阅读说明：本技术 药液、药液的制造方法及被检液的分析方法 (Chemical liquid, method for producing chemical liquid, and method for analyzing test liquid ) 是由 上村哲也 于 2019-01-10 设计创作，主要内容包括：本发明的课题在于提供一种即使在应用于利用KrF准分子激光曝光及ArF准分子激光曝光进行的抗蚀剂工艺时也具有优异的缺陷抑制性能的药液。并且,本发明的课题还在于提供一种被检液的分析方法及药液的制造方法。本发明的药液含有：有机溶剂；及含金属粒子,含有金属原子且粒径为10～100nm,所述药液中,含金属粒子的含有粒子数为1.0×10<Sup>-2</Sup>～1.0×10<Sup>12</Sup>个/cm<Sup>3</Sup>。(The present invention addresses the problem of providing a chemical solution that has excellent defect suppression performance even when applied to a resist process using KrF excimer laser exposure and ArF excimer laser exposure, and also addresses the problem of providing a method for analyzing a test solution and a method for producing a chemical solution, the chemical solution containing an organic solvent and metal-containing particles having a particle size of 10 to 100nm and containing metal atoms, wherein the number of the metal-containing particles in the chemical solution is 1.0 × 10 ‑2 ～1.0×10 12 Per cm 3 。)

1. A medical solution comprising:

an organic solvent; and

metal-containing particles containing metal atoms and having a particle diameter of 10 to 100nm,

the number of the contained metal-containing particles is 1.0 × 10^-2Per cm³～1.0×10¹²Per cm³。

2. The chemical liquid according to claim 1, which is used for manufacturing a semiconductor device.

3. The medical solution according to claim 1 or 2, wherein,

the metal-containing particles comprise at least one selected from the group consisting of:

particles A containing the simple substance of the metal atom,

Particles B of an oxide containing the metal atom, and

and particles C containing the simple substance of the metal atom and an oxide of the metal atom.

4. The medical solution according to claim 3, wherein,

the particles C are particles D each having the simple metal atom and an oxide of the metal atom disposed so as to cover at least a part of the surface of the simple metal atom.

5. The medical solution according to claim 3 or 4,

the ratio of the number of particles contained in the particles C to the number of particles contained in the particles B per unit volume of the chemical solution is 1.0 or more.

6. The medical liquid according to any one of claims 3 to 5,

a ratio of a number of contained particles of the particles a to a total number of contained particles of the particles B and the particles C per unit volume of the chemical solution is less than 1.0.

7. The medical liquid according to any one of claims 3 to 6,

the ratio of the number of particles contained in the particles A to the total number of particles contained in the particles B and the particles contained in the particles C per unit volume of the chemical solution is 1.0 × 10^-1The following.

8. The medical liquid according to any one of claims 3 to 7,

the particles A include particles E containing a single metal atom and particles F containing 2 or more metal atoms,

the ratio of the number of particles contained in the particles E to the number of particles contained in the particles F per unit volume of the chemical solution is 1.0 × 10^-2～1.0×10²。

9. The drug solution according to any one of claims 1 to 8, further comprising an organic compound having a boiling point of 300 ℃ or higher.

10. The medical solution of claim 9, wherein,

at least a part of the metal-containing particles is particles U containing the organic compound.

11. The medical solution according to claim 9 or 10, wherein,

at least a part of the metal-containing particles are particles U containing the organic compound and particles V not containing the organic compound,

the ratio of the number of particles contained in the particles U to the number of particles contained in the particles V per unit volume of the chemical solution is 1.0 × 10¹The above.

12. The medical solution according to claim 10 or 11,

the number of particles contained in the particles U per unit volume of the drug solution is 5.0 × 10^-2Per cm³～1.0×10¹¹Per cm³。

13. The medical liquid according to any one of claims 1 to 12,

at least a part of the metal-containing particles is at least one selected from the group consisting of Pb-containing particles containing Pb atoms and Ti-containing particles containing Ti atoms.

14. The medical liquid according to any one of claims 1 to 13,

at least a part of the metal-containing particles are Pb-containing particles containing Pb atoms and Ti-containing particles containing Ti atoms,

the ratio of the number of contained particles of the Pb-containing particles to the number of contained particles of the Ti-containing particles per unit volume of the chemical solution is 1.0 × 10^-5～1.0。

15. A method for producing a chemical solution according to any one of claims 1 to 14, comprising a filtration step of obtaining the chemical solution by filtering a purified product containing an organic solvent with a filter.

16. The method for producing chemical liquid according to claim 15, wherein,

the purified product contains an organic compound having a boiling point of 300 ℃ or higher,

the manufacturing method further comprises a distillation process of distilling the purified material to obtain a distilled purified material before the filtration process,

the content of the organic compound in the distilled purified product was 1.0 × 10^-3Mass ppt-1.0 × 10³Mass ppm.

17. The method for producing chemical liquid according to claim 15 or 16,

the filtration step is a multistage filtration step in which the purified product is passed through at least 2 different types of filters selected from the group consisting of a material of the filter, a pore diameter, and a pore structure.

18. The method for producing chemical liquid according to any one of claims 15 to 17,

in the case of using 1 filter, the pore diameter of the filter is 5nm or less, and in the case of using 2 or more filters, the pore diameter of the filter having the smallest pore diameter among the filters is 5nm or less.

19. A method for analyzing a liquid sample, comprising:

a step A of applying a liquid to be tested onto a substrate and forming a liquid layer to be tested on the substrate, wherein the liquid to be tested contains an organic solvent and metal-containing particles containing metal atoms and having a particle diameter of 10nm to 100 nm; and

and analyzing the number of the metal-containing particles per unit area on the substrate.

Technical Field

The present invention relates to a chemical liquid, a method for producing the chemical liquid, and a method for analyzing a test liquid.

Background

In the case of manufacturing a semiconductor device by a wiring forming process including photolithography, a Chemical solution containing water and/or an organic solvent may be used as it is or as a diluent for a pre-wetting solution, a resist solution (resist composition), a developing solution, a rinse solution, a stripping solution, a Chemical Mechanical Polishing (CMP) slurry, a cleaning solution after CMP, and the like.

In recent years, the miniaturization of patterns has been progressing with the progress of photolithography. As a method for miniaturizing the pattern, a method of shortening the wavelength of an exposure light source can be used, and it has been attempted to form a pattern using ultraviolet rays, KrF excimer laser light, ArF excimer laser light, or the like, which have been conventionally used, as an exposure light source.

In the patterning by the KrF excimer laser, ArF excimer laser, or the like, the resist pattern is developed with a line and/or space width of 20 to 80nm as a target, and the chemical used in this step is required to have more excellent defect suppression performance. The defect suppressing performance is a performance that makes it difficult for defects to occur in a semiconductor substrate when the semiconductor substrate is processed with a chemical solution in a manufacturing process of a semiconductor device.

As a method for producing a chemical solution for forming a resist pattern in the related art, patent document 1 describes "a method for producing a resist composition used in a semiconductor device production process, the method being characterized in that a production apparatus for a resist composition is cleaned with a cleaning solution, the cleaning solution is taken out from the production apparatus, spin-coated on an evaluation substrate, and cleaned until a change in defect density among defects having a size of 100nm or more before and after coating on the evaluation substrate becomes 0.2 pieces/cm²Thereafter, a resist composition was produced by the production apparatus. ", the above documents describe: as a result of ArF exposure using the chemical solution (resist composition) produced by this method, pattern defects and the like can be suppressed.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-049395

Disclosure of Invention

Technical problem to be solved by the invention

As a result of patterning by KrF excimer laser exposure and ArF excimer laser exposure using a resist composition containing the chemical solution produced by the above-described production method, the present inventors have found that the suppression of defects is not necessarily sufficient.

Accordingly, an object of the present invention is to provide a chemical solution which is less likely to cause defects even when applied to a resist process by KrF excimer laser exposure and ArF excimer laser exposure, in other words, which has excellent defect suppression performance even when applied to a resist process by KrF excimer laser exposure and ArF excimer laser exposure.

Another object of the present invention is to provide a method for analyzing a liquid to be tested and a method for producing a chemical solution.

Means for solving the technical problem

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following constitution.

[1]A chemical liquid comprising an organic solvent and metal-containing particles containing metal atoms and having a particle diameter of 10 to 100nm, wherein the number of the metal-containing particles in the chemical liquid is 1.0 × 10^-2～1.0×10¹²Per cm³。

[2] The chemical liquid according to [2], which is used for manufacturing a semiconductor device.

[3] The chemical liquid according to [1] or [2], wherein the metal-containing particles include at least one selected from the group consisting of particles A containing a simple metal atom, particles B containing an oxide of a metal atom, and particles C containing a simple metal atom and an oxide of a metal atom.

[4] The chemical solution according to item [3], wherein the particles C are particles D having a simple metal atom and an oxide of the metal atom disposed so as to cover at least a part of the surface of the simple metal atom.

[5] The chemical liquid according to [3] or [4], wherein a ratio of a number of contained particles of the particles C to a number of contained particles of the particles B per unit volume of the chemical liquid is 1 or more.

[6] The chemical liquid according to any one of [3] to [5], wherein a ratio of a number of contained particles of the particles A to a total number of contained particles of the particles B and the number of contained particles of the particles C per unit volume of the chemical liquid is less than 1.0.

[7]According to [3]To [6]]The chemical solution according to any one of, wherein a ratio of a number of contained particles of the particles A to a total number of contained particles of the particles B and a number of contained particles of the particles C per unit volume of the chemical solution is 1.0 × 10^-1The following.

