JP2007218943A - Substrate and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate which has at least a silicon resin film for antireflection and a photoresist film sequentially formed on an organic film, and which can further reliably form a nearly vertical resist pattern on the silicon resin film for antireflection. <P>SOLUTION: The substrate has at least the silicon resin film for antireflection and the photoresist film sequentially formed on the organic film, wherein the silicon resin film for antireflection has a hardness by a nanoindenter of 0.4-1.1 GPa. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a substrate on which an antireflection silicon resin film used in a microfabrication process in a manufacturing process of a semiconductor element or the like, in particular, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ laser light. The present invention relates to a substrate on which an antireflection silicon resin film used in lithography using an exposure light source of high energy rays such as (157 nm), electron beam, and X-ray is formed.

  In recent years, with the increasing integration and speed of LSIs, there is a need for finer pattern rules. In lithography using light exposure, which is currently used as a general-purpose technology, the essence derived from the wavelength of the light source The resolution limit is approaching.

  As a light source for lithography used in forming a resist pattern, light exposure using a g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source is widely used, but as a means for further miniaturization. A method of shortening the wavelength of exposure light has been considered effective. For this reason, for example, in a mass production process of a 64-Mbit DRAM processing method, a short wavelength KrF excimer laser (248 nm) is used as an exposure light source instead of i-line (365 nm). However, in order to manufacture a DRAM having a degree of integration of 1G or more, which requires a finer processing technique (for example, a processing dimension of 0.13 μm or less), a light source with a shorter wavelength is required, particularly an ArF excimer laser (193 nm). Lithography using a material has been studied.

As a method of forming a pattern on a substrate using such a lithography technique, there is a multilayer resist process.
For example, in order to prevent the resist pattern from deteriorating due to the influence of halation or standing waves, a method of providing an anti-reflection coating (Anti-Reflective Coating) between the substrate and the photoresist film is known.

Further, in order to form a pattern with a high aspect ratio on a stepped substrate, a method is known that uses a substrate in which an organic film is formed on the substrate, a silicon-containing film is formed thereon, and a photoresist film is formed thereon. (See, for example, Non-Patent Document 1). From the viewpoint of resolution, a thinner photoresist film is desirable. On the other hand, it is desirable that the photoresist film is thicker from the viewpoint of the embedding characteristics of the substrate step and the resistance to substrate etching. Therefore, by using three layers as described above, it is possible to divide into a layer with high embedding characteristics of substrate steps and high resistance to dry etching and a layer with high resolution, and a pattern with a high aspect ratio is formed on a substrate with steps. can do.
Here, examples of the silicon-containing film include an antireflection silicon resin film which is one of the antireflection films.

  In order to form a pattern on the substrate using such a substrate, first, the pattern circuit region of the photoresist film is exposed, and then developed with a developer to form a resist pattern on the photoresist film. Further, a pattern is formed on the antireflection silicon resin film using the photoresist film as a mask. In this way, the resist pattern is transferred one after another, and finally a pattern is formed on the substrate.

  However, conventionally, when a silicon resin film for antireflection is formed, a photoresist film is formed thereon, and a resist pattern is formed on the photoresist film, the resist pattern shape on the silicon resin film for antireflection is In some cases, it was not a vertical shape but a skirt or undercut shape. In the case of the skirt shape, a dimensional conversion difference occurs after etching of the antireflection silicon resin film, and in the case of an undercut shape (also referred to as a reverse taper shape), the resist pattern may collapse after development.

J. et al. Vac. Sci. Technol. , 16 (6), Nov. / Dec. 1979

  The present invention has been made in view of such problems, and is a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed on an organic film, and at the time of pattern formation. Another object of the present invention is to provide a substrate that can more reliably make the resist pattern on the antireflection silicon resin film substantially vertical.

  The present invention has been made to solve the above problems, and is a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed on at least an organic film, the antireflection film A silicon resin film having a hardness by a nanoindenter of 0.4 GPa or more and 1.1 GPa or less is provided (claim 1).

  As described above, the substrate of the present invention has a silicon resin film for antireflection having a hardness of 0.4 GPa or more and 1.1 GPa or less by a nanoindenter. If a resist pattern is formed using such a substrate of the present invention, the resist pattern on the antireflection silicon resin film can be more surely made substantially vertical.

  In the substrate of the present invention, the antireflection silicon resin film may be formed of a material containing a light-absorbing silicone resin and an organic solvent (claim 2).

  The silicon resin film for antireflection whose hardness by the nanoindenter of the substrate of the present invention is 0.4 GPa or more and 1.1 GPa or less, for example, using a material containing a light-absorbing silicone resin and an organic solvent in this way, It can be formed by adjusting various conditions such as the silicon and carbon content of the light-absorbing silicone resin, the amount of the cyclic skeleton and cross-linking group in the side chain, and the baking temperature when forming the anti-reflection silicon resin film. .

  In the substrate of the present invention, the light-absorbing silicone resin includes an organic group having one or more of a carbon-oxygen single bond and a carbon-oxygen double bond, a light-absorbing group, and a terminal having Si—OH, Si— It is preferable to contain one or more silicon atoms of OR (R is a saturated or unsaturated alkyl group having 1 to 6 carbon atoms) (Claim 3).

  Such an anti-reflection silicon resin film containing a silicone resin exhibits an excellent anti-reflection effect by setting it to an appropriate film thickness, etc., and has little film thickness fluctuation even during long-term storage, and excellent storage stability Showing gender.

  In the substrate of the present invention, the organic group of the light-absorbing silicone resin may include one or more groups selected from the group consisting of an epoxy group, an ester group, an alkoxy group, and a hydroxy group. (Claim 4).

  As a result, when forming a silicon resin film for antireflection, epoxy groups, ester groups, alkoxy groups, and hydroxy groups in organic groups form crosslinks with silanol groups without the need to add a crosslinking agent. can do.

  In the substrate of the present invention, the light-absorbing group of the light-absorbing silicone resin may contain one or more rings selected from the group consisting of an anthracene ring, a naphthalene ring, and a benzene ring. Item 5). Moreover, in the board | substrate of this invention, the light absorption group of the said light absorptive silicone resin shall be a thing containing a silicon- silicon bond (Claim 6).

