WO2007091569A1 - Method for producing film-forming material - Google Patents

Abstract

Disclosed is a method for producing a film-forming material wherein a metal compound (W) having two or more isocyanate groups is dissolved in a solvent (S). Specifically, the method for producing a film-forming material comprises a step for removing isocyanic acid in a solution (R1) which is obtained by dissolving the metal compound (W) in the solvent (S), and a step for filtering the solution (R1) in an inert gas atmosphere after the removal of isocyanic acid.

Description

 Method for manufacturing film forming material

 Technical field

 [0001] The present invention relates to the production of a film-forming material capable of forming a metal oxide film such as a silica (SiO 2) film.

 2

 Regarding the method.

 This application claims priority based on Japanese Patent Application No. 2006-033571 filed in Japan on February 10, 2006, the contents of which are incorporated herein by reference.

 Background art

 Conventionally, a chemical vapor deposition method (hereinafter referred to as a CVD method) has been used to form a silica-based film such as a SiO film.

 2

 SOG (spin-on-glass) method is used. The SOG method is generally a film containing SiO as a main component (hereinafter referred to as SOG) by applying a solution in which a key compound is dissolved in an organic solvent (hereinafter also referred to as SOG solution) and heat-treating it. Coating

 2

 (See, for example, Patent Documents 1 to 3).

 The metal oxide film such as the silica-based film is expected to be applied to various uses with high strength.

 However, when trying to form such a metal oxide film, it is necessary to perform heat treatment at a very high temperature as described above. For example, in the case of the CVD method or the SOG method, it is 400 ° C. It is necessary to bake at a high temperature of C or higher to form a dense metal oxide film. Such a high temperature process is time consuming and costly, and the production efficiency is poor.

In recent years, a sol-gel method has been proposed as a method for forming a metal oxide film at a relatively low temperature. The sol-gel method is a method using a metal compound having a functional group capable of generating a hydroxyl group by hydrolysis, forming a coating film using a solution in which the metal compound is dissolved in an organic solvent, and contacting the coating film with water. Then, in the coating film, hydroxyl groups generated by hydrolysis are dehydrated and condensed to form a metal oxide film. For example, Patent Document 4 describes a method of forming a metal oxide film using a metal compound such as a metal alkoxide.

Patent Document 1: Japanese Patent Publication No. 8-3074 Patent Document 2: Japanese Patent No. 2739902

 Patent Document 3: Japanese Patent No. 3228714

 Patent Document 4: Japanese Patent Laid-Open No. 2005-205584

 Patent Document 5: JP 2002-62667 A

 Disclosure of the invention

 Problems to be solved by the invention

However, a solution (film forming material) in which the above metal compound is dissolved in an organic solvent may cause solids (foreign matter) such as fine particles in the film forming material. In this specification, for the sake of convenience, the presence of foreign matter in the solution is defined as foreign matter characteristics. Such foreign matter may impair the smoothness of the film surface formed using the film forming material, the uniformity of the film thickness, and the like, and the improvement thereof is demanded.

 By the way, JP 2002-62667 A (Patent Document 5) discloses a method for producing a photoresist composition in which the amount of fine particles in the photoresist composition for circulating the line is reduced by passing the photoresist composition through a filter. Has been proposed.

 As described in Patent Document 5, it is known that a photoresist composition is passed through a filter in the production of a photoresist composition. The characteristics are not improved sufficiently and may be adversely affected.

[0005] Therefore, an object of the present invention is to provide a method for producing a film forming material that can form a metal oxide film at a low temperature and also has good foreign matter characteristics.

 Means for solving the problem

[0006] As a result of extensive studies, the present inventors have found that when a metal compound having an isocyanate group is used as the metal compound, the isocyanate compound S is generated by decomposition of the metal compound, and The main causes of foreign substances are compounds formed from isocyanic acid and not soluble in solvents, and the formation of isocyanic acid and the above compounds from isocyanic acid is induced by water, particularly during filtration. The present invention was completed.

That is, the method for producing a film forming material according to the aspect of the present invention is a method for producing a film forming material in which a metal compound (W) having two or more isocyanate groups is dissolved in a solvent (S). Manufacturing method,

 Removing isocyanate from the solution (R1) obtained by dissolving the metal compound (W) in the solvent (S);

 And a step of filtering the solution (R1) under an inert gas atmosphere after removing the isocyanic acid.

 In the present specification and claims, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified.

 The “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified.

 The invention's effect

 [0007] According to the present invention, it is possible to provide a method for producing a film-forming material capable of forming a metal oxide film at a low temperature and having excellent foreign matter characteristics.

 Brief Description of Drawings

FIG. 1 is a schematic configuration diagram showing an example of a filtration device used in the present invention.

 FIG. 2A is an explanatory view showing an example of a procedure of a pattern forming method using a film forming material, and describes a laminate forming process and a method of forming a resist film on an organic film of the laminate It is a figure for doing.

 FIG. 2B is an explanatory view showing an example of a procedure of a pattern forming method using a film forming material, for explaining a resist pattern forming step.

 FIG. 2C is an explanatory view showing an example of a procedure of a pattern forming method using a film forming material, for explaining a coating layer forming step.

 FIG. 2D is an explanatory view showing an example of a procedure of a pattern forming method using a film forming material, for explaining an etching process.

 Explanation of symbols

[0009] 1 substrate

 2A organic membrane

 2B organic film pattern

3A resist film 3B resist pattern

 4 Mask

 5 Coating layer

 11 Filtration equipment

 12 First filtration section

 13 Second filtration section

 14 Mother liquor reservoir

 15 Filtrate storage tank

 21-23 flow path

 31 Pressure piping

 32-33 piping

 BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The method for producing a film-forming material of the present invention is a method for producing a film-forming material in which a metal compound (W) having two or more isocyanate groups is dissolved in a solvent (S), A step of removing isocyanic acid in a solution (R1) obtained by dissolving a metal compound (W) having two or more isocyanate groups in a solvent (S) (hereinafter sometimes referred to as an isocyanic acid removing step). And, after removing the isocyanate, filtering the solution (R1) under an inert gas atmosphere (hereinafter sometimes referred to as a filtration step).

In the present invention, the foreign matter characteristics can be improved by removing isocyanic acid from the solution (R1) and further filtering the solution (R1). The following reasons are conceivable as reasons for the strong effect.

 That is, conventionally, a film forming material used in the sol-gel method is simply used by dissolving a metal compound having a functional group capable of generating a hydroxyl group by hydrolysis (metal alkoxide, etc.) in a solvent and filtering it as it is. It is common.

 However, when a metal compound (W) having two or more isocyanate groups is used, if there is water in the system, an extremely large amount of foreign matter is confirmed. According to the study by the present inventors, the main cause is generation of isocyanic acid.

Metal compounds (W) having two or more isocyanate groups are highly reactive with water. If water is present, it reacts with water and decomposes to produce isocyanic acid (HN = C = 0). For example, tetraisocyanate silane (Si (NCO)) reacts with water to produce silanol (Si (N

 Four

 It decomposes into (CO) -OH) and isocyanic acid, and silanol is structurally unstable and immediately

Three

 Reacts with (NCO) to form a silicon-based polymer and isocyanic acid.

Four

It will increase in a chain.

 Furthermore, after preparing a solution by dissolving the metal compound (w) in a solvent, when filtration is performed in the air, the metal compound in the solution comes into contact with moisture in the air and reacts to produce isocyanic acid. Will be.

 Isocyanic acid is a colorless gas (melting point: about 80 ° C) at room temperature, and is soluble in organic solvents such as ether. Isocyanic acid is a tautomer of cyanic acid and usually exists as a tautomeric mixture easily converted to cyanic acid (HO—C≡N).

 Isocyanic acid usually forms a cyclic compound such as lamellid, cyanuric acid, isocyanuric acid, etc., in which a plurality of molecules spontaneously polymerize and do not dissolve in organic solvents or hardly dissolve in these solvents. It is presumed that the product was precipitated in the solution and deteriorated the foreign material characteristics. In the present invention, by removing isocyanic acid in the solution (R1), the cause of foreign matters existing in the solution (R1) is reduced, and the solution (R1) is filtered in an inert gas atmosphere. Therefore, it is considered that the generation of isocyanic acid and the generation of cyclic compounds such as isocyanuric acid can be suppressed, and this can improve the foreign matter characteristics.

 Hereinafter, each process will be described in more detail.

<Isocyanic acid removal process>

 In the present specification and claims, “removing isocyanic acid” means reducing the concentration of isocyanic acid in the solution (R1). For example, removing isocyanic acid itself, This includes changing to a compound insoluble in the solvent (S) (for example, the above-mentioned cyclic compounds such as siamelide, cyanuric acid, and isocyanuric acid) and indirectly reducing the concentration of isocyanic acid.

 The removal methods preferably used in the present invention include the following methods (1) and (2).

Method (1): A method of degassing the solution (R1) under reduced pressure. Method (2): A method in which the solution (Rl) is allowed to stand under normal pressure.

[0013] Method (1) is preferably used when it is intended to directly remove isocyanic acid from the solution (R1). Since isocyanic acid and Z or cyanic acid are gases at room temperature, they can be removed from the solution (R1) by degassing under reduced pressure.

 The pressure during the degassing treatment is preferably set to a pressure that is lower than atmospheric pressure (atmospheric pressure (latm (101325Pa))) and that does not volatilize the solvent (S).

 Considering the stability of the metal compound (W), the temperature during the degassing treatment is preferably 10 ° C or less, more preferably 0 ° C or less. The lower limit is not particularly limited, but is preferably 5 ° C or higher in view of the removal efficiency of isocyanic acid.

 The treatment time may be appropriately determined in consideration of the type of solvent (S) to be used, degassing treatment pressure, temperature, and the like. Usually, 1 to: LO time is preferred 2 to 8 hours is more preferred.

 The deaeration process can be performed using, for example, an apparatus having a pressure reducing function such as an evaporator.

 [0014] The method (2) is preferably used when it is intended to indirectly remove the isocyanic acid in the solution (R1).

 That is, by allowing the solution (R1) to stand under normal pressure, the isocyanic acid in the solution (R1) is intentionally changed to a cyclic compound such as isocyanuric acid and deposited as a foreign substance. The amount of isocyanic acid itself in the solution (R1) is reduced.

 The deposited foreign matter can be removed in the subsequent filtration step.

 Further, before the filtration step, the solution (R1) may be separately filtered to remove foreign matters. Separately, when the solution (R1) is filtered, the filtration may be performed in the air or in an inert gas atmosphere as in the filtration step described later, but in an inert gas atmosphere. Is preferred.

 Considering the production efficiency of cyclic compounds such as isocyanuric acid, the temperature at the time of standing is preferably 10 ° C or higher, more preferably 20 ° C or higher. The upper limit is not particularly limited, but considering the stability of the metal compound (W) and the like, it is preferably 35 ° C or lower, more preferably 30 ° C or lower. Most preferred is room temperature (about 25 ° C).

The standing may be performed in the atmosphere, but since the effect of the present invention is excellent, the solution (R1) is allowed to stand still. It is preferable to perform the placement in an inert gas atmosphere as in the filtration step described later.

 The standing time may be appropriately determined in consideration of the type of solvent (S) to be used, the presence / absence of the degassing treatment, the standing temperature, and the like.

 For example, when performing a deaeration process, 10 to 24 hours are usually preferable. When deaeration treatment is not performed, 2 to 14 days is generally preferable, and 5 to 14 days is more preferable, and 7 to 14 days is most preferable.

 [0015] The methods (1) and (2) may be performed either alone or both.

 In the present invention, at least it is most preferable to perform both methods (1) and (2) where it is preferable to perform the standing of method (2).

 [0016] <Filtration process>

 Next, a filtration step is performed in which the solution (R1) after removing the isocyanic acid is filtered under an inert gas atmosphere.

 Here, in this specification and claims, the term “filtration” includes the commonly used chemical “filtration” (“the phase of a fluid using a porous membrane or phase [gas or In addition to the meaning of “permeating only the liquid” and separating the semi-solid or solid from the fluid phase ”, published on July 31, 1971, Kyoritsu Shuppan Co., Ltd. The case of passing through a membrane is also included. In other words, there are cases where what can be visually confirmed (semi-solid or solid) is separated from the fluid phase by filtration, and what is separated from the fluid phase cannot be visually confirmed. included.

In the present invention, the filtration step is performed in an inert gas atmosphere. Thereby, generation | occurrence | production of a foreign material can be suppressed and a foreign material characteristic becomes favorable.

 As described above, the isocyanate group reacts with water to produce isocyanic acid, which causes foreign matter. Therefore, by performing the filtration in an inert gas atmosphere that does not contain moisture, it is possible to suppress the generation of isocyanic acid during the filtration, and as a result, it is possible to suppress the precipitation of foreign matters.

 As the inert gas, for example, nitrogen gas, argon gas, and a mixture thereof can be used.

[0018] The temperature during filtration (temperature of the solution (R1)) is preferably 35 ° C or less, more preferably 10-30 ° C. The preferred range is 15 to 25 ° C. When the temperature is 35 ° C or lower, the stability of the metal compound (W) is good and the foreign matter characteristics are further improved.

 [0019] Filtration of the solution (R1) can be performed, for example, by passing the solution (R1) through a filter having a porous membrane.

 Here, in the present invention, the “filter” includes at least a porous membrane and a support member that supports the membrane. As a powerful filter, various materials such as ultrapure water, high-purity chemicals, fine chemicals, etc. are filtered from filter manufacturers such as Nippon Pole Co., Ltd., Advantech Toyo Co., Microlith Co., Ltd. Those with pore sizes are manufactured or sold. In the present invention, the form of the filter is not particularly limited as long as it has a membrane, and those generally used, for example, a so-called disc type, cartridge type, etc., in which a membrane is housed in a container. Etc. can be used.

 [0020] The material of the membrane is not particularly limited, and commercially available materials can be used. Specifically, a membrane made of nylon, a membrane made of polyethylene, a membrane made of polypropylene, polytetrafluoroethylene (PTFE ) And the like. These films may be used alone or in combination of two or more.

 In the filtration step, it is particularly preferable to use a filter provided with a nylon membrane (hereinafter sometimes referred to as a filter (fl)). Use of the filter (fl) improves the effect of reducing foreign matter.

