JP4985987B2 - Pattern formation method - Google Patents

Description

  The present invention particularly relates to a pattern forming method for forming an oxide film on a resist pattern for a sidewall spacer method in which a line pattern having a half pitch is formed by one exposure.

In recent years, with the higher integration and higher speed of LSIs, there is a demand for finer pattern rules. In light exposure currently used as a general-purpose technology, the intrinsic resolution limit derived from the wavelength of the light source Is approaching. As exposure light used for forming a resist pattern, light exposure using g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source was widely used in the 1980s. As a means for further miniaturization, the method of shortening the exposure wavelength is effective, and mass production after 64 Mbit (process size is 0.25 μm or less) DRAM (Dynamic Random Access Memory) in the 1990s In the process, a KrF excimer laser (248 nm) having a short wavelength was used as an exposure light source instead of i-line (365 nm). However, in order to manufacture DRAMs with a density of 256M and 1G or more that require finer processing technology (processing dimensions of 0.2 μm or less), a light source with a shorter wavelength is required, and an ArF excimer has been used for about 10 years. Photolithography using a laser (193 nm) has been studied in earnest. Initially, ArF lithography was supposed to be applied from the device fabrication of the 180 nm node, but KrF excimer lithography was extended to 130 nm node device mass production, and full-scale application of ArF lithography is from the 90 nm node. Further, a 65 nm node device is being studied in combination with a lens whose NA is increased to 0.9. For the next 45 nm node device, the exposure wavelength has been shortened, and F ₂ lithography with a wavelength of 157 nm was nominated. However, the cost of the scanner is increased by using a large amount of expensive CaF ₂ single crystal for the projection lens, the optical system is changed due to the introduction of the hard pellicle because the durability of the soft pellicle is extremely low, and the etching resistance of the resist film is reduced. Due to various problems, it has been proposed to advance F ₂ lithography and early introduction of ArF immersion lithography (Non-Patent Document 1: Proc. SPIE Vol. 4690 xxix (2002)).

  In ArF immersion lithography, it has been proposed to impregnate water between the projection lens and the wafer. The refractive index of water at 193 nm is 1.44, and pattern formation is possible even with a lens having an NA (numerical aperture) of 1.0 or more. Theoretically, the NA can be increased to near 1.44. Initially, it was pointed out that the resolution was deteriorated and the focus shifted due to the change in refractive index accompanying the change in water temperature. It was confirmed that the water temperature was controlled within 1/100 ° C. and the influence of the heat generated from the resist film due to exposure was almost no worry, and the problem of refractive index change was solved. It was feared that microbubbles in the water could be transferred to the pattern, but it was confirmed that the water was sufficiently degassed and that there was no risk of bubble formation from the resist film due to exposure. In the early stage of immersion lithography in the 1980s, a method was proposed in which all stages were immersed in water, but water was inserted only between the projection lens and the wafer to accommodate the operation of the high-speed scanner, and water was supplied and drained. A partial fill system with a nozzle was adopted. In principle, lens design with an NA of 1 or more became possible by immersion using water, but the conventional optical system based on the refractive index system became a huge lens, and the lens was deformed by its own weight. There was a problem. A catadioptric optical system has been proposed for a more compact lens design, and a lens design with NA of 1.0 or more has been accelerated. The possibility of a 45 nm node is shown by combining a lens with NA 1.2 or higher and strong super-resolution technology (Non-patent Document 2: Proc. SPIE Vol. 5040 p724 (2003)), and further development of a lens with NA 1.35. Has also been done.

  As a lithography technique for the 32 nm node, vacuum ultraviolet light (EUV) lithography with a wavelength of 13.5 nm is cited as a candidate. Problems with EUV lithography include higher laser output, higher resist film sensitivity, higher resolution, lower linewidth roughness (LWR), defect-free MoSi multilayer mask, and lower reflection mirror aberration. There are a lot of problems to overcome.

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

  Recently, a double patterning process in which a pattern is formed by the first exposure and development and a pattern is formed just between the first pattern by the second exposure (Non-Patent Document 3: Proc.SPIE Vol.5992 p557 (2005)). Many processes have been proposed as a double patterning method. For example, the first exposure and development form a photoresist pattern with 1: 3 line and space spacing, the lower hard mask is processed by dry etching, and another hard mask is laid on the first hard mask. In this method, a line pattern is formed by exposing and developing a photoresist film in a space portion of the exposure, and a hard mask is processed by dry etching to form a line and space pattern that is half the pitch of the initial pattern. Further, a photoresist pattern having a space and line spacing of 1: 3 is formed by the first exposure and development, the underlying hard mask is processed by dry etching, and a photoresist film is applied thereon. A second space pattern is exposed to the portion where the hard mask remains, and the hard mask is processed by dry etching. In either case, the hard mask is processed by two dry etchings.

  In the above-described method, it is necessary to lay a hard mask twice. In the latter method, only one hard mask is required, but it is necessary to form a trench pattern that is difficult to resolve compared to a line pattern. In the latter method, there is a method using a negative resist material for forming a trench pattern. This can use the same high contrast light as forming a line with a positive pattern, but the negative resist material has a lower dissolution contrast than the positive resist material. Compared with the case of forming a line, the case of using a negative resist material to form a trench pattern having the same dimensions is compared. The latter method uses a positive resist material to form a wide trench pattern, then heats the substrate to shrink the trench pattern, or coats a water-soluble film on the developed trench pattern. Although it is conceivable to apply the RELACS method in which the trench is shrunk by heating and then crosslinking the resist film surface, there is a disadvantage that the proximity bias is deteriorated and the process is further complicated and the throughput is reduced. .

  Even in the former method and the latter method, etching for substrate processing is required twice, so that there is a problem in that throughput is reduced and pattern deformation and displacement occur due to the two etchings.

  In order to complete the etching once, there is a method in which a negative resist material is used in the first exposure and a positive resist material is used in the second exposure. There is also a method in which a positive resist material is used in the first exposure, and a negative resist material dissolved in a higher alcohol having 4 or more carbon atoms in which the positive resist material is not dissolved in the second exposure. In these cases, if a negative resist material with low resolution is used, the resolution deteriorates.

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

Since it is difficult to divide one pattern into two due to the problem of alignment accuracy of the scanner, a method of halving the pitch by one exposure has been studied.
A method has been proposed in which a film is attached to the side walls on both sides of the line pattern to thereby halve the pitch (Non-Patent Document 4: J. Vac. Sci. Technol. B 17 (6), Nov / Dec 1999). As the sidewall process, in the fourth immersion symposium (2007), lecture number: PR-01, title: Implementation of immersion lithography to NAND / CMOS lithography to NAND / CMOS device manufacturing (Non-patent Document 5) A spacer space method that uses a hard mask and a film attached to the side wall of the hard mask and a film embedded in a space between the films as an etching pattern, and a spacer line method that uses a film attached to the hard mask side wall under the resist as an etching pattern. Proposed. In either method, a film attached to the side wall of the hard mask under the resist is used as an etching mask.

  When the resist line deviates from the target dimension, the line CD used as an etching mask in the spacer spacer method varies, and the spacer line method leads to variations in line position. In either method, it is necessary to improve both the thickness control of the sidewall spacer and the dimension control of the resist pattern after development. The side wall spacer method can halve the pitch with one exposure, but the end point of the line becomes a donut shape, and the end line may be unnecessary, so this is erased. Exposure is required, and at least two exposures are required. However, in this case, very high-precision alignment is not required for halving the pitch in the second exposure.

In general, polysilicon, a silicon oxide film, a silicon nitride film, a silicon nitride oxide film, a titanium nitride film, an amorphous carbon film, or the like is used as a hard mask. These films are formed by chemical vapor deposition or chemical vapor deposition (CVD). As the sidewall pattern thereon, a material different from the hard mask is used in order to process the hard mask and the underlying substrate.
In the sidewall spacer method, in order to obtain an etching pattern based on a film attached only to the sidewall of the hard mask, the film on the hard mask and the spacer must be removed. In the spacer space method, it is necessary to remove the side wall pattern after filling the space. In the space line method, after the space pattern is formed on the side wall of the hard mask, only the hard mask has to be removed. This is an expensive process with many etching processes and film removal steps, low throughput and low throughput.

A method of reducing the hole pattern diameter by forming a silicon oxide film on a resist pattern by a low temperature CVD method has been proposed (Non-Patent Document 6: Proc. SPIE Vol. 6923 p692333-1 (2008)). Studies to directly attach a silicon oxide film are in progress. Atomic Layer Deposition: ALD (Atomic Layer Deposition) is a type of CVD method and is a method of laminating silicon oxide at the atomic level (Non-patent Document 7: Hitachi Review, April 2007 issue, 45 nm node) Corresponding vertical ALD film forming apparatus “ALDINNA”, Vertical Batch Atomic Layer Equipment Equipment ALDINA for 45-nm Node Devices). It is considered that the film is excellent in conformality and film thickness uniformity and suitable for forming a silicon oxide film for a sidewall spacer. The disadvantage of the ALD method is that the throughput is low, but the throughput per hour has been increased by batch processing of a large number of wafers.
Chlorosilane and alkoxysilane (Patent Document 5: Japanese Patent Application Laid-Open No. 2005-197561) are used as gas species to be a silicon source for forming a silicon oxide film by a CVD method or an ALD method.

Proc. SPIE Vol. 4690 xxix (2002) Proc. SPIE Vol. 5040 p724 (2003) Proc. SPIE Vol. 5992 p557 (2005) J. et al. Vac. Sci. Technol. B 17 (6), Nov / Dec 1999 4th Immersion Symposium (2007) Lecture number; PR-01, Title; Implementation of immersion lithography to NAND / CMOS lithography to NAND / CMOS device manufacturing Proc. SPIE Vol. 6923 p692333-1 (2008) Hitachi review April 2007, 45nm node vertical ALD deposition system "ALDINA", Vertical Batch Atomic Layer Deposition ALDINA for 45-nm Node Devices JP-A-5-102029 Japanese Patent Laid-Open No. 6-80413 JP 2006-286711 A JP 2008-109093 A JP 2005-197561 A

  As described above, when the silicon oxide film is formed on the side wall of the resist pattern and the substrate is processed based on the silicon oxide film, when the silicon oxide film is directly formed on the resist pattern, the raw silane gas As a result, the growth rate of the silicon oxide film decreases, and the LWR after forming the silicon oxide film on the resist pattern decreases.

