０９は炭素数３〜１０のアルキレン基を示す。）

Wherein R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ 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. ²⁰⁵ and R ²⁰⁶ may form a ring, and in the case of forming a ring, R ²⁰⁵ and R ²⁰⁶ each represent an alkylene group having 1 to 6 carbon atoms, A ⁻ represents a non-nucleophilic counter ion. represents ^{.R 207, R 208, R 209} , R 210 ^is, R ^204, R ^205, is similar to ^{R 206,} which may be a hydrogen atom ^{.R 207} and ^{R 208, R 20} And the ^{R 208} and ^{R 209} may form a ring, when they form a ^{ring, R 207} and ^{R 208} and ^{R 207, R 208} and ^{R 209} represents an alkylene group having 3 to 10 carbon atoms. )

R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ , and R ²¹⁰ 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 aryl groups include phenyl group, naphthyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxy. Alkyl such as alkoxyphenyl group such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group Alkyl naphthyl groups such as phenyl group, 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 groups such as And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like. And 2-oxoethyl group.

A ^- of the non-nucleophilic counter hydroxide ions as an ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate Acid ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, p-methylbenzoate ion, pt-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion , Salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, chlorate ion, perchlorate ion, bromine Monovalent ions such as acid ions and iodate ions Monovalent or divalent oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate Acid ion, glutarate ion, adipate ion, itaconic acid ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, carbonate ion and the like can be mentioned.

  Specifically, as the sulfonium compound, triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butanoate, triphenylsulfonium pentanoate, triphenylsulfonium hexanoate, triphenylsulfonium heptanoate, octane Triphenylsulfonium acid, triphenylsulfonium nonanoate, triphenylsulfonium decanoate, triphenylsulfonium oleate, triphenylsulfonium stearate, triphenylsulfonium linoleate, triphenylsulfonium linolenate, triphenylsulfonium benzoate, p-methyl Triphenylsulfonium benzoate, triphenylsulfonium pt-butylbenzoate, triphthalate phthalate Phenylsulfonium, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate Phenylsulfonium, triphenylsulfonium hydroxide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, dimethyl Triphenylsulfonium malonate, diethylmalon Triphenylsulfonium, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylcitraconic acid Sulfonium, triphenylsulfonium citrate, triphenylsulfonium carbonate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, triphenylsulfonium nitrate, triphenylsulfonium chlorate, triphenylsulfonium perchlorate, bromic acid Triphenylsulfonium, triphenylsulfonium iodate, bistriphenylsulfonium oxalate Bistriphenylsulfonium malonate, bistriphenylsulfonium methylmalonate, bistriphenylsulfonium methylmalonate, bistriphenylsulfonium dimethylmalonate, bistriphenylsulfonium dimethylmalonate, Bistriphenylsulfonium succinate, bistriphenylsulfonium methyl succinate, bistriphenylsulfonium glutarate, bistriphenylsulfonium adipate, bistriphenylsulfonium itaconate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconic acid, citric acid Bistriphenylsulfo Um, and the like carbonate, bis triphenylsulfonium.

  Specific examples of the iodonium compound include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium pentanoate, diphenyliodonium hexanoate, diphenyliodonium heptanoate, diphenyliodonium octoate, and nonanoic acid. Diphenyliodonium, diphenyliodonium decanoate, diphenyliodonium oleate, diphenyliodonium stearate, diphenyliodonium linoleate, diphenyliodonium linolenate, diphenyliodonium benzoate, diphenyliodonium p-methylbenzoate, diphenyliodonium p-t-butylbenzoate , Diphenyliodonium phthalate, isophthalate Diphenyliodonium, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, diphenyliodonium oxalate, Diphenyliodonium malonate, diphenyliodonium methylmalonate, diphenyliodonium ethylmalonate, diphenyliodonium propylmalonate, diphenyliodonium butylmalonate, diphenyliodonium dimethylmalonate, diphenyliodonium diethylmalonate, diphenyliodonium succinate, methyl Diphenyliodonium succinate, diphenyliodonium glutarate, diphenyliodonium adipate, diphenyliodonium itaconate, diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodonium citrate, diphenyliodonium citrate, diphenyliodonium carbonate, diphenyliodonium chloride, bromide Diphenyliodonium, diphenyliodonium iodide, diphenyliodonium nitrate, diphenyliodonium chlorate, diphenyliodonium perchlorate, diphenyliodonium bromate, diphenyliodonium iodate, bisdiphenyliodonium oxalate, bisdiphenyliodonium malonate, bisdiphenyl methylmalonate Iodonium, bisdiethylmalonate Phenyliodonium, Bisdiphenyliodonium propylmalonate, Bisdiphenyliodonium butylmalonate, Bisdiphenyliodonium dimethylmalonate, Bisdiphenyliodonium diethylmalonate, Bisdiphenyliodonium succinate, Bisdiphenyliodonium methylsuccinate, Bisdiphenyliodonium glutarate, Adipine Examples thereof include bisdiphenyliodonium acid, bisdiphenyliodonium itaconate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

