JP4328963B2 - Pattern formation method - Google Patents

Description

The present invention relates to a pattern forming method using the pattern formation material used in microfabrication in a process of manufacturing a semiconductor device.

  With the high integration and high speed of LSI, pattern rule miniaturization is progressing rapidly. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. In particular, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought a great change. Furthermore, for high resolution and high sensitivity of the resist material, a chemically amplified positive resist material using an acid catalyst (Patent Documents 1 and 2: JP-B-2-27660, JP-A-63-27829) Etc.) has excellent characteristics and has become a mainstream resist material particularly in deep ultraviolet lithography.

  Resist materials for KrF excimer lasers are generally used in 0.3 micron processes, and after passing through the 0.25 micron rule, mass production of the 0.13 micron rule is now being applied to the mass production of the 0.18 micron rule. It has been started and the momentum of miniaturization has been accelerated. The shortening of the wavelength from KrF to ArF (193 nm) is expected to make the design rule finer to 0.13 μm or less, but novolak resins and polyvinylphenol resins that have been used in the past are around 193 nm. Therefore, it cannot be used as a base resin for resist. In order to ensure transparency and necessary dry etching resistance, acrylic resins and cycloolefin-based alicyclic resins have been studied (Patent Documents 3 to 6: JP-A-9-73173 and JP-A-9-73173). 10-10739, JP-A-9-230595, WO 97/33198). Currently, mass production of 90 nm using ArF lithography is in progress.

In recent years, it has been pointed out that the etching resistance of a resist film is lowered. In order to prevent pattern collapse due to the reduction in pattern size and the accompanying increase in aspect ratio, the resist film has been made thinner and the thickness of the substrate that can be processed has been reduced. In addition, the polyhydroxystyrene-based KrF resist material, the acrylic-based ArF resist material, and the fluorine-substituted F ₂ resist material, and the resist base resin have been changed along with the shortening of the exposure wavelength. Etching resistance is reduced. Etching resistance is drastically reduced by thinning and changing materials.

  In order to solve the problem of etching resistance reduction, Solid State Technology, 26 (5), 105 (1983) (Non-patent Document 1) includes an organic underlayer film on a substrate, a silicon-based intermediate film, There has been proposed a multilayer resist process in which a three-layer film of a resist film is formed, a resist pattern is transferred to an intermediate layer, an intermediate layer pattern is transferred to a lower layer film, and a substrate is processed.

  In JP 2004-46060 A (Patent Document 7), as a contact hole size reduction technique for ArF resist, coating and baking are performed on a developed pattern containing a water-soluble polymer, a crosslinking agent, and a cyclic compound. A method for forming a protective film on the resist surface is shown. As the cyclic compound, a polyhydric phenol compound, a polyvalent naphthol compound, an aromatic carboxylic acid, or the like is used, thereby increasing etching resistance.

  Japanese Patent Laid-Open No. 2001-85397 (Patent Document 8) discloses a method of embedding a metal film by plating in a space portion of a pattern after development of a resist film, and Japanese Patent Laid-Open No. 2003-316019 (Patent Document 9) includes: There has been proposed a method of embedding a material having high etching resistance in the space portion of the resist film, such as a method of forming a photosensitive polysilazane film in the space portion of the pattern after developing the resist film. In this case, since the pattern after development is reversed, in order to obtain a positive pattern, the resist pattern after development requires a negative pattern.

  The organic antireflection film that is usually used has structural components that are very similar to those of a resist film, and therefore it is in principle difficult to increase the etching rate overwhelmingly than the resist film. However, in the multilayer resist method, by using a silicon-based film for the intermediate layer, the etching rate of the intermediate layer can be made faster than that of the resist film by performing etching using a fluorocarbon gas. Next, when the lower layer is etched using the silicon-containing intermediate layer pattern as a mask, the pattern is transferred to the lower layer film by etching containing a gas such as oxygen, hydrogen, or ammonia. If an intermediate layer such as a spin-on glass (SOG) with a high silicon content is used, the intermediate layer has high etching resistance in the etching with the gas, so that etching with a high selectivity can be performed on the lower layer film. . If a material having a high carbon content such as an amorphous carbon film or a novolac resin is used as the lower layer film, sufficient etching resistance for etching the substrate can be obtained.

  The disadvantage of the multi-layer process is that the process is long and thus the cost of the device is high. For example, dry etching, which was once in a single layer process, is increased to three times in a three layer process.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP 2004-46060 A JP 2001-85397 A Japanese Patent Laid-Open No. 2003-316019 Solid State Technology, 26 (5), 105 (1983)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of forming a high aspect etching pattern without accompanying positive / negative reversal and without increasing the number of times of dry etching.

  As a result of intensive studies to achieve the above object, the present inventor has found that titanium having a high etching resistance is compensated for in order to compensate for a decrease in the etching resistance accompanying the thinning for improving the resolution in the single layer resist process. A film made of a material containing the resist pattern is formed on the resist pattern surface, and the portion without the resist film is removed by rinsing with pure water. More specifically, the resist pattern after development is composed mainly of a water-soluble titanium compound. By coating with a material to be baked, this is baked to cause a cross-linking reaction with the resist film, and by rinsing with pure water, the material mainly composed of excess water-soluble titanium compound is removed, and the titanium compound is applied only to the resist pattern surface. By increasing the number of dry etching without positive / negative reversal by forming a patterned hard mask film containing And without found that can form a high aspect etching pattern, the present invention has been accomplished.

（式中、Ｒ ⁰¹ は炭素数１〜１０の酸素原子を含んでいてもよいアルキル基又はアシル基であり、Ｒ ⁰² は炭素数１〜２０の窒素原子を含むアルキル基又はアシル基であり、ヒドロキシ基、エーテル基又はエステル基を有していてもよい。０≦ａ＜４、０≦ｂ＜３、０≦ｃ＜２、０≦ｄ≦１０，０００、０≦ｅ＜３の範囲である。）
請求項２：
フォトレジスト膜以外の部分に存在するパターン形成材料を水に溶解除去することを特徴とする請求項１記載のパターン形成方法。
請求項３：
チタン化合物で保護されたフォトレジストパターンをマスクにしてドライエッチングによって下地基板を加工することを特徴とする請求項１又は２記載のパターン形成方法。
請求項４：
フォトレジストパターンが、水溶性チタン化合物の窒素含有基と架橋反応するカルボキシル基を有するか又はレジストパターン形成の際にカルボキシル基を形成する基を有する、ポリアクリル酸及びその誘導体、シクロオレフィン誘導体−無水マレイン酸交互重合体、シクロオレフィン誘導体と無水マレイン酸とポリアクリル酸又はその誘導体との３あるいは４元以上の共重合体、シクロオレフィン誘導体−αトリフルオロメチルアクリル共重合体、ポリノルボルネン、並びにメタセシス開環重合体から選択される１種又は２種以上の高分子重合体をベース樹脂とするレジスト材料を用いて形成されたものであることを特徴とする請求項１，２又は３記載のパターン形成方法。
請求項５：
ベース樹脂の高分子重合体が、下記一般式（６）で示されるものであることを特徴とする請求項４記載のパターン形成方法。

