Pattern formation method

Abstract

This invention provides a pattern formation method that involves forming a resist pattern using a non-chemically amplified resist composition with excellent sensitivity and critical resolution, and then reversing the pattern with an organotitanium compound-containing material that has high etching resistance. [Solution] A method for forming a pattern, comprising: (i) forming a resist pattern on a support using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent; (ii) applying a material containing an organic titanium compound and a solvent to the support on which the resist pattern has been formed to form a pattern inversion film; and (iii) removing the resist pattern by etching to form an inversion pattern.

Description

[Technical Field]

[0001] The present invention relates to a method for forming a pattern. [Background technology]

[0002] With the expansion of the IoT market, there is an increasing demand for higher integration, higher speed, and lower power consumption in LSIs, leading to rapid miniaturization of pattern rules. Logic devices, in particular, are driving this miniaturization. As cutting-edge miniaturization technology, mass production of 10nm node devices is underway using double, triple, and quadruple patterning in ArF immersion lithography, and further research is progressing on 7nm node devices using next-generation 13.5nm extreme ultraviolet (EUV) lithography.

[0003] As miniaturization progresses, image blurring due to acid diffusion has become a problem (Non-Patent Literature 1). To ensure resolution in fine patterns with processing dimensions of 45 nm or more, it has been suggested that controlling acid diffusion is important, in addition to improving the dissolution contrast as has been conventionally proposed (Non-Patent Literature 2). However, since chemically amplified resist compositions increase sensitivity and contrast through acid diffusion, if acid diffusion is suppressed to the extreme by lowering the post-exposure bake (PEB) temperature or shortening the PEB time, sensitivity and contrast decrease significantly.

[0004] Adding an acid generator that produces bulky acids to suppress acid diffusion is effective. Therefore, copolymerizing an onium salt acid generator with a polymerizable olefin into a polymer has been proposed. However, for pattern formation of resist films with processing dimensions of 16 nm or more, chemically amplified resist compositions are considered insufficient from the standpoint of acid diffusion, and the development of non-chemically amplified resist compositions is desired.

[0005] Polymethyl methacrylate (PMMA) is an example of a material for non-chemically amplified resist compositions. PMMA is a positive-type resist material in which the main chain is cleaved by EUV irradiation, reducing its molecular weight and improving its solubility in organic solvents and developers.

[0006] Hydrogen silsesquioxane (HSQ) is a negative-type resist material that becomes insoluble in alkaline developers due to crosslinking caused by the condensation reaction of silanols induced by EUV irradiation. Chlorine-substituted calixarenes also function as negative-type resist materials. These negative-type resist materials have small molecular sizes before crosslinking and do not blur due to acid diffusion, resulting in low edge roughness and very high resolution. They are used as pattern transfer materials to demonstrate the resolution limit of exposure equipment. However, these materials have insufficient sensitivity and require further improvement.

[0007] One factor that makes material development for EUV lithography difficult is the low number of photons in EUV exposure. The energy of EUV is far higher than that of ArF excimer laser light, and the number of photons in EUV exposure is 1 / 14th of that of ArF exposure. Furthermore, the dimensions of patterns formed by EUV exposure are less than half those of ArF exposure. For this reason, EUV exposure is susceptible to variations in the number of photons. Variations in the number of photons in the ultrashort wavelength synchrotron radiation region are a physical phenomenon called shot noise, and this effect cannot be eliminated. For this reason, so-called stochastics is attracting attention. Although the effect of shot noise cannot be eliminated, how to reduce this effect is being discussed. In addition to the increase in dimensional uniformity (CDU) and line width roughness (LWR) due to the effect of shot noise, a phenomenon of hole blockage has been observed with a probability of one in several million. When holes are blocked, it results in poor electrical conductivity and the transistor does not operate, so it negatively affects the overall performance of the device. When considering practical sensitivity, resist compositions primarily composed of PMMA or HSQ are significantly affected by stochastics and have not been able to achieve the desired resolution performance.

[0008] As a method to reduce the effects of shot noise on the resist side, the introduction of elements that strongly absorb EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms that strongly absorb EUV light. However, as mentioned above, chemically amplified resist compositions cannot achieve excellent resolution performance in EUV lithography, where processing dimensions will become increasingly miniaturized in the future. In particular, in line-and-space patterns, as the pattern dimensions become smaller, pattern distortion and breaks increase significantly, so reducing these will lead to an improvement in critical resolution.

[0009] Patent Document 2 proposes a negative-type resist composition using a tin compound. Because it mainly consists of tin, which has high absorption of EUV light, its stochastics are improved, enabling high sensitivity and high resolution. However, so-called metal resists of this type have many problems, such as insufficient solubility in resist solvents, storage stability, and defects due to etching residue.

[0010] Patent Document 3 proposes a non-chemically amplified resist composition using an organic polymer and an iodine compound. While this composition exhibits excellent sensitivity and resolution due to its inclusion of iodine, which has high absorption of EUV light, it suffers from insufficient etching resistance because it is composed of organic components. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Publication No. 2018-005224 [Patent Document 2] Special Publication No. 2021-503482 [Patent Document 3] Japanese Patent Publication No. 2024-092963 [Non-patent literature]

[0012] [Non-Patent Document 1] SPIE Vol.5039 p1 (2003) [Non-Patent Document 2] SPIE Vol.6520 p65203L-1 (2007) [Overview of the project] [Problems that the invention aims to solve]

[0013] The present invention has been made in view of the above circumstances, and aims to provide a pattern formation method that forms a resist pattern using a non-chemically amplified resist composition that is excellent in sensitivity and limiting resolution, and further reverses the pattern with an organotitanium compound-containing material that has high etching resistance. [Means for solving the problem]

[0014] To solve the above problems, the present invention provides a method for forming a pattern, (i) A step of forming a resist pattern on a support using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent, (ii) A step of forming a pattern inversion film by applying a material containing an organic titanium compound and a solvent onto a support on which the resist pattern has been formed, (iii) a step of removing the resist pattern by etching and forming an inverted pattern, The present invention provides a pattern formation method that includes [specific details].

[0015] With this pattern formation method, a resist pattern can be formed using a non-chemically amplified resist composition that has excellent sensitivity and critical resolution, and the pattern can be reversed using an organotitanium compound-containing material with high etching resistance.

[0016] Furthermore, in the present invention, it is preferable to use at least one hypervalent iodine compound selected from the hypervalent iodine compounds represented by the following general formulas (1) to (10) as the hypervalent iodine compound. [ka] (In the formula, m1 is an integer between 0 and 2. When m1 is 0, n1 is an integer between 1 and 3, n2 is an integer between 0 and 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is an integer between 1 and 3, n2 is an integer between 0 and 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is an integer between 1 and 3, n2 is an integer between 0 and 9, and 1 ≤ n1 + n2 ≤ 10.) n3 is either 1 or 2, n4 is an integer between 0 and 4, and 1 ≤ n3 + n4 ≤ 5, n5 is either 1 or 2, and n6 is an integer between 0 and 4, and 1 ≤ n5 + n6 ≤ 5. n7 is an integer between 0 and 4, and n8 is an integer between 1 and 4. m2 is an integer between 0 and 2. When m2 is 0, n9 is an integer between 0 and 4; when m2 is 1, n9 is an integer between 0 and 6; and when m2 is 2, n9 is an integer between 0 and 8. m3 is an integer between 0 and 2. When m3 is 0, n10 is an integer between 0 and 4; when m3 is 1, n10 is an integer between 0 and 6; and when m3 is 2, n10 is an integer between 0 and 8. m4 is either 0 or 1. When m4 is 0, n11 is an integer between 0 and 4, and when m4 is 1, n11 is an integer between 0 and 6. m5 is either 0 or 1. When m5 is 0, n12 is an integer between 0 and 4, and when m5 is 1, n12 is an integer between 0 and 6. n13 and n14 are integers between 0 and 6. n15 and n16 are integers between 0 and 3. m6 is an integer between 0 and 2. When m6 is 0, n17 is an integer between 0 and 4; when m6 is 1, n17 is an integer between 0 and 6; and when m6 is 2, n17 is an integer between 0 and 8. m7 is an integer between 0 and 2. When m7 is 0, n18 is an integer between 0 and 3; when m7 is 1, n18 is an integer between 0 and 5; and when m7 is 2, n18 is an integer between 0 and 7. m8 is an integer from 0 to 2. When m8 is 0, n19 is an integer from 0 to 3, and n20 is 0 or 1. When m8 is 1, n19 is an integer from 0 to 5, and n20 is 0 or 1. When m8 is 2, n19 is an integer from 0 to 7, and n20 is 0 or 1. R 1 ~R 22 is each independently a hydrocarbyl group having 1 to 10 carbon atoms which may contain a halogen atom or a heteroatom. Also, R 1 and R 2 、R 3 and R 4 、R 5 and R 6 、R 7 and R 8 、R 9 and R 10 、R 11 and R 12 、R 13 and R 14 、R 15 and R 16 、R 17 and R 18 、R 19 and R 20 、or R 21 and R 22 may combine with each other to form a ring together with the carbon atoms to which they are attached and the atoms between these carbon atoms. R 31 ~R 34 、R 37 、R 39 ~R 46 、R 49 、and R 50 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31 may be the same as or different from each other, and a plurality of R 31 may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. When n4 is 2 or more, each R 32 may be the same as or different from each other, and a plurality of R 32 may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. When n6 is 2 or more, each R 33These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45 These may be the same or different from each other, and there may be multiple R 45However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. R 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. R 36 This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. R 38 This is a carbonyl group or a hydroxylene group having 1 to 10 carbon atoms, which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is unbonded, single-bonded, -O-, -S-, -NH-, or -CH2-. R 47This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. X is either a nitrogen atom or a sulfur atom, and if it is a nitrogen atom, R 48 It may have. R 48 This is a hydrocarbyl group or ester having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

[0017] In the pattern formation method of the present invention, it is preferable to use such hypervalent iodine compounds.

[0018] Furthermore, in the present invention, it is preferable to use a carboxyl group-containing polymer containing repeating units represented by the following general formula (11) or a carboxylic acid compound represented by the following general formula (12) as the carboxyl group-containing compound. [ka] (In the formula, R A This is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A This is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond with a carbon atom of the main chain. t is an integer between 1 and 4. R 29 is a t-valent hydrocarbon group having 1 to 40 carbon atoms or a t-valent heterocyclic group having 2 to 40 carbon atoms, and when t is 2, R 29This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the t-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 30 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a heteroatom. When t is 2 to 4, each R 30 They may be the same or different from each other.

