TW201120567A - Radiation-sensitive resin composition and resist pattern formation method - Google Patents

Abstract

A radiation-sensitive resin composition which can be used as a radiation-sensitive resin composition for use in a resist pattern formation method, which comprises a polymer (A), a radiation-sensitive acid generator (B), and a solvent (C), wherein the polymer (A) has at least one repeating unit selected from the group consisting of repeating units respectively represented by general formulae (1-1) to (1-4) (wherein R1 represents a hydrogen atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms; R2sindependently represent a hydrogen atom or a hydroxy group; R3 represents a hydroxyalkyl group; A represents an alkylene group; and B represents an ester bond, an amide bond, a carbonyl group or an amino group) and a repeating unit having an acid labile group.

Description

201120567 VI. Description of the Invention: [Technical Field] The present invention relates to a sensitive radiation linear resin composition and a photoresist pattern forming method, and more particularly to a water use method for use in a dual patterning process The sensitized radiation linear resin composition which can be suitably used in the immersion exposure process and the formation method using the photoresist pattern. [Prior Art] In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain higher integration, a fine photoresist pattern having a line width of about 45 nm has recently been required. As a means for forming such a fine photoresist pattern, it is considered that the wavelength of the light source of the exposure device is shortened, and the number of apertures (NA) of the lens is increased. However, in addition to the need to add a high-priced exposure device, and the increase in the number of apertures (ΝΑ) of the lens, there is also a trade-off between the resolution and the depth of focus, even if the resolution is increased and the depth of focus is lowered. Recently, as a lithography technique that can solve such a problem, a method of liquid immersion exposure (Liquid Immersion Lithography) has been reported. When a liquid immersion exposure method is used and a lens mounted on a conventional device is used, a photoresist pattern which is more excellent in resolution and excellent in depth of focus can be formed at a low cost, and it is widely recognized as a simultaneous Practical. However, the advancement of the exposure technology by the liquid immersion exposure method is considered to be only 45 nm hp (hp: half pitch), and the technology development of the 3 2 nm hp generation which is more necessary for microfabrication is being carried out. In recent years, with the demand for the complexity and high density of the 201120567 device, it has been proposed to shift the half-cycle by shifting the line pattern or the isolated channel pattern called double patterning or double exposure. A technique of patterning 32 nm LS (LS: line width and line pattern) (for example, refer to Non-Patent Document 1).尙, double patterning (hereinafter, also referred to as "DP") means that a photoresist film is further formed on the first photoresist pattern obtained by the first exposure and development, and is formed by The second exposure technique and the second photoresist pattern obtained by the development, double exposure (Double Exposure) means that after the first exposure, the second exposure is continuously performed without performing imaging, and then borrowed. A technique for forming a photoresist pattern by development. An example of a technique for patterning a 32 nm LS, as disclosed in Non-Patent Document 2, forms a 32 nm line pattern of a pitch of 1:3, and hard masks such as SiO 2 by etching (hereinafter also referred to as After "HM") processing, a 3 2 nm line pattern of 1: 3 pitch is formed in the same position as the retardation pattern of the first layer, and the HM is processed by etching again. The ground forms a 32 nm line pattern (32 nm line width and line pattern, Line and Space Pattern) with a pitch of 1: 1 (the ratio of the width of the line width to the width of the line portion is 1:1). [prior technical literature] [Non-patent literature]

[Non-Patent Document 1] SPIE2006 61531K [Non-Patent Document 2] 3rd International Symposium on Immersion Lithography PO-1 1 201120567 [Summary of the Invention] However, although several processes as described above have been proposed, they are suitable for use in the current situation. A proposal for a specific material for the dual patterning process using the immersion exposure process has not been proposed. Moreover, in the proposed process, after the first photoresist pattern is formed, when the second photoresist pattern is formed, the first photoresist pattern is defective or deformed, and the dimensional accuracy of the line width is problematic. . The present invention has been made in view of the problems of the prior art, and the object thereof is to provide not only a suitable liquid immersion exposure process but also a first photoresist layer in a dual patterning process. A sensitive linear resin composition is formed. Moreover, the problem is that in the double patterning process, when the exposure for forming the second photoresist pattern is used, the first photoresist pattern does not become alkali-soluble even when photosensitive, and the first photoresist can be maintained. A photoresist pattern forming method in which a second photoresist pattern is formed in a pattern state and a variation in line width of the first photoresist pattern can be suppressed. The photoresist pattern forming method of the present invention can also be suitably used in a liquid immersion exposure process. In order to achieve the above-mentioned problems, the inventors of the present invention have found that the above problems can be attained by applying the following constitution, and the present invention has been completed. Namely, according to the present invention, the sensitive radiation linear resin composition and the photoresist pattern forming method shown below can be provided. 〔! A sensitive radiation linear resin composition characterized by containing a repeating unit selected from at least one of the 201120567 group represented by the repeating units represented by the following general formulas (1_1) to (1_4) and a repeating unit having an acid labile group. a polymer (A), a radiation sensitive linear acid generator (B), and a solvent (C), wherein the polymer (A) comprises a first resistive linear resin composition, and a first photoresist pattern is formed on the substrate. a step (1) of forming a first photoresist pattern to insolubilize the second photosensitive radiation linear resin composition (2), and using the foregoing substrate on the substrate on which the first photoresist pattern is formed The second photosensitive radiation linear resin composition is used in the photoresist pattern forming method of the step (3) of forming the second photoresist pattern, and is used as the first photosensitive liquid linear resin composition. 【化1】

In the above general formula (1-1) to (1-4), R1 each independently represents a hydrogen atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and R2 each independently represents a hydrogen atom or a hydroxyl group. In the above general formula (I-4), R3 represents a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms. In the above general formula (1-1), 'A' represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and the hydrogen atom thereof may be substituted by an alkyl group having 1 to 5 carbon atoms. In the above general formula (1-3), B represents a group 'n' represented by any one of the following formulas (B-1) to (B-6), and represents an integer of 1 to 3. 6) 201120567 【化2】