 As the filter (fl), a filter with a nylon membrane that is generally commercially available, such as a filter with a nylon 6 membrane, a filter with a nylon 66 membrane, etc. can be used.

 The pore diameter of the nylon membrane used for the filter (f 1) can define a preferable range by the nominal value of the filter manufacturer. The preferable range is appropriately adjusted from the viewpoint of productivity and the effect of the present invention, depending on the combination of the filtration units (combination of filter form, membrane type, number of times of passage through the membrane, etc.).

In terms of effect, the nylon membrane in the filter (fl) preferably has a membrane pore size of 0.2 / zm or less, more preferably 0.1 m or less, and even more preferably 0.04 / zm. It is as follows. However, if it is too small, productivity (through the production and coating of film forming materials) The lower limit value is preferably about 0.01 m, because (put) tends to decrease.

More preferably, it is 0.02 / z m or more.

 In consideration of the effect of improving foreign matters and productivity, the pore diameter of the membrane used for the filter (fl) is more preferably in the range of 0.01 μm to 0.1 μm. Is 0.02 ~

0. l ^ m, more preferably 0.02-0.04 / z m. From the viewpoint of achieving both the effect of improving foreign matter and the productivity, about 0.04 m is most preferable.

[0023] The surface area (filtration area) of the filter (f 1), the filtration pressure [anti-differential pressure], and the flow rate of the solution (R1) passing through the filter (f 1) is appropriately determined depending on the throughput of the solution (R1). Adjustment is not particularly limited.

[0024] In the present invention, before passing through the filter (fl) and after Z or further,

The solution (R1) is filtered with a filter (hereinafter referred to as a polyethylene or polypropylene film).

Sometimes called filter (f2). ) Is preferable because the effect of the present invention is further improved. In particular, it is preferable to pass the filter (f 2) after passing through the filter (fl) because the force S and the effect of the present invention are further improved.

 [0025] The filter (f2) is not particularly limited as long as it is provided with a film made of polyethylene or polypropylene, and those conventionally used for filtering applications such as resist compositions can be used. Here, the polypropylene film includes a film made of high-density polypropylene (HDPE) and a film made of ultra-high molecular weight polypropylene (UPE) in addition to a normal polypropylene film.

 Specifically, examples of the polyethylene filter include “Macroguard UPE filter” (product name, manufactured by Microlith) and “Poor Polyfix” (product name, manufactured by Kick).

 Examples of polypropylene filters include “Polyfix” (product name, manufactured by Kits).

[0026] The pore diameter of the membrane used for the filter (f2) is preferably the nominal value of the manufacturer of the filter, and the range can be defined. The preferable range is appropriately adjusted from the viewpoint of productivity and the effect of the present invention, depending on the combination of the filtration units (combination of filter form, type of membrane, number of times of passage through the membrane, etc.). In terms of effect, the filter (f 2) preferably has a membrane pore size of 0.2 / zm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. It is.

 However, if it becomes too small, the productivity (throughput of the film forming material and the throughput of coating) tends to decrease, so the lower limit is preferably about 0.01 m. 0.02 m or more. In consideration of the effect of improving foreign matters and productivity, the pore diameter of the membrane used for the filter (f2) is preferably in the range of 0.01 μm to 0.1 μm. Is 0. 01-0. 04 / zm. From the standpoint of achieving both effect and productivity, 0.02 m is most preferable.

 [0027] The surface area (filtration area) of the filter (f 2), the filtration pressure [differential pressure resistance], and the flow rate of the solution (R1) passing through the filter (f 2) are determined appropriately depending on the throughput of the solution (R1), etc. Adjustment is not particularly limited.

 [0028] In the present invention, the solution (R1) and the filter (f3) other than the filter (f1) and the filter (f2) are further passed before and after passing through the filter (fl) or after Z. May be passed.

 As the filter (f3), it is possible to use a commonly used filter having a film having a material strength other than nylon, polyethylene and polypropylene, and in particular, a film made of fluorine resin such as polytetrafluoroethylene (PTFE). Prefer a filter with.

 As a filter equipped with a fluororesin membrane, specifically, PTFE “Enflon” (product name, Nippon Pall Co., Ltd., flat membrane type, pore size 0.05 m), PTFE “Fluoroline” (Product name, manufactured by Microlith, flat membrane type, pore size 0.03 m).

 [0029] The pore diameter of the membrane used for the filter (f3) is preferably the nominal value of the filter manufacturer, and the range can be defined. The preferable range is appropriately adjusted from the viewpoint of productivity and the effect of the present invention, depending on the combination of the filtration units (combination of filter form, type of membrane, number of times of passage through the membrane, etc.).

 In terms of effects, the filter (f3) preferably has a membrane pore size of 0.2 m or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less.

However, if it is too small, the productivity (through the production and coating throughput of film forming materials) G) tends to decrease, so the lower limit is preferably about 0.01 m, more preferably 0.02 m or more. In consideration of the effect of improving foreign matters and productivity, the pore diameter of the membrane used for the filter (f3) is preferably in the range of 0.01 μm to 0.1 μm. Preferably it is 0.02-0.1 m, More preferably, it is 0.02-0.06 m. From the viewpoint of achieving both effect and productivity, 0.05 m is most preferable.

 [0030] The surface area (filtration area) of the filter (f 3), the filtration pressure [differential pressure resistance], and the flow rate of the solution (R1) that passes through the filter (f 3) are determined appropriately depending on the throughput of the solution (R1), etc. Adjustment is not particularly limited.

 Hereinafter, an embodiment of the film forming material of the present invention will be described. First, FIG. 1 shows an example of a filtration device suitably used in the present embodiment.

 The filtration device 11 includes a first filtration unit 12 provided with a first filter, and a second filtration unit 13 provided with a second filter.

 The filtration device 11 includes a mother liquid storage tank 14 that stores the solution (R1), and a filtrate storage tank 15 that stores the solution (R1) that has passed through the second filtration unit 13, and the mother liquid storage tank 14 and the first filtration unit 12, between the first filtration unit 12 and the second filtration unit 13, and between the second filtration unit 13 and the filtrate storage tank 15, respectively. Contacted by 21, 22, 23.

 [0032] A pressurization pipe 31 is connected to the mother liquor storage tank 14, and an inert gas such as nitrogen gas (N) is supplied through the pressurization pipe 31 so that the solution (R1 )

 2

 Thus, the solution (R1) can be fed from the mother liquor reservoir 14 to the filtrate reservoir 15.

 The filtrate storage tank 15 includes a pipe 32 for introducing an inert gas into the filtrate storage tank 15, and a pipe for discharging excess inert gas in the filtrate storage tank 15 to the outside of the apparatus. 33 is connected.

 [0033] When using the powerful filtration device 11, the filtration step can be performed, for example, as follows.

First, an inert gas is supplied from the pressurizing pipe 31 and the pipe 32 to fill the mother liquid storage tank 14 and the filtrate storage tank 15 with the inert gas. Specifically, for example, the openings of the mother liquid storage tank 14 and the filtrate storage tank 15 are respectively connected to the flow paths 21 and 23 shown in FIG. Closed with pressure caps 14a and 15a to which pipe 31 and pipes 32 and 33 are connected, and by supplying inert gas from pressure pipe 31 and pipe 32, inside mother liquid storage tank 14 and filtrate storage tank 15 The gas phase can be replaced with an inert gas.

 Next, the solution (R1) from which isocyanic acid has been removed is placed in the mother liquor storage tank 14, and an inert gas is supplied from the pressurizing pipe 31 to pressurize it. From this point, the solution (R1) is supplied to the first filtration unit 12 and filtered through the first filter provided in the first filtration unit 12. It is supplied to the section 13 and filtered through a second filter provided in the second filtration section 13. The filtrate that has passed through the second filter is collected in the filtrate storage tank 15.

 At this time, excess inert gas in the filtrate storage tank 15 is discharged out of the apparatus through the pipe 33.

 [0034] The filtrate (film-forming material) collected in the filtrate storage tank 15 may be used as it is or stored in another container as a product. Alternatively, the filtrate may be supplied to a coating apparatus and used for film formation. It's good.

 [0035] Prior to the filtration, it is preferable to wash the first filter and the second filter in advance by flowing a cleaning solvent into the filtration device 11.

 The solvent used for cleaning is preferably the same as the solvent (S) used for the solution (R1), particularly the same solvent (S) used for the solvent (R1) to be filtered. I prefer to use! / ,.

 [0036] In the present invention, the number of times the solution (R1) is filtered (the number of times it passes through the filter), the type of the filter, and the like are not particularly limited, and can be appropriately adjusted according to the purpose.

 In the above embodiment, at least one of the first filter and the second filter

1S Filter (f 1) with nylon membrane is preferred.

 At this time, the filter (fl) may be used as the first filter, and then the filter (f2) may be used as the second filter, and the filter (fl) may be used as the second filter. Before use, the filtration step may be performed using the filter (f 2) as the first filter.

Also, both the first filter and the second filter may be the filter (f 1)! /. In this case, the filter (f 1) can be easily passed through more than once.

[0037] In the above embodiment, force indicating a step of performing filtration twice. The present invention is not limited to this. For example, the solution (R1) is directly supplied from the mother liquor storage tank 14 to the second filtration unit 13. Thus, filtration can be performed only once. Also, it is possible to perform filtration only once as described above by arranging a filter only in one of the filtration units and not arranging a filter in the other filtration unit.

 Further, after supplying the liquid to be treated (solution (R1)) to the first filtration unit 12 and / or the second filtration unit 13 by a conventional method, the obtained filtrate is recycled to the same filtration unit again. If the filtration device configuration is adopted, the solution (R1) can be easily passed through the same filter multiple times.

 [0038] The filtration device is not limited to the embodiment shown in Fig. 1, and various types of filtration devices can be adopted as long as a filter is provided on the solution (R1) flow path. . For example, a third filtration unit is provided downstream of the second filtration unit 13 of the filtration device 11 shown in FIG.

[0039] In the production method of the present invention, for example, a multi-functional coating device equipped with a coating device such as a spinner and a filtration device equipped with a filter can be used. In this case, in the same apparatus, subsequent to the production of the film forming material, a process of forming the film by applying the produced film forming material can be performed.

 In the multi-function coating device, the coating device mounted together with the filtering means is not particularly limited, and is not limited to a device having only a coating function such as a spinner, but also a developing device such as a coating and developing device. A coating device integrated with other devices can also be used.

 Such a coating apparatus usually has a coating part provided with a nozzle or the like. In the coating part, a film forming material is supplied onto the nozzle force wafer (substrate) and applied onto the wafer. It becomes the mechanism which becomes.

Therefore, as the multi-function coating device used in the present invention, before being supplied onto the wafer from this nozzle, the filtration device is placed upstream of the coating device so that the film-forming material passes through the membrane of the filtering device. Are preferably incorporated. As a result, before the material for film formation is supplied onto the wafer, the material that may cause foreign matters in the material for film formation is removed. Left.

 In addition, when comprising a coating device in this way, it is preferable that the filter is detachable from the multifunctional coating device. In other words, in a multi-function coating device equipped with a filtration device, it is preferable that only the filter can be removed and replaced.

[0040] [Material Used in Method for Producing Film Forming Material]

 The method for producing a film-forming material includes at least a solution (R1) containing a metal compound (W) having two or more isocyanate groups and a solvent (S) for dissolving the metal compound (W). Is used.

[0041] [Metal Compound (W)]

 The metal compound (W) has two or more isocyanate groups.

 The isocyanate group generates a hydroxyl group by hydrolysis. Therefore, if a film-forming material containing a metal compound (W) is applied to the pattern surface, or if water, preferably deionized water is further applied after coating, the metal is formed even at low temperatures (for example, about room temperature). The isocyanate group of the compound (W) reacts with moisture in the atmosphere or applied water, and hydrolyzes to form a hydroxyl group. The generated hydroxyl groups are dehydrated and condensed, and a plurality of metal compound (W) molecules are bonded to each other to form a dense metal oxide film having a high film density.

 Therefore, the film-forming material containing the metal compound (W) can easily form a metal oxide film with high activity without any particular heat treatment.

 Therefore, for example, when the film forming material is used to cover a pattern (resist pattern, etc.) formed on a substrate in a pattern forming method described later, the surface can be formed even under low temperature conditions of about room temperature. As a result, a pattern coated with a metal oxide film (coating pattern) is obtained and can be coated at a low temperature, so that the shape of the coated pattern is not impaired. Further, since the metal oxide film formed in this way is excellent in etching resistance, the formed coating pattern has a substrate or an organic film provided between the substrate and the coating pattern. If it is, it is useful as a mask for etching the organic film, and also useful as a mask for etching the substrate.

Further, the film forming material is applied onto the pattern to form a metal oxide film. In this case, when a functional group that reacts with the metal compound (W) (hereinafter simply referred to as a reactive group) exists on the pattern surface, the metal compound (W) reacts with the reactive group (dehydration condensation). , Adsorption, etc.) to form a metal oxide film firmly adhered to the pattern surface.

 Here, the “functional group that reacts with the metal compound (W)” means a group that forms a chemical bond by reacting with an isocyanate group and a hydroxyl group formed by hydrolysis of Z or an isocyanate group. .

 Examples of the functional group (reactive group) that reacts with the metal compound (W) include a group having a carbon-carbon double bond such as a vinyl group, a hydroxyl group, a carboxy group, and a halogen atom.

 [0043] In the metal compound (W), it is desirable that the isocyanate group is directly bonded to the metal atom.

 The number of isocyanate groups is preferably 2 or more, more preferably 2 to 4, particularly 4 per metal atom. When the number of isocyanate groups per metal atom is 2 or more, the hydroxyl groups generated by hydrolysis of the isocyanate groups undergo dehydration condensation, and multiple metal compound (W) molecules are continuously bonded together. A strong metal oxide film is formed.

[0044] In the present invention, the metal constituting the metal compound (W) includes boron, caustic, germanium, antimony, selenium, tellurium and the like in addition to ordinary metals. Suitable metals constituting the metal compound (W) include, for example, titanium, zircoum, ano- mium, niobium, silicon, boron, lanthanides, yttrium, norlium, cobalt, iron, zirconium. And metal atoms such as tantalum are preferable, and titanium and key are preferable, and key is particularly preferable.

 Further, the number of metal atoms in the metal compound (W) may be 1 or 2 or more, preferably 1.

