CN1943013A - Liquid for immersion exposure and immersion exposure method - Google Patents

Liquid for immersion exposure and immersion exposure method Download PDF

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CN1943013A
CN1943013A CN 200580005118 CN200580005118A CN1943013A CN 1943013 A CN1943013 A CN 1943013A CN 200580005118 CN200580005118 CN 200580005118 CN 200580005118 A CN200580005118 A CN 200580005118A CN 1943013 A CN1943013 A CN 1943013A
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carbon atoms
immersion exposure
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CN100492588C (en )
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宫松隆
根本宏明
王勇
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Jsr株式会社
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本发明的目的在于提供一种在浸液曝光方法中,折射率大于纯水,防止光致抗蚀膜或其上层膜成分的洗脱或溶解,能够抑制抗蚀图案生成时的缺陷的浸液曝光用液体、以及利用该液体的浸液曝光方法。 Object of the present invention is to provide a liquid immersion exposure process, a refractive index greater than water, to prevent immersion liquid photo resist film or the elution or dissolution of the upper layer film composition, can suppress the defects of the resist pattern generation exposure with a liquid, and a method using the immersion exposure liquid. 一种浸液用曝光液体,其在通过投影光学系统的透镜和基板之间充满的液体进行曝光的浸液曝光装置或浸液曝光方法中使用,在浸液曝光装置工作的温度区域内是液体,是包含脂环烃化合物或在环结构中含有硅原子的环烃化合物。 One kind of an immersion exposure liquid, the immersion exposure apparatus using the immersion exposure method or the exposure by the liquid is filled between the lens substrate and the projection optical system, the liquid in the temperature range of the liquid immersion exposure apparatus work is a compound containing an alicyclic hydrocarbon or cyclic hydrocarbon compounds containing silicon atoms in the ring structure.

Description

浸液曝光用液体以及浸液曝光方法 Immersion exposure liquid immersion exposure method and

技术领域 FIELD

本发明涉及浸液曝光用液体以及浸液曝光方法,详细地讲,除了这些液体以及方法以外,涉及该浸液曝光用液体的制备方法、作为浸液曝光用液体的评价方法、新型液体组合物。 The present invention relates to liquid immersion exposure and the immersion exposure method, detail, in addition to these methods as well as liquids, to a method for preparing the liquid immersion exposure as a method of evaluating the immersion liquid, the liquid composition is exposed novel .

背景技术 Background technique

在制造半导体元件等时,使用通过投影光学系统将作为光掩膜的标线片的图案转印至涂布有光致抗蚀剂的晶片上的各拍摄区域的分步型或步进扫描方式的投影曝光装置。 In the manufacture of semiconductor elements, a projection optical system by using a photomask pattern of the reticle is transferred to a step and scan type or a stepwise manner each shot area on the wafer is coated with photoresist the projection exposure apparatus.

使用的曝光波长越短,投影光学系统的数值孔径越大,投影曝光装置所具备的投影光学系统的分辨率的理论阈值越高。 The shorter the exposure wavelength used, the larger the numerical aperture of projection optical system, the higher the resolution of the projection optical system provided in the projection exposure apparatus theoretical threshold. 因此,随着集成电路的微细化,投影曝光装置中使用的作为放射线波长的曝光波长逐年变短,投影光学系统的数值孔径也逐渐增大。 Thus, with the miniaturization of integrated circuits, projection exposure apparatus used in the exposure wavelength as the radiation wavelength is shortened year by year, the numerical aperture of the projection optical system also increases.

另外,当进行曝光时,焦点深度与分辨率同样地也变得重要。 Further, when the exposure, the depth of focus and the resolution likewise become important. 分辨率R和焦点深度δ的理论阈值分别用以下数学式表示。 Theoretical threshold resolution R and depth of focus δ are represented by the following equation.

R=k1·λ/NA (i)δ=k2·λ/NA2(ii)其中,λ是曝光波长,k1、k2是工艺参数,NA是投影光学系统的数值孔径,当空气的折射率设为1时,以下式(ii')定义。 R = k1 · λ / NA (i) δ = k2 · λ / NA2 (ii) where, [lambda] is the wavelength of the exposure, k1, k2 are the process parameters, NA is the numerical aperture of the projection optical system, when the refractive index of air is set 1, define the following formula (ii '). 即,当获得相同的分辨率R时,使用了具有短波长的放射线的一方能够获得大的焦点深度δ。 That is, when obtaining the same resolution R, the use of radiation having a short wavelength one can obtain a large depth of focus δ.

NA=sinθ(θ=曝光的光在抗蚀剂表面的最大入射角)(ii')如上所述,至今,通过曝光光源的短波长化、数值孔径的增大,不断满足集成电路的微细化要求,现在,正在研究使用了ArF准分子激光(波长193nm)作为曝光光源的1L1S(1∶1线和空间)半间距90nm节点的大量生产。 NA = sinθ (θ = the maximum incident angle of light exposure on the resist surface) (ii ') described above, so far, by an exposure light source of short wavelength, the numerical aperture is increased, miniaturization of integrated circuits continue to meet requirements, are now being studied using ArF excimer laser (wavelength 193 nm) as an exposure light source 1L1S mass production (1:1 line and space) 90nm half pitch node. 然而,对于进一步微细化的下一代半间距65nm节点或45nm节点,认为只通过使用ArF准分子激光是难以达成的。 However, for the next generation 45nm half pitch of 65nm node or a node further miniaturization, that only by using the ArF excimer laser it is difficult to achieve. 因此,针对这些下一代技术,正在研究F2准分子激光(波长157nm)、EUV(波长13nm)等短波长光源的使用。 Thus, for these next-generation technology, an F2 excimer being studied using a laser (wavelength 157nm) EUV (wavelength 13nm) of the short wavelength light source and the like. 然而,对于这些光源的使用来说,技术上的难度高,现在还处于使用困难的状况。 However, using these light sources, the high technical difficulties, is still in use difficult situation.

在上述曝光技术中,在曝光的晶片表面上形成光致抗蚀膜,在该光致抗蚀膜上转印图案。 In the exposure technique to form a photoresist film on the exposed surface of the wafer, the photoresist film transfer pattern. 在以前的投影曝光装置中,配置有晶片的空间被折射率为1的空气或氮气充满。 In previous projection exposure apparatus, the configuration space is a refractive index of the wafer 1 is filled with air or nitrogen. 此时,当用折射率n的介质充满晶片和投影曝光装置的透镜之间的空间时,据报告分辨率R、焦点深度δ的理论阀值用以下数学式表示。 At this time, when filled space between the wafer and the lens of the projection exposure apparatus with a medium refractive index n, the theoretical threshold reported resolution R, depth of focus δ is represented by the following equation.

R=k1·(λ/n)/NA (iii)δ=k2·nλ/NA2(iv)其中,NA不是实际的投影光学系统的数值孔径,表示用上述式(ii')定义的常量(准确地讲,投影光学系统的数值孔径NA'用NA'=nsinθ(n与上述定义相同)表示)。 R = k1 · (λ / n) / NA (iii) δ = k2 · nλ / NA2 (iv) wherein, NA than the numerical aperture of the actual projection optical system, represented by a constant defined by the above formula (ii ') (accurate speaking, the numerical aperture NA of the projection optical system 'by NA' = nsinθ (n are the same as defined above) represented).

上式表示通过在投影曝光装置的透镜和晶片之间充满折射率n的液体,设定适当的光学系统,在理论上能够分别使分辩率的阀值和焦点深度为1/n、n倍。 Represented by the formula of liquid between the lens and the wafer projection exposure apparatus is filled with the refractive index n, setting an appropriate optical system, in theory, enable the threshold resolution and depth of focus to 1 / n, respectively, n times. 例如,在ArF工艺中,如果使用水作为上述介质,波长193nm的光在水中的折射率n为n=1.44,因此,与以空气或氮气为介质的曝光时相比,在理论上能够设计分辩率R达到69.4%(R=k1·(λ/1.44)/NA)、焦点深度达到144%(δ=k2·1.44λ/NA2)的光学系统。 For example, in the ArF process, if water is used as the medium, the wavelength of 193nm light refractive index n of the water is n = 1.44, and therefore, when compared with air or nitrogen as the exposure medium, in theory, can be designed to differentiate R ratio reached 69.4% (R = k1 · (λ / 1.44) / NA), the focal depth of 144% (δ = k2 · 1.44λ / NA2) of the optical system.

将这样缩短用于曝光的放射线的有效波长,能够转印更微细图案的投影曝光方法称为浸液曝光,对于今后的光刻蚀的微细化,特别是数10nm单位的光刻蚀,被认为是必需的技术,其投影曝光装置也是已知的(参照专利文献1)。 The thus shorten the effective wavelength of the radiation used for exposure, a fine pattern can be transferred more projection exposure method is called immersion exposure for the next finer photolithography, especially photolithography 10nm number of units, it is believed to technology is required, projection exposure apparatus which are also known (see Patent Document 1).

以前,在浸液曝光方法中,作为投影光学系统的透镜和基板之间充满的液体,在ArF准分子激光中研究了纯水,在F2准分子激光中,出于157nm下的透明性高的理由,研究了氟类惰性液体等的使用。 Previously, in the immersion exposure method, a liquid filled between the lens substrate and the projection optical system, pure water was studied in the ArF excimer laser, the F2 excimer laser, at 157nm for a high transparency reason, studied to use a fluorine-based inert liquid or the like.

对于纯水来说,在半导体制造工厂中容易得到,在环境上也没有问题。 For water, the be easily obtained in a semiconductor manufacturing factory, there is no problem in the environment. 另外,容易进行温度调节,能够防止由曝光中产生的热引起的基板的热膨胀,被用作ArF用浸液液体(参照专利文献2),已确实在65nm半间距节点的装置的大量生产中采用。 Further, a temperature easily adjusted, the thermal expansion of the substrate can be prevented from heat generation caused by the exposure, is used for ArF immersion liquid (refer to Patent Document 2), has been employed in mass production is indeed apparatus 65nm half pitch node .

另一方面,还公知了添加甲醇等作为减少纯水的表面张力,同时增大表面活性力的添加剂得到的液体(参照专利文献3)。 On the other hand, also known as cicadas adding a liquid to reduce the surface tension of pure water, while increasing the force of the surface-active additives such as methanol to give (refer to Patent Document 3).

然而,由于使用纯水,水浸透于光致抗蚀膜中,有时产生光致抗蚀图案的截面形状成为T-顶端形状的形状劣化,分辨率降低。 However, the use of water, saturated with water in the photoresist film, the cross-sectional shape may be generated photoresist pattern shape becomes deteriorated T- shaped tip, resolution reduction. 另外,由于构成光致抗蚀剂的光酸发生剂、碱性添加剂、由曝光产生的酸等水溶性成分洗脱至水中,有时还会引起T-顶端形状等形状劣化,产生分辨率、焦点深度的降低、桥接缺陷,在显像后的图案中产生缺陷,污染透镜表面。 Further, since the water-soluble component constituting the photoacid generator of the photoresist, basic additive, acid generated by the exposure to the water elution, and sometimes cause deterioration of the shape T- shape to the top, to create the resolution, focus reduce the depth of the bridging defect, defects in the pattern after development, the contamination of the lens surface. 另外,这些成分洗脱到液体中会同时引起液体的污染,难以进行液体的再利用。 Further, these components eluted into the liquid simultaneously causes contaminated liquid, the liquid is difficult to be reused. 因此,频繁地需要复杂的精制处理。 Accordingly, a complicated refining process frequently.

因此,为了隔断光致抗蚀膜和水,有在光致抗蚀膜上形成上层膜的方法,但存在对于曝光的足够的透光性或与光致抗蚀膜的混合性等不够充分的情况,还存在工时变复杂的问题。 Accordingly, in order to cut off the photoresist film and water, the photoresist film in the method of forming the upper layer film, but there is a sufficient light exposure or mixed with the photoresist film and the like insufficient case, there is work becomes complicated. 此外,还报道了以前在透镜材料中使用的CaF2被水侵蚀(非专利文献1),因此,还产生了需要涂布透镜表面的涂布材料的问题。 In addition, the use of CaF2 has been reported previously in the lens material eroded by water (Non-Patent Document 1), therefore, a problem arises also the need of applied coating material of the lens surface.

另一方面,如上述式(iii)所示,分辨率的阀值约为ArF干式曝光的1.44倍,从而可以预测:在进一步微细化,尤其是半间距45nm以下的下一代技术中,其使用变得困难。 On the other hand, as the above-described formula (iii), the resolution threshold of about ArF 1.44 times the dry exposure, can be predicted: in which further miniaturization, especially in next generation technology 45nm half pitch or less, use difficult.

如上所述,在进一步微细化的下一代浸液曝光方法中,需要在曝光波长(例如波长193nm等)下折射率大于纯水,对于这些波长的光的透光性高的液体。 As described above, in the next generation immersion exposure method further miniaturization, it is necessary at the exposure wavelength (e.g., 193nm wavelength, etc.) is greater than the refractive index of pure water, the light of these wavelengths are highly translucent liquid. 同时还需要该液体是不会引起添加剂从光致抗蚀膜洗脱、抗蚀膜的溶解、图案的劣化等对光致抗蚀膜的不良影响,而且不会侵蚀透镜的液体。 It also requires that the liquid is unlikely to cause an adverse effect liquid additive photo-resist film is eluted from the photoresist film, the resist film was dissolved, the deterioration of the pattern and the like, and does not attack the lens. 同时随着由引入浸液曝光引起的高NA化,作为曝光的光研究了偏振光的引入,期待该液体是满足上述要求以外,例如利用旋光性等性质不使偏振光方向弯曲的液体。 Simultaneously with the introduction of high NA immersion exposure caused, as the exposure light polarized studied introduction, the liquid is expected to meeting the above requirements, for example using an optically active properties and the like without polarization direction of the bending of the liquid.

作为达到该目的的方法,例如,尝试了将各种盐溶解于水而提高折射率(非专利文献2)。 As a method for this purpose, for example, various salts attempted to increase the refractive index is dissolved in water (Non-Patent Document 2). 然而,该方法难以进行盐的浓度控制,此外,与水同样地存在由水溶性成分的洗脱而引起的显像缺陷、透镜的污染等问题。 However, this method is difficult to control the concentration of salts, in addition, developing defects caused by the presence of water-soluble components caused the elution of water in the same manner, the lens pollution problems.

另一方面,在F2曝光用中进行了研究的全氟聚醚等氟类惰性液体,例如在193nm下的折射率小,因此难以在该波长下使用。 On the other hand, in the F2 exposure studies perfluoropolyether fluorine-based inert liquid, such as a small refractive index at 193nm, it is difficult to use at this wavelength. 另外,由于在波长589nm下的高折射率而作为显微镜用的浸液曝光液体而到目前为止公知的有机溴化物、碘化物,例如在193nm下的透光性差,而且对于光致抗蚀膜的稳定性差。 Further, since the high refractive index at a wavelength of 589nm as a liquid immersion exposure with a microscope so far known organic bromides, iodides, for example, poor light transmission at 193nm, and for a photoresist film poor stability.

专利文献1:特开平11-176727号公报专利文献2:国际公开WO99/49504号公报专利文献3:特开平10-303114号公报非专利文献1:NIKKEI MICRODEVICE 2004年4月号p77非专利文献2:Proc.SPIE Vol.5377(2004)p.273发明内容本发明是为了解决上述问题而完成的,目的在于提供一种在浸液曝光方法中,折射率大于纯水,在该浸液曝光波长下具有优异的透光性,能够防止光致抗蚀膜或其上层膜成分(尤其是亲水性成分)的洗脱或溶解,不侵蚀透镜,能够抑制抗蚀图案生成时的缺陷,当用作浸液曝光用液体时,能够抑制图案形状的劣化,形成分辨率以及焦点深度更优异的图案,而且液体易于再利用和精制的浸液曝光用液体以及使用了该液体的浸液曝光方法。 Patent Document 1: JP 11-176727 A Patent Document 2: International Publication WO99 / ​​49504 Patent Document No. 3: Japanese Patent Publication No. 10-303114 Non-Patent Document 1: NIKKEI MICRODEVICE April 2004 Non-Patent Document No. 2 p77 : Proc.SPIE Vol.5377 (2004) p.273 the present invention is made to solve the above problems, and an object is to provide a liquid immersion exposure process, a refractive index greater than water, the immersion exposure wavelength having the excellent light transmittance, it is possible to prevent defects of the photoresist film or the upper layer film composition (in particular a hydrophilic component) eluting or dissolving, does not attack the lens, the resist pattern generation can be suppressed, when using when the liquid for liquid immersion exposure, it is possible to suppress deterioration of pattern shape, depth of focus is formed more excellent resolution and pattern, and the liquid is easy to reuse and immersion exposure liquid and purified using a method of the liquid immersion exposure.

另外,除了上述浸液曝光用液体和浸液曝光方法之外,本发明的目的还在于提供该浸液曝光用液体的制备方法、作为浸液曝光用液体的评价方法、新型液体组合物。 Further, in addition to the liquid immersion exposure and immersion exposure method other than an object of the present invention is to provide a method for preparing the liquid immersion exposure as a method of evaluating liquid immersion exposure, the novel liquid compositions.

为了解决上述课题,在能够用于本目的的曝光波长下具有高的透射率,而且与水相比折射率足够高是浸液曝光用液体必需满足的条件。 To solve the above problems, having a high transmittance at the exposure wavelength can be used for this purpose, and compared with the refractive index of water is high enough to meet the required conditions of liquid immersion exposure. 另一方面,一般都知道液体的紫外区域的折射率与构成液体的分子极化率有关。 On the other hand, is generally known that the refractive index in the ultraviolet region of the liquid constituting the liquid polarizability of the molecule concerned. 作为提高极化率的方法,一般来说向分子中引入例如硫、溴、碘等具有容易迁移的n电子的元素以及引入具有比较易于迁移的π电子的碳-碳双键、碳-碳三键,尤其是芳香环是有效的。 As a method of improving the rate of polarization, in general, for example, introduced into the molecule having n electrons easily migrate sulfur, bromine, iodine and other elements having incorporated relatively easy migration of [pi] electrons carbon - carbon double bond, a carbon - carbon triple bond, an aromatic ring is particularly effective. 然而,含这些元素和分子结构的化合物一般例如在193nm等远紫外区域具有强吸收,不能用于本目的。 However, compounds containing these elements, for example, the general molecular structure and having a strong absorption in the far ultraviolet region 193nm etc., can not be used for this purpose. 另一方面,作为对于远紫外区域吸收小的化合物,可以列举非取代的烃化合物、氰基化烃化合物、氟代烃化合物、磺酸酯化合物、一部分醇等,但这些化合物一般折射率比水高,其折射率与现在的水差别不大。 On the other hand, as a compound for the far ultraviolet region of small absorption include non-substituted hydrocarbon compounds, cyanated hydrocarbon compound, a fluorinated hydrocarbon compounds, sulfonate compounds, part of the alcohol, but these compounds are generally refractive index than that of water high refractive index and the water is not very different now.

另一方面,作为液体的折射率更准确的理论式,提出了下述式(Lorentz-Lorenz式),报道了利用下述式能够准确地预测苯的折射率n的结果(J.Phy.Chem.A.,Vol.103,No.42,1999 p8447)。 On the other hand, the refractive index of the liquid is more accurate theoretical formula, proposed the following formula (Lorentz-Lorenz formula), it is reported to predict the refractive index n of benzene accurately by the following formula (J.Phy.Chem .A., Vol.103, No.42,1999 p8447).

N=(1+4πNαeff)0.5在上式中,N表示单位体积中的分子数,部分摩尔体积越小,其值越大。 N = (1 + 4πNαeff) 0.5 In the above formulas, N represents the number of molecules per unit volume, the smaller the molar portion, the greater the value.

由上述式可以预测:通过引入高吸收的官能团,即使不能提高α,但通过增大N也能够提高折射率。 It can be predicted by the formula: by introducing a functional group highly absorbent, if not increase the [alpha], but N can be improved by increasing the refractive index. 基于以上描述,对液体的分子结构进行了各种研究,结果发现:由于具有紧凑的结构,密度高的本发明的脂环烃、或含有硅且具有环烃骨架的液体兼具透明性和折射率,而且当用作浸液曝光用液体时,能够防止光致抗蚀膜或其上层膜成分(尤其是亲水性成分)的洗脱或溶解,进而解决抗蚀图案生成时的缺陷、透镜的侵蚀等问题,能够形成分辨率和焦点深度更优异的图案,从而完成本发明。 Based on the above description, the molecular structure of liquid conducted various studies and found that: Due to a compact structure, alicyclic hydrocarbons present invention has high density, or a silicon-containing liquid and having a cyclic hydrocarbon skeleton, both transparency and refractive rate, and when used as the liquid immersion exposure time, can prevent a photoresist film or an upper layer film composition (in particular a hydrophilic component) eluted or dissolved, and then solve the defects of the resist pattern generation, the lens erosion and other problems, the resolution and depth of focus can be formed more excellent pattern, thereby completing the present invention.

即,本发明的浸液曝光用液体是在通过投影光学系统的透镜和基板之间充满的液体进行曝光的浸液曝光装置或浸液曝光方法中使用的液体,其特征在于:该液体在浸液曝光装置工作的温度范围内是液体,是脂环烃化合物或在环结构中含有硅原子的环烃化合物。 That is, immersion exposure liquid according to the present invention is exposed through a liquid is filled between the lens substrate and the projection optical system of a liquid immersion exposure or immersion exposure apparatus used in the method, wherein: the liquid immersion the working fluid within the temperature range of the exposure apparatus is a liquid, alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure.

特别地,脂环烃化合物或在环结构中含有硅原子的环烃化合物,其特征在于:在波长193nm下每1mm光程的放射线透射率为大于等于70%,D射线的折射率为大于等于1.4,优选为1.4~2.0。 In particular, alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure, wherein: in each of 1mm at a wavelength of 193nm light path of the radiation transmittance of 70% or more, the refractive index of D ray is not less than 1.4, preferably 1.4 to 2.0.

本发明的浸液曝光方法,是用曝光光束照明掩膜,通过在投影光学系统的透镜和基板之间充满的液体,利用曝光光束对基板进行曝光的浸液曝光方法,其特征在于:上述液体是所述的浸液曝光用液体。 Immersion exposure method of the present invention, a mask is illuminated with the exposure light through a liquid between the lens and the substrate is filled with the projection optical system, exposure apparatus for exposing the substrate is exposed to immersion exposure method, wherein: the liquid It is the liquid immersion exposure.