[0019] In the pattern formation method of the present invention, it is preferable to use such a carboxyl group-containing compound.

[0020] Furthermore, in the present invention, it is preferable to form a resist underlayer film between the support and the resist film.

[0021] In the pattern formation method of the present invention, a resist underlayer film can also be formed between the support and the resist film.

[0022] Furthermore, in the present invention, it is preferable to use an organotitanium compound represented by the following general formula (13). [ka] (In the formula, R 51 , R 52 , R 53 , and R 54 These are monovalent organic groups having 1 to 30 carbon atoms, which may be the same or different. 51 and R 52 These elements may be joined to each other to form a ring structure. (n is a real number greater than or equal to 1.)

[0023] In the pattern formation method of the present invention, it is preferable to use such an organotitanium compound. [Effects of the Invention]

[0024] As described above, the pattern formation method of the present invention forms a resist pattern using a non-chemically amplified resist composition that is excellent in sensitivity and critical resolution, and is particularly useful for forming fine patterns in electron beam and EUV lithography, as it achieves both high resolution and etching resistance. [Brief explanation of the drawing]

[0025] [Figure 1] This figure illustrates an example of the pattern formation method of the present invention. [Modes for carrying out the invention]

[0026] As described above, there was a need to develop a pattern formation method that involves forming a resist pattern using a non-chemically amplified resist composition with excellent sensitivity and critical resolution, and then reversing the pattern with an organotitanium compound-containing material that has high etching resistance.

[0027] As a result of diligent research to achieve the above objective, the present inventors have discovered that by forming a pattern using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent, then applying a material containing an organotitanium compound and a solvent, and finally forming an inverted pattern by an etching process, it is possible to form a pattern with excellent etching resistance, which is extremely effective for precise microfabrication, leading to the present invention.

[0028] In other words, the present invention is a method for forming a pattern, (i) A step of forming a resist pattern on a support using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent, (ii) A step of forming a pattern inversion film by applying a material containing an organic titanium compound and a solvent onto a support on which the resist pattern has been formed, (iii) a step of removing the resist pattern by etching and forming an inverted pattern, This is a pattern formation method that includes [something].

[0029] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0030] [Resist composition] The resist composition used in the pattern formation method of the present invention comprises a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent.

[0031] [Hypervalent iodine compounds] It is preferable to use at least one hypervalent iodine compound selected from the hypervalent iodine compounds represented by the following general formulas (1) to (10) as the above-mentioned hypervalent iodine compound. [ka] (In the formula, m1 is an integer between 0 and 2. When m1 is 0, n1 is an integer between 1 and 3, n2 is an integer between 0 and 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is an integer between 1 and 3, n2 is an integer between 0 and 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is an integer between 1 and 3, n2 is an integer between 0 and 9, and 1 ≤ n1 + n2 ≤ 10.) n3 is either 1 or 2, n4 is an integer between 0 and 4, and 1 ≤ n3 + n4 ≤ 5, n5 is either 1 or 2, and n6 is an integer between 0 and 4, and 1 ≤ n5 + n6 ≤ 5. n7 is an integer between 0 and 4, and n8 is an integer between 1 and 4. m2 is an integer between 0 and 2. When m2 is 0, n9 is an integer between 0 and 4; when m2 is 1, n9 is an integer between 0 and 6; and when m2 is 2, n9 is an integer between 0 and 8. m3 is an integer from 0 to 2. When m3 is 0, n10 is an integer from 0 to 4; when m3 is 1, n10 is an integer from 0 to 6; when m3 is 2, n10 is an integer from 0 to 8. m4 is 0 or 1. When m4 is 0, n11 is an integer from 0 to 4; when m4 is 1, n11 is an integer from 0 to 6. m5 is 0 or 1. When m5 is 0, n12 is an integer from 0 to 4; when m5 is 1, n12 is an integer from 0 to 6. n13 and n14 are integers from 0 to 6. n15 and n16 are integers from 0 to 3. m6 is an integer from 0 to 2. When m6 is 0, n17 is an integer from 0 to 4; when m6 is 1, n17 is an integer from 0 to 6; when m6 is 2, n17 is an integer from 0 to 8. m7 is an integer from 0 to 2. When m7 is 0, n18 is an integer from 0 to 3; when m7 is 1, n18 is an integer from 0 to 5; when m7 is 2, n18 is an integer from 0 to 7. m8 is an integer from 0 to 2. When m8 is 0, n19 is an integer from 0 to 3, n20 is 0 or 1; when m8 is 1, n19 is an integer from 0 to 5, n20 is 0 or 1; when m8 is 2, n19 is an integer from 0 to 7, n20 is 0 or 1. R 1 ~R 22 are each independently a hydrocarbyl group having 1 to 10 carbon atoms which may contain a halogen atom or a heteroatom. Also, R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , R 19 and R20 , or R 21 and R 22 These atoms may bond with each other to form a ring together with the carbon atoms to which they bond and the atoms between the carbon atoms. R 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , and R 50 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31 These may be the same or different from each other, and there may be multiple R 31 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 32 These may be the same or different from each other, and there may be multiple R 32 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45 These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. R 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. R 36 This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. R 38 This is a carbonyl group or a hydroxylene group having 1 to 10 carbon atoms, which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is unbonded, single-bonded, -O-, -S-, -NH-, or -CH2-. R 47 This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. X is either a nitrogen atom or a sulfur atom, and if it is a nitrogen atom, R 48 It may have. R 48 This is a hydrocarbyl group or ester having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

[0032] In the general formula (1) above, m1 is an integer between 0 and 2. When m1 is 0, n1 is an integer between 1 and 3, n2 is an integer between 0 and 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is an integer between 1 and 3, n2 is an integer between 0 and 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is an integer between 1 and 3, n2 is an integer between 0 and 9, and 1 ≤ n1 + n2 ≤ 10.

[0033] In the general formula (2) above, n3 is 1 or 2, n4 is an integer from 0 to 4, and 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2, n6 is an integer from 0 to 4, and 1 ≤ n5 + n6 ≤ 5.

[0034] In the general formula (3) above, n7 is an integer between 0 and 4, and n8 is an integer between 1 and 4.

[0035] In the general formula (4) above, m2 is an integer between 0 and 2. When m2 is 0, n9 is an integer between 0 and 4; when m2 is 1, n9 is an integer between 0 and 6; and when m2 is 2, n9 is an integer between 0 and 8.

[0036] In the general formula (5) above, m3 is an integer between 0 and 2. When m3 is 0, n10 is an integer between 0 and 4; when m3 is 1, n10 is an integer between 0 and 6; and when m3 is 2, n10 is an integer between 0 and 8.

[0037] In the general formula (6) above, m4 is either 0 or 1. When m4 is 0, n11 is an integer between 0 and 4, and when m4 is 1, n11 is an integer between 0 and 6. m5 is either 0 or 1. When m5 is 0, n12 is an integer between 0 and 4, and when m5 is 1, n12 is an integer between 0 and 6.

[0038] In the general formula (7) above, n13 and n14 are integers between 0 and 6.

[0039] In the general formula (8) above, n15 and n16 are integers between 0 and 3.

[0040] In the general formula (9) above, m6 is an integer between 0 and 2. When m6 is 0, n17 is an integer between 0 and 4; when m6 is 1, n17 is an integer between 0 and 6; and when m6 is 2, n17 is an integer between 0 and 8.

[0041] In the above general formula (10), m7 is an integer between 0 and 2. When m7 is 0, n18 is an integer between 0 and 3; when m7 is 1, n18 is an integer between 0 and 5; and when m7 is 2, n18 is an integer between 0 and 7. m8 is an integer between 0 and 2. When m8 is 0, n19 is an integer between 0 and 3, and n20 is 0 or 1; when m8 is 1, n19 is an integer between 0 and 5, and n20 is 0 or 1; and when m8 is 2, n19 is an integer between 0 and 7, and n20 is 0 or 1.

[0042] In the above general formulas (1) to (3), (5) to (8), and (10), R 1 ~R 22 Each of these is independently a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , R 19 and R 20 , or R 21 and R 22 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms.

[0043] R 1 ~R 22 Examples of halogen atoms represented by R include fluorine, chlorine, bromine, and iodine atoms. 1 ~R 22The C1-C10 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms, such as decyl groups and adamantyl groups; alkenyl groups having 2 to 10 carbon atoms, such as vinyl groups and allyl groups; aryl groups having 6 to 10 carbon atoms, such as phenyl groups and naphthyl groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- groups of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, the group may contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), etc. 1 ~R 22 A hydrocarbyl group having 1 to 4 carbon atoms is preferred.

[0044] In the above general formulas (1) to (10), R 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , and R 50 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31These may be the same or different from each other, and there may be multiple R 31 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 32 These may be the same or different from each other, and there may be multiple R 32 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45 These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded.

[0045] R 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , and R 50 Examples of halogen atoms represented by R include fluorine, chlorine, bromine, and iodine atoms. 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , and R 50The C1-C40 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C40 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as decyl groups, adamantyl groups, and adamantylmethyl groups; and aryl groups having 6 to 40 carbon atoms, such as phenyl groups, naphthyl groups, and anthracenyl groups. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- groups of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, which may result in the presence of hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), etc.

[0046] In the above general formula (3), R 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms.

[0047] R 35 The (n8)-valent hydrocarbon group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. The (n8)-valent hydrocarbon group is obtained by removing (n8) hydrogen atoms from a hydrocarbon. Examples of the hydrocarbons include alkanes with 1 to 40 carbon atoms, alkenes with 2 to 40 carbon atoms, alkynes with 2 to 40 carbon atoms, cyclic saturated hydrocarbons with 3 to 40 carbon atoms, cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms, and aromatic hydrocarbons with 6 to 40 carbon atoms.

[0048] Specific examples of the aforementioned alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0049] Specific examples of alkenes having 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0050] Specific examples of alkynes having 2 to 40 carbon atoms include acetylene, propyne, butyne, pentine, hexine, heptine, octin, nonine, decine, and their structural isomers.

[0051] Specific examples of the cyclic saturated hydrocarbons having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, and the like.