  On the other hand, specific examples of ammonium compounds include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, tetramethylammonium pentanoate, tetramethylammonium hexanoate, tetramethylammonium heptanoate, Tetramethylammonium octoate, tetramethylammonium nonanoate, tetramethylammonium decanoate, tetramethylammonium oleate, tetramethylammonium stearate, tetramethylammonium linoleate, tetramethylammonium linolenate, tetramethylammonium benzoate, p- Tetramethylammonium methylbenzoate, tetramethylammonium pt-butylbenzoate, phthalic acid Tramethylammonium, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, trichloroacetic acid Tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium methylmalonate, tetramethylammonium ethylmalonate, tetramethylammonium propylmalonate, tetramethylammonium butylmalonate, Tetramethylammonium dimethylmalonate Tetramethylammonium acid, tetramethylammonium succinate, tetramethylammonium methylsuccinate, tetramethylammonium glutarate, tetramethylammonium adipate, tetramethylammonium itaconate, tetramethylammonium maleate, tetramethylammonium fumarate, citraconic acid Tetramethylammonium, tetramethylammonium citrate, tetramethylammonium carbonate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium chlorate, tetramethylammonium perchlorate, Tetramethylammonium bromate, tetramethylammonium iodate, bistetramethylan oxalate Monium, bistetramethylammonium malonate, bistetramethylammonium methylmalonate, bistetramethylammonium ethylmalonate, bistetramethylammonium propylmalonate, bistetramethylammonium butylmalonate, bistetramethylammonium dimethylmalonate, diethyl Bistetramethylammonium malonate, bistetramethylammonium succinate, bistetramethylammonium methylsuccinate, bistetramethylammonium glutarate, bistetramethylammonium adipate, bistetramethylammonium itaconate, bistetramethylammonium maleate, fumarate Bistetramethylammonium acid, Bistetramethylammonium citraconic acid, Bistetramethylammonium citrate Monium, Bistetramethylammonium carbonate, Tetrapropylammonium formate, Tetrapropylammonium acetate, Tetrapropylammonium propionate, Tetrapropylammonium butanoate, Tetrapropylammonium pentanoate, Tetrapropylammonium hexanoate, Tetrapropylammonium heptanoate, Octanoic acid Tetrapropylammonium, tetrapropylammonium nonanoate, tetrapropylammonium decanoate, tetrapropylammonium oleate, tetrapropylammonium stearate, tetrapropylammonium linoleate, tetrapropylammonium linolenate, tetrapropylammonium benzoate, p-methylbenzoic acid Tetrapropylammonium acid, pt-butylbenzoic acid Tetrapropylammonium, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dichloroacetic acid Tetrapropylammonium, tripropylacetate tetrapropylammonium hydroxide, tetrapropylammonium oxalate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium methylmalonate, tetrapropylammonium ethylmalonate, tetrapropylammonium propylmalonate, butyl Malonic acid tetrapropi Ruammonium, tetrapropylammonium dimethylmalonate, tetrapropylammonium diethylmalonate, tetrapropylammonium succinate, tetrapropylammonium methylsuccinate, tetrapropylammonium glutarate, tetrapropylammonium adipate, tetrapropylammonium itaconate, tetramaleic acid tetra Propyl ammonium, tetrapropyl ammonium fumarate, tetrapropyl ammonium citrate, tetrapropyl ammonium citrate, tetrapropyl ammonium carbonate, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrapropyl ammonium iodide, tetrapropyl ammonium nitrate, chloric acid Tetrapropylammonium, tetrapropylaperchlorate Monium, tetrapropylammonium bromate, tetrapropylammonium iodate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium methylmalonate, bistetrapropylammonium ethylmalonate, bistetrapropyl propylmalonate Ammonium, bistetrapropylammonium butylmalonate, bistetrapropylammonium dimethylmalonate, bistetrapropylammonium diethylmalonate, bistetrapropylammonium succinate, bistetrapropylammonium methylsuccinate, bistetrapropylammonium glutarate, bisadipate Tetrapropylammonium, bistetrapropylammonium itaconate, maleic acid Stetrapropylammonium, bistetrapropylammonium fumarate, bistetrapropylammonium citraconic acid, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, butanoic acid Tetrabutylammonium, tetrabutylammonium pentanoate, tetrabutylammonium hexanoate, tetrabutylammonium heptanoate, tetrabutylammonium octanoate, tetrabutylammonium nonanoate, tetrabutylammonium decanoate, tetrabutylammonium oleate, tetrabutyl stearate Ammonium, tetrabutylammonium linoleate, tetrabutyl linolenate Ammonium, tetrabutylammonium benzoate, tetrabutylammonium p-methylbenzoate, tetrabutylammonium benzoate, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate , Tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium oxalate, tetrabutyl malonate Ammonium, tetrabutylammonium methylmalonate, tetrabutylethylmalonate Ammonium, tetrabutylammonium propylmalonate, tetrabutylammonium butylmalonate, tetrabutylammonium dimethylmalonate, tetrabutylammonium diethylmalonate, tetrabutylammonium succinate, tetrabutylammonium methylsuccinate, tetrabutylammonium glutarate, adipic acid Tetrabutylammonium, tetrabutylammonium itaconate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconic acid, tetrabutylammonium citrate, tetrabutylammonium carbonate, tetrabutylammonium chloride, tetrabutylammonium bromide, Tetrabutylammonium iodide, tetrabutylammonium nitrate, chlorate Butylammonium, tetrabutylammonium perchlorate, tetrabutylammonium bromate, tetrabutylammonium iodate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium methylmalonate, bistetrabutyl ethylmalonate Ammonium, bistetrabutylammonium propylmalonate, bistetrabutylammonium butylmalonate, bistetrabutylammonium dimethylmalonate, bistetrabutylammonium diethylmalonate, bistetrabutylammonium succinate, bistetrabutylammonium methylsuccinate, glutaric acid Bistetrabutylammonium, bistetrabutylammonium adipate, bistetrabutylammonium itaconate Examples thereof include bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citraconic acid, bistetrabutylammonium citrate, and bistetrabutylammonium carbonate.