（式中、Ｒ ⁰⁰¹ は水素原子、フッ素原子、メチル基、トリフルオロメチル基又はＣＨ ₂ ＣＯ ₂ Ｒ ⁰⁰³ を示す。Ｒ ⁰⁰² は水素原子、メチル基又はＣＯ ₂ Ｒ ⁰⁰³ を示す。Ｒ ⁰⁰³ は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。
Ｒ ⁰⁰⁴ は水素原子、又は炭素数１〜１５のカルボキシ基もしくは水酸基を含有する一価の炭化水素基又は親水性の密着性基を示す。Ｒ ⁰⁰⁵ 〜Ｒ ⁰⁰⁸ の少なくとも１個は炭素数１〜１５のカルボキシ基もしくは水酸基を含有する一価の炭化水素基、又はβ位にフッ素原子もしくはフッ素化されたアルキル基を持つヒドロキシ基を示し、残りはそれぞれ独立に水素原子、フッ素原子、又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基又はフッ素化されたアルキル基を示す。また、Ｒ ⁰⁰⁵ 〜Ｒ ⁰⁰⁸ は親水性の密着性基であってもよい。Ｒ ⁰⁰⁵ 〜Ｒ ⁰⁰⁸ は互いに環を形成していてもよく、その場合にはＲ ⁰⁰⁵ 〜Ｒ ⁰⁰⁸ の少なくとも１個は炭素数１〜１５のカルボキシ基又は水酸基を含有する二価の炭化水素基を示し、残りはそれぞれ独立に単結合、又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキレン基を示す。
Ｒ ⁰⁰⁹ は炭素数３〜１５の−ＣＯ ₂ −部分構造を含有する一価の炭化水素基又は親水性の密着性基を示す。Ｒ ⁰¹⁰ 〜Ｒ ⁰¹³ の少なくとも１個は炭素数２〜１５の−ＣＯ ₂ −部分構造あるいはスルホン又はスルホンアミドを含有する一価の炭化水素基を示し、残りはそれぞれ独立に水素原子、又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。また、Ｒ ⁰¹⁰ 〜Ｒ ⁰¹³ は親水性の密着性基であってもよい。Ｒ ⁰¹⁰ 〜Ｒ ⁰¹³ は互いに環を形成していてもよく、その場合にはＲ ⁰¹⁰ 〜Ｒ ⁰¹³ の少なくとも１個は炭素数１〜１５の−ＣＯ ₂ −部分構造を含有する二価の炭化水素基を示し、残りはそれぞれ独立に単結合、又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキレン基を示す。
Ｒ ⁰¹⁴ は炭素数７〜１５の多環式炭化水素基又は多環式炭化水素基を含有するアルキル基を示す。Ｒ ⁰¹⁵ は酸不安定基を示す。Ｒ ⁰¹⁶ はメチレン又は酸素原子を示す。Ｒ ⁰¹⁷ は単結合、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基であり、ヒドロキシ基、アルコキシ基、アセチル基から選ばれるヘテロ原子を含む置換基を含んでもよい。Ｒ ⁰¹⁸ は水素原子、又は炭素数１〜１０のアルキル基を示す。
ｋは０又は１である。ａ１、ａ２、ａ３、ｂ１、ｂ２、ｂ３、ｃ１、ｃ２、ｃ３、ｄ１、ｄ２、ｄ３、ｅは０以上１未満の数であり、ａ１＋ａ２＋ａ３＋ｂ１＋ｂ２＋ｂ３＋ｃ１＋ｃ２＋ｃ３＋ｄ１＋ｄ２＋ｄ３＋ｅ＝１である。） Accordingly, the present invention provides a pattern forming process described below.
Claim 1:
A pattern forming material containing a water-soluble titanium compound represented by the following general formula (1) or (2) is applied onto the developed photoresist pattern, and the titanium compound-containing film is attached to the surface of the photoresist pattern. A pattern forming method, wherein only the surface of a photoresist pattern is protected with a titanium compound by removing the pattern forming material existing in a portion other than the photoresist pattern.

(In the formula, R ⁰¹ is an alkyl group or an acyl group which may contain an oxygen atom having 1 to 10 carbon atoms, R ⁰² is an alkyl group or an acyl group containing a nitrogen atom having 1 to 20 carbon atoms, It may have a hydroxy group, an ether group or an ester group, in the range of 0 ≦ a <4, 0 ≦ b <3, 0 ≦ c <2, 0 ≦ d ≦ 10,000, 0 ≦ e <3. is there.)
Claim 2:
2. The pattern forming method according to claim 1, wherein the pattern forming material existing in a portion other than the photoresist film is dissolved and removed in water.
Claim 3:
3. The pattern forming method according to claim 1, wherein the base substrate is processed by dry etching using a photoresist pattern protected by a titanium compound as a mask .
Claim 4:
Polyacrylic acid and its derivatives, cycloolefin derivatives-anhydrous having a photoresist pattern having a carboxyl group that undergoes a crosslinking reaction with a nitrogen-containing group of a water-soluble titanium compound or a group that forms a carboxyl group during the formation of a resist pattern Maleic acid alternating polymer, three or four or more copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or its derivative, cycloolefin derivative-α trifluoromethyl acrylic copolymer, polynorbornene, and metathesis 4. The pattern according to claim 1, 2 or 3, wherein the pattern is formed by using a resist material having one or more polymer polymers selected from ring-opening polymers as a base resin. Forming method.
Claim 5:
The pattern forming method according to claim 4, wherein the high molecular polymer of the base resin is represented by the following general formula (6).