[8]According to [3]To [ 7]]The chemical solution according to any one of the above, wherein the particles A comprise particles E containing a single metal atom and particles F containing 2 or more metal atoms, and the ratio of the number of particles contained in the particles E to the number of particles contained in the particles F per unit volume of the chemical solution is 1.0 × 10^-2～1.0×10²。

[9] The drug solution according to any one of [1] to [8], further comprising an organic compound having a boiling point of 300 ℃ or higher.

[10] The chemical solution according to [9], wherein at least a part of the metal-containing particles are particles U containing an organic compound.

[11]According to [9]]Or [10]]The chemical solution, wherein at least a part of the metal-containing particles are particles U containing an organic compound and particles V containing no organic compound, and the ratio of the number of particles contained in the particles U to the number of particles contained in the particles V per unit volume of the chemical solution is 1.0 × 10¹The above.

[12]According to [10]]Or [11]The chemical solution, wherein the number of particles contained in the particles U per unit volume of the chemical solution is 5.0 × 10^-2～1.0×10¹¹Per cm³。

[13] The chemical liquid according to any one of [1] to [12], wherein at least a part of the metal-containing particles is at least one selected from the group consisting of Pb-containing particles containing Pb atoms and Ti-containing particles containing Ti atoms.

[14]According to [1]To [13]]The chemical solution according to any one of the above, wherein at least a part of the metal-containing particles are Pb-containing particles containing Pb atoms and Ti-containing particles containing Ti atoms, and the Pb-containing particles are contained per unit volume of the chemical solutionThe ratio of the number of particles to the number of particles including Ti particles was 1.0 × 10^-5～1.0。

[15] A method for producing a chemical solution according to any one of [1] to [14], comprising a filtration step of filtering a purified product containing an organic solvent with a filter to obtain the chemical solution.

[16]According to [15]]The method for producing a chemical solution, wherein the purified product contains an organic compound having a boiling point of 300 ℃ or higher, and the method further comprises a distillation step of distilling the purified product to obtain a distilled purified product, prior to the filtration step, wherein the content of the organic compound in the distilled purified product is 1.0 × 10^-3Mass ppt-1.0 × 10³Mass ppm.

[17] The method for producing a chemical solution according to [15] or [16], wherein the filtration step is a multistage filtration step of passing the purified product through at least 2 different filters selected from a group consisting of a material of the filter, a pore diameter, and a pore structure.

[18] The method for producing a chemical solution according to any one of [15] to [17], wherein the pore diameter of the filter is 5nm or less when 1 filter is used, and the pore diameter of the filter having the smallest pore diameter among the filters is 5nm or less when 2 or more filters are used.

[19] A method for analyzing a liquid sample, comprising: a step A of coating a substrate with a liquid to be tested, the liquid to be tested containing an organic solvent and metal-containing particles having a particle diameter of 10 to 100nm and containing metal atoms, and forming a liquid layer to be tested on the substrate; and analyzing the number of metal-containing particles per unit area on the substrate.

Effects of the invention

According to the present invention, it is possible to provide a chemical solution having excellent defect suppression performance even when applied to a resist process by KrF excimer laser exposure and ArF excimer laser exposure. The present invention can also provide a method for analyzing a test solution and a method for producing a chemical solution.

Drawings

Fig. 1 is a schematic diagram showing a typical example of a purification apparatus capable of performing a multi-stage filtration process.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value.

In the present invention, "ppm" means "parts-per-million (10)^-6): parts per million and "ppb" refers to "parts-per-billion (10)^-9): parts per billion and "ppt" refers to "parts-per-trillion (10)^-12): per millionth and ppq are referred to as "parts-per-quadratics (10)^-15): one giga ".

In the labeling of the group (atomic group) in the present invention, the label not labeled with substitution and unsubstituted includes not only a group having no substituent but also a group having a substituent within a range not impairing the effect of the present invention. For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). The same applies to each compound.

[ medicinal solution ]

A chemical solution according to an embodiment of the present invention (hereinafter, also referred to as "the chemical solution") includes an organic solvent, and metal-containing particles having a particle diameter of 10 to 100nm and containing metal atoms, wherein the number of the metal-containing particles per unit volume in the chemical solution is 1.0 × 10^-2～1.0×10¹²Per cm³。

Although the mechanism by which the above problems are solved by the present chemical solution is not clear, the present inventors speculate as follows. The following mechanism is assumed to be included in the scope of the present invention even when the effects of the present invention are obtained by a different mechanism.

One of the characteristics of the chemical solution is that the number of the metal-containing particles with the particle size of 10-100 nm in the chemical solution is controlled to 01.0 × 10^-2～1.0×10¹²Per cm³。

In the processes using KrF excimer laser exposure and ArF excimer laser exposure, it is required to reduce the pattern pitch of the resist, the pattern width, and the pitch of the pattern obtained by adding the pattern pitch to the 1 pattern width and the pattern width that are periodically arranged, and to reduce the pitch of the wiring that is obtained by adding the wiring pitch to the 1 wiring width and the wiring width that are periodically arranged.

Specifically, the pattern width and the pattern interval are usually about 20 to 80nm (as the pitch, about 40 to 160 nm). In this case, the present inventors have found that it is required to control finer particles in units of the number thereof, which does not cause a problem in the conventional process.

Of the above particles, particles having a particle diameter of less than 10nm are more likely to aggregate when the chemical solution is applied to the substrate, and as a result, it is estimated that coarse particles are generally formed. Therefore, the resist is usually removed in the resist step (for example, in a form such as a rinse), and it is presumed that the defect suppressing performance of the chemical solution is not greatly affected.

On the other hand, among the particles, particles having a particle diameter of 100nm or more are sufficiently larger than the required pattern pitch and resist pitch, and therefore, as described above, are generally removed in the step, and it is estimated that the influence on the defect suppression performance of the chemical solution is not so large.

It is estimated that the metal-containing particles having a particle diameter of 10 to 100nm have a greater influence on the defect suppression performance of the chemical solution. In particular, in the KrF excimer laser exposure and ArF excimer laser exposure steps, the required pattern width and pattern interval are about 20 to 80nm, and it is estimated that the metal-containing particles having a particle size of 10 to 100nm have a particularly large influence on the defect suppression performance of the chemical solution.

The chemical solution of the present invention is a unit of chemical solutionThe number of particles contained in the volume of the metal-containing particles was 1.0 × 10^-2Per cm³As described above, the metal-containing particles are easily aggregated with each other and are more easily removed in the step, and as a result, the chemical solution is presumed to have excellent defect suppression performance.

On the other hand, in the chemical solution of the present invention, the number of particles contained in the metal-containing particles per unit volume of the chemical solution is 1.0 × 10¹²Per cm³The metal-containing particles themselves are suppressed from causing defects, and as a result, it is presumed that the chemical solution has excellent defect suppression performance.

[ organic solvent ]

The liquid medicine contains an organic solvent. The content of the organic solvent in the chemical solution is not particularly limited, but is usually preferably 98.0 mass% or more, more preferably 99.0 mass% or more, further preferably 99.9 mass% or more, and particularly preferably 99.99 mass% or more, based on the total mass of the chemical solution. The upper limit is not particularly limited, but is usually less than 100 mass%.

The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In the case where 2 or more organic solvents are used simultaneously, the total content is preferably within the above range.

In the present specification, the organic solvent refers to a liquid organic compound containing 1 component at a content of more than 10000 ppm by mass relative to the total mass of the chemical solution. That is, in the present specification, the liquid organic compound contained in an amount exceeding 10000 ppm by mass relative to the total mass of the chemical solution corresponds to the organic solvent.

In the present specification, the term "liquid" means a liquid at 25 ℃ under atmospheric pressure.

The type of the organic solvent is not particularly limited, and a known organic solvent can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

Further, as the organic solvent, for example, those described in Japanese patent laid-open Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379 can be used.

As the organic solvent, at least one selected from the group consisting of propylene glycol monomethyl ether, Propylene Glycol Monoethyl Ether (PGME), propylene glycol monopropyl ether, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Ethyl Lactate (EL), methyl methoxypropionate, cyclopentanone, Cyclohexanone (CHN), γ -butyrolactone, diisoamyl ether, butyl acetate (nBA), isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, Propylene Carbonate (PC), sulfolane, cycloheptanone, 1-hexanol, decane, and 2-heptanone is preferable. Among them, CHN, PGMEA, PGME, nBA, PC, and a mixture thereof are preferable from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention.

In addition, the organic solvent can be used alone in 1, also can be used simultaneously more than 2.

In addition, the type and content of the organic solvent in the chemical solution can be measured using a gas chromatography-mass spectrometer.

[ Metal-containing particles ]

The chemical solution contains metal-containing particles containing metal atoms and having a particle diameter of 10 to 100 nm.

Although a preferred embodiment of the method for producing the chemical liquid will be described later, the chemical liquid can be produced by purifying a purified product containing the organic solvent and the impurities described above. The metal-containing particles may be intentionally added in the process of producing the chemical solution, may be originally contained in the purified product, or may be transferred from the apparatus for producing the chemical solution or the like in the process of producing the chemical solution (so-called contamination).

The metal atom is not particularly limited, but examples thereof include an Fe atom, an Al atom, a Cr atom, a Ni atom, a Pb atom, a Zn atom, a Ti atom, and the like. Among these, when the number of particles containing the metal-containing particles containing at least one selected from the group consisting of Fe atoms, Al atoms, Pb atoms, Zn atoms, and Ti atoms is controlled within the above range, more excellent defect suppression performance is easily obtained, and when the number of particles containing the metal-containing particles containing at least one selected from the group consisting of Pb atoms and Ti atoms is controlled within the above range, further excellent defect suppression performance is easily obtained.