 [0045] The metal compound (W) may have an atom other than the isocyanate group and the metal atom, and Z or a group.

The metal compound (W) may have, but examples of the other atom include a hydrogen atom. Examples of the other group that the metal compound (w) may have include an alkyl group (preferably a lower alkyl group having 1 to 5 carbon atoms), and an ethyl group and a methyl group are preferable.

[0046] The metal compound (W) is particularly preferably a compound represented by the following general formula (w-1).

M (NCO) · · · (w-1)

 a

 In the formula (w-1), M is a metal atom, and a is an integer of 2-4.

 Examples of the metal atom of M include the same as those exemplified as the “metal constituting the metal compound (W)”.

 Specific examples of the compound represented by the general formula (w-1) include tetraisocyanate silane (

Si (NCO)), titanium tetraisocyanate (Ti (NCO)), zirconium tetraisocyanate

 4 4

 1 HZr (NCO)), aluminum triisocyanate (Al (NCO)) and the like.

 4 3

 [0047] As the metal compound (W), an isocyanate group is particularly preferable because it is highly active and can easily form a metal oxide film with high etching resistance without any particular heat treatment. A key compound having 2 or more is particularly preferable, and a key compound having 2 to 4 isocyanate groups is preferable.

 The number of key atoms in one molecule of the key compound may be 1 or 2 or more, preferably 1. Among these, a compound represented by the following general formula (W-2) is preferable.

 Si (NCO) (2)

 b

 In the formula (w-2), b is an integer of 2 to 4, and is preferably 4.

[0048] The metal compound (W) may be used alone or in combination of two or more.

[0049] [Solvent (S)]

 As the solvent (S), a solvent that dissolves the metal compound (W) is used. In the present invention, since the solvent) is excellent in the effects of the present invention, it is preferable that the solvent does not have a functional group that reacts with the metal compound (W)! / Sodium solvent (S 1). If the solvent (S 1) has no functional group, the metal compound (W) is stably present in the solvent (S), so that the film-forming ability of the obtained film-forming material is improved. .

The solvent (S1) may be selected from conventionally known organic solvents as long as it does not have a functional group that reacts with the metal compound (W) and can dissolve the metal compound (W) to be used. It is possible to be.

 Examples of the functional group that reacts with the metal compound (W) are the same as those mentioned in the section of the metal compound (W).

 [0050] In the present invention, the solvent (S) may have been dehydrated in advance before dissolving the metal element compound (W), that is, before preparing the solution (R1). preferable. By using such a solvent, the effect of the present invention is further improved. That is, as described above, water is involved in the generation of isocyanate. Therefore, by removing the water in the solvent) in advance, the generation of isocyanic acid during the preparation of the solution (R1) can be suppressed, and the foreign matter characteristics are further improved.

 The dehydrated solvent may be a commercially available solvent that may be prepared by dehydrating the solvent to be used before preparing the solution (R1). In particular, it is preferable to perform a dehydration treatment immediately before preparing the solution (R1) (for example, within 12 hours).

 The dehydration treatment of the solvent can be performed by a known method, and examples thereof include a method of evaporating the solvent at a temperature of about 50 to 100 ° C.

 The moisture content in the dehydrated solvent is preferably 5 ppm or less, more preferably 3 ppm or less, and most preferably 1 ppm or less.

 The water content in the solvent can be measured by a commercially available moisture measuring device such as a moisture measuring device CA-100 manufactured by Daiinsmenm Co., Ltd.

[0051] In the present invention, the solvent (S1) preferably has a boiling point of 155 ° C or higher, more preferably 160 ° C or higher, and further preferably 165 ° C or higher. By using a strong solvent, the coating selectivity is improved. For example, the film forming material is formed on the organic film of the laminate including the substrate and the organic film according to the pattern forming method described later. The pattern surface can be selectively coated, for example, when used to coat a patterned pattern (such as a resist pattern). In addition, since the pattern surface can be selectively coated, an organic film such as an organic BARC (Bottom Antireflective Coating) developed on the lower substrate of the non-pattern part (hereinafter referred to as “non-pattern”). Etching selectivity to “partial substrate etc.” is also good.

The upper limit of the boiling point is not particularly limited, but it is preferably 300 ° C or lower in consideration of applicability and the like. More preferably 250 ° C or less.

 Here, in this specification, the “etching selection ratio” means a coating pattern and a non-pattern part when etching a non-pattern part substrate or the like using a pattern (cover pattern) covered with a metal oxide film as a mask. This means the difference in apparent etching rate between the substrate and the like.

 Normally, when a film-forming material is applied to the pattern surface, especially when an organic film such as organic BARC is provided on the substrate, the surface of the non-patterned substrate or the like where the coating selectivity is low is also a metal oxide film. It will be covered. Therefore, when etching is performed using a pattern (covering pattern) covered with a metal oxide film as a mask, etching of the non-battery substrate or the like is hindered by the metal oxide film, and apparently the coating pattern and There is a problem that a sufficient etching selectivity cannot be obtained between the non-patterned part substrate and the like.

 However, by using the solvent (S1) as described above, the coating selectivity is improved and the etching selectivity with respect to the non-patterned portion is improved. This is because the solvent (S1) hardly volatilizes after the film forming material containing the solvent (S1) is applied on the pattern and before the metal compound (W) is hydrolyzed to form a film. It is presumed that. That is, in the process of etching using the pattern formed on the substrate as a mask, after a film-forming material is applied on the pattern to form a coating film, the solvent in the coating film becomes a metal. If the compound (W) volatilizes before it hydrolyzes into a film, the metal compound (W) is physically adsorbed on the surface of the non-patterned substrate as well as the pattern surface, and the metal oxide. A film is formed, which may reduce the apparent etching selectivity. On the other hand, it is presumed that by containing a solvent having a boiling point of 155 ° C. or higher, volatilization of the solvent (S) is suppressed and these problems are improved.

In particular, as will be described later, when the surface is washed (rinsed) after the film forming material is applied, the etching selectivity with respect to the non-patterned substrate or the like is further improved. This is because the solvent (S) remains with almost no volatilization until cleaning, so the metal compound (W) on the pattern surface, which adheres relatively strongly due to chemical adsorption or the like, is cleaned. However, the metal compound (W) on the surface of the non-patterned substrate, etc., which remains relatively weak due to physical adsorption or the like, is removed by washing, and as a result, the surface of the non-patterned substrate etc. Acid It is presumed that almost no material film is formed.

 Here, “chemical adsorption” in this specification refers to a functional group (preferably a hydroxyl group or a carboxy group) that reacts with a metal compound (W), which exists on the surface of a pattern such as a resist pattern, and a metal compound. A chemical bond (covalent bond, hydrogen bond, coordination bond, etc.) or electrostatic bond (ionic bond, etc.) is formed between (W) and a metal compound (

W) and its metal ions are combined!

 “Physical adsorption” means that the metal compound (W) or its metal ion is bound to the surface of the pattern underlayer film by weak intermolecular forces such as van der Waalska. To do.

 [0054] The solvent (S1) is preferably an aliphatic compound because it is excellent in the effects of the present invention. The aliphatic compound may be a chain compound having no ring in its structure. In addition, even if it is a cyclic compound having a ring in its structure, the cyclic compound is preferable. Further, the cyclic compound is preferably a hydrocarbon, particularly a saturated hydrocarbon. Examples of such cyclic compounds include monocycloalkanes, polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes, and compounds in which substituents such as alkyl groups are bonded to these rings. Can be illustrated. The alkyl group as a substituent is preferably a lower alkyl group having 1 to 5 carbon atoms.

 Examples of the chain compound include n-hexane (boiling point: about 69 ° C), n-heptane (boiling point: about 98 ° C), and the like.

 Examples of the cyclic compound include a compound represented by the general formula (s-1) described later.

 [0055] As the solvent (S1), it is preferable to select a solvent having a small influence on the environment.

Examples of such a solvent include a solvent whose starting material is a natural substance. Solvents whose starting materials are natural substances include, for example, terpene solvents obtained from plant essential oil components (for example, monocyclic monoterpenes such as p-menthane, o-menthane, m-menthane described later, pinane, etc. And bicyclic monoterpenes). [0056] Further, in the present invention, when the film forming material is used to cover a pattern (resist pattern or the like) formed on the substrate in the pattern forming method described later, the solvent (S1) It is preferable to select and use one that does not dissolve the pattern. Therefore, it is difficult to damage the shape of the pattern when a metal oxide film (coating film) is formed on the pattern surface using a film forming material.

 [0057] As the solvent (S1), in particular, a compound represented by the following general formula (s-l) (hereinafter referred to as a compound (s

 1)) does not react with the metal compound (W), is excellent in the effects of the present invention, has little influence on the environment, and is coated with the film-forming material in the pattern forming method described later. This is preferable in that the pattern (resist pattern or the like) is not dissolved.

 [0058] [Chemical 1]

[Wherein R ^{21 to} R ²³ are each independently a hydrogen atom or a linear or branched alkyl group, and at least two of R ^{21 to} R ²³ are alkyl groups, and the alkyl group May be bonded to a carbon atom other than the carbon atom to which the alkyl group is bonded in the cyclohexane ring to form a ring. ]

During [0059] formula (s-1), among R ²¹ to R ^23, at least two linear or branched alkyl group. That is, in compound (s-1), two of R ^{21 to} R ²³ may be linear or branched alkyl groups, and the other one may be a hydrogen atom. R ^{21 to} R ²³ May be all linear or branched alkyl groups. In the present invention, it is preferable that two of R ^{21 to} R ²³ are linear or branched alkyl groups.

[0060] The linear or branched alkyl group of R ^{21 to} R ²³ is more preferably 1 to 3 carbon atoms, which is preferably a lower alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a neopentyl group. Of these, a methyl group or an isopropyl group is preferred. ^At least two alkyl groups from ¹ to may be the same or different.

In the present invention, it is preferable that at least one of R ^{21 to} R ²³ is a branched alkyl group, and it is particularly preferable that at least one is an isopropyl group.

 The compound (s-1) particularly preferably has both an isopropyl group and a methyl group.

[0061] The alkyl group of R ^{21 to} R ²³ may be bonded to a carbon atom other than the carbon atom to which the alkyl group is bonded in the cyclohexane ring to form a ring! /.

 Here, an alkyl group is “bonded to a carbon atom other than the carbon atom to which the alkyl group is bonded in the cyclohexane ring to form a ring”, by removing one hydrogen atom from the alkyl group. Means that the carbon atom on the cyclohexane ring to which the alkyl group is bonded and the other carbon atom are bridged by the other group (alkylene group).

[0062] The bonding positions of R ^{21 to} R ²³ are not particularly limited, but at least two alkyl group forces are respectively 1-position and 4-position (para-position), or 1-position and 3-position of the cyclohexane ring. It is preferable to combine with (meta position)! /.

 [0063] As the compound (s-1), specifically, p-menthane (boiling point: about 170 ° C), m-menthane (boiling point: about 170 ° C), 0-menthane (boiling point: about 170 ° C), Pinane (boiling point: about 169 ° C) and the like. These structures are shown below.

 In the present invention, in particular, the solvent (S1) is preferably p-menthane because the effects of the present invention are excellent.

 [0064] [Chemical 2]

-Mentane m-Meletane -Mentane pinane Solvent (S1) may be used alone or in combination of two or more. The ratio of the solvent (SI) in the solvent) is preferably in the range of 50-: LOO mass%. 80-: LOO mass% is more preferable, and most preferably 100 mass%.

[0066] In the present invention, the solvent (S) is a solvent having a functional group that reacts with the solvent (S2) other than the solvent (S1), that is, the metal compound (W), as long as the effects of the present invention are not impaired. It is possible to contain it.

 Examples of the solvent (S2) include alcohols such as methanol, ethanol, and propanol; aromatic compounds such as toluene, benzene, and cumene, and cumene (boiling point: about 152). ° C) is preferred.

 The solvent (S2) may be used alone or in combination of two or more.

 [0067] The amount of the solvent (S) used is not particularly limited, but preferably the molar concentration in the film-forming material (the total of the metal compound (W) and an organic compound described later used as necessary). The concentration is 1 to 200 mM, preferably 50 to 150 mM, more preferably 50 to LOOmM. A molar concentration within this range is preferable because a more uniform film can be formed.

 [0068] [Optional components]

 In addition to the metal compound (W) and the solvent (S), an optional component may be added to the solution (R1).

 Examples of the optional component include organic compounds. As a result, a composite film of a metal oxide and an organic compound can be formed.

 The organic compound is not particularly limited as long as it is soluble in the solvent (S) described above. The term “dissolution” as used herein is not limited to the case where the organic compound is dissolved alone, but also includes the case where it is dissolved in a solvent such as black mouth form by complexing with a metal alkoxide, such as 4-phenylazobenzoic acid. It is.

 There are no particular restrictions on the molecular weight of organic compounds.

[0069] The organic compound includes a plurality of reactive groups (preferably from the viewpoint of further strengthening the strength of the metal oxide film and the adhesion to a pattern such as a resist pattern coated with the metal oxide film. It is preferable to use one having a hydroxyl group or a carboxy group and having a solid property at room temperature (25 ° C.). Examples of such organic compounds include polymer compounds having a hydroxyl group or a carboxy group such as polyacrylic acid, polybutyl alcohol, polybutylphenol, polymethacrylic acid, and polyglutamic acid; starch, glycogen, colominic acid, and the like. Saccharides; disaccharides such as glucose and mannose; monosaccharides; volfilin compounds having a hydroxyl group or a carboxy group at the end, dendrimers, and the like are preferably used.

 Moreover, a cationic polymer compound can also be preferably used as the organic compound. Metal alkoxides and metal acid hydrates can interact strongly with the cations of the cationic polymer compound so that a strong bond can be realized. Specific examples of the cationic polymer compound include PDDA (polydimethyldiallyl ammonium chloride), polyethyleneimine, polylysine, chitosan, and a dendrimer having an amino group at the terminal.

[0070] These organic compounds function as structural components for forming a thin film having high mechanical strength. In addition, as a functional site for imparting a function to the obtained thin film, or as a component for removing holes after film formation and forming pores corresponding to the molecular shape in the thin film. Is also possible.

 The organic compounds can be used alone or in combination.

 When blending organic compounds, the blending amount is 100 parts by weight of metal compound (W).