本发明的浸液曝光方法使用疏水性高、在曝光波长下是高折射率的脂环烃化合物或在环结构中含有硅原子的环烃化合物作为浸液曝光用液体,从而能够防止光致抗蚀膜或其上层膜成分,尤其是亲水性成分的洗脱或溶解,能够解决抗蚀图案生成时的缺陷、透镜的侵蚀问题,另外,当用作浸液曝光用液体时,能够抑制图案形状的劣化,改善分辨率和焦点深度。 Immersion exposure method of the present invention is the use of high hydrophobicity, an alicyclic hydrocarbon compound at the exposure wavelength of a high refractive index or cyclic hydrocarbon compounds containing silicon atoms in the ring structure as the liquid immersion exposure, it is possible to prevent light-induced anti etching an upper layer film or a film component, in particular a hydrophilic component eluted or dissolved, can solve the defects resist pattern generation, the lens erosion problem, and, when used with a liquid immersion exposure, the pattern can be suppressed shape deterioration, improve the resolution and depth of focus.

具体实施方式 detailed description

能够用作浸液曝光用液体的脂环烃化合物或在环结构中含有硅原子的环烃化合物优选分别为脂环饱和烃化合物或在环结构中含有硅原子的环饱和烃化合物。 Can be used as the immersion exposure liquid alicyclic hydrocarbon compound or a silicon atom contained in the ring structure are preferably cyclic hydrocarbon compound is an alicyclic saturated hydrocarbon compounds or cyclic saturated hydrocarbon compound containing silicon atoms in the ring structure. 如果在烃化合物中存在不饱和键,曝光光束容易被浸液曝光用液体吸收。 If present in the unsaturated hydrocarbon compound bonds, exposure light is easily absorbed by liquid immersion exposure.

对于能够用作浸液曝光用液体的脂环烃化合物或在环结构中含有硅原子的环烃化合物,通过下述式(1-1)~式(1~9)进行说明。 For immersion exposure can be used as an alicyclic hydrocarbon compound with a liquid or cyclic hydrocarbon compounds containing silicon atoms in the ring structure, will be described by the following formulas (1-1) to (1-9).

式(1-1)中,R1表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n1、n2各自独立地表示1~3的整数,a表示0~10的整数,当存在多个R1时,该R1可以相同也可以不同,2个或更多个R1可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基。 In the formula (1-1), R1 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, n1, n2 each independently represent an integer of 1-3, a denotes an integer of 0 to 10, when a plurality of R1, the R1 may be the same or different, two or more R1 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

作为R1中的碳原子数1~10的脂肪族烃基,可以列举甲基、乙基、正丙基等。 R1 carbon atoms in the aliphatic hydrocarbon group having 1 to 10 include methyl, ethyl, n-propyl group. 作为2个或更多个R1相互结合形成环结构的例子,可以列举环戊基、环己基等。 Examples of two or more of R1 bonded to each other to form a ring structure include cyclopentyl, cyclohexyl and the like. 作为碳原子数3~14的脂环烃基,可以列举环己基、降冰片基(norbornyl)等。 As the alicyclic hydrocarbon group having 3 to 14 carbon atoms include cyclohexyl group, norbornyl group (norbornyl) and the like. 作为碳原子数1~10的氟取代烃基,可以列举三氟甲基、五氟乙基等。 Examples 1 to 10 carbon atoms, a fluorine-substituted hydrocarbon group may include trifluoromethyl, pentafluoroethyl and the like. 作为构成-Si(R9)3基的R9、和构成-SO3R10基的R10,表示碳原子数1~10的烷基,作为该烷基,可以列举甲基、乙基等。 As R9, and R10 constitute a -SO3R10 group constituting -Si (R9) 3 group, it represents an alkyl group having 1 to 10 carbon atoms, examples of the alkyl group include methyl, ethyl, and the like.

式(1-1)中,作为取代基R1,从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 In the formula (1-1), as the substituents R1, in view of excellent transmittance of 193nm radiation viewpoint, the number of carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,由于能够获得更高的折射率,与抗蚀剂的相互作用少,难以引起由抗蚀剂中的水溶性成分的洗脱产生的缺陷、对透镜材料的侵蚀,因而特别优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环族饱和烃基。 In the above-mentioned substituents, it is possible to obtain a higher refractive index, less interaction with the resist, it is difficult to cause defects resulting from the elution of soluble component in the resist, the erosion of the lens material, it is particularly aliphatic carbon atoms is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14.

另外,优选的n1、n2为1~3,特别优选的n1、n2为1或2,优选的a为0、1或2。 Further, preferably n1, n2 is 1 to 3, particularly preferably n1, n2 is 1 or 2, a is preferably 0, 1 or 2. 作为a,特别是在其为0的情况下,例如在193nm下的折射率增高,因而特别优选。 As a, especially in the case where it is 0, for example, at 193nm the refractive index increases, and thus particularly preferable.

以下列举式(1-1)所示优选的脂环饱和烃化合物的具体例子。 Include the following formulas (1-1) Preferred examples of the alicyclic saturated hydrocarbon compound shown. 应予说明,在本说明书中,省略了脂环饱和烃化合物中与形成环的碳原子结合的氢原子。 Incidentally, in the present specification, hydrogen atoms are omitted alicyclic saturated hydrocarbon compounds bonded to form a ring carbon atom.

以下列举式(1-1)所示优选的含有氰基的化合物的具体例子。 Include the following formulas (1-1) Preferred examples of cyano group-containing compound shown in FIG.

以下列举式(1-1)所示优选的含有氟原子的化合物的具体例子。 Include the following formulas (1-1) Preferred specific examples of the compound containing a fluorine atom as shown.

以下列举式(1-1)所示优选的氟取代饱和烃化合物的具体例子。 Include the following formulas (1-1) Specific examples of preferred fluorine-substituted saturated hydrocarbon compound shown.

在式(1-1)所示的优选化合物中,优选脂环饱和烃化合物,其中,作为特别优选的化合物,可以列举下述式(2-1)所示的化合物。 Preferred compounds of formula (1-1), preferably an alicyclic saturated hydrocarbon compound, wherein, particularly preferred compounds include compounds represented by formula (2-1) by the following formula.

在式(2-1)中,R1和a与式(1-1)的R1和a相同。 In the formula (2-1), R1 and a in the formula (1-1) R1 and a are identical.

作为式(2-1)中的具体例子,可以列举由上述(1-1-16)、(1-1-19)、(1-1-20)、(1-1-21)、(1-1-34)、(1-1-35)、(1-1-36)、(1-1-37)、(1-1-38)、(1-1-39)所列举的化合物。 Specific examples of the formula (2-1) may be exemplified by the (1-1-16) described above, (1-1-19), (1-1-20), (1-1-21), (1 -1-34) (1-1-35), (1-1-36), (1-1-37), (1-1-38), (1-1-39) exemplified compounds.

其中,不具有取代基的化合物例如在193nm下的折射率增高,因而优选,作为式(2-1)中特别优选的例子,可以列举顺-十氢化萘、反-十氢化萘。 Wherein the compound having no substituent group at 193nm, for example, increasing the refractive index, it is preferable, in the formula (2-1) are particularly preferred examples include cis - decalin, trans - decalin.

式(1-2)中,A表示单键或可以被碳原子数1~10的烷基取代的亚甲基或可以被碳原子数1~10的烷基取代的碳原子数2~14的亚烷基,R2表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,R7表示氢原子、碳原子数1~10的烷基、氰基、羟基、氟原子、碳原子数1~10的氟取代烷基、或-Si(R9)3基,n3表示2~4的整数,n4表示1~3的整数,b表示0~6的整数,当存在多个R2或R7时,该R2可以相同也可以不同,2个或更多个R2可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基。 In the formula (1-2), A represents a single bond or a carbon atom may be substituted with an alkyl group of 1 to 10 or a methylene group may be substituted with an alkyl group of 1 to 10 2 to 14 alkylene group, R2 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si ( R9) 3 group, or -SO3R10 group, R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine carbon atoms, a substituted alkyl group having 1 to 10, or -Si (R9 ) 3 group, n3 represents an integer of 2 to 4, n4 represents an integer of 1 to 3, b represents an integer of 0 to 6, when a plurality of R2 or R7, the R2 may be the same or different, two or more R2 may bond together to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

作为A中的可以被碳原子数1~10的烷基取代的亚甲基或可以被碳原子数1~10的烷基取代的碳原子数2~14的亚烷基,可以列举亚乙基、亚正丙基等。 As A may be an alkyl group of 1 to 10 or a substituted methylene carbon atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, a substituted alkylene group having 2 to 14 include ethylene , n-propylene and the like.

R2与式(1-1)的R1相同。 R1 R2 the same as in the formula (1-1).

式(1-2)中,作为取代基R2,从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 Formula (1-2), examples of the substituents R2, from the viewpoint of excellent transmittance 193nm radiation, the number of carbon atoms is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,出于与(1-1)中R1相同的理由,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环族饱和烃基。 In the above-mentioned substituents, and for (1-1) R1 in the same reason, the number of carbon atoms is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14.

优选的n3为2~4,特别优选为2或3,优选的n4为1~3,特别优选为1或2,优选的b为0或1或2。 N3 is preferably 2 to 4, particularly preferably 2 or 3, n4 is preferably 1-3, particularly preferably 1 or 2, b is 0 or preferably 1 or 2. 作为b,由于例如在193nm下的折射率增高,因而特别优选为0。 As B, for example, since the refractive index increased at 193nm, which is particularly preferably 0. 以下示出优选的(1-2)的具体例子。 The following illustrates preferred (1-2) is a specific example.

作为式(1-2)中特别优选的例子,可以列举1,1,1-三环庚基甲烷、1,1,1-三环戊基甲烷。 Formula (1-2) are particularly preferable examples include methane, 1,1,1-tricyclic heptyl, 1,1,1-cyclopentyl methane.

式(1-3)中,R3和R4表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,当R3和R4各自存在多个时,该R3和R4可各自相同也可以不同,2个或更多个R3和R4可以各自单独或相互结合形成环结构,n5和n6表示1~3的整数,c和d表示0~8的整数,R9和R10表示碳原子数1~10的烷基。 In the formula (1-3), R3 and R4 represent fluorine carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, alicyclic hydrocarbon group having 3 to 14, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, substituted hydrocarbyl, -Si (R9) 3 group, or -SO3R10 group, R3 and R4 when there are a plurality, R3 and R4 may each be the same or different, two or more R3 and R4 may each be used alone or in bonded to each other to form a ring structure, n5 and n6 represents an integer of 1 to 3, c and d represents an integer of 0 to 8, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

R3和R4与式(1-1)的R1相同。 R1 R3 and R4 are the same as the formula (1-1).

式(1-3)中,作为取代基R3和R4从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 In the formula (1-3), R3 and R4 as a substituent group from the superior radiation transmittance 193nm viewpoint, the number of carbon atoms, preferably 1 to 10 aliphatic saturated hydrocarbon, alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,出于与(1-1)中R1相同的理由,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环族饱和烃基。 In the above-mentioned substituents, and for (1-1) R1 in the same reason, the number of carbon atoms is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14.

优选的n5和n6为1~3,特别优选为1或2,c和d为0或1或2。 Preferred n5 and n6 is 1 to 3, particularly preferably 1 or 2, c and d is 0 or 1 or 2. 由于例如在193nm下的折射率增高,因而特别优选c和d两者都为0。 Because of increased refractive index, for example, at 193nm, and it is particularly preferably c and d are both 0. 以下示出优选的化合物(1-3)的具体例子。 The following shows a specific example of a preferred compound (1-3).

作为式(1-3)中优选的例子,可以列举螺[5.5]十一烷。 Examples (1-3) are preferred formula include spiro [5.5] undecane.

式(1-4)的(a)、(b)、(c)中,B表示亚甲基或亚乙基,R5表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,当存在多个R5时,该R5可以相同也可以不同,2个或更多个R5可以相互结合形成环结构,e表示0~10的整数,n7表示1~3的整数,R9和R10表示碳原子数1~10的烷基。 Of formula (1-4) (a), (b), (c), B represents a methylene group or an ethylene group, R5 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10 carbon atoms having 3 to 14 an alicyclic hydrocarbon group, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si (R9) 3 group, or -SO3R10 group, when a plurality of R5, R5 which may be the same or different , two or more R5 may be bonded to each other to form a ring structure, e represents an integer of 0 to 10, N7 represents an integer of 1 to 3, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

R5与式(1-1)的R1相同。 R1 R5 the same as in the formula (1-1).

式(1-4)中,作为取代基R5,从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 In the formula (1-4), as a substituent group R5, in view of excellent transmittance of 193nm radiation viewpoint, the number of carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,出于与(1-1)的R1相同的理由,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基。 In the above-mentioned substituents, the same as for the (1-1) R1 reason, the number of carbon atoms, preferably 1 to 10 aliphatic saturated hydrocarbon, alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms.

优选的c为0或1或2,n7为1~3,特别优选为1或2。 C is preferably 0 or 1 or 2, N7 1 to 3, particularly preferably 1 or 2. 由于例如在193nm下的折射率增高,因而特别优选e为0的情况。 Because of increased refractive index, for example, at 193nm, which is particularly preferably e is zero. 以下示出优选的化合物(1-4)的例子。 Preferred compounds shown below (1-4) is an example.

作为式(1-4)中优选的化合物,可以列举式(2-2)、式(2-2')所示的化合物。 Preferred formula (1-4) compound may include a compound of formula (2-2), the formula (2-2 ') of.

式(2-2)、(2-2')中,R5与式(1-4)中的R5相同,优选的i为0、1或2。 Of formula (2-2) and (2-2 '), the same as R5 in the formula (1-4) R5, i is preferably 0, 1 or 2. 出于与(1-1)中的a相同的理由,特别优选i为0。 For those in (1-1) a same reason, particularly preferably i is 0.

作为优选的化合物(2-2)、(2-2')的具体例子,可以列举上述(1-4-1)~(1-4-6)的化合物。 Preferred examples of the compound (2-2), (2-2 ') Specific examples of the compound (1-4-1) - (1-4-6) described above can be exemplified.

作为特别优选的具体例子,可以列举挂-四氢双环戊二烯。 As particularly preferred examples include hang - THDCPD.

式(1-5)中,R6表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,f表示0~10的整数,当存在多个R6时,该R6可以相同也可以不同,R9和R10表示碳原子数1~10的烷基。 In the formula (1-5), R6 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, f represents an integer of 0 to 10, when a plurality of R6, which may be the same or different from R6, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, .

R6与式(1-1)的R1相同。 R1 R6 the same as in the formula (1-1).

式(1-5)中,作为取代基R6,从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 Formula (1-5), examples of the substituent R6, from the viewpoint of excellent transmittance 193nm radiation, the number of carbon atoms is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,出于与式(1-1)的R1相同的理由,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环族饱和烃基。 In the above-mentioned substituents, the same reasons for R1 in the formula (1-1), the number of carbon atoms is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14.

优选的f为1或2。 Preferably f is 1 or 2. 另外,取代基的位置优选桥头位。 Further, the substituent is preferably at the bridgehead position.

作为式(1-5)中优选的例子,可以列举以下式所示的化合物。 Formula (1-5) Preferred examples of the compound represented by the following formula can be exemplified.

式(1-6)中,R8和R8'表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,g和h分别表示0~6的整数,n8和n9表示1~3的整数,R9和R10表示碳原子数1~10的烷基。 In the formula (1-6), R8 and R8 'represent an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, fluorine-substituted hydrocarbon group, -Si (R9) 3 group, or -SO3R10 group, g and h each represent an integer of 0 to 6, n8 and n9 represent an integer of 1 to 3, R9 and R10 represent alkyl having 1 to 10 carbon atoms is base.

R8和R8'与式(1-1)的R1相同。 The same as R1 R8 and R8 'in the formula (1-1).

式(1-6)中,作为取代基R8和R8',从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 In the formula (1-6), the substituent R8 and R8 ', starting from the superior radiation transmittance 193nm viewpoint, the number of carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, alicyclic saturated 3 to 14 hydrocarbon group, a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

在上述取代基中,出于与式(1-1)中R1相同的理由,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环族饱和烃基。 In the above-mentioned substituents, for formula (1-1) in the same reason as R1, the number of carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14.

优选的g和h为0、1或2,n8和n9为1~3,特别优选为1或2。 Preferred g and h is 0, 1 or 2, N8, and n9 is from 1 to 3, particularly preferably 1 or 2.

以下示出优选的化合物(1-6)的具体例子。 The following illustrates specific examples of preferred compounds (1-6).

作为式(1-6)中优选的例子,可以列举5-硅环[4,4]壬烷。 Examples (1-6) is preferred formula include silicon 5- [4, 4] nonane.

式(1-7)中,R11和R12表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n10、n11各自独立地表示1~3的整数,j、k表示0~6的整数,当R11和R12各自存在多个时,该R11和R12可以相同也可以不同,2个或更多个R11可以相互结合形成环结构,或者2个或更多个R12可以相互结合形成环结构,X表示单键、碳原子数2~10的2价的脂肪族烃基、碳原子数3~14的2价的脂环烃基,R9和R10表示碳原子数1~10的烷基。 In the formula (1-7), R11 and R12 represent a fluorine carbon atoms, an aliphatic hydrocarbon group having 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, substituted hydrocarbyl, -Si (R9) 3 group, or -SO3R10 group, n10, n11 each independently represents an integer of 1 to 3, j, k represents an integer of 0 to 6, when a plurality of R11 and R12, which R11 and R12 may be the same or different, two or more of R11 may be bonded to each other to form a ring structure, or two or more of R12 may be bonded to each other to form a ring structure, X represents a single bond, having 2 to 10 carbon atoms divalent aliphatic hydrocarbon group having 2 carbon atoms, divalent alicyclic hydrocarbon group having 3 to 14, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

R11和R12的碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基与式(1-1)中的脂肪族烃基、脂环烃基、氟取代烃基、-Si(R9)3基、-SO3R10基相同。 Carbon atoms, R11 and R12 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si (R9) 3 group, or a group of -SO3R10 in the formula (1-1) aliphatic hydrocarbon group, alicyclic hydrocarbon group, a fluorine-substituted hydrocarbon group, -Si (R9) 3 group, the same group -SO3R10.

式(1-7)中,作为取代基R11和R12,从193nm的放射线透射率优异的观点出发,优选碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基、氰基、氟原子、碳原子数1~10的氟取代饱和烃基。 In the formula (1-7), as the substituents R11 and R12, in view of excellent transmittance of 193nm radiation viewpoint, the number of carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 , a cyano group, a fluorine atom, carbon atoms and 1 to 10 fluoro-substituted saturated hydrocarbon group.

另外,作为X的碳原子数2~10的2价的脂肪族烃基,可以列举亚乙基、亚丙基,作为碳原子数3~14的2价的脂环烃基,可以列举源自环戊烷、环己烷的2价基团等。 Further, the carbon atoms X is a divalent aliphatic hydrocarbon group having 2 to 10 include ethylene, propylene, 2 carbon atoms of the monovalent alicyclic hydrocarbon group having 3 to 14 include cyclopentyl from dioxane, cyclohexane and the like divalent group.

式(1-7)中,X优选为单键。 In the formula (1-7), X is preferably a single bond. 以下示出优选的化合物(1-7)的具体例子。 The following illustrates specific examples of preferred compounds (1-7).

作为优选的式(1-7)的例子,可以列举双环己基(dicyclohexyl)、双环戊基(dicyclopentyl)。 Preferred examples of formula (1-7) include dicyclohexyl (dicyclohexyl), cyclopentyl bis (dicyclopentyl).

式(1-8)中,R13表示碳原子数大于等于2的烷基、碳原子数大于等于3的脂环烃基、氰基、羟基、氟原子、碳原子数2~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,p表示1~6的整数,当存在多个R13时,该R13可以相同也可以不同,2个或更多个R13可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基。 In the formula (1-8), R13 represents 2 or more carbon atoms of the alkyl group, number of carbon atoms greater than or equal to 3 alicyclic hydrocarbon group, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 2 to 10, -Si (R9) 3 group, or -SO3R10 -, p represents an integer of 1 to 6, when a plurality of R13, the R13 may be the same or different, two or more of R13 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.

优选的R13是碳原子数2~10的烷基、碳原子数3~14的脂环烃基,优选的p为1或2,特别优选的p为1。 R13 is preferably an alkyl group having 2 to 10 carbon atoms, alicyclic hydrocarbon group having 3 to 14 carbon atoms, p is preferably 1 or 2, p is particularly preferably 1.

上述碳原子数大于等于2的烷基优选碳原子数2~10的烷基,可以列举甲基、乙基、正丙基等。 The above-described alkyl group having a carbon number not less than 2 carbon atoms is preferably an alkyl group having 2 to 10 include methyl, ethyl, n-propyl group. 上述碳原子数大于等于3的脂环烃基优选碳原子数3~14的脂环烃基,可以列举环己基、降冰片基等。 The above-described number of carbon atoms greater than or equal alicyclic hydrocarbon group is preferably a carbon atom of the alicyclic hydrocarbon group having 3 to 14 3, may include a cyclohexyl group, norbornyl and the like. 碳原子数2~10的氟取代烃基、-Si(R9)3基、或-SO3R10基与式(1-1)中的氟取代烃基、-Si(R9)3基、或-SO3R10基相同。 Carbon atoms, a fluorine-substituted hydrocarbon group having 2 to 10, the -Si (R9) 3 group, or a group of the formula -SO3R10 (1-1) fluoro-substituted hydrocarbon group, the same as -Si (R9) 3 group, or a -SO3R10 group. 2个或更多个R13相互结合形成的环结构可以列举环戊基、环己基等。 Two or more R13 bonded to each other to form a ring structure include a cyclopentyl group, a cyclohexyl group and the like.

以下示出式(1-8)中优选化合物的具体例子。 The following shows a specific example of preferred compounds of formula (1-8).

式(1-9)中,R14表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n12表示1~3的整数,q表示0~9的整数,当存在多个R14时,该R14可以相同也可以不同,R9和R10表示碳原子数1~10的烷基。 In the formula (1-9), R14 represents aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or a group -SO3R10, N12 represents an integer of 1 to 3, q ​​represents an integer of 0 to 9, when a plurality of R14, the R14 may be the same or different, R9 and R10 represents a carbon atoms of an alkyl group having 1 to 10.

R14与式(1-1)中的R1相同。 R1 to R14 are the same as in the formula (1-1). 另外,优选的R14与优选的R1相同。 Further, R14 is preferably the same with the preferred R1. 优选的q与a相同。 Q is preferably the same as a.

以下示出式(1-9)中优选化合物的具体例子。 The following shows a specific example of preferred compounds of formula (1-9).