  In addition, the said thermal crosslinking promoter can be used individually by 1 type or in combination of 2 or more types. The amount of the thermal crosslinking accelerator added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). is there.

  In order to ensure the stability of the composition for forming a silicon-containing film of the present invention, it is preferable to add a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms to the silicon-containing compound. Acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid , Diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. In particular, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are preferable. Moreover, in order to maintain stability, you may mix and use two or more types of acids. The addition amount is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the silicon-containing compound contained in the composition. Alternatively, the organic acid is preferably converted into the pH of the composition so that 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and even more preferably 0.5 ≦ pH ≦ 6. It is good to mix.

  As the organic solvent added when producing the silicon-containing composition used for achieving the process of the present invention, a solvent that does not dissolve the resist pattern, for example, a higher alcohol having 4 or more carbon atoms is preferable. Specifically, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1- Butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1,1-dimethyl-1-propanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2 -Pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butyl 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3- Heptanol, 4-heptanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-methyl-2-hexanol, 3-methyl- 2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 2-methyl-3-hexanol, 3-methyl-3-hexanol, 4-methyl-3-hexanol, 5-methyl-3- Hexanol, 2,2-dimethyl-1-pentanol, 2,3-dimethyl-1-pentanol, 2,4-dimethyl-1- Butanol, 2-ethyl-1-pentanol, 3-ethyl-1-pentanol, 2,3-dimethyl-2-pentanol, 2,4-dimethyl-2-pentanol, 3,3-dimethyl-2- Pentanol, 3,4-dimethyl-2-pentanol, 4,4-dimethyl-2-pentanol, 3-ethyl-2-pentanol, 2,2-dimethyl-3-pentanol, 2,3-dimethyl -3-pentanol, 2,4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-methyl-2-heptano 3-methyl-2-heptanol, 4-methyl-2-heptanol, 5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol, 3-methyl-3-heptanol 4-methyl-3-heptanol, 5-methyl-3-heptanol, 6-methyl-3-heptanol, 2,2-dimethyl-1-hexanol, 2,3-dimethyl-1-hexanol, 2,4-dimethyl -1-hexanol, 2,5-dimethyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2 4-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, 3,3-dimethyl-2-hexanol, 3,4-dimethyl Lu-2-hexanol, 3,5-dimethyl-2-hexanol, 4,4-dimethyl-2-hexanol, 4,5-dimethyl-2-hexanol, 3-ethyl-2-hexanol, 4-ethyl-2- Hexanol, 2,2-dimethyl-3-hexanol, 2,3-dimethyl-3-hexanol, 2,4-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 3-ethyl-3-hexanol, 4-ethyl-3-hexanol, 2,2,3-trimethyl-1-pentanol, 2,2,4-trimethyl-1-pentanol, 2,3,3-trimethyl-1-pentanol, 2, 3 4-trimethyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 3,3,4-trimethyl-1-pentanol, 3,4,4-trime 1-pentanol, 2-ethyl-2-methyl-1-pentanol, 2-ethyl-3-methyl-1-pentanol, 2-ethyl-4-methyl-1-pentanol, 3-ethyl- 2-methyl-1-pentanol, 3-ethyl-3-methyl-1-pentanol, 3-ethyl-4-methyl-1-pentanol, 3-ethyl-3-methyl-2-pentanol, 3- Ethyl-4-methyl-2-pentanol, 2-propyl-1-pentanol, 1-nonanol, 2-nonanol, 3-nonanol, 3,5,5-trimethyl-1-hexanol, 2,6-dimethyl- 4-heptanol, 3-ethyl-2, 2-dimethyl-3-pentanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 3, 7-dimethyl-1-octanol, 3 7-dimethyl-3-octanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol.

