TWI260467B - Positive resist composition and method of forming resist pattern - Google Patents

Abstract

A positive resist composition for an immersion exposure process is provided which satisfies (1) and (2) below. (1) Taking X1 to be the sensitivity when forming a 150-nm pattern, in which the lines and spaces are in a ratio of 1 to 1, by means of ordinary exposure which uses a KrF excimer laser using a positive resist composition, and taking X2 to be the sensitivity when forming a similar pattern by simulated immersion lithography which adds the step of bringing a solvent into contact with a resist film in the period between exposure and post-exposure baking to a step similar to the step by ordinary exposure, the absolute value of [(X2/X1)-1]x100 is 5 or less. (2) The positive resist composition for an immersion exposure process contains a resin component (A) comprising hydroxystyrene units.

Description

1260467 (1) Description of the Invention [Technical Field of the Invention] ^ The present invention relates to a positive photoresist composition and a photoresist pattern forming method. The present invention is based on Japanese Patent Application No. 2004-24579, which was filed with the Japanese Patent Office on January 30, 2010, and Japanese Patent Application No. 2 0 0 4 - 1 1 9 4 9 6 applied to the Japan Patent Office on April 14, 2004. The number claims priority and its content is hereby invoked. [Prior Art] In the manufacture of fine structures in various electronic devices such as semiconductor devices and liquid crystal devices, the lithography method is versatile, and the device structure is miniaturized. In the lithography method, the miniaturization of the photoresist pattern is required. . In the current mass production of semiconductor elements using the lithography method, for example, for KrF excimer laser or ArF excimer laser. Therefore, in the future, more detailed pattern formation will be required. φ In order to achieve the formation of a fine pattern, development of the exposure apparatus and the corresponding photoresist is the first priority. In the exposure apparatus, ArF excimer laser, F2 laser, EUV (extreme ultraviolet light), electron beam, short-wavelength wavelength of light source such as X-ray, or the number of apertures (NA) of the lens are generally large. However, in the case of a novel exposure apparatus in which the wavelength of the light source is short-wavelength, it is necessary, and in addition, in the case of high NA, since the resolution and the depth of focus are in a trade-off relationship, even if the resolution is increased, the depth of focus is lowered. The problem. In the above, a method of immersing (i m m e 1· s i ο η ) lithography is reported (2) 1260467 (for example, Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3). This method is conventionally known to have a refractive index greater than the refractive index of air in a portion between the lens of the inert gas such as air or nitrogen and the photoresist layer (the photoresist film) on the wafer wafer. The solvent of the rate can be satisfied, for example, by a solvent such as pure water or a fluorine-containing inert liquid. Since these solvents can be used, even when a light source of the same exposure wavelength is used, in the case of using a light source of a shorter wavelength or in the case of using a high NA lens, it is considered that there is no high resolution while achieving high resolution. The depth of focus is reduced. When such immersion lithography is used, the lens which is currently assembled in a certain device is used, and at a low cost, the formation of a photoresist pattern which is excellent in high resolution and excellent in depth of focus is widely accepted. Attention. [Non-Patent Document 1] Journal Of Vacuum Science & Technology B (USA), 1 999, Vol. 17, No. 6, 3306-3309 Page φ [Non-Patent Document 2] Vacuum Science And Technology Monthly (USA), 2001, Vol. 19, No. 6, 23 5 3 - 23 5 6 Η . [Non-Patent Document 3] SPIE (Proceedings of SPIE) (USA) 2002, No. 4691, 459 - 465 pages· # 【 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明- (3) 1260467 Predictable effects on the semiconductor industry. However, as described above, since the photoresist film is in contact with the solvent during the exposure, the photoresist film is deteriorated, and the component which is adversely affected by the solvent from the photoresist may bleed out to change the refractive index of the solvent. There will be problems such as damage to the original strength of the lithography method, and whether it can form a good photoresist pattern with the same degree of conventional exposure processing. There are still many unknown points. In fact, a conventional KrF excimer laser with a positive photoresist composition φ or the like can be applied to the immersion lithography method, which is affected by the solvent, and the sensitivity is deteriorated or the resulting photoresist pattern becomes a T-top shape. The roughness of the surface of the resistive pattern (degraded contour shape), or the problem of expansion of the photoresist pattern. The present invention has been made in view of the above problems, and an object thereof is to provide a positive resist composition and a resist pattern forming method suitable for a processing step using a KrF excimer laser having a wavelength of 248 nm. Without impairing the resolution and depth of focus of the immersion lithography method, it is difficult to be adversely affected by the solvent used in the immersion lithography step, the sensitivity is deteriorated, the φ is small, the resist pattern is excellent in contour shape, and the immersion lithography is contained. A positive photoresist composition and a photoresist pattern forming method used in the method for forming a photoresist pattern in the method step. [Means for Solving the Problem] In order to achieve the above object, the present invention adopts the following configuration. The first aspect of the positive-type photoresist composition of the present invention comprises a positive-type photoresist composition used in the method for forming a photoresist pattern in a immersion exposure step, which satisfies the following (1) and (2) The condition is characterized by a positive photoresist composition (4) 1260467.

• (1) Using this positive-type photoresist composition, a KrF* excimer laser with a wavelength of 24 8 nm is used in the normal exposure lithography step of the light source to form a line of 150 nm and a gap of 1 The sensitivity of the photoresist pattern of 1 is X 1 . On the other hand, in the same step as the lithography method of the usual exposure of the KrF excimer laser having the aforementioned wavelength of 24 8 nm, the B-exposure is selected in the same step. A step of impulsive immersion lithography in which the solvent for exposing the immersion exposure is contacted with the photoresist film is added between the post-exposure heating (PEB), and a line of 10.5 nm and a gap of 1 to 1 are formed. The sensitivity of the type is X2, [(X 2 / X 1 ) - 1 ] The absolute 値 of X 1 0 0 is 5 or less. The solvent is at least one selected from the group consisting of water and a fluorine-containing inert solvent, and is preferably at least one selected from the group consisting of water and a fluorine-containing inert solvent, and particularly preferably water. (2) The positive-type photoresist composition contains a resin component (a) and a compound (acid generator) (B) which is produced by exposure of φ to an acid, and the component (a) has the following general formula (Ϊ) Non-benzidine forming unit (al ) ° [Chemical 1]