式(1-1)~式(1-9)中,特别优选的化合物是具有式(1-1)、式(1-4)所示化学结构,并且这些化合物是非取代、或被碳原子数1~10的脂肪族饱和烃基、碳原子数3~14的脂环饱和烃基取代的化合物,其中特别优选非取代的化合物。 Formula (1-1) to (1-9), particularly preferred compounds are those having the formula (1-1), the formula (1-4) shown in the chemical structure, and these compounds are non-substituted, or the number of carbon atoms 1 to 10 aliphatic saturated hydrocarbon, alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms substituted compounds, especially preferred unsubstituted compounds.

上述化合物在浸液曝光装置工作的温度下是液体,出于上述(iii)式、(iv)式的理由,优选折射率高于纯水。 The above-described compound is liquid at the temperature of liquid immersion exposure apparatus to work for the reasons above-mentioned formula (iii), (iv) the formula, preferably higher refractive index than water.

具体地讲,优选折射率是水与曝光前的抗蚀膜(或者浸液用上层膜)之间的值,并且为与水相比更高的值,在25℃下,波长193nm下的折射率为1.45~1.8,优选为1.6~1.8的范围,在25℃下,波长248nm下的折射率为1.42~1.65,优选为1.5~1.65的范围。 Specifically, preferably a refractive index of the resist film (or an immersion upper layer film) between the value before water exposure, and to a higher value compared to water at 25 ℃, refraction at a wavelength of 193nm ratio of 1.45 to 1.8, preferably in the range 1.6 to 1.8, at 25 ℃, a refractive index at a wavelength of 248nm is 1.42 to 1.65, preferably in the range 1.5 to 1.65. 另外,在25℃下,D射线(波长589nm)下的折射率为大于等于1.4,优选为1.4~2.0,更优选为1.40~1.65的范围。 Further, at 25 ℃, refractive index at a D-ray (wavelength 589 nm) greater than or equal to 1.4, preferably 1.4 to 2.0, and more preferably in the range 1.40 to 1.65.

另外,由于使用环境的变化引起的折射率变化成为散焦的原因,因此本化合物优选为折射率不易受温度、压力等影响的化合物。 Further, the use of the refractive index change caused by a change in the environment cause defocus, and thus the present compound is preferably a refractive index less susceptible to temperature, pressure and the like compounds. 可以预测由于透镜、抗蚀剂材料的光吸收带来的发热,温度在使用时会发生变化,因此特别优选折射率的温度依赖性低。 Can predict the heat generation due to light absorption of a lens, a resist material, a temperature change will occur in use, so low temperature dependence of the refractive index particularly preferred. 具体地说,温度(T)产生的折射率(n)的变化率dn/dT的绝对值优选为5.0×10-3(℃-1)以内,更优选为7.0×10-4(℃-1)以内。 Specifically, the refractive index of the temperature (T) to generate (n) of the rate of change dn / dT is preferably an absolute value of 5.0 × 10-3 or less (-1 deg.] C), more preferably 7.0 × 10-4 (℃ -1 ) or less.

另外,从本观点出发,优选本化合物的比热为大值,具体地讲,比热的值优选大于等于0.1cal/g·℃,更优选大于等于0.30cal/g·℃。 Further, from this viewpoint, the specific heat of the present compound is preferably a large value, in particular, the value of the specific heat is preferably greater than or equal 0.1cal / g · ℃, more preferably greater than or equal 0.30cal / g · ℃.

另外,上述化合物优选其折射率不易受色差产生的影响,优选在曝光波长周边的折射率的波长依赖性小。 Further, the compound preferably has a refractive index less susceptible to chromatic aberration is generated, preferably a small wavelength dependency of the refractive index outside the exposure wavelength.

另外,作为其他特性,在远紫外区域的透光性高,粘度、氧气、氮气等气体的溶解度、与透镜、抗蚀剂(或者抗蚀剂上层膜)的接触角、表面张力、闪点等优选在下述范围内,此外,还期望与透镜、抗蚀剂材料的化学相互作用小。 As another characteristic, the light-transmissive high gas solubility, viscosity, oxygen, nitrogen, and other far ultraviolet region, the lens, the contact angle of a resist (resist upper layer or film), the surface tension, flash point preferably in the range of, in addition, a lens with desired chemical interaction small resist material. 以下详细地描述这些特性。 These characteristics described in detail below.

193nm下的放射线透射率在25℃下优选光程1mm的透射率大于等于70%,特别优选大于等于90%,进一步优选大于等于95%。 The radiation transmittance at 193nm at 25 deg.] C preferably 1mm light path transmittance of 70% or more, particularly preferably 90% or more, more preferably 95% or more. 此时,如果透射率低于70%,容易引起由液体的光吸收产生的热能引起的发热,容易产生由温度上升引起的折射率改变带来的光学像的散焦和变形。 At this time, if the transmittance is less than 70%, prone to heat the heat generated due to light absorption by the liquid, defocus easily generated by a change in refractive index caused by temperature rise and the optical image deformation. 另外,由于液体的吸收,成为到达抗蚀膜的光量减少,引起产量大幅降低的原因。 Further, due to absorption of the liquid, the amount of light becomes reduced reaching the resist film, the cause of the yield is significantly reduced.

对于粘度,20℃的粘度为小于等于0.5Pa·s,尤其当在晶片与透镜材料之间的间隙为小于等于1mm的环境中使用时,优选为小于等于0.01Pa·s,特别优选为小于等于0.005Pa·s。 When the viscosity, a viscosity of less than 20 ℃ equal to 0.5Pa · s, especially when the gap between the wafer and the lens material is 1mm or less used in an environment, preferably less than equal to 0.01Pa · s, particularly preferably less than or equal 0.005Pa · s. 如果粘度超过0.5Pa·s,液体难以浸入抗蚀膜(或者浸液用上层膜)与透镜材料之间的间隙,或者不能获得当利用局部浸液法作为浸液液体的供给方法,利用通过移动承载晶片的载物台对晶片进行全面曝光的步进扫描方式作为曝光方式时足够的扫描速度,引起产量的大幅降低,另外,还存在容易产生由摩擦引起的温度上升的倾向,容易受到由温度变化引起的光学特性变化的影响。 If the viscosity is more than 0.5Pa · s, the liquid immersion resist film is difficult (or an immersion upper layer film) and the gap between the lens material, or can not be obtained when using a local liquid immersion method as a method of supplying a liquid immersion, the use of mobile a step-stage carrying the wafer on the wafer as a blanket exposure of the exposure system a sufficient scanning speed, causing a significant decrease of the yield, in addition, there is also likely to occur due to friction tends to temperature rise, the temperature susceptible Effect of changes in the optical characteristics due to change. 另外,尤其在晶片与透镜材料之间的间隙为小于等于1mm的情况下,根据上述理由,粘度优选为小于等于0.01Pa·s,此时,通过降低间隙的距离(液膜的厚度),能够提高液体的透射率,能够使之难以受到液体吸收的影响,因而是合适的。 In the case where, in particular, the gap between the wafer and the lens material is 1mm or less, according to the above reasons, viscosity is preferably less 0.01Pa · s, this time, by reducing the clearance distance (thickness of the liquid film), can be improving the transmittance of the liquid, so that it can be hardly affected by liquid absorption, and thus is suitable.

另外,粘度增大时,容易产生液中生成气泡(纳米泡、微泡),另外,该气泡的寿命延长,因而不合适。 Further, when the viscosity increases, the generation of the bubble generation liquid is easy (nano-bubbles, microbubbles), further, to extend the lifetime of the bubbles, and therefore inappropriate.

另外,对于气体在本发明涉及的液体中的溶解度,以氧气和氮气在25℃、分压为1个大气压(atm)时液体中的气体摩尔分数表示的溶解度优选为0.5×10-4~70×10-4,进一步优选为2.5×10-4~50×10-4,当这些气体的溶解度为小于等于0.5×10-4时,由抗蚀剂等产生的纳米泡难以消失,因此,由于气泡引起的光散射,在图案形成时容易产生抗蚀剂的缺陷。 Further, the solubility of the gas in the liquid in the present invention relates to oxygen and nitrogen at 25 ℃, a partial pressure of 1 atmosphere (atm) the mole fraction of gas in the liquid is preferably represented by the solubility of 0.5 × 10-4 ~ 70 × 10-4, more preferably 2.5 × 10-4 ~ 50 × 10-4, when the solubility of the gas is 0.5 × 10-4 or less, the resist or the like generated by the nano-bubbles disappear difficult, therefore, because light scattering caused by bubbles, prone to defects in the resist pattern formation. 另外,如果为大于等于70×10-4,在曝光时会吸收周围的气体,容易受到由气体吸收引起的光学特性变化的影响。 Further, if not less than 70 × 10-4, upon exposure absorbs ambient gas is easily affected by optical characteristics caused by gas absorption changes.

另外,本发明的液体与抗蚀剂(或者浸液用上层膜)之间的接触角优选为20°~90°,进一步优选为50°~80°,另外,与石英玻璃或CaF2等透镜材料的接触角优选为小于等于90°,更优选为小于等于80°。 Further preferably the contact angle between the liquid and the resist of the present invention (or an immersion upper layer film) is 20 ° ~ 90 °, more preferably 50 ° ~ 80 °, addition, and the like quartz glass or CaF2 lens material the contact angle is preferably less than or equal to 90 °, more preferably less than equal to 80 °. 如果本发明的液体与曝光前的抗蚀剂(或者浸液上层膜)的接触角为小于等于20°,液体难以浸入间隙,另外,当利用上述局部浸液法和步进扫描方式的组合作为曝光方式时,液体容易飞散到膜中。 If the contact angle before the liquid according to the present invention and the exposure of the resist (or the immersion upper layer film) is less than or equal to 20 °, the liquid immersion space is difficult. Further, when using a combination of the local liquid immersion method and a step-and-as exposure mode, the liquid is likely to scatter into the film. 另一方面,如果本发明的液体与曝光前的抗蚀剂(或者浸液上层膜)的接触角大于等于90°,在具有凹凸的抗蚀剂(或者上层膜)界面处容易吸收气体,容易产生气泡。 On the other hand, if the contact angle before the liquid according to the present invention and the exposure of the resist (or the immersion upper layer film) is not less than 90 °, having a concavo-convex resist (or the upper film) easily absorbed gas interface, easy bubbles. 这样的现象记载于ImmersionLithography Modeling 2003 Year-End Report(InternationalSEMATECH)。 This phenomenon is described in ImmersionLithography Modeling 2003 Year-End Report (InternationalSEMATECH).

另外,如果本发明的液体与透镜材料的接触角超过90°,存在透镜表面和液体之间产生气泡的倾向。 Further, if the contact angle of the liquid with the lens material of the present invention is more than 90 °, tends to produce bubbles between the lens surface and the liquid.

另外,尤其当用于与现在水的浸液曝光中使用的同样的利用局部浸液法进行浸液的步进扫描方式的曝光装置时,扫描时的液体的飞散成为问题,因此本发明的液体优选表面张力高。 Further, particularly when used in a scanning exposure apparatus by a step of the immersion embodiment is now using the same local liquid immersion water immersion exposure method used, the scattering of the liquid during scanning becomes a problem, so that the liquid of the present invention preferred high surface tension. 具体地讲,20℃的表面张力优选为5dyn/cm~90dyn/cm,进一步优选为20dyn/cm~80dyn/cm。 Specifically, 20 ℃ surface tension is preferably 5dyn / cm ~ 90dyn / cm, more preferably from 20dyn / cm ~ 80dyn / cm.

当本发明的液体与抗蚀剂表面的接触角不合适时,通过使用适当的浸液上层膜能够改善接触角。 When the contact angle of the liquid with the resist surface of the present invention not suitable, by using an appropriate immersion upper layer film can improve the contact angle. 特别是由于本发明的液体是低极性,因而通过使用高极性上层膜能够提高接触角。 In particular, since the liquid of the present invention are low polarity, by using a high polarity and thus can improve the contact angle of the upper film.

该液体产生的光酸发生剂、碱性成分等的抗蚀剂成分的洗脱不仅对抗蚀剂的图案形成性能产生缺陷,对轮廓劣化等产生不良影响,而且还引起液体本身的污染,例如成为液体的光学特性的变化或透镜的侵蚀等的原因。 Elution of the resist composition photoacid generator, basic component of the liquid or the like to produce not only a resist pattern is formed on a defect performance, an adverse effect on deterioration of the profile, but also cause contamination of the liquid itself, for example, be or the reasons for the changes of the optical characteristics of the lens erosion like liquid. 另外,因此液体的再利用变得困难,需要频繁的进行液体精制。 Further, thus recycling the liquid becomes difficult, the need for frequent purified liquid. 因此,优选由液体的洗脱引起的污染少。 Thus, preferably less pollution caused by elution liquid. 可以利用采用HPLC等的方法评价洗脱量,但是,更准确地说,193nm下的吸光度对于抗蚀剂中的成分的混入非常敏感,因此可以通过跟踪后者的变化进行评价。 And the like may be utilized by HPLC method for evaluating the elution volume, but, more specifically, the absorbance at 193nm is very sensitive to the resist composition is mixed, it can be evaluated by tracking changes in the latter. 作为具体对于液体的要求,在后述评价方法中采用“抗蚀剂接触时的吸光度变化”的浸渍试验中浸渍180秒后每1cm的吸光度变化(浸渍后的吸光度-浸渍前的吸光度)为小于等于0.05,优选为小于等于0.02,进一步优选为小于等于0.005。 The liquid requirements, the "absorbance changes resist contacting" as a specific evaluation method described later after the immersion test was immersed in 180 seconds per 1cm absorbance change (absorbance after immersion - absorbance before immersion) of less than equal to 0.05, preferably 0.02 or less, more preferably 0.005 or less.

本发明的液体优选为在使用环境下爆炸、着火、引火等危险性低的化合物。 The present invention is preferably liquid at ambient explosion, fire, low risk of ignition and the like compounds. 具体地讲,闪点优选为大于等于25℃,进一步优选为大于等于50℃,燃点优选为大于等于180℃,进一步优选为大于等于230℃。 Specifically, the flash point is preferably not less than 25 ℃, more preferably not less than 50 ℃, ignition point is preferably not less than 180 ℃, more preferably not less than 230 ℃. 另外,25℃的蒸汽压优选为小于等于50mmHg,进一步优选为小于等于5mmHg。 Further, 25 ℃ preferably less vapor pressure 50mmHg, more preferably 5 mmHg or less.

另外,优选对人体、环境的危害性低,具体地讲,关于对于人体的有害性,优选急性毒性低,没有致癌性、致变异性、促畸形性、生殖毒性等的化合物。 Further, preferably human low, harmful environment, in particular, are harmful to human bodies on, preferably low acute toxicity, no carcinogenicity, induced variability, pro malformation, reproductive toxicity like compound. 具体地讲,容许浓度优选为大于等于30ppm,进一步优选为大于等于70ppm,优选Ames试验结果为阴性的液体。 Specifically, the allowable concentration is preferably not less than 30 ppm or, more preferably not less than 70ppm, preferably Ames test was negative liquid. 关于对于环境的有害性,优选没有残留性、生态累积性的化合物。 Harmful on the environment, there is no residual property, the compounds of the preferred cumulative ecological.

另外,本发明的液体优选利用气相色谱测定的纯度为大于等于95.0重量%,特别优选为大于等于99.0重量%,进一步优选纯度为大于等于99.9重量%。 Further, the present invention is preferably liquid by gas chromatographic purity of greater than or equal to 95.0% by weight, particularly preferably not less than 99.0% by weight, more preferably having a purity of not less than 99.9% by weight.

优选特别在193nm等曝光波长下吸光度大的含有烯烃的化合物、含有芳香环的化合物、含有硫(硫化物、亚砜、砜结构)、卤素、羰基、醚基的化合物等的比例低于0.01重量%,特别优选低于0.001重量%。 In particular the ratio is preferably at the exposure wavelength of 193nm absorbance large like the olefin-containing compound, an aromatic ring-containing compound, sulfur (sulfide, sulfoxide, sulfone structure), a halogen, a carbonyl group, an ether group, and the like containing compound is less than 0.01 wt. %, particularly preferably less than 0.001 wt%.

另外,由本化合物组成的液体用于半导体集成电路制造工序,因此优选金属或金属盐含量低,具体地讲,金属含量为小于等于100ppb,优选为小于等于10ppb,进一步优选为小于等于1.0ppb。 Further, the liquid composition of the present compound for a semiconductor integrated circuit manufacturing process, and therefore preferably low content of metal or metal salt, in particular, a metal content of 100 ppb or less, preferably 10 ppb or less, more preferably 1.0 ppb or less. 如果金属含量超过100ppb,金属离子或金属成分可能会给抗蚀膜等带来不良影响,污染晶片。 If the metal content exceeds 100 ppb or, metal ion or metal component may give an adverse effect on the resist film, contamination of the wafer.

作为金属,可以列举选自Li、Na、K、Mg、Cu、Ca、Al、Fe、Zn、Ni的至少1种金属。 Examples of the metal include at least one metal selected from Li, Na, K, Mg, Cu, Ca, Al, Fe, Zn, Ni is. 这些金属能够通过原子吸光法进行测定。 These metals can be measured by atomic absorption spectrometry.

另外,该液体中的氧浓度为小于等于100ppm(100μg/ml),优选为小于等于10ppm,更优选为小于等于2ppm。 Further, the oxygen concentration in the liquid is less 100ppm (100μg / ml), preferably not greater than 10ppm, more preferably less than equal to 2ppm. 另外,尤其在曝光时优选为小于等于1ppm,进一步优选为小于等于10ppb。 Further, especially when the exposure is preferably 1 ppm or less, more preferably less than equal to 10ppb. 如果氧浓度超过100ppm,存在容易产生由溶解氧引起的氧化反应等造成的透射率下降的趋势。 If the oxygen concentration exceeds 100 ppm, the transmittance of trends easily occur by the oxidation reaction due to dissolved oxygen, etc. due to the decline. 另外,即使不引起氧化反应等,如果溶解有氧,例如如实施例所示,由于溶解氧以及在向氧照射放射线时产生的臭氧的吸收,因此根据溶解氧浓度而液体的吸光度降低。 Further, without causing oxidation reactions, if dissolved oxygen, for example, as shown in the embodiment, since the absorption of the dissolved oxygen and ozone generated when radiation is irradiated to an oxygen, and thus dissolved oxygen concentration according to the decrease in the absorbance of the liquid. 另外,如果在氧共存下曝光液体,生成的臭氧会氧化液体,加速液体的劣化。 Further, if the exposure liquid coexistence of oxygen, ozone generated by the oxidation of liquid, accelerated deterioration of the liquid.

另外,特别当进行偏振光曝光时,如果具有旋光性,会导致光学对比度降低,因此,本液体优选为不具有旋光性的液体。 Further, especially when the polarized light exposure, if optically active, leads to reduced optical contrast, therefore, the present liquid is preferably a liquid having no optically active. 具体地讲,构成本液体的化合物优选为不具有旋光性(没有光学活性)的化合物,当构成液体的化合物是具有旋光性(光学活性)的化合物时,优选含有等量的光学异构体(作为消旋体存在),液体整体不具有光学活性。 In particular, the present compounds constituting the liquid is preferably a compound having no optically active (optically inactive) when the compound constituting the liquid is an optically active compound (optically active) having preferably contains the same amount of optical isomers ( present as racemates), an optically inactive liquid whole.

本发明的化合物能够以市售的化合物得到,或者能够通过已知的各种合成法,由可以获得的原料进行制造。 The compounds of this invention can be obtained commercially available compounds, or can be synthesized by various known methods, can be produced from the obtained raw materials. 以下,通过列举具体例子,对本化合物的制备方法进行说明。 Below, the method of preparation of the present compounds will be explained by listing specific examples.

例如,对于式(2-1)所示的化合物,能够通过使用适当的催化剂,采用接触氢化对产自煤炼焦炉的干馏油、石油类接触重整油和流动接触分解油、以及在乙烯的制造副产物的石脑分解油等所含的萘或萘衍生物进行核加氢而制造。 For example, the formula (2-1) compound represented by the use of a suitable catalyst can be used for the catalytic hydrogenation of coal produced from coke oven carbonization oil, petroleum oil and contacted with the reforming oil fluid catalytic cracking, as well as ethylene producing naphtha decomposition byproducts of naphthalene or naphthalene derivatives of the oil contained in the nuclear hydrogenation is manufactured.

在上述接触重整油、流动重整油、石脑分解油中,除了萘、烷基萘之外,还含有苯、烷基苯、菲、蒽、其他多环芳香族及其衍生物、苯并噻吩及其衍生物等含硫化合物、吡啶及其衍生物等含氮化合物,作为原料的萘和萘衍生物能够通过由这些的混合物中进行分离精制而得到。 In the contact reformate, reformate flow, naphtha decomposition oil, in addition to naphthalene, alkylnaphthalenes, also contains benzene, alkylbenzenes, phenanthrene, anthracene, and other polycyclic aromatic derivatives, phenylenediamine nitrogen-containing compounds and sulfur-containing thiophene compounds and derivatives thereof, pyridine and its derivatives such as naphthalene and naphthalene derivatives can be obtained by starting material was separated and purified by a mixture of these.

在用于制造上述化合物(2-1)的萘和萘衍生物中,优选上述中含硫化合物的含量低。 Naphthalene and naphthalene derivatives used in the above-mentioned compound (2-1), a low content of sulfur-containing compound is preferably above. 此时,含硫化合物的含量优选为小于等于100ppm,进一步优选为小于等于50ppm。 In this case, the content of the sulfur-containing compound is preferably 100 ppm or less, more preferably less than equal to 50ppm. 如果含硫化合物的含量超过100ppm,该含硫化合物会引起接触氢化时的催化剂中毒,妨害核加氢反应的进行,此外,在化合物(2-1)中混入源自该含硫化合物的含硫杂质,通过精制不能除去时,会引起本发明液体在193nm等曝光波长下的透射率降低。 If the content of the sulfur-containing compound exceeds 100 ppm, the sulfur-containing compound can cause poisoning of the catalytic hydrogenation catalyst, hinder the nuclear hydrogenation reaction, in addition, the compound (2-1) is mixed in the sulfur-containing compound from the sulfur-containing impurities can not be removed through refining, it causes the liquid present invention reduces the transmittance at the exposure wavelength such as 193nm.