  Furthermore, the stability can be improved by adding the following organic solvents as stabilizers to these organic solvents. For example, it is preferable to add a water-soluble organic solvent (addition solvent) having one or more hydroxyl groups or nitrile groups in the molecule. Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, glycerin, 2-methoxyethanol, 2-ethoxy Ethanol, 2- (methoxymethoxy) ethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Pill ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2 -Propanol, 1-isopropoxy-2-propanol, 2-methoxy-1-propanol, 2-ethoxy-1-propanol, 2-propoxy-1-propanol, 2-isopropoxy-1-propanol, dipropylene glycol, di Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl Pills ether, furfuryl alcohol, tetrahydrofurfuryl alcohol, diacetone alcohol, trifluoroethanol, methyl lactate, ethyl lactate, acetonitrile, and the like.

  Furthermore, the stability of the silicon-containing film forming composition can be improved by adding an ether compound represented by the following structure as a stabilizer. That is, it is a cyclic ether compound having one or more hydroxyl groups as substituents in the molecule. As such a thing, the compound shown below can be mentioned.

Here, R ^90a is a hydrogen atom, a linear, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms, R ⁹¹ O— (CH ₂ CH ₂ O) _n1 — (CH ₂ ) _n2 — (here 0 ≦ n1 ≦ 5, 0 ≦ n2 ≦ 3, R ⁹¹ is a hydrogen atom or a methyl group), R ⁹² O— [CH (CH ₃ ) CH ₂ O] _n3 — (CH ₂ ) _n4 — (where, 0 ≦ n3 ≦ 5, 0 ≦ n4 ≦ 3, R ⁹² is a hydrogen atom or a methyl group), and R ^90b is a linear group having 1 to 10 carbon atoms having a hydroxyl group, one or more hydroxyl groups , Branched, cyclic hydrocarbon group, HO— (CH ₂ CH ₂ O) _n5 — (CH ₂ ) _n6 — (where 1 ≦ n5 ≦ 5, 1 ≦ n6 ≦ 3), HO— [CH (CH ₃₎ CH ₂ O] _{n7 - (CH 2) n8 -} ( wherein a 1 ≦ n7 ≦ 5,1 ≦ n8 ≦ 3).

  In addition, the said stabilizer can be used individually by 1 type or in combination of 2 or more types. The addition amount of the acid stabilizer is preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). . Moreover, these acid stabilizers can be used individually by 1 type or in mixture of 2 or more types. When such an acid stabilizer is added, the charge of the acid is further stabilized and contributes to the stabilization of the silicon-containing compound in the composition.

  In the present invention, water may be added to the composition. When water is added, the silicon-containing compound is hydrated, so that the lithography performance is improved. The content of water in the solvent component of the composition is more than 0% and less than 50%, particularly preferably 0.3 to 30%, more preferably 0.5 to 20%. If each component is added in an excessive amount, the uniformity of the coating film is deteriorated, and in the worst case, repelling occurs. On the other hand, if the addition amount is small, the lithography performance deteriorates, which is not preferable. In addition, the usage-amount of all the solvents containing water is 500-100,000 mass parts with respect to 100 mass parts of base polymers, Especially 400-50,000 mass parts is suitable.

