# Patent

## Title
Composition for forming a coating type silicon-containing film, substrate, and patterning process

## Abstract

A composition for forming a coating type silicon-containing film, containing one or more silicic acid skeletal structures represented by the formula (1) and one or more silicon skeletal structures represented by the formula (2), wherein the composition contains a coupling between units shown in the formula (2). There can be provided a composition capable of forming a silicon-containing film that has excellent adhesiveness in fine patterning, and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly of carbon which is required in the patterning process.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a composition for forming a coating type silicon-containing film usable in a process for producing a semiconductor device and so forth, a substrate having a film formed from the composition, and a patterning process using the composition.
2. Description of the Related Art
In 1980s, photo-exposure using g-beam (436 nm) or i-beam (365 nm) of mercury lamp as a light source had been widely used in the resist patterning. As a means for finer patterning, shifting to a exposure light having shorter wavelength was assumed to be effective, so that, for the mass production process of DRAM (Dynamic Random Access Memory) with 64 MB (work size of 0.25 μm or less) in 1990s and later ones, KrF excimer laser (248 nm), whose wavelength is shorter than i-beam (365 nm), had been used in place of i-beam as the exposure light source.
However, for production of DRAM with integration of 256 MB and 1 GB or higher requiring further finer processing technologies (work size of 0.2 μm or less), a light source having a further shorter wavelength was required, and thus, a photolithography using ArF excimer laser (193 nm) has been investigated seriously over a decade. It was expected at first that the ArF lithography would be applied to the fabrication of 180 nm-node devices. However, the KrF excimer lithography survived to the mass production of 130 nm-node devices, so that a full-fledged application of the ArF lithography started from the 90 nm-node.
Furthermore, mass production of the 65 nm-node devices is now underway by combining the ArF lithography with a lens having an increased numerical aperture (NA) of 0.9. For the next 45 nm-node devices, further shortening the wavelength of exposure light is progressing, and the F2 lithography with 157 nm wavelength became a candidate. However, there are many problems in the F2 lithography: cost-up of a scanner due to use of a large quantities of expensive CaF2 single crystal for a projection lens; extremely poor durability of a soft pellicle, which leads to change of an optical system due to introduction of a hard pellicle; decrease in etching resistance of a resist film, and so forth. Because of these problems, development of the F2 lithography was suspended, and ArF immersion lithography was introduced. In the ArF immersion lithography, water having a refractive index of 1.44 is introduced between a projection lens and a wafer by a partial fill method. This enables high speed scanning, and further, mass production of the 45 nm-node devices is now underway by using a lens with a NA of 1.3.
For the 32 nm-node lithography, which is a next promising fine processing technology, a lithography with an extreme-ultraviolet beam (EUV) of 13.5 nm-wavelength is considered to be a candidate. Unfortunately, this technology has problems such as needs for a higher output power of the laser, a higher sensitivity of the resist film, a higher resolution, a lower line edge roughness (LER), a non-defect MoSi laminate mask, a lower aberration of the reflective mirror, and so forth; and thus, there are innumerable problems to be solved at present. Development of the immersion lithography with a high refractive index, which is another candidate for the 32 nm-node, was suspended because of low transmittance of LUAG, a candidate for a high refractive index lens, and an inability to obtain a target value of a liquid's refractive index at 1.8. As mentioned above, in the photo-exposure used as a general technology, resolution based on the wavelength of a light source is approaching to its inherent limit.
Accordingly, development has been promoted in fine processing technology for obtaining a work size exceeding a limiting resolution of the existing ArF-immersion exposure technology. As this technology, double patterning technology is proposed. One example of the double patterning technology is a method (1) that includes forming a first photoresist pattern by first exposure and development with an interval rate of a line to a space of 1:3; processing an under layer hard mask by dry etching; laying another hard mask thereon; forming a second line pattern by subjecting the photoresist film to second exposure and development at a space obtained by the first exposure; processing the hard mask by dry etching to form the first pattern and the second pattern alternately. This method allows to form a line and space pattern with half pitch of the exposure pattern.
Also, there is another method (2) that includes forming a first photoresist pattern by first exposure and development with an interval rate of a line to a space of 3:1; processing an under layer hard mask by dry etching; forming a photoresist film thereon; forming a pattern on a remaining portion of the hard mask by second exposure; and processing the hard mask by dry etching using the pattern as a mask. In both methods, the hard mask is processed by dry etching twice, and a pattern with half pitch of the exposure pattern can be formed. The method (1) requires hard mask formation twice, while the method (2) requires hard mask formation only once, but further requires additional formation of a trench pattern which is more difficult to resolve than a line pattern.
As another example, there has been proposed a method (3) that includes forming a line pattern in X direction with a positive resist film by using a dipole light; curing the resist pattern; applying a resist composition thereon again; exposing a line pattern in Y direction by using a dipole light to form a hole pattern from the gap of the grid-like line pattern (Non-Patent Document 1). Moreover, there has also been proposed a method for halving a pitch by one-time pattern exposure by using spacer technology in which a resist pattern, an organic hard mask, or a polysilicon film having a transferred pattern is used as a core pattern, and after forming a silicon oxide film around the core pattern at a low temperature, the core pattern is removed by dry etching or other method.
Accordingly, finer processing is difficult to achieve only by using a resist film present in the upper layer, and a finer patterning process cannot be readily introduced without using a hard mask formed under the resist film. Under the circumstances, multilayer resist method is known as a method in which a hard mask is used as a resist under layer film. In this method, an intermediate film (e.g. a silicon-containing resist under layer film) whose etching selectivity is different from a photoresist film (i.e. an upper layer resist film) is formed between the upper layer resist film and a substrate to be processed, then a pattern is formed with the upper layer resist film, and the pattern is transferred to the resist under layer film by dry etching using the upper layer resist pattern as a dry etching mask, and further the pattern is transferred to the substrate to be processed or a core film of the spacer process by dry etching using the resist under layer film as a dry etching mask.
The present inventors have proposed a composition for forming a silicon-containing resist under layer film as disclosed in Patent Documents 1 and 2 for a patterning in the semiconductor manufacturing process which exceeds the limit of resolution of ArF liquid immersion lithography in recent years. However, it has inherently been used in a process exceeding the limit of resolution of the ArF liquid immersion lithography, whose difficulty is extremely high; therefore it is virtually impossible to pass through the patterning with a yield of 100%, which may result in a retry of the application of upper layer resist due to abnormalities in application of the upper layer resist or in exposure. If the above-mentioned double patterning process becomes the mainstream of the patterning process in the future, difficulty of the patterning process is further increased, and the frequency of the retrying process is expected to be higher.
The retrying process until now is to remove all the multilayered resist under layer film by dry etching, or to remove the silicon-containing resist under layer film by a removing liquid containing hydrofluoric acid, etc., after peeling the upper layer resist by a solvent, so that damage to the substrate to be processed is concerned.
On the other hand, in the cutting-edge semiconductor, technologies such as three-dimensional transistor and through interconnection, etc., have been used to improve properties of the semiconductor. In a patterning process to be used for forming such a structure in the semiconductor, patterning by the multilayer resist method has been employed. In such a patterning, after pattern formation, a step of removing the silicon-containing resist under layer film without causing damage to the pattern is occasionally required. However, main constitutional elements of the conventional silicon-containing resist under layer film and main constitutional elements of the pattern are both silicon in many cases, so that even if one wishes to selectively remove the resist under layer film, it is difficult to suppress the damage to the pattern by either of dry etching or wet etching using a hydrofluoric acid type removing liquid, because these constitutional components are similar.
PRIOR ART DOCUMENTS
Patent Documents


    Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-302873
    Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-262230
    Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-126940
    Patent Document 4: Japanese Patent Laid-Open Publication No. 2010-085893
    Patent Document 5: Japanese Patent Laid-Open Publication No. 2010-085912
    Patent Document 6: Japanese Patent Laid-Open Publication No. 2010-139764
    Non-Patent Document 1: Proc. SPIE Vol. 5377 p 255 (2004)


SUMMARY OF THE INVENTION
As mentioned above, when the conventional silicon-containing resist under layer film is used, problem arises that dry etching or a hydrofluoric acid type removing liquid causes damage to the substrate in the retrying process of patterning or in the manufacturing process of the semiconductor structure.
The present invention has been accomplished in view of the above-mentioned problem, and an object thereof is to provide a composition for forming a coating type silicon-containing film that has excellent adhesiveness in fine pattern, and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which are necessary in the patterning process.
To accomplish the above-mentioned object, the present invention provides a composition for forming a coating type silicon-containing film, comprising
one or more silicic acid skeletal structures represented by the formula (1) and one or more silicon skeletal structures represented by the formula (2), wherein the composition contains a coupling between units in the formula (2),




wherein R1, R2, R3, R4, R5, and R6 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); R7, R8, R9, R10, R11, and R12 each represent a methyl group, a phenyl group, or a hydroxyl group; m10, m11, m12, and m13 each represent a molar fraction in the silicic acid skeletal structure, and satisfy m10+m11+m12+m13=1, 0≦m10≦0.3, 0≦m11≦0.5, 0≦m12≦0.7and 0<m13≦1; and m20, m21, m22, and m23 each represent a molar fraction in the silicon skeletal structure, and satisfy m20+m21+m22+m23=1, 0≦m20≦1, 0≦m21≦1, 0≦m22≦1, and 0≦m23≦1.

The composition for forming a coating type silicon-containing film of the present invention can give a silicon-containing film that has excellent adhesiveness in fine pattern and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which is required in the patterning process. Moreover, the composition for forming a coating type silicon-containing film can give a silicon-containing film in which generation of particles is suppressed by forming it in the coating process. Particularly, when an organic group substituted by a halogen atom is introduced thereinto, the peelability is improved. In addition, the Si—Si bond obtained when units constituting the silicon skeletal structures represented by the formula (2) are bonded to each other is cleaved under alkaline conditions, so that the introduction thereof can enhance the peelability by an alkaline chemical solution.
In this case, the composition for forming a coating type silicon-containing film preferably comprises a solvent and (A) one or more polymers selected from a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more polysilane compounds represented by the formula (A-2-1),

R1R2R3SiOR  (A-1-1)

R4R5Si(OR)2  (A-1-2)

R6Si(OR)3  (A-1-3)

Si(OR)4  (A-1-4)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R1, R2, R3, R4, R5, and R6 have the same meanings as defined above,

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (A-2-1)

wherein R7, R8, R9, R10, R11, and R12 have the same meanings as defined above; and a1, a2, a3, and a4 each represent a molar fraction, and satisfy a1+a2+a3+a4=1, 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, and 0≦a4≦1.

By using such silicon compounds and polysilane compounds for component (A), the composition for forming a coating type silicon-containing film having the silicic acid skeletal structure and the silicon skeletal structure as mentioned above can be obtained.
Further, it is preferred that the compound represented by the formula (A-2-1) to be used in the composition for forming a coating type silicon-containing film have a weight average molecular weight of 1,000 or less.
When the weight average molecular weight is 1,000 or less, a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing the polysilane compound represented by the formula (A-2-1) easily dissolves in a solvent component in the composition for forming a coating type silicon-containing film, and generation of particles during film formation can be prevented.
Alternatively, the composition for forming a coating type BPSG film may comprise a solvent; (A) one or more polymers selected from a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4); and (B) one or more polysilane compounds represented by the formula (B-1),

R1R2R3SiOR  (A-1-1)

R4R5Si(OR)2  (A-1-2)

R6Si(OR)3  (A-1-3)

Si(OR)4  (A-1-4)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R1, R2, R3, R4, R5, and R6 have the same meanings as defined above,

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (B−1)

wherein R7, R8, R9, R10, R11, and R12 have the same meanings as defined above; and a1, a2, a3, and a4 each represent a molar fraction, and satisfy a1+a2+a3+a4=1, 0≦a2≦1, 0≦a2≦1, 0≦a3≦1, and 0≦a4≦1.

By using such silicon compounds for component (A), and further adding the polysilane compounds represented by the formula (B-1) as component (B), the composition for forming a coating type silicon-containing film having the silicic acid skeletal structure and the silicon skeletal structure as mentioned above can be obtained.
Further, it is preferred that the compound represented by the formula (B-1) have a weight average molecular weight of 1,000 or less.
When the weight average molecular weight is 1,000 or less, the compound of formula (B-1) easily dissolves in a solvent component in the composition for forming a coating type silicon-containing film, and generation of particles during film formation can be prevented.
Also, the composition for forming a coating type silicon-containing film preferably further comprises (C) one or more members selected from one or more silicon compounds represented by the formula (C-1), a hydrolysate, a condensate, and a hydrolysis condensate thereof,

R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3)  (C-1)

wherein R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C, and R3C each represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; and c1, c2, and c3 are each 0 or 1, and satisfy 1≦c1+c2+c3≦3.