  By appropriately selecting these light absorbing groups, the antireflection silicon resin film can exhibit an excellent antireflection effect.

  In the substrate of the present invention, the material for forming the antireflection silicon resin film may further contain an acid generator (Claim 7).

  Thus, if it contains an acid generator, the crosslinking reaction can be further promoted by generating an acid from the acid generator by heat or the like.

  In the substrate of the present invention, the material for forming the antireflection silicon resin film may further contain a neutralizing agent (Claim 8).

  If the silicon resin film material for antireflection further contains a neutralizing agent, it is possible to more effectively prevent the generated acid from diffusing into the upper photoresist film of the silicon resin film for antireflection. it can. For this reason, a resist pattern can be made into a perpendicular | vertical shape more reliably.

  The present invention also relates to a method for forming a pattern on a substrate by lithography, wherein at least the substrate of the present invention is prepared, the pattern circuit region of the photoresist film on the substrate is exposed, and then developed with a developer. Forming a resist pattern on the photoresist film, etching the antireflection silicon resin film using the photoresist film on which the resist pattern is formed as a mask, and using the antireflection silicon resin film on which the pattern is formed as a mask There is provided a pattern forming method characterized in that an organic film is etched and a substrate is further etched to form a pattern on the substrate.

  Thus, if a pattern is formed on a substrate by lithography using the substrate of the present invention, a fine pattern can be formed on the substrate with high accuracy.

  As described above, the substrate of the present invention is a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed on at least an organic film, and the antireflection silicon resin film includes The hardness by the nanoindenter is 0.4 GPa or more and 1.1 GPa or less. By using such a substrate of the present invention and forming a resist pattern on the photoresist film, the resist pattern on the antireflection silicon resin film can be more surely made into a substantially vertical shape.

Hereinafter, the present invention will be described in more detail.
As described above, conventionally, when a resist pattern is formed on a substrate in which an antireflection silicon resin film is formed on an organic film and a photoresist film is sequentially formed thereon, the resist pattern shape is not a vertical shape, There has been a problem that there is a case where the bottom or undercut may occur in the vicinity of the antireflection silicon resin film. Therefore, the present inventors have made extensive studies to develop a substrate that can more reliably make the resist pattern shape on the antireflection silicon resin film almost vertical when the resist pattern is formed.

  As a result, the present inventors have found that when the anti-reflection silicon resin film under the photoresist film has a nanoindenter hardness of 0.4 GPa to 1.1 GPa, the anti-reflection silicon resin film The present inventors have found that the resist pattern shape can be more surely made substantially vertical, thereby completing the present invention.

FIG. 1 is a schematic sectional view showing an example of the substrate of the present invention.
In this substrate 1, an organic film 11 is formed on a substrate 10 to be processed, an antireflection silicon resin film 12 is formed thereon, and a photoresist film 13 is sequentially formed thereon. Further, the antireflection silicon resin film 12 has a hardness by a nanoindenter of 0.4 GPa to 1.1 GPa.

  By using such a substrate and forming a resist pattern on the photoresist film 13 on the antireflection silicon resin film 12, the resist pattern can be more surely made substantially vertical.

  Here, the nanoindenter measures the hardness of an object by applying an indenter with a nanoscale tip radius to the surface of the object, pressing it into the object and measuring the indentation depth and applied load simultaneously. (See, for example, JP-A-2004-122283).

Such a substrate of the present invention can be manufactured, for example, by the method shown in FIG.
First, a substrate to be processed 10 on which a pattern is formed as shown in FIG.

Next, as shown in FIG. 2B, an organic film 11 is formed on the substrate 10.
The organic film 11 is formed on the substrate 10 by a spin coat method or the like. Since the organic film 11 acts as a mask when the substrate 10 is etched, it is desirable that the etching resistance is high under the substrate etching conditions, and it is required not to mix with the antireflection silicon resin film 12 as an upper layer. It is desirable to crosslink with heat or acid after coating with a coat or the like.

Next, as shown in FIG. 2C, an antireflection silicon resin film 12 having a hardness of 0.4 GPa or more and 1.1 GPa or less is formed on the organic film 11.
Similarly to the organic film 11, the antireflection silicon resin film 12 can be formed by applying an antireflection silicon resin film material on the organic film 11 by spin coating or the like. After application by spin coating or the like, it is desirable to evaporate the organic solvent and to bake to promote the crosslinking reaction in order to prevent mixing with the upper photoresist film 13. The baking temperature is preferably in the range of 80 to 300 ° C., and the baking time is preferably in the range of 10 to 300 seconds.

  Examples of the anti-reflection silicon resin film material used at this time include a material containing a light-absorbing silicone resin and an organic solvent. The hardness of the antireflection silicon resin film is, for example, using such a material, the silicon and carbon contents of the silicon resin in the antireflection silicon resin film material, the amount of the side chain cyclic skeleton and the crosslinking group. By adjusting the conditions such as the baking temperature when forming the silicon resin film for antireflection, it can be made 0.4 GPa or more and 1.1 GPa or less.

  At this time, if the hardness of the silicon resin film for antireflection is less than 0.4 GPa, the film structure is fragile, so that it is attacked by the solvent used when applying the photoresist film material, or the pattern is developed when the upper photoresist film is developed. It is not preferable because a fall or the like easily occurs. On the other hand, if the hardness of the silicon resin film for antireflection exceeds 1.1 GPa, the adhesiveness with the upper photoresist film is deteriorated, and the resist pattern collapse easily occurs.

Next, as shown in FIG. 2D, a photoresist film 13 is formed on the antireflection silicon resin film 12.
As a method for forming the photoresist film 13, a spin coating method is preferably used as in the formation of the organic film 11 and the like. It is preferable to pre-bake after applying the photoresist film material by spin coating or the like. As prebaking conditions, a time range of 10 seconds to 300 seconds in a temperature range of 80 ° C. to 180 ° C. is preferable.

  Through the above steps, the substrate 1 of the present invention in which the antireflection silicon resin film 12 and the photoresist film 13 are sequentially formed on the organic film 11 shown in FIG. 1 can be manufactured.

  Here, as the light-absorbing silicone resin used for the silicon resin film material for antireflection, an organic group having one or more of a carbon-oxygen single bond and a carbon-oxygen double bond, a light-absorbing group, and a terminal of Si- It is preferable that it contains one or more silicon atoms of OH and Si-OR (R is a saturated or unsaturated alkyl group having 1 to 6 carbon atoms).