(wherein R represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3.) (5) 1260467 Second aspect system, a positive type resist composition used in a method for forming a photoresist pattern containing an immersion exposure step a compound containing a resin component (A) and a compound which is produced by exposure to an acid (under-producer) (B) 'Mai Hai (A) component having the above-described hydroxybenzene represented by the formula (I) The ethylene structural unit (a1) and the structural unit (a2) having an acid dissociable dissolution inhibiting group, φ. The structural unit (a2) contains two or more constituent units having acid-dissolving dissolution inhibiting groups having different structures. Positive photoresist composition. Further, the method for forming a photoresist pattern of the present invention is a method for forming a photoresist pattern using the photoresist composition of the present invention, which is a method for forming a photoresist pattern characterized by an immersion exposure step. In the scope of the present specification and the patent application, "normal exposure" means that the lens of the exposure apparatus and the photoresist film on the wafer are exposed to an inert gas such as air or nitrogen, which is conventionally used. Φ "methacrylic acid" means one or both of methacrylic acid and acrylic acid. "(Meth)acrylate" means a general term for methacrylic acid and acrylate. "Constituent unit" means a monomer unit constituting a polymer. The "lithography method" generally comprises the steps of performing pre-baking, selective exposure, post-exposure heating, and alkali development in accordance with the sequence, ^, as the case may be, after the above-mentioned alkali development, post-exposure baking step . [Effect of the Invention] In the present invention, in the positive resist composition and the resist pattern forming method which are applied to the processing step using the wavelength of 24 8 nm KrF excimer Ray (6) 1260467, the damage is not impaired. When the resolution of the immersion immersion method and the depth of focus are improved, it is obtained, and it is difficult to be adversely affected by the solvent used in the lithography step, the sensitivity is small, the resist pattern shape is excellent, and the like is excellent. [Best Mode for Carrying Out the Invention] The present inventors have, in the completion of the present invention, a method for evaluating the suitability of a resist film used in a method for forming a resist pattern containing an immersion exposure step, which is analyzed in the following manner. As a result of the analysis, a method of forming a photoresist pattern using the positive resist composition and the composition was evaluated. That is, when the formation performance of the photoresist pattern due to immersion exposure is evaluated, if (i) the performance of the optical system by the immersion exposure method can be confirmed, (ii) the photoresist film (the photoresist layer) with respect to the immersion solvent The influence of (iii) the deterioration of the photoresist film caused by the impregnation solvent can be judged to be necessary and sufficient. Regarding the performance of the optical system of (i), for example, assuming that the photographic photosensitive plate having a surface water resistance is immersed in water, the case where the surface is irradiated with pattern light is apparent, in the interface between the water surface and the surface of the water and the photosensitive plate. If there is no light transmission loss such as reflection, then there is no problem after that. In principle, there should be no doubt. The light propagation loss in this case can be easily solved by the appropriate angle of incidence of the exposure light -10- (7) 1260467. Therefore, if the object to be exposed is a photoresist film, or a photosensitive film for photography, or an image forming screen, the particles are inert with respect to the impregnation solvent, that is, are not affected by the impregnation solvent, and are impregnated. The solvent is also unaffected, and it is considered that there is no change in the performance of the optical system. Therefore, regarding this point, it is no longer necessary to perform a new confirmation experiment. The influence of the photoresist film derived from the impregnation solvent of (ii), specifically, the composition of the photoresist film is dissolved in the liquid, and the refractive index of the impregnation solvent is changed. When the refractive index of the impregnating solvent changes, the optical resolution of the pattern exposure is changed, which is not necessary to be experimental, and the theory can be established. In this case, when the photoresist film is immersed in the impregnation solvent, if the composition is eluted, the composition of the impregnation solvent is changed, or if the refractive index changes, it is sufficient. The pattern light is illuminated and developed to confirm the resolution. φ In contrast, when the photoresist film in the immersion solvent is irradiated with pattern light and developed to confirm the resolution, it is confirmed whether the resolution is good or not, which is the effect of the deterioration of the immersion solvent. ? Or is it the effect of resolution caused by the deterioration of the photoresist film? Or both? Then it becomes indistinguishable. Regarding the deterioration of the photoresist film caused by the impregnation solvent of (iii) and the deterioration of the resolution, the solvent is impregnated between the selective exposure and the post-exposure heating (PEB), for example, as in the case of rinsing. The evaluation test of the contact treatment by the photoresist film and then development to check the resolution of the obtained photoresist pattern is sufficient. Moreover, this evaluation method directly sprinkles the impregnated -11 - (8) 1260467 agent on the photoresist film, and is too harsh in terms of impregnation conditions. In this regard, the case where the exposure test is carried out in the completely immersed state is the influence of the deterioration of the impregnation solvent. Is it the cause of deterioration caused by the impregnating solvent of the photoresist composition? Or the influence of both parties, making the resolution change? It is not obvious that the above phenomena (ii) and (iii) mean that the phenomenon in the table is confirmed by the deterioration of the shape of the pattern or the deterioration of the sensitivity caused by the impregnation solvent of the photoresist film, and Can grasp it. Therefore, verification only at point (iii) is also included in the verification relating to point (i i ). According to such analysis, the immersion exposure suitability of the photoresist film formed by the appropriate novel photoresist composition in the immersion exposure treatment step can be impregnated, for example, between selective exposure and post-exposure heating (PEB), for example It can be confirmed by performing an evaluation test by contact treatment with a photoresist film after rinsing, and then developing and performing a resolution test of the obtained photoresist pattern. [Positive-type photoresist composition] ♦ The photoresist composition of the first embodiment of the sample embodiment is a positive-type photoresist composition used in the photoresist pattern forming method including the immersion exposure step, so as to satisfy the following The conditions of (1) and (2) are characteristic. (1) Using the positive-type photoresist composition, a K r F excimer laser having a wavelength of 248 nm is used in the lithography step of the normal exposure of the light source, and the light is one-to-one with a line of 150 nm and a gap of 1 The sensitivity of the resist pattern is XI, -12- (9) 1260467. On the other hand, the KrF excimer laser of the aforementioned wavelength of 24 8 nm is used in the same step of the usual exposure lithography step of the light source, A step of impulsive immersion lithography in which the solvent for exposing the immersion exposure is contacted with the photoresist film is added between the selective exposure and the post-exposure heating (PEB), and the line and the gap become a one-to-one light with a line of 15 〇 nm. When the resistance pattern is formed, the sensitivity is X2, [(X2 / XI ) — 1] The absolute 値 of xl 00 is 5 or less. The solvent is at least one selected from the group consisting of water and a fluorine-containing inert solvent, and is preferably at least one selected from the group consisting of water and a fluorine-containing inert solvent, and particularly preferably water. (2) The positive-type photoresist composition contains a resin component (a) and a compound (acid generator) (b) which is produced by exposure to an acid, and the component (A) has the general formula (I) The hydroxystyrene structural unit (a 1 ) 关于 • About the condition (1 ) # The absolute enthalpy of the above [(X2 / XI ) - l]xl〇〇 is 5 or less, preferably 3 or less, and further preferably 1 or less. It is better to be close to Yu. Since the KrF excimer laser is used as the immersion exposure treatment step for the exposure processing step, the resist composition is excellent, and it is difficult to be adversely affected by the solvent used in the lithography step. The effect is small, and the shape of the photoresist pattern is excellent. When the absolute 値 exceeds 5, it is not appropriate to use the photoresist composition as the immersion exposure treatment step for the KrF excimer laser exposure processing step, and the photoresist pattern will become a T-top shape, which will produce a photoresist pattern. The collapse or the like is not -13- (10) 1260467 is appropriate. The above absolute enthalpy may be changed by a change in the composition of the photoresist composition such as a resin component or an acid generator. It is preferable to use a positive resist composition of the second embodiment described later. Further, as shown in the above condition (2), even if the resin component having the hydrophilic group-constituting unit (a1) having the hydroxyl group is contained, the photoresist composition having a small range of absolute enthalpy can be formed, and On the contrary, φ is such that the same constituent unit (a 1 ) is contained, and the above-mentioned absolute enthalpy is also large. Therefore, it is difficult to specify the invention relating to the present embodiment by the specific composition of the photoresist composition other than the unit (a1). Therefore, in the invention relating to the present embodiment, the condition (1) is specified by the above-described absolute enthalpy. Further, in the photoresist composition of the invention according to the embodiment, the absolute flaw can be easily specified by a simple test which satisfies the scope of the invention of the present embodiment. Using a KrF excimer laser with a wavelength of 248 nm for the normal φ exposure lithography step of the light source, a KrF excimer laser with a wavelength of 248 nm is used as the light source, and the lens and wafer of the conventional exposure device are used. Exposing the upper photoresist film with an inert gas such as air or nitrogen is usually performed by exposure, on a substrate such as a sand wafer, by a micro-step, that is, photoresist coating. , pre-baking, selective exposure, post-exposure heating, and alkali development are carried out in sequence. The alkali-developing post-exposure post-baking treatment step may be included as the case may be, and an organic or inorganic anti-reflection film may be provided between the substrate and the coating layer of the photoresist composition. -14- (11) 1260467 Next, the lithography step of this normal exposure forms a photoresist pattern of 1 to 1 in the line and gap formed by 150 nm (hereinafter referred to as "1 50 nm L&" S)) Sensitivity XI refers to the exposure of 150 nm L&S, which is a technical term frequently used by practitioners. It is obviously self-evident. To be more cautious, 'about this sensitivity, one time' First, the horizontal axis is used as the exposure amount, and the vertical axis is taken as the line width of the photoresist formed by the exposure amount thereof, and the logarithmic approximation curve is obtained by the least square method from the obtained pattern. The formula is Y=aLog e(Xl + b, where XI represents the amount of exposure, Y is not the line width of the photoresist, and a and b represent the fixed number. Further, when this formula is expanded and XI is changed to the expression, it becomes Xl=Exp[(Y — b / a]. In this formula, Y = 1 50 ( nm ) is imported, and the calculated ideal sensitivity XI can be calculated. Also, the condition of this is the number of rotations of the photoresist coating, pre-baking temperature' exposure conditions. 'The post-exposure heating conditions and the development conditions are also the conditions that are currently used. The range in which the 150 nm L & S can be formed is self-explanatory. § The rotation number is about 1000~4000 rpm, more specifically about 200 rpm, and the prebaking (PAB) temperature is in the range of 70~140T: 'by this' the photoresist film thickness is 200~400 nm, Specifically, it is within the scope of the present invention to form 350 nm 任一 at any point in the range [(X2 / XI ) - l] xi 〇〇 if the absolute 値 is 5 or less. It is also possible to expose through a mask using a KrF excimer laser exposure apparatus with a wavelength of 24 8 nm or Nikon or a Canon company (ΝΑ=0.68). In the selective exposure, the mask is used -15- ( 12) 1260467 In general, the binary mask can also be used as a mask. The post-exposure heating (PEB) temperature is in the range of 90~140T: the development condition is 2.38% by weight of TMAH (tetramethyl hydride hydroxide) developer, developed at 23 ° C for 15 to 90 seconds, more specifically for 60 seconds, and then rinsed with water. In addition, PAB and PEB The temperature condition can be optimized by using each photoresist composition φ. The method of obtaining the optimum condition is familiar to the item. Yi who is self-evident.