0.1 to 50 parts by weight is preferable 1 to 20 parts by weight is particularly preferable.

[0071] [Film-forming material obtained by the method for producing a film-forming material of the present invention]

 The film-forming material obtained as described above is excellent in the foreign matter characteristics in which the amount of foreign matter in the solution is small. In addition, the generation of foreign matter over time during storage is suppressed, and the foreign matter temporal characteristics (storage stability) are also good.

[0072] The foreign matter characteristics and foreign matter aging characteristics in the film-forming material can be evaluated by measuring the number of foreign matters using a particle counter, for example.

 For example, the foreign material characteristics can be measured by measuring the value immediately after filtration of the film-forming material using, for example, an in-liquid particle counter (Rion, product name: particle sensor KS-41 or KL-20K). Can be evaluated.

In addition, the aging characteristics of the foreign matter are the above-mentioned foreign matter characteristics after freezing, refrigeration, or storage at room temperature (25 ° C). It can be evaluated in the same way as sex.

The particle counter counts the number of particles with a particle size of 0.15 m to 0.3 m or more per lcm ³ . The limit of measurement is usually more than 20,000 Zcm ³ rank. Specifically, the particle sensor KL 22 can measure the number of particles having a particle size of 0.15 m or more.

[0073] A film formed using the film-forming material has excellent surface smoothness, uniformity of film thickness, and the like because of excellent foreign matter characteristics and the like.

 By using such a film forming material, a uniform film with high etching resistance can be formed on the pattern surface at a low temperature.

[0074] A film-forming material produced by the method for producing a film-forming material of the present invention (hereinafter sometimes simply referred to as a film-forming material of the present invention) has high etching resistance and is low in temperature. Since a film that can be formed can be formed, it is useful as a pattern coating material used in a process of etching using a pattern formed on a substrate as a mask.

 That is, conventionally, the silica film has been formed by a method that requires high-temperature treatment such as the SOG method. However, when a brilliant method is applied to the above process, the pattern to be covered by the high-temperature treatment is thermally damaged. Will be caused. On the other hand, since the film forming material of the present invention can form a metal oxide film at a low temperature, the coating layer having high etching resistance without impairing the shape of the pattern covered with the film forming material. Can be formed.

 In this case, the pattern to be coated includes a nanoimprint pattern, a resist pattern using a resist composition, and the like, and a resist pattern is preferable from the viewpoint of fine processing.

 In particular, the film-forming material of the present invention is suitably used when the pattern is formed on the organic film of a laminate including a substrate and an organic film. That is, the film forming material of the present invention is particularly preferably used for a pattern forming method as described later.

This is because a coating pattern having an excellent etching selectivity with respect to the organic film can be obtained. When etching is performed using the coating pattern as a mask, the organic film without damaging the pattern shape can be etched. Therefore, a pattern with a high aspect ratio is formed. This is preferable.

 The aspect ratio is expressed as the ratio of the pattern height to the width below the pattern (substrate side).

 The organic film may be etched by oxygen plasma etching or CF gas.

 It is preferable from the viewpoint of efficiency that 4 uses etching using CHF gas. These guys

Three

 The film-forming material of the present invention exhibits good etching resistance even with respect to the ching method. Of these, oxygen plasma etching is preferred.

In addition, according to the film forming material of the present invention, a uniform film can be formed. Therefore, when etching is performed using the covering pattern covered with the metal oxide film as a mask, the pattern surface (metal) Occurrence of pinholes in the oxide film) and peeling of the metal oxide film are suppressed. Therefore, when the substrate is etched using the pattern covered with the metal oxide film and the pattern formed on the organic film as a mask, and then the pattern is transferred to the substrate, it is transferred to the substrate. The shape of the pattern to be formed, resolution, etc. are improved

 In addition, the pattern can be covered by low-temperature treatment (a metal oxide film can be formed by heat treatment or a metal oxide film can be formed without heat treatment). Since the processing method is simple, production efficiency can be improved and costs can be reduced, and it can be applied to patterns made of various materials.

Hereinafter, an embodiment of a pattern forming method using the film forming material will be described.

 The pattern forming method of the present embodiment includes a step of covering a pattern formed on the organic film of a laminate including a substrate and an organic film using the film forming material,

 Etching the organic film using a pattern coated with the film forming material as a mask.

[0078] Each step can be performed using a conventionally known method except that the pattern is coated with the film forming material of the present invention.

 The pattern covered with the film forming material can be formed by using a conventionally known pattern forming technique such as an imprint method or a lithography method. In particular, the lithospheric method is preferable for forming a fine pattern with high accuracy.

As described above, as described above, nanoimprint pattern, resist composition Resist patterns etc. are used, and resist patterns are preferred!

 Hereinafter, a preferred example of the pattern forming method of the present invention will be described step by step with reference to FIGS. 2A to 2D.

 2A to 2D show an example of the procedure of the pattern forming method of the present invention. In this example, as shown in FIG. 2A, the pattern forming method includes a step of forming an organic film 2A on a substrate 1 to obtain a laminate (hereinafter referred to as a laminate formation step),

 A resist film 3A is formed on the organic film 2A of the obtained laminate, and the resist film 3A is selectively exposed to form a resist pattern 3B as shown in FIG. , Referred to as resist pattern forming step)

 On the resist pattern 3B, as shown in FIG. 2C, a step of forming the covering layer 5 using the film forming material of the present invention (hereinafter referred to as a covering layer forming step);

 Using the resist pattern 3B covered with the coating layer 5 as a mask, the organic film 2A underneath is etched to form an organic film pattern 2B as shown in FIG. 2D (hereinafter referred to as an etching process). And done.

 Hereinafter, each step will be described more specifically.

[0080] [Laminate Forming Step]

 First, as shown in FIG. 2A, an organic film 2A is formed on a substrate 1.

 The substrate 1 is not particularly limited, and a conventionally known substrate can be used. Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.

[0081] The organic film 2A is formed by, for example, applying an organic film material in which a resin component or the like is dissolved in an organic solvent to the substrate 1 with a spinner or the like, preferably at 200 to 300 ° C for 30 to 300 seconds, preferably It can be formed by beta treatment under heating conditions of 60 to 180 seconds.

The thickness of the organic film 2A is preferably 10 to 500 nm, more preferably 50 to 450 nm. By setting it within this range, there are effects such that a pattern with a high aspect ratio can be formed and sufficient etching resistance can be ensured during substrate etching. The organic film material will be described later.

 [0082] [Resist pattern forming step]

 Next, a resist film 3A is formed on the organic film 2A in the laminated body composed of the substrate 1 and the organic film 2A thus formed.

 For the resist film 3A, for example, a resist composition is applied on the organic film 2A with a spinner or the like. It can be formed by applying a prebeta for 40 to 120 seconds, preferably 60 to 90 seconds under the temperature condition of C.

 The thickness of the resist film 3A is preferably 50 to 500 nm, more preferably 50 to 450 nm. By setting it within this range, there are effects that a resist pattern can be formed with high resolution and sufficient resistance to etching is obtained.

 The material for the resist composition will be described later.

[0083] Then, the resist film 3A is exposed through the mask 4, and PEB (post-exposure heating) is applied for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150 ° C. Te subjected, for example, 0.1 to 10 weight _^0/0 tetramethylammonium concentrations - with al force re developed with Umuhidorokishido (TMAH) aqueous solution, the exposed area is removed, as shown in FIG. 2B, on the organic film 2A Resist pattern 3B is formed.

 In this example, the resist composition is a positive type.

[0084] [Coating layer forming step]

 Next, as shown in FIG. 2C, a coating layer 5 is formed on the resist pattern 3B using the film forming material of the present invention.

Specifically, a film-forming material is applied to the surface of resist pattern 3B to form a coating film, and then the coating film 5 is washed with an organic solvent and dried to form coating layer 5 The That is, after forming the coating film, washing is performed to remove excess metal compound (W) (for example, metal compound (W) attached on the organic film), and then drying is completed. In addition, the metal compound (W) in the coating film is gradually hydrolyzed by moisture in the air to generate a hydroxyl group, and this hydroxyl group is dehydrated and condensed to form a metal oxide on the surface of the resist pattern 3B. A thin film (covering layer 5) is formed. When the film-forming material contains an organic substance (organic compound), a composite thin film (thin film composite film) of the organic substance and the metal oxide is formed. It is. According to a powerful method, a film can be formed at a low temperature (for example, room temperature).

 At this time, if the resist pattern 3B has a reactive group (preferably a hydroxyl group or a carboxy group), this reactive group reacts with a functional group (such as a isocyanate group) of the metal compound (W) contained in the film forming material. Or, it is adsorbed and the bond between the resist pattern 3B and the coating layer 5 becomes strong, which is preferable.

 The operation for forming the coating layer 5 is preferably performed in an inert gas atmosphere from the viewpoint of reactivity control. In this case, it will be processed without using moisture in the air.

As a coating method of the film forming material, a known method can be used. For example, a method of immersing the laminate on which the resist pattern 3 B is formed in the film forming material (dip coating method), film shape An example is a method of applying the composition material onto the resist pattern 3B by spin coating. It can also be formed by a method such as an alternating adsorption method.

 [0086] The temperature at which the film-forming material is applied onto the resist pattern 3B (application temperature) varies depending on the activity of the metal compound (W) used, and cannot be generally limited. What is necessary is just to determine within the range of 0-100 degreeC.

 In addition, the time required for applying a film-forming material on the resist pattern 3B and drying it (including coating, washing, and adsorption treatment performed as necessary), that is, the coating film before hydrolysis The contact time between the resist pattern 3B and the temperature between the resist pattern 3B (contact temperature) varies depending on the activity of the metal compound (W) used, and cannot be generally limited. What is necessary is just to determine within the range similar to the said coating temperature.

 [0087] As the organic solvent used for washing, the same solvents as those mentioned as the solvent (S) for the film-forming material can be preferably used.

For cleaning, for example, a method of supplying an organic solvent to the surface of a coating film made of a film-forming material by spraying or the like, and then sucking excess organic solvent under reduced pressure, or a method of immersing and cleaning in an organic solvent A spray cleaning method, a steam cleaning method, and the like are preferably employed. The temperature condition during the cleaning is preferably the same temperature as the operation temperature for applying the film forming material. [0088] In the present invention, after a film-forming material is applied to the surface of the resist pattern 3B, cleaning is performed to remove excess metal compound (W) on the resist pattern 3B and the organic film 2A. Thus, a film excellent in film thickness uniformity can be formed. That is, when cleaning is performed, for example, the metal compound (W) adsorbed mainly by weak physical adsorption is removed, and the chemically adsorbed metal compound (W) remains uniformly on the surface of the resist pattern 3B. A nanometer-level thin film is formed with a uniform film thickness, extremely high accuracy, and high reproducibility. Therefore, the intensive cleaning operation is particularly effective when chemical adsorption occurs between the resist pattern 3B and the metal compound (W).

 Furthermore, by performing the cleaning, the coating layer 5 has an excellent etching selectivity with respect to the organic film 2A. That is, the organic film material usually used as organic BARC or the like has almost no reactive group such as a hydroxyl group, and therefore, chemical adsorption hardly occurs with the metal compound (W). On the other hand, since the resist pattern contains a relatively large amount of reactive groups such as hydroxyl groups, chemical adsorption tends to occur. However, physical adsorption may occur in any layer, and if cleaning is not performed, a coating layer is formed on the surface of the organic film 2A due to excess metal compound (W), and the etching selectivity is reduced. There is a fear. However, by performing the cleaning operation, a coating layer is formed on the surface of the organic film 2A, and the etching selection ratio is improved.

 [0089] After washing, the membrane surface is dried. As the drying method, a known method with no particular limitation can be used. For example, a drying gas such as nitrogen gas may be used. When a film forming material is applied using a spinner, the material is shaken off as it is. Let's dry it.

 [0090] In this step, during the period from application of the film-forming material to drying, chemical adsorption between the resist pattern 3B and the metal compound (W) in the coating and Z or You may perform the process of leaving to advance physical adsorption | suction.

[0091] In the present invention, after washing the coating film and before drying, the coating film and water are brought into contact with each other to hydrolyze the metal compound (W) on the film surface, thereby generating a hydroxyl group on the film surface. Hydrolysis may be performed. As a result, a coating layer in which a plurality of coating films are laminated is formed, and the thickness of the coating layer 5 can be adjusted as described later. That is, the hydroxyl group formed on the surface of the coating film and the metal compound in the coating film formed by coating the film-forming material thereon ( reacts with w) and adheres firmly, and a coating layer in which a plurality of coating films are laminated is obtained.

 As a means for the hydration treatment, a known method can be used without particular limitation. For example, the sol-gel method in which the coating film is brought into contact with water is the most common. More specifically, there are a method of applying water to the surface of the coating film, and a method of immersing the laminate on which the coating film is formed in an organic solvent containing a small amount of water.

 When the metal compound (W) includes a compound having high reactivity with water, it is hydrolyzed by reacting with water vapor in the atmosphere by leaving it in the air. May be.

 As water, it is preferable to use deionized water in order to prevent contamination of impurities and produce high-purity metal oxides.

 In addition, by using a catalyst such as an acid or a base in the hydrolysis treatment, the time required for these steps can be significantly shortened.

 [0092] The thickness of the coating layer 5 is preferably 0.1 nm or more, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. By setting the thickness to 0.1 nm or more and 50 nm or less, there is an effect that sufficient resistance to etching, preferably dry etching can be obtained.

 [0093] The thickness of the coating layer 5 can be adjusted, for example, by repeatedly applying, cleaning, and hydrolyzing the film-forming material. That is, a uniform film having a desired thickness is formed by applying a film-forming material to form a coating film, washing it, leaving it if necessary, and repeating a series of hydrolysis treatments. A thin film can be formed.

 By such an operation, for example, the coating layer 5 having a thickness of several nanometers to several tens of nanometers, and depending on conditions, can be formed with high accuracy.

 For example, when a film forming material containing a metal alkoxide containing one kind of metal atom such as silicon tetraisocyanate or titanium butoxide is used as the metal compound (W), depending on the contact conditions, several angstroms (note that 1 angstrom is used) = 0.lnm A thin film having a thickness of) can be sequentially laminated.

 In this case, the increase in film thickness per cycle corresponds to the number of times the film forming material is stacked.