  The present invention is an improvement of the above situation, and a silicon oxide film is formed on the side wall of the resist pattern, and a silicon oxide film is formed on the resist pattern in the side wall spacer method in which the base is processed based on this film. It is an object of the present invention to provide a pattern forming method for securing a sufficient growth rate and preventing deformation of a resist pattern and increase in LWR.

  In order to solve the above-mentioned problems, according to the present inventors, a side wall spacer for forming a silicon oxide film on the side wall of a resist pattern, thereby processing a half-pitch pattern of the resist pattern after development. In this method, a method in which a silane compound having an amino group or an ammonium salt is adsorbed on the resist surface and a silicon oxide film is formed on the silane compound using silane, chlorosilane, alkoxysilane, or isocyanatesilane is effective. I found out.

（式中、Ｒ¹、Ｒ²、Ｒ⁷、Ｒ⁸、Ｒ⁹は水素原子、炭素数１〜１０のアミノ基、エーテル基、エステル基又はヒドロキシ基を有していてもよい直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、又は炭素数７〜１２のアラルキル基である。又はＲ¹とＲ²、Ｒ⁷とＲ⁸、Ｒ⁸とＲ⁹又はＲ⁷とＲ⁹とが結合してこれらが結合する窒素原子と共に環を形成していてもよい。Ｒ³、Ｒ¹⁰は炭素数１〜１２の直鎖状、分岐状又は環状のアルキレン基で、エーテル基、エステル基、チオエーテル基、フェニレン基又はヒドロキシ基を有していてもよく、Ｒ⁴〜Ｒ⁶、Ｒ¹¹〜Ｒ¹³は水素原子、炭素数１〜６のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、炭素数１〜６のアルコキシ基、炭素数６〜１０のアリーロキシ基、炭素数２〜１２のアルケニロキシ基、炭素数７〜１２のアラルキロキシ基、又はヒドロキシ基であり、Ｒ⁴〜Ｒ⁶、Ｒ¹¹〜Ｒ¹³の内少なくとも一つがアルコキシ基又はヒドロキシ基である。Ｘ^-は陰イオンを表す。）
請求項３：
１分子内に少なくとも１つのアミノ基又はアンモニウム塩を有するアミノシラン化合物が、下記一般式（３）又は（４）で示されるものであることを特徴とする請求項１記載のパターン形成方法。

（式中、Ｒ²⁰は水素原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、又は炭素数２〜１２のアルケニル基であり、ヒドロキシ基、エーテル基（−Ｏ−）、エステル基（−ＣＯＯ−）又はアミノ基を有していてもよい。ｐは１又は２であり、ｐが１の場合、Ｒ²¹は炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基、エステル基又はフェニレン基を有していてもよい。ｐが２の場合、Ｒ²¹は上記アルキレン基より水素原子が１個脱離した基である。Ｒ²²〜Ｒ²⁴は水素原子、炭素数１〜６のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、炭素数１〜６のアルコキシ基、炭素数６〜１０のアリーロキシ基、炭素数２〜１２のアルケニロキシ基、炭素数７〜１２のアラルキロキシ基、又はヒドロキシ基であり、Ｒ²²〜Ｒ²⁴の内少なくとも一つがアルコキシ基又はヒドロキシ基である。）

（式中、Ｒ³〜Ｒ⁶、Ｒ¹¹は請求項２で定義した通りであり、Ｒ²¹〜Ｒ²⁴、ｐは上記の通りである。）
請求項４：
レジストパターンを形成するレジスト材料が、ヒドロキシ基、ヒドロキシナフチル基、カルボキシ基、２，２，２−トリフルオロ−１−ヒドロキシエチル基から選ばれる少なくとも１個の密着性基を有する繰り返し単位と、酸不安定基を有する繰り返し単位とを含む高分子化合物をベースポリマーとする化学増幅ポジ型レジスト材料であることを特徴とする請求項１乃至３のいずれか１項記載のパターン形成方法。
請求項５：
フォトレジストパターン上に１分子内に少なくとも１つのアミノ基又はアンモニウム塩を有するアミノシラン化合物を吸着させる方法が、スピンコート法、ベーパープライム法、ＣＶＤ法又はＡＬＤ法であることを特徴とする請求項１乃至４のいずれか１項記載のパターン形成方法。
請求項６：
シラン、クロロシラン、アルコキシシラン及びイソシアネートシランから選ばれるシランガスを酸化するためのガスが、Ｈ₂Ｏ、Ｄ₂Ｏ、Ｏ₂、Ｏ₃、Ｈ₂Ｏ₂、ＮＯ、ＮＯ₂の少なくとも１つから選ばれることを特徴とする請求項１乃至５のいずれか１項記載のパターン形成方法。
請求項７：
フォトレジストパターン上に形成した珪素酸化膜のスペース部分とフォトレジストパターン上部の珪素酸化膜を除去し、フォトレジストパターン両側の側壁に珪素酸化膜パターンを残し、これを用いてピッチ間の距離を減少させることを特徴とする請求項１乃至６のいずれか１項記載のパターン形成方法。
請求項８：
被加工基板上にＣＶＤ法又はスピンコート法で作製した炭素の割合が７５質量％以上の膜上にフォトレジストパターンを形成し、このフォトレジストパターン上に形成した珪素酸化膜のスペース部分とフォトレジストパターン上部の珪素酸化膜を除去し、フォトレジストパターン両側の側壁に珪素酸化膜パターンを形成し、これをマスクとして炭素膜をドライエッチングにより加工し、炭素膜をマスクにして被加工基板を加工することを特徴とする請求項１乃至７のいずれか１項記載のパターン形成方法。
請求項９：
被加工基板上に気相成長法又はスピンコート法で作製した炭素の割合が７５質量％以上の膜とフォトレジスト膜との間に炭化水素材料からなる反射防止膜を敷くことを特徴とする請求項８記載のパターン形成方法。 Accordingly, the present invention provides the following pattern forming method and a resist material used therefor.
Claim 1:
An aminosilane compound having at least one amino group or ammonium salt in one molecule is adsorbed on the photoresist pattern, and silane, chlorosilane, alkoxysilane is deposited thereon by CVD (Chemical Vapor Deposition) method or ALD (Atomic Layer Deposition) method. And a silicon oxide film formed by oxidizing a silane gas selected from isocyanate silane.
Claim 2:
The pattern forming method according to claim 1, wherein the aminosilane compound having at least one amino group or ammonium salt is represented by the following general formula (1) or (2).

(In the formula, R ¹ , R ² , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a linear group optionally having an amino group having 1 to 10 carbon atoms, an ether group, an ester group or a hydroxy group, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, or R ¹ and R ² , R ⁷ and R ^8. , R ⁸ and R ⁹ or R ⁷ and R ⁹ may be combined to form a ring together with the nitrogen atom to which these are bonded, R ³ and R ¹⁰ are linear or branched having 1 to 12 carbon atoms. A cyclic or cyclic alkylene group which may have an ether group, an ester group, a thioether group, a phenylene group or a hydroxy group, and R ^{4 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom and have 1 to 6 carbon atoms. Alkyl group, aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 12 carbon atoms, and 1 to 6 carbon atoms Alkoxy group, an aryloxy group having 6 to 10 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms or an Ararukirokishi group, or a hydroxy group of 7 to 12 carbon atoms, at least of ^{R 4 ~R 6, R 11 ~R} 13 One is an alkoxy group or a hydroxy group. X ⁻ represents an anion.)
Claim 3:
2. The pattern forming method according to claim 1, wherein the aminosilane compound having at least one amino group or ammonium salt in one molecule is represented by the following general formula (3) or (4).

(Wherein R ²⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; Group, an ether group (—O—), an ester group (—COO—) or an amino group, p is 1 or 2, and when p is 1, R ²¹ has 1 to 20 carbon atoms. A linear, branched or cyclic alkylene group which may have an ether group, an ester group or a phenylene group, and when p is 2, R ²¹ is one hydrogen atom removed from the alkylene group. R ^{22 to} R ²⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. An aryloxy group having 6 to 10 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, (It is an aralkyloxy group having 7 to 12 carbon atoms or a hydroxy group, and at least one of R ^{22 to} R ²⁴ is an alkoxy group or a hydroxy group.)

(Wherein R ^{3 to} R ⁶ and R ¹¹ are as defined in claim 2, and R ^{21 to} R ²⁴ and p are as described above.)
Claim 4:
A resist material for forming a resist pattern includes a repeating unit having at least one adhesive group selected from a hydroxy group, a hydroxy naphthyl group, a carboxy group, and a 2,2,2-trifluoro-1-hydroxyethyl group, an acid 4. The pattern forming method according to claim 1, wherein the pattern forming method is a chemically amplified positive resist material having a base compound of a polymer compound containing a repeating unit having an unstable group.
Claim 5:
2. The method of adsorbing an aminosilane compound having at least one amino group or ammonium salt in one molecule on a photoresist pattern is a spin coating method, a vapor prime method, a CVD method or an ALD method. The pattern formation method of any one of thru | or 4.
Claim 6:
A gas for oxidizing a silane gas selected from silane, chlorosilane, alkoxysilane, and isocyanate silane is selected from at least one of H ₂ O, D ₂ O, O ₂ , O ₃ , H ₂ O ₂ , NO, and NO _2. The pattern forming method according to claim 1, wherein the pattern forming method is performed.
Claim 7:
The silicon oxide film space formed on the photoresist pattern and the silicon oxide film above the photoresist pattern are removed, leaving the silicon oxide film pattern on the sidewalls on both sides of the photoresist pattern, and using this to reduce the distance between pitches. The pattern forming method according to claim 1, wherein the pattern forming method is performed.
Claim 8:
A photoresist pattern is formed on a film having a carbon ratio of 75% by mass or more formed on a substrate to be processed by CVD or spin coating, and a space portion of the silicon oxide film formed on the photoresist pattern and the photoresist. The silicon oxide film above the pattern is removed, the silicon oxide film pattern is formed on the sidewalls on both sides of the photoresist pattern, the carbon film is processed by dry etching using this as a mask, and the substrate to be processed is processed using the carbon film as a mask. The pattern forming method according to claim 1, wherein:
Claim 9:
An antireflection film made of a hydrocarbon material is laid between a film having a carbon ratio of 75% by mass or more and a photoresist film formed by vapor deposition or spin coating on a substrate to be processed. Item 9. The pattern forming method according to Item 8.