  An antireflection silicon resin film formed of such an antireflection silicon resin film exhibits an excellent antireflection effect by setting it to an appropriate film thickness, etc. Less and shows excellent storage stability.

  Such a light-absorbing silicone resin can be obtained, for example, by hydrolyzing and condensing one or a mixture of two or more silicon-containing compounds represented by the following general formula (1).

（上記式中、Ｒ^１ａは炭素−酸素単結合、炭素−酸素二重結合の１以上を有する有機基であり、Ｒ^２は光吸収基を有する１価の有機基であり、Ｘは同一又は異種のハロゲン原子、水素原子、ヒドロキシ基、炭素数１〜６のアルコキシ基、又は炭素数１〜６のアルキルカルボニルオキシ基である。ｍとｎは各々０〜３の整数であって、０＜（４−ｍ−ｎ）≦４の関係を満足する。）

(In the above formula, R ^1a is an organic group having one or more of a carbon-oxygen single bond and a carbon-oxygen double bond, R ² is a monovalent organic group having a light absorbing group, and X is the same or A different halogen atom, a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an alkylcarbonyloxy group having 1 to 6 carbon atoms, wherein m and n are each an integer of 0 to 3, and 0 < (4-mn) ≦ 4 is satisfied.)

  The preferable mass average molecular weight of the silicon resin obtained from the silicon-containing compound represented by the general formula (1) is 500 to 1,000,000, more preferably 1000 to 50 in terms of polystyrene as measured based on GPC (gel permeation chromatography). Ten thousand.

  The organic group having one or more carbon-oxygen single bonds and carbon-oxygen double bonds in the general formula (1) preferably has 2 to 30 carbon atoms, and more preferably an epoxy group, an ester group, or an alkoxy group. , One or more groups selected from the group consisting of hydroxy groups. The organic group means a group containing carbon and may contain hydrogen, nitrogen, sulfur and the like. Examples of the organic group having at least one carbon-oxygen single bond and carbon-oxygen double bond in the general formula (1) include the following.

_{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 -
(In the above formula, P is a hydrogen atom, a hydroxyl group, an epoxy ring (OCH ₂ CH—), an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkyl having 1 to 6 carbon atoms. Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently —C _q H _(2q-p) P _p — (wherein P is the same as above, and p is 0 to 3). Q is an integer of 0 to 10.), u is an integer of 0 to 3, and S ₁ and S ₂ are each independently —O—, —CO—, —OCO—, — Represents COO- or -OCOO-, each of v1, v2, and v3 independently represents 0 or 1. Together with these, examples of T are shown below: The position where T ₂ is bonded to Q ₂ and Q ₃ is Although not particularly limited, it is suitable considering the reactivity due to steric factors and the availability of commercially available reagents used in the reaction. (You can choose it.)

  Preferable examples of the organic group having one or more carbon-oxygen single bonds and carbon-oxygen double bonds in the general formula (1) include the following. In addition, in the following formula, (Si) is described in order to indicate the bonding site with Si.

  Next, the light absorbing group in the general formula (1) includes, for example, a group having absorption at a wavelength of 150 to 300 nm, and is preferably selected from the group consisting of an anthracene ring, naphthalene ring, and benzene ring. Those containing one or more rings are mentioned. Or these rings may have one or more substituents. The substituent is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, or an acetal group having 1 to 6 carbon atoms, more preferably a methyl group or a methoxy group. Group, t-butoxy group, t-amyloxy group, acetoxy group, 1-ethoxyethoxy group and the like. An example of this can be given below.

The methoxy group, acetoxy group, and acetal group of the light absorbing group can be deprotected during polymerization or after polymerization to form a hydroxy group.
In particular, for lithography with a wavelength of 200 nm or less, it is preferable that the light absorbing group contains a benzene ring.

  In addition to the aromatic light absorbing group, a light absorbing group containing a silicon-silicon bond can also be used. Specifically, the following can be mentioned.

The light-absorbing silicone resin in the silicon resin film material for antireflection can be synthesized, for example, by co-condensing the silicon-containing compound (monomer) represented by the general formula (1) by hydrolysis.
The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid Acids such as sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide , Bases such as choline hydroxide and tetrabutylammonium hydroxide, tetraalkoxytitanium, trialkoxymono (acetylacetonato) titanium, tetraalkoxyzirconium, trialkoxymono (acetylacetonato) zirconium Which metal chelate compound can be mentioned.

  As a reaction operation, water and a catalyst may be dissolved in an organic solvent, and a monomer may be added thereto. At this time, the monomer may be diluted with an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. when dropping the monomer and then raising the temperature to 40 to 80 ° C. for aging is preferable.

  As another operation, a water-free catalyst may be dissolved in an organic solvent, and water or water diluted with an organic solvent may be added thereto. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. when dropping the monomer and then raising the temperature to 40 to 80 ° C. for aging is preferable.

  As an organic solvent, a water-soluble thing is preferable, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether , Ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether and mixtures thereof are preferred. .

  Thereafter, an organic solvent that is hardly soluble or insoluble in the above water is added, the organic solvent layer is separated and washed with water to remove the catalyst used for the hydrolytic condensation. At this time, the catalyst may be neutralized as necessary.

  As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether. , Ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate -Butyl, tert-butyl propionate, propylene glycol mono tert Butyl ether acetate, γ- butyrolactone, and mixtures thereof.

  Thereafter, the organic solvent layer is separated and dehydrated. It is necessary to sufficiently perform the remaining of water in order to advance the condensation reaction of the remaining silanol. Preferable examples include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.

  As another operation method, an organic solvent that is hardly soluble or insoluble in water can also be used as the organic solvent used for the hydrolysis and condensation of the monomer. For example, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert- Butyl ether acetate, γ-butyl lactone and A mixture thereof are preferred.

The monomer is dissolved in the organic solvent, and water is added to initiate the hydrolysis reaction.
The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable.