另外,当制造化合物(2-1)中的顺-十氢化萘或反-十氢化萘及其混合物时,特别优选作为原料的萘的纯度高,优选萘的纯度为大于等于99.0%,特别优选的萘的纯度为大于等于99.9%。 Further, when manufacturing a cis compound (2-1) - or trans decalin - when decalin and mixtures thereof, particularly preferred as a raw material of high purity naphthalene, preferably naphthalene purity of not less than 99.0%, particularly preferably naphthalene purity not less than 99.9%. 此时,当作为杂质的含硫化合物等的含量高时,除了会引起上述问题之外,当含有作为杂质的其他萘衍生物、芳香族化合物及其衍生物时,生成这些杂质进行加氢得到的难以分离的烃化合物,十氢化萘的纯度控制变得困难。 At this time, when high sulfur-containing compound as an impurity content such as, in addition to the above-described problems caused when the other contains a naphthalene derivative as an impurity, aromatic compounds and derivatives thereof, these impurities generated was hydrogenated to give difficult to separate the hydrocarbon compounds, decalin purity difficult to control.

另外,作为接触氢化的催化剂,除了镍类、铂、铑、钌、铱、钯等贵金属类催化剂,还可以使用钴·钼、镍·钼、镍·钨等的硫化物。 As the hydrogenation catalyst, in addition to nickel-based, platinum, rhodium, ruthenium, iridium, palladium and other precious metal catalysts, may also be used cobalt-molybdenum sulfide, nickel-molybdenum, nickel-tungsten, or the like. 其中,考虑到其催化活性、成本,优选镍类催化剂。 Wherein, considering the catalytic activity, cost, preferably nickel-based catalyst.

另外,这些金属催化剂优选负载在适当的载体上使用,此时,通过使催化剂高度分散在载体上,氢化的反应速度提高,此外,尤其防止高温、高压条件下的活性中心劣化,而且提高对于催化剂中毒的抵抗力。 Further, these metal catalysts used is preferably supported on a suitable carrier, this time, by making the catalyst highly dispersed in the carrier, the hydrogenation reaction rate increase, in addition, in particular to prevent the active centers of degradation under high temperature and pressure conditions, and to improve the catalyst resistance to poisoning.

作为该载体,可以优选使用SiO2、γ-Al2O3、Cr2O3、TiO2、ZrO2、MgO、ThO2、硅藻土、活性炭等。 Examples of the carrier, can be preferably used SiO2, γ-Al2O3, Cr2O3, TiO2, ZrO2, MgO, ThO2, diatomaceous earth, activated carbon.

另外,作为上述接触氢化的方法,可以利用不使用溶剂的气相法和将原料溶解于适当溶剂进行反应的液相法。 Further, as the method of catalytic hydrogenation can be utilized without using a solvent and a vapor phase method starting material dissolved in a suitable solvent in the liquid-phase reaction method. 其中,由于在成本以及反应速度方面优异,因而优选气相法。 Wherein, due to cost, and excellent in terms of reaction speed, a gas phase method is preferable.

当使用气相法时,作为催化剂,优选镍、铂等。 When a vapor phase method, or the like as a catalyst, preferably nickel, platinum. 使用的催化剂的量越多,反应速度越高,但从成本方面考虑,并不优选。 The more amount of the catalyst used, the higher the reaction rate, but in view of cost, it is not preferable. 因此,为了加快反应速度而使反应结束,优选减少催化剂量,在温度以及氢压高的条件下进行反应。 Accordingly, in order to accelerate the completion of the reaction the reaction rate, reduce the amount of the catalyst is preferably carried out at a temperature and a high hydrogen pressure conditions. 具体地优选在催化剂量相对于原料萘(萘衍生物)为0.01~10重量份、氢压为5~15MPa、反应温度为100℃~400℃左右下进行反应。 Particularly preferably in a catalytic amount with respect to the raw material naphthalene (naphthalene derivative) is 0.01 to 10 parts by weight, a hydrogen pressure of 5 ~ 15MPa, reaction temperature is about 100 ℃ ~ 400 ℃ the reaction.

另外,利用例如专利文献(特开2003-160515)中记载的方法,采用使用镍或铂、钯系催化剂由中间体四氢化萘中除去萘的方法,在温和的条件下也能够得到目标产物。 Further, a method using, for example Patent Document (Laid-Open 2003-160515) describes, using a nickel or platinum, a palladium-based catalyst naphthalene removed from the intermediate tetralin, under mild conditions, the target product can be obtained.

在上述反应中,反应转化率优选为大于等于90%,进一步优选为大于等于99%。 In the above reaction, the reaction conversion rate is preferably greater than or equal to 90%, more preferably greater than or equal to 99%.

上述反应后,优选通过进行适当的精制,除去未反应原料、催化剂等杂质。 After the above reaction is preferably carried out by an appropriate purification, to remove the unreacted starting material impurities and catalyst.

作为上述精制方法,可以利用精馏、水洗、浓硫酸洗涤、过滤、晶析等精制方法以及它们的组合。 As the purification method, it can be utilized, washed with distillation, sulfuric acid washing, filtration, crystallization and other purification methods, and combinations thereof. 其中,对于非挥发性的源自催化剂的金属及其他金属的去除、源自原料的成分两者的去除有效,因而优选精馏。 Wherein, for the removal of metals and other metals from the non-volatile catalyst, the raw material is removed from both the active ingredients, distillation is preferable. 另外,为了除去源自催化剂的金属,优选进行与催化剂相应的脱金属处理。 In order to remove the metal from the catalyst, preferably with a catalyst corresponding demetallation.

上述化合物中的四氢双环戊二烯能够通过下列步骤制得:在适当的条件下对已知作为光学透镜、光学薄膜用树脂的原料单体有用的双环戊二烯(外(exo)、内(endo)混合物)或内双环戊二烯进行加氢,通过蒸馏等方法精制所得四氢双环戊二烯。 THDCPD obtained in the above compounds can be prepared by the steps of: under appropriate conditions known as an optical lens, an optical film with the base resin useful monomers dicyclopentadiene (outer (Exo), the hydrogenated dicyclopentadiene (Endo) mixture), or within, the resulting tetrahydro-dicyclopentadiene purification method such as distillation. 当由双环戊二烯中要选择性地得到外异构体时,通过利用适当的催化剂对双环戊二烯异构体混合物进行异构化,从而选择性地得到外体,进行上述加氢反应,或者利用适当的催化剂对通过内(内、外混合)的双环戊二烯的加氢得到的内(内,外混合)四氢双环戊二烯进行异构化,从而能够选择性地得到外四氢双环戊二烯。 When the dicyclopentadiene to be selectively obtained exo isomers, by dicyclopentadiene isomer mixture using a suitable isomerization catalyst to selectively obtain the outer body, the above hydrogenation reaction , or within a suitable hydrogenation catalyst by using the (internal and external mixing) dicyclopentadiene obtained (internal and external mixing) THDCPD isomerization, can be selectively obtained outer THDCPD.

上述双环戊二烯一般通过对石脑油的热分解产物中的所谓C5馏分中大量含有的环戊二烯进行二聚而制造。 The above-described dicyclopentadiene typically produced by dimerization of cyclopentadiene in naphtha thermal decomposition product of a so-called large amount of C5 fraction. 该双环戊二烯例如含5-异丙烯基降冰片烯等源自C5馏分的烃成分作为杂质,如果含有这些化合物,加氢、异构化后,会残留源自这些杂质的烃产物,使得最终产物四氢双环戊二烯的精制变得困难。 The dicyclopentadiene-containing 5- e.g. isopropenyl drop from C5 hydrocarbon component fraction norbornene and the like as impurities, if containing these compounds, hydrogenation, after isomerization, hydrocarbon product may remain from these impurities, such the final product was purified THDCPD difficult. 因此,优选使用预先通过精制等方法高纯度化的物质。 Accordingly, it is preferable to use purified in advance by a method such as high purity material. 此时的纯度优选为大于等于95重量%,进一步优选为大于等于97重量%。 In this case preferably has a purity not less than 95 wt%, more preferably not less than 97 wt%.

另外,上述双环戊二烯优选例如导致加氢反应催化剂中毒的含硫成分的含量少,具体地讲,双环戊二烯中存在的含硫成分优选为小于等于500ppb,进一步优选为小于等于50ppb。 Further, the above-described dicyclopentadiene content of preferably, for example, results in less sulfur components poisoning the hydrogenation catalyst, in particular, dicyclopentadiene in the presence of a sulfur-containing component is preferably 500ppb or less, more preferably less than equal to 50ppb. 如果含硫成分的量为500ppb,容易妨害后续工序的加氢反应。 If the amount of the sulfur-containing component is 500ppb, easily hinder the subsequent hydrogenation step.

这里所谓该含硫成分,是指例如以游离硫、单质硫、硫化氢、硫醇类、二硫化物类、噻吩等无机或有机化合物的形式存在的硫元素的总量,能够利用具备硫化学发光检测器(SCD)的气相色谱等进行分析。 Here, the term of the sulfur components, means the total amount in the form of free sulfur, elemental sulfur, hydrogen sulfide, mercaptans, disulfides, thiophenes and other inorganic or organic compounds such as elemental sulfur, the sulfur can be provided by using the chemical analysis luminescence detector (SCD) by gas chromatography. 该硫馏分例如能够通过特开2001-181217的方法除去。 The sulfur fraction can be removed, for example by the method of Laid-Open 2001-181217. 该双环戊二烯的加氢能够利用公知的碳-碳双键的加氢催化剂进行。 Carbon double bond hydrogenation catalyst - the hydrogenated dicyclopentadiene can be a known carbon. 该加氢能够通过例如特开昭60-209536、特开2004-123762中公开的方法进行。 The hydrogenation can be carried out by, for example, Kokai 60-209536, the method disclosed in Laid-Open 2004-123762. 上述加氢后,通过进行蒸馏能够制得四氢双环戊二烯,例如要选择性地制得外体,已知利用各种路易斯酸进行异构化的方法。 After the above hydrogenation, can be prepared by distillation THDCPD, for example, to the outer body is selectively obtained, using a variety of Lewis acids are known isomerization method. 本异构化例如能够通过使用卤化铝、硫酸等作为路易斯酸的方法进行(特开2002-255866)。 This isomerization can be performed, for example, (Laid-Open 2002-255866) by using an aluminum halide, sulfate or the like as a Lewis acid method. 在本反应中,已知作为副产物生成金刚烷,但当大量存在金刚烷时,193nm下的透射率下降,因而必须使最终液体中共存的金刚烷的量为小于等于0.5重量%,优选为小于等于0.1重量%,进一步优选为小于等于0.05重量%。 In this reaction, the amount, known as a by-product adamantyl, but when a large number transmittance adamantane, at 193 nm decreases, and therefore must adamantane final liquid coexisting of 0.5 wt% or less, preferably 0.1 wt% or less, more preferably 0.05 wt% or less. 该金刚烷能够通过适当地设定上述异构化反应的条件或各种公知的精制方法除去。 Adamantane can be appropriately setting the isomerization reaction conditions or by various known purification method for removing.

以下,优选的浸液曝光用液体的结构和物性值的具体例子示于表1。 Or less, preferably by immersion exposure and a specific example of the structure of a liquid physical property values ​​are shown in Table 1.

表1 Table 1

另外,反-十氢化萘、挂-四氢双环戊二烯的各种物性数据示于表2。 Further, trans - decalin, hang - tetrahydro-dicyclopentadiene various physical properties data are shown in Table 2.

表2 Table 2

在表2中,氧溶解度和氮溶解度的值是分压1个大气压时的值,单位是ppm。 In Table 2, the solubility of nitrogen and oxygen solubility value is a value when the partial pressure of 1 atm, the unit is ppm.

本发明的浸液曝光用液体具有选自上述式(1-1)~(1-9)的结构,因而例如在193nm下的吸光度小,是合适的,但该波长范围的吸光度容易受到微量杂质的影响。 Immersion exposure liquid according to the present invention has a structure selected from the above formulas (1-1) to (1-9), such as a small and therefore the absorbance at 193nm, is suitable, the wavelength range of absorbance trace impurities vulnerable Impact. 另外,当在这些液体中存在碱成分时,即使非常微量,也会给抗蚀剂轮廓产生大影响。 Further, when the alkali component is present in the liquid, even a very small amount, will have a big impact on the resist profile. 这些杂质能够通过利用适当的方法精制上述液体而除去。 These impurities can be removed by purifying the liquid by an appropriate method. 例如,对于具有(1-1)~(1-5)、(1-7)~(1-9)的结构的饱和烃化合物,能够通过浓硫酸洗涤、水洗、碱洗涤、硅胶柱精制、精馏、碱条件下的高锰酸盐处理以及它们的组合进行精制。 For example, (1-5), (1-7) ~ ~ saturated hydrocarbon compound structure (1-9) having a (1-1), through concentrated sulfuric acid washing, water washing, alkali washing, purified by a silica gel column, fine evaporated, permanganate treatment under alkaline conditions, and combinations thereof purified.

具体地讲,例如能够通过下列步骤进行适当的精制:反复进行浓硫酸洗涤直到浓硫酸的着色消失,然后,通过水洗、碱洗涤除去浓硫酸,进而进行水洗、干燥后,进行精馏。 Specifically, for example, can be appropriately purified by the steps of: repeatedly washed with concentrated sulfuric acid until the sulfuric acid coloring disappears, then washed with water, washed with concentrated sulfuric acid to remove alkali and then washed with water, dried, and then distillation.

另外,因化合物的不同,在进行前期处理之前,通过在碱性条件下利用高锰酸盐进行处理,能够更高效地除去杂质。 Further, due to the different compounds, prior to performing the pre-treatment, the impurities can be more efficiently removed by treatment with permanganate under basic conditions.

在上述精制操作中,浓硫酸洗涤对于在193nm下吸收大的芳香族化合物、具有碳-碳不饱和键的化合物的去除是有效的,此外,对于微量碱性化合物的去除也是有效的,是优选的精制方法。 In the refining operation, the concentrated sulfuric acid washing a large absorption at 193 nm of the aromatic compound, having a carbon - carbon unsaturated bond remove compounds are effective, in addition, to remove traces of the basic compound is also effective, preferred purification method. 该处理优选根据精制的化合物,选择最佳的搅拌方法、温度范围、处理时间、处理次数进行处理。 The treatment is preferably purified compound according to choose the best method of stirring, the temperature range, the processing time, the processing times for processing.

具体地讲,温度越高,杂质除去的效率越高,但同时由于副反应容易生成导致吸收的杂质。 Specifically, the higher the temperature, the higher the efficiency of removal of impurities, but since side reactions leading to impurities generated easily absorbed. 优选的处理温度为-20℃~40℃,特别优选的处理温度为-10℃~20℃。 The preferred treatment temperature is -20 ℃ ~ 40 ℃, particularly preferred treatment temperature is -10 ℃ ~ 20 ℃.

处理时间越长,与上述芳香族化合物、具有碳-碳不饱和键的杂质的反应进一步进行,上述杂质的除去效率越高,但存在副反应产生的导致吸收的杂质的生成量增加的趋势。 The longer the treatment time with the aromatic compound having a carbon - carbon unsaturated bond reaction impurities further, the higher the efficiency of removing the impurities, but the present production amount results in the absorption of impurities produced by side reactions increase.

当利用上述浓硫酸处理进行精制时,为了完全除去处理后本发明的液体中残留的源自浓硫酸的酸性杂质、由浓硫酸处理生成的磺酸成分,优选进行碱洗涤、纯水洗涤和用于除去水分的干燥处理。 When using the purified concentrated sulfuric acid, in order to completely remove acid impurities from the liquid according to the present invention, concentrated sulfuric acid remaining after treatment, concentrated sulfuric acid component generated by the process is preferably carried out alkali washing, washing with water and drying process for removing moisture.

另外,通过在浓硫酸洗涤后进行精馏,能够更高效地除去导致吸收的杂质。 Further, after washing rectified by concentrated sulfuric acid, result in the absorption can be more efficiently remove impurities.

该精馏优选根据应当除去的杂质与本发明液体的沸点差,利用具有该分离所需的理论塔板数以上的理论塔板数的蒸馏塔进行。 The distillation boiling impurities should preferably be removed in accordance with the present invention, the difference between the liquid using a distillation column having a theoretical plate number of the theoretical plate number than required for the separation. 从除去杂质的观点出发,优选的理论塔板数为10~100,提高理论塔板数时,由于设备、制造成本提高,因此通过与其他精制方法组合,可以用比上述更低的塔板数进行精制。 From the viewpoint of removing impurities, it is preferable to theoretical plate number of 10 to 100, while increasing the number of theoretical plates, because the equipment, manufacturing cost, and thus by a combination of other purification methods, may be lower than the number of trays for purification. 特别优选的理论塔板数为30~80。 Particularly preferred theoretical plate number of 30 to 80.

此外,该精馏优选在适当的温度条件下进行。 Furthermore, the rectification is preferably performed under suitable temperature conditions. 蒸馏温度升高,存在吸收的降低效果因化合物的氧化反应等而减小的倾向。 Distillation temperature rise, tends to reduce the effect of absorption of the compound by an oxidation reaction which decreases the like. 优选的蒸馏温度为30℃~120℃,特别优选的蒸馏温度为30℃~80℃。 The preferred distillation temperature of 30 ℃ ~ 120 ℃, particularly preferred distillation temperature 30 ℃ ~ 80 ℃.

为了进行上述温度范围内的蒸馏,优选根据需要在减压下进行该精馏。 In order to carry out the distillation within the above temperature range, preferably in accordance with the required rectification under reduced pressure.

上述精制处理优选在氮或氩等惰性气体气氛下进行。 Above purification treatment is preferably carried out under an inert gas atmosphere such as nitrogen or argon. 此时,优选惰性气体中的氧浓度、有机成分浓度低。 At this time, the oxygen concentration is preferably an inert gas, a low concentration of organic components. 优选的氧浓度为小于等于1000ppm,进一步优选为小于等于10ppm,特别优选为小于等于1ppm。 The preferred oxygen concentration is less than equal to 1000ppm, more preferably less than or equal to 10ppm, particularly preferably less than or equal to 1ppm.

另外,在上述处理中,利用高锰酸盐的处理对于非芳香族的含有碳-碳不饱和键的化合物的去除特别有效,但对于具有叔碳的化合物,容易引起叔碳的氧化反应,因此适于不具有叔碳的化合物的精制。 Particularly effective in removing carbon unsaturated bond of the compound, but the compound having a tertiary carbon, it is easy to cause oxidation reaction of a tertiary carbon, therefore - In the above process, the non-aromatic carbon-containing treatment with permanganate adapted purified compound having no tertiary carbon.

另外,从防止副反应的观点出发,该处理优选在小于等于室温的低温下进行。 Further, from the viewpoint of preventing side reactions, the treatment is preferably carried out at a low temperature of room temperature or less.

作为具体例子,(顺、反混合物:Aldrich公司制造)十氢化萘、反-十氢化萘(东京化成公司制造)、采用后述实施例1所示的方法进行了精制的精制后的反-十氢化萘(1)、双环己基、异丙基环己烷、环辛烷、环庚烷、采用实施例2所示的方法进行了精制的精制后的反-十氢化萘(2)、采用实施例3所示的方法进行了精制的精制后的挂-四氢双环戊二烯(1)、采用实施例4所示的方法进行了精制的精制后的挂-四氢双环戊二烯(2)、采用实施例5所示的方法进行了精制的精制后的反-十氢化萘(3)、采用实施例6所示的方法进行了精制的精制后的挂-四氢双环戊二烯(3)、采用实施例7所示的方法进行了精制的精制后的双环己基、异丙基环己烷、环辛烷、环庚烷的折射率和透射率的测定结果示于表3和表4。 Trans decalin (manufactured by Tokyo Kasei), the method shown in Example 1 of the embodiment will be described using the purified after purification - - ten: (Aldrich Corp. cis, trans mixture) decalin, trans Specific examples tetrahydronaphthalene (1), dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane, using the method illustrated in Example 2 were purified after purification anti - decahydronaphthalene (2), using the embodiment the method shown in Example 3 were purified after purification hanging - THDCPD (1), the method shown in Example 4 were purified after purification hanging - tetrahydrodicyclopentadiene (2 ), using the method shown in Example 5 were purified after purification anti - decahydronaphthalene (3), using the method shown in Example 6 were purified after purification hanging - tetrahydrodicyclopentadiene ( 3), after purification were conducted using purified dicyclohexylammonium method shown in Example 7, isopropyl cyclohexane, cyclooctane, cycloheptane measurement result of the refractive index and transmittance are shown in tables 3 and 4. 另外,使用作为参比液体的乙腈、用作浸液曝光用液体的纯水、二碘甲烷作为比较例。 Further, acetonitrile was used as a reference liquid, as a liquid immersion exposure using pure water, methylene iodide as a comparative example.

对于折射率,针对顺、反-十氢化萘以及精制后的反-十氢化萘、双环己基、异丙基环己烷、环辛烷、环庚烷、乙腈测定在紫外范围的折射率。 Refractive index, for the cis, trans - decalin and the purified trans - decalin, bicyclo hexyl group, isopropyl cyclohexane, cyclooctane, cycloheptane, acetonitrile measuring the refractive index of the UV range. 测定装置使用MOLLER-WEDEL公司制造的测角分光计1型UV-VIS-IR,测定方法采用最小偏转角法、在25℃的测定温度下进行测定。 Using the measured angle measuring apparatus manufactured by MOLLER-WEDEL spectrometer type 1 UV-VIS-IR, measuring method using the minimum deflection angle method measured at a measuring temperature 25 ℃.

透射率采用测定法A或测定法B进行。 A transmittance measurement method or using the assay for B. 测定法A通过下列步骤进行测定:在氧浓度控制在小于等于0.5ppm的氮气气氛的手套箱中,在聚四氟乙烯制的加盖的光程10mm的池内进行液体的取样,利用日本分光公司制造的JASCO-V-550,使用上述池,以空气作为参比进行测定。 A Assay were determined by the following steps: controlling the oxygen concentration 0.5ppm or less in a nitrogen atmosphere in a glove box, sampling of the liquid pool in the optical path of 10mm polytetrafluoroethylene capped by Nippon Bunko Company JASCO-V-550 manufactured using the pool, with air as the reference measurement. 表中的值是通过计算校正池的反射后,根据该值换算成光程1mm的值。 Values ​​in the table is calculated by reflecting a correction value after the pool, based on the value into the optical path of 1mm.