[0052] Specific examples of the cyclic unsaturated hydrocarbons having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0053] Specific examples of aromatic hydrocarbons having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0054] R 35 The (n8)-valent heterocyclic group represented by is a group obtained by the elimination of (n8) hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and thiazolidine.

[0055] R 35 The (n8)-valent hydrocarbon group or (n8)-valent heterocyclic group represented by may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and as a result may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the (n8)-valent hydrocarbon group may have some of its constituent -CH2- substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0056] In the above general formula (4), R 36 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 36 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by the same symbols as those exemplified are also included.

[0057] In the above general formula (4), R 38This is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. The C1-C10 hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkylene groups with 1 to 10 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-2,3-diyl group, butane-1,4-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, etc.; cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, adamantanediyl group, tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbylene groups having 3 to 10 carbon atoms, such as decanediyl groups; alkenylene groups having 2 to 10 carbon atoms, such as vinylene groups and propynylene groups; arylene groups having 6 to 10 carbon atoms, such as phenylene groups, methylphenylene groups, ethylphenylene groups, n-propylphenylene groups, isopropylphenylene groups, n-butylphenylene groups, and naphthylene groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, it may contain a hydroxyl group, a cyano group, an alkyl halide, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc. 38 Preferred members include carbonyl groups, C1-C4 hydrocarbylene groups, or C1-C4 fluorinated hydrocarbylene groups.

[0058] In the general formula (4) above, *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. There are seven possible combinations of *1, *2, and m2, as shown below. [ka] (In the formula, n9, R 37 , and R 38 This is the same as above. The dashed line is R 36 (This represents a bond between -C(=O)-O-.)

[0059] In the general formula (6) above, L1 is bondless, single bonded, -O-, -S-, -NH-, or -CH2-.

[0060] In the above general formula (9), R 47 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 47 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by the same symbols as those exemplified are also included.

[0061] In the above general formula (9), X is a nitrogen atom or a sulfur atom, and in the case of a nitrogen atom, R 48 It may have R 48 R is a hydrocarbyl group having 1 to 20 carbon atoms, or an ester, which may contain a hydrogen atom, a halogen atom, or a heteroatom. 48 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by R are similar to those exemplified. 48 A specific example of an ester represented by R is, 1 ~R 22 Among the examples of hydrocarbyl groups represented by , those having an ester bond are similar to those mentioned above.

[0062] Specific examples of hypervalent iodine compounds represented by the above general formula (1) are listed below, but are not limited to these.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] Specific examples of hypervalent iodine compounds represented by the general formula (2) above include, but are not limited to, those listed below.

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] Specific examples of hypervalent iodine compounds represented by the above general formula (3) are listed below, but are not limited to these.

[0081] [ka]

[0082] [ka]

[0083]

Chem.

[0084]

Chem.

[0085]

Chem.

[0086]

Chem.

[0087] Specific examples of the hypervalent iodine compound represented by the above general formula (4) include, but are not limited to, those shown below. In the following formulas, Me represents a methyl group.

[0088]

Chem.

[0089]

Chem.

[0090]

Chem.

[0091]

Chem.

[0092]

Chem.

[0093]

Chem.

[0094]

change

[0095]

change

[0096]

change

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

change

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] Specific examples of hypervalent iodine compounds represented by the general formula (5) above include, but are not limited to, those listed below.

[0145] [ka]

[0146] [ka]

[0147]

change

[0148]

change

[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

change

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] Specific examples of hypervalent iodine compounds represented by the general formula (6) above include, but are not limited to, those listed below. In the following formulas, L1 is the same as described above.

[0162] [ka]

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168]

change

[0169]

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[0170]

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[0171]

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[0172]

change

[0173]

change

[0174]

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[0175]

change

[0176]

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[0177]

change

[0178] Specific examples of hypervalent iodine compounds represented by the general formula (7) above include, but are not limited to, those listed below.

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] Specific examples of hypervalent iodine compounds represented by the above general formula (8) are listed below, but are not limited to these.

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] Specific examples of hypervalent iodine compounds represented by the general formula (9) above include, but are not limited to, those listed below. In the following formulas, Me represents a methyl group.

[0197] [ka]

[0198] [ka]

[0199]

change

[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

change

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] Specific examples of hypervalent iodine compounds represented by the above general formula (10) are listed below, but are not limited to these.

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] [ka]

[0221]

change

[0222]

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[0223]

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[0224]

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[0225]

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[0226]

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[0227]

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[0228]

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[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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[0250]

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[0251]

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[0252]

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[0253]

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[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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[0260]

change

[0261]

change

[0262]

change

[0263] [ka]

[0264] [ka]

[0265] [ka]

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [Carboxylate-containing compounds] It is preferable to use a carboxyl group-containing polymer containing repeating units represented by the following general formula (11) or a carboxylic acid compound represented by the following general formula (12) as the carboxyl group-containing compound. [ka] (In the formula, R A This is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A This is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond with a carbon atom of the main chain. t is an integer between 1 and 4. R 29 is a t-valent hydrocarbon group having 1 to 40 carbon atoms or a t-valent heterocyclic group having 2 to 40 carbon atoms, and when t is 2, R 29 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the t-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 30 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a heteroatom. When t is 2 to 4, each R 30 They may be the same or different from each other.

[0270] In the above general formula (11), R A X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A This is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond with a carbon atom of the main chain.

[0271] In the general formula (12) above, t is an integer between 1 and 4.

[0272] In the above general formula (12), R 29is a t-valent hydrocarbon group having 1 to 40 carbon atoms or a t-valent heterocyclic group having 2 to 40 carbon atoms, and when t is 2, R 29 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the t-valent hydrocarbon group may be substituted with a group containing a heteroatom.

[0273] In the above general formula (12), R 30 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a heteroatom. When t is 2 to 4, each R 30 They may be the same as or different from each other.

[0274] R 29 The t-valent hydrocarbon group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. The t-valent hydrocarbon group is a group obtained by removing t hydrogen atoms from a hydrocarbon. Examples of the hydrocarbon include alkanes having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms, alkynes having 2 to 40 carbon atoms, cyclic saturated hydrocarbons having 3 to 40 carbon atoms, cyclic unsaturated hydrocarbons having 3 to 40 carbon atoms, and aromatic hydrocarbons having 6 to 40 carbon atoms.

[0275] Examples of alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0276] Examples of alkenes having 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0277] Examples of alkynes having 2 to 40 carbon atoms include acetylene, propyne, butyn, pentyn, hexyn, heptyn, octin, nonine, decine, and their structural isomers.

[0278] Examples of the cyclic saturated hydrocarbons having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, and the like.

[0279] Examples of cyclic unsaturated hydrocarbons having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0280] Examples of aromatic hydrocarbons having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0281] R 29 The t-valent heterocyclic group represented by is a group obtained by the elimination of t hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and thiazolidine.

[0282] The t-valent hydrocarbon group or t-valent heterocyclic group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and as a result may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the t-valent hydrocarbon group may have some of its constituent -CH2- substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0283] R 30The hydrocarbylene group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,1 Examples include alkanediyl groups with 1 to 20 carbon atoms, such as 2-diyl groups; cyclic saturated hydrocarbylene groups with 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl groups; unsaturated aliphatic hydrocarbylene groups with 2 to 20 carbon atoms, such as vinylene and propene-1,3-diyl groups; arylene groups with 6 to 20 carbon atoms, such as phenylene and naphthylene groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- groups constituting the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, and as a result, the material may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, and the like.

[0284] Of the carboxylic acid compounds represented by the above general formula (12), those in which t is 2, 3, or 4 are preferred. In this case, when mixed with a hypervalent iodine compound, it is easier to form a high molecular weight, robust resist film, which is preferred from the viewpoint of etching resistance and developer resistance.

[0285] Specific examples of carboxyl group-containing polymers containing the repeating unit represented by the general formula (11) above are, but are not limited to, those listed below. In the following formulas, R A This is the same as described above.

[0286] [ka]

[0287] [ka]

[0288] Examples of carboxylic acid compounds represented by the above general formula (12) include, but are not limited to, those listed below.

[0289] [ka]

[0290] [ka]

[0291] [ka]

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] A carboxyl group-containing polymer containing the repeating unit represented by the above general formula (11) may further contain repeating units other than the repeating unit represented by the above general formula (11) (hereinafter also referred to as other repeating units). The other repeating units are not particularly limited, but those that can improve the solubility in solvents of polymers that are poorly soluble with only the repeating unit represented by the above general formula (11) are preferred. The other repeating units are preferably repeating units having a rigid skeleton and a cyclic structure that is expected to have high etching resistance, or repeating units containing a styrene skeleton.

[0296] Specific examples of the aforementioned other repeating units include, but are not limited to, those listed below. Note that in the following formula, R A This is the same as above, and X B These are, independently, -CH2- or -O-.

[0297] [ka]

[0298] [ka]

[0299] [ka]

[0300] [ka]

[0301] [ka]

[0302] [ka]

[0303]

change

[0304]

change

[0305]

change

[0306]

change

[0307]

change

[0308]

change

[0309]

change

[0310]

change

[0311]

change

[0312]

change

[0313]

change

[0314]

change

[0315]

change

[0316]

change

[0317]

change

[0318]

change

[0319]

change

[0320]

change

[0321]

change

[0322]

change

[0323]

change

[0324] [ka]

[0325] [ka]

[0326] [ka]

[0327] In the resist composition, the content ratio of the hypervalent iodine compound to the carboxyl group-containing compound (if the carboxyl group-containing compound is a carboxyl group-containing polymer, the content ratio of the hypervalent iodine compound to the carboxyl group-containing repeating units in the polymer) is preferably, in molar ratio, hypervalent iodine compound:carboxyl group-containing compound = 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The hypervalent iodine compound may be used alone, or two or more compounds with different composition ratios, Mw, and / or Mw / Mn may be used in combination. The carboxyl group-containing compound may be used alone, or two or more compounds with different composition ratios, Mw, and / or Mw / Mn may be used in combination.