(B-1) (B-2) (B-3) (B-4) (B-5) (B [2] A method for forming a photoresist pattern characterized by containing the first sensitivity of the above [1] a step (1) of irradiating the linear resin composition in the resistive pattern of the substrate, and forming the first photoresist pattern in the step (2) of inactivating the first resistive pattern-type di敏 radiation linear resin composition a step of forming a second photoresist pattern on the substrate by using a front-end radiation linear resin composition (3: [3] the photoresist pattern forming method of the above [2], the resistive pattern and the second The photoresist pattern has a line width portion which is parallel to the ridge shape, and a photoresist pattern of the line portion of the plurality of adjacent line width portions adjacent to each other, in the first photoresist pattern 5 The line width portion of the second photoresist pattern is formed in parallel with the first line width portion. [4] The method for forming a photoresist pattern according to the above [2], which has a photoresist pattern And the second photoresist pattern respectively has a line width portion of a convex shape parallel to i, and a photoresist pattern of a plurality of line distance portions between the adjacent line width portions The method of forming the second photoresist pattern portion and the line width portion of the first photoresist pattern are formed. [5] The photoresist pattern S method according to any one of the above [1] to [4], Wherein the polymer (A) contains the repeating unit of the above general formula (1-1). The first number arrangement of the line portion pattern for forming the first alignment of the second alignment is used. The line width formed by the formation is represented by -9-201120567 The sensitive radiation linear resin composition of the present invention is suitable for the liquid immersion exposure process, and in the double patterning, the first photoresist layer is also formed. The method for forming the photoresist pattern of the present invention is not only suitable for the process, but in the double patterning, when the second photoresist is used to form the second photoresist, the first photoresist pattern does not become alkali-soluble even if it is photosensitive. A second photoresist pattern is formed in a state of a photoresist pattern, and a photoresist pattern of a line width of the first photoresist pattern is formed. [Embodiment] Hereinafter, an embodiment of the present invention will be described, but it should not be It is limited to the following embodiments, as long as it is not off The scope of the present invention is based on the general knowledge of the trader, and the following is also incorporated in the scope of the present invention. The method of forming the resist pattern is: The step of forming the photoresist pattern of the present invention includes the step 3) The double-patterned photoresist pattern forming method. The following describes an implementation of the photoresist pattern forming method of the present invention. 1. Step (1): FIG. 1A to FIG. 1D show the photoresist pattern of the present invention. A pattern diagram of one example of the step (1) is formed. In the step (1), first, the use of the first sensitive radiation linear resin composition on the substrate i is suitable not only for the exposure for the immersion exposure pattern, but The method can be guaranteed and can be suppressed. It is understood that the invention is within the embodiments of the invention. Step (1)~(, using the pattern form. The step in the method is as shown in Fig. 1A to form the first -10 201120567 photoresist layer 2. Secondly, as shown in Fig. 1B, in the first photoresist layer The field used in the second embodiment is sequentially exposed through the mask 4 and the lens 6 of the predetermined pattern, and arbitrarily through the liquid immersion exposure liquid 3 such as water, and the radiation is irradiated (arrow of FIG. 1B) as shown in FIG. 1C. In the same manner, the alkali developing portion 5 is formed in the field used for the first photoresist layer 2. Thereafter, by performing development, as shown in FIG. 1D, the line width portion 12a and the line portion are formed on the substrate 1. 12b first photoresist pattern 12 (1 L3 S: width ratio of line width to line spacing is 1:3). 1 -1 · Formation of first photoresist layer: First photoresist layer 2 It is formed by applying a coating liquid composed of a first sensitive radiation linear resin composition onto the substrate 1. The coating method is not particularly limited, and may be suitably applied by spin coating, cast coating, roll coating, or the like. The coating method is not particularly limited, and is usually 10 to 1, and 〇〇〇 nm, preferably 10 to 500 nm. After the coating liquid composed of the sensitive radiation linear resin composition is applied, the solvent in the coating film may be volatilized by prebaking (PB: Pre-Bake, hereinafter also referred to as "PB") as needed. The heating condition of the PB may be appropriately selected depending on the composition of the first sensitive radiation linear resin composition, and is usually 30 to 120 seconds at 30 to 200 ° C, and preferably 40 to 100 seconds at 50 to 150 ° C. Further, in order to prevent the influence of the alkaline impurities and the like contained in the environmental atmosphere, for example, as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei-5-8 8 8 9 8 or the like, the first photoresist layer 2 may be provided with protection. Further, in order to prevent the outflow of the acid generator or the like from the first photoresist layer 2, for example, as disclosed in Japanese Laid-Open Patent Publication No. 2005-35, No. A protective film for liquid immersion (upper film) is disposed on the photoresist layer 2. Further, these techniques may be used alone or in combination with 1-1 -3 - first sensitive radiation linear resin composition: first sensitive radiation The linear resin composition is a sensitive radiation linear resin composition of the present invention to be described later. Further, regarding the first sensitive radiation The polymer (A), the radiation sensitive linear acid generator (B), the solvent (C), and the like contained in the resin composition are also described later. 1-1-2. Substrate: The substrate is not particularly limited, and for example, A conventionally known substrate such as a silicon wafer or a wafer coated with aluminum. Further, in order to maximize the potential of the first sensitive radiation linear resin composition, for example, Japanese Patent Publication No. 6-12452 or An organic or inorganic antireflection film may be formed on the substrate to be used in advance, as disclosed in Japanese Laid-Open Patent Publication No. 59-93-44. 1-2. Exposure: As shown in FIG. 1B, in the field of the first photoresist layer 2, the exposure of the radiation pattern is performed through the mask 4 and the lens 6' of the predetermined pattern in sequence. As shown in FIG. 1C, the alkali developing unit 5 is formed in the first photoresist layer 2.尙, at the time of exposure, may be arbitrarily interposed between the liquid immersion exposure liquid 3 such as water or a fluorine-based inactive liquid which is interposed between the lens 6 and the first photoresist layer 2. -12- 201120567 The radiation used for exposure can be based on the type of sensitive radiation linear acid generator (B) contained in the first sensitive radiation linear resin composition, from visible light, ultraviolet light, far ultraviolet light, X-ray, charged particles. It is suitable for selection in lines and the like. Among them, far ultraviolet rays generated by ArF excimer laser (wavelength I93nm) or KrF excimer laser (wavelength 248nm) are preferable, and far ultraviolet rays generated by ArF excimer laser (wavelength 193 nm) are preferable. It is especially good. Further, the exposure conditions such as the amount of exposure can be appropriately selected depending on the compound composition of the first sensitive radiation linear resin composition, the kind of the additive, and the like. Further, it is preferable to perform heat treatment (PEB: Post-Exposure Bake. Hereinafter also referred to as "PEB") after exposure. By carrying out P E B, the dissociation reaction of the acid labile group in the first photosensitive radiation linear resin composition can be smoothly carried out. The heating condition of P E B can be appropriately selected according to the composition of the first sensitive radiation linear resin composition, and is usually 30 to 120 seconds in 30 to 200 ° C, and preferably 40 to 100 seconds in 50 to 170 ° C. 1-3. Formation of First Photoresist Pattern: By developing the first photoresist layer 2 as a developing liquid, the alkali developing portion 5 is dissolved, and a line as shown in FIG. 1D can be formed. The first photoresist pattern 12 of the positive type of the wide portion 1 2a and the line portion 1 2b. Further, it is usually washed with water and dried after development. 1 - 3 -1 . Developing solution: Suitable examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, and η-propyl. Amine, II-13- 201120567 ethylamine, di-η-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole , piperidine, choline, 1,8-dioxabicyclo-[5.4.0]-7-undecene, 1,5-dioxabicyclo-[4.3.0]-5-decene, etc. An alkaline aqueous solution of a compound. These basic compounds may be used alone or in combination of two or more. The concentration of the basic compound in the developing solution is usually 1% by mass or less. When the concentration of the basic compound exceeds 1% by mass, the non-exposed portion is also dissolved in the developing solution. Further, an organic solvent may be added to the developing solution. Specific examples of the organic solvent include acetone, methyl ethyl ketone, methyl i. butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexane. Ketones such as ketones; methanol, ethanol, η-propanol, i-propanol, η-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1, Alcohols such as 4-hexanedihydroxymethanol; ethers such as tetrahydrofuran and dioxane; esters of ethyl acetate, η·butyl acetate, i-amyl acetate, etc.; aromatic hydrocarbons such as toluene and hydrazine; In addition, there are phenol, adipone, dimethylformamide and the like. Further, these organic solvents may be used singly or in combination of two or more. The use ratio of the organic solvent in the developing solution is 1 part by volume or less based on 100 parts by volume of the alkaline aqueous solution. When the ratio of use of the organic solvent is more than 1 part by volume, the development property is lowered and the image retention of the exposed portion is increased. Further, a developer or the like may be added in an appropriate amount to the developer.尙, where volume refers to the volume measured at 25 °C. 1-3-2. Development method: -14-201120567 The development method is not particularly limited, and a conventionally known method can be used, and a development method such as a liquid-filled type, an LD nozzle type, or a GP nozzle type is preferably used. Moreover, the development time is preferably 10 to 90 seconds. 2. Step (2): The step (2) of the photoresist pattern forming method of the present invention is a step of insolubilizing the first photoresist pattern 12 with respect to the second radiation-sensitive linear resin composition. Specifically, it includes the step (2) of heating or irradiating the first photoresist pattern 12 to the radiation. Fig. 2 is a schematic view showing an example of the above step (2). As shown in Fig. 2, the line width portion 12a of the first photoresist pattern 12 formed in the step (1) is heated by a temperature of 120 ° C or higher (PDB: Post-Development Bake. Also known as "PDB") and the treatment of one of the radiation (arrows in Fig. 2), heating can be obtained for the width of the line 1 2 a in forming the first photoresist pattern (step ( 3) PB, PEB) or radiation exposure (exposure of step (3)) to make it inactive. The first photoresist pattern of the second sensitive radiation linear resin composition is insoluble. 2 2 a. The condition of P D B is usually 3 〇 to 1 2 〇 seconds in the range of 1 2 〇 or more, and 1 5 ～ 1 〇 〇 second in the range of 1 4 0 °C or more. Further, the heating temperature of P D B is preferably a temperature higher than the PEB temperature at the time of forming the first photoresist pattern. The condition of the radiation irradiation is preferably a radiation having an irradiation wavelength of 300 nm or less. Further, it is preferable that the exposure amount is 2 to 20 times the optimum exposure amount for forming the first photoresist pattern 12. -15- 201120567 Specific examples of the lamp used for radiation irradiation include an Arjf lamp, a Kr2 lamp, a XeCl lamp, and a Xe2 lamp (above, Niu Mei Electric Co., Ltd.), and these inactivation methods may use only one type or Further, by performing radiation irradiation, the hydroxyl group or acid uneasiness contained in the polymer (A) described later in 12a of the first photoresist pattern 12 is changed by polarity due to crosslinking or condensation. It is also possible to form a line width portion 22a which is insoluble to the sensitive radiation linear resin composition and which is inactive to the first photoresist pattern 22. In the present specification, "inactive to light" means passing through the radiation. The radiation-sensitive radiation linear resin composition is still not sensitized. That is, the line width portion 22a of the pattern 22 is neither exposed nor alkali-soluble, and "inactive to heat" means that it is about to be used. The heating of the second photoresist pattern of the second sensitive polymer composition is still not deformed, melted, etc., that is, even after heating the shape of the pattern. 3 · Step (3): Fig. 3 A~ 3D is a view showing an example of the method (3) of forming a photoresist pattern of the present invention; In the step (3), first, as shown in the figure, the second photoresist layer 32 is formed on the line portion 22b of the resist pattern 22 on the substrate 1 by using the second-sensitive radiation linear resin composition. Next, as shown, The order of the first photoresist pattern 22 and the second photoresist layer 32 is transmitted through the mask 4 and the lens 6 of a predetermined pattern, arbitrarily via water, KrCl, etc., by the line width portion. The secondized ray is a photoresist. The ray-induced component is not inferior. Step 3A shows the first light as shown in Figure 3B. The liquid is equal to the liquid-16-201120567 immersion exposure liquid 3, which is made by irradiating radiation (arrow of Fig. 3B). The alkali developing portion 35 is formed in the second photoresist layer 32 as shown in FIG. 3C. Thereafter, the line width portion 4 2 a of the second photoresist pattern 42 is formed by performing the development of the line portion 22b of the first photoresist pattern 22 formed on the substrate 1 as shown in FIG. 3D. 3-1. Formation of the second photoresist layer: The second photoresist layer 32 is a first photoresist pattern 22 formed by forming a coating liquid from the second sensitive radiation linear resin composition from the substrate 1. It is formed by coating on the top. The method of applying the coating liquid is not particularly limited, and can be carried out by a suitable coating means such as rotary coating, cast coating, or roll coating. Further, the thickness of the second photoresist layer 32 is not particularly limited, and is usually 10 to 1, and 〇〇〇 nm, preferably 10 to 500 nm. Further, after the coating liquid composed of the second sensitive radiation linear resin composition is applied, the solvent in the coating film can be volatilized via PB if necessary. The heating condition of PB can be appropriately selected according to the composition of the second sensitive radiation linear resin composition, and is usually 10 to 200 seconds in 30 to 200 ° C, preferably 15 to 12 seconds in 50 to 150 ° C, 60 to 120 ° C in 30 to 100 seconds is better. The second sensitive radiation linear resin composition contains the polymer (a), the sensitive radiation generator (b), the solvent (c) and the like. The polymer (a), the sensitive radiation linear acid generator (b), and the solvent (c) are equal to the following description -17-201120567 3-2. Exposure: After forming the second photoresist layer 32, as shown in FIG. 3B As shown in FIG. 3C, on the line portion 22b of the first photoresist pattern 22 on the substrate 1 on which the second photoresist layer 32 is formed, the radiation is irradiated via the mask 4 of a predetermined pattern (the arrow of the figure) The resulting exposure 'forms the alkali developing portion 35 on the second photoresist layer 32. Further, at the time of exposure, the exposure liquid 3 can be arbitrarily immersed in water or a fluorine-based inert liquid or the like. In other words, the exposure conditions and the like can be described in the same manner as the above-described exposure conditions and the like in the step (1). 3-3. Formation of the second photoresist pattern: Next, as shown in FIG. 3D, the line width of the second photoresist pattern is formed at the line portion of the first photoresist pattern 22 by performing development. Part 42a. That is, the development method can be described in the same manner as the above-described development method in the step (1). Thus, by performing steps (1) to (3), the line width portion 22a and the second photoresist pattern 42 of the first photoresist pattern 22 can be formed on the substrate 1 by double patterning. The line width portion 42a is a photoresist pattern in which 1L1S (the ratio of the width of the line width portion to the width of the line portion is 1:1) which are alternately arranged at equal intervals. Further, according to the double patterning, for example, as shown in FIG. 4 and FIG. 5, the line width portion 42a and the first photoresist pattern 22 of the second photoresist pattern 42 formed in the step (3) can be obtained. The line width portion 22a is formed vertically on the line width portion 22a of the first photoresist pattern 22, thereby forming a photoresist pattern (contact hole pattern 15 -18-201120567 and more based on double patterning, for example As shown in FIG. 6, the second photoresist pattern u formed in the step (3) is formed on the line distance portion 2 2 b of the first light, and may be formed via the first photoresist pattern portion 22 a and the first The pattern of the checkerboard pattern formed by the line width portion 42a of the two photoresist pattern 42 (contact hole pattern 15). The method for forming the photoresist pattern of the present invention, that is, using double, can form a more The fine line pattern and the finer contact hole will be referred to by the photoresist pattern forming method of the present invention (double patterning resist pattern (line width and line pattern and contact hole pattern) is called j) The method for forming the photoresist pattern of the present invention, as shown in FIGS. 4-6, the line width portion 22a of the first photoresist pattern 22 and the second photoresist pattern portion 42a are perpendicular, and at the first photoresist It is preferable to form the pattern 42 on the pattern 22. The pattern of the photoresist pattern when the contact hole pattern is formed as described above, and the width of the line portion is simultaneously 40 to 100 nm (lLlS) as the portion and the line portion. The width is 40 to 6 5 nm (1L1S) at the same time and the width of the wide portion and the line portion is 4 〇 to 5 〇 nm (1L1S) j II. The radiation sensitive linear resin composition: the sensitive radiation linear resin of the present invention When the composition is exposed to an acid generated by the acid generator, the base is dissociated in the polymer to form a carboxyl group, and as a result, the solubility in the exposed portion is increased, and the solution is dissolved by the alkali developing solution. In addition, if the pattern of the step width pattern 22 22 is linearized (hereinafter referred to as the "DP pattern", the line width of the second photoresist is 4 2 line width. The part is better, the line width is better, and the line # is better. The acid-irradiation alkali solution of the sensitive radiation forms the photoresist pattern of the positive type -19-201120567. That is, the sensitive radiation linear resin composition of the present invention is made of acid. The action is an alkali-soluble, alkali-insoluble or poorly soluble polymer, a radiation-sensitive linear acid generator, and The composition of the agent. Hereinafter, the first photosensitive radiation linear resin composition used in the formation of the first photoresist layer and the second photosensitive radiation linear resin composition used in the formation of the second photoresist layer will be described. In fact, the term "acid-unstable group" as used in this specification is also referred to as "acid-dissociable group", and refers to a group which is dissociated by acid. A polymer having an acid-labile base which is insoluble or poorly soluble, Since the acid unstable group in the polymer is dissociated by the action of an acid to form a carboxyl group, it becomes soluble in a base. Further, the term "alkali-insoluble or poorly soluble" in the present specification means that the polymer-containing polymer (A) is used. When the photoresist layer formed by the first sensitive radiation linear resin composition is developed under the condition of alkali development, when the photoresist layer is replaced and only the film formed by the polymer (A) is used for development, The film thickness of the film thickness of 50% or more of the initial film thickness remains after development. 1 . First Sensitive Radiation Linear Resin Composition The first radiation sensitive linear resin composition comprises an polymerization comprising a repeating unit represented by the following general formulas (1_1) to (1-4) and a repeating unit having an acid labile group. (A) (hereinafter, simply referred to as "polymer (A)"), a sensitive radiation linear acid generator (B) (hereinafter, simply referred to as "acid generator (B)") and a solvent (C) By. 1-1. Polymer (A): -20- 201120567 The polymer (A) is a repeating unit represented by the following general formula (ii) to (1-4) (hereinafter, also referred to as "repetition Unit (1)"), a polymer having a repeating unit of an acid labile group (hereinafter also referred to as "repeating unit (2)"). 1 -1 -1 • Repeating unit (1 ): Polymer (A) is considered to be repeated by containing at least one of repeating units (1) and irradiating with PDB and radiation in step (2) The hydroxyl group (for example, the general formula 〇-1) ~ (1 -4 ) wherein the hydroxyl group represented by R2 or R3) causes a condensation reaction with the carboxyl group or other hydroxyl group in the polymer (A). And then cross-linked. Thereby, since the polymer (A) becomes insoluble in the second-sensitive radiation linear resin composition or the alkali developing solution, and it becomes difficult to become alkali-soluble due to exposure or heating at the time of formation of the second photoresist pattern, The second photoresist pattern is formed while maintaining the first photoresist pattern. [化3]