测定法B是在氧浓度控制在小于等于0.5ppm的氮气气氛的手套箱中,在聚四氟乙烯制的加盖石英池(测定用:光程50mm,参比:光程10mm)中进行液体的取样。 Assay B is equal to the oxygen concentration was controlled at less than 0.5ppm in a nitrogen atmosphere glove box, (determined by: optical path length 50mm, reference: 10mm path length) in a covered quartz cell is a liquid made of polytetrafluoroethylene the sampling. 使用上述池,通过日本分光公司制造的JASCO-V-550,以光程50mm的池作为试样,以光程10mm的池作为参比,进行测定。 Using the above pool, JASCO-V-550 manufactured by Japan Spectroscopy Corporation, to an optical path of 50mm as a sample pool, to an optical path of 10mm pool as a reference, it was measured. 将本测定的值作为每光程40mm的吸光度。 The present value of the absorbance measured for each optical path of 40mm. 表中的值是根据该值换算成每1mm光程的值。 Values ​​in the table are converted into each 1mm light path based on the value.

表3 table 3

表4 Table 4

如表3和表4所示,折射率的波长依赖性是随着波长减小,折射率增加,上述表中的本发明的液体例如在193nm下具有大于等于1.58的高折射率。 As shown in Table 3 and Table 4, the refractive index decreases as the wavelength is the wavelength dependency of the refractive index increases, the liquid in the above table, for example, the present invention has a high refractive index of not less than 1.58 at 193nm.

另外,本发明的化合物是低极性化合物,因此氧、氮等气体的溶解度高。 Further, the compounds of the present invention is a compound of low polarity, so a high gas solubility of oxygen, nitrogen and the like. 因此,容易受到这些气体溶解的影响,例如当放置在大气气氛下时,由于溶解氧的吸收或光激发溶解氧而生成的臭氧的吸收、或者与溶解氧相关的氧化反应等,存在例如193nm的透射率降低的倾向。 Therefore, these vulnerable dissolved gas, for example, when placed in the atmosphere, due to the dissolved oxygen absorption of the excitation light or absorption of dissolved ozone generated, or the dissolved oxygen associated with the oxidation reaction or the like, in the presence of 193nm e.g. transmittance tends to decrease. 因此,这些化合物优选进行脱气处理,在氮、氩等惰性且吸收少的气体中进行保存。 Thus, these compounds degassing treatment is preferably carried out in a nitrogen, argon or the like inert gas and a low absorption saved. 具体地讲,优选使保存液体中的氧浓度为小于等于100ppm,进一步优选为小于等于10ppm而进行处理。 Specifically, the oxygen concentration is preferably stored liquid is 100 ppm or less, more preferably 10ppm or less and processed. 另外,在曝光前不能进行脱氧时,特别优选为小于等于1ppm,进一步优选为小于等于10ppb。 Further, when the deoxidation can not be performed prior to exposure, and particularly preferably 1 ppm or less, more preferably less than equal to 10ppb.

下面描述使用了本发明的浸液曝光用液体的浸液曝光方法。 The following description uses an immersion exposure method of the present invention immersion exposure liquid.

本发明的浸液曝光用液体优选如上所述在惰性气体中保存,作为此时的容器,优选用容器成分或容器的盖成分(例如,混配于塑料中的增塑剂等)不会洗脱的容器进行保存。 Immersion exposure liquid according to the present invention described above is preferably stored in an inert gas, in this case as a container, preferably a container lid component or components of the container (e.g., plastic compounding a plasticizer, etc.) will not wash save off the container. 作为优选的容器的例子,例如可以列举材料是玻璃、金属(例如SUS)、陶器、PTFE(聚四氟乙烯)、PFEP(全氟乙烯丙烯共聚物)、ECTFE(乙烯-氯三氟乙烯共聚物)、PTFE/PDD(聚四氟乙烯-全氟二茂共聚物)、PFA(全氟烷氧基链烷)、ETFE(乙烯-四氟乙烯共聚物)、PVDF(聚偏氟乙烯)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)等氟树脂的容器,但特别优选材料是玻璃、氟树脂的容器。 Preferred examples of the container, for example, may include a glass material, a metal (e.g. the SUS), ceramics, PTFE (polytetrafluoroethylene), the PFEP (perfluorinated ethylene propylene copolymer), ECTFE (ethylene - chlorotrifluoroethylene copolymer ), PTFE / PDD (polytetrafluoroethylene - perfluoro two  metallocene copolymer), the PFA (perfluoroalkoxy alkane), the ETFE (an ethylene - tetrafluoroethylene copolymer), of PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene) a container such as a fluororesin, it is particularly preferred material is a glass container fluororesin.

另外,作为优选的容器的盖的例子,例如可以列举材料是聚乙烯且不含增塑剂的盖,材料是玻璃、金属(例如SUS)、陶器、PTFE(聚四氟乙烯)、PFEP(全氟乙烯丙烯共聚物)、ECTFE(乙烯-氯三氟乙烯共聚物)、PTFE/PDD(聚四氟乙烯-全氟二茂共聚物)、PFA(全氟烷氧基链烷)、ETFE(乙烯-四氟乙烯共聚物)、PVDF(聚偏氟乙烯)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)等氟树脂的盖。 Further, examples of the preferred container lid, for example, include a plasticizer-free material is polyethylene and the cover material is glass, metal (e.g. the SUS), ceramics, PTFE (polytetrafluoroethylene), the PFEP (full fluoroethylene propylene copolymers), ECTFE (ethylene - chlorotrifluoroethylene copolymer), PTFE / PDD (polytetrafluoroethylene - perfluoro two  metallocene copolymer), PFA (perfluoroalkoxy alkane), ETFE ( ethylene - tetrafluoroethylene copolymer), of PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), PCTFE cover (polychlorotrifluoroethylene) fluorine resin.

另外,对于由容器向曝光机输液时使用的配管,优选与上述同样的不引起洗脱的配管,作为优选的配管的材料,可以列举玻璃、金属、陶器等。 Further, the container for infusion using the exposure apparatus to a pipe, preferably the pipe as described above does not cause elution, preferred as the material of the pipe include glass, metal, ceramics and the like.

本发明的浸液曝光用液体,当用于浸液曝光时,微粒、气泡(微泡)导致图案的缺陷等,因而优选在曝光前除去微粒和产生气泡的溶解气体。 Immersion exposure liquid according to the present invention, when used for liquid immersion exposure, fine bubbles (microbubbles) cause defects in the pattern or the like, it is preferable to remove particulates prior to exposure and dissolved gas bubbles to produce.

作为除去微粒的方法,可以列举使用适当的过滤器进行过滤的方法。 As a method for removing fine particles may be used include suitable filter filtering method. 作为过滤器,优选微粒的除去效率高,并且使用了无过滤时洗脱引起的曝光波长下吸收变化的材料的过滤器。 As a filter, preferably a high removal efficiency of fine particles, and the filter is used at the exposure wavelength eluted caused no change in the absorbent filter material. 作为优选的过滤器材料,例如可以列举玻璃、金属(例如SUS、银)和金属氧化物、PTFE(聚四氟乙烯)、PFEP(全氟乙烯丙烯共聚物)、ECTFE(乙烯-氯三氟乙烯共聚物)、PTFE/PDD(聚四氟乙烯-全氟二茂共聚物)、PFA(全氟烷氧基链烷)、ETFE(乙烯-四氟乙烯共聚物)、PVDF(聚偏氟乙烯)、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)等氟树脂。 Preferred filter materials include, for example, glass, metal (e.g. the SUS, silver) and metal oxides, PTFE (polytetrafluoroethylene), the PFEP (perfluorinated ethylene propylene copolymer), ECTFE (ethylene - chlorotrifluoroethylene copolymer), PTFE / PDD (polytetrafluoroethylene - perfluoro two  metallocene copolymer), PFA (perfluoroalkoxy alkane), ETFE (an ethylene - tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride ), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene) fluorine resin. 另外,对于过滤器的外壳、芯、支架、塞子等周边部件的材料,也优选为从上述过滤器的优选材料中选择的材料。 Further, for the housing surrounding the filter member, the core, the bracket, the stopper material and the like, also preferably a material selected from the preferred material of the filter.

作为溶解气体的除去方法,例如可以列举减压脱气法、超声波脱气法、利用气体透过性膜的脱气法、使用了各种脱气器的脱气法等。 As a method for removing dissolved gas, for example, include a vacuum degassing method, an ultrasonic degassing, degassing process using a gas permeable membrane, various deaerator degassing method or the like.

本发明的浸液曝光用液体在曝光时是光学系统的一部分,因而优选在对液体的折射率等光学性质的变化没有影响的环境下使用。 Immersion exposure liquid according to the present invention is a part of the optical system during exposure, it is preferable to use environmental changes in the optical properties such as refractive index of liquid of no effect. 例如,优选在使影响液体光学特性的温度、压力等恒定的环境下使用。 For example, preferably used in the liquid so that the influence of the optical characteristics of temperature, a constant pressure environment. 例如对于温度,优选控制在±0.1℃,更优选控制在±0.01℃的范围内。 For example, the temperature is preferably controlled to ± 0.1 ℃, more preferably controlled in the range of ± 0.01 ℃.

另外,使用了本发明的液体的浸液曝光,还可以在大气气氛下进行,如上所述,氧气在本发明的液体中的溶解度高,有时影响曝光波长下的吸收特性,因此优选在曝光波长下的吸收少、不会引起与液体的化学反应的惰性气体中进行曝光。 Further, the use of liquid immersion exposure of the present invention may also be in the atmosphere, as described above, a high oxygen solubility in the liquid of the present invention, may affect the absorption characteristics in the exposure wavelength, the exposure wavelength is preferably in the Uptake less, the exposure does not cause a chemical reaction with an inert gas in the liquid. 作为优选的该惰性气体,例如可以列举氮气、氩气等。 As a preferred inert gas, for example, can include nitrogen, argon and the like.

另外,从防止由空气中的有机成分引起的污染导致的液体在曝光波长下吸收特性变化的观点出发,优选将所用气氛中的有机成分浓度控制在一定水平以下。 Further, from the viewpoint of preventing contamination of the liquid due to air in the organic components of the characteristic change due to the absorption at the exposure wavelength, it is preferable to be controlled at a certain level of concentration in the atmosphere organic components. 作为该有机成分浓度的控制方法,可以列举使用高纯度的上述惰性气体气氛、以及使用吸附有机成分的过滤器、各种气体精制管(装置)的方法等。 As a method for controlling the concentration of the organic component include the above-described high-purity inert gas atmosphere, and the use of an organic component adsorption filter, a gas purification method and other tube (device). 为了浓度控制,优选定期进行周围气氛的分析,为此能够例如使用了利用了气相色谱的各种分析方法。 In order to control the concentration of, preferably periodically analyze the surrounding atmosphere, for example, can be analyzed using a variety of methods using gas chromatography.

作为曝光区域的浸液的液体供给方法,已知mooving pool法、seimming stage法、Local Fill法(局部浸液方式)(参照特别学术研讨会浸液曝光技术(2004年5月27日召开)学术研讨会资料),由于局部浸液法的浸液曝光用液体的使用量少,因而优选。 As a method of supplying a liquid immersion exposure region known method mooving pool, Academic seimming stage method, Local Fill method (local liquid immersion method) (see in particular liquid immersion exposure technique Symposium (held May 27, 2004) workshop materials), since the immersion exposure of local liquid immersion method using a small amount of liquid, which is preferable.

作为利用了本液体的浸液曝光用的最终(物镜)透镜材料,由于其光学特性而优选现行的CaF2或熔凝硅石。 As the final use of the (objective) lens material of the present liquid immersion exposure, the optical properties due to its current preferred fused silica or CaF2. 作为其他优选的透镜材料,优选例如高周期碱土类金属M的氟盐以及通式CaxM1-xF2表示的盐、CaO、SrO、BaO等碱土类金属的氧化物等,当使用该材料时,与CaF2(n@193nm=1.50)、熔凝硅石(n@193nm=1.50)相比,透镜的折射率提高,因此,在设计、加工数值孔径超过1.5的高NA的透镜时特别优选。 As another preferred lens material, preferably a fluoride salt such as an oxide high period of salts of alkaline earth metal and M is represented by the general formula CaxM1-xF2, CaO, SrO, BaO and other alkaline earth metal or the like, when the material is used, and CaF2 (n@193nm=1.50), fused silica (n@193nm=1.50) compared to the refractive index of the lens increase, therefore, in the design, machining a high numerical aperture exceeding 1.5 NA lens is particularly preferred.

由于抗蚀剂成分的洗脱非常少,因而本发明的液体能够在使用后再利用。 Since the elution of the resist components is very small, and thus the liquid can be utilized in the present invention after use. 当使用了能够忽略曝光时由抗蚀膜的洗脱等的影响的抗蚀剂(或者抗蚀剂上层膜)时,本发明的液体能够不进行精制而再利用,但是,此时优选在进行了脱气、过滤等处理后进行再利用。 When used when exposing the resist can be ignored from the elution of a resist film like effects (or resist upper layer film), the liquid of the present invention can be reused without purification, however, this time is preferably performed be reused after degassing and filtration treatment. 从简化工序的观点出发,优选在线进行这些处理。 From the viewpoint of simplifying the process, the process is preferably carried out online.

另外,在使用时,即使是在1次使用中能够忽略由上述抗蚀膜的洗脱等的水平,但当使用次数超过一定次数时,可以预测:由于积蓄的杂质的影响,液体的物性会发生变化,因此,优选在使用一定次数后进行回收、精制。 Further, when in use, even in the primary use can be ignored by the level of the eluted resist film and the like, but the frequency of use exceeds a certain number of times, can be predicted: the influence of accumulated impurities, the physical properties of the liquid will be changes, therefore, is preferably recovered and purified after certain number of uses.

作为该精制方法,可以列举水洗处理、酸洗涤、碱洗涤、精馏、使用了适当的过滤器(填充柱)的精制、过滤等方法,以及如上所述的本发明的液体的精制方法或者由这些精制方法组合产生的方法。 Examples of the purification method can include washing treatment, acid washing, alkali washing, distillation, using a suitable filter (packed column) purification, filtration, etc., and a method for purifying liquid according to the present invention as described above, or by the the method of producing these purification methods in combination. 其中,优选利用水洗处理、碱洗涤、酸洗涤、精馏或者这些精制方法的组合进行精制。 Wherein, preferably using a water washing treatment, acid washing, alkali washing or distillation combination of these refining methods for refining.

上述碱洗涤对于洗脱于本发明液体中的通过曝光产生的酸的除去是有效的,酸洗涤对于洗脱于本发明液体中的抗蚀剂中的碱性成分的去除是有效的,水洗处理对于洗脱于本发明的液体中的抗蚀膜中的光酸发生剂、碱性添加剂、曝光时产生的酸等洗脱物的去除是有效的。 Washed to remove the acid for the elution of the alkali by exposure to liquid according to the present invention is effective to produce, acid washing for removing alkali components eluted in the liquid resist in the present invention is effective, water washing treatment for the removal of eluate eluted photoacid generators in the present invention, the liquid resist film, basic additive, acid generated upon exposure is effective.

对于精馏,除了对于上述添加剂中的低挥发性化合物的去除有效外,对于除去曝光时由抗蚀剂中的保护基的分解产生的疏水性成分也是有效的。 For distillation, in addition to low volatile compounds effective for removing the above-described additives, the hydrophobic component for exposure produced by the decomposition of the resist is removed the protective group is also effective.

式(1-1)~式(1-9)所示的浸液曝光用液体能够各自单独使用,也能够混合使用。 Formula (1-1) to (1-9) shown in immersion exposure liquid to be used alone, can be mixed and used. 优选的例子是单独使用的情况。 Preferred examples are when used alone. 通过单独使用,容易设定浸液曝光条件。 By using a single, easy to set exposure conditions of immersion.

另外,本发明的液体根据需要能够与本发明以外的液体混合使用,这样能够使例如折射率、透射率等光学特性值、接触角、比热、粘度、膨胀率等物性值达到期望值。 Further, the liquid used according to the present invention can be mixed with a liquid other than the present invention according to need, so that the optical characteristic value can be e.g. refractive index, transmittance, etc., contact angle, specific heat, viscosity, physical properties such as expansion coefficient value reaches the desired value.

作为用于本目的的本发明以外的液体,除了其他能够浸液曝光的溶剂外,还能够使用各种消泡剂、表面活性剂等,对于气泡的减少、表面张力的控制是有效的。 As the liquid used in the present invention than for the present purpose, in addition to other solvents capable of immersion exposure, various defoaming agents can also be used, such as a surfactant, to reduce bubbles, the surface tension control is effective.

使用上述浸液曝光用液体进行浸液曝光。 Using the liquid immersion exposure by a liquid immersion exposure.

在基板上涂布光致抗蚀剂而形成光致抗蚀膜。 Applying on a substrate a photoresist to form a photoresist film. 基板能够使用例如硅晶片、用铝被覆的晶片等。 For example, the substrate can be a silicon wafer, wafer coated with aluminum and the like. 另外,为了最大限度地发挥抗蚀膜的潜能,如例如特公平6-12452号公报等公开那样,能够预先在所使用的基板上形成有机类或无机类的防反射膜。 Further, in order to maximize the potential of the resist film, such as disclosed, for example, an organic antireflection film can be beforehand or inorganic forms KOKOKU Publication No. 6-12452 and the like on the substrate used.

所用的光致抗蚀剂没有特别限制,能够根据抗蚀剂的使用目的适时地选择。 The photoresist used is not particularly limited, and can be selected depending on the intended use timely resist. 作为光致抗蚀剂的树脂成分,可以列举含酸解离性基团的高分子。 As the resin component of the photoresist include a polymer from the solution containing acid group. 该酸解离性基团优选不因曝光而分解,特别优选该分解后产物在曝光条件下挥发,不洗脱于本发明液体中。 The acid hydrolysis is not dissociated by exposure preferred group, particularly preferred that the volatile decomposition products under the exposure conditions, the liquid is not eluted in the present invention. 作为这些高分子的例子,可以列举高分子侧链含脂环基、内酯基以及它们的衍生物等的树脂、包含羟基苯乙烯衍生物等的树脂等。 Examples of such a polymer, a polymer side chain include a resin having an alicyclic group, lactone group and derivatives thereof and the like, comprising a hydroxystyrene resin and the like derivatives.

特别优选使用高分子侧链含脂环基、内酯基以及它们的衍生物的树脂的光致抗蚀剂。 Particularly preferred alicyclic group-containing polymer side-chain, the photoresist resin is a lactone group and derivatives thereof. 这些光致抗蚀剂含有与脂环烃化合物或在环结构中含硅原子的环烃化合物类似的化学结构,因而与本发明的浸液曝光用液体的亲和性优异。 These photoresists containing an alicyclic hydrocarbon compound or a silicon atom in the ring structure of the cyclic hydrocarbon compounds of similar chemical structure, and thus the immersion exposure of the present invention is excellent in affinity for the liquid. 另外,不使光致抗蚀膜洗脱,也不会使其溶解。 Further, the photo resist film is not eluted, nor dissolved.

作为光致抗蚀剂的例子,可以列举含有包含酸解离性基团的高分子作为树脂成分、酸发生剂、酸扩散控制剂等添加剂的化学放大型的正或负型抗蚀剂等。 Examples of the photoresist include a polymer containing acid-dissociable containing group as the resin component, acid generator, an acid diffusion-type chemically amplified positive or negative resist-type control agents and the like additives.

当使用本发明的浸液曝光用液体时,特别优选正型抗蚀剂。 When the present invention is used with a liquid immersion exposure, positive resist particularly preferred. 对于化学放大型正型抗蚀剂,在通过曝光由酸发生剂生成的酸的作用下,聚合物中的酸解离性有机基团解离,生成例如羧基,其结果,抗蚀剂的曝光部位对于碱显像液的溶解性提高,该曝光部位被碱显像液溶解而除去,得到正型抗蚀图案。 For the chemically amplified positive resist, under action of an acid generated from the acid generator upon exposure, the acid solution in the polymer dissociation organic group, e.g. carboxy generated, exposing a result, the resist parts of the alkali developing solution to improve the solubility of the exposed portion is removed by dissolving an alkali developing solution to obtain a positive resist pattern.

光致抗蚀膜通过以下过程形成:例如以0.1~20重量%的固体成分浓度将用于形成光致抗蚀膜的树脂组合物溶解在适当的溶剂中,然后,例如通过孔径30nm左右的过滤器进行过滤而调制溶液,利用旋涂、流延涂布、辊涂等适当的涂布方法,在基板上涂布该抗蚀剂溶液,进行预焙烧(以下称为“PB”)使溶剂挥发。 The photoresist film is formed by the following procedure: for example, a solid concentration of 0.1 to 20% by weight of the photoresist film for forming the resin composition is dissolved in a suitable solvent, and then, for example, filtration through a pore size of about 30nm the coating method is suitable to prepare the solution was filtered, spin coating, cast coating, roll coating, applying the resist solution on a substrate, pre-baked (hereinafter referred to as "PB") the solvent is volatilized . 另外,此时能够直接使用市售的抗蚀剂溶液。 Further, at this time can be used as a commercially available resist solution. 该光致抗蚀膜优选相比浸液上层膜和浸液曝光用液体是高折射率,具体地优选光致抗蚀膜的折射率nRES为大于等于1.65。 The photoresist film is preferably compared immersion upper layer film and the liquid immersion exposure is a high refractive index, refractive index nRES particular photoresist film is preferably not less than 1.65. 特别当NA为大于等于1.3时,nRES优选大于1.75,此时,能够防止NA的增大带来的曝光光线的对比度下降。 Especially when the NA is not less than 1.3, preferably greater than 1.75 NRES In this case, it is possible to prevent increase of the NA of the exposure light brings a reduction in contrast.

另外,在浸液曝光方法中,能够在光致抗蚀膜上进一步形成浸液用上层膜。 Further, in the immersion exposure method, a photoresist film can be further formed with an immersion upper layer film.

作为浸液用上层膜,只要是能够在光致抗蚀膜上形成保护膜而不引起对于曝光光线的波长足够的透过性和与光致抗蚀膜的混和,此外,维持稳定的被膜而不会在浸液曝光时使用的上述液体中洗脱,而且在显像前能够剥离的膜,就能够使用。 An immersion upper layer film as long as it is capable of forming a protective film, a photoresist film without causing sufficient for the wavelength of the exposure light transmitted through the mixture and the photoresist film, in addition, to maintain a stable film and the liquid will not be used during immersion exposure eluted, and can be peeled off before developing the film, can be used. 此时,该上层膜如果是容易溶解于作为显像液的碱液的膜,在显像时被剥离,因而优选。 In this case, if the top film is easily dissolved in alkaline developing solution as a film, when the developer is peeled off, thus preferable.

优选侧链具有六氟甲醇基和羧基的至少1个基团作为用于赋予碱可溶性的取代基的树脂。 Preferably a side chain having a hexafluorocarbinol group and at least one carboxyl group as a substituent group imparting alkali-soluble resin.