In the present invention, a photoacid generator may be added to the silicon-containing film forming composition. As the photoacid generator used in the present invention,
(AI) Onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
(A-II) a diazomethane derivative represented by the following general formula (P2):
(A-III) a glyoxime derivative of the following general formula (P3),
(A-IV) A bissulfone derivative of the following general formula (P4),
(AV) a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
(A-VI) β-ketosulfonic acid derivative,
(A-VII) disulfone derivative,
(A-VIII) nitrobenzyl sulfonate derivative,
(A-IX) sulfonic acid ester derivatives and the like.

（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、これらの基にある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。）

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 hydrogen atoms in these groups may be substituted with an alkoxy group or the like. R ^{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. Represents.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group. 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, etc. Is mentioned. 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 aryl groups include phenyl group, naphthyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxy. Alkyl such as alkoxyphenyl group such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group Alkyl naphthyl groups such as phenyl group, 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 groups such as And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. K ^- non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, Torifure of - DOO, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzene Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（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。Ｒ^１０３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. Examples of K ⁻ include the same ones as described in the formulas (P1a-1), (P1a-2), and (P1a-3).

（式中、Ｒ^１０５、Ｒ^１０６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−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 halogen atoms having 6 to 20 carbon atoms. An aryl 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、Ｒ^１０７、Ｒ^１０８、Ｒ^１０９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。Ｒ^１０８、Ｒ^１０９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、Ｒ^１０８、Ｒ^１０９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、Ｒ^１１０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、これらの基に含まれる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。Ｒ^１１１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 part or all of the hydrogen atoms contained in these groups are Further, 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 straight chain having 1 to 8 carbon atoms, A branched or substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, wherein some or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; carbon A phenyl group which may be substituted with an alkyl group, alkoxy group, nitro group or acetyl group of 1 to 4; a heteroaromatic group of 3 to 5 carbon atoms; or a substituent with a chlorine atom or a fluorine atom It has.)

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 of 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 group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group Methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group, methoxyhexyl group, methoxyheptyl group and the like.

  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 photoacid generators. Diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid Triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-Toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyv Nyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, butanesulfonic acid Triphenylsulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, trifluoromethane Dimethylphenylsulfonium sulfonate, dimethylphenylsulfonium p-toluenesulfonate Dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl trifluoromethanesulfonate ( Onium salts such as 2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium 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 p-toluenesulfonic acid 2,6-dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl.

  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) ) Sulfonium, onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n -Diazomethane derivatives such as -butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane , Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, 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. A sulfonic acid ester derivative is preferably used.

  In addition, the said photo-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 by mass, more preferably 0.05 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). .

Furthermore, in this invention, it is possible to mix | blend surfactant as a modifier with a silicon-containing film formation composition as needed. Here, the surfactant is preferably a nonionic one, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, fluorine-containing allganosiloxane compound. Is 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”, “KH-20”, “KH-30”, and “X-70-093” are mentioned.
In addition, the addition amount of surfactant can be made into a normal amount in the range which does not prevent the effect of this invention, and shall be 0-10 mass parts with respect to 100 mass parts of base polymers, especially 0-1 mass part. Is preferred.

  In addition to the above types, many materials for forming a silicon-containing film are already known, and basically any known material can be used, but it must have the following two functions. is there. One is a function of absorbing exposure light, which needs to be optimized by adjusting the light absorption ability of the refractive index and the film thickness. The other is that when a resist is applied on the antireflection film, it is insolubilized in the resist solvent so as not to cause so-called intermixing that crosses the resist resin near the interface. This insolubilization is usually performed by cross-linking between resins. In general, the material for forming a silicon-containing antireflection film has a type in which a cross-linking reaction occurs between side chains or between a side chain and silanol in addition to the SOG type in which a cross-linking reaction occurs between silanol groups during the film forming process as described above. Yes, either type can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Synthesis example (1)
60 g of methanol, 200 g of ion-exchanged water and 1 g of 35% hydrochloric acid were charged into a 1,000 ml glass flask, and a mixture of 50 g of tetraethoxysilane, 50 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane was added at room temperature. The product was subjected to hydrolysis and condensation for 8 hours at room temperature, and then methanol and by-product ethanol were distilled off under reduced pressure. Thereto was added 300 ml of propylene glycol propyl ether, and the mixture was concentrated under reduced pressure to obtain 300 g of a propylene glycol propyl ether solution of a silicon-containing compound (polymer concentration 20%). When the molecular weight of this in terms of polystyrene was measured, it was Mw = 2,000.

Synthesis example (2)
Of the production method shown in Synthesis Example 1, 300 g of a 4-methyl-2-pentanol solution of a silicon-containing compound (polymer concentration) except that propylene glycol propyl ether was replaced with 4-methyl-2-pentanol. 20%). When the resulting solution was analyzed for chloro ions by ion chromatography, it was not detected. When the molecular weight of this in terms of polystyrene was measured, it was Mw = 2,500.