The preferred combination of [PAB temperature (°C), PEB temperature (°C)] is [125, 110], [100, 110], [140, 140]' is better [125, 110] . The simulated immersion lithography step means that the KrF excimer laser of the same 248 nm as described above is used in the same step as the lithography step of the usual exposure for the light source, after selective exposure and post-exposure heating (PEB). Between φ, the step of increasing the step of contacting the solvent for immersion exposure with the photoresist film, that is, the conditions for the experiment when X2 is obtained, except for the step of bringing the solvent into contact with the photoresist film, The conditions are the same when X 1 is obtained. Specifically, the steps of photoresist coating, prebaking, selective exposure, contact of the solvent for immersion exposure with the photoresist film, heating after exposure, and alkali development are carried out in sequence. Depending on the case, it may also contain the above-described alkali-developed post-exposure baking treatment step. -16- (13) (13) 1260467 Contact means that the surface of the photoresist film can be sufficiently contacted with the solvent, for example, the selectively exposed photoresist film provided on the substrate is immersed in the solvent for immersion exposure. The same result can be obtained by blowing it in the same way. The contact time can be, for example, 2 to 5 minutes. Then, by the analog immersion lithography step, the sensitivity X2 finger of the photoresist pattern forming the 15 〇nm L&S can form an exposure of 150 nm L&S as in the above XI. Familiar with the technical terms that the skilled person can usually use. Further, the conditions at this time (the number of rotations of the photoresist coating, the prebaking temperature, the exposure conditions, the post-exposure heating conditions, the conditions of alkali development, etc.) are also the same as those of X 1 described above. Further, the solvent used in the immersion exposure step is water, or a fluorine-containing inert liquid or the like described later, but water is preferred. [(X2/X1) — 1] 値 100 absolute 値, X2 and XI can be self-evident if they can be obtained in the above manner. The general exposure steps for obtaining XI and the preferred specific conditions for obtaining the simulated immersion lithography step of Χ 2 are as follows. (i) Formation of a photoresist pattern using a lithography step by usual exposure (measurement of X 1) Organic anti-reflection film composition: product name D uv 4 2 p (manufactured by Brewer Scientific Co., Ltd.), using a rotator It is coated on a wafer of 6 inches or 8 inches in diameter, and dried on a hot plate at 185 ° C for 60 seconds to form an organic system with a film thickness of 65 nm. Antireflection film. Next, the positive photoresist composition is coated on the anti-reflection film -17-(14)(14)1260467 using a spinner, pre-baked (pab) on a hot plate, and dried to prevent the film on the anti-reflection film. A photoresist film having a film thickness of 350 nm was formed thereon. Then the 'marking line is selected by KrF exposure device S203B (NAkon's NA opening number = 0.68, σ 2 / 3 wheel belt illumination) through a * 値 mask, using KrF excimer laser (24 8 nm) to select Sexual exposure. Subsequently, P E B treatment was carried out, and further development was carried out at 72 ° C for 6 seconds with an alkali developer. As the alkali developer, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used. Thus, a pattern of 10.5 nm lines and a gap of 1:1 can be formed to obtain the sensitivity (Εορ) XI at this time. Further, the conditions of P A Β and Ρ Β are used to optimize the conditions for each photoresist composition. The method of obtaining the optimum conditions is self-evident to those skilled in the art. Preferably, the combination of [PAB temperature (°C), PEB temperature (°C)] is [125,110], [100,110], [140,140], more preferably [125,1 1 〇] 〇 (ϋ) Formation of a photoresist pattern using a simulated immersion lithography step (measurement of X2) In the same manner as (i) above, the sensitivity is obtained in addition to the simulated immersion exposure treatment (Eop) ) ·· X2. That is, the simulated immersion exposure treatment is performed by rotating the tantalum wafer on which the photoresist film is disposed between the selective exposure and the ruthenium treatment, and continuously dripping the pure water for 2 minutes at 23 °C. -18- (15) 1260467 • With regard to the condition (2): 'The positive-type resist composition of the present embodiment is not particularly limited, but contains a resin component which is alkali-soluble due to the action of an acid and It is preferred to expose the acid generator component which causes acid generation to a chemically enhanced type. • Resin component (A) constituent unit (a 1 ) The constituent unit (al) is represented by the above general formula (I). In the case of a positive-type photoresist composition for a KrF excimer laser, a resin component having a unit having a hydroxyl group (a1) is used. Then, in the case of containing a resin component having a hydrophilic group unit, the influence of a solvent such as water may be feared. However, by applying this embodiment, it is possible to obtain a shape that can prevent deterioration of sensitivity and good pattern shape. In the above general formula (I), the R system, a hydrogen atom or a methyl group is preferably a hydrogen atom φ. The position of the hydroxyl group may be any of the ortho, meta and para positions, and since it is easy to obtain a low price, the alignment is preferred. The compounding weight of the constituents (al) is 50 to 85 mol%, preferably 60 to 80 mol%, of the component (A). When it is more than the lower limit 値, it is preferable from the viewpoint of solubility of the developer, etc., and good resolution can be obtained. Since the upper limit 値 or less, the condition of the above (1) can be satisfied, and the condition can be suppressed. The film of the pattern is thinned and the like. The component (A) is preferably one having a composition of an acid dissociable dissolution inhibiting group (a 2 ). The effect of the acid which is exposed from the component (B) is -19-(16) 1260467, and the acid dissociable dissolution inhibiting group is dissociated in the structural unit (a2), whereby the resin component (A) becomes alkali-soluble. As a result, the photoresist pattern forming unit (a2) can be formed. Since the constituent unit (a2) is proposed in various ways, it can be arbitrarily selected and used. Φ For example, the acid dissociable dissolution inhibiting group described later is an alkoxyalkyl group (a2 - 1 ), and the acid dissociable dissolution inhibiting group is a tertiary alkoxycarbonyl group and/or a tertiary alkyl group (a2 - 2) [The structural unit (a2 - 3 ) having an aliphatic cyclic group may be contained], and the acid dissociable dissolution inhibiting group is a crosslinking group structural unit represented by the general formula (II) to be described later, and may be optionally used. Further, the main chain of the constituent unit (a2) may, for example, be a (meth)acrylic acid skeleton or a hydroxystyrene skeleton represented by the above general formula (I) (#, Hereinafter, the "(meth)acrylic skeleton" ) or "hydroxystyrene skeleton" is called "main chain"). In the case of the (meth)acrylic acid skeleton, the ethylenic double bond is cleaved, and the hydrogen of the carboxyl group is replaced, and the structure having the acid dissociable dissolution inhibiting group as a bond [C(0)-〇-R/; A constituent unit of R / acid dissociative dissolution inhibitor. In the case of the hydroxystyrene skeleton, a constituent unit in which a hydrogen group is substituted with an acid dissociable dissolution inhibiting group is used. Further, the skeleton of the main chain can be suitably selected from the types of acid dissociable dissolution inhibiting groups and the like. For example, in the case of a (meth)acrylic acid skeleton, mainly -20-(17) 1260467, a tertiary alkyl group or a crosslinking group described below or the like is used. In the case of the above-mentioned hydroxystyrene skeleton represented by the general formula (I), an alkoxyalkyl group, a tertiary alkoxycarbonyl group, a tertiary alkyl group, a crosslinking group or the like described below is used, and the unit () is contained to contain Two or more kinds of acid dissociation dissolution inhibiting group constituent units having different structures are preferred. Here, the "acid dissociative dissolution inhibiting group of different structure" means that the chemical formula of "acid dissociative dissolution inhibiting group" is different. In other words, for example, when the first constituent unit and the second constituent unit are used in combination in the constituent unit (a2), the acid dissociable dissolution inhibiting group of the first constituent unit and the acid dissociable dissolving of the second constituent unit are dissolved. The chemical formula of the inhibitory group is not the same. Thereby, the effect can be improved. The constituent units of the acid dissociative dissolution inhibiting group having mutually different structures can be mixed in three or more types, and φ is desirable in terms of the effect and ease of handling. In the structural unit (a2), in the case where the constituent units having such an acid-dissociable dissolution-inhibiting group structure are combined into a plurality of types, each of the constituent units preferably contains 1 mol% or more of the component (A), and contains 3 Moore% or more is further preferred. ^ The ratio of the constituent unit (a2) is 5 to 50 mol%, preferably 10 to 4 5 mol%, in the component (A). The improvement of the resolution at the lower limit 値 or more is preferable from the viewpoint of the solubility of the developer and the like. By the upper limit 値 or less, it is possible to adopt a balance with the constituent unit (a 1 ) or the like. -21 - (18) 1260467 The component (A) may contain a constituent unit (al) and constitute a constituent unit other than the unit (a2). The other constituent unit may be, for example, a constituent unit (a3) represented by the following general formula (III). Structural unit (a3) The constituent unit (a3) is as shown in the following general formula (III). 〔化2〕

(wherein R represents a hydrogen atom or a methyl group, R1 represents an alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 3). In the constituent unit (a3), R is a hydrogen atom or a group. Base, preferably a hydrogen atom. The above R 1 may, for example, be a linear or branched alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group or a pentyl group. , isoamyl, neopentyl and the like. Industrially, methyl or ethyl is preferred. The above 1 series, 0 or an integer of 1 to 3. Among these, 1 is preferably 0 or 1, and industrially, 0 is preferred. Further, in the case of 1 to 3, the substitution position of R1 may be either an ortho, meta or para position, and further, in the case where 1 is 2 or 3, it may be a combination of any substitution positions. The ratio of the constituent unit (a3) is 1 to 30 mol -22 - (19) 1260467 %, preferably 2 to 15 mol%, in the component (A). The shape of the resist pattern can be improved by the lower limit 値 or more, and it is preferable from the viewpoint of the solubility of the developer, etc., and by the upper limit 値, the constituent unit (a 1 ), (a 2 ) ) Equal balance. The component (A) may be used alone or in combination of two or more. The mass average molecular weight of the component (A) [Mw : GPC (gel permeation chromatography)] The mass average molecular weight in terms of polystyrene may be from 500 to 30,000, preferably from 6,000 to 15,000 ° in the photoresist composition. The compounding amount of the component (A) is 5 to 20% by mass, preferably 8 to 15% by mass. • For the acid generator (B) (B) component, a known acid generator used in a conventional chemically amplified resist composition can be used arbitrarily. That is, in terms of an acid generator, a key salt acid generator such as an iodine salt or a phosphonium salt; an oxime sulfonate acid generator; a dialkyl or bisarylsulfonyldiazomethane, a poly (disulfonyl) diazomethane, diazomethane nitrosulfonate, etc.; diazomethane acid generator; iminosulfonate acid generator, diterpenoid acid generator, etc. A wide variety of substances are known, and known acid generators are not particularly limited and can be used. In the diazomethane acid generator, specific examples of the dialkyl or bisarylsulfonyldiazomethane acid generator may be bis(isopropylsulfonyl)diazomethane, double ( p-Toluenesulfonyl) Diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)carbrium-23-(20) 1260467 Nitrogen methane, double ( Cyclopentylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and the like. In the diazomethane acid generator, the poly(disulfonyl)diazomethane acid generator may, for example, be a 1, 3-bis(phenylsulfonyldiazodiamine) having the structure shown below. Methylsulfonyl)propane (Compound A, decomposition point 1 3 5 °C), 1,4 bis(phenylsulfonyldiazomethylsulfonyl)butane (Compound B, decomposition point 1 4 7 °C), 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane (Compound C, melting point 1 3 2 ° C, decomposition point 1 4 5 ° C), 1,1 〇- Bis(phenylsulfonyldiazomethylsulfonyl)decane (Compound D, decomposition point 147 ° C), 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane ( Compound E, decomposition point 149 ° C), 1,3 - bis(cyclohexylsulfonyldiazomethylsulfonyl)propane (Compound F, decomposition point 1 5 3 ° C), 1,6 - double (ring Hexylsulfonyldiazomethanesulfonyl)hexane (Compound G, melting point 109 ° C, decomposition point 122 ° C), 1,1 〇-bis(cyclohexylsulfonyldiazomethylsulfonyl) Decane (compound Η, decomposition point 1 1 61:) and the like. -24- 1260467 Γ~~\ 3 i y y y y y y y y y y y y y y y y y y y y

/V OH-SHO 〇H1 OHIO OHf 〇0"r0 OHCUO OHroJ I zx ^ t I z2_ !"o 〇J"0 OHIO OHro 0"?-0 0"!"〇OHro 1 IIII < 2c V ommsmno 2 1N = c 1 ONSH o 0 = s = 〇2 -N = c Io=s = o 1 \M π2c H2c H2c _2c 2c _CNc

V OMMSMno2 -N = cIOHSno

Vonsno 2 -N=c - oy SMMO / ONSNO 〇=s=〇 onsno N2HC—N2=c—N2HC— _ >-1 I onMSHO ONSno ohnsno i