(1-3) (1-4) In the above general formula (1-1) to (1-4), R1 each independently represents hydrogen-21 - 201120567 atom, trifluoromethyl group, or carbon number 1 to 3 The group, R2 each independently represents a hydrogen atom or a hydroxyl group. In the above general formula (1-4), 'R3' represents a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms. In the above general formula (1-1), A represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and the hydrogen atom thereof may be substituted by an alkyl group having 1 to 5 carbon atoms. In the above general formula (1-3), B represents a group represented by any one of the following formulae (B·1) to (B_6), and η represents an integer of 1 to 3.尙’ η is better than 1. (4) (Bl) (Β-2) (Β-3) (Β-4) (Β-5) (Β-6) The repeating unit (1) is expressed by the above general formula (1-1) The repeating unit 'is particularly preferable because the above crosslinking reaction is particularly easy. The polymerizable monomer to which the repeating unit (1) is given may, for example, be a compound represented by the following formula (Ι-a) to (l-t). However, in the present invention, the polymerizable monomer to which the repeating unit (1) is given is not limited thereto. 【化5】

-22- 201120567 【化6】

HO HO HO

【化7】

(1 -k)

(1 - m)

-23- 201120567

As the polymerizable monomer to which the repeating unit (1) is given, among the compounds represented by the above formulas (la) to (lt), the compounds represented by the formulae (Ι-a) and (1-b) are preferred. . The polymer (A) may contain one such repeating unit (1) alone or two or more kinds thereof. 1-1-2. Repeating unit (2) The repeating unit (2) is a repeating unit having an acid labile group, which can be represented by the following general formula (2). -24- 201120567 【化9】 R4

(2) In the above general formula (2), r4 represents a hydrogen atom, a methyl group or a trifluoromethyl group. R5 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group having a carbon number of 4 to 20, or a carbon formed by combining two R5 groups. a 4 to 2 fluorene bivalent alicyclic hydrocarbon group or a derivative thereof, and the remaining R5 represents a linear or branched alkyl group having a carbon number or an alicyclic hydrocarbon group having a carbon number of 4 to 20 Or a derivative thereof. In the above general formula (2), specific examples of the linear or branched alkyl group having 1 to 4 carbon atoms in the group represented by R5 include a methyl group, an ethyl group, and an n-propyl group. I-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc. In the above general formula (2), among the groups represented by R5, the carbon number is 4 Specific examples of the monovalent alicyclic hydrocarbon group of ～2〇 are norbornane, tricyclodecane, tetracyclododecane, adamantane, or cyclobutane, cyclopentane, cyclohexane, cycloheptane, a group consisting of an alicyclic hydrocarbon derived from an alkyl alkane or the like, such as cyclooctane; and the group consisting of an alicyclic hydrocarbon, for example, a methyl group, an ethyl group, an η-propyl group, or the like a group substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl or butylbutyl In the above general formula (2), a specific example of a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof in which any two R5 are bonded to each other in the group represented by R5 a source of norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, cyclohexane, etc. Alicyclic hydrocarbon group consisting of; a group of such alicyclic hydrocarbon formed include the aforementioned alkyl groups may be substituted with the group. In the above general formula (2), a suitable example of the group represented by -C(R5) 3 is t.butyl, ln-(l-ethyl-1-methyl)propyl, ln-(l,l -dimethyl)propyl, 1-n-(1,1-dimethyl)butyl, 1-n-(1,1-dimethyl)pentyl, 1-(1,1-diethyl a propyl, ln-(l,l-diethyl)butyl, 1-η-(1,1-diethyl)pentyl group or the like having no alicyclic hydrocarbon; 1-(1-A Cyclopentyl, 1-(1-ethyl)cyclopentyl, 1-(1-η-propyl)cyclopentyl, propyl)cyclopentyl, 1-(1-methyl)cyclohexyl, 1-(1-ethyl)cyclohexyl, propyl)cyclohexyl, propyl)cyclohexyl, 1-(1-methyl-1-(2-northyl))ethyl, 1-(1-methyl -1-(2-tetracyclic fluorenyl)ethyl, 1-(1-methyl-1-(1-adamantyl))ethyl, 2-(2-methyl)norbornyl, 2 -(2-ethyl)norbornyl, 2-(2-n-propyl)norbornyl, 2-(2-i-propyl)norbornyl, 2-(2-methyl)tetracyclic Diyl, 2-(2-ethyl)tetradecyl, 2-(2-n-propyl)tetracyclododecyl, 2-(2-i-propyl)tetracyclododecyl, 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, 2-(2-n-propyl)-gold a group having an alicyclic hydrocarbon such as a 2-(2-i-propyl)adamantyl group; and the group having such an alicyclic hydrocarbon may, for example, be a methyl group, an ethyl group, an η-propyl group, or the like. a linear or branched alkyl group having 1 to 10 carbon atoms, such as i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl, or a cyclopentyl group , cyclohexyl, 26-201120567 cyclooctyl group and the like substituted by a cyclic alkyl group having 4 to 20 carbon atoms. A suitable example of the monomer to which the repeating unit (2) is given is exemplified by 2-methyladamantane-2-yl (meth)acrylate 2-methyl-3-hydroxyadamantane-2 (meth)acrylate-2 -yl ester, 2-ethyladamantane-2-yl (meth)acrylate, 2-ethyl-3-hydroxyadamantan-2-yl (meth)acrylate, 2-oxime (meth)acrylate · propyl adamantyl-2-yl ester, 2-isopropyl adamantyl-2-yl (meth)acrylate, 2-methylcyclo(2.2.1)hept-2-(meth)acrylate Base ester, 2-ethylbicyclo(meth)acrylate [2.2.1]heptan-2-yl, (methyl)acrylic acid-8-methyltricyclo[5.2.1.0''6]nonane_8 _ base ester, (meth)acrylic acid-8-ethyltricyclo[5.2.1.0''6]nonane-8-yl ester, (meth)acrylic acid-4-methyltetracyclo[6.2.1.13'6_02' 7] Dodecane-4-yl ester, (meth)acrylic acid _4·ethyltetracyclo [6·2·1.13'6.02'7] dodecyl-4-yl ester, (meth)acrylic acid 1- (bicyclo[2.2.1]hept-2-yl)-1-methylethyl ester, 1-(tricyclo[5.2.1.02'6]nonane-8-yl)-1-(meth)acrylate Methyl ethyl ester, (methyl) propyl Acid 1-(tetracycline [6.2.1.13'6.02'7] dodec-4-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-1-(meth)acrylate Methyl ethyl ester, 1-(3-hydroxyadamantan-1-yl)-1-methylethyl (meth)acrylate, 1,1-dicyclohexylethyl (meth)acrylate, ( 1,1-di(bicyclo[2.2.1]hept-2-yl)ethyl methacrylate, 1,1-di(tricyclo[5.2.1·02'6] fluorene (meth) acrylate Alken-8-yl)ethyl ester, 1,1-di(tetracyclo[6.2.1_13'6.02'7]dodecan-4-yl)ethyl ester (meth)acrylic acid 1 (meth)acrylic acid 1 ,1-di(adamantan-1-yl)ethyl ester, 1-methyl-1_cyclopentyl (meth)acrylate, 1-ethyl-7-(meth)acrylate-201120567 Amyl-ester 1-ethyl-1-cyclohexyl ester of 1-methyl-1-cyclo Emethyl (meth)acrylate. In fact, this Japanese J-methacrylic acid J refers to both acrylic acid and methacrylic acid. Among these, 2-methyladamantan-2-(methyl)acrylate 2-ethyladamantan-2-yl ester, (methyl-2-methylbicyclo[2.2.1]g- 2-based ester, (meth) propylene ring [2.2.1] hept-2-yl ester, (meth)acrylic acid 1-2.2.1] hept-2-yl)-1-methylethyl ester, (Methyl)propan-1-yl)-1-methylethyl ester, (meth)acrylic acid b pentyl ester, (meth) acrylate ethyl ethyl-1. cyclopentyl ester, 1-enoic acid 1- Methyl-1-cyclohexyl ester, 1-ethyl (meth)acrylate, and the like are particularly preferred. The polymer (A) may contain two or more of these repeating units (2) alone. 1-1-3. Repeating unit (3): The polymer (A) has a structure selected from the following general formula (3-1) ~ (3-i), in addition to the above repeating unit (1), and repeating The repeating unit (3) of the vinegar structure of at least one of the groups is a good base ester, (in the book, "(-2-yl ester), acrylic acid-acid-2-ethyl (bicyclo[t] Acid 1-(gold methyl-1-cyclomethyl)propyl-1-cyclohexene or may also contain units (2) 6 ) expressed as units of -28- 201120567 [Chemical 1 〇]