On the other hand, when alkoxide gel fine particles are used as the metal compound (W), one cycle On the other hand, a thin film having a thickness of about 60 nm can be laminated. In addition, when forming a coating film with a film-forming material by spin coating, the film thickness can be changed from several nm to 200 nm by changing the concentration of the solvent used, the metal compound (W), the spin speed, etc. It can be controlled arbitrarily.

 At that time, by changing the type of the metal compound (W) used for each cycle, it is also possible to obtain a laminate in which thin films of different types of metal oxides (W) are laminated.

[0094] The size of the total thickness (height) of the organic film pattern 2B, the resist pattern 3B, and the coating layer 5 takes into consideration the aspect ratio of the target pattern and the time required for etching the organic film 2A. From the balance of throughput, the total is preferably 1 μm or less, more preferably 0. or less, and most preferably 0.5 m or less. The total lower limit is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more.

 [0095] [Etching step]

 Next, as shown in FIG. 2C, the resist pattern 3B coated with the coating layer 5 is used as a mask, and the organic film 2A under the resist pattern 3B is preferably etched by dry etching. As a result, the organic film 2A and the organic film pattern 2B are formed, and a high aspect ratio pattern in which the resist pattern 3B is laminated on the organic film pattern 2B can be formed (FIG. 2D). The etching method includes oxygen plasma etching and CF gas from the viewpoint that the resist pattern 3B is sufficiently protected against etching by the coating layer 5 and production efficiency.

 Oxygen plasma etching is preferred where etching with 4 gas or CHF gas is preferred

 3 As the material of the organic film 2A, as will be described later, etching is performed by oxygen plasma etching such as novolac resin and halogen gas, specifically CF gas or CHF gas.

It is preferable to use a material with a relatively high resistance to fluorocarbon gases such as 4 3 In general, since etching of the substrate 1 and the like is performed using a halogen gas such as a fluorocarbon-based gas, the organic film pattern 2B is formed by forming the organic film 2A from the above materials. In addition to improving workability using oxygen plasma etching, in post-processes using halogen gases such as fluorocarbon gases that etch the substrate 1 etc. Etchability can be improved.

 [0096] Further, a semiconductor device or the like can be manufactured by performing a process of processing the substrate 1 thereunder by etching using the pattern thus obtained as a mask.

 Etching using halogen gas is preferred at this time, etching using fluorocarbon gas is preferred, especially etching using CF gas or CHF gas

 4 3

 Is preferred.

 The covering layer 5 exhibits the function of protecting the resist pattern 3B when the organic film 2A is etched, but when the substrate 1 is etched, it exhibits the function of protecting the organic film pattern 2B and the pattern that also has the resist pattern 3B force. The etching resistance of this laminated pattern can be improved.

 Here, as shown in FIG. 2C, the example in which the coating layer 5 is provided on the upper surface and the side wall of the resist pattern 3B has been described. However, the coating layer 5 is provided only on the upper surface and is not provided on the side wall. You can also. In order to enhance the function of the organic film 2A as an etching mask, it is preferable to provide the covering layer 5 on the upper surface and the side wall.

 In this example, the method of forming a pattern in which the organic film 2A and the resist film 3A are laminated has been described. However, for example, a coating layer having a film forming material force is formed on the pattern directly formed on the substrate 1. Then, using the pattern having the coating layer as a mask, the underlying substrate can be etched. In this case as well, the pattern is protected by the coating layer, so that it can withstand severe etching conditions with high etching resistance.

[0098] [Resist composition (pattern forming material)]

 A resist composition suitably used for forming a pattern such as the resist pattern 3B shown in FIG. 2B contains an organic compound having a hydrophilic group and a molecular weight of 500 or more. By adopting such a configuration, it is possible to satisfactorily form a coating layer such as a film forming material on the pattern formed by the composition force, and as a result, it is possible to obtain a pattern having a good shape. .

That is, when a hydrophilic group is present on the pattern surface, the hydrophilic group can be used as a functional group (reactive group) that interacts with the material of the coating layer formed on the pattern. Thereby, a coating layer with high adhesiveness with a pattern can be formed. Also pattern A high-density coating layer can be formed thereon, and a pattern having a good mechanical strength can be obtained.

 Further, when the molecular weight of the organic compound is 500 or more, a nano-level pattern can be easily formed.

 [0099] Organic compounds having a molecular weight of 500 or more blended in the resist composition are roughly classified into low molecular compounds having a molecular weight of 500 to 2000 and high molecular compounds having a molecular weight of more than 2000. In the case of a polymer compound, the “molecular weight” is the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

 [0100] The hydrophilic group in the organic compound contained in the resist composition is preferably a hydroxyl group, a carboxy group, a carbo group (C (O) —), an ester group (ester bond; C (O) — O —). One or more selected from the group power of amino group and amide group are used. Of these, a hydroxyl group, particularly an alcoholic hydroxyl group or a phenolic hydroxyl group, a carboxy group, and an ester group are more preferable.

 Of these, a carboxy group, an alcoholic hydroxyl group, and a phenolic hydroxyl group are particularly preferred because they easily form a coating layer on the pattern surface. In addition, a pattern with small line edge roughness (unevenness on the pattern side wall) can be formed at the nano level, which is preferable.

 [0101] The content ratio of the hydrophilic group in the organic compound contained in the resist composition affects the amount per unit area of the hydrophilic group present on the pattern surface. Therefore, the adhesion and density of the coating layer formed on the pattern can be affected.

 When the organic compound is the polymer compound, it preferably has a hydrophilic group of 0.2 equivalent or more, more preferably 0.5 to 0.8 equivalent, still more preferably 0.6 to 0.75 equivalent. It is. This is because when the polymer compound has a structural unit having a hydrophilic group and other structural units, the former structural unit is 20 mol% or more, more preferably 50 to 80 mol%, more preferably 60 mol. % To 75 mol%.

 In the present specification, “structural unit” and “unit” mean a monomer unit constituting a polymer.

[0102] Resist compositions include a positive type and a negative type. In the present invention, the positive type is preferable. The resist composition is preferably of a chemical amplification type containing an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as component (B)). The exposure includes radiation of electron beams and other radiation.

 That is, in the resist composition, for example, an alkali-soluble resin or a resin that can be alkali-soluble (hereinafter referred to as component (A)) can be used as the organic compound. The former has a so-called negative-type radiation sensitivity, and the latter has a so-called positive-type radiation sensitivity.

 In the case of the negative type, a crosslinking agent is blended in the resist composition together with the component (B). When an acid is generated from the component (B) by exposure when forming a pattern of the pattern by lithography, the acid acts to cause crosslinking between the component (A) and the crosslinking agent, resulting in alkali insolubility. . As the cross-linking agent, for example, an amino-based cross-linking agent such as melamine, urea or glycoluril having a methylol group or alkoxymethyl group is usually used. In the case of the positive type, component (A) is an alkali-insoluble resin having a mild acid dissociable, dissolution inhibiting group. When acid is generated from component (B) upon exposure, the acid is dissociated by the acid dissociation. By dissociating the solubility-inhibiting group, the component (A) becomes alkali-soluble.

 More preferably, the organic compound is a compound having an acid dissociable, dissolution inhibiting group in addition to the hydrophilic group. The hydrophilic group may also serve as an acid dissociable, dissolution inhibiting group.

 In the case where the organic compound is the polymer compound, the former unit comprises a unit having a hydrophilic group and a unit having an acid dissociable, dissolution inhibiting group, having a mass average molecular weight of more than 2000 and not more than 30000, the former unit Is 20 mol% or more, preferably 50 mol% or more. The mass average molecular weight is more preferably 3000 or more and 30000 or less, and further preferably 5000 or more and 20000 or less.

 The proportion of the unit having a hydrophilic group is more preferably 60 mol% or more, and even more preferably 75 mol% or more. The upper limit is not particularly limited !, but is preferably 80 mol% or less.

Preferably, the unit having a hydrophilic group is a unit having a carboxy group, an alcoholic hydroxyl group, or a phenolic hydroxyl group, and more preferably acrylic acid, methacrylic acid, alcohol. (Α lower alkyl) acrylate ester having a cholic hydroxyl group, a unit derived from hydroxystyrene.

 [0104] On the other hand, when the organic compound is the low molecular compound, the hydrophilic group preferably has 1 to 20 equivalents, more preferably 2 to 10 equivalents, per molecule of the low molecular compound.

 Here, for example, “having 1 to 20 equivalents of hydrophilic group per molecule” means that 1 to 20 hydrophilic groups are present in one molecule.

[0105] Hereinafter, preferred embodiments of the resist composition will be described.

 (1) Examples of radiation-sensitive resist compositions containing a polymer compound as an organic compound include: (A-1) a polymer compound having a hydrophilic group and an acid dissociable, dissolution inhibiting group; and (ii) an acid generator. And a resist composition containing.

 (2) Examples of radiation-sensitive resist compositions containing low-molecular compounds as organic compounds include: (2) Low-molecular compounds having hydrophilic groups and acid-dissociable, dissolution-inhibiting groups, and (2) Acid generation And a resist composition containing an agent.

 In the resist composition (1) or (2), the component (A-1) and the component (Α2) can be used in combination.

[0106] As the component (A-1) and the component (Α-2), as long as it is an organic compound having a hydrophilic group and a molecular weight of 500 or more, it is usually an organic material used for a chemically amplified resist. One or a mixture of two or more compounds can be used. This will be specifically described below.

[0107] <(8-1) component>

 The component (A-1) includes a novolak resin having a hydrophilic group and an acid dissociable, dissolution inhibiting group, a hydroxystyrene-based resin, a lower alkyl) acrylate ester resin, a structural unit derived from hydroxystyrene power, and — A copolymerized resin containing a structural unit derived from a lower alkyl) acrylate ester is preferably used.

In the present specification, “-lower alkyl) acrylic acid” means one or both of α-lower alkylacrylic acid and acrylic acid. OC lower alkylacrylic acid is one in which a carbonyl group of acrylic acid is bonded and a lower alkyl group is bonded to the carbon atom. “(Oc-lower alkyl) acrylic acid ester” represents an ester derivative of “(α-lower alkyl) acrylic acid”.

“(OC—lower alkyl) acrylic acid ester-derived structural unit” is a structural unit formed by the cleavage of the ethylenic double bond of (OC—lower alkyl) acrylic acid ester. Sometimes referred to as a lower alkyl) acrylate unit. Note that the _α- position ( _α- position carbon atom) of the structural unit from which the _acrylate ester power is also derived is a carbon atom to which a carbo group is bonded, unless otherwise specified.

 The “structural unit derived from hydroxystyrene” is a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene or lower alkylhydroxystyrene, and may hereinafter be referred to as a hydroxystyrene unit.

 “Α-lower alkylhydroxystyrene” indicates that a lower alkyl group is bonded to the carbon atom to which the phenyl group is bonded.

 In “α-lower alkyl acrylate ester-derived structural unit” and “α-lower alkylhydroxystyrene force-derived structural unit”, the lower alkyl group bonded to the steric position is: C1-C5 alkyl group, linear or branched alkyl group is preferred, methyl group, ethyl group, propyl group, isopropyl group, η-butyl group, isobutyl group, tert butyl group, pentyl Group, isopentyl group, neopentyl group and the like. Industrially, a methyl group is preferable.

 The resin component suitable as the component (A-1) is not particularly limited. For example, a unit having a phenolic hydroxyl group such as the following structural unit (al) and the following structural unit (a2 ) And the following structural unit (a3) a structural unit having an acid-dissociable, dissolution-inhibiting group selected from the group that also has a force, and an alkali-insoluble unit such as (a4) used as necessary Examples of the resin component of the positive resist.

The resin component has increased alkali solubility by the action of acid. In other words, the action of the acid generated from the acid generator upon exposure causes cleavage in the structural unit (a2) or the structural unit (a3), which is initially insoluble in an alkaline developer. In cocoa butter, its alkali solubility increases. As a result, a chemically amplified positive pattern can be formed by exposure and development. [0109] · · Unit (al)

 The structural unit (al) is a unit having a phenolic hydroxyl group, and is preferably a unit from which a hydroxystyrene force represented by the following general formula (I) is also derived.

[0110] [Chemical 3]

(In the formula, R represents a hydrogen atom or a lower alkyl group.)

[0111] R represents a hydrogen atom or a lower alkyl group. The lower alkyl group is as described above, and a hydrogen atom or a methyl group is particularly preferable. The description of R is the same below.

 The bonding position of OH to the benzene ring is not particularly limited, but the 4 position (para position) described in the formula is preferred! /.

The structural unit (al), the terms of forming a pattern, 40 to 80 mole _^0/0 during榭脂, rather preferably has is preferably contained 50 to 75 mol%. By setting it to 40 mol% or more, solubility in an alkali developer can be improved, and an effect of improving the pattern shape can be obtained. By making it 80 mol% or less, it is possible to balance with other structural units. Further, from the viewpoint of forming a coating layer on the pattern, it is preferable that the structural unit (al) is contained in the resin in an amount of 50 mol% or more, more preferably 60 mol% or more, and even more preferably 75%. More than mol%. The upper limit is not particularly limited, but is 80 mol% or less. Within the above range, due to the presence of the phenolic hydroxyl group, a good coating layer can be formed on the pattern, and a pattern with a good shape can be obtained. In addition, the adhesion between the pattern and the coating layer is good.

[0112] · · Unit (a2)

 The structural unit (a2) is a structural unit having an acid dissociable, dissolution inhibiting group, and is represented by the following general formula (Π).

[0113] [Chemical 4]

(In the formula, R represents a hydrogen atom or a lower alkyl group, and X represents an acid dissociable, dissolution inhibiting group.)

 [0114] The acid dissociable, dissolution inhibiting group X is an alkyl group having a tertiary carbon atom, and the tertiary carbon atom of the tertiary alkyl group is bonded to the ester group [C (O) O]. Examples thereof include a releasable dissolution inhibiting group, a tetrahydrovinyl group, and a cyclic acetal group such as a tetrahydrofuranyl group.

 Such an acid dissociable, dissolution inhibiting group X is used, for example, in a chemical amplification type positive resist composition, and any intermediate force other than those described above can be used arbitrarily.

 [0115] Preferred examples of the structural unit (a2) include those represented by the following general formula (ΠΙ).