That is, the metal atom is preferably at least one selected from the group consisting of an Fe atom, an Al atom, a Cr atom, a Ni atom, a Pb atom, a Zn atom, a Ti atom, and the like, more preferably at least one selected from the group consisting of an Fe atom, an Al atom, a Pb atom, a Zn atom, and a Ti atom, further preferably at least one selected from the group consisting of a Pb atom and a Ti atom, and particularly preferably the chemical liquid contains both a metal-containing particle containing a Pb atom and a metal-containing particle containing a Ti atom.

The metal-containing particles may contain 1 kind of the metal atom alone, or 2 or more kinds of the metal atom simultaneously.

The particle diameter of the metal-containing particles is 10 to 100 nm. According to the studies of the present inventors, it has been found that, in a chemical solution applied to a resist step of ArF excimer laser exposure, a chemical solution having excellent defect suppression performance can be easily obtained by controlling the number of particles of metal-containing particles having a particle diameter of 10 to 100nm contained in the chemical solution. As described above, in the resist step of KrF excimer laser exposure and ArF excimer laser exposure, a fine pattern width and/or space width of 20 to 80nm is generally required. In this case, it is required to control finer particles in units of the number thereof, which has not been a problem in the conventional process.

The number of particles contained in the liquid chemical per unit volume of the metal-containing particles was 1.0 × 10^-2～1.0×10¹²Per cm³From the viewpoint that the present chemical solution has more excellent effects of the present invention, the number of particles contained is preferably 1.0 × 10^-1Per cm³Above, more preferably 1.0 piece/cm³Above, preferably 5.0 × 10¹¹Per cm³Hereinafter, more preferably less than 1.0 × 10¹¹Per cm³More preferably 3.5 × 10¹⁰Per cm³The following.

The number of particles contained in the liquid medicine per unit volume of the metal-containing particles is 1.0 to 3.5 × 10¹⁰Per cm³The liquid medicine has more excellent defect suppression performance.

The ratio (Pb/Ti) of the number of Pb-containing particles containing Pb atoms to the number of Ti-containing particles containing Ti atoms in the chemical solution is not particularly limited, but is preferably 1.0 × 10^-63.0, more preferably 1.0 × 10^-5～1.0。

The lower limit value is more preferably 1.0 × 10^-4Above, 1.0 × 10 is particularly preferable^-3The above, most preferably 1.0 × 10^-2Above, 1.0 × 10 is more preferable^-1The above.

If the Pb/Ti ratio is 1.0 × 10^-5When the concentration is about 1.0, the chemical solution has more excellent effects of the present invention, and particularly has more excellent bridging defect suppressing performance.

The inventors of the present invention found that: the Pb nanoparticles and Ti nanoparticles are easily associated, and easily cause defects (in particular, cause bridging defects) at the time of development of the resist film.

If the Pb/Ti ratio is 1.0 × 10^-51.0, it is surprising that the generation of defects is more easily suppressed.

In the present specification, the content (number) of the metal-containing particles per unit volume of the chemical solution can be measured by the method described in the examples, and four-sheet-k and five-in are performed so that the effective number becomes 2 digits.

The metal-containing particles may contain a metal atom in a manner not particularly limited. Examples thereof include a compound containing a simple metal atom or a metal atom (hereinafter, also referred to as "metal compound"), a composite thereof, and the like. Also, the metal-containing particles may contain a plurality of metal atoms. When the metal nanoparticles contain a plurality of metals, the metal atoms having the largest content (atm%) among the plurality of metals are used as the main component. Therefore, the Pb-containing particles refer to a case where a plurality of metals are contained, and a Pb atom is a main component in the plurality of metals.

The compound is not particularly limited, but includes: a core-shell particle having a simple metal atom and a metal compound covering at least a part of the simple metal atom; solid solution particles comprising metal atoms and other atoms; eutectic particles comprising metal atoms and other atoms; aggregate particles of a simple metal atom and a metal compound; aggregate particles of different kinds of metal compounds; and a metal compound having a composition which changes continuously or intermittently from the particle surface to the center; and the like.

The atoms other than the metal atom contained in the metal compound are not particularly limited, but examples thereof include a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, a sulfur atom, a phosphorus atom and the like, and among them, an oxygen atom is preferable. The mode of the metal compound containing an oxygen atom is not particularly limited, but an oxide of a metal atom is more preferable.

< preferred mode 1 of Metal-containing particles

Among them, from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention, the metal-containing particles preferably include at least one selected from the group consisting of particles a containing a simple metal atom, particles B containing an oxide of a metal atom, and particles C containing a simple metal atom and an oxide of a metal atom.

As an embodiment of the particles C, particles D having a simple metal atom and an oxide of the metal atom disposed so as to cover at least a part of the surface of the simple metal atom are preferable.

The ratio (B/C) of the number of particles containing particles C to the number of particles containing particles B per unit volume of the chemical solution is not particularly limited, but is preferably 1.0 or more, more preferably 1.1 or more, from the viewpoint that the chemical solution has more excellent effects of the present invention, and the upper limit is not particularly limited, but is usually preferably 1.0 × 10¹The content is preferably 5.0 or less. When B/C is within the above range, the chemical solution has more excellent bridging defect inhibiting performance.

And, as granules per unit volume of the liquid medicineThe ratio of the number of particles contained in the seed a to the number of particles contained in the total of the number of particles contained in the seed B and the number of particles contained in the seed C (hereinafter also referred to as "a/(B + C)") is not particularly limited, but is preferably less than 1.0, more preferably 1.0 × 10, from the viewpoint that the chemical solution has more excellent effects of the present invention^-1The lower limit is not particularly limited, but is preferably 1.0 × 10 in general^-2The above. When a/(B + C) is within the above range, the defect suppressing performance is more excellent particularly when the chemical liquid is used as a pre-wetting liquid and/or a developing liquid. Although the reason is not clear, it is presumed that the particles B and C are more preferable to the particles a in terms of hydrophilicity, and therefore are less likely to remain on the substrate (less likely to cause residue defects) due to the relationship with the resist film which is generally hydrophobic.

< preferred mode 2 containing Metal particles

In addition, from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention, the metal-containing particles preferably contain particles E containing a single metal atom and particles F containing 2 or more metal atoms.

The ratio (E/F) of the number of particles contained in the particles D per unit volume of the chemical solution to the number of particles contained in the particles E is not particularly limited, but is preferably 1.0 × 10^-3～1.0×10³More preferably 1.0 × 10^-2～1.0×10²More preferably 1.0 × 10^-2～9.0×10¹If the E/F is 1.0 × 10^-2～1.0×10²The chemical solution has more excellent bridging defect inhibiting performance.

[ other Components ]

The chemical solution may contain other components than those described above. Examples of the other components include organic compounds other than organic solvents (particularly, organic compounds having a boiling point of 300 ℃ or higher), water, and resins.

< organic Compound other than organic solvent >

The chemical solution may contain an organic compound other than the organic solvent (hereinafter, also referred to as "specific organic compound"). In the present specification, the specific organic compound is a compound different from the organic solvent contained in the chemical solution, and means an organic compound contained in a content of 10000 ppm by mass or less with respect to the total mass of the chemical solution. That is, in the present specification, the organic compound contained in a content of 10000 ppm by mass or less relative to the total mass of the chemical solution corresponds to a specific organic compound and does not correspond to an organic solvent.

In addition, when the chemical solution contains a plurality of organic compounds and each organic compound is contained in the content of 10000 mass ppm or less, the chemical solution corresponds to a specific organic compound.

The specific organic compound may be added to the chemical solution or may be mixed at will in the process of producing the chemical solution. Examples of the case where the solvent is mixed at will in the chemical liquid production process include, for example, a case where a specific organic compound is contained in a raw material (for example, an organic solvent) for producing the chemical liquid, a case where a specific organic compound is mixed (for example, contaminated) in the chemical liquid production process, and the like, but are not limited to the above.

The content of the specific organic compound in the chemical solution can be measured by GCMS (gas chromatography mass spectrometry).

The number of carbon atoms of the specific organic compound is not particularly limited, but is preferably 8 or more, more preferably 12 or more, from the viewpoint that the chemical solution has more excellent effects of the present invention. The upper limit of the number of carbon atoms is not particularly limited, but is preferably usually 30 or less.

The specific organic compound may be, for example, a by-product produced by the synthesis of an organic solvent and/or an unreacted raw material (hereinafter, also referred to as a "by-product or the like").

Examples of the by-products include compounds represented by the following formulae I to V.

[ chemical formula 1]

In the formula I, R₁And R₂Each independently represents an alkyl group or a cycloalkyl group, or they are bonded to each other to form a ring.

As a group consisting of R₁And R₂The alkyl group or cycloalkyl group is preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 6 to 8 carbon atoms.

R₁And R₂The ring bonded to each other is a lactone ring, preferably a lactone ring having 4 to 9 members, more preferably a lactone ring having 4 to 6 members.

In addition, R is preferred₁And R₂Satisfies the relationship that the number of carbon atoms of the compound represented by the formula I is 8 or more.

In the formula II, R₃And R₄Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, or they are bonded to each other to form a ring. Wherein R is₃And R₄Neither of these will be hydrogen atoms.