该浸液用上层膜优选同时具有防止多重干涉的功能,此时,该浸液用上层膜的折射率noc优选为以下所示的数学式。 The immersion upper layer film preferably with a multiple interference while preventing function of time, the immersion upper layer film with a refractive index noc preferably equation shown below.

noc=(n1q×nRES)0.5其中,n1q、nRES分别表示浸液曝光用液体的折射率、抗蚀膜的折射率。 noc = (n1q × nRES) 0.5 wherein, n1q, nRES respectively represent the refractive index of the liquid immersion exposure, the refractive index of the resist film.

具体地讲,noc优选为1.6~1.9的范围。 Specifically, noc preferably in the range 1.6 to 1.9.

上述浸液上层膜能够通过以下过程形成:以0.01~10%固体成分浓度将浸液上层膜用树脂组合物溶解在不与抗蚀膜混合的溶剂中,然后采用与光致抗蚀膜形成时同样的方法涂布在抗蚀膜上,进行预焙烧。 The above-described immersion upper layer film can be formed by the following procedure: 0.01 to 10% solid concentration of the immersion upper layer film of the resin composition is dissolved in a resist film is not mixed with a solvent and then using the photoresist film forming the same method is applied on the resist film, pre-baking.

以本发明的浸液曝光用液体作为介质,通过具有规定图案的掩膜向该光致抗蚀膜或者形成了浸液用上层膜的光致抗蚀膜照射放射线,接着进行显像,从而形成抗蚀图案。 In the immersion exposure of the present invention with a liquid as a medium through a mask having a predetermined pattern to the photoresist film or a photoresist film is formed is irradiated with radiation immersion upper layer film followed by developing, to form a The resist pattern. 该工序是进行浸液曝光,在规定的温度下进行了焙烧后进行显像的工序。 The immersion exposure step is carried out after the developing step is performed at a predetermined temperature in the firing.

用于浸液曝光的放射线,能够根据所用的光致抗蚀膜以及光致抗蚀膜和浸液用上层膜的组合,选择使用例如可见光;g射线、i射线等紫外线;准分子激光等远紫外线;同步加速器放射线等X射线;电子射线等带电粒子射线这样的各种放射线。 The radiation used for immersion exposure, it is possible in accordance with the photoresist film and the photoresist film and the immersion upper layer film with a combination of, for example, select a visible light; ultraviolet g-line, i-rays and the like; excimer laser away UV; X-ray synchrotron radiation or the like; electron beam charged particle beam such various radiation. 特别优选ArF准分子激光(波长193nm)或KrF准分子激光(波长248nm)。 Particularly preferably ArF excimer laser (wavelength 193 nm) or KrF excimer laser light (wavelength of 248nm).

另外,为了提高抗蚀膜的分辨率、图案形状、显像性等,优选在曝光后进行焙烧(以下称为“PEB”)。 In order to improve resolution, pattern shape, the developing of the resist film and the like, preferably in a post-exposure baking (hereinafter referred to as "PEB"). 该焙烧温度根据所用的抗蚀剂等进行适当调节,通常为30~200℃左右,优选为50~150℃。 The firing temperature is suitably adjusted according to the resist agent used is usually about 30 ~ 200 ℃, preferably 50 ~ 150 ℃.

接着,用显像液对光致抗蚀膜进行显像,进行洗涤,形成期望的抗蚀图案。 Next, by developing the photoresist film developing solution, washed to form a desired resist pattern.

实施例为了评价本发明的浸液曝光用液体,使用以下所示的放射线敏感性组合物形成抗蚀膜。 Example To evaluate the immersion exposure of the present invention is shown in a liquid, using the following radiation-sensitive composition for forming the resist film. 另外,在其一部分上形成以下所示的浸液用上层膜。 Further, by forming the liquid immersion upper layer film is shown below on a part thereof. 利用该评价用抗蚀膜测定作为浸液曝光用液体的特性(洗脱试验、膜的溶解性试验、图案形成评价)。 Evaluation of the resist film was measured by using the liquid immersion exposure is used as characteristics of the liquid (elution test, solubility test film, patterning evaluation).

参考例1采用以下方法制得用于放射线敏感性树脂组合物的树脂。 A resin prepared by the following method for radiation-sensitive resin composition of Reference Example 1.

将39.85g(40摩尔%)化合物(S1-1)、27.47g(20摩尔%)化合物(S1-2)、32.68g(40摩尔%)化合物(S1-3)溶解于200g的2-丁酮中,进一步投入4.13g偶氮二异戊酸甲酯,准备单体溶液,对投入了100g的2-丁酮的1000ml的三口烧瓶进行30分钟的氮气净化。 The 39.85g (40 mole%) of compound (S1-1), 27.47g (20 mole%) of compound (S1-2), 32.68g (40 mole%) of compound (S1-3) were dissolved in 200g of 2-butanone , a further input 4.13g azobisisobutyronitrile valerate prepared monomer solution, put 100g of 2-butanone 1000ml three-necked flask is purged with nitrogen for 30 minutes. 氮气净化后,一边搅拌反应釜,一边加热至80℃,使用滴液漏斗,用3小时滴加事先准备的上述单体溶液。 After nitrogen purge, while stirring the reaction kettle was heated to 80 ℃, dropping funnel, the above monomer solution was added dropwise over 3 hours previously prepared. 以滴液开始作为聚合开始时间,进行5小时的聚合反应。 To start dropping as the start time of the polymerization, a polymerization reaction for 5 hours. 聚合结束后,聚合溶液通过水冷冷却至小于等于30℃,投入到2000g的甲醇中,过滤析出的白色粉末。 After the polymerization, the polymer solution was cooled with water to less than or equal 30 ℃, into 2000g of methanol, the precipitated white powder was filtered. 利用400g甲醇,在浆液上对过滤的白色粉末洗涤2次后过滤,在50℃下干燥17小时,制得白色粉末的聚合物(75g,收率75重量%)。 Using 400g of methanol, a white powder was filtered and washed on the filter two times in the slurry, dried at 50 ℃ 17 hours to obtain the polymer as a white powder (75g, 75% yield). 该聚合物分子量为10300,13C-NMR分析的结果是化合物(S1-1)、化合物(S1-2)、化合物(S1-3)所示重复单元,各重复单元的含有率为42.3∶20.3∶37.4(摩尔%)的共聚物。 The polymer molecular weight is 10300,13C-NMR analysis result of the compound (S1-1), was 42.3:20.3: containing compound (S1-2), the compound (S1-3) repeating units, each repeating unit 37.4 (mol%) copolymer. 将该聚合物作为树脂(A-1)。 The polymer as resin (A-1).

参考例2采用以下方法制得用于放射线敏感性树脂组合物的树脂。 Reference Example 2 using the following process for the resin composition of the radiation-sensitive resin composition.

将53.92g(50摩尔%)化合物(S2-1)、10.69g(10摩尔%)化合物(S2-2)、35.38g(40摩尔%)化合物(S2-3)溶解于187g的2-丁酮而得到单体溶液(1),准备将3.37g的二甲基2,2′-偶氮二(2-甲基丙酸酯)溶解于64g的2-丁酮得到的溶液(2),再将事先准备的28.77g单体溶液(1)、4.23g溶液(2)投入放有15g的2-丁酮的1000ml的三口烧瓶中,然后利用减压置换法进行氮气净化。 The 53.92g (50 mole%) of compound (S2-1), 10.69g (10 mole%) of compound (S2-2), 35.38g (40 mole%) of compound (S2-3) were dissolved in 187g of 2-butanone to yield a monomer solution (1), ready to 3.37g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved in a solution (2) obtained 64g of 2-butanone, and then 28.77g of the previously prepared monomer solution (1), 4.23g solution (2) placed into 15g of 2-butanone 1000ml three-necked flask, and then under reduced pressure using a nitrogen purge displacement method. 氮气净化后,一边搅拌反应釜,一边加热至80℃,15分钟之后,利用输液泵,用3小时滴入258.98g单体溶液(1)、24.64g溶液(2)。 After nitrogen purge, while stirring the reaction kettle was heated to 80 ℃, After 15 minutes, using an infusion pump, the monomer was added dropwise a solution of 258.98g (1), 24.64g solution (2) over 3 hours. 滴液结束后,再搅拌4小时。 After completion of dropping, and then stirred for 4 hours. 聚合结束后,聚合溶液通过放置冷却冷却至小于等于30℃。 After the polymerization, the polymer solution was allowed to cool to cool to less 30 ℃. 反应结束后,溶液通过放置冷却,冷却到小于等于30℃,投入到4000g异丙醇中,过滤析出的白色粉末。 After completion of the reaction, the solution was allowed to cool by cooling to less 30 ℃, into 4000g of isopropanol, the precipitated white powder was filtered. 利用2000g异丙醇,在浆液上对过滤的白色粉末洗涤2次后,进行过滤,在60℃下干燥17小时,制得白色粉末的聚合物(85g,收率85重量%)。 Using 2000g of isopropanol, as a white powder after filtration and washed twice, the slurry was filtered over dried at 60 ℃ 17 hours to obtain the polymer as a white powder (85g, 85% yield). 该聚合物的Mw为7600,13C-NMR分析的结果是化合物(S2-1)、化合物(S2-2)、化合物(S2-3)所示重复单元,各重复单元的含有率为53.1∶8.5∶38.4(摩尔%)的共聚物。 Mw of the polymer was 7600,13C-NMR analysis result of the compound (S2-1), was 53.1:8.5 containing compound (S2-2), the compound (S2-3) repeating units, each repeating unit :38.4 (mol%) copolymer. 将该聚合物作为树脂(A-2)。 The polymer as resin (A-2).

参考例3采用以下方法制得形成浸液用上层膜的树脂。 Reference Example 3 using the following process using the immersion upper layer film of resin is formed.

将50g化合物(S3-1)、5g化合物(S3-2)、25g化合物(S3-3)、20g化合物(S3-4)以及6.00g偶氮二异戊酸甲酯溶解于200g甲乙酮,准备成为均匀溶液的单体溶液。 50g of the compound (S3-1), 5g compound (S3-2), 25g compound (S3-3), 20g Compound (S3-4) and 6.00g azobisisobutyronitrile was dissolved in 200g of methyl ethyl ketone, ready to become homogeneous solution of the monomer solution. 接着,对投入有100g甲乙酮的1000ml的三口烧瓶进行30分钟的氮气净化。 Next, 100g of methyl ethyl ketone was poured into a 1000ml three-necked flask is purged with nitrogen for 30 minutes. 氮气净化后,一边搅拌烧瓶,一边加热至80℃,利用滴液漏斗,以10ml/5分钟的速度滴加事先调制的上述单体溶液。 After nitrogen purge, while stirring the flask was heated to 80 ℃, dropping funnel, at a rate of 10ml / 5 min the solution was added dropwise the monomer prepared in advance. 以滴加开始时作为聚合开始时间点,进行5小时的聚合。 Beginning dropwise as a polymerization starting point time, a polymerization for 5 hours. 聚合结束后,将反应溶液冷却至小于等于30℃,接着,将该反应溶液投入到2000g庚烷中,过滤析出的白色粉末。 After completion of the polymerization, the reaction solution was cooled to less than or equal 30 ℃, then, the reaction solution was poured into 2000g heptane, precipitated white powder was filtered. 重复2次将过滤的白色粉末与400g庚烷混合、形成浆液、搅拌的操作,洗涤后过滤,在50℃下干燥17小时,制得白色粉末树脂(E-1)(89g,收率89重量%)。 Repeated twice and the filtered white powder was mixed with 400g of heptane to form a slurry, stirring operations, washed by filtration, and dried for 17 hours at 50 ℃, as a white powdery resin (E-1) (89g, yield 89 wt. %). 树脂(E-1)的Mw为7300。 Mw resin (E-1) 7300.

参考例4采用以下的方法制得形成浸液用上层膜的树脂。 Reference Example 4 was prepared by the following method using the immersion upper layer film forming resin.

作为单体,除了使用70g化合物(S4-1)、20g化合物(S4-2)和10g化合物(S4-3)以外,与参考例3同样地制得白色粉末的树脂(E-2)(88g,收率88重量%)。 As the monomer, 70g except for using the compound (S4-1), 20g Compound (S4-2) and 10g of compound (S4-3) except the same manner as in Reference Example 3 was obtained as a white powder resin (E-2) (88g yield 88 wt%). 树脂(E-2)的Mw为6800。 Mw resin (E-2) was 6,800.

参考例5采用以下方法得到放射线敏感性树脂组合物。 Reference Example 5 using the following procedure to obtain radiation-sensitive resin composition.

混合表5所示的树脂、酸发生剂、酸扩散控制剂、溶剂,形成均匀溶液后,利用孔径200nm的膜滤器进行过滤,调制放射线敏感性树脂组合物(F1~F3)。 After mixing the resin shown in Table 5, an acid generator, an acid diffusion control agent, solvent to form a homogeneous solution, using 200nm pore size of the membrane filter filtration to prepare a radiation sensitive resin composition (F1 ~ F3). 在表5中,“份”是重量基准。 In Table 5, "parts" are by weight basis.

另外,以下示出所用的酸发生剂(B)、酸扩散控制剂(C)、溶剂(D)。 Further, the acid generator shown below (B) is used, an acid diffusion controller (C), a solvent (D).

酸发生剂(B)B-1:4-九氟正丁基磺酰氧基苯基·二苯基锍九氟正丁烷磺酸盐B-2:三苯基锍·九氟正丁烷磺酸盐酸扩散控制剂(C)C-1:2-苯基苯并咪唑溶剂(D)D-1:丙二醇单甲醚乙酸酯表5 Acid generator (B) B-1: 4- sulfonyloxy nonafluoro-n-butyl phenyl diphenyl sulfonium nonafluoro-n-butanesulfonate B-2: triphenylsulfonium nonafluoro-n-butane hydrochloric acid diffusion controller (C) C-1: 2- phenylbenzimidazole-solvent (D) D-1: propylene glycol monomethyl ether acetate table 5

参考例6采用以下方法制得浸液用上层膜组合物。 Reference Example 6 using the following process by immersion upper layer film composition.

将表6所示的树脂、溶剂混合,形成均匀溶液后,利用孔径200nm的膜滤器进行过滤,调制浸液用上层膜组合物(G1和G2)。 After the resin table, shown in FIG. 6 solvent are mixed to form a homogeneous solution, using 200nm pore size of the membrane filter filtration to prepare an immersion upper layer film composition (G1 and G2). 在表6中,n-BuOH表示正丁醇,“份”是重量基准。 In Table 6, n-BuOH denotes butanol, "parts" are by weight basis.

表6 Table 6

参考例7采用以下方法制得评价用抗蚀膜(H-1~H-5)。 Reference Example 7 was prepared by the following method for evaluation of the resist film (H-1 ~ H-5).

在8英寸硅晶片上,采用旋涂、PB(90℃、60秒)进行下层防反射膜ARC29(ブル一ワサイエンス公司制造)的涂布,形成膜厚77nm的涂膜后,在同样的条件下使用表7所示的放射线敏感性树脂组合物,形成抗蚀膜(膜厚205nm)(H-1~H-3)。 After the 8-inch silicon wafer by spin coating, PB (90 ℃, 60 seconds) underlayer antireflective film ARC29 (manufactured bu ru a wa manufactured by Science Haas Co.) was applied, forming 77nm coating film thickness, the same conditions as in using the radiation-sensitive resin composition shown in table 7, a resist film (film thickness 205nm) (H-1 ~ H-3).

另外,采用与上述同样的方法,使用放射线敏感性树脂组合物形成抗蚀膜(膜厚205nm)后,在该抗蚀膜上,采用旋涂、PB(130℃、90秒)将表7所示的浸液用上层膜组合物形成膜厚32nm的上层膜(H-4和H-5)。 Further, using the same method as described above, after the resist (film thickness of 205 nm) using the radiation-sensitive resin composition film was formed on the resist film by spin coating, PB (130 ℃, 90 sec) Table 7 an upper film having a thickness of 32nm (H-4 and H-5) shown immersion upper layer film forming composition.

表7 Table 7

实施例1采用以下方法精制市售的反-萘烷(反-十氢化萘),制得浸液曝光用液体。 Decalin (trans - - decalin) purified by the following method from commercially available trans Example 1, was prepared with a liquid immersion exposure.

将100ml市售的反-十氢化萘(东京化成公司制造,换算成1mm光程的193nm的透射率为小于等于10%)投入放有玻璃涂敷的搅拌片的200ml茄形烧瓶中,加20ml的浓硫酸(和光纯药产品),将搅拌片的旋转速度设定为500~1000rpm,在25℃下搅拌20分钟。 The 100ml commercially available trans - decalin (manufactured by Tokyo Chemical Industry Co., 1mm light path in terms of 193nm transmittance of 10% or less) placed into 200ml eggplant flask with a glass sheet coated with stirring, add 20ml concentrated sulfuric acid (Wako pure Chemical products), the rotational speed of the stirring blade was set to 500 ~ 1000rpm, stirred at 25 ℃ 20 minutes. 然后,通过分液除去浓硫酸,进行3次上述操作。 Then, concentrated sulfuric acid is removed, the above-described operation was performed three times through the liquid separation. 然后,用50ml去离子水洗涤1次分离的有机层,用饱和碳酸氢钠水溶液洗涤3次。 Then, the separated organic layer was washed once with 50ml deionized, washed three times with saturated aqueous sodium bicarbonate. 然后,用纯水洗涤有机层3次。 Then, the organic layer was washed three times with water. 在该时间点确认pH显示7(中性)。 In this time point display confirmation pH 7 (neutral). 然后,用硫酸镁进行干燥,干燥后采用倾析除去硫酸镁,在压力10mmHg下,利用装备有长20cm的卫得门型精馏塔的蒸馏装置进行减压蒸馏,回收16份10ml的馏分。 Then, dried over magnesium sulfate, the magnesium sulfate was removed by decantation and dried under a pressure of 10 mmHg, to give the door by Satellite rectification column type distillation apparatus equipped with a 20cm long distilled under reduced pressure to recover 16 parts 10ml fractions. 测定各馏分在193nm下的吸光度(测定条件采用上述测定法A的条件),换算成1mm光程的透射率为大于等于93%的馏分为12份,制得合计120ml的换算成1mm光程的透射率为大于等于90%的反-十氢化萘。 Absorbance of each fraction was measured at 193nm (measurement condition of the measurement conditions employed in the method A), in terms of 1mm light path transmittance of not less than 93% fraction of 12 parts, was prepared in terms of the total 120ml 1mm pathlength a transmittance of 90% or more of trans - decalin. 另外,使各馏分氮气饱和并进行减压脱气,保存在进行了氮气置换的玻璃容器中。 Furthermore, each fraction was saturated with nitrogen and degassed under reduced pressure, the save is performed in glass containers purged with nitrogen. 在封入容器后,通过气相色谱分析化合物的纯度,纯度(以下称为“GC纯度”)为99.92%。 After the container is filled, the compound purity analysis, purity by gas chromatography (hereinafter referred to as "GC purity") was 99.92%. 将采用实施例1的方法制得的精制后的反-十氢化萘称为精制后的反-十氢化萘(1)。 After the reaction will employ the method of Example 1 was obtained in purified embodiment - after referred to as a purified trans decalin - decahydronaphthalene (1).

另外,采用上述方法精制市售反、顺-混合十氢化萘和市售顺-十氢化萘。 Further, the above method commercially available purified trans, cis - decalin and mixing commercially available cis - decalin.

实施例2在氮气气氛下,采用与实施例1相同的方法进行硫酸处理。 Example 2 under nitrogen atmosphere, was treated in the sulfuric acid in the same manner as in Example 1. 然后采用与实施例1相同的方法,进行市售反-十氢化萘(东京化成公司制造;换算成光程1mm的193nm的透射率为小于等于10%)的精制,制得换算成1mm光程的透射率为96.8%的液体。 Then using the same method of Example 1, a commercially available anti - decalin (manufactured by Tokyo Kasei; in terms of the optical path of 1mm 193nm transmittance of 10% or less) is purified to obtain the optical path in terms of 1mm 96.8% of the transmittance of the liquid. 利用气相色谱法(检测器TCD)分析本液体的溶解氧和溶解氮浓度,溶解氧浓度为低于1ppm(检测限度以下),溶解氮浓度为119ppm。 Analysis of this dissolved oxygen and dissolved nitrogen concentration of the liquid by gas chromatography (the TCD detector), dissolved oxygen concentration of 1 ppm or below (below detection limits), the dissolved nitrogen concentration of 119ppm. 另外,采用原子吸光法测定本液体的Li、Na、K、Mg、Cu、Ca、Al、Fe、Mn、Sn、Zn、Ni的金属含量,Ca为1ppb,Zn为6ppb,其他金属为低于1ppb(低于检测限度)。 Further, using the atomic absorption method for the determination of this liquid is Li, Na, K, Mg, Cu, Ca, Al, Fe, Mn, Sn, Zn, a metal content of Ni, Ca is 1ppb, Zn is 6ppb, other metal is less than 1 ppb (below the detection limit). 将采用实施例2的方法制得的精制后的反-十氢化萘称为精制后的反-十氢化萘(2)。 After the reaction will employ the method of Example 2 was obtained in purified embodiment - after referred to as a purified trans decalin - decahydronaphthalene (2).

该液体的金属成分少,不仅用作浸液曝光用液体,还能够用于在可见光区域使用的光学装置等。 Less metal component of the liquid, not only as a liquid immersion exposure, an optical device for use in the visible region can also be used like.

另外,将上述实施例2中制得的精制后的反-十氢化萘(2)放置在空气中,达到空气饱和状态,测定193nm下的透射率。 Further, after the reaction of the above-prepared purified Example 2 - decahydronaphthalene (2) is placed in the air, saturated air, the transmittance was measured at 193nm. 结果示于表8。 The results are shown in Table 8.

表8 Table 8

如表8所示,可以确认:氧浓度没有被饱和时,透射率提高。 As shown in Table 8, it was confirmed that: when the oxygen concentration is not saturated, the transmittance was improved.

另外,采用以下方法测定由与抗蚀膜接触而引起的透射率的变化。 Further, change in the transmittance was measured by the contact with the resist film caused by the following method.

在进行氮气置换、氧浓度控制在小于等于10ppm的氮气手套箱中,在形成了抗蚀膜H-1、H-4的硅晶片上放置液体3分钟,使液膜的厚度达到0.8mm,测定193nm下的透射率的变化。 Performing nitrogen substitution, the oxygen concentration was controlled at 10ppm or less of nitrogen glovebox, a resist film is formed in the H-1, liquid is placed on the silicon wafer 3 minutes H-4, the film thickness reaches 0.8mm, measured change transmittance at 193nm. 使用纯水作为比较例。 Using pure water as a comparative example. 结果示于表9。 The results are shown in Table 9.