(In the formula, R ⁰⁰¹ represents a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or CH ₂ CO ₂ R ^003. R ⁰⁰² represents a hydrogen atom, a methyl group or CO ₂ R ^003. R ⁰⁰³ represents carbon. A linear, branched or cyclic alkyl group of 1 to 15 is shown.
R ⁰⁰⁴ represents a hydrogen atom, a monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, or a hydrophilic adhesive group. At least one of R ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, or a hydroxy group having a fluorine atom or a fluorinated alkyl group at the β-position; The rest each independently represents a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms or a fluorinated alkyl group. R ^{005 to} R ⁰⁰⁸ may be hydrophilic adhesive groups. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, and in this case, at least one of R ^{005 to} R ⁰⁰⁸ is a carboxy group having 1 to 15 carbon atoms or a divalent hydrocarbon group containing a hydroxyl group. And the rest independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms.
R ⁰⁰⁹ represents a monovalent hydrocarbon group or a hydrophilic adhesive group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms . At least one of R ^{010 to} R ⁰¹³ represents a —CO ₂ — partial structure having 2 to 15 carbon atoms or a monovalent hydrocarbon group containing sulfone or sulfonamide, and the rest each independently represents a hydrogen atom or carbon number 1-15 linear, branched or cyclic alkyl groups are shown. R ^{010 to} R ⁰¹³ may be hydrophilic adhesive groups. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms.
R ⁰¹⁴ represents a C7-15 polycyclic hydrocarbon group or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a methylene or oxygen atom. R ⁰¹⁷ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may contain a substituent containing a hetero atom selected from a hydroxy group, an alkoxy group and an acetyl group. R ⁰¹⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
k is 0 or 1. a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers from 0 to less than 1, and a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1. )

  According to the present invention, a high aspect etching pattern can be formed without positive / negative reversal and without increasing the number of times of dry etching. Further, by forming a layer containing titanium on the surface of the photoresist pattern after development, the etching resistance of the photoresist pattern can be improved, and thinning of the line due to electron beam irradiation during SEM observation can be prevented. Furthermore, the resist pattern hard mask process of the present invention has the same number of times of dry etching as that of the single layer resist. Application of the protective film material after resist development, baking, and delamination with pure water are added to the single-layer resist process, but no special apparatus is required, and a conventional track system can be used as it is.

  In the pattern forming method of the present invention, a film composed of a water-soluble titanium compound as a main component is formed on a photoresist pattern, and a material containing a titanium compound is adhered to the surface of the photoresist pattern, resulting in excessive water-solubility on the substrate surface. By removing the titanium compound-containing material film with pure water or the like, the titanium compound-containing material film is attached only to the surface of the resist pattern, thereby improving the etching resistance of the resist pattern.

  The drawings illustrate an example of this pattern forming method. First, as shown in FIG. 1A, a film to be processed 2 is formed on a base substrate 1, and an antireflection film 3 is formed thereon. Then, a resist film 4 is patterned thereon by a conventional method. Next, as shown in FIG. 1 (B), a pattern forming material film 5 containing a water-soluble titanium compound is formed on the resist film (resist pattern) 4, and this is heated, etc. ), A crosslinked layer 5a of the titanium compound is formed on the surface of the resist film (resist pattern). Further, as shown in FIG. 1D, the non-crosslinked portion of the titanium compound is washed away with water, leaving only the crosslinked layer 5a. Thereafter, as shown in FIG. 1E, the antireflection film 3 is etched and the film to be processed 2 is further etched with respect to the space portion 4a of the resist pattern.

Here, the pattern forming material used in the pattern forming method is mainly composed of a water-soluble titanium compound.
In this case, the water-soluble titanium compound is preferably one represented by the following general formula (1) or (2).

（式中、Ｒ⁰¹は炭素数１〜１０の酸素原子を含んでいてもよいアルキル基又はアシル基であり、Ｒ⁰²は炭素数１〜２０の窒素原子を含むアルキル基又はアシル基であり、ヒドロキシ基、エーテル基又はエステル基を有していてもよい。０≦ａ＜４、０≦ｂ＜３、０≦ｃ＜２、０≦ｄ≦１０，０００、０≦ｅ＜３の範囲である。）

(In the formula, R ⁰¹ is an alkyl group or an acyl group which may contain an oxygen atom having 1 to 10 carbon atoms, R ⁰² is an alkyl group or an acyl group containing a nitrogen atom having 1 to 20 carbon atoms, It may have a hydroxy group, an ether group or an ester group, in the range of 0 ≦ a <4, 0 ≦ b <3, 0 ≦ c <2, 0 ≦ d ≦ 10,000, 0 ≦ e <3. is there.)

Here, examples of R ⁰¹ include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-ethylhexyl, n-octyl, acetyl, and acetylacetonate groups. The

Examples of R ⁰² include a triethanolaminate group, a diethanolamate group, a monoethanolamate group, a morpholineethanol group, and the like, and those having a substituted or unsubstituted amino group are preferable.

  Specific examples of the titanium compound represented by the general formula (1) include diethoxy di (triethanolaminate) titanium, dipropoxy di (triethanolaminate) titanium, dibutoxy di (triethanolamate) titanium, Monopropoxy-tri (triethanolamate) titanium, tetra (triethanolamate) titanium, tripropoxy-mono (triethanolamate) titanium, dipropoxy-di (triethanolamate) titanium, dipropoxy-di (diethanolamate) ) Titanium, Dipropoxy-di (ethanolaminate) titanium, Dipropoxy-di (morpholineethoxy) titanium, Mono (acetylacetonato) -tri (triethanolaminato) titanium, Di (acetylacetonato) -di (tri Tanol aminate) titanium, di (ethyl acetoacetate) di (triethanolaminate) titanium, mono (ethyl acetoacetate) tri (triethanolaminate) titanium, tetrabutoxy di (triethanolaminate) titanium dimer, One type or two or more types such as butoxy / triethanolaminate titanium polymer may be used.

  The titanium compound used for the pattern forming material of the present invention preferably has an amino group as described above in order to promote reaction with a carboxyl group derived from a base resin described later of the resist film. In general, the crosslinking reactivity of alkoxy titanium is lower in the carboxyl group than in the hydroxy group. The organic antireflection film has a large number of hydroxy groups for crosslinking, and many hydroxy groups remain after crosslinking. For example, if a treatment with tetraalkoxytitanium is performed after pattern formation, more titanium is adsorbed on the substrate surface than on the photoresist pattern surface, and this does not enhance etching of the resist pattern. By using a titanium compound having an amino group, it becomes possible to enhance the reactivity of the carboxyl group rather than the hydroxy group, and to selectively protect only the resist pattern surface on which many carboxyl groups remain.

  In this case, the pattern forming material containing the water-soluble titanium compound is applied onto the developed photoresist pattern, the titanium compound-containing film is attached to the surface of the photoresist pattern, and this is heated to 50 to 150 ° C. A nitrogen-containing group such as an amino group of the water-soluble titanium compound undergoes a crosslinking reaction with a carboxyl group of the photoresist film, thereby changing the water-soluble titanium compound to water-insoluble. On the other hand, the portion that does not come into contact with the photoresist film and thus the nitrogen-containing group such as amino group is not crosslinked with the carboxyl group of the photoresist film is kept water-soluble, and this uncrosslinked portion is easily rinsed with water. Since it can be removed, only the surface of the photoresist pattern can be protected with the crosslinked titanium compound by rinsing and removing the pattern forming material present in portions other than the photoresist pattern with water.