(3-1). (3-2) (3-3) (3-4) (3 - 5) (3-6) In the above general formula (3-1), R6 represents a hydrogen atom or a carbon number of 1~ The substituted or unsubstituted alkyl group '1' represents an integer of from 1 to 3. In the general formulae (3-4) and (3-5), R7 represents a hydrogen atom or a methoxy group. In the general formulae (3-2) and (3-3), D represents not a single bond or a methylene group, and m represents 0 or 1. In the general formulae (3-3) and (3-5), 'E' is an oxygen atom or a methylene group. In the above general formula (3-1), specific examples of the substituted or unsubstituted alkyl group having 1 to 4 carbon atoms among the groups represented by R6 include a methyl group, an ethyl group, and an n-propyl group. I-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl and the like. A suitable example of the monomer to which the repeating unit (3) is given is (meth)acrylic acid-5-oxo-4-oxa-tricyclo[4.2.1.03'7]non-2-yl ester, (Meth)acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.03'7]non-2-yl ester, (meth)acrylic acid-5-side oxygen 4--4-oxa-tricyclo[5.2.1.0''8]non-2-yl ester, (meth)acrylic acid-10-methoxycarbonyl-5-sideoxy-4-oxa-tricyclo[ 5.2.1.03'8] ind-2-yl ester, (meth)acrylic acid-6-sideoxy-7-oxa-bicyclo[3.2.1]oct-2-yl-29- 201120567 ester, (A Acrylic acid 4-methoxycarbonyl _6_sideoxy-7_oxa-bicyclo[3_2_1]oct-2-yl ester, (meth)acrylic acid-7-sideoxy-8-oxa ― 环环 [3.3.1] 壬-2-yl ester, (meth)acrylic acid _4_methoxycarbonyl -7-sided oxo-8-oxa-bicyclo[331] 壬_2-yl ester , (meth)acrylic acid-2-oxotetrachloropyran-4-yl ester, (meth)acrylic acid _4 methyl 2 oxotetraazyl sulphate 4-yl vinegar, (meth)acrylic acid -4- Ethyl-2-oxotetrahydropyran-4-yl ester, (meth)acrylic acid _4-propyl-2-oxo 4 Pyran-4-yl ester, (meth)acrylic acid-5.oxytetrahydrofuran-3-yl ester, (meth)acrylic acid 2,2-methyl-5-oxotetrahydrofuran-3-yl ester, (methyl) )Acetyl-4,4_-methyl-5-oxotetrahydrofuran_3_yl ester, (meth)acrylic acid _2_oxytetrahydrofuran-3-yl ester, (meth)acrylic acid _4,4-dimethyl 2_oxytetrahydrofuran-3-yl ester, (meth)acrylic acid_5,5-dimethyl-2-oxotetrahydrofuran_3_yl ester, (meth)acrylic acid 2_oxytetrahydrofuran_3_yl ester, (meth)acrylic acid-5-oxotetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid _3,3 dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid _4,4 _Dimethyl_5_oxytetrahydrofuran-2-ylacetic acid and the like. The polymer (Α) may contain these repeating units (3) alone or in combination of two or more. The polymer (Α) may be one or more of repeating units (hereinafter, also referred to as "other repeating units") containing the above repeating units (1) to (3). The other repeating unit is, for example, a repeating unit represented by the following general formula (4) (hereinafter also referred to as "repetitive unit (4)"), and a repeating unit represented by the following general formula (5) (below) Also known as "repeated single-30-201120567 (5)"), the repeating unit (hereinafter also referred to as "repeating unit (6)") represented by the following general formula (6). 1-1-4. Repeating unit (4): The repeating unit (4) is a repeating single represented by the following general formula (4) [Chemical 1 1] R8

R9 (4) In the above general formula (4), 'r8 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R9 represents a substituted or unsubstituted polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms. However, when the polycyclic alicyclic hydrocarbon group has a substituent, the substituent is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclic alkyl group having a carbon number of 4 to 20, a hydroxyl group, and a cyanogen group. A hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or a pendant oxy group (except for the group represented by the above formula (I-2)). 1 -1 - 5 . Repeating unit (5 ): The repeating unit (5) is a repeating single represented by the following general formula (5) -31 - 201120567 lit 12]

In the above general formula (5), Ri 〇 represents a hydrogen atom or a methyl group, and χ ι denotes a single bond or a divalent organic group having a carbon number. X2 each independently represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and Rii each independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a group represented by COOR12. However, Ri2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms.尙, at least one of the three R11 is not a hydrogen atom, and when X1 is a single bond, at least one of the three X2 is a two-valent organic group having a carbon number of 1 to 3. 1-1-6. Repeating unit (6): The repeating unit (6) is a repeating unit represented by the following general formula (6). -32- 201120567 【化1 3】 R13

In the above general formula (6), R13 represents a hydrogen atom, a group having a carbon number of 1 to 4, a trifluoromethyl group or a hydroxymethyl group, and R14 represents a divalent organic group. In the above general formula (6), specific examples of the alkyl group having 1 to 4 carbon atoms among the groups of r13 include methyl group, ethyl 'η-propyl group, propyl group, n-butyl group, and 2- Methyl propyl, 1-methylpropyl, t-butyl and the like. In the general formula (6), the organic group having a valence of not more than R14 is preferably a hydrocarbon group having a valence of 2, and a chain or ring-shaped hydrocarbon group having a valence of 2 is more preferable. Further, the divalent organic group represented by R 14 may be an alkylene glycol group or an alkylene ester group. In the above general formula (6), a suitable example of the group represented by R1 4 is a propyl group such as a methylene group, an exoethyl group, a 1,3-propanyl group or a 1,2-extended propyl group. Tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, hexamethylene, decamethylene, undecylmethyl, dodecyl, thirteen Base, tetradecylmethyl, fifteen methylene, hexamethylene, heptamethylene, octamethylidene, nineteen methylene, extended twenty base, 1-methyl-1, 3-propyl, 2-methyl-1,3-propanyl, 2-methyl-1,2-propanyl, 1-methyl-1,4-butylene, 2-methyl- a saturated lock-like hydrocarbon group such as 1,4-butylene, ethylene, propylene, 2-propylene or the like; -33- 201120567 1,3 - cyclobutylene such as cyclobutylene, 1,3 a ring having a carbon number of 3 to 10 such as a cyclopentyl group such as a cyclopentyl group or a cyclopentyl group such as a 1,4-cyclohexylene group or a cyclopentene group such as a 1,5-cyclodextyl group or the like. Alkyl monocyclic hydrocarbon ring group; 1,4-extension sulfhydryl or 2,5 _ 伸 莰 等 等 伸 、, 1,5 - an adamantyl, 2,6-extension 2~4 ring type carbon number 4~30 of alkynyl group such as alkyl group Hydrocarbon ring group is crosslinked cyclic hydrocarbon ring group. Among these, it is preferred that the hydrocarbon group having a 2,5-extension thiol group, an ethyl group, and a 1,2-propion group be added. Further, when the group represented by R14 is a divalent alicyclic hydrocarbon group, a carbon number of 1 to 4 is inserted between the bis(trifluoromethyl)hydroxymethyl group and the divalent aliphatic cyclic hydrocarbon group. The alkyl group is preferred as the spacer. A suitable example of the monomer to which the repeating unit (6) is given is ((3,3,3-trifluoro-2-trifluoromethyl-2-hydroxypropyl) (meth)acrylate, (meth)) (4,4,4-trifluoro-3-trifluoromethyl-3-hydroxybutyl) acrylate, (meth)acrylic acid (1-(5,5,5-trifluoro-4-trifluoromethyl) -4-hydroxy)pentyl)ester, (2-(5,5,5-trifluoro-4-trifluoromethyl-4-hydroxy)pentyl)(meth)acrylate, (meth)acrylic acid ( 2-(5-(3',3,3'-Trifluoro-2,3-trifluoromethyl-2'-hydroxy)propyl)bicyclo[2.2.1]pentyl)ester, (meth)acrylic acid ( 3-(8-(3',3',3,-Trifluoro-2'-trifluoromethyl-2'-hydroxy)propyl)tetracyclo[6.2.1.13,6.02'7]dodecyl)ester The polymer (A) may contain these repeating units (6) alone or may contain two or more. 1-1-7. Mixing ratio of each repeating unit: repeating unit contained in the polymer (A) The ratio of (1) is from 5 to 80 mol%, preferably from 10 to 70 mol%, and from 10 to 60 mol%, based on the total of the repeating units contained in the polymer (A) of -34 to 201120567. Better. Repeat unit (1) ratio If it is less than 5 mol%, when the exposure for forming the second photoresist pattern is formed in the step (3), the first photoresist pattern is exposed to light, and the possibility of the first photoresist pattern cannot be maintained. On the other hand, if it exceeds 8 Omol%, there is a possibility that the resolution of the first photoresist pattern becomes insufficient in the step (1), and the ratio of the repeating unit (2) contained in the polymer (A) is The total amount of the repeating units contained in the polymer (A) is 100% by mol, preferably 5 to 70 m ο 1 %, more preferably 10 to 6 5 m ο 1 %, and 1 0 to 60 m. ο 1 % is more preferable. If the ratio of the repeating unit (2) exceeds 70 mol%, the development of the alkali developing portion is lowered. The ratio of the repeating unit (3) contained in the polymer (A), It is preferably 100 mol% or less, and preferably 45 mol% or less, based on the total of the repeating units contained in the polymer (A), and 45 mol% or less is preferable. By making the ratio of the repeating unit (3) 50 mol% or less, it is possible to suppress Reduction of solubility in alkali imaging solution or occurrence of imaging defects. The ratio of repeating unit (4) contained in polymer (A) is a repeat with respect to polymer (A) The total amount of the group is preferably 100 mol% or less, preferably 25 mol% or less, and preferably 25 mol% or less. By setting the ratio of the repeating unit (4) to 30 mol% or less, the alkali developing portion can be suppressed from being formed by the alkali developing solution. It is easy to swell or the solubility in the alkali imaging solution is lowered. The ratio of the repeating unit (5) contained in the polymer (A) is 100% by mole based on the total of the repeating units contained in the polymer (A). -35- 201120567 The following is preferred, and 25 mol% or less is preferred. By setting the ratio of the repeating single 4 to 30 mol% or less, it is possible to prevent the alkali developing portion from being easily swollen by the alkali developing solution or having a reduced solubility in the alkali developing solution. The ratio of the repeating unit (6) contained in the polymer (A)' is a total of 100% by mole of the repeating unit contained in the polymer (A), preferably 5% by weight or less. By setting the repetition ratio to 30 mol% or less, it is possible to prevent the alkali developing portion from being easily swollen by the alkali developing solution or having a reduced solubility in the alkali developing solution. The ratio of the repeating unit (7) contained in the polymer (A) to the total of 100% by mole of the repeating unit contained in the polymer (A) is preferably 5% by weight or less. By setting the repetition ratio to 30 mol% or less, it is possible to prevent the alkali developing portion from being easily swollen by the alkali developing solution or having a reduced solubility in the alkali developing solution. The first sensitive radiation linear resin composition may contain the compound (A) alone or may be contained by mixing two or more kinds. 1-1-8·Preparation of Polymer (A): The polymer (A) can be polymerized, for example, by using a hydroperoxyalkyl peroxide, a dimercapto peroxide, or an azo compound. The starter is prepared by polymerizing each of the repeating units of the polymerizable unsaturated monomer in the presence of a chain transfer agent in an appropriate manner. Specific examples of the solvent used for the polymerization include alkane such as η-pentane, η-heptane, η-octane, η-decane, and η-decane; and cyclization (5): The capacity is increased to (3) with respect to 3 0 m ο 1 %: and the content becomes the above-mentioned polymer, two, etc. with respect to 3 0 m ο 1 % (6) From the above solvent, a naphthenic group such as η-hexane, hexane, cyclo-36-201120567 heptane, cyclooctane, decahydronaphthalene or norbornane; benzene, toluene, hydrazine, ethylbenzene, Aromatic hydrocarbons such as cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, cyclohexane, chlorobenzene; ethyl acetate, η-butyl acetate, acetic acid a saturated carboxylic acid ester such as butyl ester or methyl propionate; a ketone such as acetone, 2-butanone, 4-methyl-2-pentanone or 2-butanone; tetrahydrofuran, dimethoxyethane An ether such as diethoxyethane. Further, these solvents may be used alone or in combination of two or more. As the polymerization conditions, the reaction temperature is usually 40 to 15 CTC, preferably 50 to 120 t. Further, the reaction time is usually from 1 to 48 hours, and the mass average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 24 hours (hereinafter, also referred to as Although "Mwj" is not particularly limited, it is preferably 1, 〇〇〇~1〇〇, 〇〇〇, preferably 1,000 to 30,000, and preferably 1,000 to 20,000. If Mw is less than 1,000, there is When the heat resistance of the first photoresist layer is lowered, on the other hand, if it exceeds 100,000, the developability of the alkali developing portion is lowered. Further, the Mw of each polymer and the gel of each polymer are used. The ratio (Mw/Mn) of the number average molecular weight (hereinafter, also referred to as "Μη") obtained by the permeation chromatography (GPC) is usually 1 to 5', preferably 1 to 3, and The polymer (A) also contains a low molecular weight component derived from a monomer used for the preparation of each polymer (A). The content ratio of the low molecular weight component is preferably 10,000% by mass (calculated as solid content) of each polymer (A), preferably 0.1% by mass or less, preferably 7% by mass or less. -37-201120567 It is more preferably 0.05% by mass or less. When the content ratio of the low molecular weight component is 0.1% by mass or less, the amount of the precipitate of the liquid for liquid immersion exposure such as contact with water during immersion exposure can be reduced. Further, the occurrence of foreign matter in the photoresist during storage and the occurrence of unevenness in coating during the photoresist coating are small, and the occurrence of defects in the formation of the photoresist pattern can be sufficiently suppressed. In the present specification, the "low molecular weight component" means a component having an Mw of 500 or less, and specific examples thereof include a monomer, a dimer, a trimer, and an oligomer. The low molecular weight component can be removed by various purification methods. The residual amount can be measured by high speed liquid permeation chromatography (HPLC). Specific examples of the purification method of the polymer (A) include a chemical purification method such as water washing or liquid liquid extraction, or a combination of the chemical purification method and a physical purification method such as filtration or telecentric separation. The polymer (A) is preferably one having less impurities such as halogen or metal. By removing impurities by the above-described purification method, the sensitivity, resolution, process stability, pattern shape, and the like of the formed first photoresist layer can be further improved. 1-2. Acid generator (B): The acid generator (B) is a compound which generates an acid by irradiation with radiation. The first sensitive radiation linear resin composition contains an acid generator (B), and the acid which is present in the polymer is unstable by the action of an acid generated by radiation irradiation, specifically, a repeating unit (2) The acid unstable group dissociates (the protective group is detached), and as a result, the exposed portion becomes soluble in the alkali developing solution, and a positive resist pattern can be formed. -38- 201120567 卜2·1. Acid generator (1): The acid generator (B) contains a compound represented by the following general formula (7) (hereinafter, also referred to as "acid generator (1) ") is better. [化1 4]