Synthesis example (3)
60 g of methanol, 200 g of ion-exchanged water and 1 g of 35% hydrochloric acid were charged into a 1,000 ml glass flask, and a mixture of 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane was added at room temperature. The product was subjected to hydrolysis and condensation for 8 hours at room temperature, and then methanol and by-product ethanol were distilled off under reduced pressure. Thereto, 800 ml of ethyl acetate and 300 ml of 4-methyl-2-pentanol were added, the aqueous layer was separated, and hydrochloric acid used in the reaction was removed. To the remaining organic layer, 100 ml of a 1% maleic acid aqueous solution was added, stirred, allowed to stand, and separated. After repeating this twice, 100 ml of ion-exchanged water was added, stirred, allowed to stand, and separated. This was repeated three times. 200 ml of 4-methyl-2-pentanol was added to the remaining organic layer and concentrated under reduced pressure to obtain 300 g of a 4-methyl-2-pentanol solution of a silicon-containing compound (polymer concentration 20%). When the resulting solution was analyzed for chloro ions by ion chromatography, it was not detected. When the molecular weight of this in terms of polystyrene was measured, it was Mw = 2,800.

Example 1
First, a propylene glycol monomethyl ether acetate solution of 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolak resin (molecular weight 11000) (Japanese Patent Laid-Open No. 2005-128509) on a substrate (resin 28 parts by mass, solvent 100 parts) Was spin-coated and heated to 300 ° C. for 1 minute to form a 300 nm-thick organic underlayer film.
Next, a first silicon-containing resin film was formed on the organic underlayer film. The resin of Synthesis Example 1 was used as the first silicon-containing film forming composition.

Resin of Synthesis Example 1: 10 parts by mass (50 parts by mass as a solution)
Thermal crosslinking accelerator: Triphenylsulfonium chloride 1 part by mass Organic solvent: Propylene glycol propyl ether 200 parts by mass

  The composition was spin-coated on the organic underlayer film and heated on a hot plate at 250 ° C. for 60 seconds to form a 200 nm silicon-containing antireflection film.

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
塩基性添加物：トリエタノールアミン ０．０２質量部
溶剤：プロピレングリコールメチルエーテルアセテート ８００質量部 Further, a first resist film was formed on the silicon-containing antireflection film using an ArF excimer laser light exposure resist composition.
resin

10 parts by mass Photoacid generator: Triphenylsulfonium nonafluorobutanesulfonate 0.2 parts by mass Basic additive: Triethanolamine 0.02 parts by mass Solvent: Propylene glycol methyl ether acetate 800 parts by mass

  The composition was spin-coated on a substrate on which a first silicon-containing resin film was formed, and heated at 120 ° C. for 60 seconds to form a first resist film having a thickness of 150 nm.

Next, the first resist film is subjected to pattern exposure using a light source corresponding to the resist, for example, KrF excimer laser light, ArF excimer laser light, or F ₂ laser light, according to a conventional method, and is adjusted to each resist. The resist pattern can be obtained by performing a developing operation after necessary processing.

  In the case of the resist, for example, it is exposed with an ArF exposure apparatus (Nikon Corp .; S307E, NA0.85, σ0.93, normal illumination, 6% halftone phase shift mask), heated at 110 ° C. for 60 seconds, and then 2.38. Development was performed with an aqueous solution of% tetramethylammonium hydroxide (TMAH) to obtain a repeating pattern of 70 nm lines and 210 nm space patterns at a pitch of 280 nm. No footing or the like was observed in the obtained positive first resist pattern.

Next, the first resist pattern is embedded with the second silicon-containing film forming composition. The resin shown in Synthesis Example 2 was used as the second silicon-containing film forming composition.
Resin of Synthesis Example 2: 20 parts by mass (100 parts by mass as a solution)
Thermal crosslinking accelerator: Triphenylsulfonium chloride 1 part by mass Organic solvent: 4-methyl-2-pentanol 100 parts by mass

  The composition was spin-coated on the first resist pattern obtained above and heated at 150 ° C. for 60 seconds on a hot plate to form a 200 nm second silicon-containing antireflection film.