  The pattern forming material of the present invention contains the above titanium compound as a main component, and water or an alcohol-based organic solvent is used as a solvent. In this case, a monovalent alcohol having 1 to 7 carbon atoms is preferably used as the organic solvent. Specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, t-butyl alcohol, n-heptyl alcohol, allyl alcohol, crotyl alcohol , Cyclohexyl alcohol, and benzyl alcohol, and isobutyl alcohol is particularly preferably used. The amount of water or alcohol-based organic solvent added is preferably 1 to 10,000 parts by weight, particularly 10 to 1,000 parts by weight, based on 1 part by weight of the titanium compound.

  Pattern defects occur in the photoresist film and the antireflection film due to the generation of microbubbles in the developer. Also in the pattern forming material of the present invention, it is necessary to prevent microbubbles. In order to prevent microbubbles, the addition of acetylene alcohol is introduced in JP-A-9-6007, and the present invention can also be blended with this acetylene alcohol.

  As acetylene alcohol shown here, the following general formulas (AA-1) and (AA-2) can be exemplified.

（式中、Ｒ⁰¹¹〜Ｒ⁰¹⁴、Ｒ⁰¹⁷、Ｒ⁰¹⁸は互いに同一又は異種の炭素数１〜２０のアルキル基を示し、Ｒ⁰¹⁵、Ｒ⁰¹⁶、Ｒ⁰¹⁹は互いに同一又は異種の炭素数１〜１０のアルキレン基を示し、ａ及びｂはそれぞれａ＋ｂ＝０〜６０となる整数、ｃは０〜３０の整数である。）

(Wherein R ^{011 to} R ⁰¹⁴ , R ⁰¹⁷ and R ⁰¹⁸ represent the same or different alkyl group having 1 to 20 carbon atoms, and R ⁰¹⁵ , R ⁰¹⁶ and R ⁰¹⁹ represent the same or different carbon number of 1 to 20 carbon atoms. 10 represents an alkylene group, a and b are each an integer such that a + b = 0 to 60, and c is an integer of 0 to 30.)

  Furthermore, the acetylene alcohol containing the silicon atom shown to the following general formula (AA-3), (AA-4), (AA-5), (AA-6) can also be added.

（式中、Ｒ⁰²⁰〜Ｒ⁰²³、Ｒ⁰²⁶、Ｒ⁰²⁷、Ｒ⁰²⁹〜Ｒ⁰³²、Ｒ⁰³⁵〜Ｒ⁰³⁹は互いに同一又は異種の炭素数１〜２０のアルキル基、炭素数１〜２０の部分的あるいはすべてがフッ素化されたアルキル基、又は炭素数２〜１０のアリール基を示し、Ｒ⁰²⁴、Ｒ⁰²⁵、Ｒ⁰²⁸、Ｒ⁰³³、Ｒ⁰³⁴、Ｒ⁰⁴⁰は互いに同一又は異種の炭素数１〜１０のアルキレン基を示し、ｄ及びｅはそれぞれｄ＋ｅ＝０〜６０となる整数、ｆは０〜３０の整数、ｇ及びｈはそれぞれｇ＋ｈ＝０〜６０となる整数、ｉは０〜３０の整数である。）

(Wherein R ^{020 to} R ⁰²³ , R ⁰²⁶ , R ⁰²⁷ , R ^{029 to} R ⁰³² , R ^{035 to} R ⁰³⁹ are the same or different alkyl groups having 1 to 20 carbon atoms, and partial groups having 1 to 20 carbon atoms) Alternatively, all of them represent a fluorinated alkyl group or an aryl group having 2 to 10 carbon atoms, and R ⁰²⁴ , R ⁰²⁵ , R ⁰²⁸ , R ⁰³³ , R ⁰³⁴ , and R ⁰⁴⁰ are the same or different and have 1 to 10 carbon atoms. D and e are integers such that d + e = 0 to 60, f is an integer of 0 to 30, g and h are integers of g + h = 0 to 60, and i is an integer of 0 to 30, respectively. is there.)

  This silicon-containing acetylene alcohol can be expected to have a high defoaming effect. In addition, as a synthesis method of the formula (AA-4) which is a silicon-containing acetylene alcohol, it can be obtained by reacting one chloro group of dimethylchlorosilane with alkylene glycol and reacting one chloro group with sodium acetylide. .

  The compounding quantity of the said acetylene alcohol is 0.001-50 mass parts with respect to 100 mass parts of water-soluble titanium compounds, especially 0.01-10 mass parts.

  A surfactant can be added to the pattern forming material of the present invention. The above acetylene alcohols also have an effect as a surfactant, but other surfactants can be added. Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Nonionic surfactants such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tokemuputto Duc), MegaFuck F171, F172, F173 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431, FC4430 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103 , SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (manufactured by Asahi Glass Co., Ltd.), and the like, organosiloxane polymer KP-3 1, X-70-092, X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.). Further, surfactants having a perfluoroalkyl ether group described in JP-A-9-43838 and JP-A-2001-125259 can be mentioned. These can be used alone or in combination of two or more.

  The compounding quantity of the said surfactant is 0.0001-10 mass parts with respect to 100 mass parts of water-soluble titanium compounds, especially 0.001-5 mass parts.

The pattern forming method of the present invention is performed by the above-described method using the pattern forming material. In this case, as the base substrate, Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc. are used. As a film to be processed, various low-k films such as Si, α-Si, p-Si, W-Si, MoSi, SiO ₂ , SiN, SiON, W, TiN, Al, etc., are different from the base substrate. Etc., and is usually formed to a thickness of 0.1 to 10 μm, particularly 0.2 to 5 μm. Further, as the antireflection film, there are an organic film and an inorganic film, and any of them may be used, and the thickness is usually 0.1 to 2 μm, particularly 0.2 to 1.5 μm, using a known antireflection film material. It is formed.

  The resist material used in the pattern forming method of the present invention may be positive or negative, and the base resin is preferably a repeating unit that does not contain an aromatic substituent, and preferably has or forms a carboxyl group. , Polyacrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or derivative thereof, or olefin copolymer-α One or more polymer polymers selected from a trifluoromethylacrylic copolymer, polynorbornene, and metathesis ring-opening polymer, and particularly a weight having a repeating unit represented by the following general formula (6) Average molecular weight 1,000-500,000, preferably 5,000-100,0 Preferably 0 a polymer compound, it is also possible to blend two or more of the high molecular weight polymer.

  Further, it may be a bilayer resist material containing silicon. As the polymer for the bilayer resist material, it is particularly preferable to use a silicon-based polymer (silicone polymer) such as polysilsesquioxane having an acid labile group as a base polymer.

  In this case, in order to prepare a resist material in a chemically amplified positive type, a base resin that is insoluble or hardly soluble in a developer (usually an alkali developer) and becomes soluble in an acid developer is used. Is done. For this reason, those having an acid labile group that can be cleaved by an acid are used.