R17 (7) In the above general formula (7), R15 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched carbon number of 1 to 10. a branched alkoxy group or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. Further, R10 represents a linear or branched alkyl group having a carbon number of 1 to 10, a linear or branched alkoxy group having a carbon number of 1 to 1 Å, or a linear chain having a carbon number of 1 10. , branched or cyclic alkanesulfonyl. R17 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, or a combination of two R17 groups, and a carbon number of 2 to 1 fluorene containing a sulfur cation. The basis. The phenyl group, the naphthyl group, and the valence group having a carbon number of 2 to 10 may have a substituent. q represents an integer of 0 to 2. p denotes an integer 〇~8, which is preferably an integer of 〇~2. Y· represents an anion represented by the following general formula (8-1) to (8-4) -39- 201120567

[1] R18-CrF2r-SH03' R18-S〇3 (8-1) (8-2) In the above general formulas (8-1) and (8-2), R18 represents a fluorine atom or may be substituted. a hydrocarbon group having 1 to 12 carbon atoms. In the above general formula (8_1), r represents an integer of 1 to 1 。. In the above general formulas (8-3) and (8-4), R19 each independently represents a linear or branched alkyl group having 1 to 1 carbon atom substituted by a fluorine atom, or two or two R 19 A two-valent organic group having a carbon number of 2 to 10 which is substituted by a fluorine atom formed by bonding with each other. However, the divalent organic group having 2 to 10 carbon atoms which is substituted by a fluorine atom may have a substituent other than a fluorine atom. In the above general formula (7), a suitable example of the group represented by R17 is a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, a 1-naphthyl group, and two Ri7 groups bonded to each other. A divalent group or the like of a tetrahydrothiophene ring structure containing a sulfur cation. In the above general formula (8-1), (: /21_ group is a perfluoroalkylene group having a carbon number r.) The group may be linear or may be. 尙, r is 1, 2, 4 or 8 In the above general formula (7), a suitable example of the anion represented by Y· includes a trifluoromethanesulfonate anion, a perfluoro-η-butanesulfonate anion, and a perfluoro-η-octanesulfonate. Acid anion, 2-bicyclo[2.2.1.]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate anion, 2-bicyclo[2.2.1]hept-2-yl- 1,1-—Fluorine alkaloid anion, anion of -40 to 201120567 represented by the following formula (ga)~(gg). [Chem. 1 6]

(8 a) (8b) (8 c) (8 d) Ο •Ο °y Ν'

C\F2 Ν\ Γ2 0^\\~CFz ο (8 η \卜2 (8 g), /CF2 acid generator (Β) can be used alone as the above acid generator (i) _ or can also be two The acid generator (Β) may be a linear acid generator other than the acid generator (1) (hereinafter, also referred to as "acid generator (2)"). 1-2-2. Acid generator (2): The acid generator (2) may, for example, be a key salt compound, a halogen-containing compound, an azide compound, a hydrazine compound, a sulfonic acid compound, etc. The acid generator (Β) may contain such an acid. The generating agent (2) may be used singly or in combination of two or more. In the first sensitive radiation linear resin composition, the content ratio of the acid generating agent (Β) is determined by the viewpoint of ensuring the sensitivity and developing property of the light resistor. In the case of 100 parts by mass of the polymer (Α), it is usually 0.1 to 20 parts by mass, preferably 〇.5 to 1 〇 -41 - 201120567. The content of the acid generator (B) is not full. 1. 1 part by mass, the sensitivity and the developing property tend to decrease. On the other hand, if it exceeds 20 parts by mass, the transparency to the radiation is lowered, and it becomes difficult. In the case of using the acid generator (2), the use ratio is 100% by mass based on the total of the acid generators (1) and (2), and usually 80% by mass or less. It is preferably 60% by mass or less. 1 - 3 · Solvent (C): The solvent (C) can be used without any particular limitation as long as it can dissolve the constituent components of the first sensitive radiation linear resin composition. Specific examples of C) include 2-butanone, 2-pentanone, 3-methyl-2-butanthene, 2-hexanthene, 4-methyl-2-pentamethylene, and 3-methyl-2. - linear or branched ketones such as pentamidine, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, etc.; cyclopentanone, 3-methylcyclopentanone a cyclic ketone such as cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone or isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acid ester, propylene glycol mono-η-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-η-butyl ether acetate, propylene glycol mono-i-butyl ether acetate Propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t_T ether acetate Propylene glycol monoalkyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, η-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, 2-hydroxypropane Acid η-butyl ester, 2-hydroxypropionic acid i-butyl ester, 2-hydroxypropionic acid sec-butyl ester, 2-hydroxypropionic acid t-butyl ester, etc. 2-hydroxypropionic acid alkyl esters: 3-methoxy 3-methyloxypropionate, such as methyl propyl propionate, ethyl 3-methoxypropionate-42-201120567, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate ,, 尙 can be exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-η-propyl ether, ethylene glycol mono-η-butyl ether, diethylene glycol diethylene glycol Acid, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl acid acetate, ethylene glycol mono-η-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, toluene, hydrazine, 2 - Ethyl methacrylate, ethyl ethoxyacetate, glycolic acid ethyl acetate, 2-hydroxymethyl 3-methylbutyrate, 3-methoxybutylacetic acid , 3-methylmethoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3·methyl_3·methoxybutyl butyrate, ethyl acetate, Η-propyl acetate, η_butyl vinegar, methyl acetate, ethyl acetate, methyl pyruvate, ethyl acetonate, hydrazine-methylpyrrolidone, hydrazine, hydrazine-dimethylformamidine Amine, hydrazine, hydrazine-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether 'diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, octanoic acid, acetic acid Benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethyl carbonate, propyl carbonate, and the like. Among these, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2-hydroxypropionic acid alkyl esters, 3-alkoxypropionic acid alkyl esters The class, r-butyrolactone and the like are preferred. The solvent (C) may be used alone or in combination of two or more. The amount of the solvent (C) used, the first sensitive radiation linear resin composition -43 - 201120567 The total solid content concentration is usually from 1 to 50% by mass, preferably from 1 to 25% by mass. 1-4. Additive: The first sensitive radiation linear resin composition may further contain various additives such as an acid diffusion controlling agent, an alicyclic additive, a surfactant, a sensitizer, and the like as needed. 1-4-1. Acid Diffusion Control Agent The acid diffusion control agent is a diffusion phenomenon in the first photoresist layer which suppresses the acid generated by the acid generator (B), and suppresses poorness in the non-exposure field. The component of the action of the chemical reaction. By containing such an acid diffusion controlling agent, the pattern shape of the first sensitive radiation linear resin composition can be improved. Moreover, in addition to improving the resolution as a photoresist, it is possible to suppress a change in the line width of the photoresist pattern caused by a change in the post-exposure lag time (PED) from the exposure to the post-exposure heat treatment (PEB). A composition with excellent process stability can be obtained. The acid diffusion controlling agent may, for example, be an amine compound, a guanamine-containing compound, a urea compound or a nitrogen-containing heterocyclic compound. (Amine compound) Suitable examples of the amine compound include monoalkylamines, dialkylamines, trialkylamines, anilines or derivatives thereof; ethylenediamine, N, N, N', N' -tetramethylethylenediamine, tetramethylenedi-44- 201120567 amine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-amine Phenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)- 2-(4-Hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methylethyl)benzene, 1,3-bis(1_(4-aminobenzene) ,-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)- 2-imidazolidinone, 2-quinoxalinol, N,N,N',N'-indole (2-hydroxypropyl)-extended ethylenediamine, ^^『,化'/"-pentamethyldiene Ethylenetriamine, etc. (Compound containing amidino group) Suitable examples of the compound containing amidino group include In addition to the Nt-butoxycarbonyl group-containing amine compound, hydrazine, N-methylformamide, hydrazine, hydrazine-dimethylformamide, acetamide, N-methylamine B Indoleamine, N,N-dimethylacetamide, acetamide, benzalkonium, pyrrolidone, N-methylpyrrolidone, N-acetamide-1-adamantylamine, heterotrimerization Cyanium citrate (2-hydroxyethyl), etc. (urea compound) Suitable examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, and 1,3-dimethylurea'1. 1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. -45- 201120567 (nitrogen-containing heterocyclic compound) Suitable examples of nitrogen-containing heterocyclic compounds Examples thereof include imidazoles, pyridines, and piperazines. The pyrenes include pyrazines, pyrazoles, pyridazines, quinoxalines, anthracenes, pyrrolidines, piperidines, piperidines, and 3-piperidinyls. , 2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-acetamidamine morpholine, 3-(indolyl-morpholinyl)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-dioxobicyclo[2.2.2]octane, etc. The acid diffusion controlling agent is in addition to the acid diffusion controlling agent described above, It is also possible to use a photo-disintegrating base which is sensitized by exposure to light, and a base is formed. (Photocracking base) The photodisintegrating base is a key salt compound which is decomposed by exposure and controlled to deactivate acid diffusion. The key salt compound may, for example, be an onium salt compound represented by the following general formula (9) or an onium salt compound represented by the following general formula (1): [Chem. 1 7 20 ζ· R20