 [0116] [Chemical 5]

• ■■ (III) In the formula, R is a hydrogen atom or a lower alkyl group, and ¹ and R ′ \ are each independently an alkyl group (which may be either a straight chain or a branched chain. Preferably, it has 1 to 5 carbon atoms. Lower alkyl group). Or, among R ¹ , R ¹² , and R ¹³ , R ¹¹ is a lower alkyl group, and R ¹² and R ¹³ are bonded to form a monocyclic or polycyclic alicyclic group (the carbon number of the alicyclic group is Preferably form 5 ~ 12)! / ヽ.

In the case where there is no alicyclic group, for example, ¹ , R ¹² and R ¹³ are all methyl groups Is preferred.

 [0118] In the case of having an alicyclic group, when it has a monocyclic alicyclic group, for example, those having a cyclopentyl group or a cyclohexyl group are preferred.

 Among those having a polycyclic alicyclic group, preferred examples thereof include the following general formula (I

V) can be mentioned.

[0119] [Chemical 6]

[Wherein, R represents a hydrogen atom or a lower alkyl group, and R ¹⁴ represents an alkyl group (which may be linear or branched, preferably a lower alkyl group having 1 to 5 carbon atoms.)]

 [0120] Also preferred are those represented by the following general formula (V) as having an acid dissociable, dissolution inhibiting group containing a polycyclic alicyclic group! /.

 [0121] [Chemical 7]

[Wherein, R is a hydrogen atom or a lower alkyl group, and R ¹⁵ and R ^lb are each independently an alkyl group (which may be linear or branched, preferably a lower alkyl group having 1 to 5 carbon atoms. Is.) ] [0122] The structural unit (a2) in榭脂, 5 to 50 mol%, preferably 10 to 40 mol%, further good preferred, preferably present in the range of 10 to 35 mole _^0/0 .

[0123] · · Structural unit (a3)

 The structural unit (a3) is a structural unit having an acid dissociable, dissolution inhibiting group, and is represented by the following general formula (VI).

 [0124] [Chemical 8]

(In the formula, R represents a hydrogen atom or a lower alkyl group, and X ′ represents an acid dissociable, dissolution inhibiting group.)

 [0125] The acid dissociable, dissolution inhibiting group X, is a tertiary alkyloxycarbonyl group such as a tert-butyloxycarbonyl group or a tert-amyloxycarbol group; Tertiary alkyloxycarboxylalkyl groups such as rumethyl group, tert-butyloxycarboruethyl group; Tertiary alkyl groups such as tert-butyl group, tert-amyl group; Tetrahydrobiral group, tetrahydrofuranyl group A cyclic acetal group such as a group; an alkoxyalkyl group such as an ethoxychetyl group and a methoxypropyl group.

 Of these, a tert-butyloxycarbonyl group, a tert-butyloxycarboromethyl group, a tert-butyl group, a tetrahydrovinyl group, and an ethoxyethyl group are preferable.

 The acid dissociable, dissolution inhibiting group X ′ is used, for example, in a chemically amplified positive resist composition, and any of the intermediate forces other than those described above can be used arbitrarily.

 In the general formula (VI), the bonding position of the group (—ΟΧ ′) bonded to the benzene ring is not particularly limited, but the position 4 (para position) shown in the formula is preferred! /, .

[0126] The structural unit (a3) in榭脂component, 5 to 50 mole _^0/0, preferably from 10 to 40 mole _^0/0, more preferably, is in the range of 10 to 35 mole ^_0/0.

[0127] · · Unit (a4) The structural unit (a4) is an alkali-insoluble unit and is represented by the following general formula (VII).

 [0128] [Chemical 9]

(In the formula, R represents a hydrogen atom or a lower alkyl group, R ⁴ ′ represents an alkyl group, and n represents 0 or an integer of 1 to 3.)

[0129] The alkyl group represented by R ⁴ 'may be either a straight chain or branched chain, and is preferably a lower alkyl group having 1 to 5 carbon atoms.

 n ′ is preferably 0 or a force 0 indicating an integer of 1 to 3.

[0130] The structural unit (a4) in榭脂component, 1 to 40 mole _^0/0, and preferably from 5 to 25 mole ^_0/0.

 By setting it to 1 mol% or more, the effect of improving the shape (particularly, improving film loss) is enhanced, and by setting it to 40 mol% or less, it is possible to balance with other structural units.

 [0131] For the component (A-1), the constituent unit (al) and at least one selected from the group consisting of the constituent unit (a2) and the constituent unit (a3) force are essential and optional. (A4) may be included. Further, a copolymer having all these units may be used, or a mixture of polymers having one or more of these units may be used. Alternatively, these may be combined. In addition, the component (A-1) can include any component other than the structural units (al), (a2), (a3), and (a4). These structural units It is preferred that the ratio is 80 mol% or more, preferably 90 mol% or more (100 mol% is most preferred).

[0132] In particular, "one or more kinds of the copolymer (1) having the structural unit (al) and the above (a3)" or "two or more different copolymers" or "the structural unit (al) And one or more of the copolymers (2) having the above (a2) and (a4) or two or more of the different copolymers ”may be used or mixed. It is most preferable because the effect is obtained. In addition, improvement of heat resistance However, it is preferable.

 In particular, a mixture of polyhydroxystyrene protected with a tertiary alkyloxycarbonyl group and polyhydroxystyrene protected with a 1 alkoxyalkyl group is preferred.

 The mass ratio at the time of mixing (polyhydroxystyrene protected with a tertiary alkyloxycarbonyl group Zi-polyhydroxystyrene protected with an alkoxyalkyl group) is, for example,

1Z9-9Z1, preferably 2Z8-8Z2, more preferably 28-55.

[0133] The weight average molecular weight in terms of polystyrene by GPC of component (A-1) is greater than 2000, preferably <is greater than 2000 <30000, more preferably <is 3000 or more and 30000 or less, more preferably 5000. More than 20000.

 The component (A-1) can be obtained by polymerizing the material monomer of the structural unit by a known method.

 [0134] Other than the above-mentioned resin components (A-1 ') suitable as the component (A-1), in particular, the lower resistance to etching and the formation of a pattern (α-lower alkyl) A resin component comprising an (α-lower alkyl) acrylic acid ester resin is more preferable.

 As the (a-lower alkyl) acrylate ester resin, a resin having a structural unit (a5) derived from an (ex-lower alkyl) acrylate ester group containing an acid dissociable, dissolution inhibiting group is preferred. The a-lower alkyl group (lower alkyl group bonded to the a-position) is the same as described above.

 The acid dissociable, dissolution inhibiting group of the structural unit (a5) has an alkali dissolution inhibiting property that makes the entire component (A-1 ′) before exposure insoluble in alkali, and at the same time, an acid generated from the component (B) after exposure It is a group that dissociates by action and changes the entire (A-1 ′) component to alkali-soluble.

[0135] As the acid dissociable, dissolution inhibiting group, for example, many resins proposed for ArF excimer laser resist compositions can be appropriately selected and used. Generally, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group of (α-lower alkyl) acrylic acid, or a cyclic or chain alkoxyalkyl The group is widely known.

 Here, the “group that forms a tertiary alkyl ester” is a group that forms an ester by substituting the hydrogen atom of the carboxy group of acrylic acid. That is, a structure in which the tertiary carbon atom of a chain-like or cyclic tertiary alkyl group is bonded to the oxygen atom at the terminal of the carbonyloxy group (—C (O) —0—) of the acrylate ester. Indicates. In this tertiary alkyl ester, when an acid acts, the bond is broken between the oxygen atom and the tertiary carbon atom.

 The tertiary alkyl group is an alkyl group having a tertiary carbon atom. Examples of the group that forms a chain-like tertiary alkyl ester include a tert butyl group and a tert amyl group.

 Examples of the group that forms the cyclic tertiary alkyl ester include those exemplified in the “acid dissociable, dissolution inhibiting group containing an alicyclic group” described later.

[0136] The "cyclic or chain-like alkoxyalkyl group" forms an ester by substituting for a hydrogen atom of a carboxy group. That is, the alkoxyalkyl group is bonded to the terminal oxygen atom of the carboxylic acid group [C (O) —O—] of the acrylate ester to form a structure. In a powerful structure, the bond between the oxygen atom and the alkoxyalkyl group is broken by the action of an acid.

 Examples of such cyclic or chain alkoxyalkyl groups include 1-methoxymethyl group, 1 ethoxyethyl group, 1 isopropoxycetyl, 1-cyclohexyloxychetyl group, 2 adamantoxymethyl group, 1-methyladaman Examples thereof include a toximethyl group, a 4-oxo-2-adamantoxymethyl group, a 1-adamantoxetyl group, and a 2-adamantoxetyl group.

 [0137] As the structural unit (a5), a structural unit containing an acid dissociable, dissolution inhibiting group containing a cyclic group, particularly an aliphatic cyclic group, is preferred.

 Here, “aliphatic” is as defined above, and “aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity.

The aliphatic cyclic group may be either a monocyclic ring or a polycyclic ring, and may be appropriately selected from those proposed in large numbers in, for example, ArF resists. Etch resistant A polycyclic alicyclic group is also preferable in terms of nipping power. Further, the alicyclic group is preferably a hydrocarbon group, and particularly preferably a saturated hydrocarbon group (alicyclic group).

 Examples of monocyclic alicyclic groups include groups in which one hydrogen atom has been removed from a cycloalkane. Examples of the polycyclic alicyclic group include bicycloalkane and tricycloalkane.

And a group obtained by removing one hydrogen atom from tetracycloalkane and the like.

 Specifically, examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Polycyclic alicyclic groups include adamantane, norbornane, isobornane

And a group obtained by removing one hydrogen atom from a polycycloalkane such as tricyclodecane or tetracyclododecane.

 Among these, an adamantyl group obtained by removing one hydrogen atom from adamantane, a norborn group obtained by removing one hydrogen atom from norbornane, and a tricyclodecanyl group obtained by removing one hydrogen atom from tricyclodecane. The tetracyclododecane group in which one hydrogen atom is removed from tetracyclododecane is preferred in the industry.

 [0138] More specifically, the structural unit (a5) is preferably at least one selected from the following general formulas (Γ) to (ΠΓ).

 Further, a unit derived from a lower alkyl) acrylate ester having a cyclic alkoxyalkyl group as described above at its ester part, specifically a 2-adamantoxymethyl group, 1-methyla Aliphatic polycyclic alkyloxy lower alkyl lower alkyl which may have a substituent such as damantoxymethyl group, 4-oxo-2adamantoxymethyl group, 1-adamantoxetyl group, 2-adamantoxychetyl group, etc. ) It is preferable that at least one selected from unit units derived from acrylate esters.

[0139] [Chemical 10]

[In the formula (Γ), R is a hydrogen atom or a lower alkyl group, and R ¹ is a lower alkyl group. ]

 [Chemical 11]

… (II ')

[In the formula (ΙΓ), R is a hydrogen atom or a lower alkyl group, and R ² and R ³ are each independently a lower alkyl group. ]

[Chemical 12]

(III ') [In the formula (ΠΓ), R is a hydrogen atom or a lower alkyl group, and R ⁴ is a tertiary alkyl group. ]

[0142] In formulas (Γ) to (ΠΓ), the hydrogen atom or lower alkyl group of R is the same as described above for the hydrogen atom or lower alkyl group bonded to the _α- position of the acrylate ester described above. The

As the lower alkyl group for R ¹ , a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an nbutyl group, and an isobutyl group. , A pentyl group, an isopentyl group, a neopentyl group, and the like. Of these, a methyl group and an ethyl group are preferred because they are easily available industrially.

The lower alkyl group for R ² and R ³ is preferably each independently a linear or branched alkyl group having 1 to 5 carbon atoms. In particular, it is industrially preferable that R ² and R ³ are both methyl groups. Specific examples include structural units derived from 2- (1-adamantyl) -2-propyl atelate.

[0143] R ⁴ is preferably a chain-like tertiary alkyl group or a cyclic tertiary alkyl group, and preferably has 4 to 7 carbon atoms! /.

 Examples of the chain-like tertiary alkyl group include a tert-butyl group and a tert-amyl group, and the tert-butyl group is industrially preferable. The tertiary alkyl group is an alkyl group having a tertiary carbon atom.

 The cyclic tertiary alkyl group is the same as that exemplified in the above-mentioned “acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group”, and includes a 2-methyl-2-adamantyl group, 2-ethi Examples include 2-2-adamantyl group, 2- (1-adamantyl) -2-propyl group, 1-ethylcyclohexyl hexyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclopentyl group, etc. it can.

In addition, the group 1 COOR ⁴ may be bonded to the 3 or 4 position of the tetracyclodode groups shown in the formula, but the bonding position cannot be specified. In addition, the carboxy group residue of the attalylate structural unit is also bonded to the 8 or 9 position shown in the formula.

[0144] The structural unit (a5) can be used alone or in combination of two or more.

In the (a lower alkyl) acrylate ester resin component, the proportion of the structural unit (a5) is ( A—1 ′) The content is preferably 20 to 60 mol%, more preferably 30 to 50 mol%, most preferably 35 to 45 mol%, based on the total of all structural units constituting the component. A pattern can be obtained by setting it to the lower limit value or more, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

[0145] It is preferable that the (a-lower alkyl) acrylate ester resin further has a structural unit (a6) derived from an acrylate ester having a rataton ring, in addition to the structural unit (a5). The structural unit (a6) is effective in increasing the adhesion of the resist film to the substrate and increasing the hydrophilicity with the developer. In addition, a covering layer with high adhesion to the pattern can be formed.

 In the structural unit (a6), a lower alkyl group or a hydrogen atom is bonded to the α-position carbon atom. The lower alkyl group bonded to the α-position carbon atom is the same as described for the structural unit (a5), and is preferably a methyl group.

 As the structural unit (a6), a structural unit in which a monocyclic group consisting of a latathone ring or a polycyclic cyclic group having a latathone ring is bonded to the ester side chain portion of the acrylate ester can be mentioned. At this time, the Rataton ring means one ring containing o c (o) structure, and this is counted as the first ring. Therefore, here, in the case of only a ratatone ring, it is called a monocyclic group, and in the case of having another ring structure, it is called a polycyclic group regardless of the structure.