By using the component (C), the composition for forming a coating type silicon-containing film can give a film that has further improved adhesiveness to a photoresist pattern and does not cause a pattern collapse even in a fine patterning when used as a resist under layer film.
In this case, one or more of R1C, R2C, and R3C in the formula (C-1) are preferably an organic group having a hydroxyl group or a carboxyl group each substituted by an acid-labile group.
If such component (C) is used, the pattern adhesiveness to a fine pattern can be more improved.
Also, the component (C) preferably contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more phosphorus compounds represented by the formulae (C-2-1) to (C-2-6) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,

PX3  (C-2-1)

POX3  (C-2-2)

P2O5  (C-2-3)

H(HPO3)a5OH  (C-2-4)

R13PX2  (C-2-5)

R13POX2  (C-2-6)

wherein R13 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms; and a5 is an integer of 1 or more.

When the component (C) contains the silicon compound and the phosphorous compound, pattern adhesiveness to a fine pattern can be more improved.
Alternatively, the component (C) preferably contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more boron compounds represented by the formulae (C-3-1) to (C-3-3) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,

BX3  (C-3-1)

B2O3  (C-3-2)

R14BX2  (C-3-3)

wherein R14 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

When the component (C) contains the silicon compound and the boron compound, pattern adhesiveness to a fine pattern can be more improved.
Further, the composition for forming a coating type silicon-containing film preferably further comprises an organic compound having 2 or more hydroxyl groups or carboxyl groups in one molecule.
By adding such an organic compound, collapse of the silicon-containing film is promoted during wet etching whereby peeling becomes easy.
Also, the present invention provides a substrate for use in a semiconductor manufacturing process, comprising a silicon-containing film formed on a body to be processed by applying the above-mentioned composition for forming a coating type silicon-containing film.
At this time, the silicon-containing film may function as at least one of a resist under layer film, a flattening film, and an insulating film.
Thus, the composition for forming a coating type silicon-containing film of the present invention can be applied onto the body to be processed to obtain a substrate using it as a resist under layer film, a flattening film, or an insulating film.
In the substrate, the body to be processed may be a semiconductor substrate on which a part or whole of semiconductor circuits have been formed, and the silicon-containing film may be formed by applying the composition for forming a coating type silicon-containing film by spin-coating onto the semiconductor substrate and then baking the same.
By applying the composition for forming a coating type silicon-containing film of the present invention by spin coating onto the semiconductor substrate on which a part or whole of semiconductor circuits have been formed, and then baking the same, a silicon-containing film can be formed on such a substrate.
Also, the present invention provides a patterning process comprising: forming an organic under layer film on a body to be processed by using a coating type organic under layer film material; forming a silicon-containing film on the organic under layer film by using the above-mentioned composition for forming a coating type silicon-containing film; forming an upper layer resist film on the silicon-containing film; forming a pattern with the upper layer resist film; transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and transferring the pattern to the organic under layer film by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.
Furthermore, the present invention provides a patterning process comprising: forming a hard mask mainly consisting of carbon on a body to be processed by a CVD method; forming a silicon-containing film on the hard mask by using the above-mentioned composition for forming a coating type silicon-containing film; forming an upper layer resist film on the silicon-containing film; forming a pattern with the upper layer resist film; transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and transferring the pattern to the hard mask by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.
When pattern formation is carried out by using the composition for forming a coating type silicon-containing film of the present invention, by optimizing the combination of the coating type organic under layer film or the CVD film mainly consisting of carbon as mentioned above, the pattern formed at the upper layer resist film can be transferred to the body to be processed without generating the difference in size conversion.
After forming the mask pattern for processing the body to be processed, the silicon-containing film may be removed by wet etching.
When a pattern is formed by using the composition for forming a coating type silicon-containing film of the present invention, the silicon-containing film can be readily removed by wet etching without causing damage to the coating type organic under layer film or the CVD film mainly consisting of carbon.
The wet etching is preferably performed by an alkaline solution.
A silicon-containing film obtained from the composition for forming a coating type silicon-containing film of the present invention has a Si—Si bond to be cleaved under alkaline conditions, so that it exhibits good peelability particularly when treated with an alkaline solution.
The body to be processed may be a material in which any of a metal film, an amorphous metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film or a metal oxynitride film is formed on a semiconductor substrate on which a part or whole of semiconductor circuits have been formed, as a layer to be processed.
Further, the metal constituting the body to be processed may comprise silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.
Accordingly, the patterning process of the present invention can form a pattern by processing the body to be processed as mentioned above.
Further, the pattern formation of the upper layer resist film is preferably carried out by a lithography method using light with a wavelength of 300 nm or less or EUV light, an electron beam direct drawing method, a directed self-assembly method or a nano-imprinting lithography method.
By using these methods, a fine pattern can be formed with an upper layer resist film.
The coating type silicon-containing film formed by using the composition for forming a coating type silicon-containing film of the present invention may serve as a resist under layer film that has excellent adhesiveness to a photoresist pattern formed thereon and does not cause a pattern collapse even in a fine pattern. Moreover, this coating type silicon-containing film shows high etching selectivity to both of a resist pattern formed at the upper side and an organic film formed at the lower side, so that a formed photoresist pattern can be transferred to the substrate by dry etching process. Moreover, it can be easily wet etched by a removing liquid which does not cause damage to the semiconductor substrate and the coating type organic under layer film or the CVD film mainly consisting of carbon, and the silicon-containing film can be easily wet etched also in the retrying process.
Further, when a flattening film or an insulating film is formed by using the composition for forming a coating type silicon-containing film of the present invention, the silicon-containing film can be formed without generating particles during film formation.
Moreover, when a pattern is formed by using the composition for forming a coating type silicon-containing film of the present invention, by optimizing the combination of the coating type organic under layer film or the CVD film mainly consisting of carbon, a pattern formed with the photoresist can be transferred to the substrate without generating the difference in size conversion.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As mentioned above, when the conventional silicon-containing resist under layer film is used, problems arise that dry etching or a hydrofluoric acid type removing liquid causes damage to the substrate in the retrying process of patterning or in the manufacturing process of the semiconductor structure.
Thus, it has been desired to develop a composition for forming a coating type silicon-containing film that has excellent adhesiveness in fine pattern; and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which are necessary in the patterning process, for example, by an ammonia aqueous solution containing hydrogen peroxide called SC (Standard Clean) 1, or by hydrochloric acid containing hydrogen peroxide called SC2which have been generally used in the semiconductor manufacturing process.
The present inventors have intensively studied to solve the above-mentioned problems, and consequently found that a coating film obtained from a composition containing a silicon-containing compound that has silicon skeletal structures (polysilane structure) can be readily removed by an alkaline SC1, thereby brought the present invention to completion.
In the prior art regarding the silicon-containing resist under layer film, there are techniques disclosed in Patent Documents 3 to 6 as a material containing boron or phosphorus, and further containing an organic cross-linking agent. However, said prior art references do not disclose wet-etching property that is exhibited by combining polysilane structure and an organic cross-linking agent as disclosed in the present invention.
In the following, embodiments of the present invention are explained, but the present invention is not limited thereto. Herein, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents a butyl group, and “Ac” represents an acetyl group.
The present invention is directed to a composition for forming a coating type silicon-containing film which contains one or more silicic acid skeletal structures represented by the formula (1) and one or more silicon skeletal structures represented by the formula (2), and further contains a coupling between units in the formula (2). Herein, “containing a coupling between units in the formula (2)” indicates that the composition contains a Si—Si bond formed by bonding units of one or more kinds shown in the formula (2) to each other.




wherein R1, R2, R3, R4, R5, and R6 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); R7, R8, R9, R10, R11, and R12 each represent a methyl group, a phenyl group, or a hydroxyl group; m10, m11, m12, and m13 each represent a molar fraction in the silicic acid skeletal structure, and satisfy m10+m11+m12+m13=1, 0≦m10≦0.3, 0≦m11≦0.5, 0≦m12≦0.7and 0<m13≦1; and m20, m21, m22, and m23 each represent a molar fraction in the silicon skeletal structure, and satisfy m20+m21+m22+m23=1, 0≦m20≦1, 0≦m21≦1, 0≦m22≦1, and 0≦m23≦1.

In the formula (1), R1, R2, R3, R4, R5, and R6 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a hydrogen atom in the organic group may be substituted by a halogen atom. The halogen atom is preferably a fluorine atom or chlorine atom. If an organic group substituted by such a halogen atom is introduced, a silicon-containing film obtained from the composition for forming a coating type silicon-containing film of the present invention is improved in peelability.
In the formula (1), m10, m11, m12, and m13 each represent a molar fraction in the silicic acid skeletal structure, and satisfy m10+m11+m12+m13=1, 0≦m10≦0.3, 0≦m11≦0.5, 0≦m12≦0.7, and 0<m13≦1.
SiO2 is an essential unit in the silicic acid skeletal structure. When the respective units satisfy the above ratio, a composition for forming a coating type silicon-containing film having good dry etching resistance, pattern adhesiveness, and wet etching property with good balance, can be obtained.
In the formula (2), m20, m21, m22, and m23 each represent a molar fraction in the silicon skeletal structure, and satisfy m20+m21+m22+m23=1, 0≦m20≦1, 0≦m21≦1, 0≦m22≦1, and 0≦m23≦1.
These units constitute the silicon skeletal structure, and the structure may be any of linear, branched, and cyclic.
Such a composition for forming a coating type silicon-containing film can form a silicon-containing film that has excellent adhesiveness in fine pattern, and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which are necessary in the patterning process. In particular, the composition for forming a coating type silicon-containing film of the present invention has a Si—Si bond to be cleaved in an alkaline solution, so that it can give a silicon-containing film excellent in peelability with an alkaline solution.
[Component (A)]
The component (A) in the composition for forming a coating type silicon-containing film of the present invention is preferably one or more polymers selected from a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more polysilane compounds represented by the formula (A-2-1),

R1R2R3SiOR  (A-1-1)

R4R5Si(OR)2  (A-1-2)

R6Si(OR)3  (A-1-3)

Si(OR)4  (A-1-4)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R1, R2, R3, R4, R5, and R6 have the same meanings as defined above,

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (A-2-1)

wherein R7, R8, R9, R10, R11, and R12 have the same meanings as defined above; and a1, a2, a3, and a4 each represent a molar fraction, and satisfy a1+a2+a3+a4=1, 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, and 0≦a4≦1.

[Silicon Compound]

The silicon compound that can be used for component (A) may be exemplified by a material represented by the formula (A-1-1),

R1R2R3SiOR  (A-1-1)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R1, R2, and R3 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s).

Preferable examples of the silicon compound represented by the formula (A-1-1) include trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl ethyl methoxy silane, dimethyl ethyl ethoxy silane, dimethyl phenyl methoxy silane, dimethyl phenyl ethoxy silane, dimethyl benzyl methoxy silane, dimethyl benzyl ethoxy silane, dimethyl phenethyl methoxy silane, dimethyl phenethyl ethoxy silane, etc.
The silicon compound that can be used for component (A) may be exemplified by a material represented by the formula (A-1-2),

R4R5Si(OR)2  (A-1-2)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R4 and R5 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s).