  According to the present invention, in the sidewall spacer method in which a silicon oxide film is directly formed on a resist pattern and thereby the pitch of the resist pattern after development is reduced, the resist pattern is formed with a silane compound having an amino group or an ammonium salt. By covering the surface, the subsequent CVD method or ALD method promotes the formation of a silicon oxide film, prevents the deformation of the pattern and the increase in LWR when the silicon oxide film is attached, and forms the sidewall spacer pattern with high accuracy. Can do. The sidewall spacer method in which an oxide film is directly applied to a resist pattern has a large cost merit because it requires fewer etching steps than the conventional sidewall spacer method in which a resist mask is attached to a hard mask.

  In the side wall spacer method in which a film is formed on both side walls of a pattern to halve the pitch, the present inventors have prepared a resist pattern pretreatment material with aminosilane for directly forming a silicon oxide film on the side wall of the resist pattern. We conducted an intensive study.

  That is, the present inventors adsorbed an aminosilane compound having an amino group or an ammonium salt on the resist surface in a sidewall spacer method in which a silicon oxide film is directly formed on a resist pattern by a CVD method or an ALD method. The present invention has been completed by finding that the growth of the silicon oxide film is performed smoothly, and that deformation of the resist pattern after the oxide film is formed and increase in LWR can be prevented.

（式中、Ｒ¹、Ｒ²、Ｒ⁷、Ｒ⁸、Ｒ⁹は水素原子、炭素数１〜１０のアミノ基、エーテル基、エステル基又はヒドロキシ基を有していてもよい直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、又は炭素数７〜１２のアラルキル基である。又はＲ¹とＲ²、Ｒ⁷とＲ⁸、Ｒ⁸とＲ⁹又はＲ⁷とＲ⁹とが結合してこれらが結合する窒素原子と共に環を形成していてもよい。Ｒ³、Ｒ¹⁰は炭素数１〜１２の直鎖状、分岐状又は環状のアルキレン基で、エーテル基、エステル基、チオエーテル基、フェニレン基又はヒドロキシ基を有していてもよく、Ｒ⁴〜Ｒ⁶、Ｒ¹¹〜Ｒ¹³は水素原子、炭素数１〜６のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、炭素数１〜６のアルコキシ基、炭素数６〜１０のアリーロキシ基、炭素数２〜１２のアルケニロキシ基、炭素数７〜１２のアラルキロキシ基、又はヒドロキシ基であり、Ｒ⁴〜Ｒ⁶、Ｒ¹¹〜Ｒ¹³の内少なくとも一つがアルコキシ基又はヒドロキシ基である。Ｘ^-はヒドロキシイオン、塩素イオン、臭素イオン、ヨウ素イオン、硫酸イオン、硝酸イオン、アルキルカルボン酸イオン、アリールカルボン酸イオン、アルキルスルホン酸イオン又はアリールスルホン酸イオン等の陰イオンを表す。） The aminosilane compound having at least one amino group or ammonium salt used in the pattern forming method of the present invention is represented by the following general formula (1) or (2).

(In the formula, R ¹ , R ² , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a linear group optionally having an amino group having 1 to 10 carbon atoms, an ether group, an ester group or a hydroxy group, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, or R ¹ and R ² , R ⁷ and R ^8. , R ⁸ and R ⁹ or R ⁷ and R ⁹ may be combined to form a ring together with the nitrogen atom to which these are bonded, R ³ and R ¹⁰ are linear or branched having 1 to 12 carbon atoms. A cyclic or cyclic alkylene group which may have an ether group, an ester group, a thioether group, a phenylene group or a hydroxy group, and R ^{4 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom and have 1 to 6 carbon atoms. Alkyl group, aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 12 carbon atoms, and 1 to 6 carbon atoms Alkoxy group, an aryloxy group having 6 to 10 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms or an Ararukirokishi group, or a hydroxy group of 7 to 12 carbon atoms, at least of ^{R 4 ~R 6, R 11 ~R} 13 One is an alkoxy group or a hydroxy group, and X ⁻ represents a hydroxy ion, a chlorine ion, a bromine ion, an iodine ion, a sulfate ion, a nitrate ion, an alkyl carboxylate ion, an aryl carboxylate ion, an alkyl sulfonate ion, or an aryl sulfonate ion. Represents an anion such as

  The surfaces of the silicon oxide film substrate and the Si substrate are covered with silanol, and a silane gas such as silane, chlorosilane, alkoxysilane, or isocyanate silane is adsorbed to the silanol, and an oxide film is formed by a condensation reaction. On the other hand, resist films often do not have functional groups such as primary and secondary hydroxy groups that cause a condensation reaction with silane, chlorosilane, alkoxysilane, and isocyanate silane, and are compared to silicon oxide film substrates and Si substrates. Since the silicon oxide film is not formed, the initial silicon oxide film formation rate is slow, and a time lag occurs in the oxide film formation. Once the silicon oxide film starts to be formed, the lamination proceeds smoothly thereafter.

In the pattern forming method of the present invention, an aminosilane compound having at least one amino group or ammonium salt in one molecule is adsorbed on a resist pattern, and the silane gas such as silane, chlorosilane, alkoxysilane, or isocyanatesilane is used on the resist pattern. A silicon oxide film (SiO ₂ film) is formed. When a positive resist material having a base polymer containing a repeating unit that forms a carboxyl group is used, particularly when the acid labile group is eliminated, the surface of the resist pattern is a carboxyl group by partial deprotection of the acid labile group. An alkoxysilane compound having an amino group or an ammonium salt is efficiently adsorbed on a carboxyl group. The amino group or ammonium salt is adsorbed on the resist side, and a very thin SiO ₂ film is formed by hydrolysis of alkoxysilane, and a part of silanol remains, so that silane, chlorosilane, alkoxysilane, isocyanatesilane, etc. As the silane gas is oxidized while being smoothly adsorbed, the SiO ₂ film is efficiently formed without an initial time lag.

Specific examples of the aminosilane compound represented by the general formula (1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, and 3-aminopropyltrihydroxysilane. 2-aminoethylaminomethyltrimethoxysilane, 2-aminoethylaminomethyltriethoxysilane, 2-aminoethylaminomethyltripropoxysilane, 2-aminoethylaminomethyltrihydroxysilane, isopropylaminomethyltrimethoxysilane, 2 -(2-aminoethylthioethyl) trimethoxysilane, allyloxy-2-aminoethylaminomethyldimethylsilane, butylaminomethyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3- (2-amino Tilaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, piperidinomethyltrimethoxysilane, 3-allylaminopropyltrimethoxysilane, 4-methylpiperazinomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, morpholinomethyltrimethoxysilane, 4-acetylpiperazinomethyltrimethoxysilane, cyclohexylaminotrimethoxysilane, 2-piperidinoethyltrimethoxysilane, 2 -Morpholinoethylthiomethyltrimethoxysilane, dimethoxymethyl-2-piperidinoethylsilane, 3-morpholinopropyltrimethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-piperazinopropyl Limethoxysilane, 3-butylaminopropyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3- [2- (2-aminoethylaminoethyl) Amino) propyl] trimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, 3- (4-acetylpiperazinopropyl) trimethoxysilane, 3- (3-methylpi Peridinopropyl) trimethoxysilane, 3- (4-methylpiperidinopropyl) trimethoxysilane, 3- (2-methylpiperidinopropyl) trimethoxysilane, 3- (2-morpholinoethylthiopropyl) tri Methoxysilane, dimethoxymethyl-3- (4-methyl) Lupiperidinopropyl) silane, 3-cyclohexylaminopropyltrimethoxysilane, 3-benzylaminopropyltrimethoxysilane, 3- (2-piperidinoethylthiopropyl) trimethoxysilane, 3-hexamethyleneiminopropyltrimethoxysilane And 3-pyrrolidinopropyltrimethoxysilane.
The aminosilane compound represented by the general formula (1) may be used alone, or two or more aminosilane compounds may be blended. Moreover, you may use what hydrolyzed and condensed the aminosilane compound.

（式中、Ｒ²⁰は水素原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、又は炭素数２〜１２のアルケニル基であり、ヒドロキシ基、エーテル基（−Ｏ−）、エステル基（−ＣＯＯ−）又はアミノ基を有していてもよい。ｐは１又は２であり、ｐが１の場合、Ｒ²¹は炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基、エステル基又はフェニレン基を有していてもよい。ｐが２の場合、Ｒ²¹は上記アルキレン基より水素原子が１個脱離した基である。Ｒ²²〜Ｒ²⁴は水素原子、炭素数１〜６のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１２のアルケニル基、炭素数１〜６のアルコキシ基、炭素数６〜１０のアリーロキシ基、炭素数２〜１２のアルケニロキシ基、炭素数７〜１２のアラルキロキシ基、又はヒドロキシ基であり、Ｒ²²〜Ｒ²⁴の内少なくとも一つがアルコキシ基又はヒドロキシ基である。） Examples of the aminosilane compound represented by the general formula (1) include a reaction product of an oxirane-containing silane compound represented by the following general formula (3) and an amine compound.