[0328] In the carboxyl group-containing polymer, the content ratio (molar ratio) of carboxyl group-containing repeating units and other repeating units is preferably carboxyl group-containing repeating units:other repeating units = 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0329] The weight-average molecular weight (Mw) of the carboxyl group-containing polymer is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. In this invention, Mw is a polystyrene-converted value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0330] Furthermore, if the molecular weight distribution (Mw / Mn) of the carboxyl group-containing polymer is broad, there may be polymers with lower molecular weights or higher molecular weights compared to Mw, which may result in the appearance of foreign matter on the pattern or deterioration of the pattern shape after exposure. Therefore, as the pattern rule becomes finer, the influence of Mw and Mw / Mn tends to increase. To obtain a resist composition suitable for fine pattern dimensions, it is preferable that the Mw / Mn of the carboxyl group-containing polymer be narrowly dispersed, between 1.0 and 2.0.

[0331] One method for synthesizing the carboxyl group-containing polymer is to heat a monomer that provides the repeating units mentioned above in an organic solvent with a radical polymerization initiator added, and polymerize it.

[0332] Specific examples of organic solvents used in polymerization reactions include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Specific examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of radical polymerization initiator added is preferably 0.01 to 25 mol% of the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0333] The radical polymerization initiator may be added to the solution containing the monomer and supplied to the reaction vessel, or an initiator solution may be prepared separately from the monomer solution and supplied to the reaction vessel independently. Since the polymerization reaction may proceed and a superpolymer may be formed by radicals generated from the radical polymerization initiator during the waiting time, it is preferable from the viewpoint of quality control to prepare the monomer solution and the initiator solution independently and add them dropwise. In addition, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of the chain transfer agent added is preferably 0.01 to 20 mol% of the total amount of monomers to be polymerized.

[0334] The amount of each monomer in the monomer solution can be appropriately set, for example, to achieve a preferred content ratio of the repeating units described above.

[0335] [solvent] The resist composition contains a solvent. The solvent is not particularly limited as long as it can dissolve the hypervalent iodine compound, the carboxyl group-containing compound, and other components described later, and form a film. Such solvents are preferably organic solvents, and specific examples include ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isoamyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, 4-methyl-2-pentanol, and methyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, Examples include ethers such as propylene glycol dimethyl ether and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and mixed solvents thereof.

[0336] In the resist composition, the amount of solvent is preferably such that the solid content concentration in the resist composition is 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.1 to 10% by mass. In this invention, "solid content" refers to all components of the resist composition other than the solvent. The solvent may be used alone or as a mixture of two or more.

[0337] The resist composition may further contain a surfactant. A fluorine-based and / or silicone-based surfactant is preferred. Examples of such surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication 2008 / 0248425. Furthermore, surfactants other than the fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of U.S. Patent Application Publication 2008 / 0248425 may also be used.

[0338] If the resist composition contains the surfactant, its content is preferably 0.0001 to 2% by mass of the total solids. The surfactant may be used alone or in combination of two or more types.

[0339] The resist composition may further contain a radical scavenger. By adding a radical scavenger, the photoreaction during photolithography can be controlled and the sensitivity adjusted.

[0340] Examples of the radical scavengers include hindered phenols, quinones, hindered amines, and thiol compounds. Specifically, examples of hindered phenols include dibutylhydroxytoluene (BHT) and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of quinones include 4-methoxyphenol (methoquinone) and hydroquinone. Examples of hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Examples of thiol compounds include dodecanethiol and hexadecanethiol.

[0341] If the resist composition contains the radical scavenger, its content is preferably 0.01 to 10% by mass of the total solids. The radical scavenger may be used alone or in combination of two or more types.

[0342] The resist composition may further contain a crosslinking agent. Adding a crosslinking agent promotes the crosslinking reaction during photolithography, improving the glass transition temperature of the pattern and resulting in a pattern with excellent resolution at fine lines.

[0343] Examples of crosslinking agents include compounds having carbon-carbon unsaturated bonds as functional groups, such as vinyl groups, (meth)acrylate groups, allyl groups, alkynyl groups, and aromatic rings. Specifically, examples of compounds having vinyl groups include linear alkenes, branched alkenes, and cyclic alkenes, which may have substituents. Examples of compounds having (meth)acrylate groups include acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, which may have substituents. Examples of compounds having allyl groups include allyl alcohol, allyl ether, allyl ester, allyl amide, allylamine, and allyl group-containing isocyanurates, which may have substituents. Examples of compounds having alkynyl groups include linear alkynes, branched alkynes, cyclic alkynes, alkynyl alcohol, alkynyl ether, alkynyl ester, alkynyl amide, alkynylamine, and alkynyl group-containing isocyanurates, which may have substituents. Compounds having an aromatic ring include arenes, heteroarenes, styrene, stilbene, phenylacetylene, acenaphthylene, and chalcone, which may have substituents. The crosslinking agent may have only one of the above functional groups or may have multiple of them. The number of above functional groups contained in the crosslinking agent is preferably 1 to 10, and more preferably 2 to 8.

[0344] If the resist composition contains the crosslinking agent, its content is preferably 0.01 to 50% by mass of the total solids. The crosslinking agent may be used alone or in combination of two or more types.

[0345] If the resist composition contains the crosslinking agent, it may further contain a photopolymerization initiator. The photopolymerization initiator can generate radicals by irradiation with high-energy rays, thereby promoting the crosslinking of the crosslinking agent.

[0346] Specific examples of the aforementioned photopolymerization initiators include benzophenone, benzophenone derivatives such as methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morphol Acetophenone derivatives such as nopropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one, and methyl phenylglyoxylate; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl, benzyldimethylketal, benzyl Benzyl derivatives such as benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1, Oxime compounds such as 2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime);α-hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl) Examples include α-aminoalkylphenone compounds such as butan-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0347] If the resist composition contains the photopolymerization initiator, its content is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 1% by mass, based on the total solid content. A content of 0.1% by mass or more is sufficient to obtain the desired blending effect.

[0348] As described above, the resist composition mainly contains hypervalent iodine compounds and carboxyl group-containing compounds, but it does not necessarily contain acid-unstable group-containing polymers or photoacid generators, as is common in conventional chemically amplified resist compositions. However, the resist composition used in the present invention can form a positive-type pattern in which the exposed areas are soluble in the developer, or a negative-type pattern in which the exposed areas are insoluble in the developer, particularly by EB or EUV exposure. The mechanism is not fully clear, but it can be inferred, for example, as follows.

[0349] Hypervalent iodine compounds are, for example, three-coordinate compounds having an aryl group and a carboxylate ligand. It is believed that when such three-coordinate iodine compounds are mixed with a carboxylate-containing compound, an equilibrium reaction occurs in which the carboxylate ligand is exchanged. If the original carboxylate ligand can be removed by some means, a hypervalent iodine compound with a new ligand is produced. For example, by mixing 1-iodonaphthylenediacetate as a hypervalent iodine compound with a carboxylate-containing compound and removing the resulting low-boiling point acetic acid, the ligand exchange is completed. Here, the carboxylate-containing compound becomes a polymer crosslinked by the hypervalent iodine compound.

[0350] Polymers crosslinked with hypervalent iodine compounds are formed during film formation. This is because even if such crosslinked polymers are synthesized beforehand, they are insoluble in most organic solvents, making it impossible to prepare a solution. This is presumed to be because hypervalent iodine compounds, which inherently have low solvent solubility due to their high polarization, become even less soluble when carboxyl group-containing compounds are used as ligands. Therefore, it is desirable to remove the original low-molecular-weight carboxylic acid component during film formation and the subsequent baking process to complete the ligand exchange reaction and form a resist film.

[0351] The resist film obtained from the resist composition used in this invention undergoes a change in polarity when its main component, a hypervalent iodine compound, is decomposed by light, and a pattern is formed during the development process. Although the mechanism is not fully understood, it can be speculated as follows.

[0352] The resist composition used in this invention can be either positive or negative depending on the selection of its components. In the case of the positive type, it contains a polymer to which a hypervalent iodine compound is bonded during film formation. When this is decomposed by light, it becomes a monovalent iodine compound, and at the same time, the bond between the carboxyl group-containing compound and the hypervalent iodine compound is released, and the molecular weight decreases. As a result, it is presumed that a positive type pattern is formed in which the exposed areas are removed by an organic solvent.

[0353] On the other hand, in the case of the negative type, the polymer contains a hypervalent iodine compound crosslinked with a hypervalent iodine compound generated during film formation. When this is decomposed by light, crosslinking or re-bonding occurs, leading to an increase in molecular weight and a change in polarity. As a result, it is presumed that a negative type pattern is formed in which the unexposed areas are removed by an alkaline aqueous solution.

[0354] From the above inference, it can be said that the resist composition is a non-chemically amplified resist composition. The resist composition does not require acid-unstable group-containing polymers or photoacid generators like conventional chemically amplified resist compositions. Therefore, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0355] The resist composition described above is particularly effective in EUV lithography. This is due to the presence of iodine atoms with high absorption capacity for EUV light. That is, shot noise is reduced, and higher resolution and lower LWR can be achieved.

[0356] As an EUV resist composition capable of forming fine patterns, metal resists mainly composed of metallic tin compounds, which have high absorption capacity for EUV light similar to iodine atoms, have been reported (for example, Patent Document 2). However, as mentioned above, such metal resists have many problems, including insufficient solubility in solvents, storage stability, and the need for infrastructure development associated with handling novel metallic elements in lithography processes. On the other hand, the resist composition used in the present invention can be applied to conventional lithography processes and track tools as is, and there are no problems with solubility in solvents.

[0357] The resist film preferably has a thickness of 10 to 70 nm, and more preferably 20 to 50 nm.

[0358] The resist composition may also contain a photoacid generator. The presence of a photoacid generator in the resist composition used in this invention allows for the formation of positive patterns with higher sensitivity compared to a resist composition without a photoacid generator. While the mechanism is not entirely clear, it can be inferred, for example, as follows.

[0359] In the resist composition used in the present invention, the addition of a photoacid generator causes the acid generated by the photoacid generator during the resist exposure process to exchange with the ligand of the hypervalent iodine compound, becoming a new ligand and thereby releasing the bond between the carboxyl group-containing compound and the hypervalent iodine compound. Therefore, in addition to the cleavage of the IO bond by light, a change in polarity or a decrease in molecular weight (if the carboxyl group-containing compound is a polymer) occurs due to the exchange of new ligands by the acid generated by the photoacid generator, and it is presumed that a positive pattern can be formed with high sensitivity by organic solvent development.