 The structural unit (a6) has, for example, a monocyclic group except one γ-petit-mouth rataton force hydrogen atom or a polycyclic group except one rataton-containing bicycloalkane force hydrogen atom. Etc.

 More specifically, the structural unit (a6) is preferably at least one selected from the following general formulas (IV ′) to (Vir), for example.

[0146] [Chemical 13]

-(IV)

[In the formula (IV ′), R represents a hydrogen atom or a lower alkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a lower alkyl group. ]

[Chemical 14]

[In the formula (V ′), R is a hydrogen atom or a lower alkyl group, and m is 0 or 1. ] [Chemical 15]

[In the formula (VI ′), R represents a hydrogen atom or a lower alkyl group. ]

[Chemical 16]

[In the formula (νΐΓ), R represents a hydrogen atom or a lower alkyl group. ]

In general formulas (IV ′) to (Vir), the hydrogen atom or lower alkyl group of R is the same as described above for the hydrogen atom or lower alkyl group bonded to the _α- position of the acrylate ester. It is.

In general formula (IV,), R ⁵ and R ⁶ are each independently a hydrogen atom or a lower alkyl group, preferably a hydrogen atom. In R ⁵ and R ⁶ , the lower alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include tert butyl group, pentyl group, isopentyl group, neopentyl group and the like. The methyl group is preferred industrially.

[0151] Among the structural units represented by the general formulas (IV ') to (νΐ), the structural unit represented by (IV') is inexpensive and industrially preferred (IV ') Among the units, a-methacryloyloxy γ-butyrola, where the R-catayl group and R ⁶ are hydrogen atoms, and the ester bond between the methacrylic acid ester and γ-butyrolataton is the α-position of the latatatone ring. Most preferred to be thatton.

 The structural unit (a6) can be used alone or in combination of two or more.

The proportion of the structural unit (a6) in the (a lower alkyl) acrylate ester resin component is preferably 20 to 60 mol% with respect to the total of all the structural units constituting the component (A-1 '). 20 to 50 mol% is more preferred. 30 to 45 mol% is most preferred. Lithography characteristics are improved by setting it above the lower limit, and balun with other structural units when set below the upper limit. You can take

 [0152] In the component (A-1 ′) !, (a lower alkyl) acrylate ester resin component strength In addition to the structural unit (a5) or the structural units (a5) and (a6) In addition, it is preferable to further have a structural unit (a7) derived from an acrylate ester containing a polar group-containing polycyclic group.

 The structural unit (a7) increases the hydrophilicity of the entire (oc lower alkyl) acrylate ester resin component, increases the affinity with the developer, improves the alkali solubility in the exposed area, and improves the resolution. Contributes to improvement. In addition, a coating layer having high adhesion to the pattern can be formed.

 In the structural unit (a7), a lower alkyl group or a hydrogen atom is bonded to the α-position carbon atom. The lower alkyl group bonded to the α-position carbon atom is the same as described for the lower alkyl group in the structural unit (a5), and is preferably a methyl group.

 Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and an amino group, and a hydroxyl group is particularly preferable.

 As the polycyclic group, among the aliphatic cyclic groups exemplified in the above-mentioned “a acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group” which is the unit (a5), a polycyclic one is used as appropriate. Select and use.

 The structural unit (a7) is preferably at least one selected from the following general formulas (VIII ′) to (IX ′) forces.

[0153] [Chemical 17]

[In the formula (νΐΠ ′), R represents a hydrogen atom or a lower alkyl group, and n represents an integer of 1 to 3. ]

 [0154] R in the equation (νΐΠ ') is the same as R in the above equations (Γ) to (ΙΠ,).

 Among these, those in which η is 1 and the hydroxyl group is bonded to the 3-position of the adamantyl group are preferable.

[0155] [Chemical 18]

[In the formula (ΙΧ ′), R is a hydrogen atom or a lower alkyl group, and k is an integer of 1 to 3. [0156] Among these, those in which k is 1 are preferable. In addition, it is preferable that the cyan group is bonded to the 5th or 6th position of the norbornal group.

[0157] The structural unit (a7) can be used alone or in combination of two or more.

 The proportion of the structural unit (a7) in the (a lower alkyl) acrylate ester resin component is preferably 10 to 50 mol% with respect to the total of all the structural units constituting the component (A-1 '). 15 to 40 mol% is more preferable, and 20 to 35 mol% is more preferable. Lithographic properties are improved by setting it to the lower limit value or more, and balancing with other structural units can be achieved by setting the upper limit value or less.

 [0158] The (a lower alkyl) acrylate ester resin component may contain structural units other than the structural units (a5) to (a7), but preferably these structural units (a5) It is preferable that the total of ~ (a7) is 70 ~: LOO mol% with respect to the total of all structural units constituting the component (Α-1 ') 80 ~: LOO mol% More preferred.

[0159] The (a lower alkyl) acrylate ester resin component includes the structural units (a5) to (a7). Including other structural units (a8).

 The structural unit (a8) is not particularly limited as long as it is not classified into the structural units (a5) to (a7) described above. /.

 For example, a structural unit containing a polycyclic aliphatic hydrocarbon group and derived from an (α-lower alkyl) acrylic ester force is preferable. The polycyclic aliphatic hydrocarbon group is appropriately selected from, for example, polycyclic ones among the aliphatic cyclic groups exemplified in the aforementioned “acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group”. Can be used. In particular, at least one selected from a tricyclodecanyl group, an adamantyl group, a tetracyclododecyl group, a norbornyl group, and an isobornyl group is preferable in terms of industrial availability. The structural unit (a8) is most preferably an acid non-dissociable group.

 Specific examples of the structural unit (a8) include those having the following general formulas (X) to ()).

 [0160] [Chemical 19]

(In the formula, R is a hydrogen atom or a lower alkyl group.)

[0161] [Chemical 20]

(In the formula, R is a hydrogen atom or a lower alkyl group.)

[0163] In the general formulas (X) to (ΧΠ), the hydrogen atom or lower alkyl group represented by R includes the description of the hydrogen atom or lower alkyl group bonded to the _a- position of the acrylate ester described above. It is the same.

When the structural unit (a8) is included, the proportion of the structural unit (a8) in the (a lower alkyl) acrylate ester resin component is based on the total of all structural units constituting the component (Α—1 ′). to 253 mole _^0/0 preferably tool 5 to 20 mol _^0/0 is more preferable.

 The (a lower alkyl) acrylate ester resin component is preferably a copolymer having at least the structural units (a5), (a6) and (a7). As such a copolymer, for example, the above structural units (a5), (a6) and (a7) are powerful copolymers, and the above structural units (a5), (a6), (a7) and (a8) are also forces. A copolymer etc. can be illustrated.

[0164] The (a lower alkyl) acrylate ester resin component includes a monomer related to each structural unit, for example, a radical polymerization initiator such as azobisisobutyryl-tolyl (AIBN). It can obtain by making it superpose | polymerize by the well-known radical polymerization etc. which were used.

In the (a lower alkyl) acrylate ester resin component, the acid dissociable, dissolution inhibiting group is dissociated by the acid whose (a5) unit is generated from the component (B), and carboxylic acid is generated. Due to the presence of the generated carboxylic acid, a coating layer having high adhesion to the pattern can be formed.

The mass average molecular weight of the (a lower alkyl) acrylate ester resin component (polystyrene equivalent mass average molecular weight by gel permeation chromatography, the same shall apply hereinafter) is, for example, 30000 or less, preferably 20000 or less, preferably 12000 or less Force S is more preferable, and most preferably 10000 or less.

 The lower limit is not particularly limited, but is preferably 4000 or more, and more preferably 5000 or more in terms of suppressing pattern collapse and improving resolution.

[0165] <Ingredient 8-2>

 The component (A-2) has a molecular weight of 500 or more and 2000 or less, has a hydrophilic group, and an acid dissociable, dissolution inhibiting group X or X ′ as exemplified in the above description of (A-1). As long as it has, it can be used without particular limitation.

 Specific examples include those in which some of the hydrogen atoms of the hydroxyl group of the compound having a plurality of phenol skeletons are substituted with the acid dissociable, dissolution inhibiting group X or X ′.

 The component (A-2) contains, for example, a part of the hydrogen atom of the hydroxyl group of a low molecular weight phenol compound known as a heat sensitizer in a non-chemically amplified g-line or i-line resist. Those substituted with the above-mentioned acid dissociable, dissolution inhibiting group can be arbitrarily used from those preferred.

 [0166] Examples of the low molecular weight phenol compound that can be used include the following.

Bis (4 hydroxyphenol) methane, bis (2,3,4 trihydroxyphenyl) methane, 2- (4 hydroxyphenol) 2— (4, monohydroxyphenol) propane, 2— ( 2, 3, 4— Trihydroxyphenol) 1 2— (2, 3, 3 ', 4, Monotrihydroxyphenol) propane, Tris (4-hydroxyphenol) methane, Bis (4 Hydroxy-3) , 5 Dimethylphenol) 1-2 Hydroxyphenol methane, bis (4 hydroxy-1, 2, 5 dimethylphenol) 2 Hydroxymethane, bis (4-hydroxy-1,3,5-dimethylphenyl) 3, 4-dihydroxy Diphenylmethane, bis (4-hydroxy-1,2,5-dimethylphenyl) 3,4 Dihydroxymethane, bis (4-hydroxy-1-methylphenyl) 3,4-dihydroxyphenyl, bis (3-cyclohexyl 4- Hydroxy mono 6-methylphenol) 4-Hydroxyphenol methane, bis (3-cyclohexyl 4-hydroxy mono-6-methylphenol) —3, 4-dihydroxyphenol, (4-hydroxyphenol) Isopropyl] — 4— [1, 1-bis (4 hydroxyphenol) ethyl] 2, 3, 4 nuclei of formalin condensates of phenols such as benzene, phenol, m-cresol, ρ taresol or xylenol Etc. Of course, it is not limited to these.

 The acid dissociable, dissolution inhibiting group is not particularly limited, and examples thereof include those described above.

 [0167] Succinic acid generator (B)>

 As the component (B), any conventionally known acid generator for chemically amplified resists can be appropriately selected and used. As such an acid generator, various types have been known so far, such as an onium salt acid generator, an oxime sulfonate acid generator, and a diazomethane acid generator.

 Specific examples of diazomethane acid generators include bis (isopropylsulfol) diazomethane, bis (p-toluenesulfol) diazomethane, bis (1,1-dimethylethylsulfol) diazomethane, and bis (cyclohexane). Hexylsulfo) diazomethane, bis (2,4 dimethylsulfuryl) diazomethane, and the like. Of these, bis (alkylsulfonyl) diazomethane is preferred.

 [0168] Specific examples of o-um salts include diphenyl-trifluoromethane sulfonate, (4-methoxyphenol) felt-trifluoromethanesulfonate, bis

(p-tert-butylphenol) odo-umtrifluoromethanesulfonate, triphenylsulfo-mutrifluoromethanesulfonate, (4-methoxyphenyl) diphenylsulfo-trifluoromethylsulfonate, (4- Methylphenol) diphenylsulfo-fluoro-no-nafluorobutane sulfonate, (p-tert butylphenol) di-phenylsulfo-fluoromethane sulfonate, di-phenyl-nonafluorobutane sulfonate, Examples thereof include bis (p-tert butylphenol) jordon nonafluorobutane sulfonate and triphenylsulfon munonafluorobutane sulfonate. Among these Form salts with fluorinated alkyl sulfonate ions as the ion are preferred.

[0169] Examples of oxime sulfonate compounds include at- (methylsulfo-oxyximino) -phenylacetonitrile, α- (methylsulfonyloxyximino) -ρ-methoxyphenylacetonitryl, a- (trifluoro) Methylsulfo-luoxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloximino) -ρ-methoxyphenylacetonitrile, _α- (ethylsulfo-ruximino) -ρ-methoxyphenylacetonitrile, α- ( Propylsulfo-hydroxyimino) -ρ-methylphenylacetonitrile, α- (methylsulfo-luoxyimino) -ρ-bromophenylacetonitrile, and the like. Of these, a- (methylsulfo-ruximino) -p-methoxyphenylacetonitrile is preferred.

 In the present invention, an ohm salt and Z or bis (alkylsulfol) are preferred, among which an onium salt and Z or a diazomethane acid generator are preferred. ) Diazomethane is preferred.

 [0170] As the component (B), one type of acid generator may be used alone, or two or more types may be used in combination.

 Component (B) is used in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight per 100 parts by weight of component (A-1) and Z or component (A-2). By setting it above the lower limit of the above range, a sufficient pattern can be formed. If it is below the upper limit of the above range, the uniformity of the solution can be obtained and good storage stability can be obtained immediately.

[0171] <Optional component>

 The resist composition further includes an optional component (D) in order to improve the resist pattern shape, post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, etc. It is possible to add a nitrogen-containing organic compound.

 A wide variety of components (D) have already been proposed, and any known one may be used. Amines, particularly secondary lower aliphatic amines, are preferably tertiary lower aliphatic amines. .

Here, the lower aliphatic amine refers to an alkyl or alkyl alcohol amine having 1 to 5 carbon atoms, and examples of the secondary and tertiary amines include trimethylamine, jeti. Examples include noreamine, triethinoleamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine, and triisopropanolamine. Especially, triethanolamine and triisopropanolamine are included. 3rd class alcoholic amine like Min!

 These can be used alone or in combination of two or more.

Component (D) is usually used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of component (A-1) and component Z or (A-2).

 [0172] Further, for the purpose of preventing sensitivity deterioration due to the blending with the component (D) and improving the pattern shape, retention stability with time, etc., an organic carboxylic acid or phosphorus is further added as an optional component (E). The oxo acid or its derivative can be contained. The component (D) and the component (E) can be used in combination, or one force can be used.

 As the organic carboxylic acid, for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.

 Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives such as esters thereof, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid. Phosphonic acids such as acid-di-n-butyl ester, phenol phosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof, such as phosphinic acid, phenol phosphinic acid, etc. Derivatives such as phosphinic acid and esters thereof are mentioned, and among these, phosphonic acid is particularly preferable.

 Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A-1) and component Z or (A-2).

 [0173] The resist composition may further contain a miscible additive as desired, for example, an additional resin for improving the performance of the coating film of the resist composition, a surfactant for improving the coating property, A dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, and the like can be added as appropriate.

 [0174] The resist composition can be produced by dissolving the material in an organic solvent.