Finally, the same composition as the resist composition in which the first resist film is formed on the second silicon-containing film is spin-coated and heated at 120 ° C. for 60 seconds to form a second resist film having a thickness of 150 nm. Filmed.
As in the first resist pattern formation, exposure was performed with an ArF exposure apparatus, development was performed through the same procedure, and a repeated pattern of 70 nm lines and 210 nm space patterns was obtained at a pitch of 280 nm. At this time, the exposure mask was adjusted so that the second resist pattern could be formed in the center of the space portion of the first resist pattern. No footing or the like was observed in the completed positive pattern.

(Example 2)
First, an organic underlayer film having a thickness of 300 nm was formed on the substrate in the same manner as in Example 1. Next, a first silicon-containing film was formed on the organic underlayer film. The resin of Synthesis Example 1 was used as the first silicon-containing film forming composition.

Resin of Synthesis Example 1: 10 parts by mass (50 parts by mass as a solution)
Thermal crosslinking accelerator: Triphenylsulfonium chloride 1 part by mass Organic solvent: Propylene glycol propyl ether 200 parts by mass

  The composition was spin-coated on the organic underlayer film and heated on a hot plate at 250 ° C. for 60 seconds to form a 200 nm silicon-containing antireflection film.

  Further, the same first resist composition as that of Example 1 was spin-coated on the silicon-containing antireflection film on the first silicon-containing resin film, heated at 120 ° C. for 60 seconds, and a first film having a thickness of 150 nm was formed. A resist film was formed

  By the same treatment as in Example 1, a repeated pattern of a 70 nm line and a 210 nm space pattern was obtained at a pitch of 280 nm. No footing or the like was observed in the obtained positive first resist pattern.

Next, the first resist pattern is embedded with the second silicon-containing film forming composition. The resin shown in Synthesis Example 3 was used as the second silicon-containing film forming composition.
Resin of Synthesis Example 3: 20 parts by mass (100 parts by mass as a solution)
Thermal crosslinking accelerator: Triphenylsulfonium chloride 2 parts by mass Organic solvent: 4-methyl-2-pentanol 100 parts by mass

  The composition was spin-coated on the first resist pattern obtained above and heated at 150 ° C. for 60 seconds on a hot plate to form a 200 nm second silicon-containing antireflection film.

  Next, a third silicon-containing resin film was formed on the second silicon-containing film. The resin of Synthesis Example 1 was used as the third silicon-containing film forming composition.

Resin of Synthesis Example 1: 10 parts by mass (50 parts by mass as a solution)
Thermal crosslinking accelerator: Triphenylsulfonium chloride 1 part by mass Organic solvent: Propylene glycol propyl ether 200 parts by mass

Finally, the same composition as the resist composition in which the first resist film is formed on the third silicon-containing film is spin-coated and heated at 120 ° C. for 60 seconds to form a second resist film having a thickness of 150 nm. Filmed.
As in the first resist pattern formation, exposure was performed with an ArF exposure apparatus, development was performed through the same procedure, and a repeated pattern of 70 nm lines and 210 nm space patterns was obtained at a pitch of 280 nm. At this time, the exposure mask was adjusted so that the second resist pattern could be formed in the center of the space portion of the first resist pattern. No footing or the like was observed in the completed positive pattern.

The substrates obtained in Examples 1 and 2 were dry etched by the following operation.
First, using the second resist pattern as an etching mask, the organic material was etched under dry etching conditions where the etching rate of silicon oxide was significantly high. As conditions, a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., chamber pressure 40 Pa, RF power 1300 W, gap 9 mm, CHF 3 gas flow rate 30 ml / min, CF ₄ gas flow rate 30 ml / min, ArF gas flow rate 100 ml / min are used. did. When the second and third silicon-containing films are etched by this dry etching, a silicon-containing film pattern can be obtained almost without being affected by the pattern change caused by the side etching of the resist film. That is, since the first resist pattern has a slower etching rate than the silicon-containing film, the first resist pattern remains in the space portion of the second resist pattern. Further, the etching is continued and the first silicon-containing film is etched to form an etching pattern with a half pitch of the pattern formed at the time of exposure.

Next, with respect to the substrate having the pattern-transferred silicon-containing film obtained above, as a dry etching condition in which the etching rate of the organic underlayer film material is significantly higher than that of silicon, reactive dry etching (chamber The organic film was etched by pressure 60 Pa, RF power 600 W, Ar gas flow rate 40 sccm, O ₂ gas flow rate 60 sccm, gap 9 mm), and the exposure pattern obtained as a resist pattern was transferred to the organic underlayer film at half the pitch. .

  As examples of dry etching conditions used at this time, in addition to the above-described method using gas plasma containing oxygen, a method using gas plasma containing hydrogen-nitrogen can be used. Although the pattern of the organic lower layer film is obtained by this etching process, the uppermost resist film layer is usually lost at the same time, and the outermost layer becomes a silicon oxide film when an antireflection film or stronger etching is performed.