[0360] Based on the above inference, the resist composition used in the present invention is a non-chemically amplified resist composition that may contain a photoacid generator and does not require an acid-unstable group-containing polymer like conventional chemically amplified resist compositions. Therefore, the acid generated from the photoacid generator reacts with the ligand of the hypervalent iodine compound in the exposed area to form a new hypervalent iodine ligand. In other words, since it does not have an amplification mechanism that regenerates acid by reacting with acid-unstable groups like chemically amplified resist compositions, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0361] Specific examples of the aforementioned photoacid generator include the following onium salt compounds.

[0362] [Onium salt compounds] The onium salt compound contains, as a cation, a sulfonium cation represented by the following general formula (5-1) or an iodonium cation represented by the following general formula (5-2). [ka]

[0363] In the above general formulas (5-1) and (5-2), R 61 ~R 65 Each of these is independently a hydrocarbyl group having 1 to 30 carbon atoms, which may contain a halogen atom or a heteroatom.

[0364] R 61 ~R 65 Specific examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms.

[0365] R 61 ~R 65The hydrocarbyl group, represented by , having 1 to 30 carbon atoms, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include C1-C30 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups; C3-C30 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; C2-C30 alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl groups; C3-C30 cyclic unsaturated hydrocarbyl groups such as cyclohexenyl groups; C6-C30 aryl groups such as phenyl, naphthyl, and thienyl groups; C7-C30 aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl groups; and groups obtained by combining these, but aryl groups are preferred. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0366] Also, R 61 and R 62 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, specific examples of the structure of the ring include those represented by the following formula. [ka] (In the formula, the dashed line represents R 63 (This is a combination of the two.)

[0367] Specific examples of sulfonium cations represented by the general formula (5-1) above include, but are not limited to, those listed below.

[0368] [ka]

[0369] [ka]

[0370] [ka]

[0371] [ka]

[0372] [ka]

[0373] [ka]

[0374] [ka]

[0375] [ka]

[0376] [ka]

[0377] [ka]

[0378]

change

[0379]

change

[0380]

change

[0381]

change

[0382]

change

[0383]

change

[0384]

change

[0385]

change

[0386]

change

[0387]

change

[0388]

change

[0389] [ka]

[0390] [ka]

[0391] [ka]

[0392] [ka]

[0393] [ka]

[0394] [ka]

[0395] Specific examples of iodonium cations represented by the general formula (5-2) above include, but are not limited to, those listed below.

[0396] [ka]

[0397] [ka]

[0398] The onium salt compound includes, as anions, halide ions, nitrate ions, bisulfate ions, bicarbonate ions, tetraphenylborate ions, and any of the following general formulas (5-3) to (5-9). [ka]

[0399] In the above general formulas (5-3) and (5-5), k1 and k2 are each independent integers between 1 and 4. Rf 1 and Rf 2 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorine-containing alkyl group having 1 to 6 carbon atoms, but all Rf 1 and Rf 2 They cannot simultaneously become hydrogen atoms.

[0400] In the above general formula (5-3), R 71 This is a hydrocarbyl group having 1 to 50 carbon atoms, which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom.

[0401] In the above general formula (5-4), R 72 This refers to a C1-C50 hydrocarbyl group which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom. However, this excludes cases where the hydrogen atoms on the α and β carbon atoms of the sulfo group are substituted with a fluorine atom or a fluoroalkyl group.

[0402] In the above general formula (5-5), R 81 This is a hydrocarbyl group having 1 to 50 carbon atoms, which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom.

[0403] In the above general formulas (5-6), R 82 This refers to a C1-C50 hydrocarbyl group which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom. However, this excludes cases where the hydrogen atoms on the α and β carbon atoms of the carboxyl group are substituted with a fluorine atom or a fluoroalkyl group.

[0404] In the above general formulas (5-7), R 91 and R 92 Each of these is independently a hydrocarbyl group having 1 to 50 carbon atoms, which may contain heteroatoms.

[0405] In the above general formulas (5-8), R 101 ~R 103 Each of these is independently a hydrocarbyl group having 1 to 50 carbon atoms, which may contain heteroatoms.

[0406] In the above general formulas (5-9), R 111 This is a fluorine atom or a fluorinated hydrocarbyl group having 1 to 10 carbon atoms, and the fluorinated hydrocarbyl group may contain a hydroxyl group, an ether bond, or an ester bond. 112 R is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the hydrocarbyl group may contain a hydroxyl group, an ether bond, or an ester bond. 111 and R 112 However, they may bond with each other to form a ring with the atom they bond to.

[0407] The anions of the onium salt compound are preferably halide ions, nitrate ions, and anions represented by any of the above general formulas (5-3) to (5-9), and more preferably halide ions, nitrate ions, or anions represented by the above general formulas (5-4), (5-6), or (5-8).

[0408] R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 , and R 103The C1-C50 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C50 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 50 carbon atoms, such as decyl groups, adamantyl groups, and adamantylmethyl groups; alkenyl groups having 2 to 50 carbon atoms, such as vinyl groups, 1-propenyl groups, 2-propenyl groups, butenyl groups, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 50 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 50 carbon atoms, such as phenyl groups, naphthyl groups, and anthracenyl groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- constituting the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0409] R 111 A fluorinated hydrocarbyl group having 1 to 10 carbon atoms, represented by R, is a group in which some or all of the hydrogen atoms of a hydrocarbyl group having 1 to 10 carbon atoms are replaced with fluorine atoms. The hydrocarbyl group having 1 to 10 carbon atoms may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R 71 , R 72 , R 81 , R82 , R 91 , R 92 , R 101 , R 102 , and R 103 Among the examples of hydrocarbyl groups with 1 to 50 carbon atoms represented by , those with 1 to 10 carbon atoms are cited.

[0410] R 112 The hydrocarbyl group, represented by , having 1 to 20 carbon atoms, can be saturated or unsaturated, and can be linear, branched, or cyclic. A specific example is R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 , and R 103 Among the examples of hydrocarbyl groups with 1 to 50 carbon atoms represented by , those with 1 to 20 carbon atoms are particularly noteworthy.

[0411] Anions represented by any of the above general formulas (5-3) to (5-9) may contain polymerizable functional groups in their structure and may have a hydrocarbyl group having 2 to 50 carbon atoms, which may also contain heteroatoms. Specific examples include, but are not limited to, those listed below (A-1 to A-57).

[0412] [ka]

[0413] [ka]

[0414] [ka]

[0415] [ka]

[0416] Specific examples of anions represented by the general formula (5-3) above include, but are not limited to, those listed below. In the formula below, Ac is an acetyl group, and Rf 1 This is the same as above.

[0417] [ka]

[0418] [ka]

[0419] [ka]

[0420] [ka]

[0421] [ka]

[0422] [ka]

[0423] [ka]

[0424] [ka]

[0425] [ka]

[0426] [ka]

[0427] [ka]

[0428] [ka]

[0429] [ka]

[0430] Specific examples of anions represented by the general formula (5-4) above include, but are not limited to, those listed below.

[0431] [ka]

[0432] [ka]

[0433] [ka]

[0434] [ka]

[0435] [ka]

[0436] [ka]

[0437] Specific examples of anions represented by the above general formula (5-5) are listed below, but are not limited to these.

[0438] [ka]

[0439] [ka]

[0440] Specific examples of anions represented by the above general formula (5-6) are listed below, but are not limited to these.

[0441] [ka]

[0442] [ka]

[0443] [ka]

[0444] [ka]

[0445] Specific examples of anions represented by the above general formula (5-7) are listed below, but are not limited to these.

[0446] [ka]

[0447] [ka]

[0448] Specific examples of anions represented by the above general formula (5-8) are listed below, but are not limited to these.

[0449] [ka]

[0450] [ka]

[0451] [ka]

[0452] Specific examples of anions represented by the above general formula (5-9) are listed below, but are not limited to these.

[0453] [ka]

[0454] [ka]

[0455] Specific examples of onium salts include any combination of anion and cation as mentioned above.

[0456] The photoacid generator may be used alone or in combination of two or more types. When using two or more photoacid generators in combination, it is preferable to use photoacid generators with different acidity levels of the generated acid. The photoacid generator with lower acidity quenches the acid generated in the resist-exposed area, preventing it from diffusing into the unexposed area, thereby suppressing diffusion and enabling the formation of a high-resolution pattern.

[0457] In the resist composition used in the present invention, the molar ratio of hypervalent iodine compound to photoacid generator is preferably hypervalent iodine compound:photoacid generator = 1:1000 to 1000:1, and more preferably 1:500 to 500:1.

[0458] When the onium salt has a large molecular weight and bulky substituents introduced, it has a large excluded volume and highly suppresses the diffusion of generated acids, making it suitable for forming fine patterns.

[0459] When the onium salt contains elements with high EUV light absorption effects, such as fluorine atoms and iodine atoms, the amount of secondary electrons generated increases, promoting cation decomposition, making it suitable for highly sensitive fine pattern formation.

[0460] [Organic Titanium Compounds] The pattern formation method of the present invention involves forming a resist pattern using a resist film obtained from a resist composition containing the hypervalent iodine compound, carboxylic acid compound, and solvent described above, then applying and firing a material containing an organotitanium compound and a solvent (hereinafter referred to as the inversion film forming material) to form a pattern inversion film, and then performing an etching treatment to form an inversion pattern. It is preferable to use an organotitanium compound represented by the following general formula (13) at this time. [ka] (In the formula, R 51 , R 52 , R 53 , and R 54 These are monovalent organic groups having 1 to 30 carbon atoms, which may be the same or different.51 and R 52 These elements may be joined to each other to form a ring structure. (n is a real number greater than or equal to 1.)

[0461] In the above general formula (13), R 51 , R 52 , R 53 , and R 54 These are monovalent organic groups having 1 to 30 carbon atoms, which may be the same or different. 51 and R 52 These elements may be joined to each other to form a ring structure. n is a real number greater than or equal to 1. 51 , R 52 , R 53 , and R 54 Specifically, these include alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, tert-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group; cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, norbornyl group, tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms, such as decyl groups and adamantyl groups; alkenyl groups having 2 to 30 carbon atoms, such as vinyl groups and allyl groups; aryl groups having 6 to 30 carbon atoms, such as phenyl groups and naphthyl groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the organic group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, the organic group may contain a hydroxyl group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0462] In the above general formula (13), n is a real number of 1 or more. In this case, n represents the average value of the repeating units. Preferably, n is 2 to 10, more preferably 2 to 8. If n is too large, the coating properties of the inversion film forming material will deteriorate, making it difficult to embed it between the resist patterns.