Onsno 2 1 nhc I ommsmno i 0 1* \^/ n2c 1 onsno 2 -Nnc -onsHO Noodle, main 亘 亘 (B-based benzoic acid I acid-based amine salt oxysulfonate In the sulfomethyl a oxy icILul E sulfothiol a -25- (22) 1260467 imino)-P-methoxyphenyl phenyl acetonitrile, α - (trifluoromethylsulfonyl fluorenyl) Oxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-p-methoxyphenylethylate ^ ^ - (ethyl oxyimino) a pair Oxyphenyl acetonitrile, α-(propylsulfonyloxyimino)p-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-p-bromophenylacetonitrile, and the like. Among these, α-(methylsulfonyloxyimido)-ρ-methoxyphenylacetonitrile is preferred. The ferrous salt-based acid generator is as described above, and is a cation-containing iodine-containing ferrous salt-based acid generator and a cation-containing sulfur-containing sulfonium-based acid generator. Specific examples of the iodine-based acid generator include trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-tributylphenyl) iodine Trifluoromethanesulfonate or nonafluorobutanesulfonate. Specific examples of the phosphonium salt acid generator include triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and tris(4-methylphenyl). Trifluoromethanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, dimethyl(4-hydroxynaphthyl)phosphonium trifluoromethanesulfonate, heptafluoropropanesulfonate or Its nonafluorobutane sulfonate, triphenylmethanesulfonate of monophenyldimethylhydrazine, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, trifluoromethane of diphenylmonomethylhydrazine a sulfonate', a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof. In addition, the (Β) component is preferably selected from the group consisting of the type of the acid dissociative dissolution inhibiting group of the component (A), and is not particularly limited. However, if a guanidine-based acid generator and a diazo are used, When one or more kinds of methane acid generators are used, it is difficult to be affected by the solvent, and the effect of the present embodiment is -26-(23) (23) 1260467. It is preferable to use a salt selected from the group consisting of sulfonium salts. In the case of one or more kinds of the agent and the diazomethane acid generator, the component (B) is preferably 50% by mass or more, preferably 80% by mass or more. Further, in the case of the diazomethane acid generator, a dialkyl or bisarylsulfonyldiazomethane acid generator is preferred. The component (B) may be used alone or in combination of two or more. The amount of the component (B) to be used is 0.5 to 30 parts by mass, preferably 1 to 1 part by mass, per 100 parts by mass of the component (A). The formation of the pattern can be sufficiently carried out by a mass ratio of 5% or more, and a uniform solution can be obtained at 30 parts by mass or less, and the storage stability is good. In the positive-type resist composition of the present embodiment, in order to improve the shape of the resist pattern, storage stability and the like can be stored, and further, a component can be added, and a nitrogen-containing organic compound (D) can be blended (hereinafter, referred to as (D). )ingredient). • ( D ) Nitrogen-containing organic compounds Many of these (D) components have been proposed and can be used arbitrarily, but amines, especially a second-grade aliphatic amine or a third-grade aliphatic amine are preferred. The aliphatic amine refers to an alkyl group having an alkyl group of 15 or less or an amine of an alkanol. In the case of the second or third amine, trimethylamine, diethylamine and triethyl are exemplified. Amine, di-n-propylamine, tri-n-propylamine, tripentylamine, tridodecylamine, trioctylamine, diethanolamine, triethanolamine, triisopropanol, etc. 'especially triethanolamine' The third-order alkanolamine like isopropanolamine is preferably -27-(24) (24)1260467, three (2-methoxymethoxyethyl)amines, three ones 2- ( 2 - Three polyalkoxyalkylamines such as methoxy(ethoxy))ethylamine, three mono(2-(2-methoxyethoxy)methoxyethyl)amine. Among them, three 2-(2-methoxy(ethoxy))ethylamine are preferred among the nitrogen-containing organic compounds, three- 2 -(2-methoxy(ethoxy)) The solubility of ethylamine with respect to the solvent used in the immersion lithography step is preferably small. These may be used alone or in combination of two or more. The component (D) is usually used in an amount of from 0. 0 1 to 5 · 0 parts by mass based on 100 parts by mass of the component (A). Further, it is possible to prevent the deterioration of the sensitivity due to the blending of the component (D), to improve the shape of the resist pattern, to preserve the storage stability, and the like, and to further contain an oxyacid of an organic carboxylic acid or phosphorus. Or its derivative (E) (hereinafter referred to as (E) component). Further, the component (D) and the component (E) may be used singly or in any of them. • (E) Ingredients (E), for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are appropriate. The phosphorus oxyacid or a derivative thereof may, for example, be phosphoric acid, di-n-butyl phosphate, diphenyl phosphate or the like, or an ester-like derivative thereof, phosphonic acid or phosphonic acid dimethyl group. An ester, a phosphonium di-n-butyl ester, a phenylphosphonic acid, a diphenyl phosphonate, a phosphonic acid dibenzyl ester, and the like, and the likes of the esters 28-(25) (25) 1260467 The phosphinic acid such as the derivative 'phosphinic acid' phenylphosphinic acid and the like, and such ester-like derivatives are preferred among these. (E) ingredient, each of the ingredients (A)! The mass parts are used in a ratio of 001 to 5.0 parts by mass. • Other optional components are positive-type photoresist compositions of the present embodiment, and may be added as appropriate, and have additives for blending properties, such as added resins for improving the properties of the photoresist film, and interfacial activity for coating properties. Agent, dissolution inhibitor, plasticizer 'stabilizer, colorant, antihalation agent, etc. The positive resist composition of this embodiment can be produced by dissolving each material in an organic solvent. For example, the components may be mixed in a usual manner and stirred, and may be dispersed and mixed by using a dissolver such as a dissolver, a homogenizer or a 3-roll mill as needed. Further, after mixing, a sieve, a membrane filter or the like may be used for filtration. • The organic solvent dissolves the components used in the organic solvent. If it is a solution that can be made homogeneous, it is customary that the solvent of the chemically-enhanced photoresist can be selected from any of the well-known materials. Use two or more types. For example, ketones such as r - butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone or ethylene glycol, ethylene glycol monoacetate, Diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol -29 - (26) 1260467 monoacetate 'dipropylene glycol, or monopropyl ether of dipropylene glycol monoacetate, monoethyl ether, a polyvalent alcohol such as monopropyl ether, monobutyl ether or monophenyl ether or a derivative thereof, or a cyclohexane-like cyclic ether or methyl lactate, ethyl lactate (EL), methyl acetate Ethyl acetate, butyl acetate, methyl pyruvate 'ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate and the like. These organic solvents may be used singly or as a mixture of two or more kinds. Further, a mixed solvent of propylene glycol monomethyl ether acetate (P G Μ E A ) and a polar solvent is preferred. Next, the compounding ratio can be appropriately determined in consideration of the compatibility of P G Μ E A with a polar solvent, etc., but is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Or preferably 1: 9 to 8: 2, more preferably 2: 8 to 5: 5 within the range. More specifically, the polar solvent is in the case of E L , and the mass of P G Μ E A : E L is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Or preferably 2: 8~5: 5, more preferably 3: 7~4: 6. Further, the organic solvent is preferably a mixed solvent of at least one selected from the group consisting of PGMEA and EL and r-butyrolactone. In this case, in terms of the mixing ratio, the former and the latter are preferably of a mass of 70: 3 0 to 95: 5 ° The amount of the organic solvent used is not particularly limited, but may be applied to a coating such as a substrate. Thick and suitable for setting. Generally, the solid concentration of the photoresist composition is in the range of 2 to 20% by mass, preferably 5 to 15% by mass. -30- (27) 1260467 ♦ Second embodiment: The second embodiment is a positive resistive composition of the first embodiment, wherein the component (A) has acid dissociation dissolution inhibition. The structural unit (a2) is a structural unit (a2) containing an acid dissociable dissolution inhibiting group which is a constituent unit (a 2 - 丨) of a hospital oxygen base. (A) component••constituting unit (a2) In the second embodiment, 'the constituent unit (a2) is a slept unit having an acid dissociable dissolution inhibiting group which is an alkoxyalkyl group (a2 - Π. In the case of the constituent unit (a2-1), for example, the constituent unit (al) may, for example, be a monoterpenes in which a hydrogen atom of a hydroxyl group of a hydroxystyrene skeleton (main chain) is replaced by an alkoxy group. In the case of constituting the unit (a1) in the description of the main chain, the preferred embodiment is also the same as the constituent unit (al). In the case of the alkoxyalkyl group, for example, 1-ethoxyethyl group can be exemplified. 1-ethoxypropyl ' 1 -methoxypropyl ' 1 - ethoxypropyl and the like, alkoxy group having 1 to 5 carbon atoms and lower alkoxyalkyl group having 1 to 5 carbon atoms. Further, in the second embodiment, the structural unit (a2) is further composed of an acid dissociable dissolution inhibiting group as a second-stage oxycarbonyl group and/or a third stage. It is better to form the unit of the base (a2-2). This is relative to the acid dissociation dissolution which is easy to dissociate with an alkoxyalkyl group. The constituent unit of the base (a2 - 1 ), which has an acid dissociable solubility -31 - (28) (28) 1260467, is more difficult to dissociate at the active energy level for dissociation. a constituent unit (a2-2) of a tertiary alkoxycarbonyl group and/or a tertiary alkyl group, which can improve both the shape and the resolution of the pattern. In the constituent unit (a2-1) and the constituent unit (a2- 2) In the case of combination, the ratio of each constituent unit (a2), in terms of the effect, in the component (A), the constituent unit (a2-1) is 20 to 45 mol%, preferably 25 to 40. The molar %, the constituent unit (a2-2) is 5 to 20 mol%, preferably 7 to 15 mol%. The main chain of the constituent unit (a2-2) may, for example, be a (meth)acrylic acid. The skeleton or the hydroxystyrene skeleton which is the same as the structural unit (al) represented by the above general formula (I), and the like, may be appropriately selected depending on the type of the acid dissociable dissolution inhibiting group, etc. Among them, a hydroxystyrene skeleton is preferred. The third-stage alkoxycarbonyl group may, for example, be an alkoxycarbonyl group having a carbon number of 4 or 5 in the alkoxy group, for example, a tertiary butoxycarbonyl group. a pentyloxycarbonyl group, etc. The third-stage alkyl group may, for example, be an alkyl group having 4 or 5 carbon atoms, such as a tertiary butyl group, a tertiary pentyl group, etc. wherein a third-order alkoxycarbonyl group is preferred, and further three The butoxycarbonyl group is preferably a (C) crosslinkable polyvinyl ether compound in the second embodiment of the photoresist composition, and further includes the component (C) in terms of contour shape or depth of focus enhancement or the present embodiment. The effect of the aspect is preferably -32- (29) 1260467 • (C) The crosslinkable polyvinyl ether compound (C) component acts as a crosslinking agent with respect to the above component (a). In other words, when the photoresist composition of the present embodiment is applied to a substrate or the like and pre-baked at a temperature of 8 Torr to 150 ° C, preferably i 20 ° C or higher, by heating, (C) The crosslinking reaction of the component with the component (a), for example, with the radical of the constituent unit (a1), occurs, and an alkali-insoluble or poorly soluble photoresist film is formed on the substrate. Next, in the exposure step, in the PEB step, the cross-linking is decomposed due to the action of acid from the component (B), and the exposed portion is changed to alkali solubility, and the unexposed portion does not change in the alkali-insoluble state. Therefore, the exposed portion is removed by alkali development to form a photoresist pattern. Therefore, the type of the component (C) is not particularly limited as long as it has such a function. In terms of the component (C), specifically, at least two crosslinkable vinyl ether-based compounds can be used. Specifically, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol diethylene ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether Ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl acid, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, hydrazine Pentaerythritol divinyl ether 'neopentyl alcohol trivinyl ether' cyclohexane dimethanol diethyl ether ether and the like. Among these, a crosslinkable divinyl ether compound is preferred. Next, in terms of the divinyl ether compound, it is preferred to be represented by the following general formula (1). -33- (30) (30)1260467 [Chemical 4] ch2 = ch - o - r11- o - CH = CH2 (1) In the above general formula (1), the R11 system may have a substitution The group is a branched chain having a carbon number of 1 to 10, a linear alkylene group, or a compound represented by the following general formula (2). Further, the alkylene group may have an oxygen bond (ether bond) in the main chain. 〔化5〕