(Wherein R ²⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; Group, an ether group (—O—), an ester group (—COO—) or an amino group, p is 1 or 2, and when p is 1, R ²¹ has 1 to 20 carbon atoms. A linear, branched or cyclic alkylene group which may have an ether group, an ester group or a phenylene group, and when p is 2, R ²¹ is one hydrogen atom removed from the alkylene group. R ^{22 to} R ²⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. An aryloxy group having 6 to 10 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, (It is an aralkyloxy group having 7 to 12 carbon atoms or a hydroxy group, and at least one of R ^{22 to} R ²⁴ is an alkoxy group or a hydroxy group.)

In the aminosilane compound represented by the general formula (1), in particular, an aminosilane having a secondary amino group in which R ¹ is a hydrogen atom or an aminosilane having a primary amino group in which both R ¹ and R ² are hydrogen atoms When a silane compound having oxirane is mixed, a silane compound represented by the following general formula (4) is generated by the reaction shown below. When a mixture of an aminosilane having a primary or secondary amino group and a silane compound having an oxirane is used, the following silane compound is adsorbed on the resist surface.

（式中、Ｒ¹〜Ｒ⁶、Ｒ¹¹、Ｒ²¹〜Ｒ²⁴、ｐは上記の通りである。）

(In the formula, R ^{1 to} R ⁶ , R ¹¹ , R ^{21 to} R ²⁴ , and p are as described above.)

The oxirane-containing silane compound used here will be described later.
The amine compound is preferably a primary or secondary amine compound, particularly a primary amine compound. As primary amine compounds, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine Cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, ethanolamine, N-hydroxyethylethylamine, N-hydroxypropylethylamine, etc. Grade aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine. , Diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N , N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.
The aminosilane compound can also be blended with other silane compounds. For example, JP-A-2005-248169 discloses a blend of aminosilane and silane having an epoxy group.

  Examples of the silane compound having an ammonium salt represented by the general formula (2) include 3-trimethylammonium hydroxide propyltriethoxysilane, 3-trimethylammonium hydroxide propyltrimethoxysilane, and 3-trimethylammonium hydroxide propyltripropoxysilane. 3-tributylammonium hydroxide propyltrimethoxysilane, 3-triethylammonium hydroxide propyltrimethoxysilane, 3-tripropylammonium hydroxide propyltrimethoxysilane, 3-trimethylammonium hydroxide benzylethyltrimethoxysilane. Although the hydroxy anion was mentioned as the above anion, halogen atoms such as chlorine and bromine, acetic acid, formic acid, oxalic acid, citric acid, nitric acid, sulfonic acid, methanesulfonic acid, tosylic acid, benzenesulfonic acid can also be mentioned, In order for ammonium ions to be adsorbed by exchange of anions with carboxyl groups on the resist surface, the ions are preferably weak acids or bases, and most preferably hydroxy anions.

In addition, the aminosilane compound and the ammonium salt-containing silane compound can be blended with the following silane compound, and this silane compound can be represented by the following general formula (5).
R ³¹ _m1 R ³² _m2 R ³³ _m3 Si (OR) _(4-m1-m2-m3) (5)
(In the formula, R is an alkyl group having 1 to 3 carbon atoms, and R ³¹ , R ³² and R ³³ may be the same as or different from each other, and are a hydrogen atom or a monovalent organic having 1 to 30 carbon atoms. And m1, m2, and m3 are 0 or 1. m1 + m2 + m3 is preferably 0 to 3, particularly preferably 0 or 1.)

Here, the organic group means a group containing carbon, further contains hydrogen, and may contain nitrogen, oxygen, sulfur, silicon or the like. Examples of the organic group for R ³¹ , R ³² , and R ³³ include linear, branched, or cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and other unsubstituted monovalent hydrocarbon groups, and these A group in which one or more of the hydrogen atoms of the group is substituted with an epoxy group, an alkoxy group, a hydroxy group, or the like, or -O-, -CO-, -OCO-, -COO-, -OCOO- are interposed And organic groups containing a silicon-silicon bond, which will be described later.

Preferred as R ³¹ , R ³² and R ³³ of the monomer represented by the general formula (5) are hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and iso-butyl. Group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and other alkyl groups, Examples thereof include alkenyl groups such as vinyl group and allyl group, alkynyl groups such as ethynyl group, aryl groups such as light absorbing group phenyl group and tolyl group, and aralkyl groups such as benzyl group and phenethyl group.

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

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

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

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

Another example of the organic group represented by R ³¹ , R ³² , or R ³³ is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of an epoxy group, an ester group, an alkoxy group, and a hydroxy group. Examples of the organic group having one or more of a carbon-oxygen single bond and a carbon-oxygen double bond in the general formula (5) include those represented by the following general formula (6).

炭素数１〜４のアルコキシ基、炭素数２〜６のアルキルカルボニルオキシ基、又は炭素数２〜６のアルキルカルボニル基であり、Ｑ₁とＱ₂とＱ₃とＱ₄は各々独立して−Ｃ_qＨ_(2q-p)Ｐ_p−（式中、Ｐは上記と同様であり、ｐは０〜３の整数であり、ｑは０〜１０の整数（但し、ｑ＝０は単結合であることを示す。）である。）、ｕは０〜３の整数であり、Ｓ₁とＳ₂は各々独立して−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−又は−ＯＣＯＯ−を表す。ｖ１、ｖ２、ｖ３は、各々独立して０又は１を表す。これらとともに、Ｔはヘテロ原子を含んでもよい脂環又は芳香環からなる２価の基であり、Ｔの酸素原子等のヘテロ原子を含んでもよい脂環又は芳香環の例を以下に示す。ＴにおいてＱ₂とＱ₃と結合する位置は、特に限定されないが、立体的な要因による反応性や反応に用いる市販試薬の入手性等を考慮して適宜選択できる。） _{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 - (6)
(In the above formula, P is a hydrogen atom, a hydroxyl group,

An alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or an alkylcarbonyl group having 2 to 6 carbon atoms, and Q ₁ , Q ₂ , Q _3, and Q ₄ are each independently- C _q H _(2q-p) P _p — (wherein P is the same as above, p is an integer of 0 to 3, q is an integer of 0 to 10 (provided that q = 0 is a single bond) And u is an integer of 0 to 3, and S ₁ and S ₂ are each independently —O—, —CO—, —OCO—, —COO— or —OCOO—. Represents. v1, v2, and v3 each independently represent 0 or 1. Together with these, T is a divalent group composed of an alicyclic ring or an aromatic ring which may contain a hetero atom, and examples of the alicyclic ring or aromatic ring which may contain a hetero atom such as an oxygen atom of T are shown below. The position where Q ₂ and Q ₃ are bonded to each other in T is not particularly limited, but can be appropriately selected in consideration of reactivity due to steric factors, availability of commercially available reagents used in the reaction, and the like. )

  Preferable examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (5) include the following. In addition, in the following formula, (Si) is described in order to indicate the bonding site with Si.

Moreover, as an example of the organic group of R ³¹ , R ³² , and R ³³ , an organic group containing a silicon-silicon bond can be used. Specifically, the following can be mentioned.

  The aminosilane compound used in the pattern forming method of the present invention can be mixed with a titanium compound described in JP-A-2006-65035 in order to promote the condensation reaction of silane.

  In order to adsorb aminosilane on the resist pattern surface, spin coating, vapor prime, CVD using aminosilane gas, or ALD can be used. In the case of the spin coating method, the aminosilane compound is dissolved in a solvent.

The solvent is preferably dissolved in an alcohol having 3 to 8 carbon atoms, water, or a mixed solution thereof. Since the base polymer for the positive resist is not dissolved in the alcohol having 3 to 8 carbon atoms, the generation of the mixing layer of the polymer compound having a hydroxy group and the resist pattern of the present invention is suppressed. Specific examples of the alcohol having 3 to 8 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3 -Pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol 2-methyl-2-pentanol, 2-methyl-3-pentanol 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3 -Pentanol, n-octanol, cyclohexanol are mentioned.

  Furthermore, in order to prevent mixing with the resist film, in addition to the above solvents, water, heavy water, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, decane, toluene, xylene Anisole, hexane, cyclohexane, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8-difluoro-1 , 4-Benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2-propanol, 2 ', 4'-difluoropropiophenone, 2,4-difluorotoluene, trifluoroacetaldehyde ethyl hemiacetate , Trifluoroacetamide, trifluoroethanol, 2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutaryl methyl, ethyl-3-hydroxy-4, 4,4-trifluorobutyrate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate, ethyl pentafluorobenzoate, ethyl pentafluoropropionate, ethyl pentafluoropropynyl acetate, ethyl perfluorooctanoate Ethyl-4,4,4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyl trifluorosulfonate, ethyl-3- ( bird Fluoromethyl) butyrate, ethyl trifluoropyruvate, S-ethyl trifluoroacetate, fluorocyclohexane, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 1,1,1,2,2 , 3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,4 , 4,5,5,5-heptafluoro-2-pentanol, 3,3,4,4,5,5,5-heptafluoro-2-pentanone, isopropyl 4,4,4-trifluoroacetoacetate, Methyl perfluorodenanoate, methyl perfluoro (2-methyl-3-oxahexanoate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl 2,3,3,3-tetrafluoropropionate, methyl trifluoroacetoacetate, 1,1,1,2,2,6,6,6-octafluoro-2,4-hexanedione, 2, 2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6- Dioxane anionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6-dioxanonane, 1H, 1H, 2H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 9H-per Fluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1H, 2H, 2H-perfluorooctanol, 2H-perfluoro-5,8,11,14-tetra Tyl-3,6,9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid methyl ester Perfluorotripentylamine, perfluorotripropylamine, 1H, 1H, 2H, 3H, 3H-perfluoroundecane-1,2-diol, trifluorobutanol 1,1,1-trifluoro-5-methyl-2 , 4-hexanedione, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 1,1,1-trifluoro-2-propyl acetate, perfluorobutyltetrahydrofuran Perfluoro (butyltetrahydrofuran), perfluorodecalin, -Fluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, trifluoromethyl acetate butyl, 3-trifluoromethoxypropion Acid methyl, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,3,3 , 3-hexafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 2,2,3,4,4,4-hexafluoro-1- Butanol, 2-trifluoromethyl 2-propanol, 2,2,3,3-tetrafluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 4,4,4-trifluoro-1-butanol or the like Two or more kinds can be mixed and used.