As a group consisting of R₃And R₄The alkyl group represented by (A) is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

As a group consisting of R₃And R₄The alkenyl group represented by (A) is preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

As a group consisting of R₃And R₄The cycloalkyl group represented by (A) is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

As a group consisting of R₃And R₄The cycloalkenyl group represented by (a) is, for example, preferably a cycloalkenyl group having 3 to 12 carbon atoms, and more preferably a cycloalkenyl group having 6 to 8 carbon atoms.

R₃And R₄The ring formed by bonding is a cyclic ketone structure, and may be a saturated cyclic ketone or an unsaturated cyclic ketone. The cyclic ketone is preferably 6 to 10-membered ring, more preferably 6 to 8-membered ring.

In addition, R₃And R₄Preferably satisfies the formula IIThe number of carbon atoms of the compound is 8 or more.

In the formula III, R₅Represents an alkyl group or a cycloalkyl group.

Preferably from R₅The alkyl group is an alkyl group having 6 or more carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.

The alkyl group may have an ether bond in the chain or may have a substituent such as a hydroxyl group.

Preferably from R₅The cycloalkyl group is a cycloalkyl group having 6 or more carbon atoms, more preferably a cycloalkyl group having 6 to 12 carbon atoms, and still more preferably a cycloalkyl group having 6 to 10 carbon atoms.

In the formula IV, R₆And R₇Each independently represents an alkyl group or a cycloalkyl group, or they are bonded to each other to form a ring.

As a group consisting of R₆And R₇The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

As a group consisting of R₆And R₇The cycloalkyl group represented by (A) is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

R₆And R₇The rings formed by bonding to each other are cyclic ether structures. The cyclic ether structure is preferably a 4-to 8-membered ring, more preferably a 5-to 7-membered ring.

In addition, R is preferred₆And R₇Satisfies the relationship that the number of carbon atoms of the compound represented by the formula IV is 8 or more.

In the formula V, R₈And R₉Each independently represents an alkyl group or a cycloalkyl group, or they are bonded to each other to form a ring. L represents a single bond or an alkylene group.

As a group consisting of R₈And R₉The alkyl group represented by (A) is preferably an alkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.

As a group consisting of R₈And R₉The cycloalkyl group represented by (A) is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms.

R₈And R₉The rings formed by bonding to each other are cyclic diketone structures. The cyclic diketone structure is preferably a 6-to 12-membered ring, more preferably a 6-to 10-membered ring.

The alkylene group represented by L is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.

In addition, R₈、R₉And L satisfies the relationship that the number of carbon atoms of the compound represented by the formula V is 8 or more.

Although not particularly limited, when the organic solvent is an amide compound, an imide compound, or a sulfoxide compound, one embodiment of the amide compound, the imide compound, or the sulfoxide compound having 6 or more carbon atoms is exemplified. Further, as the specific organic compound, for example, the following compounds can be mentioned.

[ chemical formula 2]

[ chemical formula 3]

Further, specific organic compounds include: antioxidants such as dibutylhydroxytoluene (BHT), distearyl thiodipropionate (DSTP), 4 '-butylidenebis- (6-tert-butyl-3-methylphenol), 2' -methylenebis- (4-ethyl-6-tert-butylphenol), and the antioxidants described in Japanese patent laid-open publication No. 2015 200775; unreacted starting materials; structural isomers and by-products generated in the production of organic solvents; and a dissolved material from a member constituting a manufacturing apparatus of an organic solvent or the like (for example, a plasticizer dissolved from a rubber member such as an O-ring); and the like.

Further, specific examples of the organic compound include dioctyl phthalate (DOP), bis (2-ethylhexyl) phthalate (DEHP), bis (2-propylheptyl) phthalate (DPHP), dibutyl phthalate (DBP), benzylbutyl phthalate (BBzP), diisodecyl phthalate (DIDP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dihexyl phthalate, diisononyl phthalate (DINP), tris (2-ethylhexyl) trimellitate (TEHTM), tris (n-octyl-n-decyl) trimellitate (ATM), bis (2-ethylhexyl) adipate (DEHA), monomethyl adipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), dibutyl maleate (DBM), Diisobutyl maleate (DIBM), azelaic acid ester, benzoic acid ester, terephthalic acid (e.g., dioctyl terephthalate (DEHT)), diisononyl 1, 2-cyclohexanedicarboxylate (DINCH), epoxidized vegetable oil, sulfonamide (e.g., N- (2-hydroxypropyl) benzenesulfonamide (HP BSA), N- (N-butyl) benzenesulfonamide (BBSA-NBBS)), organic phosphate (e.g., tricresyl phosphate (TCP), tributyl phosphate (TBP)), acetylated monoglyceride, triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), trioctyl citrate (TOC), acetyl trioctyl citrate (ATOC), trihexyl citrate (THC), acetyl trihexyl citrate (ATHC), epoxidized soybean oil, ethylene propylene rubber, Polybutene, an addition polymer of 5-ethylene-2-norbornene, and the following examples of the polymeric plasticizers.

It is presumed that these specific organic compounds are mixed into the purified product or the chemical solution from a filter, piping, a tank, an O-ring (O-ring), a container, and the like which are brought into contact in the purification step. In particular, compounds other than alkyl olefins are associated with the generation of bridging defects.

[ chemical formula 4]

(organic Compound having a boiling point of 300 ℃ or higher)

The chemical solution may contain an organic compound having a boiling point of 300 ℃ or higher (high-boiling organic compound). When the chemical contains an organic compound having a boiling point of 300 ℃ or higher, the boiling point is high and the chemical is not easily volatilized in the photolithography step. Therefore, in order to obtain a chemical solution having excellent defect-inhibiting performance, it is necessary to strictly control the content, the existence pattern, and the like of the high-boiling organic compound in the chemical solution.

Examples of such high-boiling organic compounds include dioctyl phthalate (having a boiling point of 385 ℃), diisononyl phthalate (having a boiling point of 403 ℃), dioctyl adipate (having a boiling point of 335 ℃), dibutyl phthalate (having a boiling point of 340 ℃) and ethylene propylene rubber (having a boiling point of 300 to 450 ℃).

The inventors of the present invention found that: when the chemical liquid contains a high boiling point organic compound, there are various modes. Examples of the mode of existence of the high boiling point organic compound in the chemical solution include: particles obtained by aggregating particles containing a metal atom or a metal compound with particles of a high boiling point organic compound; particles having particles containing a metal atom or a metal compound and a high-boiling organic compound disposed so as to cover at least a part of the particles; and particles formed by coordination bonding of a metal atom and a high boiling point organic compound; and the like.

(preferable mode 3 for containing Metal particles)

In addition, from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention, an embodiment in which at least a part of the metal-containing particles is particles U containing an organic compound (preferably a high boiling point organic compound) and particles V not containing an organic compound (preferably a high boiling point organic compound) is also preferable.

At this time, the ratio (U/V) of the number of particles contained in the particles U to the number of particles contained in the particles V per unit volume of the chemical solution is not particularly limited, but is preferably 1.0 or more, more preferably 1.0 × 10, from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention¹The above. The upper limit value is not particularly limited, but is usually preferably 50 or less.

When the U/V is within the above range, the chemical solution has more excellent defect-suppressing performance. Although the reason is not clear, it is presumed that: in particular, when a chemical solution is used as the developing solution, the particles U are more easily removed than the particles V, and thus are more difficult to remain on the resist film.

< water >)

The chemical solution may contain water. The water is not particularly limited, and for example, distilled water, ion-exchanged water, pure water, or the like can be used. In addition, the organic impurities do not contain water.

The water may be added to the chemical solution, or may be optionally mixed with the chemical solution in the process of producing the chemical solution. Examples of the case where the solvent is mixed at will in the chemical liquid production process include, for example, a case where water is contained in a raw material (for example, an organic solvent) for producing the chemical liquid, and a case where water is mixed (for example, contaminated) in the chemical liquid production process, but the present invention is not limited to the above.

The content of water in the chemical solution is not particularly limited, but is preferably 0.05 to 2.0 mass% based on the total mass of the chemical solution. The content of water in the chemical liquid means a water content measured using an apparatus using a Karl Fischer (Karl Fischer) water measurement method as a measurement principle.

< resin >

The chemical solution may further contain a resin. As the resin, a resin P having a group which is decomposed by the action of an acid to generate a polar group is more preferable. As the resin, a resin having a repeating unit represented by formula (AI) described later, which is a resin whose solubility in a developer mainly containing an organic solvent is reduced by the action of an acid, is more preferable. The resin having a repeating unit represented by formula (AI) described later has a group which is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter, also referred to as "acid-decomposable group").

Examples of the polar group include alkali-soluble groups. Examples of the alkali-soluble group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfonic acid group.

In the acid-decomposable group, the polar group is protected by a group (acid leaving group) which is removed by an acid. As the acid leaving group, for example, there may be mentioned-C (R)₃₆)(R₃₇)(R₃₈)、-C(R₃₆)(R₃₇)(OR₃₉) and-C (R)₀₁)(R₀₂)(OR₃₉) And the like.

In the formula, R₃₆～R₃₉Each independently represents an alkaneA group, cycloalkyl, aryl, aralkyl or alkenyl. R₃₆And R₃₇May be bonded to each other to form a ring.

R₀₁And R₀₂Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The resin P whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid will be described in detail below.

(formula (AI): repeating unit having acid-decomposable group)

Preferably, the resin P contains a repeating unit represented by formula (AI).

[ chemical formula 5]

In the formula (AI), the reaction mixture is,

Xa₁represents a hydrogen atom or an alkyl group which may have a substituent.

T represents a single bond or a 2-valent linking group.