In the above general formula, R14 is also a branched chain, a linear alkylene group having a substituent of 1 to 1 Å, and an alkylene group having an oxygen bond in the main chain (ether bond) Knot). γ is 〇 or 1. In the case of R11, it is preferred to use -C4H8-, -C2H4OC2H4-, -C2H4OC2H4OC2H4-, and the general formula (2), wherein the general formula (2) is preferred, especially R14 is the sub- The group having a Y content of 1 (cyclohexane dimethanol divinyl ether [hereinafter, abbreviated as CHDVE]) is preferred. The component (C) may be used alone or in combination of two or more. In addition, the amount thereof is from 0 to 5 to 20 parts by mass, preferably from 1 to 10 parts by mass, per 100 parts by mass of the component (A). • The component (B) is the same as in the first embodiment. -34- (31) (31) 1260467 • The component (D) is the same as in the first embodiment. • (E) component is the same as in the first embodiment. • Other arbitrary components are the same as in the first embodiment. • The organic solvent is the same as in the first embodiment. ♦ Third embodiment: The positive resist composition of the third embodiment is the positive resist composition of the first embodiment, and the component (A) has the constituent unit (a 1) And a unit (a2) having an acid dissociable dissolution inhibiting group, wherein the structural unit (a2) contains an acid dissociable dissolution inhibiting group which is a basic structural unit (a2 to 3) having an aliphatic cyclic group. • (A) component••constitutive unit (a2—3) Here, “the acid dissociable dissolution inhibiting group is a group having an aliphatic cyclic group” means that the acid dissociable dissolution inhibiting group is in the action of acid The portion from the decomposition of the resin 'has an aliphatic cyclic group. -35- (32) 1260467 having such a constituent unit (a2 - 3 ) ' improves the shape. In particular, the photoresist pattern obtained by the lithography step of the immersion treatment, 'compared with the photoresist pattern obtained by the lithography step without immersion treatment, tends to obtain high verticality of the sidewall, which is good. The shape of the rectangle. The constituent unit (a2-3) may, for example, be an acid-dissociable dissolution inhibiting group, a third-order alkyl group containing an aliphatic polycyclic group, and/or a third-order alkane having an aliphatic monocyclic group. Base. φ In the case of the aliphatic monocyclic group, a group in which one hydrogen atom is removed from the cycloalkane or the like can be exemplified. In the case of the aliphatic polycyclic group, a group in which one hydrogen atom is removed from a bicyclic alkane, a tricyclic chain, a tetracyclic chain or the like can be exemplified. Specifically, in terms of the aliphatic monocyclic group, a group in which one hydrogen atom is removed from cyclopentane or cyclohexane is preferred, and a cyclohexyl group is preferred. The aliphatic polycyclic group may, for example, be a polycycloalkane such as adamantane, norbornene, iso-serane, tricyclodecane or tetracyclododecane, and the like may be removed by one hydrogen atom. Further, such a polycyclic group, for example, in the resin for φ photoresist composition of the ArF excimer laser, the acid dissociable dissolution inhibiting group can be suitably selected from most of the proposers. Among these, cyclohexyl, adamantyl, norbornyl and tetracyclododecyl groups are industrially easy to obtain. Among them, a cyclohexyl group and an adamantyl group are preferred. In the case of a third-stage alkyl group containing a polycyclic group and/or a tertiary alkyl group having an aliphatic monocyclic group, generally, a constituent unit represented by the general formula (V) described later is used. Or 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, (meth)acrylic acid -36-(33) !26〇467, The hydrogen atom of __ is substituted by an aliphatic monocyclic or polycyclic group bonded to a lower alkyl group, so that an acid-dissociable third-order alkyl ester is formed on the substituted ring. Alternatively, the constituent unit represented by the general formula (VI) described later may be substituted for the lower hydrogen group of the third-order carbon atom instead of the hydrogen atom of the carboxyl group of the methacrylic acid, and the one having the fat form is formed. The key is at the end. The solution is to know that the other part of the week is also the base of the original element. The graded grade is low and the low grade 3 is the single type. The formula is based on the formula of the base, and the ring-bearing one, the mono-alkane before the one-to-one knot or the grade is the body-bonded base. Said that it is more than a ring before the alkane multi-element 2 a

V

Good for tlmll species 1 less to I V 6

P20 RIC -c

The V base is lower than 2 R or the original hydrogen is R. Formula -37- (34) (34) 1260467 [Chem. 7]

R

(wherein r is a hydrogen atom or a methyl group, and R2 2 and R2 3 are each a respective lower alkyl group.) wherein, in the case of R21, a lower linear or branched alkyl group having a carbon number of 1 to 5 is Preferably, methyl 'ethyl' propyl 'isopropyl 'm-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and the like are exemplified. Among them, an alkyl group having a carbon number of 2 or more, preferably 2 to 5, is more excellent in acid dissociation than in the case of a methyl group, and is preferable in that it can be highly sensitive. Further, it is preferable that the above-mentioned R22 and R23 are industrially independent, and it is preferably a lower-grade hospital base having a carbon number of 1 to 5. These bases tend to become higher in acid dissociation than the 2-methyl-2-nonion base. More specifically, R22 and R23 are each independently, preferably the same as the above-mentioned R21, which is a lower linear or branched alkyl group. Among them, R2 2 and R2 3 are both methyl groups, which is industrially preferable. Specifically, a constituent unit derived from 2-(1 'adamantyl)-2-hydroxy(meth)acrylate can be exemplified. -38- (35) 1260467 • Example 1 of the preferred resin component (A) Further, in the third embodiment, a preferred embodiment can be exemplified. That is, the component (A) has a constituent unit (a 1 ) and further constitutes a unit (a2), and the acid dissociable dissolution inhibiting group is a (meth) group having an aliphatic polycyclic group-containing tertiary alkyl group. A unit derived from acrylic acid and having a constituent unit (a3). Further, it is preferably a copolymer of the three constituent units. • Example 2 of the preferred resin component (A) Further, in the third embodiment, further preferred embodiments include the following. In other words, the structural unit (a2) contains a constituent unit (a2 to 4) having an acid dissociable dissolution inhibiting group other than the group having the aliphatic cyclic group. In this aspect, the constituent unit (a2) is contained. The acid dissociable dissolution inhibiting group has a structural unit (a2 - 3 ) having an aliphatic cyclic group, and further does not correspond to the structural unit (a2 - 3), and contains the above structural unit (a 2 - 4). By this configuration, it is surprising that the pattern of the pattern shape has a high verticality and a good rectangular pattern for performing the immersion treatment step. Since the solvent which can be used for immersion exposure is worried about the sensitivity, the deterioration of the photoresist pattern, etc., but by selecting the composition of the photoresist composition, and not using the immersion exposure -39- (36) 1260467 Good comparisons can be obtained for the situation. In the contact hole pattern, since the exposure area is small, it tends to be easily affected by the impregnation of the solvent, and in this configuration, not only L&S, but also a good pattern shape can be obtained in the contact hole pattern. The reason why the effect can be obtained is not clear, but it is assumed that the acid dissociation dissolution inhibiting system between the constituent unit (a2 - 3) and the constituent unit (a2 - 4) is caused by the difference in the active energy level. In the case where the constituent unit (a2-3) is combined with the constituent unit (a2-4), in the component (A), the constituent unit (a2 to 3) is 3 to 25 mol% in terms of the effect. Preferably, it is 6 to 20 mol%, and the constituent unit (a2-4) is 1 to 20 mol%, preferably 3 to 15 mol%. • The constituent unit (a2 - 4) is not particularly limited as long as it does not correspond to the constituent unit (a2 - 3), and the acid dissociable dissolution inhibiting group is selected from the group consisting of One or more of a tertiary alkoxycarbonyl group, a third-order alkyl group, and a crosslinking group represented by the following general formula (11) are preferred.