(10) (9) In the above general formulas (9) and (10), R2Q independently represents a hydrogen atom -46-201120567, alkoxy, hydroxy or a halogen atom, Z- is 0Η·, ch3COO- or less The anions represented by the formulae (11-1) to (11-5) are preferred. [化1 8]

Specific examples of the OH \\ Ί photo-disinfecting base are OH·, CH 3 COO·, or an anionic triphenyl sulfonium salt represented by any one of the above formulas (11-2) to (11-3). . The above acid diffusion controlling agents may be used singly or in combination of two or more. In the first sensitive radiation linear resin composition, the content of the acid diffusion controlling agent is preferably 1 part by mass to 1 part by mass based on 1 part by mass of the polymer (A). It is preferably 1 to 10 parts by mass, more preferably 0.05 to 5 parts by mass. When the content ratio of the acid diffusion controlling agent exceeds 15 parts by mass, the sensitivity of the photoresist may be lowered. On the other hand, if it is less than 0.001 part by mass, the shape of the resist or the degree of faithfulness of the size may be lowered depending on the process conditions. (11-4) (11-5) -47- 201120567 1-4-2. Alicyclic additive: The alicyclic additive is characterized by improved dry etching resistance, pattern shape, adhesion to the substrate, and the like. Ingredients: Specific examples of alicyclic additives include: adamantane substituted by polar group; deoxycholate; stone cholate: alkyl carboxylate; 尙 3- ( 2- Hydroxy-2,2-bis(trifluoromethyl)ethyl)tetracyclo[6.2.1.13'6.02'7]dodecane and the like. Further, these alicyclic additives may be used alone or in combination of two or more. 1-4-3. Surfactant: The surfactant is a component having an effect of improving coatability, streaking, developing property, etc. Specific examples of the surfactant include polyoxyethylene lauryl ether and polyoxygen Ethylene stearate, polyoxyethylene oleyl ether, polyoxyethylene η-octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilauryl ester, polyethylene glycol distearate, etc. Other than the ionic surfactant: 以下 341 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, Ν · 95 (above, Kyoeisha Chemical Co., Ltd.), Eftop EF301, and EF 3 03 'With EF3 52 (above, manufactured by Tohkem Products Co., Ltd.), Megafac F171, F173 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Florad FC43 0, and FC 4 3 1 (above, Sumitomo 3 Co., Ltd.) Asahiguide AG710, Surflon S-3 8 2. Same as SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.). Further, these surfactants may be used alone or in combination of two or more. 1 - 4 - 4 . Sensitizer ·- Sensitizer is the energy that absorbs radiation and transmits its energy to the component of acid generator (B). Thereby, the effect of increasing the amount of acid generated can be improved, and the sensitivity as the appearance of the photoresist can be improved. Examples of the sensitizer include oxazoles, acetophenones, benzophenones, naphthalenes, phenols, diacetamidines, eosin, rose bengal, anthraquinones, oximes, phenothiazines, and the like. . Further, these sensitizers may be used alone or in combination of two or more. 1-4-5. Other additives: The first sensitive radiation linear resin composition may also contain additives other than the above additives (hereinafter also referred to as "other additives"). Examples of the other additives include an alkali-soluble resin, a low-molecular alkali solubility control agent having an acid-dissociable protecting group, an antihalation agent, a storage stabilizer, and a defoaming agent. Further, by including a dye or a pigment, the latent image of the exposed portion can be visualized, and the influence of the halation at the time of exposure can be alleviated. Further, by including a bonding aid, the adhesion between the photoresist and the substrate can be improved. 2. Second Sensitive Radiation Linear Resin Composition: The second sensitive radiation linear resin composition contains a polymer having the aforementioned repeating unit (6) and the aforementioned repeating unit (2) (hereinafter, also simply referred to as "polymer (a) ))), a sensitive radiation linear acid generator (b) (hereinafter, -49-201120567 is simply referred to as "acid generator (b)") and solvent (c) is preferred. 2-1. Polymer (a): 2-1-1. Repeating unit (6): As the repeating unit (6) contained in the polymer (a), it can be used in the linear composition of the first sensitive radiation. The repeating unit (6) contained in the polymer (A) is the same repeating unit. Further, the repeating unit (6) contained in the polymer (a) may be the same as the repeating unit (6) contained in the polymer (A), or may be different. The polymer (a) may contain one repeating unit (6) alone or may contain two or more kinds. 2-1-2. Repeating unit (2): As the repeating unit (2) contained in the polymer (a), a repeating unit contained in the polymer (A) in the first sensitive radiation linear resin composition can be used. (2) The same repeating unit. Further, the repeating unit (2) contained in the polymer (a) may be the same as the repeating unit (2) contained in the polymer (A), or may be different. 2-1-3. Other repeating units: The polymer (a) may contain other repeating units in addition to the above repeating units (6) and (2). Other repeating units include, for example, repeating units (3) to (5) and (7) in the first sensitive radiation linear resin composition. Further, the repeating unit (3) -50-201120567~(5) and (7) contained in the polymer (a) and the repeating unit (3) to (5) and (7) contained in the polymer (A), They may be the same or different. 2-1-4. Mixing ratio of each repeating unit: The ratio of the repeating unit (6) contained in the polymer (a) is 10% by mole based on the total of the repeating units contained in the polymer (a). It is preferably 15 to 90 mol%, more preferably 30 to 90 mol%, more preferably 30 to 80 mol%, and more preferably 40 to 80 mol%. If the ratio of the repeating unit (6) is less than 30 m〇l%, the solubility of the polymer (a) to the alcohol solvent may be lowered. On the other hand, when it exceeds 90 mol%, the resolution of the alkali developing unit deteriorates. The ratio of the repeating unit (2) contained in the polymer (a) is 100 m〇1% based on the total of the repeating units contained in the polymer (a), preferably 10 to 70 mol, preferably 10 to 60 mol%. 20~60mol% is better. When the ratio of the repeating unit (2) is less than 1 mol%, the resolution of the alkali developing portion deteriorates. On the other hand, when it exceeds 70 mol%, the resolution of the alkali developing unit deteriorates. The ratio of the repeating unit (3) contained in the polymer (a) is preferably 〇〇mol% based on the total of the repeating units contained in the polymer (a), preferably 5 〇mol% or less, and 45 mol% or less. Preferably. If the ratio of the repeating unit (3) exceeds 50 mol%, the solubility in the alkali developing solution is lowered, and development defects may occur. The ratio of the repeating unit (4) contained in the polymer (a) is 1 〇 m ο 1 % ' with respect to the total of the repeating units contained in the polymer (a) at 3 0 m ο 1 °/. -51 - 201120567 The following is preferred, and 25 mol% or less is preferred. When the ratio of the repeating unit (4) exceeds 30 mol%, the alkali developing portion is likely to swell due to the alkali developing solution, or the solubility in the alkali developing solution is lowered. The ratio of the repeating unit (5) contained in the polymer (a) is preferably 100% by mole based on the total of the repeating units contained in the polymer (a), preferably 30% by mole or less, and preferably 25% by mole or less. When the ratio of the repeating unit (5) exceeds 30 mol%, the alkali developing portion is likely to swell due to the alkali developing solution, or the solubility in the alkali developing solution is lowered. The ratio of the repeating unit (7) contained in the polymer (a) is preferably 10,000 mol% based on the total of the repeating units contained in the polymer (a), preferably 30 mol% or less, and preferably 25 mol% or less. When the ratio of the unit (7) exceeds 30 m ο 1 %, the alkali developing portion is likely to swell due to the alkali developing solution, or the solubility in the alkali developing solution is lowered. The second-sensitive radiation linear resin composition may contain one kind of the above-mentioned polymer (a) alone or may be contained by mixing two or more kinds. 2-1-5. Modulation of Polymer (a): The polymer (a) can be prepared in the same manner as the above polymer (A). The Mw of the polymer (a) is not particularly limited, and is preferably 1, 〇〇〇 〜 1 〇〇, 〇〇〇, 1,000 to 30, 〇〇〇 is preferred, ιοοο Ο, ΟΟΟ is better. . If the Mw of the polymer (a) is less than 〗, 〇〇(), when the second photoresist layer is formed, the heat resistance is lowered. On the other hand, when it exceeds 100,000, the developability of the alkali developing unit is lowered. Further, the ratio of Mw to Μη (Mw - 52 - 201120567 / Μη) of the polymer (a) is usually 1 to 5', preferably 1 to 3. Further, the polymer (a) also contains a low molecular weight component derived from a monomer used in the preparation. The content ratio of the low molecular weight component is preferably 0.1% by mass or less based on 100% by mass of the polymer (a) (solid content conversion), preferably 0.07% by mass or less, and more preferably 5% by mass or less. . The content ratio of the low molecular weight component is 〇.1 mass. /. In the following, the amount of the precipitate of the liquid for immersion exposure such as contact with water during the immersion exposure can be reduced. Further, no foreign matter is generated in the photoresist during storage of the photoresist, and coating unevenness is not caused during the photoresist coating, and the occurrence of defects at the formation of the photoresist pattern can be sufficiently suppressed. Further, the polymer (a) is preferably one having less impurities such as a halogen or a metal. Thus, by reducing impurities, the sensitivity, resolution, and process stability of the second photoresist layer can be further improved. The method for purifying the polymer (a) is the same as the above-mentioned polymer (A). 2-2. Acid generator (b): The second-sensitive radiation linear resin composition is usually one containing a radiation-sensitive linear acid generator. The acid generator (b) may be the same as the acid generator (B) in the above first radiation sensitive linear resin composition. Further, the acid generator (B) and the acid generator (b) may be the same or different. . The content of the acid generator (b) is preferably -53 to 201120567 0.1 to 20 parts by mass, preferably from -53 to 201120567, from the viewpoint of ensuring sensitivity and developability as a photoresist. It is 0.5 to 10 parts by mass. If the content is less than 0.1 part by mass, the sensitivity and the developing property tend to decrease. On the other hand, when it exceeds 20 parts by mass, the transparency to the radiation is lowered, and it becomes difficult to obtain a rectangular second resist pattern. When the acid generator (b) and the acid generator (1) contain other acid generators at the same time, the use ratio is usually 80% by mass or less, preferably 60% by mass based on 100% by mass of the acid generator (b). % below 2-3. Solvent (c): The solvent (c) is not particularly limited, and it is preferred that the polymer (a) is soluble but the first photoresist pattern is not dissolved. For example, propylene glycol monomethyl ether acetate, cyclohexanone, an alcohol solvent, an ether solvent, and the like can be given. The solvent (c) is used in an amount such that the total solid content of the second sensitive radiation linear resin composition is usually from 1 to 50% by mass, preferably from 1 to 25% by mass. 2-4. Additive: Second sensitive The radiation linear resin composition may also contain an additive. Further, as the additive, the same ones as the various additives such as the acid diffusion controlling agent described above in the first sensitive radiation linear resin composition can be mentioned. When the first sensitive radiation linear resin composition contains an acid diffusion controlling agent as an additive, its content is preferably 1 to 15 parts by mass based on 1 part by mass of the polymer (a). 〇.〇1~1 The mass fraction is preferably 5%, and 5 to 5 parts by mass is more preferably. When the content exceeds 15 parts by mass, there is a case where the sensitivity of the photoresist is lowered from -54 to 201120567. On the other hand, if the condition is less than 0.001, the pattern shape or size of the photoresist is faithful. [Embodiment] Hereinafter, embodiments based on the present invention will be specifically described based on the examples. The evaluation methods of various physical properties are as follows. [mass average molecular weight (Mw) and number average: GPC column manufactured by Tosoh Corporation (2 G2000HXL below, 1 "G3000HXL", "), flow rate: 1.0 mL/min, precipitation solvent: four-column column Temperature: 40 ° C under the conditions of analysis, monodisperse, by gel permeation chromatography (GPC) for measurement [pattern shape]: Using a scanning electron microscope (trade name "S-Tester Co., Ltd.") It is observed that the resist pattern of the third embodiment and the comparative example has a loss or that the bottom portion of the opening portion is not "defective", and the pattern in which both the scum and the first photoresist pattern are formed is evaluated as " good". The substrate C of 18 to 20 has no scum, and the second photoresist pattern is formed vertically, and the contact hole formed at 48 nm x 48 nm is "good". Quantities, according to the degree of process reduction. However, the present invention and the measurement method and the specific amount (Μη)], the trade name is "G4000HXL" 1 furan (THF), polystyrene is the standard 9 3 8 0", Hitachi meter C, will be Evaluation of the pattern and the second photoresist in the case of a photo-soluble matter. Evaluation of the case of the embodiment and the first photoresist pattern pattern - 55 - 201120567 [Line width variation]: Using a scanning electron microscope (trade name) "S-93 80" and manufactured by Hitachi Metro Co., Ltd.) observed the line width variation of the photoresist pattern of the substrate C. For the line widths of any five of the line width portions of the photoresist pattern of the substrate C, the line width is measured at any two points, and the line width of any of the five line width portions is calculated. The average 値 of 00 points is taken as the average line width. The difference between the average line width after the formation of the first photoresist pattern and the average line width after the double patterning (formation of the second photoresist pattern) is used as the variation of the line width variation. When the variation of the measured line width variation was less than 4 nm, it was evaluated as "good J, 4 nm or more but less than 8 nm was evaluated as "good", and 8 nm or more was evaluated as "poor". The change in the line width variation 値 (nm) and the evaluation ("good", "good", or "bad") are shown in Table 2.尙, if the change in line width variation is less than 3 nm, it is expressed as "<3" in Table 2. [Top Loss]: The top-loss of the resist pattern of the substrate C was observed using a scanning electron microscope (trade name "S-48 00", manufactured by Hitachi Metro Co., Ltd.). The enthalpy (reduced enthalpy) of the height of the first photoresist pattern is subtracted from the thickness (height) of the first photoresist layer in the step (1) as the evaluation of the top loss. The photoresist pattern having a reduced 値 of less than 5 nm was evaluated as "excellent", and the resist pattern of 5 nm or more but less than 15 nm was evaluated as "good", and the resist pattern of I5 nm or more was evaluated as "poor". The reduction of 値(nm) and evaluation ("good", "good", or "bad") are shown in Table 2.尙, decrease -56- 201120567 値 If it is less than 5 nm, it is expressed as "<5" in Table 2. <Preparation of the first sensitive radiation linear resin composition> (Example 1) A polymer (A-1) having a repeating unit represented by the following formula (A-1) as the polymer (A) 1 〇〇 parts by mass, 7.5 parts by mass of the acid generator (B-1) (triphenylsulfonium nonafluoro-n-butanesulfonate) as the acid generator (b), and a solvent (C) as a solvent (C) -1) (propylene glycol monomethyl ether acetate) 1287 parts by mass and solvent (C-2) (cyclohexanone) 551 parts by mass, and an acid diffusion controlling agent (D -1 ) as an acid diffusion controlling agent (Nt - Butoxy base-based masculine B) 0.9 parts by mass were mixed to form a homogeneous solution. The obtained uniform solution was filtered using a membrane filter having a pore size of 200 nm to prepare a coating liquid (1) composed of a first sensitive radiation linear resin composition. Further, the Mw of the polymer (A-1) was 10,000, and the total solid concentration of the first sensitive radiation linear composition was about 7% by mass. [化1 9]