By adjusting the reaction conditions at this time, the proportion of silicon atoms whose terminal is one or more of Si—OH and Si—OR (where R is a saturated or unsaturated alkyl group having 1 to 6 carbon atoms) is increased. For example, a light-absorbing silicone resin of 0.1 to 50 mol% can be obtained. The terminal group at this time can be easily obtained by using ²⁹ Si-NMR. Assuming that the ratio of silicon atoms whose terminal is one or more of Si—OH and Si—OR is A (mol%), the following formula is obtained.

Here, Q ₁ , Q ₂ , Q ₃ , and Q ₄ are the number of siloxane bonds formed by tetrafunctional Si atoms, and T ₁ , T ₂ , and T ₃ are the siloxane bonds formed by trifunctional Si atoms. The numbers D ₁ and D ₂ represent the number of siloxane bonds formed by the bifunctional Si atom. The amount of each bond is calculated by integrating the ²⁹ Si-NMR peak values.

  At this time, when A is 0.1 mol% or less, the number of terminal SiOH and SiOR used for crosslinking of the resin is too small, and the coating film cannot be sufficiently cured, and the resist is used in the next step. Mixing may occur and a resist pattern with good rectangularity may not be obtained. On the other hand, if A is 50 mol% or more, condensation may be insufficient, and only a coating film having a weak strength may be obtained, and a resist pattern may collapse, which may be undesirable.

Furthermore, when A is between 0.1 mol% and 50 mol% and the ratio of Si—OH and Si—OR is a predetermined ratio, a more fully cured coating film can be obtained. That is, more preferably, the ratio is Si—OH / Si—OR = (100/0) to (20/80). At this time, the ratio of —SiOH / —SiOR can be determined using ¹³ C-NMR, using the integrated intensity (B) per one carbon atom at the α-position of the Si atom as an internal standard. That is, determined -SiO C H ₂ -Rx next when the R of -SiOR and Rx-CH _2, Si-OR content from the ratio of integrated intensity of the carbon atoms of the underlined portion (B).

^{In 29} Si-NMR, since the total amount (C) of Si—OH and Si—OR is determined, the ratio of SiOH and SiOR is Si—OH / Si—OR = (C—B) / B.
If the ratio of Si-OR is less than Si-OH / Si-OR = 20/80, condensation between Si-OH and condensation between Si-OH and Si-OR proceed easily and there is sufficient strength. A coating film that hardly generates intermixing can be obtained.

  Furthermore, when an epoxy group is contained in an organic group containing a carbon-oxygen bond, after the silicone resin is formed, it is converted into a silicone resin having a different type of organic group having a carbon-oxygen bond by a modification reaction. can do. Examples of the repeating unit of the modified silicone resin are given below.

  Here, Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. Specifically, , Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl Group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, cyclohexylcarbonyl group, methoxy group Examples include carbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, t-butoxycarbonyl group, etc. It can be.

  Conversion from the original silicone resin is possible by generally known methods. For example, it can be easily converted into a modified silicone resin by heating alcohols or carboxylic acids in the presence of an acid, alkali or quaternary ammonium catalyst. In the reaction with carboxylic acids, carboxylic acid itself becomes a catalyst, so there is no need to add a catalyst.

  Acid catalysts used at this time include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, acetic acid, propionic acid Acids such as oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid can be used. Examples of the alkali catalyst include bases such as ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, triethylamine, triethanolamine, benzyldiethylamine, tetraethylammonium hydroxide, choline hydroxide, and tetrabutylammonium hydroxide. Examples of the quaternary ammonium catalyst include benzyltriethylammonium chloride and benzyltriethylammonium bromide.

  The original silicone resin and modified silicone resin thus obtained (hereinafter referred to as a silicone resin including both and a blend of both) can also be used by blending. Since the blend ratio at this time greatly affects the performance of the resulting anti-reflection silicon resin film material, it can be blended at an arbitrary ratio so that the performance is maximized. In the obtained mixture, it is more preferable to make the polymer compound into a uniform composition by operations such as heating, stirring, ultrasonic irradiation, and kneading.

  The organic solvent used for the silicon resin film material for antireflection may be any organic solvent that can dissolve a light-absorbing silicone resin, an acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and ethyl 2-n-amyl ketone, 3-methoxybutanol, 3-ethyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2- Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, ethyl 3-methoxypropionate, 3-ethoxypropyl Examples include esters such as ethyl pionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. One of these may be used alone or two or more may be used. Although it can be used in mixture, it is not limited to these. Of these organic solvents, diethylene glycol diethyl ether, 1-ethoxy-2-propanol, propylene glycol monoethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used.

  The amount of the organic solvent used is preferably 400 to 500,000 parts by mass, particularly 500 to 100,000 parts by mass with respect to 100 parts by mass of the silicone resin.

  Further, an acid generator can be added to the antireflection silicon resin film material in order to further accelerate the crosslinking reaction by heat. The acid generator includes those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added.

As an acid generator to be added,
i. An onium salt of the following general formula (P1a-1), (P1a-2), (P1a-3) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

(In the above formula, R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and having 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, part or all of hydrogen atoms of which may be substituted with an alkoxy group, etc. R ^101b and R ^101c and may form a ring, when they form a ring, R ^101b, .K indicating each is R ^101c alkylene group having 1 to 6 carbon atoms ^- .R ^101d is representative of a non-nucleophilic counter ion R ^101e , R ^101f and R ^101g are represented by adding a hydrogen atom to R ^101a , R ^101b and R ^101c , R ^101d and R ^101e , and R ^101d , R ^101e and R ^101f may form a ring. Well, when forming a ring, R ^101d and R ^101e and R ^101d and R ^101e and R ^101f represent an alkylene group having 3 to 10 carbon atoms.

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f and R ^101g may be the same as or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylethyl, 4- Examples thereof include an ethylcyclohexyl group, a cyclohexylethyl group, a norbornyl group, an adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Ethylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, diethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group, etc. Groups and the like.

Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzene. Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

  (P1a-1) and (P1a-2) have the effects of both a photoacid generator and a thermal acid generator, while (P1a-3) acts as a thermal acid generator.

(In the above formula, R ^102a and R ^102b each independently represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear or branched alkyl group having 1 to 10 carbon atoms. R ^104a and R ^104b each independently represents a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.

Specific examples of R ^102a and R ^102b include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylethyl group, 4-ethylcyclohexyl group, cyclohexylethyl group and the like.

R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like.

^Examples of R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group.