[0463] When n is 1, specific examples of titanium monomers include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium alyroxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybis-ethyl acetate, titanium dibutoxybis-ethyl acetate, titanium dipropoxybis-2,4-pentanedione, and titanium dibutoxybis-2,4-pentanedione.

[0464] When synthesizing titanium oligomers where n is 2 or greater, the method is not particularly limited, but for example, they can be synthesized by adding a mixture of water and a water-soluble solvent to the above-mentioned titanium monomer and performing hydrolysis.

[0465] After synthesizing the tetraalkoxytitanium oligomer, reacting it with a diol compound yields R in the above general formula (13). 51 and R 52 It is also possible to synthesize titanium oligomers in which these molecules bond to each other to form a ring structure. 51 and R 52 Specifically, the following structure can be given as an example.

[0466] [ka]

[0467] The organotitanium compounds used in this invention are used after being dissolved in a solvent. Any solvent that can dissolve the organotitanium compounds without decomposition may be used as the solvent, but organic solvents are preferred. Specifically, these include ketones such as cyclohexanone, methyl isobutyl ketone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; and mixed solvents thereof. The concentration of the organotitanium compound in the solution can be adjusted as appropriate depending on the application, but is preferably 0.1% to 50% by mass, and more preferably 1% to 30% by mass.

[0468] [Pattern formation method] The present invention relates to a method for forming a pattern, comprising the steps of: (i) forming a resist pattern on a support using a resist film obtained from a resist composition comprising a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent; (ii) applying a material comprising an organic titanium compound and a solvent to the support on which the resist pattern has been formed to form a pattern inversion film; and (iii) removing the resist pattern by etching to form an inversion pattern.

[0469] Furthermore, it is preferable to form a resist underlayer film between the support and the resist film.

[0470] The pattern formation method of the present invention will be described in detail with reference to Figure 1. In Figure 1(a), a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent is applied to a substrate 1 on which a resist underlayer 2 is formed. A resist film 3 of a predetermined thickness is then formed through a drying process such as heating. At this time, there are no particular restrictions on the resist underlayer 2 as long as it does not degrade the resist performance and a sufficient selectivity ratio with the pattern inversion film is obtained in the etching process described later. For example, an organic underlayer or a silicon-containing film may be used. Depending on the application, it is also possible to form the resist film 3 directly on the substrate 1 without providing a resist underlayer 2.

[0471] After forming the resist film 3 as shown in Figure 1(a), exposure is performed by irradiation with radiation through a mask of a predetermined pattern. A resist composition is applied to the resist underlayer film 2 using an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, so that the coating thickness is 0.01 to 2 μm. This is then pre-baked on a hot plate, preferably at 60 to 200°C for 10 seconds to 30 minutes, more preferably at 80 to 180°C for 30 seconds to 20 minutes, to form the resist film 3.

[0472] Next, the resist film 3 is exposed using high-energy rays. Examples of high-energy rays include ultraviolet rays, far ultraviolet rays, electron beams (EB), extreme ultraviolet rays (EUV), X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When using ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. as the high-energy rays, the exposure amount is preferably 1 to 300 mJ / cm², either directly or using a mask to form the desired pattern. 2 To the extent, more preferably 10-200 mJ / cm² 2 Irradiate to a degree that results in the desired exposure. When using electroluminescence (EB) as the high-energy beam, the exposure amount is preferably 0.1 to 8,000 μC / cm², either directly or using a mask to form the desired pattern. 2To a degree, more preferably 0.5 to 5,000 μC / cm² 2 The pattern is drawn to a certain extent. Furthermore, the resist composition used in this invention is particularly suitable for fine patterning using EB or EUV, among other high-energy rays.

[0473] After exposure, PEB (Photopolymerization) is performed as needed. In this case, it is preferable to perform the PEB on a hot plate or in an oven at 30 to 200°C for 10 seconds to 30 minutes, more preferably at 60 to 120°C for 30 seconds to 20 minutes.

[0474] Subsequently, a resist pattern 31 is formed by development, as shown in Figure 1(b). The development process can be dry or wet, as long as it forms the resist pattern 31. In the case of wet development, alkaline development or organic solvent development can be considered, but organic solvent development is preferred. Examples of organic solvents used in development include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, isopropyl alcohol, n-butanol, n-pentanol, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotate, ethyl crotate, methyl propionate, ethyl propionate, and ethyl 3-ethoxypropionate. Examples of developer solutions include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenyl acetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 2-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, and 4-methyl-2-pentanol. These developers can be used individually or in combination of two or more. After development, rinsing may be performed as needed. As a rinsing solution, a solvent that mixes with the developer and does not dissolve the resist pattern 31 is preferred. Preferred solvents include alcohols with 3 to 10 carbon atoms, ether compounds with 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6 to 12 carbon atoms. Water may also be used as a rinse solution instead of an organic solvent.

[0475] Next, the inversion film-forming material is applied so as to be embedded between the patterns of the resist pattern 31. After application, the inversion film-forming material is hardened by heat treatment or the like, and a pattern inversion film 4 is formed as shown in Figure 1(c). The method of applying the inversion film-forming material is not particularly limited, and known means such as spinners, coaters, and dispensers can be used. The application should be carried out so as to form a pattern inversion film 4 of the desired thickness. At this time, the difference between the thickness of the pattern inversion film 4 and the height of the resist pattern 31 is preferably 1 to 20 nm, and more preferably 1 to 10 nm, considering the subsequent resist pattern exposure process.

[0476] After application, it is preferable to perform a bake treatment in the range of 80 to 250°C for purposes such as drying the coating film (volatilization of organic solvents).

[0477] Subsequently, planarization is performed so that the upper surface of the resist pattern 31 is exposed. Planarization methods include the etch-back method and the CMP method (Figure 1(d)). Halogen-based gases are preferred for use in etch-back. Examples of halogen-based gases include tetrachloromethane (CCl4) gas, hydrogen chloride (HCl) gas, hydrogen bromide (HBr) gas, boron trichloride (BCl3) gas, and hydrocarbon gases in which some or all of the hydrogen atoms are replaced with halogen atoms such as fluorine atoms or chlorine atoms. Specifically, examples include carbon fluoride gases and carbon chloride gases. Examples of carbon fluoride gases include CF gases such as tetrafluoromethane (CF4) gas and CHF gases such as trifluoromethane (CHF3) gas.

[0478] These etching gases may be used individually or in mixtures of two or more. Furthermore, nitrogen gas, noble gases (such as argon gas), etc., may be mixed with the etching gases.

[0479] Next, a dry etching process is performed to remove the resist pattern 31 and form an inverted pattern 41 as shown in Figure 1(e). The type of gas selected for dry etching is appropriately selected considering the etching selectivity ratio with respect to the resist pattern 31 and the resist underlayer film 2, and examples include oxygen (O2) gas, sulfur dioxide gas, carbon monoxide gas, carbon dioxide gas, and the halogen gases mentioned above. These etching gases may be used individually or mixed together. In addition, nitrogen gas, noble gases (such as argon gas), etc. may be mixed with the etching gas. Oxygen plasma etching (dry etching using plasma obtained from O2 gas) is particularly preferred.

[0480] Pattern formation methods using such reversal materials have been reported before. For example, Japanese Patent Publication No. 2008-287176 describes a reversal material and pattern formation method using a polysiloxane-containing resin composition. In this report, chemically amplified resist compositions for ArF and KrF are used as resist materials. That is, the mechanism involves polarity conversion of the exposed area by an acid-catalyzed reaction, with an acid-unstable group-containing polymer and a photoacid generator as essential components.

[0481] On the other hand, the resist composition applied to the pattern formation method of the present invention is a non-chemically amplified material containing a hypervalent iodine compound, a carboxylic acid compound, and a solvent, as described above. Therefore, especially in applications where fine patterns are formed using EUV light, it can achieve resolution performance that cannot be achieved with conventional chemically amplified resists.

[0482] On the other hand, resist compositions using hypervalent iodine compounds have the problem of insufficient etching resistance. Therefore, by inverting the pattern using an inversion film-forming material with excellent etching resistance, it is possible to obtain an upper layer pattern that functions well as an etching mask.

[0483] Furthermore, the present invention is characterized by the use of an organotitanium compound as the inversion film forming material. Organotitanium compounds are easily processed into a form suitable for coating materials (e.g., oligomers), and their fluidity can be adjusted to embed fine patterns. In addition, they can undergo condensation and curing reactions at lower temperatures than silicon compounds, allowing for the formation of an inversion film without damaging the resist pattern. The titanium-containing inversion film formed in this manner has superior etching resistance compared to polymer resists made of organic compounds or silicon-containing materials.

[0484] In other words, the pattern formation method of the present invention, by forming an inverted pattern using the above-mentioned resist composition and the above-mentioned inversion film forming material, simultaneously achieves the resolution of fine patterns and the assurance of etching resistance, which could not be solved with conventional materials and pattern formation methods, and is therefore of great value. [Examples]

[0485] The present invention will be specifically described below with reference to synthesis examples, preparation examples, comparative preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0486] [1] Polymer synthesis The monomers a-1 to a-3 and b-1 to b-2 shown below were used to synthesize polymers P-1 to P-3.

[0487] [ka]

[0488] [ka]

[0489] [Synthesis Example 1-1] Synthesis of Polymer P-1 Under a nitrogen atmosphere, monomer a-1 (56g), monomer a-3 (36g), V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.4g, and MEK 180g were placed in a flask to prepare a monomer-polymerization initiator solution. In another flask under a nitrogen atmosphere, 55g of MEK was placed and heated to 80°C with stirring, and then the monomer-polymerization initiator solution was added dropwise over 4 hours. After the addition was complete, stirring was continued for 2 hours while maintaining the polymerization solution temperature at 80°C, and then it was cooled to room temperature. The obtained polymerization solution was added dropwise to 4,000g of hexane that had been vigorously stirred, and the precipitated polymer was filtered off. The obtained polymer was washed twice with hexane (1,200g), and then vacuum dried at 50°C for 20 hours to obtain a white powdery polymer P-1 (yield 90g, yield 98%). The Mw of polymer P-1 was 8,000, and the Mw / Mn ratio was 1.42. Note that Mw is a polystyrene-converted measurement value obtained by GPC using THF as the solvent. [ka]

[0490] [Synthesis Examples 1-2, 1-3] Synthesis of polymers P-2 and P-3 The polymers shown in Table 1 below were synthesized using the same method as in Synthesis Example 1-1, except that the types and proportions of each monomer were changed.