Preferable examples of the silicon compound represented by the formula (A-1-2) include dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl dipropoxy silane, dimethyl diisopropoxy silane, methyl ethyl dimethoxy silane, methyl ethyl diethoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diethyl dipropoxy silane, diethyl diisopropoxy silane, dipropyl dimethoxy silane, dipropyl diethoxy silane, dipropyl dipropoxy silane, dipropyl diisopropoxy silane, diisopropyl dimethoxy silane, diisopropyl diethoxy silane, diisopropyl dipropoxy silane, diisopropyl diisopropoxy silane, dibutyl dimethoxy silane, dibutyl diethoxy silane, dibutyl-dipropoxy silane, dibutyl diisopropoxy silane, di-sec-butyl dimethoxy silane, di-sec-butyl diethoxy silane, di-sec-butyl dipropoxy silane, di-sec-butyl diisopropoxy silane, di-tert-butyl dimethoxy silane, di-tert-butyl diethoxy silane, di-tert-butyl dipropoxy silane, di-tert-butyl diisopropoxy silane, dicyclopropyl dimethoxy silane, dicyclopropyl diethoxy silane, dicyclopropyl dipropoxy silane, dicyclopropyl diisopropoxy silane, dicyclobutyl dimethoxy silane, dicyclobutyl diethoxy silane, dicyclobutyl dipropoxy silane, dicyclobutyl diisopropoxy silane, dicyclopentyl dimethoxy silane, dicyclopentyl diethoxy silane, dicyclopentyl dipropoxy silane, dicyclopentyl diisopropoxy silane, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, dicyclohexyl dipropoxy silane, dicyclohexyl diisopropoxy silane, dicyclohexenyl dimethoxy silane, dicyclohexenyl diethoxy silane, dicyclohexenyl dipropoxy silane, dicyclohexenyl diisopropoxy silane, dicyclohexenylethyl dimethoxy silane, dicyclohexenylethyl diethoxy silane, dicyclohexenylethyl dipropoxy silane, dicyclohexenylethyl diisopropoxy silane, dicyclooctyl dimethoxy silane, dicyclooctyl diethoxy silane, dicyclooctyl dipropoxy silane, dicyclooctyl diisopropoxy silane, dicyclopentadienylpropyl dimethoxy silane, dicyclopentadienylpropyl diethoxy silane, dicyclopentadienylpropyl dipropoxy silane, dicyclopentadienylpropyl diisopropoxy silane, bis(bicycloheptenyl) dimethoxy silane, bis(bicycloheptenyl) diethoxy silane, bis(bicycloheptenyl) dipropoxy silane, bis(bicycloheptenyl) diisopropoxy silane, bis(bicycloheptyl) dimethoxy silane, bis(bicycloheptyl) diethoxy silane, bis(bicycloheptyl) dipropoxy silane, bis(bicycloheptyl) diisopropoxy silane, diadamantyl dimethoxy silane, diadamantyl diethoxy silane, diadamantyl dipropoxy silane, diadamantyl diisopropoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dipropoxy silane, diphenyl diisopropoxy silane, etc.
The silicon compound that can be used for component (A) may be exemplified by a material represented by the formula (A-1-3),

R6Si(OR)3  (A-1-3)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R6 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s).

Preferable examples of the silicon compound represented by the general formula (A-1-3) include trimethoxy silane, triethoxy silane, tripropoxy silane, triisopropoxy silane, methyl trimethoxy silane, methyl triethoxy silane, methyl tripropoxy silane, methyl triisopropoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tripropoxy silane, ethyl triisopropoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, propyl trimethoxy silane, propyl triethoxy silane, propyl tripropoxy silane, propyl triisopropoxy silane, isopropyl trimethoxy silane, isopropyl triethoxy silane, isopropyl tripropoxy silane, isopropyl triisopropoxy silane, butyl trimethoxy silane, butyl triethoxy silane, butyl tripropoxy silane, butyl triisopropoxy silane, sec-butyl trimethoxy silane, sec-butyl triethoxy silane, sec-butyl tripropoxy silane, sec-butyl triisopropoxy silane, tert-butyl trimethoxy silane, tert-butyl triethoxy silane, tert-butyl tripropoxy silane, tert-butyl triisopropoxy silane, isobutyl trimethoxy silane, isobutyl triethoxy silane, allyl trimethoxy silane, allyl triethoxy silane, cyclopropyl trimethoxy silane, cyclopropyl triethoxy silane, cyclopropyl tripropoxy silane, cyclopropyl triisopropoxy silane, cyclobutyl trimethoxy silane, cyclobutyl triethoxy silane, cyclobutyl tripropoxy silane, cyclobutyl triisopropoxy silane, cyclopentyl trimethoxy silane, cyclopentyl triethoxy silane, cyclopentyl tripropoxy silane, cyclopentyl triisopropoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxy silane, cyclohexyl tripropoxy silane, cyclohexyl triisopropoxy silane, cyclohexenyl trimethoxy silane, cyclohexenyl triethoxy silane, cyclohexenyl tripropoxy silane, cyclohexenyl triisopropoxy silane, cyclohexenylethyl trimethoxy silane, cyclohexenylethyl triethoxy silane, cyclohexenylethyl tripropoxy silane, cyclohexenylethyl triisopropoxy silane, cyclooctyl trimethoxy silane, cyclooctyl triethoxy silane, cyclooctyl tripropoxy silane, cyclooctyl triisopropoxy silane, cyclopentadienylpropyl trimethoxy silane, cyclopentadienylpropyl triethoxy silane, cyclopentadienylpropyl tripropoxy silane, cyclopentadienylpropyl triisopropoxy silane, bicycloheptenyl trimethoxy silane, bicycloheptenyl triethoxy silane, bicycloheptenyl tripropoxy silane, bicycloheptenyl triisopropoxy silane, bicycloheptyl trimethoxy silane, bicycloheptyl triethoxy silane, bicycloheptyl tripropoxy silane, bicycloheptyl triisopropoxy silane, adamantyl trimethoxy silane, adamantyl triethoxy silane, adamantyl tripropoxy silane, adamantyl triisopropoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tripropoxy silane, phenyl triisopropoxy silane, benzyl trimethoxy silane, benzyl triethoxy silane, benzyl tripropoxy silane, benzyl triisopropoxy silane, anisyl trimethoxy silane, anisyl triethoxy silane, anisyl tripropoxy silane, anisyl triisopropoxy silane, tolyl trimethoxy silane, tolyl triethoxy silane, tolyl tripropoxy silane, tolyl triisopropoxy silane, phenethyl trimethoxy silane, phenethyl triethoxy silane, phenethyl tripropoxy silane, phenethyl triisopropoxy silane, benzoyloxymethyl trimethoxy silane, benzoyloxymethyl triethoxy silane, benzoyloxymethyl tripropoxy silane, benzoyloxymethyl tributoxy silane, benzoyloxypropyl trimethoxy silane, benzoyloxypropyl triethoxy silane, benzoyloxypropyl tripropoxy silane, benzoyloxypropyl tributoxy silane, naphthyl trimethoxy silane, naphthyl triethoxy silane, naphthyl tripropoxy silane, naphthyl triisopropoxy silane, etc.
Moreover, examples of the silicon compound in which a hydrogen atom(s) in the organic group represented by R1R2, R3, R4, R5, and R6 is/are substituted by a halogen atom(s) are shown below.




































































































The silicon compound that can be used for component (A) may be exemplified by a material represented by the formula (A-1-4),

Si(OR)4  (A-1-4)

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms.

Preferable examples of the silicon compound represented by the formula (A-1-4) include tetramethoxy silane, tetraethoxy silane, tetrapropoxy silane, tetraisopropoxy silane, etc.
Especially preferable examples of the silicon compound represented by the formulae (A-1-1) to (A-1-4) include tetramethoxy silane, tetraethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, propyl trimethoxy silane, propyl triethoxy silane, isopropyl trimethoxy silane, isopropyl triethoxy silane, butyl trimethoxy silane, butyl triethoxy silane, isobutyl trimethoxy silane, isobutyl triethoxy silane, allyl trimethoxy silane, allyl triethoxy silane, cyclopentyl trimethoxy silane, cyclopentyl triethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxy silane, cyclohexenyl trimethoxy silane, cyclohexenyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, benzyl trimethoxy silane, benzyl triethoxy silane, tolyl trimethoxy silane, tolyl triethoxy silane, anisyl trimethoxy silane, anisyl triethoxy silane, phenethyl trimethoxy silane, phenethyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, methyl ethyl dimethoxy silane, methyl ethyl diethoxy silane, dipropyl dimethoxy silane, dibutyl dimethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, trimethyl methoxy silane, dimethyl ethyl methoxy silane, dimethyl phenyl methoxy silane, dimethyl benzyl methoxy silane, dimethyl phenethyl methoxy silane, etc.
Other examples of the organic groups represented by R1, R2, R3, R4, R5, and R6 include an organic group having one or more of carbon-oxygen single bond or carbon-oxygen double bond. Specifically, 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 hydroxyl group may be mentioned. Illustrative example thereof include an organic group shown by the formula (3).

{U-Q1-(S1)v1-Q2-}u-(T)v2-Q3-(S2)v3-Q4-  (3)

wherein U represents a hydrogen atom, a hydroxyl group,

epoxy ring:





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; Q1, Q2, Q3and Q4 independently represent —CqH(2q-p)Up—, wherein U has the same meaning as defined above, p represents an integer of 0 to 3, q represents an integer of 0 to 10 (where q=0 means a single bond); u represents an integer of 0 to 3S1 and S2 independently represent —O—, —CO—, —OCO—, —COO—or —OCOO—; v1, v2, and v3 independently represent 0 or 1and T represents a divalent group comprising an alicycle or an aromatic ring optionally containing a heteroatom. Illustrative examples of the alicycle or the aromatic ring T optionally containing a heteroatom such as an oxygen atom are shown below. In T, a bonding site between Q2 and Q3 is not particularly restricted; and the site is appropriately selected by considering reactivity due to steric factors, availability of commercially reagents, and so on.





Preferable examples of the organic group having one or more of a carbon-oxygen single bond or a carbon-oxygen double bond in the formula (3) are shown below. Meanwhile, in the following formulae, (Si) is described to show the bonding sites to the Si.






















Further, as the organic groups represented by R1, R2R3, R4, R5, and R6, an organic group having Si—Si bond can also be used. Illustrative examples thereof include groups shown below.




[Polysilane Compound]

The polysilane compound that can be used for component (A) may be exemplified by a material represented by the formula (A-2-1),

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (A-2-1)

wherein R7, R8, R9, R10, R11, and R12 each represent a methyl group, a phenyl group, or a hydroxyl group; and a1, a2, a3and a4 each represent a molar fraction, and satisfy a1+a2+a3+a4=1, 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, and 0≦a4≦1.