(Π) (R3 and R4 are each independently a lower alkyl group, η is an integer of 1 to 3, and A represents a single bond or an η10-valent organic group.) In the third-stage alkoxycarbonyl group, for example, Tert-butyloxycarbonyl-40-(37) (37) 1260467, tertiary pentyloxycarbonyl and the like. The second-stage yard base may, for example, be a secondary butyl group, a base group, and an aliphatic polycyclic group or an aliphatic monocyclic group. Tertiary butyl is preferred. A cross-linking system that bonds between at least two constituent units. The constituent unit to which the crosslinking group is bonded has a carboxyl group, a hydroxyl group and the like. Next, the number of constituent units combined by the crosslinking group is preferably two or three. Examples of the lower alkyl group of R3 and R4 (preferably having a carbon number of 5 or less) may, for example, be methyl, ethyl, m-propyl, isopropyl, m-butyl, isobutyl or tert-butyl. , n-pentyl and so on. Further, the oxime is an organic group having a single bond or a combination of (n=1) bonds, preferably a hydrocarbon group having 1 to 20 carbon atoms. In the case of the hydrocarbon group in the case where η is 1, a linear or branched alkylene group, a cycloalkylene group or an extended aryl group, and the hydrocarbon group in the case where η is 2, the alkylene group may be exemplified. One of the hydrogen atoms in the cycloalkylene group or the extended aryl group is a trivalent group which is detached. Further, in the case of the hydrocarbon group in the case where η is 3, two of the hydrogen atoms in the above alkylene group, the cycloalkylene group or the exoaryl group are quaternary groups which are detached and are particularly excellent. ), a linear alkylene group of 2 to 10, and R3 and R4 are a methyl group. The main chain structure of the constituent unit to be crosslinked by the crosslinking group is not particularly limited, and examples thereof include the hydroxystyrene structural unit or the (meth)acrylic acid skeleton similar to the above structural unit (a 1 ). The (methyl)-propyl-41-(38) 1260467 enoic acid skeleton is preferred. That is, it is preferable that the cross-linking structure which constitutes the following -^ Z formula (4) is not preferable

One O CH2 — 〒 31 one HgC — C one

c=o I R4^ C~a

(4) H4, and A are as defined above (in the above formula, R31 is a methyl group or a hydrogen atom, and R3 is the same.) The parent y structure m, preferably at least two acrylic acid or methacrylic acid first-order fluorene groups The ester, h over A (organic or single bond) is a linked crosslinked unit. Therefore, in this crosslinked structure, the ester group is changed to a carboxyl group by the action of an acid generated by exposure, and the resin component of the exposed portion is made alkali-soluble. Φ On the other hand, in the unexposed portion, the crosslinking group remains as it is, so that the resin component is maintained to be alkali-insoluble. Such cross-linking structures, such as acrylic acid or methacrylic acid or such reactive functional derivatives, for example, a halide of 2 or 4 molecules of (meth)acrylic acid, and a third group having a hydroxyl group bonded at each terminal a diol of a carbon atom, a triol or a tetrahydrol (teUol) type, having a hydroxyl group of 2 or 4 alcohols, and a diester having 2 to 4 ethylenically unsaturated bonds, 3 Derived from an ester or a tetraester. The above diols may, for example, be 2,3-dimethyl- 2 -42 - (39) 1260467, 3-butanediol, 2,3-diethyl-2,3-butane Glycol, 2,3 di-n-dipropyl- 2,3-butanediol, 2,4-dimethyl- 2,4-pentanediol, 2,4-diethyl- 2,4 Monopentanediol, 2,4-di-n-propyl- 2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-diethyl- 2,5-hexanediol, 2,5-di-n-propyl-2,5-hexanediol, 2,6-dimethyl- 2,6-heptanediol, 2,6-two Ethyl-2,6-heptanediol, 2,6-di-n-propyl-2,

6-heptanediol-like diols, in the case of triols, such as 2,4-dimethyl-2,4-dihydroxy-3-(2-hydroxypropyl)pentane, 2,4 — Diethyl- 2,4-dicarboxylic acid-3-(2-propyl propyl) pentylene ' 2' 5 - dimethyl - 2,5 - dihydroxy - 3 - (2-hydroxypropyl) Alkane, 2,5-diethyl- 2,5-di-diyl- 3-(2-propionylpropyl)-hexatriol, furan (tetrol with furan), may be exemplified by red algae Erythritol (erythritol), neopentyl alcohol, 2,3,4,5 - hexanol furan. Among these diesters or triesters, the general formula (5)

(5) (wherein R31 has the same meaning as described above, P is 〇, 1 or 2) and the general formula (6) - 43- (40) 1260467 [Chemical 1 l] A HpC-R31 r31

C H2— =〇—a ch2— R31 (6) or a general formula [Chemical 1 2] A H2C - (7)

(The triester shown in the formula (7) R31 has the same meaning as described above). In terms of the acid dissociable dissolution inhibiting group of the unit (a2 - 4 ), -44- (41) 1260467 wherein a tertiary butyl group, in the above general formula (5), P is preferably a crosslinking group of 2 diester. . In the second example of the preferred resin component (A), the following two examples are preferred (Examples 2 - 1, Examples 2 - 2). •• Preferred resin component (A) Example 2 - 1 In this example, the acid-dissociable glutinous solution inhibiting group of the constituent unit (a 2 to 3) is a second stage containing an aliphatic polycyclic group. The sulfhydryl group (A) can be used as the acid dissociable dissolution inhibiting group constituting the element (a2 - 4). The acid dissociable dissolution inhibiting group of the constituent unit (a2 - 3) is exemplified as the description of the constituent unit (a2-3) in terms of the third-stage alkyl structural unit containing an aliphatic polycyclic group. Among them, those having an adamantyl group are preferred, and in the above general formula (V), 'R21 is preferably a methyl group or an ethyl group. φ In the case where the constituent unit (a2-3) is combined with the constituent unit (a2-4), the ratio of each constituent unit 'in the component (A), the effect point, for example, the constituent unit (a 2 - 3) It is 2 to 20% by mole, preferably 5 to 10% by mole, and the constituent unit (a2-4) is 2 to 20% by mole, preferably 5 to 10% by mole. The acid dissociable dissolution inhibiting group of the above-mentioned structural unit (a2 - 4) is a third-order alkyl structural unit, and the above-mentioned structural unit (a2 - 4) can be suitably used as exemplified. Among them, the second-stage butoxybenzene-containing group in which the hydrogen atom of the hydroxyl group in the hydroxystyrene skeleton is substituted with a tertiary butyl group constitutes a unit - 45- (42) 1260467, a tertiary butyl (meth) acrylate. Preferably, the unit is preferably used in combination. In the case where the two constituent units are used in combination, the molar ratio is, for example, 1:1 or 丨:3. • The preferred resin component (A) Example 2 - 2 In this example, the acid dissociable dissolution inhibiting group constituting monoterpene (a2 - 3 ) is a tertiary alkyl group containing an aliphatic monocyclic group. In the above-mentioned acid dissociable dissolution inhibiting group constituting the mono-φ element (a2 - 4 ), the resin component (A) of the crosslinked structure represented by the above general formula (II) can be used. According to this configuration, in particular, the verticality of the pattern side wall in the case of performing the immersion exposure step becomes high, and a very good rectangular pattern can be obtained. Therefore, not only L & S, but also a good pattern shape can be obtained in the contact hole pattern. The acid-dissociable dissolution inhibiting group of the structural unit (a2 - 3) may be exemplified as the above-mentioned structural unit (a2-3) in terms of the third-order alkyl structural unit containing an aliphatic monocyclic group. Among them, a φ group having a cyclohexyl group is preferred, and a unit comprising a methyl hexyl group or a 1-ethylcyclohexyl group as a methacrylate group is preferred. The acid dissociable dissolution inhibiting group of the above-mentioned structural unit (a 2 - 4 ) can be exemplified by the description of the above-mentioned structural unit (a2 - 4 ) in terms of the crosslinked structure constituent unit represented by the above general formula (Π). By. The same is true for the better one. • The component (B) is the same as in the first embodiment. -46- (43) 1260467 In the same manner as in the first embodiment, the component (B) is one or more selected from the group consisting of a phosphonium-based acid generator and a diazomethane-based acid generator. The effect of the effect is better. Further, in the third embodiment, the component (B) is preferably a component containing a key salt-based acid generator. In the third embodiment, when a component (B) containing an onium salt acid generator or an iodine salt generator is used, a photoresist composition which is hardly affected by φ to a solvent or the like can be obtained. Among them, an iodonium salt-based acid generator is preferred. It can be speculated that the composition of the component (A) is a test result. In the case of the iron salt acid generator, the same as those exemplified in the first embodiment can be used. In the third embodiment, the onium salt-based acid generator in the component (B) is preferably 50% by mass or more, preferably more than 5% by mass (preferably 1% by mass). • (D) component is the same as in the first embodiment. • (E) component is the same as in the first embodiment. • Other arbitrary components are the same as in the first embodiment. • Organic solvent -47- (44) l26〇467 is the same as in the first embodiment. ♦Fourth Embodiment: The fourth embodiment includes a positive photoresist composition for use in a photoresist pattern forming method for immersing an exposure step, wherein the resin component (A) is contained and an acid is produced by exposure. Compound (acid generator) (B) 'The component (A) has a hydroxystyrene-constituting % unit (al) represented by the above general formula (I), and a constituent unit having an acid-dissociable dissolution-inhibiting group (a2) The structural unit (a2) is a positive-type photoresist composition containing two or more kinds of constituent units having acid-dissociable dissolution inhibiting groups having different structures. The fourth embodiment differs from the first embodiment in that it is not necessary to satisfy the condition (1). In addition, the structural unit (a2) having an acid-dissociable dissolution-inhibiting group is required to contain two or more constituent units of the acid-dissociating "Yuguya® bovine inhibitory group" having different structures. The preferred embodiment and the like are the same as in the first embodiment or the third embodiment [photoresist pattern forming method], and the photoresist pattern forming method of the invention is used, and the light of the light-blocking composition is used. A pattern forming method in which a step of immersing exposure is characterized. For example, in the case of 'first on a substrate such as a germanium wafer, a -48-(45) 1260467 photoresist composition is a rotator or the like. After the application, prebaking (PAB treatment) is carried out. In addition, a two-layer laminate of an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition. An organic antireflective film 2 layer laminate is provided on the coating layer of the photoresist composition, and a three-layer laminate of the lower layer antireflection film is provided. φ Further, the photoresist composition can be formed. A protective film is formed on the coating layer. The steps up to now can be carried out by a well-known method, and the operating conditions and the like can be appropriately set according to the composition or characteristics of the photoresist composition to be used, and then the coating film with respect to the photoresist composition obtained as described above. The photoresist film 'selectively immerses exposure through the desired mask pattern (liquid immersion lithography 1 iquidimmersi ο η 1 ith 〇graphy ). At this time, the photoresist film and the lens at the lowest position of the exposure device are preliminarily It is preferable to perform exposure in a state filled with a solvent having a refractive index greater than that of air. The exposure light source is a KrF excimer laser. It has a refractive index larger than that of air and is composed of a photoresist which is used. The solvent of the refractive index of the material having a smaller refractive index may, for example, be water or a fluorine-containing inert liquid. Specific examples of the fluorine-containing inert liquid include C3HC12F5, C4F9〇CH3, C4F9OC2H5, C5H3F7, and the like. a compound having a boiling point of 7 0 to 1 8 0 〇C as a liquid component or a perfluoroalkyl compound containing a fluorine-containing compound as a main component, more preferably a compound having a boiling point of 80 to 160 ° C -49-(46) 1260467 In terms of the perfluoroalkyl compound, specifically, a perfluoroether ether compound or a perfluoroalkylamine compound may be exemplified. Further, specifically, the above perfluoroalkyl ether compound In the above, perfluoro(2-butyl-tetrahydrofuran) (boiling point: 1 2 2 ΐ:) may be mentioned, and perfluoroalkylamine compound may, for example, be perfluorotributylamine (boiling point: 1 74 t). Among the inert liquids having fluorine, those having the boiling point in the above range, and the removal of the immersion liquid after the completion of the exposure can be carried out in a simple manner, so that water is cost, safety, environmental problems and versatility. The words are better. Next, after the exposure step is completed, PEB (post-exposure heating) is performed, and then an alkali-developing solution is formed using an alkaline aqueous solution. Thereafter, water rinsing is carried out using preferably pure water. The water rinsing system, for example, dries or sprays water on the surface of the substrate while rotating the substrate, and brushes the developer on the substrate and the photoresist composition in which the developer is dissolved. Then, drying is performed, and the coating film of the photoresist composition is patterned in accordance with the shape of the mask pattern such as L&S or the hole pattern type, and the photoresist pattern can be obtained. Thus, the photoresist pattern is obtained. The formation of the light-resistance pattern of the fine line width can be produced with good resolution, especially the line and gap (L&S) pattern with small pitches, and the spacing between the line and the gap pattern refers to the pattern In the line width direction, the total distance between the resist pattern width and the gap width. -50- (47) 1260467 [Embodiment] [Examples] ♦ Production of positive-type photoresist composition (Example 1) The following (A) or (D) component was dissolved in a homogeneous solution of an organic solvent. A positive photoresist composition is produced. Resin component (A) 100 parts by mass In the following chemical formula, Xl: yl: Zl = 70 mol%: 5 mol%: 25 mol% of a random copolymer (Mwl 2000) [Chem. 1 3]