The mixing of water and heavy water accelerates the hydrolysis and condensation reaction of the amino group-containing silane compound after coating. Alternatively, the silane compound can be oligomerized in advance by hydrolytic condensation in a solution before coating by adding water and heavy water.
In this case, the alcohol having 3 to 8 carbon atoms is 10% by mass or more, preferably 30 to 99.9999% by mass in a resist pattern protective film material containing a silicon compound having a hydrolysis reaction group having at least one amino group. % Content is preferable. Further, the silicon compound having a hydrolysis reaction group having an amino group is preferably contained in the protective film material in an amount of 0.0001 to 10.0% by mass, particularly 0.001 to 5% by mass.

  The amount of water added is 0.0001% by mass or more, preferably 0.001 to 98% by mass in the protective film material containing a silicon compound having a hydrolysis reaction group having at least one amino group.

In the pattern forming method of the present invention, after adsorbing the silane compound represented by the general formula (1) or (2) on the resist pattern surface, an SiO ₂ film is directly formed on the resist pattern by a CVD method or an ALD method.
Silane gas such as silane, chlorosilane, alkoxysilane, and isocyanatesilane can be used as a gas for forming the SiO ₂ film by the CVD method or the ALD method. Examples of the silane gas include silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, disilane, methyldisilane, dimethyldisilane, and the like. Examples of the chlorosilane include monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, chloromethylsilane, dichloromethylsilane, trichloromethylsilane, dichlorotetrachlorodisilane, and the like. Alkoxysilanes include methoxysilane, dimethoxysilane, trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, ethyltrimethoxy Examples of silane and isocyanate silane include triisocyanate silane, tetraisocyanate silane, and methyl triisocyanate silane.

In order to prevent deformation of the resist pattern and deterioration of the LWR when forming the SiO ₂ film by the CVD method or the ALD method, a resist material that can form a stronger film can be preferably used on the resist side.
The hardness as resist film strength in this case preferably has a mechanical strength of 0.4 GPa or more or a Young modulus of 9.2 GPa or more, and such a positive resist material has only lactone as an adhesive group. Not achievable with base polymer. In addition to lactone, a hydroxyl group having hydrogen bonding properties is required as an adhesive group. The glass transition point (Tg) and mechanical strength of the polymer are improved by hydrogen bonding of the hydroxyl group. Examples of the adhesive group having hydrogen bonding include a hydroxy group, a hydroxy naphthyl group, a carboxy group, and a 2,2,2-trifluoro-1-hydroxyethyl group. These are classified as repeating unit a, and among these, a hydroxynaphthyl group is most preferred.
The repeating unit having a hydroxynaphthyl group can be represented by the following general formula (a).

（式中、Ｒ¹⁴は同一又は異種の水素原子又はメチル基を示す。Ｘ’は単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙ’は単結合、又は炭素数１〜６の直鎖状又は分岐状のアルキレン基で、エステル基又はエーテル基を有していてもよい。ｍ’は１又は２である。）’

(In the formula, R ¹⁴ represents the same or different hydrogen atom or methyl group. X ′ is a single bond, or —C (═O) —O—, and Y ′ is a single bond, or a carbon number of 1-6. A linear or branched alkylene group which may have an ester group or an ether group, m ′ is 1 or 2.) ′

  Here, as a C1-C6 alkylene group, a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, Examples include a cyclopentylene group, an n-hexylene group, and a cyclohexylene group.

The monomer for obtaining the repeating unit represented by the general formula (a) is represented by the following general formula (Ma). Here, R ¹⁴ , X ′, Y ′, and m ′ are the same as described above.

Specific examples of the monomer Ma include the following.

Examples of the monomer for obtaining a repeating unit having a hydroxy group or a carboxy group can be given below.

Examples of the repeating unit having a 2,2,2-trifluoro-1-hydroxyethyl group include the following.

  Copolymerizes repeating unit b having lactone, ether group, carbonyl group, carbonate group, sulfonic acid amide in addition to the above hydroxy group, hydroxy naphthyl group, carboxy group, 2,2,2-trifluoro-1-hydroxyethyl group You can also

  Among the lactones, the repeating unit having a 7-oxanorbornane ring represented by the following general formula (b1) or (b2) has a cross-linking reaction caused by an acid and heat, thereby improving the mechanical strength of the film. It can be preferably used.

（式中、Ｒ⁴¹、Ｒ⁴⁶は水素原子又はメチル基を示す。Ｒ⁴²、Ｒ⁴⁷は単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基又はエステル基を有していてもよいが、炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基の場合、式中のエステル基に連結した炭素原子は１級又は２級である。Ｒ⁴³〜Ｒ⁴⁵、Ｒ⁴⁸〜Ｒ⁵¹は水素原子、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基である。）

(In the formula, R ⁴¹ and R ⁴⁶ represent a hydrogen atom or a methyl group. R ⁴² and R ⁴⁷ are a single bond, or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and an ether group. Or an ester group, but in the case of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, the carbon atom linked to the ester group in the formula is primary or secondary. R ^{43 to} R ⁴⁵ and R ^{48 to} R ⁵¹ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

Monomers for obtaining a repeating unit having a 7-oxanorbornane ring are represented by the following general formulas (Mb1) and (Mb2). Here, R ^{41 to} R ⁵¹ are the same as described above.

  Specific examples of the monomer for obtaining the repeating units b1 and b2 include the following.

Examples of monomers having lactones other than b1 and b2 include the following.

It is also possible to copolymerize a repeating unit having both a hydroxy group, a lactone ring and a cyclic ether shown below.

Examples of the repeating unit having a sulfonamide include the following.

Examples of the repeating unit having a carbonate include the following.

  It is well known that phenol compounds are crosslinked and cured by irradiation with a wavelength of 200 nm or less. However, since cresol novolac and polyhydroxystyrene have extremely strong absorption in an ArF excimer laser having a wavelength of 193 nm for forming a pattern, the first pattern cannot be formed. Here, since hydroxy naphthyl has a phenolic hydroxyl group, it promotes crosslinking by irradiation with a wavelength of 200 nm or less. Further, since the naphthalene ring does not absorb so much at a wavelength of 193 nm, a resist material based on a polymer compound having hydroxy naphthyl as an adhesive group can be patterned in ArF excimer laser lithography.

  The primary hydroxy group and the phenolic hydroxyl group have a property of curing the film by a crosslinking reaction by acid and heat. A stronger film can be formed by combining the curing reaction of naphthol by light irradiation and the crosslinking reaction of primary hydroxyl group and naphthol by acid and heat generated by light irradiation.

  With such a chemically amplified positive resist material, the base resin has at least one adhesive group selected from a hydroxy group, a hydroxy naphthyl group, a carboxy group, and a 2,2,2-trifluoro-1-hydroxyethyl group, and By including a repeating unit having a lactone ring, an ether group, a carbonyl group, a carbonate group, or a sulfonamide group, high adhesion to the substrate can be realized. Furthermore, since the base resin has repeating units having acid labile groups, the acid labile groups are eliminated by the acid generated by the acid generator during exposure, so that the resist exposed area is dissolved in the developer. By doing so, a very highly accurate pattern can be obtained.

  Examples of the polymer compound as the base resin in the positive resist material used in the pattern forming method according to the present invention include a hydrogen group-containing hydroxy group, hydroxy naphthyl group, carboxy group, 2,2,2-trifluoro-1 Those having an adhesive group selected from -hydroxyethyl groups are preferred. The mechanical strength of the film is improved by hydrogen bonding, and deformation of the pattern when the silicon oxide film is directly formed on the resist pattern can be suppressed. The hydroxy group, hydroxy naphthyl group, carboxy group, and 2,2,2-trifluoro-1-hydroxyethyl group have further crosslinkability, and in particular, the hydroxy naphthyl group is considerably cross-linked by light irradiation with a wavelength of 200 nm. It is possible to form a strong film.

（式中、Ｒ⁵²は水素原子又はメチル基を示す。Ｒ⁵³は酸不安定基である。） The polymer compound as the base resin in the positive resist material includes a repeating unit having an acid labile group represented by the following general formula (c) in addition to the repeating unit represented by (a) and (b). It is preferable to have the unit c.

(In the formula, R ⁵² represents a hydrogen atom or a methyl group. R ⁵³ is an acid labile group.)

The monomer for obtaining the repeating unit having an acid labile group represented by the general formula (c) is represented by the following general formula (Mc). Here, R ⁵² and R ⁵³ are the same as described above.

  The repeating unit having an acid labile group is described in paragraphs [0083] to [0104] of JP-A-2008-111103, specifically, paragraphs [0114] to [0117].

  Here, the copolymerization ratio of a, b and c is 0 <a <0.9, 0 ≦ b <0.9, 0 <c <1.0, preferably 0.05 ≦ a ≦ 0.8. 0.1 ≦ b ≦ 0.8, 0.1 ≦ c ≦ 0.8, more preferably 0.1 ≦ a ≦ 0.7, 0.2 ≦ b ≦ 0.7, 0.12 ≦ c ≦ 0.7. Note that a + b + c = 1.

  The high molecular compound used as the base polymer of the resist used in the pattern forming method of the present invention has a polystyrene-reduced weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 30, as determined by gel permeation chromatography (GPC). 000 is preferred. If the weight average molecular weight is too small, the crosslinking efficiency in the thermal crosslinking after development of the resist material is lowered. If it is too large, the alkali solubility is lowered, and the trailing phenomenon may easily occur after pattern formation.

  Furthermore, in the polymer compound serving as the base polymer of the resist material used in the pattern forming method of the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present. There is a possibility that foreign matter is seen on the pattern or the shape of the pattern is deteriorated. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitably used for fine pattern dimensions, the multi-component copolymer to be used is obtained. The molecular weight distribution is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5 and narrow dispersion.