Examples of K ⁻ are the same as those described in the formulas (P1a-1), (P1a-2), and (P1a-3).

(In the above formula, R ¹⁰⁵ and R ¹⁰⁶ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogenated aryl group having 6 to 20 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like.

Examples of the halogenated alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a trifluoroethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, methylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and diethylphenyl group.

Examples of the halogenated aryl group for R ¹⁰⁵ and R ¹⁰⁶ include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group.
^Examples of the aralkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a benzyl group and a phenethyl group.

(In the above formula, R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each independently a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, aryl group or halogen having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ are each independently And represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ¹⁰⁵ is the same as described for P2.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（上記式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

(In the above formula, R ^101a and R ^101b are the same as described above.)

(In the above formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further It may be substituted with a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched group having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or an alkoxy group having 1 to 4 carbon atoms; A phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or substituted with a chlorine atom or a fluorine atom The Even if it is.)

^Examples of the arylene group for R ¹¹⁰ include a 1,2-phenylene group and a 1,8-naphthylene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a phenylethylene group, and a norbornane- 2,3-diyl group etc. are mentioned, As the alkenylene group, 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like can be mentioned.

^Examples of the alkyl group of R ¹¹¹ include the same groups as R ^{101a to} R ^101c, and examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, diethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7 -Octenyl group and the like, and the alkoxyalkyl group includes methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, methoxypropyl group, Ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl , Propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

Examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
Examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, p -Acetylphenyl group, p-nitrophenyl group, etc. are mentioned, As a C3-C5 heteroaromatic group, a pyridyl group, a furyl group, etc. are mentioned.

  Specific examples of onium salts include tetraethylammonium trifluoromethanesulfonate, tetraethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, and p-toluenesulfonic acid. Tetraethylammonium, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoro Triphenylsulfonium lomethanesulfonate, trifluoromethanesulfonic acid (p-tert-butyl) Xylphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (P-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid tri Phenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid triethylsulfonium, p-toluenesulfonic acid Liethylsulfonium, cyclohexylethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, diethylphenylsulfonium trifluoromethanesulfonate, diethylphenylsulfonium p-toluenesulfonate, Dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) ethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ethyl (2- Oxocyclopentyl) sulfonium trifluoromethanesulfona And 1,2′-naphthylcarbonylethyltetrahydrothiophenium triflate.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Etc.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-diethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-ethyl3,4-pentanedione glyoxime, bis -O- (n-butanesulfonyl) -α-diethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n Butanesulfonyl) -2-ethyl 3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-diethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-diethylglyoxime, bis-O -(1,1,1-trifluoroethanesulfonyl) -α-diethylglyoxime, bis-O- (tert-butanesulfonyl) -α-diethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α- Diethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-diethylglyoxime, bis-O- (benzenesulfonyl) -α-diethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-diethylglyoxime Oxime, bis-O- (p-tert-butylbenzenesulfonyl) -α Diethyl glyoxime, bis -O- (xylene sulfonyl)-.alpha.-diethyl glyoxime, bis -O- (camphorsulfonyl)-.alpha.-diethyl glyoxime, and the like.

  Examples of the bissulfone derivative include bisnaphthylsulfonylmethane, bistrifluoroethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.

Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

  Examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Examples include benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-triethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 -Dicarboximide p-toluenesulfonic acid ester etc. are mentioned.

Preferably, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylethyl (2-oxo) (Cyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) ethyl (2-oxocyclohexyl) sulfur Chloride, 1,2'-naphthyl carbonyl ethyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-diethylglyoxime, bis-O- (n-butanesulfonyl) -α-diethylglyoxime,
Bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid A sulfonic acid ester derivative of an N-hydroxyimide compound such as an ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, or N-hydroxynaphthalimide benzenesulfonic acid ester is used.

In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the acid generator is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 40 parts by mass with respect to 100 parts by mass of the silicone resin. If it is 0.1 mass part or more, the amount of acid generation is sufficient, and the crosslinking reaction becomes more sufficient. On the other hand, if the amount is 50 parts by weight or less, the possibility of mixing phenomenon due to the transfer of acid to the upper photoresist film is smaller.

  Moreover, a neutralizing agent can also be added to the silicon resin film material for antireflection of the present invention. The neutralizing agent is a material for preventing the generated acid from diffusing into the photoresist film applied in the next step, for example, at least selected from a methylol group, an alkoxyethyl group, and an acyloxyethyl group. An epoxy compound, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with one group can be exemplified.

  Examples of the neutralizing agent include epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.

  Specific examples of the melamine compound among the neutralizers include hexamethylol melamine, hexamethoxyethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxyethylated, and a mixture thereof, hexamethoxyethyl melamine, Examples include hexaacyloxyethyl melamine, compounds in which 1 to 5 methylol groups of hexamethylol melamine are acyloxyethylated, or mixtures thereof.

  Among the neutralizing agents, guanamine compounds include tetramethylolguanamine, tetramethoxyethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxyethylated, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine. And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxyethylated, and mixtures thereof.

  Among the neutralizing agents, as the glycoluril compound, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxyethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxyethylated, or its Examples thereof include a mixture, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxyethylated, or a mixture thereof.

  Among the neutralizing agents, examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are converted to methoxyethyl group, or a mixture thereof. It is done.

  The addition amount of the neutralizing agent is preferably 0 to 50 parts, more preferably 0 to 40 parts, with respect to 100 parts (parts by mass, the same applies hereinafter) of the light absorbing silicone resin.

  Next, as the photoresist film material used for forming the photoresist film 13 of the substrate of the present invention, a known material can be used. For example, a combination of a base resin, an organic solvent, and an acid generator can be used. As the base resin, polyhydroxystyrene and derivatives thereof, polyacrylic acid and derivatives thereof, polymethacrylic acid and derivatives thereof, a copolymer selected from hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof, Three or more copolymers selected from cycloolefin and derivatives thereof, maleic anhydride and acrylic acid and derivatives thereof, three or more copolymers selected from cycloolefin and derivatives thereof and maleimide, acrylic acid and derivatives thereof, polynorbornene And one or more polymers selected from the group consisting of metathesis ring-opening polymers. In addition, the main skeleton remains after the induction, such as acrylic acid derivatives such as acrylic acid esters, methacrylic acid derivatives such as methacrylic acid derivatives, and alkoxystyrenes such as hydroxystyrene derivatives. Means what

  In particular, as a photoresist film material for KrF excimer laser, polyhydroxystyrene (PHS), a copolymer selected from hydroxystyrene, styrene, acrylic acid ester, methacrylic acid ester, and maleimide N carboxylic acid ester Photoresist film materials for ArF excimer laser include polyacrylate ester, polymethacrylate ester, alternating copolymer of norbornene and maleic anhydride, alternating copolymer of tetracyclododecene and maleic anhydride Systems, polynorbornene systems, and metathesis polymerization systems based on ring-opening polymerization, but are not limited to these polymerization polymers.