  Furthermore, an acid generator, an organic solvent, and the like are used for these resist materials, and a dissolution inhibitor, a basic compound, a surfactant, and the like can be blended as necessary. It can be used in a known blending amount and can be formed into a known composition.

  The thickness of the resist film is preferably 30 to 500 nm, particularly 50 to 300 nm.

  Furthermore, the film thickness formed on the resist pattern made of the pattern forming material is preferably 1 to 200 nm, particularly preferably 5 to 150 nm.

  Hereinafter, the base resin used for the resist material will be described in detail. As described above, as the base resin, those having a carboxyl group that undergoes a crosslinking reaction with a nitrogen-containing group such as an amino group of the water-soluble titanium compound in the pattern forming method, or a resist Those having a group capable of forming a carboxyl group during pattern formation are preferred, and those represented by the following general formula (6) are particularly preferred.

Here, R ⁰⁰¹ represents a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or CH ₂ CO ₂ R ⁰⁰³ . R ⁰⁰² represents a hydrogen atom, a methyl group or CO ₂ R ^003. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert -Butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group, butyladamantyl group Examples include groups. R ⁰⁰⁴ represents a hydrogen atom, a monovalent hydrocarbon group (preferably a linear, branched or cyclic alkyl group) containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, or a hydrophilic adhesive group, Specific examples include groups such as carboxyethyl, carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like. At least one of R ^{005 to} R ^{008 is} a C 1-15 carboxy group or a monovalent hydrocarbon group containing a hydroxyl group (preferably a linear, branched or cyclic alkyl group), or fluorine at the β-position. A hydroxy group having an atom or a fluorinated alkyl group, and the rest each independently a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms or a fluorinated alkyl Indicates a group. R ^{005 to} R ⁰⁰⁸ may be hydrophilic adhesive groups.

Specific examples of the monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, and 2-carboxyethoxy. Carbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxy Carbonyl, hydroxynorbornyloxycarbonyl, hydroxyadamantyloxycarbonyl Group can be exemplified a. Examples of the straight, the branched or cyclic alkyl group, specifically exemplified the same ones as exemplified for R ^003.

R ^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group ( Preferably, it represents a linear or branched alkylene group, and the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group include one hydrogen atom from those exemplified for the monovalent hydrocarbon group containing a carboxy group or a hydroxyl group. Excluded are examples.

Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 . R ⁰⁰⁹ represents a monovalent hydrocarbon group or a hydrophilic adhesive group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms, specifically 2-oxooxolan-3-yl, 4, 4-dimethyl-2-oxooxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolane- Groups such as 5-yl can be exemplified. At least one of R ^{010 to} R ⁰¹³ represents a —CO ₂ — partial structure having 2 to 15 carbon atoms or a monovalent hydrocarbon group containing sulfone or sulfonamide, and the rest each independently represents a hydrogen atom or 1 carbon atom. -15 linear, branched or cyclic alkyl groups are shown. R ^{010 to} R ⁰¹³ may be hydrophilic adhesive groups.

Specific examples of the monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms include 2-oxooxolan-3-yloxycarbonyl and 4,4-dimethyl-2-oxooxo. Lan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane-5 -Groups such as yloxycarbonyl can be exemplified. Examples of the straight, the branched or cyclic alkyl group, specifically exemplified the same ones as exemplified for R ^003.

R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms include 1-oxo-2-oxapropane-1,3-diyl and 1,3-dioxo-2. - oxa-1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - partial structure The thing etc. which remove | excluded one hydrogen atom from what was illustrated with the monovalent | monohydric hydrocarbon group containing this can be illustrated. Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 .

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5. 2.1.0 ^2,6 ] decyl, adamantyl, ethyladamantyl, butyladamantyl, norbornylmethyl, adamantylmethyl and the like. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a methylene or oxygen atom. R ⁰¹⁷ does not exist (single bond), or is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may contain a substituent containing a hetero atom such as a hydroxy group, an alkoxy group or an acetyl group. Good. R ⁰¹⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

  k is 0 or 1. a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers from 0 to less than 1. In this case, a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1.

Specific examples of the acid labile group for ^R015 include groups represented by the following general formulas (L1) to (L5), a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, and each alkyl group. Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

In the above formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may form a ring, and in the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each have 1 to 18 carbon atoms, Preferably 1-10 linear or branched alkylene groups are shown.

R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula ( And a tertiary alkyl group specifically includes a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, 1 -Ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, etc. Specifically, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like can be given as an oxoalkyl group. Specific examples include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-5-oxooxolan-4-yl group. a is an integer of 0-6.

R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, as a linear, branched or cyclic alkyl group. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, A cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, etc. can be exemplified. Specific examples of the aryl group which may be substituted include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl. Group, pyrenyl group and the like. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

R ^L06 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, and specific examples thereof are the same as those of R ^L05. it can. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, Linear, branched or cyclic alkyl groups such as cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxy groups Carbonyl group, oxo group, amino group, alkylamino group, cyano group, mercapto group, Kiruchio group, can be exemplified those sulfo group. R ^{L07 to} R ^L16 may form a ring with each other (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 And R ^L14 ), in which case a divalent hydrocarbon group which may contain a heteroatom having 1 to 15 carbon atoms is shown, and one hydrogen atom is removed from those exemplified above for the monovalent hydrocarbon group The thing etc. can be illustrated. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

  Among the acid labile groups represented by the general formula (L1), specific examples of the linear or branched ones include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, 3 -Ethyl-1-cyclohexen-3-yl and the like can be exemplified.

  Specific examples of the acid labile group of the above formula (L4) include the following groups.

In addition, examples of the tertiary alkyl group, trialkylsilyl group, and oxoalkyl group of the acid labile group represented by ^R015 include those exemplified above.

  Specific examples of the acid labile group of the above formula (L5) include the following groups.

  Further, the following silicon-containing acid labile groups can be used as the acid labile group.

Here, R ¹ and R ² are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, R ³ , R ⁴ and R ⁵ are the same or different alkyl groups having 1 to 20 carbon atoms, haloalkyl groups, and carbon numbers 6 Or a silicon-containing group in which each alkyl group is bonded to a silicon atom in the formula by a siloxane bond or a silethylene bond. R ¹ and R ² may combine to form a ring having 3 to 10 carbon atoms together with the carbon atom to which they are bonded.

Furthermore, R ³ and R ⁴ , R ³ and R ⁵ , R ⁴ and R ⁵ may be bonded to each other to form a polysiloxane ring having 3 to 10 silicon atoms together with the silicon atom to which they are bonded.