Ra₁～Ra₃Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

Ra₁～Ra₃2 of which may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

As a result of Xa₁Examples of the optionally substituted alkyl group include a methyl group and a group represented by-CH₂-R₁₁The group shown. R₁₁Represents a halogen atom (e.g., fluorine atom), a hydroxyl group, or a 1-valent organic group.

Xa₁Preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the linking group having a valence of 2 in T include an alkylene group, a-COO-Rt-group, and a-O-Rt-group. Wherein Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a-COO-Rt-group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably-CH₂-radical, - (CH)₂)₂-radical or- (CH)₂)₃-a radical.

As Ra₁～Ra₃The alkyl group of (2) is preferably a C1-4 alkyl group.

As Ra₁～Ra₃The cycloalkyl group of (2) is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group.

As Ra₁～Ra₃The cycloalkyl group in which 2 of them are bonded is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group. More preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

Ra₁～Ra₃In the above cycloalkyl group in which 2 of them are bonded, for example, 1 of methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

Repeating units preferably represented by formula (AI) such as Ra₁Is methyl or ethyl, and Ra₂And Ra₃And bonded to form the cycloalkyl group.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the number of carbon atoms is preferably 8 or less.

The content of the repeating unit represented by the formula (AI) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and further preferably 30 to 80 mol% with respect to all repeating units in the resin P.

(repeating Unit having lactone Structure)

Further, the resin P preferably contains a repeating unit Q having a lactone structure.

The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and a repeating unit derived from a (meth) acrylic acid derivative monomer is more preferred.

The repeating unit Q having a lactone structure may be used alone in 1 kind or in combination of 2 or more kinds, but it is preferable to use 1 kind alone.

The content of the repeating unit Q having a lactone structure is preferably 3 to 80 mol%, more preferably 3 to 60 mol% with respect to all repeating units in the resin P.

The lactone structure is preferably a 5-to 7-membered ring lactone structure, and more preferably a structure in which other ring structures are condensed in a form of a bicyclic structure or a spiro structure formed in the 5-to 7-membered ring lactone structure.

It is preferable that the lactone compound has a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17) as a repeating unit of the lactone structure. The lactone structure is preferably a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5) or formula (LC1-8), and more preferably a lactone structure represented by formula (LC 1-4).

[ chemical formula 6]

The lactone moiety may have a substituent (Rb)₂). As preferred substituent (Rb)₂) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group and the like. n is₂Represents an integer of 0 to 4. n is₂When it is 2 or more, a plurality of substituents (Rb)₂) May be the same or different, and a plurality of substituents (Rb) are present₂) May be bonded to each other to form a ring.

(repeating Unit having phenolic hydroxyl group)

The resin P may contain a repeating unit having a phenolic hydroxyl group.

Examples of the repeating unit having a phenolic hydroxyl group include a repeating unit represented by the following general formula (I).

[ chemical formula 7]

In the formula (I), the compound is shown in the specification,

R₄₁、R₄₂and R₄₃Each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is₄₂May be reacted with Ar₄Bonded to form a ring, in which case R₄₂Represents a single bond or an alkylene group.

X₄Represents a single bond, -COO-or-CONR₆₄-，R₆₄Represents a hydrogen atom or an alkyl group.

L₄Represents a single bond or an alkylene group.

Ar₄An aromatic ring group having a (n +1) valence as defined in the formula₄₂When the bond forms a ring, it represents an (n +2) -valent aromatic ring group.

n represents an integer of 1 to 5.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group (b) is preferably an alkyl group having not more than 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, which may have a substituent, more preferably an alkyl group having not more than 8 carbon atoms, and still more preferably an alkyl group having not more than 3 carbon atoms.

As R in the general formula (I)₄₁、R₄₂And R₄₃The cycloalkyl group of (b) may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

As R in the general formula (I)₄₁、R₄₂And R₄₃Examples of the halogen atom of (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group contained in the alkoxycarbonyl group of (1) is preferably the same as the above-mentioned R₄₁、R₄₂And R₄₃The alkyl groups in (1) are the same.

Examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, an urea group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms in the substituent is preferably 8 or less.

Ar₄Represents an (n +1) -valent aromatic ring group. When n is 1, the 2-valent aromatic ring group may have a substituent, and examples thereof include arylene groups having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracenylene, and heterocyclic ring-containing aromatic ring groups such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

Specific examples of the (n +1) -valent aromatic ring group in which n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the specific examples of the 2-valent aromatic ring group.

The (n +1) -valent aromatic ring group may further have a substituent.

Examples of the substituent which the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n +1) -valent aromatic ring group may have include R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl groups mentioned in (1); alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl.

As a result of X₄Represented by-CONR₆₄-(R₆₄Represents a hydrogen atom or an alkyl group. ) R in (1)₆₄Examples of the alkyl group of (b) include alkyl groups having not more than 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group and a dodecyl group, which may have a substituent, and an alkyl group having not more than 8 carbon atoms is more preferable.

As X₄Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.

As L₄The alkylene group in (1) is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.

As Ar₄The aromatic ring group having 6 to 18 carbon atoms which may have a substituent is preferable, and the benzene ring group and the naphthalene ring group are more preferableOr a biphenylene ring group.

The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. Namely, Ar₄Preferably a benzene ring group.

The content of the repeating unit having a phenolic hydroxyl group is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, and further preferably 0 to 40 mol% with respect to all repeating units in the resin P.

(repeating units having organic group having polar group)

The resin P may further contain a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Therefore, the substrate adhesion and the developer affinity are improved.

As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamantyl group, or a norbornyl group is preferable. As the polar group, a hydroxyl group or a cyano group is preferable.

In the case where the resin P contains a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, further preferably 5 to 25 mol%, and particularly preferably 5 to 20 mol% with respect to all repeating units in the resin P.

(repeating unit represented by the general formula (VI))

The resin P may contain a repeating unit represented by the following general formula (VI).

[ chemical formula 8]

In the general formula (VI), the compound represented by the formula (VI),

R₆₁、R₆₂and R₆₃Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Wherein R is₆₂May be reacted with Ar₆Bonded to form a ring, in which case R₆₂Represents a single bond or an alkylene group.

X₆Represents a single bond, -COO-or-CONR₆₄-。R₆₄Represents a hydrogen atomOr an alkyl group.

L₆Represents a single bond or an alkylene group.

Ar₆An aromatic ring group having a (n +1) valence as defined in the formula₆₂When the bond forms a ring, it represents an (n +2) -valent aromatic ring group.

With respect to Y₂And when n.gtoreq.2, each independently represents a hydrogen atom or a group which is removed by the action of an acid. Wherein, Y₂At least 1 of which represents a group that is removed by the action of an acid.

n represents an integer of 1 to 4.

As a group Y leaving by the action of an acid₂The structure represented by the following general formula (VI-A) is preferable.

[ chemical formula 9]

L₁And L₂Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.

M represents a single bond or a 2-valent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

Q、M、L₁At least 2 of which may be bonded to form a ring (preferably a 5-or 6-membered ring).

The repeating unit represented by the above general formula (VI) is preferably a repeating unit represented by the following general formula (3).

[ chemical formula 10]

In the general formula (3), in the formula,

Ar₃represents an aromatic ring group.

R₃Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

M₃Represents a single bond or a 2-valent linking group.

Q₃Represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

Q₃、M₃And R₃At least 2 of which may be bonded to form a ring.

Ar₃The aromatic ring group represented by (VI) and Ar in the general formula (VI) in the case where n in the general formula (VI) is 1₆Likewise, phenylene or naphthylene is preferred, and phenylene is more preferred.

(repeating unit having silicon atom in side chain)

The resin P may further contain a repeating unit having a silicon atom on a side chain. Examples of the repeating unit having a silicon atom in a side chain include a (meth) acrylate-based repeating unit having a silicon atom, a vinyl-based repeating unit having a silicon atom, and the like. Examples of the repeating unit having a silicon atom in a side chain include a repeating unit having a group having a silicon atom in a side chain, and examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a tricyclohexylsilyl group, a tris (trimethylsiloxy) silyl group, a tris (trimethylsilyl) silyl group, a methyldimethylsilyl group, a methyldimethylsilyloxysilyl group, a dimethyltrimethylsilyl group, a dimethyltrimethylsiloxysilyl group, a cyclic or linear polysiloxane as described below, a cage-type or ladder-type or random-type silsesquioxane structure, and the like. In the formula, R and R¹Each independently represents a substituent having a valence of 1. The symbol represents a linear bond.

[ chemical formula 11]

As the repeating unit having the above group, for example, a repeating unit derived from an acrylate compound or a methacrylate compound having the above group or a repeating unit derived from a compound having the above group and a vinyl group is preferable.

When the resin P has a repeating unit having a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and further preferably 5 to 20 mol% with respect to all repeating units in the resin P.

The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and further preferably 5,000 to 15,000 in terms of polystyrene by GPC (Gel permeation chromatography). By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or deterioration of film forming property due to increase in viscosity can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0.

As other components (for example, an acid generator, a basic compound, a quencher, a hydrophobic resin, a surfactant, a solvent, and the like) contained in the chemical solution, known components can be used.

[ use of medicinal liquids ]

The chemical liquid of the above embodiment is preferably used for manufacturing a semiconductor device. In particular, it is more preferably used for a process including pattern formation using a KrF excimer laser and an ArF excimer laser.