κ Ο Ο 15 mol% 35 mol% 15 mol% 35 mol% (A-1) (Examples 2 to 6 and Comparative Example 1) -57 201120567 The preparation was carried out in the same manner as in Example 除 except that the preparation was carried out in accordance with the formulation described in Table 1 below. The coating liquids (2) to (6) and (13) are prepared. Further, Mw of each polymer (A) is shown in Table 1 below. <Preparation of the second-sensitive radiation linear resin composition> (Reference Example 1) The polymer (a-Ι) having the repeating unit represented by the following formula (a-1) as the polymer (a) a portion, 7.0 parts by mass of the acid generator (B-1) (triphenylphosphonium non-n-butanesulfonate) as the acid generator (b), and a solvent (C-3) as the solvent (c) ( 4-methyl-2-pentanol) 1287 parts by mass and solvent (C-1) (propylene glycol monomethyl ether acetate) 551 parts by mass, and an acid diffusion controlling agent (D _2 ) as an acid diffusion controlling agent ( 2.64 parts by mass of triphenylsulfate) was mixed to prepare a homogeneous solution. The coating liquid (7) composed of the second sensitive radiation linear resin composition was prepared by filtering the obtained homogeneous solution using a membrane filter having a pore size of 200 nm. Further, the Mw of the polymer (a-Ι) was 6,000, and the total solid concentration of the second sensitive radiation linear composition was about 6.5% by mass. [化2 0]

HO CF3 40 mol% 15 mol% 45 mol% (a-1) -58-201120567 (Reference Examples 2 to 6) A coating liquid was prepared in the same manner as in Reference Example 1 except that the preparation was carried out in accordance with the formulation described in Table 1 below. 8) ~(1 2 ). Further, the Mw - 倂 of each polymer (a) is not shown in Table 1 below. [Table 1] Polymer acid generator Solvent acid diffusion control agent Type of coating liquid Mw Usage (mass) Type of use (mass parts) Type: a (mass) Type of use (mass) Type of use Quantity (mass S) Example 1 A-X 10000 100 B- 1 7.5 C-1 1287 C-2 551 D- 1 0.94 0) Example 2 A- 2 10000 100 B- 1 7.5 C- 1 1287 C- 2 551 D- 1 0.94 0 Example 3 A-3 10000 100 B- 1 7.5 C-1 1287 C-2 551 D- 1 0.94 0) Example 4 A-4 10000 100 B- 1 7.5 C-1 1287 C - 2 551 D- 1 0.94 a) Example 5 A-5 10000 100 B- 1 7.5 C-1 1287 C-2 551 D- 1 0.94 6) Example 6 A-6 10000 100 B- 1 7.0 C-1 2014 - - D- 1 0.94 6) Reference Example 1 a— 1 6000 100 B- 1 7.0 C- 3 1287 C- 1 551 D-2 2.64 &lt;ΰ Reference Example 2 a-2 6000 100 B- 1 7.0 C- 3 1287 C- 1 551 D-2 2.64 e) Reference Example 3 a— 3 5500 100 B- 1 7.0 C-1 1287 C-4 551 D- 2 2.64 θ) Reference Example 4 a— 4 5400 100 B- 1 7.0 C-1 1287 C-3 551 D-2 2.64 α〇) Reference Example 5 a— 5 6000 100 B- 1 7.0 C-1 1287 C-3 551 D-2 2.64 αι) Reference Example 6 a— 6 5 500 100 B- 1 7.0 C-3 1287 C-4 551 D-2 2.64 Comparative Example 1 A-7 10000 100 B- 1 7.5 C-1 1287 C-2 551 D- 1 0.94 43) In Table 1 above, polymerization The materials (A-2) to (A-7) are each a polymer having a repeating unit represented by the following formula (A-2) to (A-7). -59- 201120567 【化2 1】

In the above Table 1, the polymers (a-1) to (a-6) are each a polymer having a repeating unit represented by the following formula (a-Ι) to (a-6). -60- 201120567 【化2 2】

30 mol% 20 mol% 40 mol% 10 mol% (a - 5) 20 mol% 20 mol% 20 mol% 40 mol% (a - 4 )