[0491] [Table 1]

[0492] [2] Preparation of resist composition [Preparation Examples 1-1 to 1-10, Comparative Preparation Example 1-1] Resist compositions (R-01 to R-10) were prepared by dissolving hypervalent iodine compounds and carboxyl group-containing compounds in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by Omnova) in the compositions shown in Table 2 below, and filtering the resulting solution through a 0.2 μm Teflon® filter. In addition, comparative resist composition (CR-01) was prepared by dissolving polymers, photoacid generators, and sensitivity modifiers in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by Omnova) in the compositions shown in Table 3 below, and filtering the resulting solution through a 0.2 μm Teflon® filter.

[0493] [Table 2]

[0494] [Table 3]

[0495] In Tables 2 and 3, the hypervalent iodine compounds I-1 to I-10, the carboxyl group-containing compound m-1, the photoacid generator PAG-1, the sensitivity modifier Q-1, and the solvent are as follows:

[0496] [ka]

[0497] [ka]

[0498] [ka]

[0499] [ka]

[0500] [ka]

[0501] [ka]

[0502] • Solvent: PGMEA (Propylene glycol monomethyl ether acetate) AcOH (acetic acid) GBL (γ-butyrolactone)

[0503] [3] Synthesis of organotitanium compounds [Synthesis Example 2-1] A mixture of 28.4 g of titanium tetraisopropoxide and 50 g of isopropyl alcohol (IPA) was mixed with 0.9 g of pure water and 50 g of IPA, and the mixture was refluxed for 30 minutes. Subsequently, 17.8 g of organotitanium compound A1 was obtained by distilling off the IPA in the system under reduced pressure.

[0504] [Synthesis Example 2-2] A mixture of 34.0 g of titanium tetrabutoxide and 50 g of n-butyl alcohol was added dropwise to a mixture of 0.9 g of pure water and 50 g of n-butyl alcohol, and the mixture was refluxed for 30 minutes. Subsequently, 20.4 g of organotitanium compound A2 was obtained by distilling off the n-butyl alcohol present in the system under reduced pressure.

[0505] [Synthesis Example 2-3] The mixture of organotitanium compound A1 (9.1 g) obtained in Synthesis Example 2-1 and 1,2-propanediol (15.2 g) was refluxed for 2 hours. Then, 50 g of propylene glycol monomethyl ether acetate (PGMEA) was added, followed by concentration under reduced pressure, and 6.9 g of the concentrated residue was obtained as organotitanium compound A3.

[0506] [Synthesis Example 2-4] A mixture of organotitanium compound A2 (10.5 g) obtained in Synthesis Example 2-2 and 2,4-dimethyl-2,4-pentanediol (26.4 g) was refluxed for 2 hours. Then, 60 g of propylene glycol monomethyl ether acetate (PGMEA) was added, followed by concentration under reduced pressure, and 7.9 g of the concentrated residue was obtained as organotitanium compound A4.

[0507] The structures of organotitanium compounds A1 to A4 are shown below. [ka]

[0508] [4] Preparation of organic titanium-containing inversion film forming material The organotitanium compounds A1 to A4 obtained in the above synthesis examples 2-1 to 2-4 were each prepared as a 3% by mass 2-heptanone solution and filtered through a 0.1 μm fluororesin filter to prepare organotitanium-containing inversion film-forming materials, which were designated as IR-1 to IR-4.

[0509] [5] Evaluation of implantability (Examples 1-1 to 1-10, Comparative Example 1-1) A resist underlayer film with a thickness of 100 nm was formed by coating a silicon substrate with spin-on carbon ODL-301 (carbon content 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., and baking it at 350°C for 60 seconds. On top of this, a resist composition (R-01 to R-10) or a comparative resist composition (CR-01) was applied using a spinner, and a pre-bake (PAB) treatment was performed at 130°C for 60 seconds, followed by drying to form a resist film with a thickness of 25 nm. Next, the resist film was etched using an ELS-F125 manufactured by Elionix Co., Ltd. Then, a PEB treatment was performed at 90°C for 60 seconds. Furthermore, the resist films formed from R-01, R-02, and R-05 to R-08 were developed with butyl acetate for 30 seconds, and the resist films formed from R-03, R-04, R-09, R-10, and CR-01 were developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds. As a result, a line-and-space resist pattern (L / S pattern) with a line width of 20 nm and a pitch of 40 nm was formed on the resist film. The L / S patterns obtained from the resist films formed from R-01, R-02, R-05 to R-08, and CR-01 were positive-type patterns in which the exposed areas were removed by development, while the L / S patterns obtained from the resist films formed from R-03, R-04, R-09, and R-10 were negative-type patterns in which the unexposed areas were removed by development.

[0510] On the resist film on which the above L / S pattern was formed, the organic titanium-containing inversion film forming materials IR-1 to IR-4 were applied using a spinner at a rotation speed of 1500 rpm, and a bake treatment was performed at 250°C for 60 seconds to dry, thereby forming a pattern inversion film with a thickness of approximately 30 nm. The cross-section of the obtained pattern inversion film was observed using an SEM (scanning electron microscope). As a result, in Examples 1-1 to 1-10, where IR-1 to IR-4 were applied to a resist pattern using the resist composition (R-01 to R-10), the cross-section was homogeneous with no voids, confirming that each organic titanium-containing inversion film forming material was embedded without gaps in the space portion of the L / S pattern. In Comparative Example 1-1, where IR-1 to IR-4 were applied to a resist pattern using the comparative resist composition (CR-01), the cross-section showed that each organic titanium-containing inversion film forming material was mixed with the resist pattern, and the boundary between the resist pattern and the organic titanium-containing inversion film forming material could not be found.

[0511] [6] Evaluation of the formation of inverted patterns (inversion of L / S patterns) (Examples 2-1 to 2-10, Comparative Example 2-1) A resist underlayer film with a thickness of 100 nm was formed by coating a silicon substrate with spin-on carbon ODL-301 (carbon content 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., and baking it at 350°C for 60 seconds. A resist composition (R-01 to R-10) or a comparative resist composition (CR-01) was then spin-coated onto this underlayer, and a pre-bake (PAB) treatment was performed on a hot plate at 130°C for 60 seconds to produce a resist film with a thickness of 25 nm. Next, an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9, 90° dipole illumination) was used to expose a 40nm line-and-space (L / S) 1:1 pattern. The resist films formed from R-01, R-02, R-05~R-08 were then subjected to PEB treatment at 90°C for 60 seconds. These resist films were then developed with butyl acetate for 30 seconds, while the resist films formed from R-03, R-04, R-09, R-10, and CR-01 were developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds. On the resist film on which the above L / S pattern was formed, organotitanium-containing inversion film-forming materials IR-1 to IR-4 were applied using a spinner at a rotation speed of 1500 rpm, and then baked at 150°C for 60 seconds to dry, thereby forming a pattern inversion film with a thickness of approximately 30 nm.

[0512] The substrate on which the above-described pattern inversion film was formed was etched using a plasma etching apparatus (Tokyo Electron Corporation, apparatus name: Telius) with a mixed gas of CF4 gas, Ar gas, and N2 gas (flow rate ratio: CF4 / Ar / N2=9 / 57 / 34) (pressure: 4 Pa; Upper RF=500 W, Lower RF=1,800 W; temperature: 20°C; processing time: 2 seconds for both), and the film surface was planarized.

[0513] The substrate after the above etching process was subjected to oxygen plasma etching using a plasma etching apparatus (Tokyo Electron Corporation, apparatus name: Telius) with a mixed gas of O2 and N2 (flow rate ratio: O2 / N2=46 / 54) (pressure: 0.67 Pa; Upper RF=750 W, Lower RF=150 W; temperature: 0°C; processing time: 15 seconds). The cross-section of the substrate after the above etching process was observed by SEM. As a result, in Examples 2-1 to 2-10, which used the resist compositions (R-01 to R-10), the line patterns of the L / S patterns and the resist underlayer film beneath them were removed, and it was confirmed that a pattern was formed on the substrate in which space patterns with a space width of 20 nm and a height of approximately 100 nm were arranged at equal intervals. Furthermore, the above pattern had a good shape with high rectangularity in the cross-section of the top portion of the lines (pattern inversion film portion). On the other hand, in Comparative Example 2-1, which used the comparative resist composition (CR-01), no inversion pattern was formed on the substrate. Furthermore, in L / S patterns formed using R-01 to R-10 and CR-01, when the above-mentioned oxygen plasma etching treatment was performed without using an organic titanium-containing inversion film forming material, the remaining resist could not withstand the etching process, and some of the resist underlayer film regions that should have been preserved were also removed.

[0514] As is clear from the above results, with the pattern formation method according to the present invention, the organotitanium-containing inversion film forming material used has good embedding properties, and even fine resist patterns can be embedded well. Furthermore, it was found that the pattern inversion film formed using the above inversion film forming material has a large etching selectivity ratio for the resist film and the underlying resist layer film, and also exhibits excellent shape in the inversion pattern formed by removing the resist pattern by etching.