The chemical solution of the above embodiment can be preferably used as a chemical solution for a resist process in which the pattern width and/or the pattern interval is 20 to 80 nm. The chemical solution of the above embodiment can be preferably used as a chemical solution for a resist process in which the obtained wiring width and/or wiring interval is 20 to 80 nm. More specifically, a pre-wetting solution, a developing solution, a rinse solution, the resist solution itself, a solvent for the resist solution, a stripping solution, and the like used in the resist process are preferable. In other words, it is further preferable to manufacture a semiconductor device manufactured using a resist film having a pattern width and/or a pattern interval of 20 to 80 nm.

Specifically, in a manufacturing process of a semiconductor device including a photolithography step, an etching step, an ion implantation step, a peeling step, and the like, the organic material is treated after each step is completed or before the next step is transferred, and specifically, the organic material is preferably used as a pre-wetting liquid, a developing liquid, a rinse liquid, a peeling liquid, and the like. For example, the method can be used for rinsing the edge line of the semiconductor substrate before and after resist coating.

The chemical solution can also be used as a diluent for the resin contained in the resist solution or a solvent contained in the resist solution. Further, the dilution may be performed by other organic solvents and/or water. Further, the dilution may be performed by other organic solvents and/or water.

The chemical solution can be preferably used for other applications than the production of semiconductor devices, and can also be used as a developing solution, a rinse solution, or the like for polyimide, a resist for sensors, a resist for lenses, or the like.

The chemical solution can also be used as a solvent for medical use or cleaning use. In particular, the cleaning agent can be preferably used for cleaning containers, pipes, substrates (e.g., wafers, glass, etc.), and the like.

Among these, the chemical solution exerts more excellent effects when applied to a resist solution, a pre-wetting solution, a developing solution, and a rinse solution in pattern formation by KrF excimer laser exposure and ArF excimer laser exposure.

[ analysis method ]

The method for analyzing a liquid sample according to an embodiment of the present invention is a method for analyzing a liquid sample, which includes the following steps in order: a step A of applying a liquid to be tested, which contains an organic solvent and metal-containing particles containing metal atoms, onto a substrate, and forming a liquid layer to be tested on the substrate; and analyzing the number of metal-containing particles per unit area on the substrate.

(Process A)

Step a is a step of applying a liquid sample to a substrate and forming a liquid sample layer on the substrate.

The test solution is not particularly limited, but the above-mentioned chemical solution and a purified product used for the production of the chemical solution described later can be suitably used.

The method of applying the test solution to the substrate is not particularly limited, but a method of dropping the test solution onto a rotating substrate or a method of dropping a concentrated solution onto a substrate and then rotating the substrate is preferable from the viewpoint of uniformly applying a predetermined amount of the test solution to the substrate.

The amount of the test solution to be dropped is not particularly limited, but is preferably about 10 to 1000. mu.L.

The coating step may further include a step of drying the liquid detection layer and removing the organic solvent. In this case, although the method of heating is not particularly limited, a method of irradiating with light is preferable in terms of that the change of the components in the test solution is small and the heating can be performed in a short time. The light is not particularly limited, but infrared rays are preferable.

(Process B)

The step B is a step of measuring the number of metal-containing particles per unit area on the substrate²) The process (2). The method of evaluating the number of metal-containing particles per unit area on the substrate is not particularly limited, but evaluation can be performed by a combination of a defect detection apparatus and an energy-dispersive X-ray analysis apparatus, for example.

The defect detection device is a device that irradiates a chemical solution applied to a wafer with a laser beam, detects the laser beam scattered by a defect existing on the wafer, and detects the defect existing on the wafer. When the laser beam is irradiated, the wafer is rotated and measured, and therefore, the coordinate positions of the impurities and the defects can be estimated from the rotation angle of the wafer and the radial position of the laser beam. When elemental analysis is performed at the specified position of the defect by energy dispersive X-ray analysis, the composition of the defect can be evaluated. In this case, the defect containing the metal atom can be judged as the metal-containing particle.

Such an apparatus may be "SP-5" manufactured by KLA Tencor, but may be a wafer upper surface detection apparatus (typically, a next-generation product of "SP-5" or the like) having a resolution equal to or higher than the resolution of "SP-5".

Further, when the fully automatic defect review classification apparatus "SEMVision G6" of Applied Materials, inc. is used in combination with the above, the number of metal-containing particles per unit area of the substrate can be evaluated. The specific procedure is as described in the examples.

The step B may further comprise calculating the number of metal-containing particles per unit volume of the chemical solution (number of metal-containing particles/cm) from the number of metal-containing particles per unit area on the substrate³) The process (2). The number of metal-containing particles per unit volume (pieces/cm) as a chemical solution³) The calculation method (2) is not particularly limited, but can be determined from the number of metal-containing particles per unit area on the substrate and the amount (cm) of the chemical solution applied to the substrate³) And (4) obtaining. The amount (cm) of the liquid medicine applied to the substrate can be used³) Divided by the number of metal-containing particles per unit area on the substrate (number/cm)²) Area (cm) of substrate coated with test solution²) The product of (a).

[ method for producing chemical solution ]

The method for producing the chemical solution is not particularly limited, and a known production method can be used. Among these, from the viewpoint of obtaining a chemical solution having the more excellent effects of the present invention, it is preferable that the method for producing a chemical solution comprises a filtration step of filtering a purified product containing an organic solvent with a filter to obtain a chemical solution

The purified product used in the filtration step is obtained by supplying and reacting the raw materials for purchase or the like. As the purified product, a material containing a small amount of the metal-containing particles and/or impurities described above is preferably used. Examples of commercially available products of such purified products include "high-purity grades".

The method for obtaining a purified product (typically, a purified product containing an organic solvent) by reacting the raw materials is not particularly limited, and a known method can be used. For example, a method of obtaining an organic solvent by reacting one or more kinds of raw materials in the presence of a catalyst is given.

More specifically, examples thereof include: in the presence of sulfuric acidA method of obtaining butyl acetate by reacting acetic acid with n-butanol under the following conditions; in Al (C)₂H₅)₃A method of obtaining 1-hexanol by reacting ethylene, oxygen and water in the presence of (a); a method in which cis-4-methyl-2-pentene is reacted in the presence of Ipc2BH (Dipinocampheylborane: Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; a method of reacting propylene oxide, methanol and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); a method of obtaining IPA (isopropyl alcohol) by reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-alumina; and a method for obtaining ethyl lactate by reacting lactic acid with ethanol; and the like.

< filtration Process >

The method for producing a chemical solution according to the embodiment of the present invention includes a filtering step of filtering the purified product with a filter to obtain a chemical solution. The method of filtering the purified product with the filter is not particularly limited, but the purified product is preferably passed (passed) through a filter unit having a housing and a filter cartridge housed in the housing, with or without pressurization.

Pore diameter of the filter

The pore diameter of the filter is not particularly limited, and a filter having a pore diameter generally used for filtration of a purified product can be used. Among these, from the viewpoint of more easily controlling the number of particles contained in the chemical solution, the particles having a particle diameter of 10 to 100nm, the pore diameter of the filter is preferably 200nm or less, more preferably 20nm or less, still more preferably 10nm or less, particularly preferably 5nm or less, and most preferably 3nm or less. The lower limit is not particularly limited, but is preferably 1nm or more in general from the viewpoint of productivity.

In the present specification, the pore diameter and pore diameter distribution of the filter mean that isopropyl alcohol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M Company, hydrofluoroether, C)₄F₉OC₂H₅) Pore diameter and pore diameter distribution determined by the bubble point (bubbleboint).

When the pore diameter of the filter is 5nm or less, it is preferable from the viewpoint of easier control of the number of particles contained in the chemical solution, the particles having a particle diameter of 10 to 100 nm. Hereinafter, a filter having a pore diameter of 5nm or less is also referred to as a "fine pore filter".

The fine pore size filter may be used alone or in combination with a filter having another pore size. Among them, from the viewpoint of further excellent productivity, it is preferable to use the filter having a larger pore diameter together with the filter. In this case, since the purified material filtered by passing through the filter having a larger pore diameter in advance is passed through the fine pore filter, clogging of the fine pore filter can be prevented.

That is, as the pore diameter of the filter, in the case of using 1 filter, the pore diameter is preferably 5.0nm or less, and in the case of using 2 or more filters, the pore diameter of the filter having the smallest pore diameter is preferably 5.0nm or less.

The mode of sequentially using 2 or more types of filters having different pore diameters is not particularly limited, but a method of sequentially arranging the filter units described above along a pipeline through which a purified product is transported is exemplified. In this case, if the flow rate per unit time of the purified product is to be constant in the entire pipe, a larger pressure may be applied to the filter unit having a smaller pore diameter than the filter unit having a larger pore diameter. In this case, it is preferable to increase the filtration area by arranging a pressure regulating valve, a damper, and the like between the filter units so that the pressure applied to the filter unit having a small pore diameter is constant, or by arranging filter units housing the same filter in parallel along the pipe. Therefore, the number of particles contained in the chemical solution can be controlled more stably, the number of particles being 10 to 100 nm.

Material of the filters

The material of the filter is not particularly limited, and a known material can be used as the material of the filter. Specifically, in the case of a resin, there may be mentioned polyamides such as 6-nylon and 6, 6-nylon; polyolefins such as polyethylene and polypropylene; polystyrene; a polyimide; a polyamide-imide; poly (meth) acrylates; polyfluorocarbons such as polytetrafluoroethylene, perfluoroalkoxyethylene, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride; polyvinyl alcohol; a polyester; cellulose; cellulose acetate, and the like. Among them, from the viewpoint of more excellent solvent resistance and more excellent defect suppression performance of the obtained chemical solution, at least one selected from the group consisting of nylon (among them, 6-nylon is preferable), polyolefin (among them, polyethylene is preferable), poly (meth) acrylate, and polyfluorocarbon (among them, Polytetrafluoroethylene (PTFE), Perfluoroalkoxyethylene (PFA) is preferable). These polymers can be used alone or in combination of 2 or more.