As the polysilane compound represented by the formula (A-2-1), OGSOL SI-10-10 (polymethylphenylsilane), SI-10-20 (polymethylphenylsilane), SI-20-10 (polyphenylsilane), SI-20-10 (improved) (polyphenylsilane), SI-30-10 (cyclic polydiphenylsilane), available from Osaka Gas Chemicals Co., Ltd., may be used. In addition, materials obtained by subjecting these compounds to reaction for reducing the molecular weight under alkaline conditions may also be used.
Especially, it is preferred that the compound represented by the formula (A-2-1) have a weight average molecular weight of 1,000 or less. When the weight average molecular weight is 1,000 or less, a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing the polysilane compound represented by the formula (A-2-1) easily dissolves in a solvent component in the composition for forming a coating type silicon-containing film, and generation of particles during film formation can be prevented.
The solvent used in the reaction under alkaline conditions may be various solvents, and for example, one or more solvents selected from hydrocarbon solvents such as benzene, toluene, and xylene; glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and 1,4-dioxane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone; and alcohol solvents such as ethanol, isopropyl alcohol, and butanol can be used.
The base to be added may be various materials, and usable examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyl lithium, n-butyl lithium, methyl magnesium chloride, and ethyl magnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; organic bases such as triethyl amine, diisopropyl ethyl amine, N,N-dimethylaniline, pyridine, 4-dimethylamino pyridine, and diazabicycloundecene (DBU). The reaction temperature is preferably about −50° C. to the boiling point of the solvent, more preferably room temperature to 100° C.
A mixture (monomer) containing one or more silicon compounds mentioned above and one or more polysilane compounds mentioned above is subjected to hydrolysis, condensation, or hydrolysis condensation, whereby a silicon-containing compound (polymer) to constitute the component (A) in the composition for forming a coating type silicon-containing film can be synthesized.
The hydrolysis, condensation, or hydrolysis condensation reaction for obtaining the component (A) can be carried out by using one or more compounds selected from inorganic acid, aliphatic sulfonic acid, and aromatic sulfonic acid as acid catalyst. Illustrative examples of the usable acid catalyst include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc. The catalyst is preferably used in the range of 1×10−6 to 10 mol, more preferably 1×10−5 to 5 mol, and much more preferably 1×10−4 to 1 mol per 1 mol of monomers.
The amount of water to be added for obtaining a polymer by hydrolysis condensation of these monomers is preferably in the range of 0.01 to 100 mol, more preferably 0.05 to 50 mol, much more preferably 0.1 to 30 mol per 1 mol of hydrolysable substituent bonded to the monomers. If the amount is 100 mol or less, a reaction device does not become excessively large, so that it is economical.
In operation, monomers may be added to a catalyst aqueous solution to start hydrolysis condensation reaction. In this case, organic solvent may be added to the catalyst aqueous solution, or monomers may be diluted with the organic solvent, or both may be performed. The reaction temperature is preferably in the range of 0 to 100° C., more preferably 5 to 80° C. A method in which the reaction temperature is maintained in the range of 5 to 80° C. when monomers are dropped, and then the mixture is aged in the range of 20 to 80° C., is preferable.
Preferable examples of the organic solvent that can be added to the catalyst aqueous solution or can dilute monomers include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl 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-methoxy propionate, ethyl 3-ethoxy propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, and mixture thereof.
Among them, water-soluble solvent is preferable, and illustrative examples thereof include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyvalent alcohols such as ethylene glycol and propylene glycol; polyvalent alcohol condensate derivatives such as 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, and ethylene glycol monopropyl ether; acetone; acetonitrile; tetrahydrofuran, etc. Particularly preferable is solvent with a boiling point of 100° C. or less.
The amount of the organic solvent to be used is preferably in the range of 0 to 1,000 mL, and particularly preferably 0 to 500 mL, per 1 mol of monomers. If the amount of the organic solvent is 1,000 mL or less, a reaction vessel does not become excessively large, so that it is economical.
Then, if necessary, neutralization reaction of the catalyst is carried out, and alcohol produced by hydrolysis condensation reaction is removed under reduced pressure to obtain a reaction mixture aqueous solution. The amount of a basic substance to be used for neutralization is preferably 0.1 to 2 equivalent, with respect to the acid used as the catalyst. The basic substance may be any substance so long as it shows alkalinity in water.
Subsequently, it is preferable that by-products such as alcohol produced by hydrolysis condensation reaction be removed from the reaction mixture. The temperature for heating the reaction mixture is preferably in the range of 0 to 100° C., more preferably 10 to 90° C., much more preferably 15 to 80° C., though it is depending on the kinds of the added organic solvent and an alcohol produced by reaction. Degree of vacuum is preferably atmospheric pressure or less, more preferably 80 kPa or less in the absolute pressure, much more preferably 50 kPa or less in the absolute pressure, though it is depending on the kinds of the organic solvent and an alcohol to be removed, an exhausting equipment, and a condensation equipment, as well as heating temperature. In this case, although it is difficult to exactly examine the amount of the alcohol to be removed, it is preferable that about 80% by mass or more of a produced alcohol and so forth be removed.
Next, the acid catalyst used in hydrolysis condensation reaction may be removed from the reaction mixture. For removing the acid catalyst, water is mixed with the polymer, and the polymer is extracted by an organic solvent. As the organic solvent to be used, solvents that can dissolve the polymer and achieve two-layer separation by mixing with water is preferable. Illustrative examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl 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 glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc., and mixture thereof.
Moreover, mixture of water-soluble organic solvent and slightly water-soluble organic solvent can also be used. Preferable examples thereof include methanol+ethyl acetate mixture, ethanol+ethyl acetate mixture, 1-propanol+ethyl acetate mixture, 2-propanol+ethyl acetate mixture, butanediol monomethyl ether+ethyl acetate mixture, propylene glycol monomethyl ether+ethyl acetate mixture, ethylene glycol monomethyl ether+ethyl acetate mixture, butanediol monoethyl ether+ethyl acetate mixture, propylene glycol monoethyl ether+ethyl acetate mixture, ethylene glycol monoethyl ether+ethyl acetate mixture, butanediol monopropyl ether+ethyl acetate mixture, propylene glycol monopropyl ether+ethyl acetate mixture, ethylene glycol monopropyl ether+ethyl acetate mixture, methanol+methyl isobutyl ketone mixture, ethanol+methyl isobutyl ketone mixture, 1-propanol+methyl isobutyl ketone mixture, 2-propanol+methyl isobutyl ketone mixture, propylene glycol monomethyl ether+methyl isobutyl ketone mixture, ethylene glycol monomethyl ether+methyl isobutyl ketone mixture, propylene glycol monoethyl ether+methyl isobutyl ketone mixture, ethylene glycol monoethyl ether+methyl isobutyl ketone mixture, propylene glycol monopropyl ether+methyl isobutyl ketone mixture, ethylene glycol monopropyl ether+methyl isobutyl ketone mixture, methanol+cyclopentyl methyl ether mixture, ethanol+cyclopentyl methyl ether mixture, 1-propanol+cyclopentyl methyl ether mixture, 2-propanol+cyclopentyl methyl ether mixture, propylene glycol monomethyl ether+cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether+cyclopentyl methyl ether mixture, propylene glycol monoethyl ether+cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether+cyclopentyl methyl ether mixture, propylene glycol monopropyl ether+cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether+cyclopentyl methyl ether mixture, methanol+propylene glycol methyl ether acetate mixture, ethanol+propylene glycol methyl ether acetate mixture, 1-propanol+propylene glycol methyl ether acetate mixture, 2-propanol+propylene glycol methyl ether acetate mixture, propylene glycol monomethyl ether+propylene glycol methyl ether acetate mixture, ethylene glycol monomethyl ether+propylene glycol methyl ether acetate mixture, propylene glycol monoethyl ether+propylene glycol methyl ether acetate mixture, ethylene glycol monoethyl ether+propylene glycol methyl ether acetate mixture, propylene glycol monopropyl ether+propylene glycol methyl ether acetate mixture, ethylene glycol monopropyl ether+propylene glycol methyl ether acetate mixture, etc., but are not restricted to combination of these mixtures.
The mixing ratio of the water-soluble organic solvent and the slightly water-soluble organic solvent is appropriately determined. The amount of the water-soluble organic solvent is preferably in the range of 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, much more preferably 2 to 100 parts by mass, based on 100 parts by mass of the slightly water-soluble organic solvent.
Subsequently, the reaction mixture may be washed with neutral water. The neutral water may be water called deionized water or ultrapure water. The amount of the water is preferably in the range of 0.01 to 100 L, more preferably 0.05 to 50 L, much more preferably 0.1 to 5 L per 1 L of the polymer solution. The washing may be performed by putting both the reaction mixture and water into the same container, stirring them, and then leaving to stand to separate a water layer. Number of washing may be 1 time or more, and preferably about 1 to 5 times because washing of 10 times or more is not worth to have full effects thereof.
In this water-washing operation, the number of washing and the amount of water for washing may be appropriately determined in view of effects of catalyst removal and fractionation because there is a case that a part of the polymer escapes into a water layer, thereby substantially the same effect as fractionation operation is obtained.
Other methods for removing acid catalyst include a method using an ion-exchange resin, and a method for removing the acid catalyst after neutralization with an epoxy compound such as ethylene oxide and propylene oxide. These methods can be appropriately selected depending on the acid catalyst used in the reaction.
A final solvent is then added to the polymer solution even when the acid catalyst remains therein or has been removed therefrom, and solvent-exchange is performed under reduced pressure to obtain a desired polymer solution. The temperature during the solvent-exchange is preferably in the range of 0 to 100° C., more preferably 10 to 90° C., much more preferably 15 to 80° C. though it is depending on the kinds of the reaction solvent and the extraction solvent to be removed. Degree of vacuum in this operation is preferably atmospheric pressure or less, more preferably 80 kPa or less in the absolute pressure, much more preferably 50 kPa or less in the absolute pressure though it is depending on the kinds of the solvents to be removed, an exhausting equipment, condensation equipment, and heating temperature.
In this operation, sometimes the polymer may become unstable by solvent-exchange. This occurs due to compatibility of the polymer with the final solvent. Thus, in order to prevent this, a monovalent, divalent, or more polyvalent alcohol or ether compound having cyclic ether as a substituent may be added thereto as a stabilizer. The adding amount thereof is preferably in the range of 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, much more preferably 0 to 5 parts by mass, or 0.5 parts by mass or more when it is added, based on 100 parts by mass of the polymer contained in the solution before the solvent-exchange. If necessary, a stabilizer may be added to the solution before the solvent-exchange operation.
The concentration of the polymer is preferably in the range of 0.1 to 20% by mass. If the concentration is in such a range, condensation reaction of the polymer does not excessively progress; thus, the polymer does not become insoluble in an organic solvent. Further, if the concentration is in such a range, the amount of the solvent becomes appropriate, therefore it is economical.
Preferable examples of the final solvent added to the polymer include alcohol solvents, and particularly monoalkyl ether derivatives of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, etc. Illustrative examples thereof include 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, etc.
In addition, if these solvents are used as a main solvent, a non-alcoholic solvent may be added thereinto as an adjuvant solvent. Illustrative examples of this adjuvant solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.
As an alternative operation, water or a water-containing organic solvent may be added to the monomers or an organic solution of the monomers to start hydrolysis reaction. In this operation, the catalyst may be added to the monomers or the organic solution of the monomers, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably in the range of 0 to 100° C., and more preferably 10 to 80° C. A method in which the mixture is heated at 10 to 50° C. while adding dropwise water, and then further heated at 20 to 80° C. to age the mixture is preferable.
As the organic solvent, water-soluble solvent is preferable, and illustrative examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyvalent alcohol condensate derivatives such as 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 glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, etc., and a mixture thereof.
The amount of the organic solvent to be used may be the same amount as above. The obtained reaction mixture may be post-treated like the above-mentioned method to obtain a polymer.
Alternatively, the hydrolysis, condensation, or hydrolysis condensation for synthesizing the polymer may be carried out with a base catalyst. Illustrative examples of the base catalyst include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylene diamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclo cyclononene, diazabicycloundecene, hexamethylene tetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of the base catalyst to be used may be the same amount as the acid catalyst mentioned above.
The amount of water to be added for obtaining a polymer from these monomers is preferably in the range of 0.1 to 50 mol per 1 mol of a hydrolysable substituent bonded to the monomers. If the amount is 50 mol or less, a reaction device does not become excessively large, so that it is economical.
Operation procedure for the reaction may be the same as in the case of using the acid catalyst mentioned above.
As the organic solvent that can be added to the catalyst aqueous solution or can dilute the monomers, the same materials as in the case of using the acid catalyst are preferably used. Meanwhile, the amount of the organic solvent to be used is preferably 0 to 1,000 mL per 1 mol of the monomer. By using such an amount, a reaction vessel does not become excessively large, so that it is economical.
Thereafter, if necessary, neutralization reaction of the catalyst is carried out, and alcohol produced by hydrolysis condensation reaction is removed under reduced pressure to obtain a reaction mixture aqueous solution. The amount of an acidic substance to be used for neutralization is preferably 0.1 to 2 equivalent, with respect to basic substance used as the catalyst. The acidic substance may be any substance so long as it shows acidity in water.
Subsequently, it is preferable that by-products such as alcohol produced by hydrolysis condensation reaction be removed from the reaction mixture. The temperature for heating the reaction mixture and degree of vacuum may be the same temperature and degree of vacuum as in the case of using the acid catalyst.
Next, the base catalyst used in hydrolysis condensation may be removed from the reaction mixture. The organic solvent to be used for removing the base catalyst may be the same materials as in the case of using the acid catalyst.
Also, the base catalyst can be removed by using the same mixture of the water-soluble organic solvent and the slightly water-soluble organic solvent as in the case of using the acid catalyst. Meanwhile, the mixing ratio of the water-soluble organic solvent and the slightly water-soluble organic solvent may be the same ratio as in the case of using the acid catalyst.
Subsequently, the reaction mixture may be washed with neutral water. The washing method may be the same as in the case of using the acid catalyst.
A final solvent is then added to the washed polymer, and solvent-exchange operation is carried out under reduced pressure to obtain a polymer solution. The temperature and degree of vacuum of the solvent exchange operation may be the same temperature and degree of vacuum as in the case of using the acid catalyst.
At this time, a monovalent, divalent, or more polyvalent alcohol or ether compound having cyclic ether as a substituent may be added as a stabilizer similarly to the case where the acid catalyst is used. Further, the polymer solution is preferably made with a concentration of 0.1 to 20% by mass.
Preferable examples of the final solvent added to the polymer include alcohol solvents, and particularly monoalkyl ether derivatives of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. Illustrative examples thereof include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc.
If these solvents are used as a main solvent, a non-alcoholic solvent may be added thereinto as an adjuvant solvent. As the adjuvant solvent, the same solvent as in the case of using the acid catalyst may be used.
As another operation, water or a water-containing organic solvent may be added to the monomers or an organic solution of the monomers to start hydrolysis reaction. In this case, the base catalyst may be added to the monomers or the organic solution of the monomers, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably in the range of 0 to 100° C., and more preferably 10 to 80° C. A method in which the mixture is heated at 10 to 50° C. while adding dropwise water, and further heated at 20 to 80° C. to age the mixture is preferable.
As the organic solvent, water-soluble solvent is preferable, and illustrative examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyvalent alcohol condensate derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, etc., and a mixture thereof.
The amount of the organic solvent to be used may be the same amount as above. The obtained reaction mixture is post-treated like the above-mentioned method to obtain a polymer.
The molecular weight of the polymer thus obtained can be adjusted not only by selecting monomers, but also controlling reaction conditions during polymerization. The molecular weight of the obtained polymer is not particularly restricted, but the weight average molecular weight of the polymer is preferably 100,000 or less, more preferably in the range of 200 to 50,000, and much more preferably 300 to 30,000. If the weight average molecular weight is 100,000 or less, generation of foreign matters and coating spots can be suppressed. Meanwhile, the above weight average molecular weight is obtained as data, in terms of polystyrene by means of gel-permeation chromatography (GPC) using polystyrene as a reference material, refractive index (RI) detector as a detector, and tetrahydrofuran as an eluent.
Alternatively, the composition for forming a coating type silicon-containing film of the present invention may contain a solvent and, as component (A), one or more polymers selected from a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4), and as component (B), one or more polysilane compounds represented by the formula (B-1),

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (B-1)

wherein R7, R8, R9, R10, R11, R12, a1, a2, a3, and a4 have the same meanings as defined above.