  It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

  One method for synthesizing these polymer compounds is a method in which a monomer having an unsaturated bond is added to a radical initiator in an organic solvent and subjected to heat polymerization, whereby a polymer compound can be obtained. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As polymerization initiators, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) ), Benzoyl peroxide, lauroyl peroxide and the like, and preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. As the acid labile group, those introduced into the monomer may be used as they are, or the acid labile group may be once removed by an acid catalyst and then protected or partially protected. In addition, the high molecular compound which comprises the said base resin is not restricted to 1 type, and 2 or more types can be added. The performance of the resist material can be adjusted by using a plurality of types of polymer compounds.

  The resist material used for pattern formation of the present invention may contain an acid generator, particularly for functioning as a chemically amplified positive resist material. For example, a compound that generates an acid in response to actinic rays or radiation (photoacid generation) Agent). The component of the photoacid generator may be any compound that generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, and the like. Although described in detail below, these may be used alone or in combination of two or more.

  Specific examples of the acid generator are described in paragraphs [0122] to [0142] of JP-A-2008-111103.

  The resist material of the present invention can further contain any one or more of an organic solvent, a basic compound, a dissolution controller, a surfactant, and acetylene alcohols.

  Specific examples of the organic solvent include paragraphs [0144] to [0145] of JP-A-2008-111103, paragraphs [0146] to [0164] as basic compounds, and paragraphs [0165] to [0166] as surfactants. ], The dissolution control agent is described in paragraphs [0155] to [0178] of JP-A-2008-122932, and the acetylene alcohols are described in paragraphs [0179] to [0182].

Here, the double patterning of the sidewall spacer process will be described. The 4th immersion symposium (2007) Lecture number; PR-01, Title; Implementation of immersion lithography to NAND / CMOS lithography to NAND / CMOS device manufacturing The spacer spacer process reported in FIG.
FIG. 1 is a cross-sectional view for explaining an example of a double patterning method of a conventional sidewall spacer process. A substrate to be processed 20, a hard mask 30, and a resist film 40 are formed on a substrate 10, and the resist film 40 is exposed and developed. Then, the resist pattern is transferred by dry etching to the hard mask 30 under the resist film 40 (FIG. 1- <2>), and the SiO ₂ film 50 is formed on the hard mask 30 by CVD or ALD. (FIG. 1- <3>), and by dry etching, the SiO ₂ film 50 on the hard mask pattern and the space is removed to form a spacer 52 (FIG. 1- <4>). Is embedded (FIG. 1- <5>), the spacer 52 is removed (FIG. 1- <6>), and the processed substrate 20 is processed (FIG. 1- <7>).
That is, the resist pattern is transferred by dry etching to the hard mask 30 below the resist film 40 (FIG. 1- <2>), and the SiO ₂ film 50 is laminated on the hard mask 30 by the CVD method or the ALD method (FIG. 1- FIG. <3>). The SiO ₂ film 50 on the hard mask pattern and in the space is removed by dry etching to form a spacer 52 (FIG. 1- <4>), and the spacer spacer 60 is embedded in the space (FIG. 1- <5>). Is removed (FIG. 1- <6>), and the processed substrate 20 is processed (FIG. 1- <7>). The spacer 52 attached to the side wall of the hard mask 30 is reversed in pattern and transferred to the substrate 20 to be processed.

The spacer line process is shown in FIG. The steps up to the formation of the spacer are the same as those in FIGS. 1- <1> to 1- <4>. In FIG. 1- <5>, the hard mask is removed to leave a spacer line, and the substrate to be processed is processed using this as a mask. That is, FIG. 2 is a cross-sectional view for explaining a conventional spacer line process. A substrate 20 to be processed, a hard mask 30, and a resist film 40 are formed on a substrate 10, and the resist film 40 is exposed and developed (FIG. 2). -<1>), the resist pattern is transferred by dry etching to the hard mask 30 under the resist film 40 (FIG. 2- <2>), and the SiO ₂ film 50 is laminated on the hard mask 30 by the CVD method or the ALD method. (FIG. 2-<3>), the SiO ₂ film 50 on the hard mask pattern and in the space is removed by dry etching, the spacer 52 is formed (FIG. 2- <4>), the hard mask 30 is removed, and the spacer line (FIG. 2-<5>), and the processed substrate 20 is processed using this as a mask (FIG. 2- <6>).
As the hard _{mask, SiO 2, SiN, SiON,} p-Si, TiN, and carbon film is used. The hard mask may be formed by CVD, ALD, or spin coating. An organic antireflection film may be provided between the hard mask and the resist, or a trilayer made of an SOG film having a function of an antireflection film and a carbon film may be formed.

FIG. 3 is a cross-sectional view for explaining the pattern forming method of the present invention. A substrate 20 to be processed and a carbon film 70 are formed on a substrate 10, and a resist film 40 formed thereon is exposed and developed (FIG. 3). -<1>), a silane compound 80 having an amino group or an ammonium salt is adsorbed on the developed resist pattern (FIG. 3- <2>), and an SiO ₂ film 50 is formed on the side wall of the resist pattern (FIG. 3- <3>), removing the SiO ₂ film 50 on the resist film 40 and in the space to form a spacer 52 (FIG. 3- <4>). After removing the resist pattern, the carbon film 70 is formed using the spacer 52 as a mask. Processed (FIG. 3- <5>), and shows a state where the substrate 20 is processed using the carbon film 70 as a mask (FIG. 3- <6>).

That is, the double patterning method according to the present invention is as shown in FIG. A carbon film is formed under the photoresist. The carbon film may be formed by CVD or ALD, or by spin coating. An organic antireflection film may be laid between the carbon film and the resist film. Many carbon films have a k value of 0.3 or more at a wavelength of 193 nm, and the substrate reflection exceeds 1%. In a substrate having a reflectance exceeding 1%, the resist shape is degraded due to low standing waves due to substrate reflection, and the dimensional uniformity is degraded. In order to suppress the reflectance from the substrate to 1% or less, it is effective to form an organic antireflection film having a k value adjusted to 0.05 to 0.2 between the carbon film and the resist. The antireflection effect of the two-layer antireflection film of the carbon film and the organic antireflection film is excellent, and it is 1% or less even in immersion lithography with a large incident angle and high reflectance using NA of 1.0 or more. The substrate reflectance can be suppressed.
A silane compound having an amino group or an ammonium salt is adsorbed on the resist pattern after development (FIG. 3- <2>). Examples of the adsorption method include a spin coating method, a vapor prime method, a CVD method, and an ALD method. When applied by spin coating, post-coating baking can be performed to promote adsorption. The baking temperature is 40 to 150 ° C., and the range of 3 to 300 seconds is applied. Thereafter, the silane compound having an excess amino group or ammonium salt may be peeled off with water, a solvent, a developer, or the like. The silane compound is preferably attached only to the resist pattern surface, but even if it adheres to the substrate surface, it can be removed during the subsequent etching of the carbon film. The thickness of the silane adsorption layer is preferably thinner, and is preferably 10 nm or less, more preferably 5 nm or less. In the bubbling method, a gas obtained by bubbling an aminosilane solution with an inert gas such as nitrogen gas is sprayed on the resist pattern. At this time, in order to accelerate the adsorption, baking may be performed under the same conditions as in the spin coating method. In the CVD method and the ALD method, treatment with aminosilane gas is performed before treatment with silane gas, chlorosilane gas, alkoxysilane gas, or isocyanate silane gas.
Next, a SiO ₂ film is formed on the side wall of the resist pattern by a CVD method, an ALD method, or the like (FIG. 3- <3>). A spacer is formed by removing the SiO ₂ film on the resist pattern and in the space (FIG. 3- <4>), and processing the carbon film using the spacer as a mask (FIG. 3- <5>), using the carbon film as a mask. The substrate to be processed is processed (FIG. 3- <6>). The resulting pattern is the same as the spacer line method of FIG. In the pattern forming method of the present invention, since a layer made of a silane compound is formed on the resist pattern surface in FIG. 3- <2>, the formation speed when forming the SiO ₂ film in FIG. 3- <3> is high. , Pattern deformation and roughness deterioration can be prevented. The thickness of the SiO ₂ film is in the range of 5 to 100 nm, preferably 10 to 50 nm.
When the pitch 130 nm is divided into four, it becomes 32.5 nm. When a 65 nm line and space pattern with a pitch of 130 nm is thinned to 40 to 30 nm by increasing the exposure amount and an attempt is made to produce a sidewall spacer on the side wall, an SiO ₂ film having a thickness of about 32 nm is formed. When the pitch is 90 nm, it is 22.5 nm in 4 divisions, so an SiO ₂ film having a film thickness of 22 nm is formed on the side wall of the resist pattern which is finely finished to around 22 nm.
In this case, a silicon substrate is generally used as the substrate. Examples of the substrate to be processed include SiO ₂ , SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, a low dielectric film, and an etching stopper film thereof. . As the hard mask, a substrate different from the hard mask is used as described above.

  In the present invention, the thickness of the resist film is preferably 10 to 1,000 nm, particularly 20 to 500 nm. This resist film is heated (pre-baked) before exposure, and as this condition, it is preferable to carry out at 60 to 180 ° C., particularly 70 to 150 ° C. for 10 to 300 seconds, and particularly 15 to 200 seconds.