In addition to the resin, diatomaceous earth, glass, or the like may be used.

Also, the filter may be surface-treated. The method of surface treatment is not particularly limited, and a known method can be used. Examples of the surface treatment include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

The plasma treatment is preferable because the surface of the filter is hydrophilized. The contact angle of water on the surface of the filter hydrophilized by the plasma treatment is not particularly limited, but the static contact angle at 25 ℃ as measured by a contact angle meter is preferably 60 ° or less, more preferably 50 ° or less, and further preferably 30 ° or less.

As the chemical modification treatment, a method of introducing an ion exchange group into the substrate is preferable.

That is, as the filter, a filter in which each of the materials mentioned above is used as a base material and an ion exchange group is introduced into the base material is preferable. Typically, a filter comprising a substrate having ion exchange groups on the surface is preferred. The surface-modified substrate is not particularly limited, and a substrate in which an ion exchange group is introduced into the polymer is preferable from the viewpoint of easier production.

Examples of the ion exchange group include a cation exchange group, a sulfonic acid group, a carboxyl group, and a phosphoric acid group, and examples of the anion exchange group include a quaternary ammonium. The method of introducing an ion-exchange group into a polymer is not particularly limited, but a method of reacting a compound having an ion-exchange group and a polymerizable group with a polymer and typically grafting the resulting product is exemplified.

The method for introducing the ion exchange group is not particularly limited, but the fiber of the resin is irradiated with ionizing radiation (α -rays, β -rays, γ -rays, X-rays, electron beams, and the like) to generate an active moiety (radical) in the resin. The irradiated resin is immersed in a monomer-containing solution to graft-polymerize the monomer and the base material. As a result, a polymer in which the monomer is bonded to the resin fiber as a graft polymerization side chain is produced. The final product is obtained by bringing a resin having the produced polymer as a side chain into contact reaction with a compound having an anion exchange group or a cation exchange group to introduce the ion exchange group to the polymer of the graft-polymerized side chain.

The filter may be a combination of a woven or nonwoven fabric having an ion-exchange group formed by radiation graft polymerization and a conventional filter material of glass wool, woven or nonwoven fabric.

When a filter having an ion exchange group is used, the content of the particles containing metal atoms in the chemical solution can be more easily controlled to a desired range. The material of the filter having an ion exchange group is not particularly limited, but examples thereof include those obtained by introducing an ion exchange group into a polyfluorocarbon and a polyolefin, and those obtained by introducing an ion exchange group into a polyfluorocarbon are more preferable.

The pore diameter of the filter having an ion exchange group is not particularly limited, but is preferably 1 to 30nm, more preferably 5 to 20 nm. The filter having the ion exchange group may be used as the filter having the minimum pore diameter described above, or may be used separately from the filter having the minimum pore diameter. Among them, from the viewpoint of obtaining a chemical solution having more excellent effects of the present invention, a mode in which a filter having an ion exchange group and a filter having no ion exchange group and having a minimum pore diameter are used together in the filtration step is preferable.

The material of the filter having the smallest pore diameter described above is not particularly limited, but from the viewpoint of solvent resistance and the like, at least one selected from the group consisting of polyfluorocarbons and polyolefins is preferable, and polyolefins are more preferable.

Further, if the material of the filter is polyamide (particularly, nylon), the content of the high boiling point organic compound and the like in the chemical solution can be more easily controlled, and particularly, the content of the metal-containing particles containing the high boiling point organic compound in the chemical solution can be more easily controlled.

Therefore, as the filter used in the filtration step, 2 or more filters of different materials are preferably used, and more preferably 2 or more filters selected from the group consisting of polyolefins, polyfluorocarbons, polyamides, and substances obtained by introducing ion exchange groups into these.

Pore structure of the filter

The pore structure of the filter is not particularly limited, and may be appropriately selected depending on the components in the purified product. In the present specification, the pore structure of the filter means a pore diameter distribution, a position distribution of pores in the filter, a shape of the pores, and the like, and can be typically controlled by a method for manufacturing the filter.

For example, when a powder such as a resin is sintered, a porous film can be obtained, and when the powder is formed by a method such as electrospinning, electroblowing, or melt blowing, a fiber film can be obtained. Their respective pore structures are different.

The "porous membrane" refers to a membrane in which components in a purified substance such as gel, particles, colloid, cells, and oligomer are retained, but components substantially smaller than the pores pass through the pores. The retention of components in a purified product by a porous membrane may depend on operation conditions such as surface velocity, use of a surfactant, pH, and a combination thereof, and may depend on the pore size and structure of the porous membrane and the size and structure of particles to be removed (hard particles, gel, or the like).

When the purified product contains particles (which may be in the form of gel) containing a high-boiling organic compound as impurities, the particles containing the high-boiling organic compound are generally negatively charged, and in order to remove the particles, the polyamide filter functions as a non-sieve membrane. Typical non-sieving membranes include nylon membranes such as nylon-6 membrane and nylon-6, 6 membrane, but are not limited thereto.

The term "non-sieve" as used herein means a mechanism that causes interference, diffusion, adsorption, and the like, regardless of the pressure drop of the filter or the pore diameter.

The non-sieve holding includes a holding mechanism for removing particles to be removed in the purified product, such as disturbance, diffusion, and adsorption, regardless of a pressure drop of the filter or a pore diameter of the filter. The adsorption of particles on the filter surface can be carried by, for example, van der waals force between molecules, electrostatic force, or the like. In the case where particles moving in a non-sieving membrane layer having a curved path cannot change direction sufficiently quickly so as not to come into contact with the non-sieving membrane, an interference effect occurs. Diffusion-based particle transport, by generating a constant probability of a particle colliding with the filter material, results mainly from irregular or brownian motion of small particles. The non-sieve holding mechanism can become active in the absence of a repulsive force between the particles and the filter.

UPE (ultra high molecular weight polyethylene) filters, typically sieve membranes. A sieving membrane refers to a membrane that primarily captures particles via a sieve holding mechanism or a membrane optimized for capturing particles via a sieve holding mechanism.

As typical examples of the sieving membrane, a Polytetrafluoroethylene (PTFE) membrane and a UPE membrane are included, but not limited thereto.

The "screen holding mechanism" refers to holding based on the result that the particles to be removed are larger than the pore diameter of the porous membrane. The screen retention can be improved by forming a cake (aggregation of particles to be removed on the surface of the membrane). The filter cake effectively performs the function of a secondary filter.

The material of the fiber layer is not particularly limited as long as it is a polymer capable of forming the fiber layer. Examples of the polymer include polyamide. Examples of the polyamide include nylon 6 and nylon 6, 6. As the polymer forming the fiber membrane, poly (ether sulfone) may be mentioned. When the fiber membrane is on the primary side of the porous membrane, the fiber membrane preferably has a higher surface energy than a polymer that is a material of the porous membrane on the secondary side. Such a combination may be, for example, a case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).

As the filter used in the filtration step, 2 or more filters having different pore structures are preferably used, and a filter having a porous membrane and a fibrous membrane is preferred. Specifically, a filter using a nylon fiber membrane and a filter using a UPE porous membrane are preferably used together.

As described above, the filtration step of the embodiment of the present invention is preferably a multistage filtration step in which the purified product is passed through 2 or more different filters selected from the group consisting of a material of the filter, a pore diameter, and a pore structure.

(multistage filtration Process)

The multistage filtration step can be carried out using a known purification apparatus. Fig. 1 is a schematic diagram showing a typical example of a purification apparatus capable of performing a multi-stage filtration process. The purification apparatus 10 includes a production tank 11, a filtration apparatus 16, and a filling apparatus 13, and these units are connected by a pipe 14.

The filter device 16 includes a filter unit 12(a) and a filter unit 12(b) connected by a pipe 14. A control valve 15(a) is disposed in a pipe between the filter unit 12(a) and the filter unit 12 (b).

In fig. 1, the purified product is stored in a manufacturing tank 11. Subsequently, a pump, not shown, disposed in the pipe 14 is operated, and the purified product is sent from the production tank 11 to the filtration device 16 through the pipe 14. The direction of conveyance of the purified product in the purification apparatus 10 is indicated by F1 in fig. 1.

The filtering device 16 includes a filter unit 12(a) and a filter unit 12(b) connected by a pipe 14, and filter elements having at least one different filter selected from the group consisting of a pore diameter, a material, and a pore structure are housed in each of the 2 filter units. The filtering device 16 has a function of filtering the purified material supplied through the pipe with a filter.

The filter to be housed in each filter unit is not particularly limited, but a filter having the smallest pore diameter is preferably housed in the filter unit 12 (b).

The purified product is supplied to the filter unit 12(a) by the pump operation and filtered. The purified material filtered by the filter unit 12(a) is depressurized as necessary by the control valve 15(a), supplied to the filter unit 12(b), and filtered.

In addition, the purification apparatus may not have the regulating valve 15 (a). Further, even in the case of having the regulating valve 15(a), the position thereof may be not the primary side of the filter unit 12(b) but the primary side of the filter unit 12 (a).

As a device capable of adjusting the supply pressure of the purified material, a device other than the regulator valve may be used. Examples of such a member include a damper.

In the filter device 16, although the filter element is formed in each filter, the filter that can be used in the purification method of the present embodiment is not limited to the above-described embodiment. For example, the purified product may be passed through a filter formed in a flat plate shape.