The silicon-containing compound (polymer) constituting the component (A) of the above-mentioned composition for forming a coating type silicon-containing film, can be synthesized by performing hydrolysis, condensation, or hydrolysis condensation of a mixture (monomer) containing one or more silicon compounds mentioned above.
The hydrolysis, condensation, or hydrolysis condensation for obtaining the above-mentioned component (A) can be carried out in the same manner as mentioned above.
[Component (B)]
As component (B) of the composition for forming a coating type silicon-containing film of the present invention, a polysilane compound represented by the formula (B-1) is used.

(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (B-1)

As the polysilane compound represented by the formula (B-1), similarly to the polysilane compound represented by the formula (A-2-1), OGSOL SI-10-10 (polymethylphenylsilane), SI-10-20 (polymethylphenylsilane), SI-20-10 (polyphenylsilane), SI-20-10 (improved) (polyphenylsilane), SI-30-10 (cyclic polydiphenylsilane), available from Osaka Gas Chemicals Co., Ltd., may be used. In addition, materials obtained by subjecting these compounds to reaction for reducing the molecular weight under alkaline conditions may also be used. Details of the reaction under alkaline conditions is as described above.
Especially, it is preferred that the compound represented by the formula (B-1) have a weight average molecular weight of 1,000 or less. When the weight average molecular weight is 1,000 or less, the polysilane compound represented by the formula (B-1) easily dissolves in a solvent component in the composition for forming a coating type silicon-containing film, and generation of particles during film formation can be prevented.
[Component (C)]
The composition for forming a coating type silicon-containing film of the present invention may further contain (C) one or more members selected from one or more silicon compounds represented by the formula (C-1), a hydrolysate, a condensate, and a hydrolysis condensate thereof,

R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3)  (C-1)

wherein R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C, and R3C each represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; and c1, c2, and c3 are each 0 or 1, and satisfy 1≦c1+c2+c3≦3.

The silicon compound represented by the formula (C-1) may be the same material as the above-mentioned illustrative examples of the silicon compounds represented by the formulae (A-1-1) to (A-1-3) in the component (A).
One or more of R1C, R2C, and R3C in the formula (C-1) are preferably an organic group having a hydroxyl group or a carboxyl group each substituted by an acid-labile group.
Examples of the compound represented by the formula (C-1) include those having the following structures whose silicon is bonded to two or three methoxy groups, ethoxy groups, propoxy groups, or butoxy groups, as hydrolysable groups. Meanwhile, in the following structural formulae, (Si) is described to show the bonding sites to the Si.
































































By using such component (C), the composition for forming a coating type silicon-containing film can give a film that has further improved adhesiveness to a photoresist pattern and does not cause a pattern collapse even in a fine patterning when used as a resist under layer film.
Also, the component (C) preferably contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more phosphorus compounds represented by the formulae (C-2-1) to (C-2-6) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,

PX3  (C-2-1)

POX3  (C-2-2)

P2O5  (C-2-3)

H(HPO3)a5OH  (C-2-4)

R13PX2  (C-2-5)

R13POX2  (C-2-6)

wherein R13 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms; and a5 is an integer of 1 or more.

[Phosphorus Compound]

The phosphorus compound that can be used for component (C) may be exemplified by a material represented by the formula (C-2-1),

PX3  (C-2-1)

wherein X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the phosphorus compound represented by the formula (C-2-1) include phosphorus trichloride, phosphorus tribromide, phosphorus acid, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, etc.
The phosphorus compound that can be used for component (C) may be exemplified by a material represented by the formula (C-2-2),

POX3  (C-2-2)

wherein X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the phosphorus compound represented by the formula (C-2-2) include phosphorus oxytrichloride, phosphorus oxytribromide, phosphoric acid, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, etc.
The phosphorus compound that can be used for component (C) may be exemplified by a material represented by the formulae (C-2-3) and (C-2-4),

P2O5  (C-2-3)

H(HPO3)a5OH  (C-2-4)

wherein a5 is an integer of 1 or more.

Diphosphorus pentaoxide represented by the formula (C-2-3), and a polyphosphoric acid represented by the formula (C-2-4) or a polyphosphate, etc., may be used as the phosphorus compound.
The phosphorus compound that can be used for component (C) may be exemplified by a material represented by the formula (C-2-5),

R13PX2  (C-2-5)

wherein R13 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the phosphorus compound represented by the formula (C-2-5) include CH3PCl2C2H5PCl2, CH3OPCl2, etc.
The phosphorus compound that can be used for component (C) may be exemplified by a material represented by the formula (C-2-6),

R13POX2  (C-2-6)

wherein R13 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the phosphorus compound represented by the formula (C-2-6) include HPO(OCH3)2HPO(OC2H5)2, CH3PO(OH)2, CH3PO(OCH3)2, CH3POCl2, C6H5PO(OH)2C6H5POCl2, C6H5CH2PO(OC2H5)2, etc.
Thus, when the component (C) contains the silicon compound and the phosphorous compound, pattern adhesiveness to a fine pattern can be more improved.
Alternatively, the component (C) preferably contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more boron compounds represented by the formulae (C-3-1) to (C-3-3) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,

BX3  (C-3-1)

B2O3  (C-3-2)

R14BX2  (C-3-3)

wherein R14 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

[Boron Compound]

The boron compound that can be used for component (C) may be exemplified by a material represented by the formula (C-3-1),

BX3  (C-3-1)

wherein X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the boron compound represented by the formula (C-3-1) include boron trifluoride, boron trichloride, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triamyl borate, trihexyl borate, tricyclopentyl borate, tricyclohexyl borate, triallyl borate, triphenyl borate, ethyldimethyl borate, etc.
The boron compound that can be used for component (C) may be exemplified by a material represented by the formula (C-3-2),

B2O3  (C-3-2).

Boron oxide represented by the formula (C-3-2) may be used as the boron compound.
The boron compound that can be used for component (C) may be exemplified by a material represented by the formula (C-3-3),

R14BX2  (C-3-3)

wherein R14 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of the boron compound represented by the formula (C-3-3) include C6H5B(OH)2CH3B(OC3H7)2, CH3B(OH)2, C6H11B(OH)2, etc.
Thus, when the component (C) contains the silicon compound and the boron compound, pattern adhesiveness to a fine pattern can be more improved.
Incidentally, hydrolysis, condensation or hydrolysis condensation reaction in component (C) can be carried out in the same manner as in the hydrolysis, condensation or hydrolysis condensation reaction of the above-mentioned component (A).
Also, the composition for forming a coating type silicon-containing film of the present invention preferably further contains an organic compound having 2 or more hydroxyl groups or carboxyl groups in one molecule. Examples of the organic compound include the compounds shown below.



















In the above structural formulae, Y represents a hydrogen atom, a methyl group, or a hydroxymethyl group, R15 represents a methylene group, a carbonyl group, or a phenylene group, “n” is an integer of 3 or more and less than 100, “na” is an natural number of 1 to 3, “nb” represents a natural number of 1 or more, “nc” represents a natural number of 2 to 4, and “nd” represents a natural number of 2 or more.
In the above structural formulae, an enantiomer and a diastereomer can exist, and each of the structural formulae represents all of these stereoisomers. These stereoisomers may be used solely, or may be used as a mixture.
The organic compound may be used one kind alone or two or more kinds in combination. Adding amount thereof is preferably in the range of 0.001 to 50 parts by mass, more preferably 0.01 to 30 parts by mass based on 100 parts by mass of the polymer of component (A).
The addition of such an organic compound promotes collapse of the silicon-containing film during wet etching, whereby peeling becomes easy.
[Other Additive]
A thermal crosslinking accelerator may be added to the composition for forming a coating type silicon-containing film of the present invention. As the thermal crosslinking accelerator usable in the composition for forming a coating type silicon-containing film of the present invention, there may be mentioned materials described in the Japanese Patent Laid-Open Publication No. 2007-302873. The thermal crosslinking accelerator can be used one kind alone or two or more kinds in combination. Meanwhile, the amount of the thermal crosslinking accelerator to be added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the polymer of component (A).
To improve stability of the composition for forming a coating type silicon-containing film of the present invention, a monovalent, divalent, or more polyvalent organic acid having 1 to 30 carbon atoms may be added thereinto. Preferable examples of the acid to be added 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, etc. Especially, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc., are preferable. To keep stability, two or more kinds of these acids may be used. Adding amount thereof is preferably 0.001 to 25 parts by mass, more preferably 0.01 to 15 parts by mass, much more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of silicon contained in the composition. Otherwise, the organic acid is preferably added such that pH of the composition satisfies 0≦pH≦7, more preferably 0.3≦pH≦6.5, much more preferably 0.5≦pH≦6.
A monovalent, divalent, or more polyvalent alcohol or ether compound having cyclic ether as a substituent may be added to the composition for forming a coating type silicon-containing film of the present invention as a stabilizer. By adding the stabilizer, stability of the polymer can be improved. As the stabilizer usable in the composition for forming a coating type silicon-containing film of the present invention, materials described in paragraphs (0180) to (0184) of Japanese Patent Laid-Open Publication No. 2009-126940 can be mentioned.
Water may be added to the composition for forming a coating type silicon-containing film of the present invention. When water is added thereinto, the polymer is hydrated whereby improving a lithography performance. Water content in the solvent component of the composition for forming a coating type silicon-containing film is preferably more than 0% and less than 50% by mass, more preferably in the range of 0.3 to 30% by mass, much more preferably 0.5 to 20% by mass. The amount of all solvents including water is preferably in the range of 100 to 100,000 parts by mass, and more preferably 200 to 50,000 parts by mass, based on 100 parts by mass of the polymer of component (A). By adding in such an amount, lithography performance can be improved, and uniformity of the coating film does not tend to be deteriorated, thereby causing of eye holes can be suppressed.
A photo-acid generator may be added to the composition for forming a coating type silicon-containing film of the present invention. As the photo-acid generator usable in the composition for forming a coating type silicon-containing film of the present invention, materials described in paragraphs (0160) to (0179) of Japanese Patent Laid-Open Publication No. 2009-126940 can be mentioned.
A surfactant may be added to the composition for forming a coating type silicon-containing film of the present invention, if necessary. As the surfactant usable in the composition for forming a coating type silicon-containing film of the present invention, materials described in paragraph (0185) of Japanese Patent Laid-Open Publication No. 2009-126940 can be mentioned.
A phosphoric acid salt compound or a boric acid salt compound may be added to the composition for forming a coating type silicon-containing film of the present invention as a thermal crosslinking accelerator, if necessary. Examples of the phosphoric acid salt compound include ammonium salts such as ammonium phosphate, tetramethylammonium phosphate, and tetrabutylammonium phosphate; and sulfonium salts such as triphenylsulfonium phosphate. Also, examples of the boric acid salt compound include ammonium salts such as ammonium borate, tetramethylammonium borate, and tetrabutylammonium borate; and sulfonium salts such as triphenylsulfonium borate.
By using the compounds as mentioned above, the composition for forming a coating type silicon-containing film of the present invention can be obtained. As preferable embodiments of the composition for forming a coating type silicon-containing film of the present invention, there may be mentioned materials having the following structures.




wherein m1, m2, and m3 each represent a molar fraction in the composition, and satisfy m1+m2+m3=1, 0.5<m1<1, 0<m2<0.3, and 0≦m3<0.4; m10, m11, m12, m13, m20, m21, m22and m23 have the same meanings as defined above; m30, m31m32, and m33 each represent a ratio of an elemental composition in the carbon skeletal structure, and satisfy m30+m31+m32+m33=1, 0<m30≦0.4, 0<m31≦0.6, 0<m32≦0.2, and 0≦m33≦0.1; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11and R12 have the same meanings as defined above.