  Further, the substrate was dry-etched using the organic underlayer film pattern obtained here as an etching mask. Here, for example, when the above-described fluorine-based dry etching conditions are used again, the pattern is transferred to the substrate, such as silicon oxide or metal silicon, with high accuracy. This etching can basically use any single conditions, for example, dry etching used in a layer resist method in which chlorine-based dry etching may be performed. Note that, for example, when fluorine gas plasma is used as the dry etching condition, the antireflection film and the silicon oxide film remaining on the organic underlayer film are removed by etching simultaneously with the etching of the substrate.

  After the above steps, the pattern transfer to the substrate is completed, but the organic underlayer film finally remaining on the substrate can be removed by, for example, oxygen gas plasma or etching with hydrogen-nitrogen. As described above, according to the pattern forming method of the present invention, the pitch of the pattern formed at the time of exposure can be formed with a double density in one etching process.

It is explanatory drawing which shows an example of the pattern formation process which concerns on this invention. It is explanatory drawing which shows an example of the pattern formation process which concerns on this invention including the process of forming a 3rd silicon-containing film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2, 2 '... Organic underlayer film, 3 ... 1st silicon containing film | membrane,
4 ... 1st resist film, 4 '... 1st resist pattern,
5 ... second silicon-containing film, 6 ... second resist film,
6 '... second resist pattern, 7 ... silicon-containing film pattern,
8 ... Organic underlayer film pattern, 9 ... Third silicon-containing film
1 '... A pattern formed on the substrate.

Claims (11)

  In a method of forming a pattern on a substrate by lithography, at least an organic underlayer film is formed on the substrate, a first silicon-containing film is formed on the organic underlayer film, and the first silicon-containing film is formed A resist containing no silicon-containing resin as a main constituent is formed as a first resist film, and a first resist pattern is formed by exposure and development; and the first resist formed in the step A second silicon-containing film is formed on the resist pattern, and a resist that does not contain a silicon-containing resin as a main constituent component is further formed on the second silicon-containing film as a second resist film. Forming a second resist pattern by exposure and development, and etching the second silicon-containing film by dry etching using the second resist pattern formed in the step as an etching mask. And etching the first silicon-containing film using the first resist pattern exposed at the same time as an etching mask to form a pattern in which the first resist pattern and the second resist pattern are combined. And a step of forming a silicon-containing film pattern by transferring to the second silicon-containing film, and further transferring the pattern to the organic underlayer film by dry etching using the obtained silicon-containing film pattern as an etching mask. The pattern formation is characterized in that a pattern is formed on the substrate by performing a pattern forming step and a step of processing the substrate by dry etching using the obtained organic underlayer film pattern as an etching mask. Method.   Before forming the second silicon-containing film and forming the second resist film on the second silicon-containing film, a third silicon is formed on the second silicon-containing film. The pattern forming method according to claim 1, wherein a containing film is formed.   3. The silicon-containing film forming composition for forming the first silicon-containing film is used as the silicon-containing film forming composition for forming the third silicon-containing film. The pattern forming method according to 1.   A silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst as the silicon-containing film-forming composition for forming the first, second and third silicon-containing films The pattern forming method according to claim 1, wherein the pattern forming method is used.   The pattern formation method according to claim 4, wherein at least one compound selected from inorganic acids and sulfonic acid derivatives is used as a hydrolysis-condensation catalyst for the silicon-containing compound.   The pattern according to claim 4 or 5, wherein the silicon-containing film-forming composition is obtained by further blending the silicon-containing compound with at least a thermal crosslinking accelerator and an organic solvent. Forming method. The pattern forming method according to claim 6, wherein the thermal crosslinking accelerator is at least one compound represented by the following general formula (1) or (2).
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, b is 0 or 1 In the above integers, a + b is a valence of a hydroxyl group or an organic acid group.)
MA (2)
(Wherein M is sulfonium, iodonium or ammonium, and A is a non-nucleophilic counterion.)   The silicon-containing film-forming composition is further formed by blending a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms. The pattern forming method according to 1.   The silicon-containing compound obtained by substantially removing the acid catalyst from the reaction mixture of the silicon-containing compound obtained by the hydrolytic condensation is used. Pattern forming method.   The pattern forming method according to claim 1, wherein a positive chemically amplified resist is used as the resist not including the silicon-containing resin. The pattern formation method according to claim 1, wherein the organic underlayer film is an organic film having an aromatic skeleton.

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