In this case, the silicon-containing group having a siloxane bond or a silalkylene bond with a silicon atom may be represented by the following formula: —W— (SiR ₂ —W) _v —SiR ₃
(W represents O or CH ₂ , R represents an alkyl group or aryl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and v represents an integer of 0 to 10, particularly 0 to 6)
The group shown by these is mentioned.

（但し、Ｒは上記と同様であり、ｗは２〜１０、特に３〜６の整数である。） Furthermore, the following are mentioned as a polysiloxane ring.

(However, R is the same as the above, and w is an integer of 2 to 10, particularly 3 to 6.)

  Specific examples of the groups represented by the formulas (A-4), (A-5), and (A-6) include those shown below.

  A cyclic silicon-containing acid labile group represented by the general formula (A-7) or (A-8) can also be used.

Here, R ¹ and R ¹³ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ and R ¹² are hydrogen atoms. Or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ , R ⁸ and R ⁹ are hydrogen atoms, or a linear, branched or cyclic group having 1 to 20 carbon atoms. , A fluorinated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, p, q, r, and s are integers of 0 to 10 and 1 ≦ p + q + s ≦ 20. Specifically, the following can be exemplified.

  Here, the repeating unit represented by a1 and b1 includes a hydrophilic adhesive group, and examples thereof include those exemplified by the following formulas (6) -1 to (6) -52.

In the above formula, R ¹⁴ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹⁵ is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.

  Here, the repeating unit represented by a2 and b2 in the above formula (6) contains a hydrophilic adhesive group, and is exemplified by the following formulas (7) -1 to (7) -54. Things. In the following formulas (7) -1 to (7) -54, n is 0 or 1.

  In the polymer structure used as the base resin in the present invention, a1, a2, a3, a4, b1, b2, b3, b4, c1, c2, c3, c4, d1, d2, d3, d4, e It can also be copolymerized with repeating units other than those mentioned. Examples thereof include fluorinated maleic anhydride, fluorinated maleimide, vinyl ether derivatives, allyl ether derivatives, vinyl acetate, vinyl pyrrolidone, vinyl lactone derivatives and the like listed in the following formulas (8) -1 to (8) -8. .

  Further, the base resin may be a polymer structure containing a silicon atom. In this case, the silicon atom-containing repeating units are those represented by the following formulas (9) -1 to (9) -6. be able to. The weight average molecular weight is preferably in the range of 3,000 to 100,000.

Here, R ²⁰ is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, R ²¹ is a single bond or a divalent hydrocarbon group such as an alkylene group having 1 to 10 carbon atoms, R ²² , R ²³ and R ²⁴ are the same or different hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkyl group containing a fluorine atom, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond R ²² and R ²³ , R ²³ and R ²⁴ or R ²² and R ²⁴ may be bonded to each other to form a siloxane ring together with the silicon atom to which they are bonded. R ²⁵ is a repeating unit having an acid labile group or an adhesive group.

Examples of the silicon-containing group having a siloxane bond or a silalkylene bond with a silicon atom include the following formula: —W— (SiR ₂ —W) _v —SiR ₃
(W represents O or CH ₂ , R represents an alkyl group or aryl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and v represents an integer of 0 to 10, particularly 0 to 6)
The group shown by these is mentioned.

（但し、Ｒは上記と同様であり、ｗは２〜１０、特に３〜６の整数である。） Furthermore, the following are mentioned as a polysiloxane ring.

(However, R is the same as the above, and w is an integer of 2 to 10, particularly 3 to 6.)

For example, the above formula (9) -5 is more specifically exemplified by the following formulas (10) -1 to (10) -18, and the above formulas (9) -1 to (9)- -R ²¹ -SiR ²² R ²³ R ²⁴ in 4 the following formulas (10) -1 to (10) can be exemplified by the same as that in -18.

  The repeating unit represented by the above formula (9) -6 is silsesquioxane having a ladder structure, and can be specifically exemplified below.

  The repeating unit of silsesquioxane having an acid-decomposable group can be represented by any of the following general formula (11).

Here, in the above formula, R ⁶³ , R ⁶⁴ , and R ⁶⁸ are a linear, branched, or cyclic alkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. It may be substituted with a fluoromethyl group. R ⁶⁶ and R ⁶⁷ are a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group, and at least one of R ⁶⁶ and R ⁶⁷ is 1 Contains one or more fluorine atoms. R ⁶⁹ is a fluorine atom or a trifluoromethyl group. A is an acid labile group, and examples thereof include those described above. g, h, i are 1 or 2, and j is an integer of 0-4.

  The repeating unit a-1 can be exemplified below.

  Next, repeating unit a-2 can be illustrated below.

  Next, repeating unit a-3 can be illustrated below.

  The repeating units a-4 and a-5 can be exemplified as follows.

  The polysilsesquioxane of the formula (9) -6 for polymer blend in the present invention has an adhesive property having a hydrophilic group in addition to the repeating unit whose alkali solubility is improved by the acid represented by the general formula (11). These repeating units can be copolymerized. As an adhesive group, the main component is an oxygen atom such as an alcohol group, carboxyl group, ether group, ester group, acetyl group, formyl group, carbonate group, lactone ring, sulfonamide group, cyano group, or carboxylic acid anhydride. .

  Specifically, a repeating unit in which the acid labile group A of the above a-1, a-2, a-3 is a hydrogen atom can be mentioned.

  The repeating unit which has another adhesive group can be illustrated below.

  Furthermore, in order to improve transparency or optimize the molecular weight, it is possible to copolymerize repeating units pendant with alkyl groups or fluorinated alkyls represented by the following formulas (12) -1 to (12) -4. .

（式中、Ｒ⁷⁰は同一又は異種の炭素数１〜２０の直鎖状、分岐状もしくは環状の非置換又は置換の炭素数１〜１０のアルキル基であり、フッ素化されたアルキル基であってもよく、Ｒ⁷¹は酸素原子、炭素数１〜１０のアルキレン基、又は炭素数６〜１０のアリーレン基であり、０≦ｊ＜１、０≦ｋ＜１、０≦ｌ＜１、０≦ｍ＜１の範囲である。）

(In the formula, R ⁷⁰ is the same or different linear, branched or cyclic unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and is a fluorinated alkyl group. R ⁷¹ is an oxygen atom, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and 0 ≦ j <1, 0 ≦ k <1, 0 ≦ l <1, 0 ≦ m <1.)

A synthesis example of a silane monomer used for the repeating unit a of the general formula (11) is shown below. Here, a hydrosilylation reaction is performed under a platinum catalyst with norbornene and silane having a carboxylate. R ⁷² may be an acid labile group, a hydrogen atom, or an alkali hydrolyzable group. In the following reaction formula, each X is the same or different halogen atom, hydroxy group, alkoxy group having 1 to 10 carbon atoms, or acyl group having 1 to 10 carbon atoms. The reaction temperature is room temperature, in some cases, heated to a maximum of about 150 ° C., and pressurized to about 10 atmospheres in an autoclave. The catalyst is preferably chloroplatinic acid.