表9 Table 9

如表9所示,即使与抗蚀膜接触,精制后的反-十氢化萘(2)的透射率几乎没有变化。 As shown in Table 9, even if the contact with the resist film, the purified anti - decahydronaphthalene (2) the transmittance of little change.

采用以下方法测定酸发生剂对于精制后的反-十氢化萘(2)的溶解度。 Solubility decalin (2) - For the determination of anti-acid generator after purification by the following method.

使用三苯基锍·九氟正丁烷磺酸盐作为酸发生剂,向100ml精制后的反-十氢化萘中添加规定量的酸发生剂,搅拌1小时,通过目测确认是否全部溶解,对溶解度进行研究。 Use triphenylsulfonium nonafluoro n-butane sulfonate as an acid generating agent, to the purified 100ml trans - decalin predetermined amount of the acid generating agent, stirred for 1 hour, to confirm whether or not all dissolved by visual inspection of The solubility studies. 使用纯水作为比较例。 Using pure water as a comparative example. 结果示于表10。 The results are shown in Table 10.

表10 Table 10

如表10所示,酸发生剂几乎不溶解于精制后的反-十氢化萘(2)。 As shown in Table anti-acid generating agent is hardly dissolved in purified after 10 - decalin (2).

实施例3通过采用以下方法精制市售的挂-四氢双环戊二烯,从而制得浸液暴光用液体。 Example 3 Commercially available purified by the following method hanging - tetrahydro-dicyclopentadiene to prepare a liquid immersion exposure.

将100ml市售的挂-四氢双环戊二烯(东京化成公司制造,换算成1mm光程的193nm的透射率为小于等于10%)投入放有玻璃涂敷的搅拌片的200ml茄形烧瓶中,用冰水浴将内部温度冷却至5℃后,加入20ml的浓硫酸(和光纯药产品),将搅拌片的旋转速度设定为500~1000rpm,在25℃下搅拌20分钟。 The commercially available hanging 100ml - THDCPD (manufactured by Tokyo Chemical Industry Co., 1mm light path in terms of 193nm transmittance of 10% or less) placed into a glass sheet coated with stirring 200ml eggplant flask after the ice-water bath was cooled to an internal temperature of 5 ℃, 20ml of concentrated sulfuric acid (Wako pure Chemical products), the rotational speed of the stirring blade was set to 500 ~ 1000rpm, stirred at 25 ℃ 20 minutes. 然后通过分液除去浓硫酸,进行3次上述操作。 Concentrated sulfuric acid was then removed, the above-described operation was performed three times through the liquid separation. 然后,用50ml去离子水洗涤分离的有机层1次,用饱和碳酸氢钠水溶液洗涤3次。 Then, the separated organic layer was washed with water, 50ml of deionized 1, three times washed with saturated aqueous sodium bicarbonate. 然后用纯水洗涤3次有机层。 Then the organic layer was three times washed with pure water. 确认此时的pH显示7(中性)。 At this time, pH was confirmed to display 7 (neutral). 然后,使用硫酸镁干燥有机层,通过倾析除去硫酸镁。 Then, the organic layer was dried over magnesium sulfate, and magnesium sulfate was removed by decantation. 对此时得到的91ml液体进行30分钟的氮气发泡,测定193nm下的透射率(测定条件采用上述本文中记载的条件),结果换算成1mm光程为87.7%。 At this time, 91ml of liquid obtained foamed with nitrogen for 30 minutes, the transmittance was measured at 193 nm (measurement conditions employed conditions described herein above), the result in terms of optical path length 1mm 87.7%. 另外,使本液体氮气饱和并进行脱气后,保存在经过氮气置换的玻璃容器中。 Further, so that the liquid saturated with nitrogen and degassed, kept in a glass container purged with nitrogen through the. 封入容器后的化合物的GC纯度为99.94%。 GC purity of the compound after the container is sealed 99.94. 将采用实施例3的方法制得的精制后的挂-四氢双环戊二烯称为精制后的挂-四氢双环戊二烯(1)。 The use of hanging the method of Example 3 was obtained in purified embodiment - after hanging THDCPD referred purified - THDCPD (1).

实施例4在氮气气氛下,采用与实施例1相同的方法进行硫酸处理。 Example 4 Under a nitrogen atmosphere, the same as in Example 1 were treated in sulfuric acid. 然后采用与实施例3相同的方法,精制市售的挂-四氢双环戊二烯,再采用与实施例2相同的方法,在氮气气氛下进行减压蒸馏,从而制得换算成1mm光程的透射率为97.5%的液体。 Then the same manner as 3, a commercially available purified hanging Example - THDCPD, then using the same method as in Example 2, was distilled under reduced pressure in a nitrogen atmosphere, thereby preparing an optical path in terms of 1mm 97.5% of the transmittance of the liquid. 通过气相色谱(检测器TCD)分析本液体的溶解氧以及溶解氮浓度,溶解氧浓度低于1ppm(检测限度以下),溶解氮浓度为100ppm。 Analysis by gas chromatography (detector TCD) and dissolved oxygen present in the dissolved nitrogen concentration in the liquid, the dissolved oxygen concentration of 1 ppm or below (below detection limits), the dissolved nitrogen concentration of 100ppm. 将采用实施例4的方法制得的精制后的挂-四氢双环戊二烯称为精制后的挂-四氢双环戊二烯(2)。 Will be used to hang the method of Example 4 was obtained in purified embodiment - after hanging THDCPD referred purified - THDCPD (2).

实施例5除了使用通过氮气精制机精制的氮气,在氮浓度控制在小于等于0.5ppm的手套箱中进行全部操作,并且控制减压度使蒸汽温度为小于等于50℃从而进行减压蒸馏外,采用与实施例1相同的方法进行市售反-十氢化萘(东京化成产品)的精制。 Example 5 except for using purified nitrogen refiner nitrogen, the nitrogen concentration is controlled at less overall operations performed in a glove box 0.5ppm, and controls the degree of reduced pressure the steam temperature is 50 deg.] C or less to perform outer distillation under reduced pressure, using the same method as in Example 1 commercially available trans - decalin (manufactured by Tokyo Kasei product) is purified. 以采用上述测定法B测定的吸光度值为基础,计算精制后的化合物每1mm光程的透射率,结果T=99.5%。 Absorbance values ​​were determined by the above-described base B assay to calculate the transmittance of the purified compound per 1mm light path, the result T = 99.5%. 通过GC(检测器TCD)测定此时的氧浓度,结果氧浓度低于1ppm,氮浓度为119ppm。 GC (detector TCD) at this time is measured by the oxygen concentration, the oxygen concentration is below 1 ppm or result, the nitrogen concentration of 119ppm. 另外,GC纯度为99.92%。 Further, GC purity 99.92%. 将采用实施例5的方法制得的精制后的反-十氢化萘称为精制后的反-十氢化萘(3)。 After the reaction will be obtained using the purification methods of Example 5 - trans decalin called after purification - decahydronaphthalene (3).

实施例6除了使用通过氮气精制机精制的氮气,在氮浓度控制在小于等于0.5ppm的手套箱中进行全部操作,并且控制减压度使蒸汽温度为小于等于50℃从而进行减压蒸馏外,采用与实施例3相同的方法进行市售挂-四氢双环戊二烯(东京化成产品)的精制。 Example 6 except that nitrogen gas by nitrogen gas purifying refiner, the nitrogen concentration in a glove box controlled to 0.5ppm or less in all of the operations performed, and controls the degree of reduced pressure the steam temperature is 50 deg.] C or less so as distillation under reduced pressure, the marketed using the same method as in Example 3 hang - tetrahydro purified dicyclopentadiene (Tokyo Kasei product). 以采用上述测定法B测定的吸光度值为基础,计算精制后的化合物每1mm光程的透射率,结果T=99.6%。 Absorbance values ​​were determined by the above-described base B assay to calculate the transmittance of the purified compound per 1mm light path, the result T = 99.6%. 通过GC(检测器TCD)测定此时的氧浓度,结果氧浓度低于1ppm,氮浓度为100ppm。 GC (detector TCD) at this time is measured by the oxygen concentration, the oxygen concentration is below 1 ppm or result, the nitrogen concentration of 100ppm. 另外,GC纯度为97.80%。 Further, GC purity 97.80%. 将采用实施例6的方法制得的精制后的挂-四氢双环戊二烯称为精制后的挂-四氢双环戊二烯(3)。 Will be used to hang the method of Example 6 was obtained in purified embodiment - after hanging THDCPD referred purified - THDCPD (3).

实施例7通过与实施例3同样地进行硫酸处理,从而精制市售的双环己基、异丙基环己烷、环辛烷、环庚烷,制得浸液曝光用液体。 Example 7 by the same manner as in Example 3 treated with sulfuric acid, whereby purified commercially available dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane, to prepare a liquid immersion exposure.

在上述实施例中,GC纯度分析采用以下条件。 In the above embodiments, GC purity analysis using the following conditions.

采用Agilent Technology的GC6850(柱Agilent Technology HP-1(非极性型)检测器FID)进行测定。 Using Agilent Technology's GC6850 (column Agilent Technology HP-1 (non-polar type) detector FID) was measured. 测定在注入口温度250℃、柱温度70℃~300℃(升温法),载气为氦气的条件下进行。 Measurement was carried out under the conditions of inlet temperature of 250 deg.] C, a column temperature of 70 ℃ ~ 300 ℃ (heating method), the carrier gas is helium. 纯度是将FID的总峰面积作为100%,由面积比求得。 FID is the purity of the total peak area as 100%, determined by the area ratio.

实施例8~实施例22和比较例1~比较例2使用上述评价用抗蚀膜,通过洗脱试验、膜的溶解性试验、图案形成评价(浸渍图案形成评价、利用双光束干涉曝光机的浸液曝光评价)、抗蚀剂接触时的吸光度变化(或者污染)评价本发明的浸液曝光用液体。 Example 8 to Example 22 and Comparative Example 1 to Comparative Example 2 with the resist film, by elution test, solubility test film, patterning evaluation (evaluation by using the pattern forming immersed evaluated using two-beam interference exposure machine evaluation immersion exposure) absorbance change (or contaminated) when the contact evaluation resist immersion exposure liquid according to the present invention. 结果示于表11~表14。 The results are shown in Table 11 to Table 14. 另外,折射率的波长依赖性如表3所示,存在随着波长缩短而折射率值提高的相互关系。 Further, the wavelength dependence of the refractive index as shown in Table 3, there is a correlation with the shorter wavelength of the refractive index value increased. 因此,通过测定D射线(波长589nm)下的折射率,能够预测短波长下的折射率。 Thus, by measuring the refractive index at D-ray (wavelength 589 nm), the refractive index can be predicted at short wavelengths. 特别是由于本发明的浸液曝光用液体具有与表1所示的十氢化萘化学上类似的结构,因而能够由D射线(波长589nm)的折射率进行预测。 In particular, since the immersion exposure liquid according to the present invention having a similar chemical structure decalin shown in Table 1, it is possible to predict the refractive index of D ray (wavelength 589 nm) in the. 因此示出了D射线(波长589nm)下的折射率。 Thus shows a refractive index at a D-ray (wavelength 589nm). 均显示出比纯水的折射率更高的值。 They showed a higher value than the refractive index of pure water.

另外,实施例8~13中所示的浸液曝光用液体是根据实施例1精制的,实施例14~22中所示的浸液曝光用液体是根据实施例1的方法精制的。 Further, in the immersion shown in Examples 8 to 13 for exposure is an exposure with a liquid the liquid is refined according to the method of Example 1 Example 1 was purified in accordance with the immersion embodiment, Examples 14 to 22 shown in FIG.

(1)洗脱试验将涂布了上述评价用抗蚀膜的晶片在300ml的表11所示的浸液曝光用液体中浸渍30秒后,取出晶片,使用HPLC(岛津制作所制造,柱Inertsil ODS-3(内径10mm×长250mm),洗脱溶剂:乙腈/水=80/20,检测器:UV@205nm、220nm、254nm,试样注入量4μm)测定有无残存的浸液曝光用液体中的杂质。 (1) The elution test wafer for evaluation was coated with the above-described resist film shown in Table 11 300ml immersion exposure liquid was immersed for 30 seconds, the wafer was removed using HPLC (manufactured by Shimadzu Corporation, column Inertsil ODS-3 (an inner diameter of 10mm × 250mm length), elution solvent: acetonitrile / water = 80/20, detector: UV @ 205nm, 220nm, 254nm, sample injection amount measurement of 4 m) with the presence or absence of residual immersion exposure impurities in the liquid. 此时,当用任何一个检测器确认检测限度以上的杂质时,将洗脱试验结果记作×,当没有确认检测限度以上的杂质时,将洗脱试验结果记作○。 At this time, when it is confirmed by the above detection limit any impurity detector, the elution test results recorded as × when no acknowledgment detection limit above impurities, the elution test results are reported as ○.

(2)膜的溶解性试验测定涂布了上述评价用抗蚀膜的晶片的初始膜厚后,在300ml的表11所示的浸液曝光用液体中浸渍30秒后,再次进行膜厚测定。 (2) test measures the solubility of the film coated with the above evaluation after the initial film thickness of the resist film of the wafer, in the immersion shown in Table 11 300ml liquid immersed exposure for 30 seconds, the film thickness was measured again . 此时,如果膜厚的减少量在初始膜厚的0.5%以内,则判断为浸液曝光用液体没有溶解抗蚀膜,记为“○”,如果为0.5%以上,则判断为浸液曝光用液体溶解抗蚀膜,记为“×”。 At this time, if the film thickness is reduced within 0.5% of the initial film thickness, it is judged that the liquid immersion exposure resist film is not dissolved, referred to as "○", if not less than 0.5%, the immersion exposure is determined The resist film was dissolved with a liquid, referred to as "×".

(3)图案形成评价试验图案形成评价试验(1)对于涂布了上述评价用抗蚀膜的晶片,用ArF投影曝光装置S306C(ニコン(株)社制造),在NA:0.78、δ:0.85、2/3Ann的光学条件下进行曝光(曝光量30mJ/cm2),然后,用CLEAN TRACK ACT8热板进行PEB(130℃、90秒),用该CLEAN TRACK ACT8的LD喷嘴进行桨叶式搅拌显像(显像液成分:2.38重量%氢氧化四氢铵水溶液)(60秒),用超纯水进行冲洗,接着,以4000rpm进行15秒钟的离心脱水,从而旋转干燥(显像后基板A)。 (3) pattern formation evaluating test pattern forming Evaluation Test (1) for applying the above evaluation wafer resist film by ArF projection exposure device S306C (Ni Nikon Corporation (Ltd.) Co., Ltd.), in NA: 0.78, δ: 0.85 , exposure (exposure amount of 30mJ / cm2) under optical conditions 2 / 3Ann, and then PEB was carried out with a CLEAN TRACK ACT8 hot plate (130 ℃, 90 seconds), be significant with the paddle stirred CLEAN TRACK LD nozzle of ACT8 image (developing solution component: 2.38 wt% aqueous ammonium hydroxide tetrahydro-) (60 seconds), rinsed with ultrapure water, then 15 seconds at 4000rpm centrifugal dewatering, thereby rotating the drying (after the imaging substrate a ). 然后,将上述图案形成的显像后基板A在表11所示的浸液曝光用液体中浸渍30秒后,采用与上述同样的方法进行PEB、显像、冲洗,制得显像后基板B。 Then, after developing the pattern formed on the substrate 11 shown in Table A liquid immersion exposure for the PEB, developing with the same method as above was immersed in the liquid for 30 seconds, use, irrigation, imaging the substrate B prepared . 利用扫描电子显微镜(日立计测器(株)社制造)S-9360对显像后基板A和B观察相当于90nm线、90nm空间的掩膜图案的图案。 A scanning electron microscope (Hitachi Measuring Instruments (Co., Ltd.) manufactured) S-9360 A B substrate after the development was observed and the lines corresponding to 90nm, 90nm space mask pattern of a pattern. 此时,通过目视将对于显像后基板A和B能够得到相同形状的良好矩形抗蚀图案的场合记作“○”,将不能获得良好图案的场合记作“×”。 In this case, after the development was visually for the substrate A and B are the same shape can be obtained a good rectangular resist pattern is referred to as case "○", the case will not be obtained a good pattern referred to as "×". “-”表示没有进行评价。 "-" indicates no evaluation.

图案形成评价试验(2)将在与图案形成评价试验(1)相同条件下进行了曝光的晶片在浸液曝光用液体中浸渍30秒,采用与上述相同的方法进行PEB、显像、冲洗,制得显像后基板C。 Patterning Evaluation Test (2) In the pattern formation evaluating test (1) under the same conditions of exposure of the wafer is impregnated with the liquid immersion exposure for 30 seconds and then performed the PEB, developing the same manner as above, washed in, after the substrate prepared developing C. 此时,通过目视将对于基板A和C能够得到相同形状的良好矩形抗蚀图案的场合记作“○”,不能获得良好形状图案的场合记作“×”。 At this time, the visually for substrate A and C can be obtained the same rectangular shape of the resist pattern is good occasion referred to as "○", can not be obtained good pattern shape occasion referred to as "×". “-”表示没有进行评价。 "-" indicates no evaluation.

(4)接触角测定试验使用Kruss制造的Mode IDSA10L2E,测定反-十氢化萘在上述抗蚀膜H2、H4、H5、石英玻璃上的接触角(测定法Elipse(tangentl)法)。 (4) contact angle was measured using a Kruss Test Mode IDSA10L2E manufactured, measured trans - decalin in the resist film H2, H4, H5, the contact angle on the silica glass (assay Elipse (tangentl) method). 结果示于表12。 The results are shown in Table 12.

(5)使用了双光束干涉的曝光试验除了使下层防反射膜的膜厚为29nm,使抗蚀膜厚为100nm(用于45nm)、60nm(用于30nm)以外,对于涂布了采用与抗蚀膜H2相同的方法制作的评价用抗蚀膜的晶片,在双光束干涉型ArF浸液用简易曝光装置(佳能制造的45nm1L/1S用,ニコン(株)社制造的35nm1L/1S用、TE偏振光曝光使用)的透镜、晶片之间(间隙0.7mm)插入上述精制后浸液曝光用液体,进行曝光,然后,通过空气干燥除去晶片上的浸液曝光用液体,用CLEAN TRACK ACT8热板对本晶片进行PEB(115℃、90秒),用该CLEAN TRACK ACT8的LD喷嘴进行桨叶式搅拌显像(显像液成分:2.38重量%氢氧化四氢铵水溶液)(60秒),用超纯水进行冲洗,通过扫描电子显微镜(日立计测器(株)社制造)S-9360对显像后基板观察图案。 (5) using two-beam interference exposure experiment except that the underlayer antireflective film thickness of 29nm, the resist film thickness of 100 nm or so (for 45nm), other than the 60 nm (for 30nm), for use with coated H2 same resist film wafer evaluation method of making the resist film, the ArF immersion-type two-beam interference exposure apparatus with a simple (manufactured by Canon 45nm1L / 1S with, Ni Nikon Corporation (Ltd.), manufactured by 35nm1L / 1S used, after exposure using the TE polarized light) of the lens, between the wafer (0.7mm gap) is inserted into the purified liquid immersion exposure, exposure, and then, removing the liquid immersion exposure on a wafer by air-drying, heat with CLEAN TRACK ACT8 this wafer board PEB (115 ℃, 90 seconds), a stirring paddle developer (developing solution component: 2.38 wt% aqueous ammonium hydroxide tetrahydro-) using the CLEAN TRACK LD nozzle ACT8 (60 sec), with rinsed with ultrapure water, a scanning electron microscope (Hitachi measuring Instruments (Co., Ltd.) manufactured) S-9360 substrate was observed after developing the pattern. 此时,将得到期望尺寸的L/S(1L/1S)的良好抗蚀图案的场合记作“○”,将不能获得良好图案的场合记作“×”。 At this time, the resulting size of the desired L / S (1L / 1S) pattern where a good resist referred to as "○", the case can not be obtained a good pattern referred to as "×". 结果示于表13。 The results are shown in Table 13.

(6)抗蚀剂接触时的吸光度变化(或者污染)使用玻璃制的吸移管向直径6cm的培养皿中加入液体(去离子水或精制后的反-十氢化萘(2)(采用与实施例2相同的方法精制的其他批次产品)。此时,调节液量使液体的膜厚正好达到1mm。接着,用涂布了光致抗蚀剂(H1、H4)的硅晶片覆盖培养皿的上部。接着,将晶片和培养皿上下倒转,成为使液体浸渍于光致抗蚀膜的状态。此时充分密合培养皿和晶片使液体不从两者之间漏出,并且注意使晶片保持水平以使在用培养皿覆盖的整个部分上光致抗蚀剂均匀地被液体浸渍。然后用规定的浸渍时间进行浸渍,再次使晶片和培养皿上下倒转。收集这些一系列操作后的液体,采用实施例B的方法进行193.4nm的吸光度测定,根据测定值计算出每1cm吸光度的吸光度。另外,在23℃下在充满氮气的手套箱中进行上述一系列操作。结果示于表14 (6) absorbance change (or contamination) of a resist for use in contact glass pipette was added to the liquid in 6cm diameter petri dishes (trans or deionized water after purification - decahydronaphthalene (2) (in the embodiment same method as Example 2 other batches of purified product). At this time, adjusting the liquid amount of the liquid just reaches thickness 1mm. Next, a silicon wafer coated with a photoresist (H1, H4) of the covering dish the upper portion. then, the wafer and the dish upside down, to become immersed in the liquid state photoresist film. in this case the plate and the wafer sufficient adhesion of the liquid from leaking therebetween, and the wafer holding note level so that the liquid is impregnated evenly in the entire part of the coating with the photoresist covered petri dish was then impregnated with a predetermined immersion time, the wafer again turned upside down, and petri plates. these were collected after a series of operation of the liquid, using the method of Example B were 193.4nm absorbance measurement to calculate the absorbance per 1cm absorbance measured values. in addition, the above-described series of operations at 23 ℃ in a nitrogen-filled glove box. the results are shown in table 14 .