The organic solvent can dissolve each component used to make a uniform solution. As long as it is conventional, one or more of the known solvents for resist compositions can be appropriately selected and used.

 Specific examples include latones such as γ-butarate rataton; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycolate, ethylene glycolanol monoacetate, diethylene glycol , Diethyleneglycol monoremonoacetate, propylene glycol, propyleneglycolole monoacetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, or dipropylene glycol monoacetate, or these monomethyl ethers, monoethylenoateol, Polyhydric alcohols and their derivatives, such as monopropino oleore, monobutino oleore or monophenol ether; cyclic ethers such as dioxane; Methyl lactate Echiru (EL), methyl acetate, acetic Echiru, butyl acetate, methyl pyruvate, Echiru pyruvate, methyl methoxypropionate, and esters such as ethoxypropionate Echiru. Of these, PGMEA, EL, and propylene glycol monomethyl ether (PGME) are preferred!

 These organic solvents can be used alone or as a mixed solvent of two or more. The amount of the organic solvent to be used is not particularly limited, but an amount that provides a liquid having a concentration that can be applied to the solid substrate is used.

 [0175] In addition to the resist composition described above, the resist composition is a radiation-sensitive composition known as, for example, a resist composition, which is an organic compound having a hydrophilic group. A composition containing the compound can be suitably used.

 For example, a radiation-sensitive composition other than a chemically amplified type containing a photosensitive component such as a novolak resin or hydroxystyrene resin or a photosensitive component such as a naphthoquinone diazide group-containing compound can also be used as a resist composition. . If necessary, a sensitizer can be included. When a low molecular weight compound having a molecular weight of 500 or more and having a phenolic hydroxyl group is used as the sensitizer, the compound is also an essential organic compound in the resist composition. As a contribution to the effect.

 [0176] [Organic film materials]

The organic film can be etched by conventional etching, preferably dry etching. It is a film. This organic film is desirably insoluble in an alkali developer used for development after exposure.

 The organic film material used to form the organic film does not necessarily require sensitivity to electron beams or light, such as a resist film. V, etc., which are commonly used in the manufacture of semiconductor elements and liquid crystal display elements, can be used with resists and greases.

[0177] Further, since it is necessary to transfer the resist pattern 3B coated with the coating layer 5 to the organic film, the organic film material is preferably a material capable of forming an organic film that can be etched, particularly dry-etched. ,. In particular, a material capable of forming an organic film capable of etching such as oxygen plasma etching as described above is preferable.

 Such an organic film material may be a material conventionally used for forming an organic film such as an organic BARC. Examples include the ARC series manufactured by Brew Science, the AR series manufactured by Rohm and Knowth, and the SWK series manufactured by Tokyo Ohka Kogyo. In particular, as described above, when oxygen plasma etching is used in the etching process, the organic film is etched by oxygen plasma etching and is applied to a halogen gas, specifically, a fluorocarbon gas such as CF gas or CHF gas. Resistance

 4 3

 Relatively high!構成 Preferably composed of materials か ら.

 In addition, an organic film containing at least one kind of rosin component selected from the group power consisting of novolac rosin, acrylic rosin, and soluble polyimide may be formed between the organic BARC and the substrate.

 These materials are suitable because they are easy to perform etching such as oxygen plasma etching, and at the same time have high resistance to a fluorocarbon gas.

 Among these, novolak rosin and acryl resin having an alicyclic moiety or aromatic ring in the side chain are preferably used because they are inexpensive and widely used and are excellent in dry etching resistance of fluorocarbon gases. Used.

[0178] As the novolac resin, those generally used in positive resist compositions can be used, and i-line and g-line positive resists containing novolac resin as a main component can also be used. Is possible.

[0179] Novolak rosin is an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as " "Phenols". ) And aldehydes are addition-condensed in the presence of an acid catalyst.

 Examples of phenols include: phenol, ο cresol, m cresol, p tale zonore, o ethino leuenore, m- echeno leuenore, p ethino leuenore, o butylphenol, m butylphenol, p Butylphenol, 2, 3 xylenol, 2,4 xylenol, 2,5 xylenol, 2,6 xylenol, 3,4 xylenol, 3,5 xylenol, 2, 3, 5 trimethylphenol, 3, 4, 5 trimethylphenol P, p-phenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenol, bisphenol A, gallic acid, gallic acid ester, a naphthol, j8-naphthol, etc. It is done. Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetoaldehyde.

 The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

 As for the novolak tree month, a commercially available product can be used.

[0180] The lower limit of the mass average molecular weight (Mw) of the novolak rosin is preferably 3000 or more, more preferably 5000 or more, more preferably 6000 or more, and further preferably 7000 or more. The upper limit is preferably 50000 or less, more preferably 30000 or less, and most preferably 9000 or less, more preferably 10000 or less.

 If the Mw is 3000 or more, devices that are difficult to sublime when betaed at high temperatures are less likely to be contaminated. Also, by setting Mw to 5000 or more, it is preferable because it has excellent etching resistance against fluorocarbon gases.

 Further, if the Mw is 50000 or less, good embedding characteristics with respect to a substrate having fine irregularities are excellent, and if it is 10000 or less, there is a tendency to dry etching, which is preferable.

[0181] As the novolak tree essence, the Mw force is 5000 to 50000, preferably 8000 to 30000, and has a molecular weight of 500 or less, preferably 200 or less. 1% by mass or less, preferably 0.8% in the Chillon chromatography method A novolak rosin that is not more than% is preferred. The lower the content of the low nuclei, the more preferable it is, and preferably 0% by mass.

 In the novolac resin having Mw within the above range, the content of the low nucleus having a molecular weight of 500 or less is 1% by mass or less, so that the embedding property with respect to the substrate having fine irregularities is improved. The reason why the embedding property is improved by reducing the content of the low nuclei is not clear, but it is assumed that the degree of dispersion becomes small.

 Here, “low molecular weight less than 500 molecular weight” is detected as a low molecular fraction having a molecular weight of 500 or less when prayed by the GPC method using polystyrene as a standard. “Low-nuclear bodies with a molecular weight of 500 or less” include monomers that do not polymerize, those that have a low degree of polymerization, such as those that have 2-5 molecules of phenol condensed with aldehydes, depending on the molecular weight. It is.

 The content (mass%) of low-nuclear bodies with a molecular weight of 500 or less is graphed by analyzing the results of this GPC method with the horizontal axis representing the fraction number and the vertical axis representing the concentration. It is measured by determining the percentage (%) of the area under the curve of the following low molecular fraction.

 As the acrylic resin, those generally used in positive resist compositions can be used. For example, a structural unit derived from a polymerizable compound having an ether bond and a polymerizable group having a carboxy group can be used. Compound material strength Acrylic resin containing derived structural units can be mentioned.

 Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate. Examples include (meth) acrylic acid derivatives having ether bonds and ester bonds such as acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. can do. These compounds can be used alone or in combination of two or more. In the present specification, (meth) acrylate refers to one or both of attalate and metatalate.

Examples of the polymerizable compound having a carboxy group include acrylic acid, methacrylic acid, and crotonic acid. Monocarboxylic acids such as; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxychetyl succinic acid, 2-methacryloyloxychetyl maleic acid, 2-methacryloyloxychetyl Examples thereof include compounds having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxychetylhexahydrophthalic acid, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.

[0183] The soluble polyimide is a polyimide that can be made liquid by an organic solvent.

[0184] These rosin components may be used singly or as a mixture of two or more.

[0185] The organic film can be formed, for example, by applying a solution obtained by dissolving the above-described rosin component or the like in an organic solvent on a substrate according to a conventional method.

 As the organic solvent, those similar to those exemplified as the organic solvent in the resist composition described above can be used.

 Example

[0186] Example 1

 In advance, p-menthane was dehydrated by evaporation at 65 ° C for 8 hours in an evaporator.

 Next, dehydrated p-menthane (water content: lppm) is placed in a preparation container, and tetraisocyanate silane (Si (NCO)) is added to this so that it becomes lOOmM under atmospheric pressure. , Melt

 Four

 As a result, a tetraisocyanate silane solution (preparation solution) was prepared.

 After filling the gas phase in the preparation vessel with nitrogen gas (N 2), leave it at room temperature (25 ° C).

 2

 (About 20 hours) Thereafter, the prepared solution was degassed for 4 hours at 0 ° C. under reduced pressure using an evaporator.

 Next, at room temperature (25 ° C), the degassed preparation solution is placed in the mother liquor storage tank 14 of the filtration device 11 equivalent to that shown in Fig. 1, and N is supplied from the pressurization piping 31. Mother liquor storage by

 2

 The adjustment liquid in the tank 14 was pressurized, passed through the first filtration unit 12 and the second filtration unit 13, and the filtrate (film forming material) was collected in the filtrate storage tank 15.

At this time, a nylon filter having a pore size of 0.04 m (product name: poly Nylon, manufactured by Pall Japan) was used for the first filtration unit 12, and a pore size of 0.004 was used for the second filtration unit 13. 02 m high A filter made of high-density polyethylene (product name: UPOR POLYFIX, manufactured by KIT Co., Ltd.) was used. In addition, the filtration process was performed using N gas phase to prevent air from entering the filtration device 11 (in the filtration system).

 2 in the state filled. Specifically, the mother liquid storage tank 14 and the filtrate storage tank 15 are closed with pressurizing caps 14a and 15a, and each flow path and gas pipe are connected to the pressurizing caps 14a and 15a to The gas phase in the liquid storage tank 15 is completely N-substituted,

 2 After shutting off the gas, the p-menthane dehydrated as described above was flowed to wash the filter, and then the filtration treatment was performed.

[0187] Example 2

 Prepare the preparation solution in the same way as Example 1, and fill the gas phase in the preparation container with nitrogen gas (N)

 2 and then allowed to stand at room temperature for 1 week. The prepared solution after standing was filtered as it was without degassing to obtain a film-forming material. The filtration treatment was performed in the same manner as in Example 1.

 [0188] Example 3

 A preparation solution was prepared in the same manner as in Example 1 except that P-menthane (water content: 4 ppm) that had not been dehydrated was used. After filling the gas phase in the preparation container with nitrogen gas (N),

 2

 It was allowed to stand at room temperature (25 ° C) for one day (about 20 hours). Then, the prepared solution after standing is degassed for 4 hours at a temperature of 0 ° C under reduced pressure using an evaporator, and the prepared solution after degassing is filtered to obtain a film-forming material. Obtained. Filtration was performed in the same way as Example 1.

 [0189] Comparative Example 1

 A preparation solution was prepared in the same manner as in Example 1, and the obtained adjustment solution was filtered within the day without being allowed to stand and deaerate to obtain a film-forming material. The filtration treatment was performed in the same manner as in Example 1.

 [0190] Comparative Example 2

A preparation solution was prepared in the same manner as in Example 1, and the obtained adjustment solution was subjected to a filter made of polytetrafluoroethylene (PTFE) having a pore size of 0.45 ^ m without being allowed to stand and deaerate. Was used alone and filtered in the air to obtain a film-forming material. [0191] The following evaluation was performed using the obtained film-forming material.

 <Evaluation of foreign material properties>

 Immediately after the filtration treatment of the obtained film-forming material, foreign substances in the liquid (particle diameters of 0.2 μm or more, 0.3 μm ^ r, 0.3 m or more, 0.5 μm or more, respectively) m or J and 0.5 μm or more) were measured using an in-liquid particle counter (Rion, product name: KL-22). The results are shown in Table 1. In Table 1, foreign matter with a particle size of 0.3 or more and less than 0.3 / zm is "0.2 m", foreign matter with a particle size of 0.3 m or more but less than 0.5 m is "0.3 m", 0.5 Foreign matter of μm or more was described as “0.5 m”.

 [0192] <Evaluation of aging characteristics (storage stability)>

 The obtained film-forming material was stored at 25 ° C. for 2 weeks, and then the number of foreign matters in the liquid was measured in the same manner as in the evaluation of the foreign matter characteristics. The results are shown in Table 2.

 [0193] [Table 1]

[0194] [Table 2]

 [0195] In the above table, "Cell NG" means that there were more foreign objects than the measurement limit of the particle counter used, and measurement was impossible. The measurement limit of the above particle counter is 10000 pieces ZmL.

[0196] As is clear from the above results, the film-forming material obtained by removing HCNO by degassing and Z or standing treatment and performing filtration is free from foreign matter immediately after production and after storage. There were few foreign matter characteristics and foreign matter aging characteristics. Industrial applicability

 According to the present invention, it is possible to provide a method for producing a film forming material that can form a metal oxide film at a low temperature and also has excellent foreign matter characteristics.

Claims

The scope of the claims

 [1] A method for producing a film forming material comprising a metal compound (W) having two or more isocyanate groups dissolved in a solvent (S),

 Removing isocyanate from the solution (R1) obtained by dissolving the metal compound (W) in the solvent (S);

 And a step of filtering the solution (R1) under an inert gas atmosphere after removing the isocyanic acid.

[2] The method for producing a film-forming material according to [1], wherein the solution (R1) is degassed under reduced pressure.

[3] The process for producing a film-forming material according to claim 1, wherein the removal of the isocyanic acid is performed by allowing the solution (R1) to stand under normal pressure.

4. The method for producing a film-forming material according to claim 2, wherein the removal of the isocyanic acid is performed by allowing the solution (R1) to stand under normal pressure.

5. The method for producing a film forming material according to claim 1, wherein the solvent (S) is dehydrated in advance before the metal compound (W) is dissolved.

6. The method for producing a film-forming material according to claim 1, wherein the solvent (S) contains a! / Sodium solvent (S1) having no functional group that reacts with the metal compound (W).

7. The method for producing a film forming material according to claim 6, wherein the boiling point of the solvent (S1) is 155 ° C or higher.

 8. The method for producing a film forming material according to claim 6, wherein the solvent (S1) is a compound represented by the following general formula (s-1).

 [Chemical 1]

(In the formula, R ^{21 to} R ²³ are each independently a hydrogen atom or a linear or branched alkyl group, and at least two of R ^{21 to} R ²³ are alkyl groups, and the alkyl group Is The ring may be bonded to a carbon atom other than the carbon atom to which the alkyl group in the cyclohexane ring is bonded. )

 9. The method for producing a film-forming material according to claim 8, wherein the solvent (S1) force is menthane.