[0515] This specification includes the following embodiments: [1]: A method for forming a pattern, (i) A step of forming a resist pattern on a support using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent, (ii) A step of forming a pattern inversion film by applying a material containing an organic titanium compound and a solvent onto a support on which the resist pattern has been formed, (iii) a step of removing the resist pattern by etching and forming an inverted pattern, A pattern forming method characterized by including the following. [2]: The pattern formation method of [1], characterized in that at least one of the hypervalent iodine compounds represented by the following general formulas (1) to (10) is used as the hypervalent iodine compound. [ka] (In the formula, m1 is an integer between 0 and 2. When m1 is 0, n1 is an integer between 1 and 3, n2 is an integer between 0 and 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is an integer between 1 and 3, n2 is an integer between 0 and 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is an integer between 1 and 3, n2 is an integer between 0 and 9, and 1 ≤ n1 + n2 ≤ 10.) n3 is either 1 or 2, n4 is an integer between 0 and 4, and 1 ≤ n3 + n4 ≤ 5, n5 is either 1 or 2, and n6 is an integer between 0 and 4, and 1 ≤ n5 + n6 ≤ 5. n7 is an integer between 0 and 4, and n8 is an integer between 1 and 4. m2 is an integer between 0 and 2. When m2 is 0, n9 is an integer between 0 and 4; when m2 is 1, n9 is an integer between 0 and 6; and when m2 is 2, n9 is an integer between 0 and 8. m3 is an integer between 0 and 2. When m3 is 0, n10 is an integer between 0 and 4; when m3 is 1, n10 is an integer between 0 and 6; and when m3 is 2, n10 is an integer between 0 and 8. m4 is either 0 or 1. When m4 is 0, n11 is an integer between 0 and 4, and when m4 is 1, n11 is an integer between 0 and 6. m5 is either 0 or 1. When m5 is 0, n12 is an integer between 0 and 4, and when m5 is 1, n12 is an integer between 0 and 6. n13 and n14 are integers between 0 and 6. n15 and n16 are integers between 0 and 3. m6 is an integer between 0 and 2. When m6 is 0, n17 is an integer between 0 and 4; when m6 is 1, n17 is an integer between 0 and 6; and when m6 is 2, n17 is an integer between 0 and 8. m7 is an integer between 0 and 2. When m7 is 0, n18 is an integer between 0 and 3; when m7 is 1, n18 is an integer between 0 and 5; and when m7 is 2, n18 is an integer between 0 and 7. m8 is an integer between 0 and 2. When m8 is 0, n19 is an integer between 0 and 3 and n20 is 0 or 1. When m8 is 1, n19 is an integer between 0 and 5 and n20 is 0 or 1. When m8 is 2, n19 is an integer between 0 and 7 and n20 is 0 or 1. R 1 ~R 22 Each of these is independently a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , R 19 and R 20 , or R 21 and R 22 These atoms may bond with each other to form a ring together with the carbon atoms to which they bond and the atoms between the carbon atoms. R 31 ~R 34 , R 37 , R 39 ~R46 , R 49 , and R 50 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31 These may be the same or different from each other, and there may be multiple R 31 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 32 These may be the same or different from each other, and there may be multiple R 32 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45 These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. R 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. R 36 This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. R 38 This is a carbonyl group or a hydroxylene group having 1 to 10 carbon atoms, which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is unbonded, single-bonded, -O-, -S-, -NH-, or -CH2-. R 47 This is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain a halogen atom or a heteroatom. X is either a nitrogen atom or a sulfur atom, and if it is a nitrogen atom, R 48 It may have. R 48 This is a hydrocarbyl group or ester having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom. [3]: The pattern forming method according to [1] or [2] above, characterized in that the carboxyl group-containing compound is a carboxyl group-containing polymer containing repeating units represented by the following general formula (11) or a carboxylic acid compound represented by the following general formula (12). [ka] (In the formula, R A This is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A This is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond with a carbon atom of the main chain. t is an integer between 1 and 4. R 29 is a t-valent hydrocarbon group having 1 to 40 carbon atoms or a t-valent heterocyclic group having 2 to 40 carbon atoms, and when t is 2, R 29 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the t-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 30 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a heteroatom. When t is 2 to 4, each R 30 They may be the same or different from each other. [4]: A pattern formation method of any one of the above [1] to [3], characterized by forming a resist underlayer film between the support and the resist film. [5]: A pattern formation method according to any one of the above [1] to [4], characterized in that the organotitanium compound is represented by the following general formula (13). [ka] (In the formula, R 51 , R 52 , R 53 , and R 54 These are monovalent organic groups having 1 to 30 carbon atoms, which may be the same or different. 51 and R 52 These elements may be joined to each other to form a ring structure. (n is a real number greater than or equal to 1.)

[0516] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0517] 1... Substrate to be processed, 2... Resist underlayer film, 3... Resist film, 31...Resist pattern, 4...Pattern inversion coating, 41...Inversion pattern.

Claims

1. A method for forming a pattern, (i) A step of forming a resist pattern on a support using a resist film obtained from a resist composition containing a hypervalent iodine compound, a carboxyl group-containing compound, and a solvent, (ii) A step of forming a pattern inversion film by applying a material containing an organic titanium compound and a solvent onto a support on which the resist pattern has been formed, The steps (iii) are to remove the resist pattern by etching and form an inverted pattern, A pattern forming method characterized by including the following.

2. The pattern forming method according to claim 1, characterized in that at least one of the hypervalent iodine compounds represented by the following general formulas (1) to (10) is used as the hypervalent iodine compound. 【Chemistry 1】 (In the formula, m1 is an integer between 0 and 2. When m1 is 0, n1 is an integer between 1 and 3, n2 is an integer between 0 and 5, and 1 ≤ n1 + n2 ≤ 6.) When m1 is 1, n1 is an integer between 1 and 3, n2 is an integer between 0 and 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is an integer from 1 to 3, n2 is an integer from 0 to 9, and 1 ≤ n1 + n2 ≤ 10. n3 is either 1 or 2, n4 is an integer between 0 and 4, and 1 ≤ n3 + n4 ≤ 5, n5 is either 1 or 2, and n6 is an integer between 0 and 4, and 1 ≤ n5 + n6 ≤ 5. n7 is an integer between 0 and 4, and n8 is an integer between 1 and 4. m² is an integer between 0 and 2. When m² is 0, n⁹ is an integer between 0 and 4; when m² is 1, n⁹ is an integer between 0 and 6; and when m² is 2, n⁹ is an integer between 0 and 8. m3 is an integer between 0 and 2. When m3 is 0, n10 is an integer between 0 and 4; when m3 is 1, n10 is an integer between 0 and 6; and when m3 is 2, n10 is an integer between 0 and 8. m4 is either 0 or 1. When m4 is 0, n11 is an integer between 0 and 4, and when m4 is 1, n11 is an integer between 0 and 6. m5 is either 0 or 1. When m5 is 0, n12 is an integer between 0 and 4, and when m5 is 1, n12 is an integer between 0 and 6. n13 and n14 are integers between 0 and 6. n15 and n16 are integers between 0 and 3. m6 is an integer between 0 and 2. When m6 is 0, n17 is an integer between 0 and 4; when m6 is 1, n17 is an integer between 0 and 6; and when m6 is 2, n17 is an integer between 0 and 8. m7 is an integer between 0 and 2. When m7 is 0, n18 is an integer between 0 and 3; when m7 is 1, n18 is an integer between 0 and 5; and when m7 is 2, n18 is an integer between 0 and 7. m8 is an integer between 0 and 2. When m8 is 0, n19 is an integer between 0 and 3 and n20 is 0 or 1. When m8 is 1, n19 is an integer between 0 and 5 and n20 is 0 or 1. When m8 is 2, n19 is an integer between 0 and 7 and n20 is 0 or 1. R １ ~R ２２ are each independently a hydrocarbyl group having 1 to 10 carbon atoms which may contain a halogen atom or a hetero atom. Also, R １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ , R ９ and R １０ , R １１ and R １２ , R １３ and R １４ , R １５ and R １６ , R １７ and R １８ , R １９ and R ２０ , or R ２１ and R ２２ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between the carbon atoms. R ３１ ~R ３４ , R ３７ , R ３９ ~R ４６ , R ４９ , and R ５０ Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R ３１ These may be the same or different from each other, and there may be multiple R ３１ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R ３２ These may be the same or different from each other, and there may be multiple R ３２ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R ３３ These may be the same or different from each other, and there may be multiple R ３３ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R ３４ These may be the same or different from each other, and there may be multiple R ３４ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R ３７ These may be the same or different from each other, and there may be multiple R ３７ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R ３９ These may be the same or different from each other, and there may be multiple R ３９ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R ４０ These may be the same or different from each other, and there may be multiple R ４０ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R ４１ These may be the same or different from each other, and there may be multiple R ４１ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R ４２ These may be the same or different from each other, and there may be multiple R ４２ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R ４３ These may be the same or different from each other, and there may be multiple R ４３ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R ４４ These may be the same or different from each other, and there may be multiple R ４４ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R ４５ These may be the same or different from each other, and there may be multiple R ４５ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R ４６ These may be the same or different from each other, and there may be multiple R ４６ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R ４９ These may be the same or different from each other, and there may be multiple R ４９ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R ５０ These may be the same or different from each other, and there may be multiple R ５０ However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. R ３５ is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R ３５ The (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and the (n8) valent hydrocarbon group may be -CH ２ - may be partially substituted with a group containing a heteroatom, R ３４ and R ３５ However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. R ３６ This is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. R ３８ This is a carbonyl group or a 1-10 carbon dioxide hydrocarbylene group which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L １ This can be: no bond, single bond, -O-, -S-, -NH-, or -CH ２ - is the case. R ４７ This is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. X is either a nitrogen atom or a sulfur atom, and if it is a nitrogen atom, R ４８ It may have. R ４８ This is a hydrocarbyl group or ester having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

3. The pattern forming method according to claim 1 or 2, characterized in that the carboxyl group-containing compound is a carboxyl group-containing polymer containing repeating units represented by the following general formula (11) or a carboxylic acid compound represented by the following general formula (12). 【Chemistry 2】 (In the formula, R Ａ This is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X Ａ This is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X Ａ１ - is true. X Ａ１ This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * indicates a bond with a carbon atom of the main chain. t is an integer between 1 and 4. R ２９ is a t-valent hydrocarbon group having 1 to 40 carbon atoms or a t-valent heterocyclic group having 2 to 40 carbon atoms, and when t is 2, R ２９ This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group may be substituted with a group containing a heteroatom, and the -CH of the t-valent hydrocarbon group ２ - May be partially substituted with a group containing a heteroatom. R ３０ This is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, and the -CH of the hydrocarbylene group ２ - Some of the groups may be substituted with groups containing heteroatoms. When t is 2 to 4, each R ３０ They may be the same or different from each other.

4. The pattern forming method according to claim 1 or 2, characterized in that a resist underlayer film is formed between the support and the resist film.

5. The pattern forming method according to claim 1 or 2, characterized in that the organic titanium compound is represented by the following general formula (13). 【Transformation 3】 (In the formula, R ５１ , R ５２ , R ５３ , and R ５４ These are monovalent organic groups having 1 to 30 carbon atoms, which may be the same or different. ５１ and R ５２ These elements may be joined to each other to form a ring structure. (n is a real number greater than or equal to 1.)

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