  In the case of a positive type photoresist film material, it is common to lower the dissolution rate of the unexposed area by replacing the hydroxyl group of the phenol or carboxyl group with an acid labile group. That is, a hydrogen atom of a carboxyl group or a hydrogen atom of a phenolic hydroxyl group is substituted with an acid labile group having an alkali dissolution control ability, and the acid labile group is dissociated by the action of an acid generated by exposure to dissolve in an aqueous alkali solution. Can be used as a positive-type photoresist film material in combination with a base resin that increases the thickness.

  Examples of the organic solvent used for the photoresist film material include the same organic solvents as those for the antireflection silicon resin film material. Usual acid generators can be used. The addition amount of each component of the photoresist film material, for example, the addition amount of the base resin is the same as the addition amount of the silicone resin of the antireflection silicon resin film material of the present invention, The addition amount of the organic solvent and acid generator used is the same as that of the organic solvent and acid generator of the silicon resin film material for antireflection.

  Next, the organic film 11 of the substrate of the present invention can be formed using an organic film forming material. Examples of the resin used for the organic film forming material include resins such as cresol novolak, naphthol novolak, catol dicyclopentadiene novolak, amorphous carbon, polyhydroxystyrene, acrylate, methacrylate, polyimide, and polysulfone.

Furthermore, the workpiece substrate 10 used at this time is not particularly limited, and a silicon wafer or the like is used.
Moreover, the to-be-processed substrate 10 may be comprised by the base layer and the to-be-processed layer. In this case, the base layer of the substrate is not particularly limited, and Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc. are made of a material different from the layer to be processed. Is used. The layer to be _{processed, Si, SiO 2, SiON,} SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. various low dielectric (Low-k) film and a stopper A film is used, and can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

  The thickness of the organic film, the silicon resin film for antireflection, and the photoresist film is, for example, 50 to 2000 nm for the organic film, 10 to 2000 nm for the silicon resin film for antireflection, and 0.1 to 1 μm for the photoresist film (preferably 100 to 100 nm). 500 nm), but is not limited to this.

Next, the pattern forming method of the present invention will be described.
FIG. 3 is an explanatory view showing an example of the pattern forming method of the present invention.
For example, after the substrate 1 of the present invention is manufactured and prepared as shown in FIG. 2D, first, the pattern circuit region is exposed as shown in FIG.

Then, as shown in FIG. 3B, a resist pattern is formed on the photoresist film 13 by post-exposure baking (PEB) and development with a developer.
In the present invention, the resist pattern can be made substantially vertical at this time.

Next, as shown in FIG. 3C, the antireflection silicon resin film 12 is etched using the patterned photoresist film 13 as a mask, and the resist pattern is transferred to the antireflection silicon resin film 12. Then, a pattern is formed on the antireflection silicon resin film 12.
In order to etch the anti-reflection silicon resin film 12 using the photoresist film 13 as a mask, etching is performed using chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas or the like.

Next, as shown in FIG. 3D, the pattern formed on the antireflection silicon resin film 12 is transferred to the organic film 11 by oxygen plasma etching or the like, and the pattern is formed on the organic film 11. At this time, the photoresist film 13 is also etched away.
As the dry etching conditions, in addition to the above-described method using oxygen-containing plasma, a method using hydrogen-nitrogen-containing gas plasma can be used.

Next, as shown in FIG. 3E, the substrate 10 is etched using the organic film 11 on which the pattern is formed as a mask, the pattern is transferred to the substrate 10, and the pattern is formed on the substrate 10.
For example, if the part to be processed of the substrate 10 is silicon oxide, metal silicon, or the like, fluorine-based dry etching conditions may be used. If the fluorine-based dry etching conditions are used, the antireflection silicon resin film 12 remaining on the organic film 11 is also removed simultaneously with the etching of the substrate. However, the present invention is not limited to this, and any of the etching conditions used in the single layer resist method can be used. For example, chlorine dry etching may be performed.
As described above, in the present invention, a pattern can be formed on a substrate with high accuracy.

  Note that after the pattern is formed on the substrate 10 by the above steps, the organic film 11 remaining on the substrate 10 can be removed, for example, by etching with oxygen plasma or hydrogen-nitrogen (FIG. 3 ( f)).

EXAMPLES Hereinafter, although an Example, a comparative example, etc. are shown and this invention is demonstrated further more concretely, this invention is not limited by these description.
(Synthesis Example 1)
A 3000 ml glass flask was charged with 1400 g of ethanol, 700 g of pure water and 50 g of 25% tetraethylammonium hydroxide and stirred. To this mixture, a mixture of 78 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14 g of phenyltrimethoxysilane and 66 g of tetraethoxysilane was added dropwise at a liquid temperature of 40 ° C., and then stirred at 40 ° C. for 2 hours. . After completion of the reaction, 35 g of acetic acid was added to stop the reaction, and ethanol was distilled off under reduced pressure. To the obtained liquid, 2000 ml of ethyl acetate was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added, and the liquid temperature was heated to 40 ° C. The polymer 1 (Polymer 1) was obtained under reduced pressure.

The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.

(Synthesis Example 2)
Instead of a mixture of 78 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14 g of phenyltrimethoxysilane and 66 g of tetraethoxysilane, 52 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxysilane Polymer 2 (Polymer 2) was obtained in the same manner as in Synthesis Example 1 except that a mixture of 14 g of methoxysilane, 29 g of methyltrimethoxysilane and 44 g of tetraethoxysilane was used.

The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.