  Next, exposure is performed. Here, the exposure is most preferably 193 nm exposure using a high energy beam having a wavelength of 140 to 250 nm, and among these, ArF excimer laser. The exposure may be a dry atmosphere in the air or a nitrogen stream, or may be immersion exposure in water. In ArF immersion lithography, a liquid that has a refractive index of 1 or more and is highly transparent at the exposure wavelength, such as pure water or alkane, is used as the immersion solvent. In immersion lithography, pure water or other liquid is inserted between a pre-baked resist film and a projection lens. As a result, a lens with an NA of 1.0 or more can be designed, and a finer pattern can be formed. Immersion lithography is an important technique for extending the life of ArF lithography to the 45 nm node. In the case of immersion exposure, pure water rinsing (post-soak) after exposure to remove the water droplet residue remaining on the resist film may be performed, and elution from the resist film is prevented, and the surface lubricity of the film is prevented. In order to increase the thickness, a protective film may be formed on the resist film after pre-baking. As a resist protective film used in immersion lithography, for example, a polymer compound having a 1,1,1,3,3,3-hexafluoro-2-propanol residue that is insoluble in water and dissolved in an alkaline developer is used. A base and a material dissolved in an alcohol solvent having 4 or more carbon atoms, an ether solvent having 8 to 12 carbon atoms, or a mixed solvent thereof is preferable. After the photoresist film is formed, pure water rinsing (post-soak) may be performed to extract acid generators from the film surface or to wash away particles, or to remove water remaining on the film after exposure. Rinse (post-soak) may be performed.

It is preferable to expose so that the exposure amount in exposure is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

  Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The target pattern is formed on the substrate by development by a conventional method such as a dip method, a paddle method, or a spray method.

For curing the resist pattern after development, curing by crosslinking with heat, heating, or light irradiation with a wavelength of 200 nm or less and, in some cases, heating leads to an improvement in film strength. The light irradiation after the development is a high energy ray having a wavelength of 200 nm or less, specifically, ArF excimer light having a wavelength of 193 nm, Xe ₂ excimer light having a wavelength of 172 nm, F ₂ excimer light having a wavelength of 157 nm, Kr ₂ excimer light having a wavelength of 146 nm, Ar ₂ excimer light is preferable, and in the case of light, the exposure amount is in the range of 10 mJ / cm ^{2 to} 10 J / cm ² . Irradiation with an excimer laser or excimer lamp having a wavelength of 200 nm or less, particularly 193 nm, 172 nm, 157 nm, 146 nm, or 122 nm, not only generates acid from the photoacid generator, but also promotes a crosslinking reaction by light irradiation. Further, a thermal acid generator of ammonium salt as a photoresist material is added in an amount of 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the base resin of the photoresist material. It is also possible to generate an acid. In this case, the generation of acid and the crosslinking reaction proceed simultaneously. The heating conditions are preferably 100 to 300 ° C., particularly 130 to 250 ° C. and preferably 10 to 300 seconds. Thereby, a resist film with improved mechanical strength is formed.

（式中、Ｒ^101d、Ｒ^101e、Ｒ^101f、Ｒ^101gはそれぞれ水素原子、炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基によって置換されていてもよい。Ｒ^101dとＲ^101e、Ｒ^101dとＲ^101eとＲ^101fとはこれらが結合する窒素原子と共に環を形成してもよく、環を形成する場合には、Ｒ^101dとＲ^101e及びＲ^101dとＲ^101eとＲ^101fは炭素数３〜１０のアルキレン基、又は式中の窒素原子を環の中に有する複素芳香族環を示す。Ｋ^-はα位の少なくとも１つがフッ素化されたスルホン酸、又はパーフルオロアルキルイミド酸もしくはパーフルオロアルキルメチド酸である。） In addition, the following are mentioned as a thermal acid generator of the said ammonium salt.

Wherein R ^101d , R ^101e , R ^101f and R ^101g are each a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, carbon the number 6 to 20 aryl group, or an aralkyl group or an aryl oxoalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms of these groups and may .R ^101d be substituted by an alkoxy group R ^101e , R ^101d , R ^101e and R ^101f may form a ring together with the nitrogen atom to which they are bonded, and in the case of forming a ring, R ^101d and R ^101e and R ^101d , R ^101e and R ^101f Represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the formula, K ⁻ represents a sulfonic acid or perfluoroalkylimide in which at least one α-position is fluorinated. Acid or buffer Fluoroalkyl methide acid.)

Specific examples of K ⁻ include imido acids such as perfluoroalkanesulfonic acid such as triflate and nonaflate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethylsulfonyl) imide, and bis (perfluorobutylsulfonyl) imide. , Methido acids such as tris (trifluoromethylsulfonyl) methide, tris (perfluoroethylsulfonyl) methide, and sulfonate having a fluoro substituted at the α-position represented by the following general formula (K-1), And sulfonates in which the α position shown in -2) is fluoro-substituted.

In General Formula (K-1), ^R102 represents a hydrogen atom, a linear, branched or cyclic alkyl group or acyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups or aryloxy groups, which may have an ether group, an ester group, a carbonyl group, a lactone ring, or a part or all of the hydrogen atoms of these groups may be substituted with fluorine atoms Good. In general formula (K-2), R ¹⁰³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It is a group.

  When light irradiation with a wavelength of 180 nm or less is performed in the atmosphere, the resist surface is oxidized by the generation of ozone, and the film thickness is considerably reduced. Ozone oxidation by light irradiation is used for cleaning organic substances attached to the substrate. Therefore, the resist film is also cleaned by ozone, and the film disappears when the exposure amount is large. Therefore, when irradiating excimer lasers or excimer lamps having wavelengths of 172 nm, 157 nm, 146 nm, and 122 nm, an inert gas such as nitrogen gas, helium (He) gas, argon (Ar) gas, or krypton (Kr) gas is used. It is desirable to purge and irradiate light in an atmosphere having an oxygen or moisture concentration of 10 ppm or less.

  As a method for measuring the mechanical strength of the resist film, a nanoindenter method can be preferably used. In the measurement by the nano indenter, a regular triangular pyramid indenter made of a diamond tip is pressed against the thin film, and the strength of the thin film is obtained from the load applied to the indenter. When measuring the strength of the resist film, the resist solution is applied to the Si substrate, and the pre-baked film thickness is adjusted to a range of 200 to 1,000 nm. The patterning of the resist is performed with a film thickness of about 100 nm, but if the film is too thin, information on the strength of the substrate is also added, so that the original strength of the film to be measured is not required. Therefore, the strength is measured with a thicker film than when patterning.

The present invention uses a CVD (Chemical Vapor Deposition) method or an ALD (Atomic Layer Deposition) method on a photoresist pattern after adsorbing a silane compound having an amino group or an ammonium salt to the resist pattern. A pattern forming method for forming a silicon oxide film (SiO ₂ film) is proposed. As a resist pattern, a film having higher mechanical strength has less deterioration in LWR after the formation of a silicon oxide film. The mechanical strength of the resist film can be expressed as hardness by a nanoindenter method or Young's modulus. At this time, when a silicon oxide film is formed on the sidewall of a resist film material having a hardness of 0.4 GPa or less or a Young modulus of 9.2 GPa or less, pattern deformation such as shrinking of the resist top and line width roughness (LWR) is large. It becomes. In order to solve the above problems, the resist film needs to have a hardness of 0.4 GPa or more and a Young modulus of 9.2 GPa or more, preferably a hardness of 0.42 GPa or more and a Young modulus of 9.5 GPa or more, more preferably Hardness is 0.45 GPa or more and Young's modulus is 10.0 GPa or more, more preferably, the hardness is 0.5 GPa or more and Young's modulus is 10.5 GPa or more.

Examples of the CVD method and the ALD method can be shown in JP2003-7700A, JP2005-197561A, and JP2006-66587A.
Various metal oxide and metal nitride films such as SiO ₂ , SiN, HfO ₂ , and Al ₂ O ₃ can be formed by CVD or ALD. When the film is formed directly on the resist pattern, it is essential to form a film at a low temperature of 200 ° C. or lower in order to prevent the resist pattern from being deformed. For this reason, an SiO ₂ film that can be formed at the lowest temperature is preferable. When the SiO ₂ film is formed by the ALD method, silane, chlorosilane, alkoxysilane silane, isocyanate silane-based gas is provided, silane monomer is adsorbed on the resist pattern, and then silicon is oxidized by an oxidizing gas excited by plasma. Oxidize. The silane is repeatedly adsorbed and oxidized, and the silicon oxide is grown to be stacked one molecule at a time. Examples of the silane-based gas include silane, chlorosilane, alkoxysilane, and isocyanate silane, and chlorosilane is most preferably used. Chlorosilane adsorbs very well to a film made of a silane compound of aminosilane or ammonium salt attached to the resist surface. As the oxidizing gas, oxygen, water, ozone, NO, NO ₂ may be used, and a mixed gas thereof may be used, or an inert gas such as N ₂ , Ar, or He may be mixed. In order to clean the residual gas at each step, an inert gas such as N ₂ , Ar, or He may be flowed. The substrate temperature is 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 130 ° C. or lower, in order to suppress deformation of the resist pattern.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc. In addition, a weight average molecular weight (Mw) shows the polystyrene conversion weight average molecular weight by GPC.

[Synthesis example]
As a polymer compound added to the resist material, each monomer is combined and subjected to a copolymerization reaction in a tetrahydrofuran solvent, crystallized in methanol, further washed with hexane, isolated and dried, and shown below. Polymer compounds (Polymers 1 to 6) having a composition were obtained. The composition of the obtained polymer compound was confirmed by ¹ H-NMR, and the molecular weight and dispersity were confirmed by gel permeation chromatography.

Polymer 1
Molecular weight (Mw) = 8,100
Dispersity (Mw / Mn) = 1.77

Polymer 2
Molecular weight (Mw) = 8,800
Dispersity (Mw / Mn) = 1.77

Polymer 3
Molecular weight (Mw) = 7,500
Dispersity (Mw / Mn) = 1.82

Polymer 4
Molecular weight (Mw) = 8,100
Dispersity (Mw / Mn) = 1.94

Polymer 5
Molecular weight (Mw) = 7,800
Dispersity (Mw / Mn) = 1.55

Polymer 6
Molecular weight (Mw) = 7,200
Dispersity (Mw / Mn) = 1.75

塩基性化合物：Ｑｕｅｎｃｈｅｒ１（下記構造式参照）

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
ＣｙＨ（シクロヘキサノン） [Examples and Comparative Examples]
Preparation of Positive Resist Material Using the polymer compounds synthesized above (Polymers 1 to 6), a solution dissolved in the composition shown in Table 1 below was filtered through a 0.2 μm size filter to prepare a resist solution. .
Each composition in Table 1 is as follows.
Acid generator: PAG1 (see structural formula below)

Basic compound: Quencher 1 (see the structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
CyH (cyclohexanone)

Measurement of film strength The resist material shown in Table 1 was applied on a Si wafer treated with hexamethyldisilazane (HMDS) vapor prime and baked at 110 ° C. for 60 seconds to adjust the film thickness to 250 nm.
The resulting resist film was measured for Young's modulus and hardness by the nanoindenter method.
The results are shown in Table 1.