  The silane monomer for obtaining the repeating unit shown by General formula (11) is illustrated below.

Here, R ⁷² may be an acid labile group represented by A, or may be a hydrogen atom or an acyl group having 1 to 6 carbon atoms. In the case of an acyl group, —OR ⁷² is obtained by alkali hydrolysis after polymerization. A hydroxy group may be substituted with an acid labile group.

  Furthermore, the following silane compounds can be co-condensed.

  Furthermore, a silane compound having a tetrafunctional or higher functional condensation group shown below can be copolymerized.

  As a synthesis method of the polymer compound represented by the general formula (11), co-condensation by hydrolysis is performed using the silane monomer obtained by the hydrosilylation. The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid Acid such as sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, 1,8-diazabicyclo [5 4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonenone (DBN), sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. Base, tetraalkoxytitanium, trialco Shimono (acetylacetonate) titanium, tetraalkoxy zirconium, may be mentioned trialkoxy mono metal chelate compounds such as (acetylacetonato) zirconium.

  As a reaction operation, a monomer is dissolved in an organic solvent, water is added, and a hydrolysis reaction is started. The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable. As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether. , Ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate -Butyl, tert-butyl propionate, propylene glycol mono tert Butyl ether acetate, γ- butyrolactone are preferred.

  Thereafter, a neutralization reaction of the catalyst is performed, and the organic solvent layer is separated and dehydrated. The remaining water causes the condensation reaction of the remaining silanol to proceed, so dehydration must be sufficiently performed. Preferable examples of the dehydration method include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.

  Moreover, the said high molecular compound is not restricted to 1 type, 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.

  Furthermore, a polymer structure containing a fluorine atom can be used as the base resin. The repeating unit containing a fluorine atom can be represented by the following general formulas (13) -1 to (13) -8. The weight average molecular weight is preferably in the range of 3,000 to 100,000.

Here, in the general formulas (13) -1 to (13) -8, R ³⁰ , R ³¹ , and R ³² are the same or different hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups. R ^{30 to} R ³² contain at least one fluorine atom. R ³³ , R ³⁸ , R ⁴² and R ⁴⁴ are the same or different hydrogen atoms, acid labile groups, or adhesive groups. R ³⁴ , R ³⁵ , and R ³⁶ are the same or different hydrogen atom, fluorine atom, methyl group, or trifluoromethyl group, and at least one or more fluorine atoms are included in R ^{30 to} R ³² . R ³⁸ and R ⁴³ are each a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁴⁰ and R ⁴¹ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or fluorinated. It is an alkyl group, and R ⁴⁰ and R ⁴¹ contain at least one fluorine atom. R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group, and among R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ Contains at least one fluorine atom. R ⁴⁹ , R ⁵⁰ , R ⁵¹ , and R ⁵² are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and at least one or more fluorine atoms are included in R ^{49 to} R ⁵² . In the formula, R ⁵³ and R ⁵⁴ are a hydrogen atom or an acid labile group, and 0 <l <1, 0 <m <1, 0 <r <1. The acid labile groups are exemplified above.

  When forming a pattern using the above materials, as described above, an antireflection film layer is first formed on the film to be processed. The antireflection film may be an organic antireflection film formed by a spin coating method, or an inorganic antireflection film formed by a CDV method, a sputtering method, or the like. The organic antireflection film may be made of hydrocarbon or silicon.

  A photoresist layer is formed thereon, and a photoresist pattern is formed by exposure, PEB, and development.

  The pattern forming material of the present invention can be formed on a substrate by spin coating or the like, similar to the photoresist composition, on the developed photoresist film. After spin coating, the substrate is preferably heated and baked to promote the crosslinking reaction. The baking temperature is 50 to 150 ° C. for 10 to 300 seconds. The thickness of the crosslinked layer can be controlled by adjusting the temperature and time. Thereafter, the film portion containing the uncrosslinked titanium compound is removed by cooling and washing, and after spin drying, an adsorption layer of a pattern forming material can be formed on the sidewall of the photoresist pattern.

  The etching of the antireflection film and the etching of the film to be processed may be performed continuously in the same chamber, or after etching the antireflection film, the film to be processed may be etched by changing the chamber.

Etching of the film to be processed can be performed by a conventional method. For example, in the case of SiO ₂ or SiN, a fluorocarbon gas, specifically CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₂ F ₆ , C ₃ F _{8 is used.} Etching mainly using C ₄ F ₁₀ and C ₅ F ₁₂ , and p-Si, Al, and W etching mainly using chlorine and bromine gases.

In addition to the above gas species, CO, CO ₂ , SO ₂ , O ₂ , N ₂ , NH _3, He, Ar gas, or the like can be used for etching the antireflection film.

  Further, although the antireflection film and the film to be processed can be etched by a conventional method, it is preferable to employ a dry etching method, and the etching proceeds by gas molecules converted into plasma by electrode discharge. A pattern having a higher aspect and higher verticality than wet etching can be processed.

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

[Example 1]
Matsumoto Industry and Commerce made ORGATICS _{TC-400 (C 6 H 14} O 3 N) 2 -Ti (C 3 H 7 O) 2 3.65 parts by weight, by mixing 116 parts by weight of isobutanol amine, pattern the hard mask solution (pattern Forming material).
Next, a resist solution shown in Table 1 having the following composition was prepared, and an antireflection film solution (ARC-29A manufactured by Nissan Chemical Industries, Ltd.) was applied on the silicon substrate, and baked at 200 ° C. for 60 seconds. A resist solution was spin-coated on an antireflection film (78 nm film thickness) substrate, and baked at 120 ° C. for 60 seconds using a hot plate to form a 200 nm film thickness resist film. This was exposed using an ArF excimer laser microstepper (Nikon Corporation S305B, NA = 0.68, σ0.85, 2/3 annular illumination, Cr mask), and baked at 110 ° C. for 90 seconds (PEB) And developed with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds. Perform open frame exposure with a stepper, initially 3.5 mJ / cm ² of 100 shots exposure while increasing the exposure amount in steps of 0.15 mJ / cm ² with exposure performed PEB, development, residual film curve Asked.

  Next, the pattern hard mask solution is dispensed onto the developed resist film, rotated at 1,000 rpm for 30 seconds, baked at 120 ° C. to volatilize the solvent, and the pattern hard mask material is attached to the resist surface. The substrate surface and excess uncrosslinked pattern hard mask material were removed by rinsing with pure water at 1,000 rpm for 30 seconds. The resist film thickness is measured before and after the pattern hard mask material treatment, and elemental analysis of the resist surface is performed with an X-ray microanalyzer JPS-9000MC manufactured by JEOL Ltd. to determine the abundance ratio of Ti. It was. The dimensions of the 120 nm line and space line after development and after the pattern hard mask solution treatment were measured with a length measuring SEM (S-9200) manufactured by Hitachi, Ltd. The results are shown in FIG.