表11 Table 11

表12 Table 12

表13 Table 13

表14 Table 14

如表11所示,本发明的浸液曝光用液体比纯水的折射率大,具有式(1-1)~式(1-9)所示的化学结构,因此显示出优异的分辨率,而且不溶解抗蚀膜单体或形成上层膜的抗蚀膜,不洗脱膜成分,也不使生成的抗蚀图案形状变形。 As shown in Table 11, the present invention is the immersion exposure liquid is larger than the refractive index of pure water, having (1-9) a chemical structure represented by formula (1-1) to, and therefore exhibits excellent resolution, and the resist film does not dissolve the resist film forming monomer or an upper layer film, is not eluted from the membrane component, the shape of the deformation is not generated in the resist pattern. 另外,如表14所示可知,精制后的十氢化萘在浸渍时间180秒提取后的吸光度没有变化。 Further, it was found as shown in Table 14, the purified decalin no change in absorbance after 180 seconds immersion time of extraction.

另外可知:作为浸液曝光用液体的评价方法,在氮气气氛下使浸液曝光用液体与在基板上形成的光致抗蚀膜接触,测定接触前和接触后的上述液体在193nm下的吸光度变化并进行比较,从而能够评价浸液曝光用液体的污染度。 Also found: As a method of evaluating liquid immersion exposure of the immersion exposure under a nitrogen atmosphere in contact with the liquid photoresist film formed on a substrate, measuring the absorbance of the liquid in contact with the front and rear of the contacts at 193nm and comparing the change, it is possible to evaluate the degree of contamination of the immersion exposure liquid.

本发明的浸液曝光用液体是脂环烃化合物或在环结构中含有硅原子的环烃化合物,因而在浸液曝光时不会溶解光致抗蚀膜,能够形成分辨率、显像性等优异的抗蚀图案,非常适合用于制造预计今后微细化进一步发展的半导体装置。 Immersion exposure of the present invention with a liquid alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure, and thus is not dissolved when the liquid immersion exposure the photoresist film, the resolution can be formed, imaging, etc. excellent resist pattern is very suitable for the manufacture of semiconductor devices is expected in the future further development of miniaturization.

Claims (25)

  1. 1.浸液曝光用液体,该液体用于通过投影光学系统的透镜和基板之间充满的液体进行曝光的浸液曝光装置或浸液曝光方法,其特征在于:该液体在上述浸液曝光装置工作的温度范围内是液体,该液体包含脂环烃化合物或在环结构中含有硅原子的环烃化合物。 1. The liquid immersion exposure, the liquid immersion exposure apparatus for immersion exposure method of exposing through a liquid filled between the lens substrate and the projection optical system, wherein: the liquid immersion exposure apparatus in the above within a temperature range of a liquid, the liquid containing alicyclic compound or a cyclic hydrocarbon compound containing silicon atoms in the ring structure.
  2. 2.权利要求1所述的浸液曝光用液体,其特征在于:所述脂环烃化合物或在环结构中含有硅原子的环烃化合物在波长193nm下每1mm光程的放射线透射率大于等于70%,D射线的折射率大于等于1.4。 1, the immersion exposure liquid according to claim, characterized in that: said alicyclic hydrocarbon compound or a cyclic hydrocarbon compound containing silicon atoms in the ring structure at a wavelength of 193nm radiation transmittance of each optical path is not less than 1mm 70%, the refractive index of D ray is not less than 1.4.
  3. 3.权利要求2所述的浸液曝光用液体,其特征在于:所述脂环烃化合物或在环结构中含有硅原子的环烃化合物是选自下述式(1-1)~式(1-9)的至少1种化合物, 2, the immersion exposure liquid according to claim, characterized in that: said alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure is selected from the following formulas (1-1) to ( 1-9) at least one compound, 式(1-1)中,R1表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n1、n2各自独立地表示1~3的整数,a表示0~10的整数,当存在多个R1时,该R1可以相同也可以不同,2个或更多个R1可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基, In the formula (1-1), R1 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, n1, n2 each independently represent an integer of 1-3, a denotes an integer of 0 to 10, when a plurality of R1, the R1 may be the same or different, two or more R1 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, 式(1-2)中,A表示单键或可以被碳原子数1~10的烷基取代的亚甲基或可以被碳原子数1~10的烷基取代的碳原子数2~14的亚烷基,R2表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,R7表示氢原子、碳原子数1~10的烷基、氰基、羟基、氟原子、碳原子数1~10的氟取代烷基、或-Si(R9)3基,当存在多个R7时,该R7可以相同也可以不同,2个或更多个R7可以相互结合形成环结构,n3表示2~4的整数,n4表示1~3的整数,b表示0~6的整数,当存在多个R2时,该R2可以相同也可以不同,2个或更多个R2可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基, In the formula (1-2), A represents a single bond or a carbon atom may be substituted with an alkyl group of 1 to 10 or a methylene group may be substituted with an alkyl group of 1 to 10 2 to 14 alkylene group, R2 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si ( R9) 3 group, or -SO3R10 group, R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine carbon atoms, a substituted alkyl group having 1 to 10, or -Si (R9 ) 3 group, when a plurality of R7, the R7 may be the same or different, two or more R7 may be bonded to each other to form a ring structure, n3 represents an integer of 2 to 4, n4 represents an integer of 1 to 3, b It represents an integer of 0 to 6, when a plurality of R2, R2 which may be the same or different, two or more R2 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, 式(1-3)中,R3和R4表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,当R3和R4各自存在多个时,该R3和R4可各自相同也可以不同,2个或更多个R3和R4可以各自单独或相互结合形成环结构,n5和n6表示1~3的整数,c和d表示0~8的整数,R9和R10表示碳原子数1~10的烷基, In the formula (1-3), R3 and R4 represent fluorine carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, alicyclic hydrocarbon group having 3 to 14, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, substituted hydrocarbyl, -Si (R9) 3 group, or -SO3R10 group, R3 and R4 when there are a plurality, R3 and R4 may each be the same or different, two or more R3 and R4 may each be used alone or in bonded to each other to form a ring structure, n5 and n6 represents an integer of 1 to 3, c and d represents an integer of 0 to 8, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, 式(1-4)的(a)、(b)、(c)中,B表示亚甲基或亚乙基,R5表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,e表示0~10的整数,n7表示1~3的整数,当存在多个R5时,该R5可以相同也可以不同,2个或更多个R5可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基, Of formula (1-4) (a), (b), (c), B represents a methylene group or an ethylene group, R5 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10 carbon atoms having 3 to 14 an alicyclic hydrocarbon group, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si (R9) 3 group, or -SO3R10 group, e represents an integer of 0 to 10, 1 to 3 N7 represents integer, when a plurality of R5, R5 which may be the same or different, two or more R5 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, 式(1-5)中,R6表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,f表示0~10的整数,当存在多个R6时,该R6可以相同也可以不同,R9和R10表示碳原子数1~10的烷基, In the formula (1-5), R6 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, f represents an integer of 0 to 10, when a plurality of R6, which may be the same or different from R6, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, , 式(1-6)中,R8和R8'表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,g和h分别表示0~6的整数,n8和n9表示1~3的整数,R9和R10表示碳原子数1~10的烷基, In the formula (1-6), R8 and R8 'represent an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, fluorine-substituted hydrocarbon group, -Si (R9) 3 group, or -SO3R10 group, g and h each represent an integer of 0 to 6, n8 and n9 represent an integer of 1 to 3, R9 and R10 represent alkyl having 1 to 10 carbon atoms is base, 式(1-7)中,R11和R12表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n10、n11各自独立地表示1~3的整数,j、k表示0~6的整数,当R11和R12各自存在多个时,该R11和R12可以相同也可以不同,2个或更多个R11可以相互结合形成环结构,或者2个或更多个R12可以相互结合形成环结构,X表示单键、碳原子数2~10的2价脂肪族烃基、碳原子数3~14的2价脂环烃基,R9和R10表示碳原子数1~10的烷基, In the formula (1-7), R11 and R12 represent a fluorine carbon atoms, an aliphatic hydrocarbon group having 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, having 1 to 10 carbon atoms, substituted hydrocarbyl, -Si (R9) 3 group, or -SO3R10 group, n10, n11 each independently represents an integer of 1 to 3, j, k represents an integer of 0 to 6, when a plurality of R11 and R12, which R11 and R12 may be the same or different, two or more of R11 may be bonded to each other to form a ring structure, or two or more of R12 may be bonded to each other to form a ring structure, X represents a single bond, having 2 to 10 carbon atoms divalent aliphatic hydrocarbon, divalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms, 式(1-8)中,R13表示碳原子数大于等于2的烷基、碳原子数大于等于3的脂环烃基、氰基、羟基、氟原子、碳原子数2~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,p表示1~6的整数,当存在多个R13时,该R13可以相同也可以不同,2个或更多个R13可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基, In the formula (1-8), R13 represents 2 or more carbon atoms of the alkyl group, number of carbon atoms greater than or equal to 3 alicyclic hydrocarbon group, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 2 to 10, -Si (R9) 3 group, or -SO3R10 -, p represents an integer of 1 to 6, when a plurality of R13, the R13 may be the same or different, two or more of R13 may be bonded to each other to form a ring structure, R9 and R10 represents an alkyl group having 1 to 10 carbon atoms, 式(1-9)中,R14表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,n12表示1~3的整数,q表示0~9的整数,当存在多个R14时,该R14可以相同也可以不同,R9和R10表示碳原子数1~10的烷基。 In the formula (1-9), R14 represents aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or a group -SO3R10, N12 represents an integer of 1 to 3, q ​​represents an integer of 0 to 9, when a plurality of R14, the R14 may be the same or different, R9 and R10 represents a carbon atoms of an alkyl group having 1 to 10.
  4. 4.权利要求3所述的浸液曝光用液体,其特征在于:上述式(1-1)所示的化合物由下述式(2-1)表示,上述式(1-4)所示的化合物由下述式(2-2)表示, 3, the immersion exposure liquid according to claim, wherein: the above-described formula (1-1) a compound represented by represented by the following formula (2-1), represented by the above formula (1-4) a compound represented by the following formula (2-2), 式(2-1)中,R1表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,a表示0~10的整数,当存在多个R1时,该R1可以相同也可以不同,2个或更多个R1可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基,式(2-2)中,R5表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,i表示0~2的整数,当存在多个R5时,该R5可以相同也可以不同,2个或更多个R5可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基。 In the formula (2-1), R1 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, a represents an integer of 0 to 10, when a plurality of R1, the R1 may be the same or different, two or more R1 may be bonded to each other to form a ring structure , R9 and R10 represent an alkyl group the number of carbon atoms, of formula (2-2) 1 to 10, R5 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si (R9) 3 group, or -SO3R10 group, i denotes an integer of 0 to 2, when there are a plurality of R5, R5 may be the same or different, two or more R5 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.
  5. 5.权利要求1所述的浸液曝光用液体,其特征在于:使液膜的厚度为1mm、在氮气气氛下使该液体在光致抗蚀膜上接触180秒时,接触前与接触后的液体在193nm下每1cm光程的吸光度变化小于等于0.05。 After the film thickness is 1mm, when the front of the liquid in contact with the photoresist film 180 seconds, the contact with the contact in a nitrogen atmosphere: the liquid immersion exposure according to claim 1 with a liquid, wherein liquid at 193nm absorbance change per 1cm pathlength less than or equal 0.05.
  6. 6.权利要求1所述的浸液曝光用液体,其特征在于:相对于全部浸液曝光用液体,含有大于等于95重量%所述脂环烃化合物或在环结构中含有硅原子的环烃化合物。 1, the immersion exposure liquid according to claim, wherein: with respect to the total immersion exposure liquid, containing not less than 95% by weight of the alicyclic hydrocarbon or cyclic hydrocarbon compounds containing silicon atoms in the ring structure compound.
  7. 7.权利要求1所述的浸液曝光用液体,其特征在于:该液体的溶解氧量小于等于2ppm。 1, the immersion exposure liquid according to claim, characterized in that: the amount of dissolved oxygen in the liquid is less than equal to 2ppm.
  8. 8.权利要求1所述的浸液曝光用液体,其特征在于:该液体含有的金属总量小于等于10ppb。 1, the immersion exposure liquid according to claim, characterized in that: the total amount of metal contained in the liquid is less than equal to 10ppb.
  9. 9.权利要求8所述的浸液曝光用液体,其特征在于:所述金属是选自锂、钠、钾、镁、铜、钙、铝、铁、锌、镍的至少1种金属。 9. The immersion exposure of the liquid to claim 8, wherein: said metal is at least one metal selected from lithium, sodium, potassium, magnesium, copper, calcium, aluminum, iron, zinc, nickel.
  10. 10.权利要求1所述的浸液曝光用液体,其特征在于:该液体在25℃下的粘度小于等于0.01Pa·s。 10. The immersion exposure according to claim 1 with a liquid, wherein: the viscosity of the liquid at 25 deg.] C or less 0.01Pa · s.
  11. 11.权利要求1所述的浸液曝光用液体,其特征在于:在波长193nm下的折射率大于等于1.63。 11. The immersion exposure according to claim 1 with a liquid, wherein: the refractive index at a wavelength of 193nm is not less than 1.63.
  12. 12.权利要求11所述的浸液曝光用液体,其特征在于:在波长193nm下每1mm光程的放射线透射率大于等于95%。 12. The immersion exposure according to claim 11 with a liquid, wherein: the radiation transmittance at a wavelength of 193nm per 1mm light path is greater than or equal to 95%.
  13. 13.权利要求4所述的浸液曝光用液体,其特征在于:上述式(2-1)所示的化合物是反-十氢化萘,在波长193nm下每1mm光程的放射线透射率大于等于95%,溶解氧量小于等于2ppm。 13. The immersion exposure according to claim 4 with a liquid, characterized in that: a compound of the above formula (2-1) is trans - decalin at 193nm wavelength radiation transmittance of each optical path is not less than 1mm 95% dissolved oxygen amount is smaller than 2ppm.
  14. 14.权利要求13所述的浸液曝光用液体,其特征在于:是在氮气气氛下通过对反-十氢化萘原料进行浓硫酸洗涤和蒸馏而得到的纯度大于等于95重量%的液体。 14. The immersion exposure according to claim 13 with a liquid, wherein: the anti-by under a nitrogen atmosphere - decalin liquid feedstock and distillation was washed with concentrated sulfuric acid to obtain a purity of not less than 95% by weight.
  15. 15.权利要求4所述的浸液曝光用液体,其特征在于:上述式(2-2)所示的化合物是挂-四氢双环戊二烯,在波长193nm下每1mm光程的放射线透射率大于等于95%,溶解氧量小于等于2ppm。 15. The immersion exposure according to claim 4 with a liquid, wherein: the compound represented by formula (2-2) are linked to the above-described formula - THDCPD, the radiation transmittance at a wavelength of 193nm per 1mm pathlength greater than equal to 95% dissolved oxygen amount is smaller than 2ppm.
  16. 16.权利要求15所述的浸液曝光用液体,其特征在于:是在氮气气氛下通过对挂-四氢双环戊二烯原料进行浓硫酸洗涤和蒸馏而得到的纯度大于等于95重量%的液体。 16. The immersion exposure according to claim 15 with a liquid, wherein: under a nitrogen atmosphere by hanging - THDCPD purity raw material is washed and concentrated sulfuric acid obtained by distillation is not less than 95% by weight liquid.
  17. 17.权利要求1所述的浸液曝光用液体的制造方法,其特征在于:包括在氮气气氛下对包含上述脂环烃化合物或在环结构中含有硅原子的环烃化合物的液体进行浓硫酸洗涤和蒸馏的至少1个工序。 17. The immersion exposure according to claim 1, the method for manufacturing a liquid, characterized by: a liquid comprising concentrated sulfuric acid for the alicyclic hydrocarbon compound or a cyclic hydrocarbon compound containing silicon atoms in the ring structure under a nitrogen atmosphere at least one step of washing and distillation.
  18. 18.浸液曝光方法,该浸液曝光方法是用曝光光束照明掩膜,通过在投影光学系统的透镜和基板之间充满的液体,用上述曝光光束使基板曝光,其特征在于:上述液体是权利要求1所述的浸液曝光用液体。 18. The immersion exposure method, the immersion exposure method with the exposure light illumination mask through a liquid between the lens substrate and the projection optical system is filled with the exposure light beam exposing the substrate, wherein: the liquid is immersion exposure according to claim 1 with a liquid.
  19. 19.权利要求18所述的浸液曝光方法,其特征在于:在上述基板上的抗蚀膜表面形成浸液用上层膜,该浸液用上层膜是含有可溶于碱显像液、且不溶于权利要求1所述的浸液曝光用液体的树脂成分的浸液用上层膜,具有六氟甲醇基和羧基的至少一个基团作为用于赋予该碱可溶性的取代基。 19. The immersion exposure method according to claim 18, wherein: the surface of the resist film formed on the substrate with an immersion upper layer film using the immersion upper layer film is a developing solution containing an alkali-soluble, and insoluble in claim 1, said immersion liquid immersion exposure liquid resin component with an upper layer film having a hexafluorocarbinol group and at least one carboxyl group as a substituent imparting the alkali-soluble group.
  20. 20.浸液曝光用液体的污染度评价方法,该污染度评价方法用于评价通过在投影光学系统的透镜与基板之间充满的液体进行曝光的浸液曝光装置或浸液曝光方法中使用的液体的浸液曝光使用时的污染度,其特征在于:在氮气气氛下使浸液曝光用液体与在上述基板上形成的光致抗蚀膜接触,测定接触前和接触后的上述液体在波长193nm下的吸光度变化并进行比较,从而评价浸液曝光用液体的污染度。 20. The liquid immersion exposure method of evaluating the degree of contamination, the contamination evaluation method for the evaluation of exposure by immersion fluid between the lens and the substrate is filled with the projection optical system or immersion exposure apparatus used in the exposure method degree of contamination of the liquid immersion exposure during use, wherein: under a nitrogen atmosphere so that immersion exposure liquid contact with the photoresist film formed on the substrate, the liquid was measured before and after exposure in contact with a wavelength change in absorbance at 193nm and compared to evaluate the degree of contamination of the immersion exposure liquid.
  21. 21.浸液曝光液体组合物,其特征在于:含有大于等于95重量%的下述式(2-1)或下述式(2-2)所示的化合物,溶解氧量小于等于2ppm, 21. The immersion exposure liquid composition, comprising: 95% by weight of a compound of the following formula (2-1) or (2-2) by the following formula containing greater than or equal amount of dissolved oxygen 2ppm or less, 式(2-1)中,R1表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,a表示0~10的整数,当存在多个R1时,该R1可以相同也可以不同,2个或更多个R1可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基,式(2-2)中,R5表示碳原子数1~10的脂肪族烃基、碳原子数3~14的脂环烃基、氰基、羟基、氟原子、碳原子数1~10的氟取代烃基、-Si(R9)3基、或-SO3R10基,i表示0~2的整数,当存在多个R5时,该R5可以相同也可以不同,2个或更多个R5可以相互结合形成环结构,R9和R10表示碳原子数1~10的烷基。 In the formula (2-1), R1 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10 , -Si (R9) 3 group, or -SO3R10 group, a represents an integer of 0 to 10, when a plurality of R1, the R1 may be the same or different, two or more R1 may be bonded to each other to form a ring structure , R9 and R10 represent an alkyl group the number of carbon atoms, of formula (2-2) 1 to 10, R5 represents an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 10, -Si (R9) 3 group, or -SO3R10 group, i denotes an integer of 0 to 2, when there are a plurality of R5, R5 may be the same or different, two or more R5 may be bonded to each other to form a ring structure, R9 and R10 represent an alkyl group having 1 to 10 carbon atoms.
  22. 22.权利要求21所述的液体组合物,其特征在于:该液体组合物含有的金属总量小于等于10ppb。 The liquid composition according to claim 21, wherein: the total amount of metal contained in the liquid composition is less than equal to 10ppb.
  23. 23.权利要求21所述的液体组合物,其特征在于:上述式(2-1)所示的化合物是反-十氢化萘,在波长193nm下每1mm光程的放射线透射率大于等于95%。 23. A liquid composition as claimed in claim 21, wherein: a compound of the above formula (2-1) is trans - decalin, at a wavelength of 193nm at each 1mm light path of the radiation transmittance of 95% or more .
  24. 24.权利要求21所述的液体组合物,其特征在于:上述式(2-2)所示的化合物是挂-四氢双环戊二烯,在波长193nm下每1mm光程的放射线透射率大于等于95%。 The liquid composition of claim 21 to claim 24., characterized in that: a compound of the above formula (2-2) shown are linked - THDCPD, the radiation transmittance of each optical path length 1mm at wavelengths greater than 193nm equal to 95%.
  25. 25.权利要求21所述的液体组合物,其特征在于:在氮气气氛下采用浓硫酸洗涤和蒸馏的至少1种方法对上述式(2-1)或式(2-2)所示的化合物进行精制。 The liquid composition of claim 21 to claim 25., characterized in that: at least one compound with concentrated sulfuric acid washing method and distilled under a nitrogen atmosphere the above formula (2-1) or (2-2) shown in FIG. for purification.
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Cited By (6)

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CN101969026A (en) * 2010-08-27 2011-02-09 上海交通大学 Electrode preparation method based on ink jet printing and laser interference exposure
US8182982B2 (en) 2008-04-19 2012-05-22 Rolith Inc Method and device for patterning a disk
US8192920B2 (en) 2008-04-26 2012-06-05 Rolith Inc. Lithography method
US8425789B2 (en) 2007-06-09 2013-04-23 Rolith, Inc. Method and apparatus for anisotropic etching
US8518633B2 (en) 2008-01-22 2013-08-27 Rolith Inc. Large area nanopatterning method and apparatus
US9069244B2 (en) 2010-08-23 2015-06-30 Rolith, Inc. Mask for near-field lithography and fabrication the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8425789B2 (en) 2007-06-09 2013-04-23 Rolith, Inc. Method and apparatus for anisotropic etching
US9645504B2 (en) 2008-01-22 2017-05-09 Metamaterial Technologies Usa, Inc. Large area nanopatterning method and apparatus
US8518633B2 (en) 2008-01-22 2013-08-27 Rolith Inc. Large area nanopatterning method and apparatus
US8182982B2 (en) 2008-04-19 2012-05-22 Rolith Inc Method and device for patterning a disk
US8192920B2 (en) 2008-04-26 2012-06-05 Rolith Inc. Lithography method
US9069244B2 (en) 2010-08-23 2015-06-30 Rolith, Inc. Mask for near-field lithography and fabrication the same
CN101969026B (en) 2010-08-27 2012-07-18 上海交通大学 Electrode preparation method based on ink jet printing and laser interference exposure
CN101969026A (en) * 2010-08-27 2011-02-09 上海交通大学 Electrode preparation method based on ink jet printing and laser interference exposure

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