As described above, the composition for forming a coating type silicon-containing film of the present invention can give a silicon-containing film that has excellent adhesiveness in fine pattern and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which is required in the patterning process.
[Substrate]
Also, the present invention provides a substrate for use in a semiconductor manufacturing process, including a silicon-containing film formed on a body to be processed by applying the above-mentioned composition for forming a coating type silicon-containing film thereonto.
At this time, the silicon-containing film formed by applying the composition for forming a coating type silicon-containing film of the present invention onto a body to be processed may function as at least one of a resist under layer film, a flattening film, and an insulating film.
The silicon-containing film formed from the composition for forming a coating type silicon-containing film of the present invention has excellent adhesiveness in fine pattern and can be easily wet etched by a removing liquid which does not cause damage to a semiconductor substrate and a coating type organic film or a CVD film mainly consisting of carbon which is required in the patterning process, so that it is suitable for a resist under layer film.
Moreover, the silicon-containing film obtained from the composition for forming a coating type silicon-containing film of the present invention can be formed without generating particles, and can be easily flattened by subjecting to heat treatment. Therefore it is suitable for a flattening film.
Further, the silicon-containing film formed from the composition for forming a coating type silicon-containing film of the present invention is also suitable for an insulating film since it is a coating type and can be formed without generating particles.
In addition, the above-mentioned silicon-containing film may be formed by using a semiconductor substrate on which a part or whole of semiconductor circuits have been formed as the body to be processed, and applying the composition for forming a coating type silicon-containing film by spin coating onto the semiconductor substrate and then baking the same.
[Patterning Process]
In the present invention, a pattern can be formed by: forming an organic under layer film on a body to be processed by using a coating type organic under layer film material; forming a silicon-containing film on the organic under layer film by using the composition for forming a coating type silicon-containing film of the present invention; forming an upper layer resist film on the silicon-containing film; forming a pattern with the upper layer resist film; transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and transferring the pattern to the organic under layer film by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.
Further, in the present invention, a pattern also can be formed by: forming a hard mask mainly consisting of carbon on a body to be processed by a CVD method; forming a silicon-containing film on the hard mask by using the composition for forming a coating type silicon-containing film of the present invention; forming an upper layer resist film on the silicon-containing film; forming a pattern with the upper layer resist film; transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and transferring the pattern to the hard mask by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.
The body to be processed used in the patterning process of the present invention may be a material in which any of a metal film, an amorphous metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film or a metal oxynitride film is formed on a semiconductor substrate on which a part or whole of semiconductor circuits have been formed, as a layer to be processed.
As the semiconductor substrate, silicon substrate is generally used. However, the substrate is not limited to this and may be Si, an amorphous silicon (α-Si), p-Si, SiO2, SiN, SiON, W, TiN, Al, or the like. The substrate may be composed of a material different from the layer to be processed.
Examples of the metal used for the body to be processed include silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof. The layer to be processed may be made of Si, SiO2, SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, W, Al, Cu, Al—Si, or the like; various low dielectric constant (low-k) films, or etching stopper films. The thickness of the layer is preferably in the range of 50 to 10,000 nm, more preferably 100 to 5,000 nm.
In the patterning process of the present invention, an organic under layer film, or a hard mask mainly consisting of carbon can be formed on the body to be processed. Among these, the organic under layer film can be formed from the coating type organic under layer film material by using the spin coating method, etc., and the hard mask mainly consisting of carbon can be formed form a material of an organic hard mask mainly consisting of carbon by using the CVD method. Such a coating type organic under layer film and a CVD film mainly consisting of carbon are not particularly limited, and preferably a material which shows a sufficient function as the antireflective film when the upper layer resist film is subjected to pattern formation by exposure. By forming such a coating type organic under layer film or a CVD film mainly consisting of carbon, a pattern formed with the upper layer resist film can be transferred to the body to be processed without generating the difference in size conversion.
The silicon-containing film used in the patterning process of the present invention can be formed on a body to be processed by the spin coating method, etc., similarly to the photoresist film (upper layer resist film) by using the composition for forming a coating type silicon-containing film of the present invention. After spin coating, it is desired to be baked for evaporating the solvent, preventing from mixing with the upper layer resist film, and promoting the cross-linking reaction. The baking temperature is preferably in the range of 50 to 500° C., and the heating time is preferably in the range of 10 to 300 seconds. Particularly preferable temperature range is 400° C. or less for reducing heat damage to the devices, though it is depending on the structure of the devices to be fabricated.
Also, pattern formation of the upper layer resist film is preferably carried out by a lithography method using light with a wavelength of 300 nm or less or EUV light, an electron beam direct drawing method, a directed self-assembly method or a nano-imprinting lithography method. By using these methods, a fine pattern can be formed with the upper layer resist film.
The composition for forming an upper layer resist film may be appropriately selected depending on the method for forming a pattern with the upper layer resist film. For example, when lithography using light with a wavelength of 300 nm or less or EUV light is carried out, a chemically amplified photoresist film material may be used as the composition for forming an upper layer resist film. Such a photoresist film material may be exemplified by a material, in which a photoresist film is formed and exposed, and then, the exposed part is dissolved by using an alkaline developer to form a positive pattern, or the unexposed part is dissolved by using a developer composed of an organic solvent to form a negative pattern.
Also, when the lithography is carried out by using an ArF excimer laser light as the light with a wavelength of 300 nm or less, any material can be used as the composition for forming an upper layer resist film so long as it is a usual resist composition for ArF excimer laser light. As such a resist composition for the ArF excimer laser light, many candidates have been well-known. When the well-known resins are roughly classified, there are a poly(meth)acryl type, a COMA (Cycloolefin Maleic Anhydride) type, a COMA-(meth)acrylic hybrid type, a ROMP (Ring Opening Metathesis Polymerization) series, and a polynorbornene type material, etc. Among them, the resist composition using the poly(meth)acryl type resin secures its etching resistance by introducing an alicyclic skeletal structure at the side chain, so that it is excellent in resolution property as compared with the other resin type, therefore it is preferably used.
The patterning process of the present invention is excellent in pattern adhesiveness of the resist under layer film, so that even when a fine pattern is formed at the upper layer resist film, it cause no pattern collapse or the like. It is also excellent in etching selectivity to the organic film or the silicon-containing film, so that by optimizing the combination of the coating type organic under layer film or the CVD film mainly consisting of carbon, pattern transfer can be carried out without generating the difference in size conversion.
After forming the mask pattern for processing the body to be processed, the silicon-containing film may be removed by wet etching.
When the silicon-containing film of the present invention is wet etched, a removing liquid containing hydrogen peroxide is preferably used. At this time, it is further preferable to adjust the pH by adding an acid or a base to promote peeling. As the pH adjusting agent, there may be mentioned inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, oxalic acid, tartaric acid, citric acid, and lactic acid, nitrogen-containing basic compounds such as ammonia, ethanolamine, tetramethylammonium hydroxide, etc., and nitrogen-containing organic acid compounds such as EDTA (ethylenediamine tetraacetic acid), etc.
The silicon-containing film obtained from the composition for forming a coating type silicon-containing film of the present invention has a Si—Si bond which is to be cleaved under alkaline conditions, and therefore it is excellent in peelability, in particular, under alkaline conditions. Preferable examples of the removing liquid include SC1.
The wet etching may be carried out only by preparing a removing liquid at 0° C. to 80° C., preferably at 5° C. to 60° C., and dipping a silicon wafer formed with a target substrate to be processed thereinto. If necessary, it is possible to remove the silicon-containing film easily in the conventional manner such as spraying a removing liquid onto the surface, applying a removing liquid while rotating the wafer, etc.
Thus, when a pattern is formed by using the composition for forming a coating type silicon-containing film of the present invention, it is possible to readily wet etch the silicon-containing film without causing damage to the coating type organic under layer film or the CVD film mainly consisting of carbon.
EXAMPLES
Hereinafter, the present invention will be specifically described with reference to Preparation Examples, Synthesis Examples, Examples, and Comparative Examples, but the present invention is not restricted thereto. In the following examples, “%” represents “% by mass”, and molecular weight was measured by GPC. Molecular weight was calculated by GPC in terms of polystyrene, using RI detector and tetrahydrofuran as an eluent.
Preparation of Polysilane Compound
[Preparation Example (X1)]
10.0 g of OGSOL SI-10-20 (Mw 1,900) available from Osaka Gas Chemicals Co., Ltd., was dissolved in 100.0 g of tetrahydrofuran, and then 6.0 g of triethylamine and 16.0 g of ultrapure water were added thereto. After the resulting solution was reacted for 7 hours under reflux, 375 g of propylene glycol monoethyl ether (PGEE) was added thereto, and the mixture was concentrated under reduced pressure to obtain 91.3 g of a PGEE solution containing polysilane compound (X1) (polymer concentration: 11%) with a Mw of 980.
[Preparation Example (X2)]
10.0 g of OGSOL SI-20-10 (Mw 1,300) available from Osaka Gas Chemicals Co., Ltd., was dissolved in 100.0 g of tetrahydrofuran, and then 2.0 g of 29% aqueous ammonia and 6.0 g of ultrapure water were added thereto. After the resulting solution was reacted 6.5 hours under reflux, 250 g of propylene glycol monoethyl ether (PGEE) was added thereto, and the mixture was concentrated under reduced pressure to obtain 70.3 g of a PGEE solution containing polysilane compound (X2) (polymer concentration: 15%) with a Mw of 870.
[Preparation Example (X3)]
10.0 g of OGSOL SI-20-10 (improved) (Mw 1,400) available from Osaka Gas Chemicals Co., Ltd., was dissolved in 100.0 g of tetrahydrofuran, and then 6.0 g of triethylamine and 16.0 g of ultrapure water were added thereto. After the resulting solution was reacted for 12 hours under reflux, 250 g of propylene glycol monoethyl ether (PGEE) was added thereto, and the mixture was concentrated under reduced pressure to obtain 71.3 g of a PGEE solution containing polysilane compound (X3) (polymer concentration: 14%) with a Mw of 830.
In the following, formulation amounts of Preparation Examples (X1) to (X3) are summarized in Table 1









TABLE 1





Preparation




Examples
Raw materials for reaction
Mw

















X1
SI-10-20: 10.0 g
980


X2
SI-20-10: 10.0 g
870


X3
SI-20-10 (improved): 10.0 g
830









[Synthesis Example (A1)]

To a mixture comprising 120 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 17.0 g of methyl trimethoxy silane (M1), 5.0 g of phenyl trimethoxy silane (M2), 45.7 g of tetramethoxy silane (M5), and 54.6 g of the PGEE solution containing polysilane compound (X1), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution containing polymer (A1) (polymer concentration: 12%) with a Mw of 3,000.
[Synthesis Example (A2)]
To a mixture comprising 80 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 17.0 g of methyl trimethoxy silane (M1), 5.0 g of phenyl trimethoxy silane (M2), 45.7 g of tetramethoxy silane (M5), and 43.6 g of the PGEE solution containing polysilane compound (X3), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 320 g of a PGEE solution containing polymer (A2) (polymer concentration: 11%) with a Mw of 2,900.
[Synthesis Example (A3)]
To a mixture comprising 100 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 17.0 g of methyl trimethoxy silane (M1), 5.4 g of 4-fluorophenyl trimethoxy silane (M3), 49.5 g of tetramethoxy silane (M5), and 20.4 g of the PGEE solution containing polysilane compound (X2), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 310 g of a PGEE solution containing polymer (A3) (polymer concentration: 11%) with a Mw of 2,700.
[Synthesis Example (A4)]
To a mixture comprising 70 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 5.8 g of 4-chlorophenyl trimethoxy silane (M4), 64.7 g of tetramethoxy silane (M5), and 54.6 g of the PGEE solution containing polysilane compound (X1), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution containing polymer (A4) (polymer concentration: 12%) with a Mw of 3,500.
[Synthesis Example (A5)]
To a mixture comprising 80 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 13.6 g of methyl trimethoxy silane (M1), 5.0 g of phenyl trimethoxy silane (M2), 45.7 g of tetramethoxy silane (M5), 9.3 g of 2-acetoxy-1,1,1-trifluoro-2-(trifluoromethyl)butyl trimethoxy silane (M6), and 43.6 g of the PGEE solution containing polysilane compound (X3), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 310 g of a PGEE solution containing polymer (A5) (polymer concentration: 13%) with a Mw of 3,000.
[Synthesis Example (A6)]
To a mixture comprising 120 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added a mixture comprising 17.0 g of methyl trimethoxy silane (M1), 5.0 g of phenyl trimethoxy silane (M2), and 53.3 g of tetramethoxy silane (M5), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution containing polymer (A6) (polymer concentration: 11%) with a Mw of 2,900.
In the following, formulation amounts of Synthesis Examples (A1) to (A6) are summarized in Table 2