(Synthesis Example 3)
Instead of a mixture of 78 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14 g of phenyltrimethoxysilane and 66 g of tetraethoxysilane, 45 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxysilane Polymer 3 (Polymer 3) was obtained in the same manner as in Synthesis Example 1 except that a mixture of 14 g of methoxysilane, 31 g of methyltrimethoxysilane and 47 g of tetraethoxysilane was used.

The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by ¹³ C-NMR as follows.

(Synthesis Example 4)
A 2000 ml glass flask was charged with 600 g of methanol, 10 g of acetic acid, 200 g of tetraethoxysilane and 8 g of phenyltrimethoxysilane, and stirred at 40 ° C. To this mixture, 70 g of deionized water was slowly added and then stirred at 40 ° C. for 2 hours. After completion of the reaction, 600 g of propylene glycol monopropyl ether (PnP) was added, and the solvent was changed under reduced pressure while heating the liquid temperature to 40 ° C. to obtain Polymer 4 (Polymer 4).

  The molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC), and the copolymerization ratio was determined by the charged composition as follows.

Example 1
First, a 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin-containing (molecular weight 11,000) composition (28 parts by mass of resin, 100 parts of solvent) is spin-coated on a substrate, and 200 ° C. for 1 minute. Then, heating was performed to form an organic film having a thickness of 300 nm.

Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 180 ° C. for 60 seconds to form an antireflection silicon resin film having a thickness of 100 nm.
The anti-reflective silicon resin film material used at this time was 100 parts of polymer 1 obtained in Synthesis Example 1, 2000 parts of organic solvent (PGMEA), 1 part of thermal acid generator (benzyltributylammonium chloride), and interface. It contains 1 part of activator (FC-430 (manufactured by Sumitomo 3M)).

  It was 0.7 GPa when the hardness of this anti-reflection silicon resin film was measured using a nanoindenter.

  Therefore, in the same manner as described above, an organic film and an antireflection silicon resin film are formed on the substrate, and then a photoresist film material having the following composition is spin-coated on the antireflection silicon resin film, and 130 ° C. For 60 seconds to form a 200 nm-thick photoresist film.

（Ｍｅは、メチル基であり、Ｅｔは、エチル基である）
光酸発生剤 ：トリフェニルスルホニウムノナフルオロブタンスルホネート
０．２質量部
塩基性添加物：トリエタノールアミン ０．０２質量部
溶剤 ：ＰＧＭＥＡ ６００質量部
界面活性剤 ：ＦＣ−４３０（住友スリーエム社製） ０．１質量部 The composition of the photoresist film material used at this time is as follows.
Resin: Polymer A (polymer A) (refer to the following structural formula)
10 parts by mass

(Me is a methyl group and Et is an ethyl group)
Photoacid generator: Triphenylsulfonium nonafluorobutanesulfonate
0.2 parts by mass Basic additive: Triethanolamine 0.02 parts by mass Solvent: PGMEA 600 parts by mass Surfactant: FC-430 (manufactured by Sumitomo 3M) 0.1 parts by mass

  In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. 2. Development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution gave a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, no footing or the like was observed, and it was confirmed that the pattern was rectangular, that is, a substantially vertical pattern (see FIG. 4A).

Next, using this resist pattern as an etching mask, etching was performed under dry etching conditions in which the etching rate of the antireflection silicon resin film was superior to the organic material. As conditions, dry etching apparatus TE-8500P manufactured by Tokyo Electron Ltd., chamber pressure 40 Pa, RF power 1300 W, gap 9 mm, CHF ₃ gas flow rate 30 ml / min, CF ₄ gas flow rate 30 ml / min, ArF gas flow rate 100 ml / min were used. . By etching the antireflection silicon resin film by this dry etching, it was possible to form a pattern on the antireflection silicon resin film with almost no influence of the pattern change due to the side etching of the photoresist film.

Next, the substrate having the antireflection silicon resin film to which the pattern was transferred in this manner was further subjected to dry etching in which the etching rate of the lower organic film was superior to the antireflection silicon resin film. As conditions, reactive dry etching using oxygen plasma (chamber pressure 60 Pa, RF power 600 W, Ar gas flow rate 40 sccm, O ₂ gas flow rate 60 sccm, gap 9 mm) was used. By this reactive dry etching, the exposure pattern obtained as a resist pattern was transferred to the lower organic film with high accuracy.

  Next, the substrate was etched using the organic film having the pattern transferred in this way as an etching mask to form a pattern on the substrate. At this time, since the layer to be processed of the substrate was silicon oxide, fluorine dry etching conditions were used. Under these dry etching conditions, a pattern was formed on the processed layer of the substrate, and at the same time, the antireflection silicon resin film on the organic film was etched away.

Thereafter, the organic film remaining on the substrate was removed by etching with oxygen gas plasma.
When the pattern formed on the substrate was observed, it was confirmed that a good pattern was formed.

(Example 2)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 180 ° C. for 60 seconds to form an antireflection silicon resin film having a thickness of 100 nm.
The silicon resin film material for antireflection used at this time is 100 parts of the polymer 2 obtained in Synthesis Example 2, 2000 parts of the organic solvent (PGMEA), 1 part of the thermal acid generator (benzyltributylammonium chloride), and the interface. It contains 1 part of activator (FC-430 (manufactured by Sumitomo 3M)).

  It was 0.4 GPa when the hardness of this anti-reflection silicon resin film was measured using a nanoindenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. Development was performed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, it had a slightly negative profile but had no practical problem, and was almost vertical (see FIG. 4B).

  Next, in the same manner as in Example 1, the antireflection silicon resin film is etched using the photoresist film on which the resist pattern is formed as a mask, and the antireflection silicon resin film on which the pattern is formed is used as an organic mask. The film was etched, and the substrate was further etched to form a pattern on the substrate.

  When the pattern formed on the substrate was observed, it was confirmed that a good pattern was formed.

(Example 3)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 150 ° C. for 60 seconds to form an antireflection silicon resin film having a thickness of 100 nm.
The silicon resin film material for antireflection used at this time contains 100 parts of the polymer 4 obtained in Synthesis Example 4 and 2000 parts of an organic solvent (PnP).

  It was 1.1 GPa when the hardness of this antireflection silicon resin film was measured using a nanoindenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. Development was performed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, it was a substantially vertical shape with no practical problem (see FIG. 4C).