(B) Component The acid generator represented by the following chemical formula (B1): 3.7 parts by mass The acid generator represented by the following chemical formula (B2): 1.0 parts by mass

(B1) -51 - 1260467

(D) component

3 - 2 - (2-methoxy(ethoxy))ethylamine oxime · 8 parts by mass of organic solvent PGMEA: EL = mass ratio 6: 4 mixed solution! I 900 parts by mass (Example 2) A positive resist composition is produced by dissolving the following (A) or (D) component and a surfactant in a homogeneous solution of an organic solvent. Resin component (A) 100 parts by mass (A2 - 1) In the following chemical formula, x2: y2 = 61 mol%: 39 mol% of random copolymer (Mw 10000) and (A2-2) the following chemical formula Medium, x3: y3 = 64 mol%: 36 mol% of a random copolymer (M w 1 0 0 0 0 ), with a resin composition of 7 〇: 3 0 (mass ratio) mixed -52 - 1260467 (49) 16]

Y3 γ (Β) component The acid generator represented by the following chemical formula (Β 3 ) 3 · 5 parts by mass of the acid generator represented by the following chemical formula (B 4 ): 1.5 parts by mass of the above chemical formula (Β 1 ) Acid generator 1.0 mass parts [化1 7]

(c) Component CHDVE 3.0 parts by mass (D) Component -53- (50) 1260467 Triethanolamine oxime. 2 parts by mass of triisopropanolamine 0.0 5 parts by mass of surfactant 曰 ink fluorosurfactant Megafucks XR -104 (manufactured by Daisei Co., Ltd.) 〇 5 parts by mass of organic solvent PGMEA 900 parts by mass (Example 3) The agent was dissolved in a solution having the following (A) or (D) component and a surfactant solvent to produce a positive solution. Type resist composition. Resin component (A) 100 parts by mass: y 5 : z 5 = equal % : 2.5 moiety component (A3 - 1 ) in the following chemical formula, x4: y4: zz 72.5 mol % · · 5 mol % : 7.5 mo Ear % : 12.5 Mo: Each unit of the ear % is a random polymer (Mw 1 20 00 ) tree -54- (51) 1260467 [Chemical 1 9]

(B) component The acid generator represented by the above formula (B1) 2.19 parts by mass of the acid generator represented by the above formula (B2) 0. 18 parts by mass of the component (D) triethanolamine 0. 1 2 6 mass Triisopropanolamine 0. 10 8 parts by mass of surfactant fluorosurfactant Megafucks XR-104 (manufactured by Dainippon Ink Co., Ltd.) 〇. 5 parts by mass of organic solvent - 55- (52) 1260467 PG Μ EA : EL = mass ratio 6 : 4 mixed solution ij 9000 parts by mass (Example 4) The following (A) or (E) component and a surfactant are dissolved in a homogeneous solution of an organic solvent to produce a positive solution. Type resist composition. Resin component (A) 100 parts by mass (A4 - 1) In the following chemical formula, x6: y6: z6: w = 73.6 mol%: 6.6 mol%: 15 mol%: 5 mol% of each unit is Random polymer (Mw3 0000) resin component [Chemical 20]

(B) component The acid generator represented by the following chemical formula (B 5 ) is 3.0 parts by mass -56-(53)1260467 [Chemical 2 1]

CF3S〇3 a ... (B5) (D) component Triethanolamine 〇 · 15 parts by mass

(E) Component Phenylphosphonic acid 0.15 8 parts by mass of surfactant Fluoroquinone surfactant Megafucks R-60 (manufactured by Dainippon Ink Co., Ltd.) 〇·〇2 parts by mass of organic solvent ethyl lactate 9000 quality (Comparative Example 1) In the photoresist composition of Example 1, except that the resin component (A) was replaced by a copolymer having the following structural formula ((M w 1 0 0 0 0), the others were similarly Manufacturing photoresist composition. -57- 1260467

X7+y7=20 Mohr% # Z7 + t7 二80 Mohr% ♦ Evaluation Method 1 (Examples 1 to 4, Evaluation of Comparative Example 1) (Test Method 1: Measurement of Sensitivity) (i) Using a general exposure Formation of the photoresist pattern resulting in the lithography step:

XI First, a positive photoresist composition is used to form a photoresist pattern using a lithography step caused by usual exposure. # Organic anti-reflection film composition: The product name DUV42P (manufactured by Brewer Scientific Co., Ltd.) was coated on a wafer of 8 inches in diameter using a spinner, and dried on a hot plate at 185 ° C for 60 seconds. It is dried to form a film. Organic anti-reflection film with a thickness of 65 nm. Next, the positive-type photoresist composition was applied onto the anti-reflection film using a spinner, and pre-baked (PAB) was performed on a hot plate for 90 seconds under the conditions shown in Table 1 below, and dried on the anti-reflection film. A photoresist film having a film thickness of 305 n ill was formed.

Then, the reticle is transmitted through the 値 mask by the K r F exposure device S 2 0 3 B -58- (55) 1260467 (N ik ο η NA opening number = 0.66, σ = 2 / 3 Wheel illumination), selective exposure using a KrF excimer laser (24 8 nm). Then, the PEB treatment was carried out for 90 seconds under the conditions shown in Table 1, and 2.38% by mass of tetramethylammonium hydroxide solution was used for the alkali developer which was further developed with an alkali developer at 60 ° C at 20 ° C. . Thus, a photoresist pattern with a line of 10.5 nm and a gap of 1:1 can be formed, and the sensitivity (Eop) is obtained: XI. (ii) Formation of a resist pattern using a simulated immersion lithography step: X2 A pattern is formed in the same manner as in the above (i) except that the following simulated immersion exposure treatment is performed, and the sensitivity X2 is obtained. In the simulated immersion exposure treatment, between the selective exposure and the P E B treatment, the germanium wafer on which the photoresist film is disposed is rotated, and pure water is continuously dropped on the photoresist film at 2 3 ° C for 2 minutes. φ The above examples, the PAB conditions of the comparative examples, and the PEB conditions are as follows. In addition, these conditions are optimized for each photoresist composition. -59- (56) 1260467 [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 PAB Condition 125 100 125 140 100 Temperature (°C) peb Condition 110 110 110 140 110 Temperature fC ) -- ----- The results are summarized as shown in Table 2 [Table 2] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 XI 3 5.15 17.66 33.16 15.38 26.43 X2 3 6.93 17.74 34.2 1 16.09 2 9.18 [(X2 /X1)-1] X 100 absolute 値5 . 1 -------- 0.5 ______ 3.2 4.6 10.4 Embodiment 2 of the second embodiment; Example 1 and 3 regarding the third embodiment 4, all are absolute 値5 or less, and the sensitivity is less deteriorated' is good. (Test Method 2: Evaluation of Pattern Shape) The pattern of L & S formed in the above Test Method 1 (there are no immersion treatments, two of them) was observed by a scanning electron microscope (SEM). Observe the cross-sectional shape of the pattern. -60- (57) 1260467 Also, the hole pattern is also evaluated. Regarding the evaluation of the hole pattern, a halftone (ha 1 ft ο ne ) mask formed by a hole having a diameter of 200 nm is used, and the exposure amount faithfully reproduced in a hole pattern of 160 nm in diameter (sensitivity: Εορ) In addition to the formation of a hole pattern of 1 60 nm in diameter, the pattern is formed according to Test Method 1. The results are shown in Table 3.