TABLE 2









Raw materials for reaction











Synthesis

Polysilane



Examples
Silicon compound
compound
Mw













(A1)
M1: 17.0 g, M2: 5.0 g, M5: 45.7 g
(X1): 54.6 g
3,000


(A2)
M1: 17.0 g, M2: 5.0 g, M5: 45.7 g
(X3): 43.6 g
2,900


(A3)
M1: 17.0 g, M3: 5.4 g, M5: 49.5 g
(X2): 20.4 g
2,700


(A4)
M4: 5.8 g, M5: 64.7 g
(X1): 54.6 g
3,500


(A5)
M1: 13.6 g, M2: 5.0 g, M5: 45.7 g,
(X3): 43.6 g
3,000



M6: 9.3 g


(A6)
M1: 17.0 g, M2: 5.0 g, M5: 53.3 g,

2,900









Synthesis of Component (C)

[Synthesis Example (C1)]

To a mixture comprising 120 g of methanol, 1 g of methanesulfonic acid, and 60 g of deionized water was added a mixture comprising 34.1 g of methyl trimethoxy silane (M1) and 26.0 g of trimethyl borate (M11), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution containing polymer (C1) (polymer concentration: 13%). The molecular weight of the obtained polymer was measured in terms of polystyrene, consequently finding a Mw of 3,200.
[Synthesis Example (C2)]
To a mixture comprising 120 g of methanol, 1 g of methanesulfonic acid, and 60 g of deionized water was added a mixture comprising 9.9 g of phenyl trimethoxy silane (M2), 54.5 g of methyl trimethoxy silane (M1), and 12.5 g of tributyl phosphate (M7), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 310 g of a PGEE solution containing polymer (C2) (polymer concentration: 12%). The molecular weight of the obtained polymer was measured in terms of polystyrene, consequently finding a Mw of 3,500.
[Synthesis Example (C3)]
To a mixture comprising 120 g of methanol, 1 g of methanesulfonic acid, and 60 g of deionized water was added a mixture comprising 61.3 g of methyl trimethoxy silane (M1) and 7.6 g of tetramethoxy silane (M5), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 300 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution containing polymer (C3) (polymer concentration: 11%). The molecular weight of the obtained polymer was measured in terms of polystyrene, consequently finding a Mw of 3,500.
[Synthesis Example (C4)]
To a mixture comprising 120 g of methanol, 1 g of methanesulfonic acid, and 60 g of deionized water was added a mixture comprising 34.1 g of methyl trimethoxy silane (M1) and 67.6 g of 4-tert-butoxyphenyl trimethoxy silane (M8), and the resulting mixture was maintained at 40° C. for 12 hours to carry out hydrolysis condensation. After completion of the reaction, 500 g of PGEE was added thereto, and a by-produced alcohol and excess water were distilled off under reduced pressure to obtain 570 g of a PGEE solution containing polymer (C4) (polymer concentration: 12%). The molecular weight of the obtained polymer was measured in terms of polystyrene, consequently finding a Mw of 2,700.
[Synthesis Examples (C5) to (C11)]
PGEE solutions containing polymers (C5) to (C11) were obtained in the same manner as in Synthesis Example (C4) by using monomers shown in Table 3.
In the following, formulation amounts of Synthesis Examples (C1) to (C11) are summarized in Table 3











TABLE 3







Synthesis





Examples
Raw materials for reaction
Mw









(C1)
M1: 34.1 g, M11: 26.0 g
3,200



(C2)
M2: 9.9 g, M1: 54.5 g, M7: 12.5 g
3,500



(C3)
M1: 61.3 g, M5: 7.6 g
3,500



(C4)
M1: 34.1 g, M8: 67.6 g
2,700



(C5)
M1: 34.1 g, M9: 74.6 g
3,000



(C6)
M1: 34.1 g, M10: 81.6 g
2,900



(C7)
M1: 34.1 g, M11: 83.1 g
3,300



(C8)
M1: 34.1 g, M12: 74.6 g
2,500



(C9)
M1: 34.1 g, M13: 83.6 g
3,000



(C10)
M1: 34.1 g, M14: 89.2 g
3,300



(C11)
M1: 34.1 g, M15: 82.6 g
3,200










In the following, structural formula of the compounds used in Synthesis Examples (A1) to (A6) and (C1) to (C11) are shown below.







[Examples and Comparative Examples]

Polymers (A1) to (A6) as component (A), polysilane compounds (X1) to (X3) as component (B), polymers (C1) to (C11) as component (C) each obtained in Preparation Examples and Synthesis Examples, additives, and solvents were mixed with the ratios shown in Table 4, and the respective mixtures were filtered through a 0.1 m filter made of a fluorine resin to prepare respective solutions of composition for forming a coating type silicon-containing film, which were named Sols. 1 to 19Formulation ratio of components (A), (B), and (C) was based on values in terms of solid content.












TABLE 4











Additives

















Compo-
Compo-
Compo-
Thermal
Photo-






nent (A)
nent (B)
nent (C)
crosslinking
acid

Other




(Parts
(Parts
(Parts
accelerator
generator
Organic acid
additives
Solvent



by 
by 
by 
(Parts by
(Parts by
(Parts by
(Parts by
(Parts by


No.
mass)
mass)
mass)
mass)
mass)
mass)
mass)
mass)





Sol. 1
A1
—
—
TPSMA
—
Maleic acid
—
PGEE/water



(4.0)


(0.04)

(0.04)

(150/15)


Sol. 2
A2
—
—
TPSMA
—
Maleic acid
—
PGEE/water



(4.0)


(0.04)

(0.04)

(150/15)


Sol. 3
A2
—
C1
TPSNO3
—
Maleic acid
—
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)

(150/15)


Sol. 4
A2
X1
C2
TPSH2PO4
TPSNf
Oxalic acid
XYTOL
PGEE/water



(3.4)
(0.4)
(0.2)
(0.04)
(0.04)
(0.04)
(0.04)
(150/15)


Sol. 5
A3
—
C3
TPSMA
—
Maleic acid
—
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)

(150/15)


Sol. 6
A3
—
C4
TPSH2BO3
—
Oxalic acid
PEOL
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 7
A3
—
C5
QMANO3
TPSNf
Maleic acid
—
PGEE/water



(3.6)

(0.4)
(0.04)
(0.04)
(0.04)

(150/15)


Sol. 8
A4
—
C6
TPSMA
—
Maleic acid
—
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)

(150/15)


Sol. 9
A4
—
C7
TPSMA
—
Oxalic acid
PEOL
PGEE/water



(3.6)

(0.4)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 10
A4
X2
C7
TPSMA
—
Maleic acid
TEAOH
PGEE/water



(3.6)
(0.2)
(0.2)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 11
A3
—
C8
TPSMA
—
Maleic acid
—
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)

(150/15)


Sol. 12
A5
—
C9
QMANO3
—
Oxalic acid
TMOL
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 13
A5
—
C10
TPSMA
—
Maleic acid
—
PGEE/water.



(3.6)

(0.4)
(0.04)

(0.04)

(150/15)


Sol. 14
A6
X2
C11
TPSMA
TPSNf
Oxalic acid
—
PGEE/water



(3.6)
(0.4)
(0.2)
(0.04)
(0.04)
(0.04)

(150/15)


Sol. 15
A6
X1
—
TPSNO3
—
Maleic acid
—
PGEE/water



(3.8)
(0.2)

(0.04)

(0.04)

(150/15)


Sol. 16
A6
X3
C1
TPSMA

Maleic acid
SORBOL
PGEE/water



(3.6)
(0.4)
(0.2)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 17
A6
X3
C1
TPSNO3
—
Maleic acid
XYTOL
PGEE/water



(3.6)
(0.2)
(0.2)
(0.04)

(0.04)
(0.04)
(150/15)


Sol. 18
A6
—
—
TPSMA
—
Maleic acid
—
PGEE/water



(4.0)


(0.04)

(0.04)

(150/15)


Sol. 19
A6
—
C1
TPSMA
—
Maleic acid
XYTOL
PGEE/water



(3.8)

(0.2)
(0.04)

(0.04)
(0.04)
(150/15)









Additives in Table 4 used are as follows:

    TPSH2PO4: Mono(triphenylsulfonium) phosphate
    TPSH2BO3: Mono(triphenylsulfonium) borate
    TPSMA: Mono(triphenylsulfonium) maleate
    TPSNO3: Triphenyl sulfonium nitrate
    QMANO3: Tetramethyl ammonium nitrate
    TPSNf: Triphenyl sulfonium nonafluorobutanesulfonate
    TEAOH: Triethanolamine
    PEOL: Pentaerythritol
    TMOL: Trimethylolethane
    SORBOL: Sorbitol
    XYTOL: Xylitol

[Coating Film Wet Etching Test]



The solutions of the composition for forming a coating type silicon-containing film, Sols. 1 to 19, were each applied on a silicon wafer by spin coating, and heated at 240° C. for 160 seconds to form silicon-containing films, Films 1 to 19, each having a film thickness of 35 nm. These silicon-containing films were dipped in a 1% aqueous hydrogen peroxide containing 0.6% ammonia (hereinafter referred to as “ammonia per-water”) at 65° C. for 10 minutes, and the thickness of the remaining film was measured by M-2000 High-speed Spectroscopic Ellipsometer manufactured by J.A. Woollam Co., Inc. The results are shown in Table 5











TABLE 5








Film thickness
Film thickness




before
after



Film
treatment (Å)
treatment (Å)





















Example 1-1
Film 1
349
2 or less



Example 1-2
Film 2
352
2 or less



Example 1-3
Film 3
347
2 or less



Example 1-4
Film 4
352
2 or less



Example 1-5
Film 5
350
2 or less



Example 1-6
Film 6
349
2 or less



Example 1-7
Film 7
348
2 or less



Example 1-8
Film 8
351
2 or less



Example 1-9
Film 9
354
2 or less



Example 1-10
Film 10
347
2 or less



Example 1-11
Film 11
351
2 or less



Example 1-12
Film 12
350
2 or less



Example 1-13
Film 13
346
2 or less



Example 1-14
Film 14
349
2 or less



Example 1-15
Film 15
353
2 or less



Example 1-16
Film 16
352
2 or less



Example 1-17
Film 17
354
2 or less



Comparative
Film 18
351
56



Example 1-1



Comparative
Film 19
348
84



Example 1-2










As shown in Table 5, Films 1 to 17, which are silicon-containing films formed by using the composition for forming a coating type silicon-containing film of the present invention, each showed a film thickness of 2 Å or less after treatment with ammonia per-water, and thus could be removed sufficiently. On the other hand, in Films 18 and 19, which contain no silicon skeletal structure, the thicknesses of the film treated with ammonia per-water were each 50 Å or more, and thus the films could not be sufficiently removed.
[Patterning Test by Positive Development]
A spin-on carbon film ODL-50 (Carbon content: 80% by mass) available from Shin-Etsu Chemical Co., Ltd., was formed on a silicon wafer so as to have a film thickness of 200 nm. The solutions of the composition for forming a coating type silicon-containing film, Sols. 1 to 17, were each applied thereon and heated at 240° C. for 60 seconds to form silicon-containing films, Films 1 to 17 with a film thickness of 35 nm, respectively.
Subsequently, the ArF resist solution for positive development (PR-1) described in Table 6 was applied on the silicon-containing film, and baked at 110° C. for 60 seconds to form a photoresist film having a film thickness of 100 nm. Further, the liquid immersion top coat (TC-1) described in Table 7 was applied on the photoresist film and baked at 90° C. for 60 seconds to form a top coat with a film thickness of 50 nm.
Next, these were exposed by an ArF liquid immersion exposure apparatus (NSR-S610C manufactured by Nikon Corporation, NA: 1.30, σ: 0.98/0.65, 35° polarized dipole illumination, 6% halftone phase shift mask), baked at 100° C. for 60 seconds (PEB), and developed by a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain 43 nm 1:1 positive line and space pattern.
A cross-sectional shape of the thus obtained substrate was observed by an electron microscope (S-9380) manufactured by Hitachi Ltd., and pattern collapse of the same was observed by an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation.
The composition of the ArF resist solution for positive development (PR-1) to be used for the above-mentioned patterning test by positive development is shown











TABLE 6






Polymer
Acid generator
Base
Solvent


No.
(Parts by mass)
(Parts by mass)
(Parts by mass)
(Parts by mass)







PR-1
ArF resist
PAG1
Quencher
PGMEA



polymer 1
(7.0)
(1.0)
(2,500)



(100)









Molecular weight, dispersity, and structural formula of ArF resist polymer 1 described in Table 6 are shown below.
ArF resist polymer 1: Molecular weight (Mw)=7,800


    
    
        Dispersity (Mw/Mn)=1.78
    
    






Structural formula of the acid generator: PAG1 described in Table 6 is shown below.