  Next, in the same manner as in Example 1, the antireflection silicon resin film is etched using the photoresist film on which the resist pattern is formed as a mask, and the antireflection silicon resin film on which the pattern is formed is used as an organic mask. The film was etched, and the substrate was further etched to form a pattern on the substrate.

  When the pattern formed on the substrate was observed, it was confirmed that a good pattern was formed.

(Comparative Example 1)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 180 ° C. for 60 seconds to form an intermediate layer having a thickness of 100 nm.
The anti-reflective silicon resin film material used at this time is 100 parts of the polymer 3 obtained in Synthesis Example 3, 2000 parts of the organic solvent (PGMEA), 1 part of the thermal acid generator (benzyltributylammonium chloride), and the interface. It contains 1 part of activator (FC-430 (manufactured by Sumitomo 3M)).

  It was 0.3 GPa when the hardness of this anti-reflection silicon resin film was measured using a nanoindenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. 2. Development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution was attempted to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, tailing was observed in the vicinity of the silicon resin film for antireflection, and it was found that it could not withstand the subsequent pattern formation (see FIG. 4D).

(Comparative Example 2)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 150 ° C. for 60 seconds to form an intermediate layer having a thickness of 100 nm.
The anti-reflective silicon resin film material used at this time is 100 parts of the polymer 3 obtained in Synthesis Example 3, 2000 parts of the organic solvent (PGMEA), 1 part of the thermal acid generator (benzyltributylammonium chloride), and the interface. It contains 1 part of activator (FC-430 (manufactured by Sumitomo 3M)).

  It was 0.2 GPa when the hardness of this silicon resin film for antireflection was measured using the nano indenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. 2. Development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution was attempted to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, a heavy tailing was observed in the vicinity of the silicon resin film for antireflection, and it was found that it could not withstand the subsequent pattern formation (see FIG. 4 (e)). .

(Comparative Example 3)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 180 ° C. for 60 seconds to form an antireflection silicon resin film having a thickness of 100 nm.
The silicon resin film material for antireflection used at this time contains 100 parts of the polymer 4 obtained in Synthesis Example 4 and 2000 parts of an organic solvent (PnP).

  It was 1.2 GPa when the hardness of this silicon resin film for antireflection was measured using the nano indenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. 2. Development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution was attempted to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, it was found that the pattern had a severe negative profile and the pattern collapse was barely observed, but could not withstand the subsequent pattern formation (FIG. 4 (f)). reference).

(Comparative Example 4)
First, in the same manner as in Example 1, an organic film was formed on a substrate.
Next, an antireflection silicon resin film material was spin-coated on the organic film and baked at 250 ° C. for 60 seconds to form an antireflection silicon resin film having a thickness of 100 nm.
The silicon resin film material for antireflection used at this time contains 100 parts of polymer 4 obtained in Synthesis Example 4 and 2000 parts of organic solvent (PnP).

  It was 1.3 GPa when the hardness of this anti-reflection silicon resin film was measured using a nanoindenter.

Therefore, after the organic film and the antireflection silicon resin film were formed on the substrate in the same manner as described above, a photoresist film was formed on the antireflection silicon resin film in the same manner as in Example 1.
In this way, a substrate was produced in which an antireflection silicon resin film was formed on the organic film, and a photoresist film was formed thereon.

  Next, the patterned circuit area of the photoresist film is exposed with an ArF exposure apparatus (Nikon Corp .; S305B, NA 0.68, σ 0.85, 2/3 annular illumination, chrome mask), and heated at 110 ° C. for 90 seconds. 2. Development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution was attempted to form a 90 nm line and space pattern.

  When the obtained positive resist pattern was observed, it was found that the pattern collapse was so severe that it could not withstand the pattern formation (see FIG. 4G).

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

It is a schematic sectional drawing which shows an example of the board | substrate of this invention. It is a schematic sectional drawing which shows an example of the manufacturing method of the board | substrate of this invention. It is a schematic explanatory drawing which shows an example of the pattern formation method of this invention. It is the photograph of the observed resist pattern (Example 1-3, Comparative Example 1-4).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 10 ... Substrate to be processed, 11 ... Organic film,
12 ... Silicon resin film for antireflection, 13 ... Photoresist film.

Claims (9)

  At least a substrate in which an antireflection silicon resin film and a photoresist film are sequentially formed on an organic film, wherein the antireflection silicon resin film has a nanoindenter hardness of 0.4 GPa or more 1 . A substrate characterized by being 1 GPa or less.   2. The substrate according to claim 1, wherein the antireflection silicon resin film is formed of a material containing a light absorbing silicone resin and an organic solvent.   The light-absorbing silicone resin comprises an organic group having one or more of a carbon-oxygen single bond and a carbon-oxygen double bond, a light-absorbing group, a terminal having Si-OH, and a Si-OR (R has 1 carbon atom. The substrate according to claim 2, wherein the substrate comprises one or more silicon atoms (which is a saturated or unsaturated alkyl group of ˜6).   4. The substrate according to claim 3, wherein the organic group of the light-absorbing silicone resin contains one or more groups selected from the group consisting of epoxy groups, ester groups, alkoxy groups, and hydroxy groups.   The substrate according to claim 3 or 4, wherein the light absorbing group of the light absorbing silicone resin includes one or more rings selected from the group consisting of an anthracene ring, a naphthalene ring, and a benzene ring. .   The substrate according to any one of claims 3 to 5, wherein the light-absorbing group of the light-absorbing silicone resin contains a silicon-silicon bond.   The substrate according to any one of claims 2 to 6, wherein the material for forming the antireflection silicon resin film further contains an acid generator.   The substrate according to any one of claims 2 to 7, wherein the material for forming the antireflection silicon resin film further contains a neutralizing agent.   A method of forming a pattern on a substrate by lithography, wherein at least the substrate according to any one of claims 1 to 8 is prepared, and after exposing a pattern circuit region of a photoresist film of the substrate, The resist pattern is formed on the photoresist film by developing with a developer, and the antireflection silicon resin film is formed by etching the antireflection silicon resin film using the photoresist film on which the resist pattern is formed as a mask. A pattern forming method comprising: etching an organic film using a film as a mask; and further etching the substrate to form a pattern on the substrate.

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