-61 - 1260467

u漱] Comparative example 1 Rectangular T top shape Rectangular τ top shape Example 4 Pulse book η Waist cut _ 驭 4 < _ JIL | Qg 峨S Beam Μ β ^1 _ _ ^ lv Deputy thief shame waist $e Lai Cut nr waist cut 辁 龆 龆 S 4< _ ,: 岖 铝 aluminum S to 崔 _ _ g ίν M m _ 鹧 鹧 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 t t 4 4 4 4 4 4 A rectangle with a high verticality and a non-circular head cut E 瞟 to _ g 龉 _ 4< a rectangle with a high verticality of the thief's side wall and a rounded head. Embodiment 2 The outline of the head is a round rectangle The head of the general pattern is a circle of a rectangle. The head of the figure is a rectangle of a circle. The head of the figure is a rectangle of a circle. Embodiment 1 The head of several figures of the rectangle is prominent but still remains a rectangular rectangle. ^ ^ ^ $ to 51 1® *33 ^ 屮俅 屮俅 载 L L & S S line shape shape (no impregnation) L & S line shape shape (with impregnation) contact hole pattern Shape (no impregnation) Pattern shape of the hole of the contact hole (with impregnation) -62- (59) 1260467 As shown in Table 3, water immersion in the comparative example FIG become the top T-shaped, confirmed significant impact on the leaching of the solvent ditch, whereas no changes were observed related to the embodiment of the present invention due to the absence of the immersion treatment of the large pattern shape. Among them, surprisingly, it can be confirmed that in the examples 3 and 4 for the immersion treatment, the vertical shape of the pattern shape is high, and a good rectangular pattern can be obtained. Therefore, although the solvent for immersion exposure is used, Deterioration of sensitivity, photoresist pattern, etc., but by selecting the composition of the photoresist composition, it was confirmed that good characteristics can be obtained by performing the immersion exposure. (Example 5) The same photoresist composition as in Example 2 was used and evaluated by the following evaluation method 2. (Example 6) A photoresist layer was formed using the same photoresist composition as in Example 2, and a protective film material was applied thereon, and a layer of a top coat layer (t 〇p C 〇at ) (protective film) was provided. The compound was evaluated by the following evaluation method 2. The protective film material system, DemnamS-20 (product name, manufactured by Daikin Industries Co., Ltd.) and cytop (product name, manufactured by Asahi Glass Co., Ltd.) are mixed trees. [Mixed mass ratio (the former: the latter) is 1: 5], dissolved In the perfluorotributylamine, the resin concentration was 2.5% by mass. -63 (60) 1260467 (Example 7) The same photoresist composition as in Example 3 was used and evaluated by the following evaluation method 2. (Example 8) A photoresist layer was formed using the same photoresist composition as in Example 3, and further, a protective film material similar to that of the user of Example 6 was used thereon to provide lamination of the top coat layer. Evaluation by the following evaluation method 2 评价 ♦ Evaluation method 2 (Evaluation of Examples 5 to 8) First, the organic anti-reflection film composition: product name DUV42P (manufactured by Brewer Scientific Co., Ltd.), using a rotator at a diameter of 8 inches The coating on the wafer was carried out on a hot plate, and it was dried on a hot plate for 6 seconds, and dried to form an organic anti-reflection film having a thickness of 6 5 nm. Then, the positive-type photoresist composition obtained above was applied onto the anti-reflection film by using a spinner, and dried on a hot plate for 90 seconds under the temperature conditions shown below, and dried on the anti-reflection film. A photoresist film having a film thickness of 3 5 On m was formed. Example 6 'Sinus Example 8, further, on the photoresist film, the protective film material was spin-coated, and heated at 9 〇〇c for 6 〇 seconds to form a film thickness of 7 nm. membrane. Then, the immersion exposure was carried out by using a two-beam interference exposure machine LEIES1 93-1 (manufactured by Nikon Co., Ltd.) to perform liquid immersion two-beam interference caused by interference of krypton and water with two beams of wavelengths of 248-64-(61) 1260467 nm. exposure. The same method is also disclosed in the aforementioned Non-Patent Document 2, which is a method for simply obtaining a line and gap (L&S) pattern at the laboratory stage. Next, the 90-second p E B treatment was carried out under the temperature conditions shown below, and further developed at 2 3 C to test the developer into fj 60 seconds. For the developer, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used. The temperature conditions of prebaking and P E B treatment were the same as in Example 2 as shown in Table 1 above. Examples 7 and 8 are the same as Example 3 shown in Table 1 above. Thus, the formation of a photoresist pattern of 6 4.5 n m L & S of 1:1 can be solved even in any of the embodiments. Next, each of them was observed by a scanning electron microscope (SEM) to observe the cross-sectional shape of the pattern. The results are shown in Table 4. [Table 4] Example 5 Example 6 Example 7 Example 8 6 4 · 5 mmmm Approximate pattern Approximate pattern Approximate pattern Approximate pattern L&s line head is the head of the head The rectangular shape of the rectangular circle with the rounded rectangular circle of the dog is shown in Table 4. In Examples 5-8, the L&S pattern of 64.5 nm of the rectangle can be formed using the KrF excimer laser ' . Further, the exposure pattern can be formed by dipping without forming a top layer. -65- (62) 1260467 [Industrial Applicability] The positive resist composition and the photoresist pattern forming method of the present invention are formed by using a resist pattern forming method including an immersion exposure step.

-66 -

Claims (1)

1260467 Patent Application No. 94102361, amended on February 21, 1995, "Chinese Patent Application Revision Amendment 10, Patent Application No. 1 · A positive-type photoresist composition, which is formed by a photoresist pattern containing an immersion exposure step The positive-type photoresist composition used in the method is a condition satisfying the following conditions (1) and (2), (1) using the positive-type photoresist composition by making Ki*F having a wavelength of 248 nm The excimer laser is used in the lithography step of the normal exposure of the light source, and the sensitivity is XI when the line of the 150 nm line and the gap become a one-to-one photoresist pattern, and on the other hand, the wavelength is 248 nm. The KrF excimer laser is used in the same step as the lithography step of the usual exposure, and the step of contacting the solvent for the immersion exposure with the photoresist film is increased between selective exposure and post-exposure heating (PEB). The simulated immersion lithography step, the sensitivity of the line forming the 150 nm line and the gap becoming a one-to-one photoresist pattern is X2, [(X 2 / X 1 ) - 1 ] X 1 0 0 absolute値 is 5 or less, (2) the positive resist composition contains a resin component (A) And a compound (acid generator) (B) which is produced by exposure to an acid, and the component (A) has the following general formula (I) which is not substantially constituted by the basic formula (al), [1] 1260467 (wherein R represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3). 2. The positive resist composition according to claim 1, wherein the component (A) contains a constituent unit (a2) having an acid dissociable dissolution inhibiting group, and the constituent unit (a2) contains and has a different Two or more kinds of positive-type photoresist compositions which are constituent units of the acid dissociative dissolution inhibiting group of the structure. 3. The positive resist composition according to claim 1 or 2, wherein the component (A) contains a constituent unit (a2) having an acid dissociable dissolution inhibiting group, and the constituent unit (a2) contains an acid. The dissociative dissolution inhibiting group is a positive-type photoresist composition of the alkoxyalkyl group-constituting unit (a2 - 1). 4. The positive-type resist composition according to claim 3, wherein the structural unit (a2) further contains, the acid-dissociable dissolution inhibiting group is a tertiary alkoxycarbonyl group and/or a tertiary alkyl group. A positive photoresist composition constituting the unit (a2 - 2). 5. The positive-type photoresist composition according to claim 1 or 2, further comprising (C) a positive-type photoresist composition of a crosslinkable polyvinyl ether compound. 6. The positive-type photoresist composition according to claim 1 or 2, wherein the component (A) contains a unit (a2) having an acid-dissociable dissolution inhibiting group, and the constituent unit (a2) contains acid dissociation The dissolution inhibiting group is a positive photoresist composition of a constituent unit (a2 to 3) having an aliphatic cyclic group. -2-C-A 1260467 7. The positive-type light as described in claim 6 wherein the acid-dissociablely-dissolving aliphatic-polycyclic group-containing tertiary alkyl group of the above-mentioned constituent unit (a2-3) / or a positive photoresist composition of a fat-containing tertiary alkyl group. 8. The positive-type light according to the sixth aspect of the invention, wherein the structural unit (a2) contains a positive-type resist composition having a structure I) having an acid-dissociable dissolution inhibiting group other than the above-mentioned lipid group. 9. The positive-type light as described in claim 8 wherein the acid dissociation of the above-mentioned constituent unit (a2 - 4) is dissolved from the third-stage oxycarbonyl group, the third-stage yard base, and the general cross-linking as described below. One or more kinds of positive-type photoresist compositions of the group, (Chemical Formula 2) (R3 and R4 are each independently a lower alkyl group, and n represents 1 to Α represents a single bond or an η+1 organic group). 10. The positive-type light according to claim 9 wherein the acid-dissociable dissolution of the structural unit (a2-3) contains an aliphatic polycyclic group-containing tertiary alkyl group, and the aforementioned constituent unit (a2-4) The acid-dissociating composition of the third-order alkyl group other than the base of the aliphatic cyclic group, the inhibiting group, the group monocyclic group-blocking composition, the aliphatic ring-based group [a2 - 4 Blocking composition, suppressing the basic formula (II) ••(II) 3 integer, resisting composition, suppressing the base system, suppressing the base with a positive resist group 1260467. I 1 ·If the patent application scope The positive-type resist composition according to Item 9, wherein the acid dissociable dissolution inhibiting group of the structural unit (a 2 - 3 ) contains an aliphatic monocyclic group-containing tertiary alkyl group, and the above constituent unit (a) 2 - 4 ) an acid-dissociating dissolution inhibiting base, a positive-type resist composition of the crosslinked structure represented by the above general formula (11). 12. A positive-type resist composition as described in claim 1 or 2 And (B) an acid generator, the component (B) comprising, selected from the group consisting of strontium salts A positive resistive composition of one or more kinds of a reagent and a diazomethane acid generator. The positive resist composition according to claim 6, which contains (B) an acid generator, B) The composition contains a positive photoresist composition of a gun salt acid generator. 1 4. A positive photoresist composition which is a positive photoresist composition used in a photoresist pattern forming method including an immersion exposure step. And a compound (A) containing a resin component (A) and an acid generated by exposure, the component (A) having a hydroxystyrene composition represented by the following general formula (I) Unit (a 1 ), [3] (wherein R is a hydrogen atom or a methyl group, η is an integer of 1 to 3) - 4- 1260467 and a constituent unit (a 2) having an acid dissociable dissolution inhibiting group, and the constituent unit (a2) contains different Two or more constituent units of the acid dissociative dissolution inhibiting group of the structure. A method for forming a photoresist pattern, which is characterized by using a photoresist pattern forming method of a photoresist composition as described in claim 1, 2 or 14 which is in the aforementioned immersion exposure step In the case where the photoresist film formed by the photoresist composition is formed, a solvent having a refractive index greater than that of air is filled between the photoresist film and the lens at the lowest position of the exposure device. -5-