Structural formula of the base: Quencher described in Table 6 is shown below.




The composition of the liquid immersion top coat (TC-1) to be used in the patterning test by positive development is shown in Table 7.










TABLE 7







Polymer
Organic solvent



(Parts by mass)
(Parts by mass)




















TC-1
Top coat polymer
Diisoamylether(2700)




(100)
2-methyl-1-butanol(270)










Molecular weight, dispersity, and structural formula of Top coat polymer described in Table 7 are shown below.
Top coat polymer: Molecular weight (Mw)=8,800


    
    
        Dispersity (Mw/Mn)=1.69
    
    






The results of observing the cross-sectional shape of the substrates and pattern collapse of the same obtained by the patterning test by positive development are shown in Table 8.












TABLE 8







Silicon-

Cross-sectional




containing
Film
pattern shape
Pattern



film
formability
after development
collapse




















Example 2-1
Film 1
Good
Vertical shape
None


Example 2-2
Film 2
Good
Vertical shape
None


Example 2-3
Film 3
Good
Vertical shape
None


Example 2-4
Film 4
Good
Vertical shape
None


Example 2-5
Film 5
Good
Vertical shape
None


Example 2-6
Film 6
Good
Vertical shape
None


Example 2-7
Film 7
Good
Vertical shape
None


Example 2-8
Film 8
Good
Vertical shape
None


Example 2-9
Film 9
Good
Vertical shape
None


Example 2-10
Film 10
Good
Vertical shape
None


Example 2-11
Film 11
Good
Vertical shape
None


Example 2-12
Film 12
Good
Vertical shape
None


Example 2-13
Film 13
Good
Vertical shape
None


Example 2-14
Film 14
Good
Vertical shape
None


Example 2-15
Film 15
Good
Vertical shape
None


Example 2-16
Film 16
Good
Vertical shape
None


Example 2-17
Film 17
Good
Vertical shape
None









As shown in Table 8, in the positive development, the substrates that used the silicon-containing film formed from the composition for forming a coating type silicon-containing film of the present invention as a resist under layer film gave a resist cross-section of a vertical shape. Also, pattern collapse was not found in such substrates.
[Patterning Test by Negative Development]
A spin-on carbon film ODL-50 (Carbon content: 80% by mass) available from Shin-Etsu Chemical Co., Ltd., was formed on a silicon wafer so as to have a film thickness of 200 nm. The solutions of the composition for forming a coating type silicon-containing film, Sols. 2, 4, 5, 10, 16, and 17 were each applied thereon and heated at 240° C. for 60 seconds to form silicon-containing films, Films 2, 4, 5, 10, 16, and 17 with a film thickness of 35 nm, respectively.
Subsequently, the ArF resist solution for negative development (PR-2) described in Table 9 was applied on the silicon-containing film, and baked at 100° C. for 60 seconds to form a photoresist film having a film thickness of 100 nm. Further, the liquid immersion top coat (TC-1) described in Table 7 was applied on the photoresist film and baked at 90° C. for 60 seconds to form a top coat with a film thickness of 50 nm.
Next, these were exposed by an ArF liquid immersion exposure apparatus (NSR-S610C manufactured by Nikon Corporation, NA: 1.30, σ: 0.98/0.65, 35° polarized dipole illumination, 6% halftone phase shift mask), and baked at 100° C. for 60 seconds (PEB). Thereafter, while rotating with 30 rpm, butyl acetate was discharged for 3 seconds from a development nozzle as a developer, rotation was then stopped, and paddle development was performed for 27 seconds. The resulting wafer was rinsed with diisoamyl ether, spin dried, and baked at 100° C. for 20 seconds to evaporate the rinsing solvent. According to this patterning, 43 nm 1:1 negative line and space pattern was obtained.
A cross-sectional shape of the thus obtained substrate was observed by an electron microscope (S-4700) manufactured by Hitachi Ltd., and pattern collapse of the same was observed by an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation.
The composition of the ArF resist solution for negative development (PR-2) to be used for the patterning test by negative development is shown in Table 9.













TABLE 9









Acid







generator
Base
Solvent




Polymer
(Parts by
(Parts by
(Parts by



No.
(Parts by mass)
mass)
mass)
mass)









PR-2
ArF resist
PAG2
Quencher
PGMEA




polymer 2
(7.0)
(1.0)
(2,500)




(100)










Molecular weight, dispersity, and structural formula of ArF resist polymer 2 described in Table 9 are shown below.
ArF resist polymer 2: Molecular weight (Mw)=8,600


    
    
        Dispersity (Mw/Mn)=1.88
    
    






Structural formula of the acid generator: PAG2 described in Table 9 is shown below.




Meanwhile, the base: Quencher shown in Table 9 was used the same one as that used in PR-1 of the patterning test by positive development.
The results of observing the cross-sectional shape of the substrates and pattern collapse of the same obtained by the patterning test by negative development are shown in Table 10.












TABLE 10







Silicon-

Cross-sectional




containing
Film
pattern shape
Pattern



film
formability
after development
collapse




















Example 3-1
Film 2
Good
Vertical shape
None


Example 3-2
Film 4
Good
Vertical shape
None


Example 3-3
Film 5
Good
Vertical shape
None


Example 3-4
Film 10
Good
Vertical shape
None


Example 3-5
Film 16
Good
Vertical shape
None


Example 3-6
Film 17
Good
Vertical shape
None









As shown in Table 10, also in the negative development, the substrates that used the silicon-containing film formed from the composition for forming a coating type silicon-containing film of the present invention as a resist under layer film gave a resist cross-section of a vertical shape. Moreover, pattern collapse was not found in such substrates.
From the above results, it could be clarified that the coating type silicon-containing film formed by using the composition for forming a coating type silicon-containing film of the present invention can be easily wet etched by a removing liquid such as SC-1 (ammonia per-water), which does not cause damage to the coating type organic under layer film or the CVD film mainly consisting of carbon. Further, it could be also clarified that the coating type silicon-containing film formed by using the composition for forming a coating type silicon-containing film of the present invention may serve as a resist under layer film that has excellent adhesiveness to the photoresist pattern formed thereon, and does not cause pattern collapse even in fine pattern.
It should be noted that the present invention is not limited to the foregoing embodiment. The embodiment is just an exemplification, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept described in claims of the present invention are included in the technical scope of the present invention.

## Claims

1. A composition for forming a coating type silicon-containing film, comprising
one or more silicic acid skeletal structures represented by the formula (1) and one or more silicon skeletal structures represented by the formula (2), wherein the composition contains a polysilane structure obtained by a coupling between units in the formula (2),
a solvent, and
(A) one or more polymers selected from a hydrolysate, a condensate, and a hydrolysis condensate of a mixture containing one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more polysilane compounds represented by the formula (A-2-1), the compound represented by the formula (A-2-1) having a weight average molecular weight of 1,000 or less,





wherein R1, R2, R3, R4, R5, and R6 each represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); R7, R8, R9, R10, R11, and R12 each represent a methyl group, a phenyl group, or a hydroxyl group; m10, m11, m12, and m13 each represent a molar fraction in the silicic acid skeletal structure, and satisfy m10+m11+m12+m13=1, 0≦m10≦0.3, 0≦m11≦0.5, 0≦m12≦0.7, and 0<m13≦1; and m20, m21, m22, and m23 each represent a molar fraction in the silicon skeletal structure, and satisfy m20+m21+m22+m23=1, 0≦m20≦1, 0≦m21≦1, 0≦m22≦1and 0≦m23≦1,


R1R2R3SiOR  (A-1-1)



R4R5Si(OR)2  (A-1-2)



R6Si(OR)3  (A-1-3)



Si(OR)4  (A-1-4)


wherein R represents a hydrocarbon group having 1 to 6 carbon atoms; and R1, R2, R3, R4, R5 , and R6 have the same meanings as defined above,


(R7R8R9Si)a1(R10R11Si)a2(R12Si)a3(Si)a4  (A-2-1)


wherein R7, R8, R9, R10, R11, and R12 have the same meanings as defined above; and a1, a2, a3, and a4 each represent a molar fraction, and satisfy a1+a2+a3+a4=1, 0≦a1≦1, 0≦a2≦1, 0≦a3≦1, and 0≦a4<1.

2. The composition for forming a coating type silicon-containing film according to claim 1, wherein the composition further comprises (C) one or more members selected from one or more silicon compounds represented by the formula (C-1), a hydrolysate, a condensate, and a hydrolysis condensate thereof,


R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3)  (C-1)


wherein R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C, and R3C each represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; and c1, c2, and c3 are each 0 or 1, and satisfy 1≦c1+c2+c3≦3.

3. The composition for forming a coating type silicon-containing film according to claim 2, wherein one or more of R1C, R2C, and R3C in the formula (C-1) are an organic group having a hydroxyl group or a carboxyl group each substituted by an acid-labile group.

4. The composition for forming a coating type silicon-containing film according to claim 2, wherein the component (C) contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more phosphorus compounds represented by the formulae (C-2-1) to (C-2-6) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,


PX3  (C-2-1)



POX3  (C-2-2)



P2O5  (C-2-3)



H(HPO3)a5OH  (C-2-4)



R13PX2  (C-2-5)



R13POX2  (C-2-6)


wherein R13 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms; and a5 is an integer of 1 or more.

5. The composition for forming a coating type silicon-containing film according to claim 2, wherein the component (C) contains one or more members selected from one or more silicon compounds represented by the formulae (A-1-1) to (A-1-4) and one or more boron compounds represented by the formulae (C-3-1) to (C-3-3) each alone, a mixture thereof, and a hydrolysate, a condensate, or a hydrolysis condensate thereof,


BX3  (C-3-1)



B2O3  (C-3-2)



R14BX2  (C-3-3)


wherein R14 represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, wherein a hydrogen atom(s) in the organic group may be substituted by a halogen atom(s); and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

6. The composition for forming a coating type silicon-containing film according to claim 1, wherein the composition further comprises an organic compound having 2 or more hydroxyl groups or carboxyl groups in one molecule.

7. A substrate for use in a semiconductor manufacturing process, comprising a silicon-containing film formed on a body to be processed by applying the composition for forming a coating type silicon-containing film according to claim 1.

8. The substrate according to claim 7, wherein the silicon-containing film functions as at least one of a resist under layer film, a flattening film, and an insulating film.

9. The substrate according to claim 7, wherein the body to be processed is a semiconductor substrate on which a part or whole of semiconductor circuits have been formed, and the silicon-containing film is formed by applying the composition for forming a coating type silicon-containing film by spin-coating onto the semiconductor substrate and then baking the same.

10. A patterning process comprising:
forming an organic under layer film on a body to be processed by using a coating type organic under layer film material;
forming a silicon-containing film on the organic under layer film by using the composition for forming a coating type silicon-containing film according to claim 1;
forming an upper layer resist film on the silicon-containing film;
forming a pattern with the upper layer resist film;
transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and
transferring the pattern to the organic under layer film by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.

11. A patterning process comprising:
forming a hard mask mainly consisting of carbon on a body to be processed by a CVD method;
forming a silicon-containing film on the hard mask by using the composition for forming a coating type silicon-containing film according to claim 1;
forming an upper layer resist film on the silicon-containing film;
forming a pattern with the upper layer resist film;
transferring the pattern to the silicon-containing film by etching using the upper layer resist film having the formed pattern as a mask; and
transferring the pattern to the hard mask by etching using the silicon-containing film having the transferred pattern as a mask to form a mask pattern for processing the body to be processed.

12. The patterning process according to claim 10, further comprising removing the silicon-containing film by wet etching after forming the mask pattern for processing the body to be processed.

13. The patterning process according to claim 11, further comprising removing the silicon-containing film by wet etching after forming the mask pattern for processing the body to be processed.

14. The patterning process according to claim 12, wherein the wet etching is performed by an alkaline solution.

15. The patterning process according to claim 13, wherein the wet etching is performed by an alkaline solution.

16. The patterning process according to claim 10, wherein the body to be processed is a material in which any of a metal film, an amorphous metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film or a metal oxynitride film is formed on a semiconductor substrate on which a part or whole of semiconductor circuits have been formed, as a layer to be processed.

17. The patterning process according to claim 16, wherein the metal constituting the body to be processed comprises silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

18. The patterning process according to claim 10, wherein pattern formation of the upper layer resist film is carried out by a lithography method using light with a wavelength of 300 nm or less or EUV light, an electron beam direct drawing method, a directed self-assembly method or a nano-imprinting lithography method.