Preparation of Resist Pattern Protective Film Material A silicon protective compound shown in Table 2 and a solvent were mixed and a pattern protective film solution filtered through a 0.2 μm Teflon (registered trademark) filter was prepared.

As the carbon-based lower layer film, ODL-50 manufactured by Shin-Etsu Chemical Co., Ltd. was used, applied onto a Si wafer by spin coating, and baked at 300 ° C. for 60 seconds to prepare a carbon film having a thickness of 200 nm. The carbon ratio (carbon ratio) of the carbon film was 86% by mass. On top of that, an organic antireflection film ARC-29A manufactured by Nissan Chemical Industries, Ltd. was applied and baked at 200 ° C. for 60 seconds to prepare an antireflection film having a thickness of 80 nm, which was used as a substrate.
Resist materials 1 to 6 shown in Table 1 were spin-coated on the substrate, and baked at 110 ° C. for 60 seconds using a hot plate, so that the thickness of the resist film was 120 nm.
This is exposed using an ArF excimer laser scanner (Nikon Corporation, NSR-S307E, NA0.85, σ0.93 / 0.69, 20 degree dipole illumination, 6% halftone phase shift mask), and after exposure Immediately after baking at 100 ° C. for 60 seconds, development was carried out with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 30 seconds to obtain a positive isolated pattern having dimensions of 50 nm and a pitch of 130 nm.
On the resist pattern, various silane gases shown in Table 3 of STEP (1) and ozone described in STEP (3) by the method described in paragraphs [0046] to [0053] of Examples in JP-A-2005-197561. Was changed to water, and a 30 nm thick SiO ₂ film was formed using an ALD apparatus while keeping the substrate temperature at 100 ° C. The roughness (LWR) of the pattern before and after the SiO ₂ film formation was measured using a length measuring SEM (S-9380) manufactured by Hitachi High-Technologies Corporation.

As a pretreatment for performing the ALD method, in Examples 1 to 6, 22, and 23, the pattern protective film material shown in Table 2 was applied and baked at 80 ° C. for 60 seconds. In Examples 9 to 21, the pattern protective film material shown in Table 2 was applied, baked at 80 ° C. for 60 seconds, rinsed with pure water for 20 seconds at 1,500 rpm, and spin dried at 2,000 rpm for 15 seconds, Excess pattern protective film material was peeled off. In Example 7, while heating the substrate at 90 ° C., 3-aminopropyltriethoxysilane was sprayed on the resist pattern for 60 seconds while bubbling nitrogen. In Example 8, before the SiO ₂ film was formed by ALD using tris (dimethylamino) silane gas, adsorption onto the resist pattern was performed using 3-aminopropyltriethoxysilane gas with an ALD apparatus.
The results are shown in Table 3.

It is sectional drawing explaining an example of the double patterning method of the conventional side wall spacer process, forms a to-be-processed substrate, a hard mask, a resist film on a board | substrate, exposes and develops a resist film (FIG. 1- <1>) The resist pattern is transferred to the hard mask under the resist by dry etching (FIG. 1- <2>), and the SiO ₂ film is laminated on the hard mask by the CVD method or the ALD method (FIG. 1- <3>). Remove the SiO ₂ film on the hard mask pattern and the space by dry etching, form a spacer (FIG. 1- <4>), embed the spacer in the space (FIG. 1- <5>), and remove the spacer (FIG. 1- <6>), shows a state of processing the substrate to be processed (FIG. 1- <7>). It is sectional drawing explaining the conventional spacer line process, forms a to-be-processed substrate, a hard mask, and a resist film on a board | substrate, exposes and develops a resist film (FIG. 2- <1>), The hard mask under a resist The resist pattern is transferred by dry etching (FIG. 2- <2>), and a SiO ₂ film is laminated on the hard mask by CVD or ALD (FIG. 2- <3>). Take the top and space SiO ₂ films, form spacers (Fig. 2- <4>), remove the hard mask to leave the spacer lines (Fig. 2- <5>), and use this as a mask for processing The state which processed the board | substrate is shown (FIG. 2- <6>). It is sectional drawing explaining the pattern formation method of this invention, forms a to-be-processed substrate and a carbon film on a board | substrate, exposes and develops the resist film formed on it (FIG. 3- <1>), After image development A silane compound having an amino group or an ammonium salt is adsorbed on the resist pattern (FIG. 3- <2>), and a SiO ₂ film is formed on the side wall of the resist pattern (FIG. 3- <3>). The SiO ₂ film is removed to form a spacer (FIG. 3- <4>), and after removing the resist pattern, the carbon film is processed using the spacer as a mask (FIG. 3- <5>). The state which processed the to-be-processed substrate is shown (FIG. 3- <6>).

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Substrate 20 Substrate 30 Hard mask 40 Photoresist 50 Silicon oxide film 52 Spacer 60 Spacer spacer 70 Carbon film 80 Aminosilane or ammonium salt containing silane film

Claims (9)

  An aminosilane compound having at least one amino group or ammonium salt in one molecule is adsorbed on the photoresist pattern, and silane, chlorosilane, alkoxysilane is deposited thereon by CVD (Chemical Vapor Deposition) method or ALD (Atomic Layer Deposition) method. And a silicon oxide film formed by oxidizing a silane gas selected from isocyanate silane. The pattern forming method according to claim 1, wherein the aminosilane compound having at least one amino group or ammonium salt is represented by the following general formula (1) or (2).

(In the formula, R ¹ , R ² , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a linear group optionally having an amino group having 1 to 10 carbon atoms, an ether group, an ester group or a hydroxy group, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, or R ¹ and R ² , R ⁷ and R ^8. , R ⁸ and R ⁹ or R ⁷ and R ⁹ may be combined to form a ring together with the nitrogen atom to which these are bonded, R ³ and R ¹⁰ are linear or branched having 1 to 12 carbon atoms. A cyclic or cyclic alkylene group which may have an ether group, an ester group, a thioether group, a phenylene group or a hydroxy group, and R ^{4 to} R ⁶ and R ^{11 to} R ¹³ are a hydrogen atom and have 1 to 6 carbon atoms. Alkyl group, aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 12 carbon atoms, and 1 to 6 carbon atoms Alkoxy group, an aryloxy group having 6 to 10 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms or an Ararukirokishi group, or a hydroxy group of 7 to 12 carbon atoms, at least of ^{R 4 ~R 6, R 11 ~R} 13 One is an alkoxy group or a hydroxy group. X ⁻ represents an anion.) 2. The pattern forming method according to claim 1, wherein the aminosilane compound having at least one amino group or ammonium salt in one molecule is represented by the following general formula (3) or (4).

(Wherein R ²⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; Group, an ether group (—O—), an ester group (—COO—) or an amino group, p is 1 or 2, and when p is 1, R ²¹ has 1 to 20 carbon atoms. A linear, branched or cyclic alkylene group which may have an ether group, an ester group or a phenylene group, and when p is 2, R ²¹ is one hydrogen atom removed from the alkylene group. R ^{22 to} R ²⁴ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. An aryloxy group having 6 to 10 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, (It is an aralkyloxy group having 7 to 12 carbon atoms or a hydroxy group, and at least one of R ^{22 to} R ²⁴ is an alkoxy group or a hydroxy group.)

(Wherein R ^{3 to} R ⁶ and R ¹¹ are as defined in claim 2, and R ^{21 to} R ²⁴ and p are as described above.)   A resist material for forming a resist pattern includes a repeating unit having at least one adhesive group selected from a hydroxy group, a hydroxy naphthyl group, a carboxy group, and a 2,2,2-trifluoro-1-hydroxyethyl group, an acid 4. The pattern forming method according to claim 1, wherein the pattern forming method is a chemically amplified positive resist material having a base compound of a polymer compound containing a repeating unit having an unstable group.   2. The method of adsorbing an aminosilane compound having at least one amino group or ammonium salt in one molecule on a photoresist pattern is a spin coating method, a vapor prime method, a CVD method or an ALD method. The pattern formation method of any one of thru | or 4. A gas for oxidizing a silane gas selected from silane, chlorosilane, alkoxysilane, and isocyanate silane is selected from at least one of H ₂ O, D ₂ O, O ₂ , O ₃ , H ₂ O ₂ , NO, and NO _2. The pattern forming method according to claim 1, wherein the pattern forming method is performed.   The silicon oxide film space formed on the photoresist pattern and the silicon oxide film above the photoresist pattern are removed, leaving the silicon oxide film pattern on the sidewalls on both sides of the photoresist pattern, and using this to reduce the distance between pitches. The pattern forming method according to claim 1, wherein the pattern forming method is performed.   A photoresist pattern is formed on a film having a carbon ratio of 75% by mass or more formed on a substrate to be processed by CVD or spin coating, and a space portion of the silicon oxide film formed on the photoresist pattern and the photoresist. The silicon oxide film above the pattern is removed, the silicon oxide film pattern is formed on the sidewalls on both sides of the photoresist pattern, the carbon film is processed by dry etching using this as a mask, and the substrate to be processed is processed using the carbon film as a mask. The pattern forming method according to claim 1, wherein:   An antireflection film made of a hydrocarbon material is laid between a film having a carbon ratio of 75% by mass or more and a photoresist film formed by vapor deposition or spin coating on a substrate to be processed. Item 9. The pattern forming method according to Item 8.

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