The purification apparatus 10 is configured to transport the purified material after the filtration by the filter unit 12(b) to the filling apparatus 13 and store the purified material in the container, but the filtration apparatus for performing the purification method is not limited to the above, and may be configured to return the purified material filtered by the filter unit 12(b) to the manufacturing tank 11 and pass the purified material through the filter unit 12(a) and the filter unit 12(b) again. The filtration method as described above is called a loop filtration. In the purification of a purified product by the circulation filtration, at least 1 of 2 or more filters is used 2 or more times. In addition, in the present specification, the number of cycles of returning the filtered purified material filtered by each filter unit to the manufacturing tank is counted as 1.

The number of cycles may be appropriately selected based on the components in the purified product, etc.

The material of the liquid-contacting portion of the purification apparatus (which refers to the inner wall surface or the like with which the object to be purified and the chemical liquid may come into contact) is not particularly limited, but is preferably formed of at least one selected from the group consisting of a non-metallic material and an electropolished metallic material (hereinafter, these are also collectively referred to as "corrosion-resistant material"). For example, the liquid-receiving portion of the production tank is formed of a corrosion-resistant material, and examples thereof include a case where the production tank itself is formed of a corrosion-resistant material, and an inner wall surface of the production tank is covered with a corrosion-resistant material.

The non-metallic material is not particularly limited, and a known material can be used.

Examples of the non-metallic material include at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, a polyethylene-polypropylene resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-ethylene copolymer, a chlorotrifluoroethylene-ethylene copolymer, a vinylidene fluoride resin, a chlorotrifluoroethylene copolymer, and a vinyl fluoride resin, but are not limited thereto.

The metal material is not particularly limited, and a known material can be used.

Examples of the metal material include metal materials in which the total content of chromium and nickel is more than 25 mass% based on the total mass of the metal material, and among them, 30 mass% or more is preferable. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90 mass% or less.

Examples of the metal material include stainless steel and nickel-chromium alloy.

The stainless steel is not particularly limited, and known stainless steel can be used. Among these, alloys containing 8 mass% or more of nickel are preferable, and austenitic stainless steels containing 8 mass% or more of nickel are more preferable. Examples of the austenitic Stainless Steel include SUS (Steel Use Stainless: japanese Stainless Steel standard) 304(Ni content 8 mass%, Cr content 18 mass%), SUS304L (Ni content 9 mass%, Cr content 18 mass%), SUS316(Ni content 10 mass%, Cr content 16 mass%), SUS316(Ni content 12 mass%, Cr content 16 mass%), and SUS316L (Ni content 16 mass%).

The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass% and a chromium content of 1 to 30 mass% is preferable.

Examples of the nickel-chromium alloy include hastelloy (trade name, hereinafter the same), monel (trade name, hereinafter the same), inconel (trade name, hereinafter the same), and the like. More specifically, Hastelloy C-276(Ni content 63 mass%, Cr content 16 mass%), Hastelloy C (Ni content 60 mass%, Cr content 17 mass%), Hastelloy C-22(Ni content 61 mass%, Cr content 22 mass%), and the like can be given.

The nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, as necessary, in addition to the above alloys.

The method for electropolishing the metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs 0011 to 0014 of Japanese patent laid-open No. 2015-227501 and paragraphs 0036 to 0042 of Japanese patent laid-open No. 2008-264929 can be used.

It is presumed that the metallic material has a chromium content in the passivation layer of the surface more than that of the parent phase by electropolishing. Therefore, it is presumed that when a purifying apparatus in which the liquid-contacting portion is formed of an electropolished metal material is used, the metal-containing particles in the purified material do not easily flow out.

In addition, the metal material may be polished. The polishing method is not particularly limited, and a known method can be used. The size of the polishing particles used for the finish polishing is not particularly limited, but is preferably #400 or less from the viewpoint that unevenness of the surface of the metal material is more easily reduced. In addition, polishing is preferably performed before electropolishing.

< other working procedures >

The method for producing a chemical solution according to the embodiment of the present invention is not particularly limited as long as it has a filtering step, and may have a step other than the filtering step. Examples of the step other than the filtration step include a distillation step, a reaction step, and a neutralization step.

(distillation step)

The distillation step is a step of distilling the purified product containing the organic solvent to obtain a distilled purified product. The method for distilling the purified product is not particularly limited, and a known method can be used. Typically, a method is employed in which a distillation column is disposed on the primary side of the purification apparatus described above, and the purified product after distillation is introduced into a production tank.

In this case, the liquid-receiving portion of the distillation column is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

In view of obtaining a chemical solution having more excellent effects of the present invention, it is more preferable that the purification target substance contains an organic solvent and an organic compound having a boiling point of 300 ℃ or higher, and the content of the organic compound in the distilled purification target substance is 1.0 × 10^-3Mass ppt-1.0 × 10³And (5) mass ppm.

The content of the organic compound in the distilled purified product is more preferably 1.0 mass ppt to 1.0 mass 1.0 × 10³Mass ppm, more preferably 1.0 mass ppb to 1.0 × 10²Mass ppm.

(reaction procedure)

The reaction step is a step of reacting the raw materials to produce a purified product containing an organic solvent as a reactant. The method for producing the purified product is not particularly limited, and a known method can be used. Typically, a method is mentioned in which a reaction tank is disposed on the primary side of the production tank (or distillation column) of the purification apparatus described above, and a reactant is introduced into the production tank (or distillation column).

In this case, the liquid-receiving portion of the reaction tank is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

(Charge removal Process)

The neutralization step is a step of neutralizing the purified material to reduce the charge potential of the purified material.

The method of removing charges is not particularly limited, and a known method of removing charges can be used. As a method for removing the electricity, for example, a method of bringing a substance to be purified into contact with a conductive material is given.

The contact time of the purified material with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and still more preferably 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, glassy carbon, and the like.

As a method of bringing the purified product into contact with the conductive material, for example, a method of disposing a grounded screen made of a conductive material inside the duct and passing the purified product through the screen may be mentioned.

Purification of the chemical solution, unsealing of the container attached thereto, cleaning of the container and the apparatus, storage of the solution, analysis, and the like are preferably performed in a clean room. The dust-free room is preferably the dust-free room of the international standard ISO 14644-1: a clean room having a cleanliness of class 4 or more as defined in 2015. Specifically, it preferably satisfies any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably satisfies ISO class 1 or ISO class 2, and still more preferably satisfies ISO class 1.

The storage temperature of the chemical solution is not particularly limited, but from the viewpoint that a trace amount of impurities and the like contained in the chemical solution is less likely to be eluted, and as a result, the storage temperature is preferably 4 ℃ or higher from the viewpoint that the effect of the present invention is more excellent.

[ other embodiment of the method for producing chemical liquid ]

Another embodiment of the method for producing a chemical solution according to the present invention is a method for producing a chemical solution, including the steps of: a step 1 of purifying a purified product containing metal-containing particles containing metal atoms and having a particle diameter of 10 to 100nm to obtain a purified product; a step 2 of obtaining a sample solution by taking out a part of the purified product; and a 3 rd step of applying the test liquid to the substrate, measuring the number of metal-containing particles per unit area on the substrate after application, and repeating the 1 st and 2 nd steps until the measured value becomes equal to or less than a predetermined value, thereby obtaining the chemical liquid.

The chemical liquid having the more excellent effects of the present invention can be easily produced by the above method for producing a chemical liquid.

(step 1)

The 1 st step is a step of purifying the purified product to obtain a purified product. The purified product and the method for purifying the purified product are as described above.

(step 2)

The 2 nd step is a step of obtaining a sample liquid by taking out a part of the purified product. The amount of the sample solution to be extracted from the purified product is not particularly limited, and may be an amount sufficient for the above-described analysis method.

The method of extracting the sample solution from the purified object is not particularly limited, and the sample solution may be extracted from a tank, a pipe, or the like in the chemical solution production apparatus, or a part of the purified object stored in a container may be used.

(step 3)

The 3 rd step is a step of applying a test solution to a substrate, measuring the number of metal-containing particles per unit area on the substrate after application, and repeating the 1 st step and the 2 nd step until the measured value becomes equal to or less than a predetermined reference value.

The method for measuring the number of metal-containing particles per unit area on the substrate is not particularly limited, but the above-described analysis method is preferably used. The reference value may be predetermined, and the value and the determination method are not particularly limited. The number of defects can be set to a reference value, for example, based on the defect suppression performance required for the chemical solution.

[ medicinal solution Container ]

The chemical solution produced by the above purification method can be stored in a container and stored until use.

Such a container and the chemical (or resist composition) contained in the container are collectively referred to as a chemical container. The liquid medicine is taken out from the stored liquid medicine container and used.

For the purpose of manufacturing semiconductor devices, it is preferable that the container for storing the chemical solution has high cleanliness and little elution of impurities.

Specific examples of usable containers include, but are not limited to, a series of "clean bottles" manufactured by AICELLO CHEMICAL co.

In order to prevent impurities from being mixed into the drug solution (contamination), it is also preferable to use a multilayer bottle having a 6-layer structure using 6 kinds of resins or a multilayer bottle having a 7-layer structure using 6 kinds of resins for the inner wall of the container. Examples of such containers include those described in Japanese patent laid-open publication No. 2015-123351.

The liquid-receiving portion of the container is preferably made of the corrosion-resistant material or glass described above. From the viewpoint of obtaining more excellent effects of the present invention, it is preferable that 90% or more of the area of the liquid-contacting portion is made of the material, and it is more preferable that the entire liquid-contacting portion is made of the material.