In the above Table 1, the acid generator (B-1), the solvents (C-1) to (C-4), and the acid diffusion controlling agents (D-1) and (D-2) are each a compound shown below. Acid generator (B-1): triphenylsulfonium nonafluoro-η·butane sulfonate solvent (C-1): propylene glycol monomethyl ether acetate solvent (C-2): cyclohexanone solvent ( C-3) : 4-methyl-2-pentanol solvent (C-4) : 1-butoxy-2-propanol acid diffusion control agent (Dl) : Nt-butoxycarbonyl pyrrolidine acid diffusion control agent (D-2): Triphenyl sulphate-61 - 201120567 &lt;Formation of photoresist pattern&gt; (Example 7) Step (1): The lower anti-reflection film (trade name "ARC66", Nissan) Manufactured by a chemical manufacturing company (trade name "CLEAN TRACK LITHIUS Pro-i", manufactured by Tokyo Electronics Co., Ltd.), spin-coated on a 12-inch wafer, and then PB (205 ° C, 60 seconds) On the other hand, a coating film having a film thickness of 105 nm was formed. The coating liquid (1) (first sensitive radiation linear resin composition) prepared in Example 1 was spin-coated and subjected to PB using a semiconductor manufacturing apparatus (trade name "CLEAN TRACK ACT12", manufactured by Tokyo Electronics Co., Ltd.). After (120 ° C, 60 seconds), a first photoresist layer having a film thickness of 90 nm was formed by cooling (23 ° C, 30 seconds). The upper film formation composition (trade name "TCX041", manufactured by JSR Corporation) was spin-coated on the formed first photoresist film using the above-described semiconductor manufacturing apparatus (CLEAN TRACK Lithius Pro-i), and then PB was performed. (90 ° C, 60 seconds) to form a film having a film thickness of 90 nm. Next, using an ArF immersion exposure apparatus (trade name "NSR-S610C j, manufactured by NIKON Co., Ltd.", under the optical conditions of NA: 1.30 and Dipole, a photoresist pattern of 3 〇 nm line width/120 nm pitch was used. The mask is exposed to a line width portion (unexposed portion) having a width of 3 Onm by water as a liquid for immersion exposure, and is exposed to a predetermined portion. In the above semiconductor manufacturing apparatus (CLEAN TRACK Lithius Pro-i) After applying PEB (1 1 5 °C, 60 seconds) on the hot plate, cooling (2 3 °C, 30 seconds), in the GP nozzle of the developing cup body -62- 201120567, 2.38 mass The aqueous solution of tetramethylammonium hydroxide was used as a developing solution for liquid imaging (within 1 sec.), and was rinsed with ultrapure water. The mixture was centrifuged at 2,000 rpm for 15 seconds to form a solution. The substrate A having the first photoresist pattern. Step (2): The first photoresist pattern of the obtained substrate A is subjected to PDB (180 ° C, on the heating plate of the above-mentioned semiconductor manufacturing apparatus (CLEAN TRACK ACT12). 60 seconds), and the substrate B was obtained. Step (3): The coating liquid (7) prepared in Reference Example 1 (second-sensitive radiation) The resin composition was spin-coated on the substrate B using the above-described semiconductor manufacturing apparatus (CLEAN TRACK ACT12), and after PB (100 〇C, 60 seconds), it was cooled (23 t, 30 seconds) to form a film thickness of 90 nm. a second photoresist layer. Using the ArF immersion exposure apparatus, under the optical condition of NA: 1.30 and Dipole, a mask for forming a photoresist pattern of 30 nm line width/120 nm pitch is used to form the first light. The center of the line portion of the resist pattern can form a line width portion (unexposed portion) having a width of 3 Onm and expose a predetermined portion. PEB is performed on the heating plate of the aforementioned semiconductor manufacturing apparatus (CLEAN TRACK Lithius Pro-i). 90 ° C, 60 seconds), after cooling (23 ° C, 30 seconds), in a GP nozzle of the developing cup body, a 2.38 mass % aqueous solution of tetramethylammonium hydroxide was used as a developing solution for liquid imaging (30 seconds), and rinsing with ultrapure water. By performing centrifugal drying at 2,000 rpm for 15 seconds, a substrate C on which a second photoresist pattern was formed was obtained on the substrate B. The evaluation of the shape of C is "good", and the evaluation of the top loss is due to its -63-20112 0567 is reduced to less than 5nm (indicated by "&lt;5" in Table 2), "excellent", and the line width is changed by less than 3ηιη (indicated by "&lt;3" in Table 2), the line width is changed. The evaluation was "excellent". The results of these evaluations are shown in Table 2 below. (Examples 8 to 20 and Comparative Examples 2 to 4) Each of the substrates C for evaluation was obtained in the same manner as in Example 7 except for the conditions described in Table 2 below. However, in Examples 18 to 20, the conditions disclosed in Table 2 below were added, and the exposure was performed with a mask for forming a photoresist pattern of 48 nm line width/96 nm pitch (48 nmL LSS). The substrate for evaluation was obtained in the same manner as in Example 7 except that the photoresist pattern was formed to be exposed by a mask having a photoresist pattern of 48 nm line width/96 nm pitch (48 nmLLS). c. Further, the evaluation results of the obtained substrates C are shown in Table 2 below. • 64- 201120567 Evaluation line width variation evaluation Excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, excellent, good, good, bad, bad, bad, bad, 値(nm), ro rn, ΓΟ &lt;Q Γ^ί ro rn ry ΓΟ rn rn rn ΓΟ oo oo Ο Ο iTi Top loss evaluation Excellent Excellent Good Good Good Excellent Excellent Good 丨 Good Good Good Good Good Good Bad Good Bad Bad 灭 (nm ο ο —Η Ο Ο in &lt;N The shape of the figure is good, good, good, good, good, good, good, good, good, good, good, good, good, good, bad, bad, bad, bad, bad, (3), time (seconds) § S § § § δ δ S § § § § SSSS § 0Q W pu, Temperature § § ON § ^Τ) Ον ^Ti σ\ § § s \Τ) 〇\ $ σ\ as ON in ON g § ON time 1 (seconds) § § g § § g § SS § § % s S ss § S P3 Ph Brew | CC)\ 〇Ο Ο 100 ο 100 ο Ο ο 〇ο ο ο ο 〇ο rH o Ο —Η 〇 Coating liquid type δ δ g gs Η s—/ Ν s—o- S—✓ S′&quot; f—1 g /-\ δ g /^s /&quot;S Radiation irradiation conditions Irradiation condition time (seconds) 1 t S 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 XeM Wavelength (nm) 1 1 CN 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 PDB condition time (seconds) § § I § § ss S § ss § S s S 1 g 1 1 Temperature CC) gg 1 180 g 180 gg ^•Η gg TH g Η g § g § 1 1 180 1 1 Step (1) Time (seconds) s § § s § δ S § s § § sssss § S m W Ph temperature (°C) r*&quot;H CM rH 120 CN 125 ^Τί ι〇CN i 120 125 125 CN (N u^&gt; (N «ο &lt;N m PB condition time (seconds) S § § § S s § § ss § ss § S Temperature CC) 宕r—H 130 ^-Η 125 130 r-^ m CN 130 130 130 130 120 f 涂敷 Type of coating liquid _·Η δ δ S / - Ν δ / -S cn / Js δ δ s - ✓ / - * &gt; S - ✓ » - H Ν δ Example 7 Example 8 Example 9 ! Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 实施 Example 18 Example 19 Example 20 Comparative Example 2 Comparative Example 3 Example 4 Comparative Example 5 Comparative Example 6 -65- 201120567 It is apparent from Table 2 that the sensitive radiation linear resin composition of the present invention is used as the first sensitive radiation linear resin composition in the double patterning. A pattern having a good pattern shape and a variation in line width variation is formed into a small photoresist pattern. The photoresist pattern of Comparative Example 4 is a linear radiation-sensitive resin composition containing a polymer (A-7) having no repeating unit (1) as a first radiation-sensitive linear resin composition, which is a pattern shape. Poor, and said the line width changes are also larger. In the photoresist pattern of Comparative Example 5, since PDB was not performed in the step (2), the pattern shape was poor and the line width variation was large. Further, in the resist pattern of Comparative Example 6, since the radiation was not irradiated in the step (2), the shape of the pattern was inferior and the line width variation was large. [Industrial Applicability] The sensitive radiation linear resin composition of the present invention can be suitably used for future miniaturization because it can form a photoresist pattern beyond the wavelength limit well and economically by using the above method. Further progress will be made in the field of microfabrication represented by the manufacture of integrated circuit components. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a schematic view showing an example of a state in which a first photoresist layer is formed on a substrate in the step (1) of the photoresist pattern forming method of the present invention. Fig. 1B is a schematic view showing an example of a state in which the first photoresist layer is exposed in the step (-66-201120567 1) of the method for forming a photoresist pattern of the present invention. Fig. 1C is a schematic view showing an example of a state in which the first photoresist layer is exposed in the step (1) of the photoresist pattern forming method of the present invention. Fig. 1D is a schematic view showing an example of a state in which the first photoresist pattern is formed in the step (1) of the photoresist pattern forming method of the present invention. Fig. 2 is a schematic view showing an example of the step (2) of the method for forming a photoresist pattern of the present invention. Fig. 3A is a schematic view showing an example of a state in which the second photoresist layer is formed on the first photoresist pattern in the step (3) of the photoresist pattern forming method of the present invention. Fig. 3B is a schematic view showing an example of a state in which the second photoresist layer is exposed in the step (3) of the photoresist pattern forming method of the present invention. Fig. 3C is a schematic view showing an example of a state in which the second photoresist layer is exposed in the step (3) of the photoresist pattern forming method of the present invention. Fig. 3D is a schematic view showing an example of a state in which the second photoresist pattern is formed in the step (3) of the photoresist pattern forming method of the present invention. Fig. 4 is a top view schematically showing an example of a state in which the line width portion of the second photoresist pattern is formed in the photoresist pattern forming method of the present invention. Fig. 5 is a side view schematically showing an example of a state in which a line width portion of a second photoresist pattern is formed in the photoresist pattern forming method of the present invention. Fig. 6 is a top view schematically showing another example of a state in which the line width portion of the second photoresist pattern is formed in the photoresist pattern forming method of the present invention. -67- 201120567 [Description of main component symbols] 1 : Substrate 2 : First photoresist layer 3 : Liquid for immersion exposure 4 : Mask 5, 35 : Alkali development unit 12, 22 : First photoresist pattern 12a , 22a : line width portion 12b of the first photoresist pattern, 22b: line distance portion of the first photoresist pattern type 1 5 : contact hole pattern 3 2 : second photoresist layer 42 : second photoresist pattern 42a: the line width portion 42b of the second photoresist pattern: the line distance portion of the second photoresist pattern-68-

Claims (1)

201120567 VII. Patent application scope: 1. A sensitive radiation linear resin composition characterized by comprising: at least one selected from the group consisting of repeating units represented by the following general formulas (1-1) to (1-4) a repeating unit and a polymer (A) having a repeating unit of an acid labile group, a radiation sensitive linear acid generator (B), and a solvent (C), wherein the polymer (A) is in a photoresist pattern forming method, The first resistive radiation linear resin composition is used, the photoresist pattern forming method comprising: the step (1) of forming a first photoresist pattern on the substrate by using the first sensitive radiation linear resin composition; The first photoresist pattern is insolubilized with respect to the second radiation-sensitive linear resin composition (2): and on the substrate on which the first photoresist pattern is formed, using the second sensitive radiation linear resin Step of forming a second photoresist pattern (3 [Chemical 1] (In the above general formula (1-1) to (1-4), R1 each independently represents -69 to 201120567 a hydrogen atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and R2 each independently represents a hydrogen atom or a hydroxyl group. In the above general formula (1-4), R3 represents a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms; in the above general formula (1-1), A represents a methylene group or a carbon number of 2 The alkyl group of ~5 may be substituted by an alkyl group having 1 to 5 carbon atoms; in the above general formula (1-3), B represents the following formula (B-1) to (B-6); Any of the groups shown by the formula, η represents an integer of 1 to 3) [Chemical 2] (Β-1) (Β-2) (Β-3) (Β-4) (Β — 5) (Β—6) 2. A method for forming a resist pattern, which is characterized by the use of claim 1 a first sensitive radiation linear resin composition, the step of forming a first photoresist pattern on the substrate (1), and the step of inactivating the first photoresist pattern relative to the second radiation-sensitive linear resin composition (2) And a step (3) of forming a second photoresist pattern using the second photosensitive radiation linear resin composition on the substrate on which the first photoresist pattern is formed. 3. The photoresist of claim 2 The pattern forming method is characterized in that the first photoresist pattern and the second photoresist pattern respectively have a line width portion which is arranged in parallel in a plurality of parallel manners, and is formed between the adjacent line width portions a photoresist pattern of a plurality of line spacing portions, wherein the line width portion of the second photoresist pattern is parallel to the line width portion of the first photoresist pattern in the line spacing portion of the first photoresist pattern Ground formation. -70-201120567 4. The method for forming a photoresist pattern according to claim 2, wherein the first photoresist pattern and the second photoresist pattern respectively have a line width portion of a convex shape arranged in parallel, and a photoresist pattern of a plurality of line spacing portions formed between the adjacent line width portions, wherein the line width portion of the second photoresist pattern intersects the line width portion of the first photoresist pattern form. The method for forming a photoresist pattern according to any one of claims 1 to 4, wherein the polymer (A) contains a repeating unit represented by the above general formula (id). It -71 -