(1) Etching test with CHF ₃ / CF ₄ -based gas A photoresist and a pattern hard mask solution are spin-coated, a film is formed by baking at 120 ° C. for 60 seconds, and a dry etching apparatus TE- manufactured by Tokyo Electron Co., Ltd. Using 8500P, the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec

(2) Etching test with Cl ₂ / BCl ₃ -based gas Using a dry etching apparatus L-507D-L manufactured by Nidec Anelva Co., Ltd., the difference in thickness of the polymer film before and after etching was similarly determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec

ＰＧＭＥＡ ポリエチレングリコールモノメチルエーテルアセテート

PGMEA Polyethylene glycol monomethyl ether acetate

  From the residual film characteristic of the photoresist film after development, the film thickness is increased after the pattern hard mask treatment, particularly in the range of 500 to 3000 mm of the residual film. Where the resist film thickness is 0 and only the antireflection film of the substrate is present, the film thickness is not changed by the pattern hard mask solution treatment. Titanium adhesion is supported by the results of XPS analysis. The line dimension of the 120 nm LS pattern is larger after the pattern hard mask process, indicating that titanium adheres to the side wall of the pattern. The titanium-containing hard mask material exhibits excellent etching resistance, and has a high effect of improving the etching resistance of the resist pattern.

It is explanatory drawing regarding the pattern formation method of this invention, (A)-(E) is, respectively, (A) Resist pattern after image development, (B) Water-soluble titanium material coat, (C) Water-soluble titanium layer bridge | crosslinking by baking , (D) Water-soluble titanium layer rinsing and peeling, (E) Antireflection film and substrate to be processed dry etching. It is a graph which shows the abundance ratio of Ti on the resist film surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base substrate 2 Processed film 3 Antireflection film 4 Resist film (resist pattern)
4a Space portion of resist pattern 5 Pattern forming material film (water-soluble titanium compound layer)
5a Cross-linked layer

Claims (5)

A pattern forming material containing a water-soluble titanium compound represented by the following general formula (1) or (2) is applied onto the developed photoresist pattern, and the titanium compound-containing film is attached to the surface of the photoresist pattern. A pattern forming method, wherein only the surface of a photoresist pattern is protected with a titanium compound by removing the pattern forming material existing in a portion other than the photoresist pattern.

(In the formula, R ⁰¹ is an alkyl group or an acyl group which may contain an oxygen atom having 1 to 10 carbon atoms, R ⁰² is an alkyl group or an acyl group containing a nitrogen atom having 1 to 20 carbon atoms, It may have a hydroxy group, an ether group or an ester group, in the range of 0 ≦ a <4, 0 ≦ b <3, 0 ≦ c <2, 0 ≦ d ≦ 10,000, 0 ≦ e <3. is there.)   2. The pattern forming method according to claim 1, wherein the pattern forming material existing in a portion other than the photoresist film is dissolved and removed in water.   3. The pattern forming method according to claim 1, wherein the base substrate is processed by dry etching using a photoresist pattern protected by a titanium compound as a mask. Polyacrylic acid and its derivatives, cycloolefin derivatives-anhydrous having a photoresist pattern having a carboxyl group that undergoes a crosslinking reaction with a nitrogen-containing group of a water-soluble titanium compound or a group that forms a carboxyl group during the formation of a resist pattern Maleic acid alternating polymer, three or four or more copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or its derivative, cycloolefin derivative-α trifluoromethyl acrylic copolymer, polynorbornene, and metathesis 4. The pattern according to claim 1, 2 or 3, wherein the pattern is formed by using a resist material having one or more polymer polymers selected from ring-opening polymers as a base resin. Forming method. The pattern forming method according to claim 4, wherein the high molecular polymer of the base resin is represented by the following general formula (6).

(Wherein R ⁰⁰¹ Is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or CH ₂ CO ₂ R ⁰⁰³ Indicates. R ⁰⁰² Is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³ Indicates. R ⁰⁰³ Represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.
R ⁰⁰⁴ Represents a hydrogen atom, a monovalent hydrocarbon group containing 1 to 15 carbon atoms or a hydroxyl group, or a hydrophilic adhesive group. R ⁰⁰⁵ ~ R ⁰⁰⁸ At least one of these represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, or a hydroxy group having a fluorine atom or a fluorinated alkyl group at the β-position, and the rest each independently A hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms or a fluorinated alkyl group is shown. R ⁰⁰⁵ ~ R ⁰⁰⁸ May be a hydrophilic adhesive group. R ⁰⁰⁵ ~ R ⁰⁰⁸ May form a ring with each other, in which case R is ⁰⁰⁵ ~ R ⁰⁰⁸ At least one of them represents a carboxy group having 1 to 15 carbon atoms or a divalent hydrocarbon group containing a hydroxyl group, and the rest each independently represents a single bond, or a straight chain, branched or cyclic group having 1 to 15 carbon atoms. The alkylene group is shown.
R ⁰⁰⁹ Is -CO having 3 to 15 carbon atoms ₂ -Represents a monovalent hydrocarbon group or a hydrophilic adhesive group containing a partial structure. R ⁰¹⁰ ~ R ⁰¹³ At least one of -CO having 2 to 15 carbon atoms ₂ -Represents a monovalent hydrocarbon group containing a partial structure or sulfone or sulfonamide, and the rest each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰¹⁰ ~ R ⁰¹³ May be a hydrophilic adhesive group. R ⁰¹⁰ ~ R ⁰¹³ May form a ring with each other, in which case R is ⁰¹⁰ ~ R ⁰¹³ At least one of -CO having 1 to 15 carbon atoms ₂ -The bivalent hydrocarbon group containing a partial structure is shown, and the rest each independently represents a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms.
R ⁰¹⁴ Represents an alkyl group containing a polycyclic hydrocarbon group having 7 to 15 carbon atoms or a polycyclic hydrocarbon group. R ⁰¹⁵ Represents an acid labile group. R ⁰¹⁶ Represents a methylene or oxygen atom. R ⁰¹⁷ Is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may contain a substituent containing a hetero atom selected from a hydroxy group, an alkoxy group and an acetyl group. R ⁰¹⁸ Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
k is 0 or 1. a1, a2, a3, b1, b2, b3, c1, c2, c3, d1, d2, d3, e are numbers from 0 to less than 1, and a1 + a2 + a3 + b1 + b2 + b3 + c1 + c2 + c3 + d1 + d2 + d3 + e = 1. )

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